WO2023075704A2 - Catalysts - Google Patents

Catalysts Download PDF

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Publication number
WO2023075704A2
WO2023075704A2 PCT/SG2022/050783 SG2022050783W WO2023075704A2 WO 2023075704 A2 WO2023075704 A2 WO 2023075704A2 SG 2022050783 W SG2022050783 W SG 2022050783W WO 2023075704 A2 WO2023075704 A2 WO 2023075704A2
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WO
WIPO (PCT)
Prior art keywords
hours
vol
rpm
supported catalyst
catalyst
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PCT/SG2022/050783
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French (fr)
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WO2023075704A3 (en
Inventor
Bin Liu
Hongbin YANG
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Nanyang Technological University
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Publication of WO2023075704A2 publication Critical patent/WO2023075704A2/en
Publication of WO2023075704A3 publication Critical patent/WO2023075704A3/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • B01J35/33—
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/067—Inorganic compound e.g. ITO, silica or titania
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/089—Alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • B01J35/30—
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present disclosure generally relates to catalysts, in particular, catalysts for oxygen evolution reactions.
  • the present disclosure also relates to a method of producing such catalysts.
  • the present disclosure further relates to uses of such catalysts.
  • PEM proton exchange membrane
  • the OER In water electrolysis systems, the largest consumer of energy is the OER due to the high overpotential required by commercial catalysts, and thus most of the energy in such hydrogen production systems are accordingly dedicated to the OER half-cell process.
  • the high cost of the OER anode catalyst is the main barrier that greatly restricts the large-scale application of the PEM water electrolysis technology for hydrogen gas.
  • IrOx has been commercially used as catalysts.
  • Ir is an expensive metal, and such IrOx catalysts are not stable in acidic media, which is commonly found in PEM electrolyzers.
  • commercial catalysts and electrodes comprising the same often need to be replaced frequently, further adding to the huge operational costs of the increased energy consumption.
  • Other metals have been tested, however their costs are comparable to Ir, and thus the costs are hardly alleviated. Additionally, such catalysts formed with other metals still face the same problem of large overpotentials as well as instability in acidic media.
  • a supported catalyst comprising Ml, M2, TM, and SI, wherein:
  • M 1 and M2 are metals independently selected from the group consisting of Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb;
  • TM is a transition metal
  • S 1 is a support; wherein the weight ratio of M1:M2:TM is in the range of about 1 : 2-10 : 2-10; the weight ratio of (M1+M2):S1 is in the range of about 1 : 5-20; and Ml, M2, and TM are different.
  • the catalysts of the present disclosure may contain strong interactions between the metals and the support, which results in an unprecedented stability in acidic media. This advantageously allows the catalysts to operate for a longer time and thus there is less need to replace the catalysts frequently.
  • the catalysts of the present disclosure may also require a significantly lower overpotential to drive the OER. This advantageously translates into both a better energy efficiency of the catalyst as well as lower energy costs.
  • the catalysts of the present disclosure may also be easily tuned by introducing various dopants to adjust the various characteristics of the catalysts, such as the overpotential, pH stability in solution or conversion efficiency.
  • the catalysts of the present disclosure may also be compatible with commercial fabrication processes of PEM water electrolyzers and other electrochemical devices, and hence may be easily and advantageously taken up and made use of in industry without any difficulty.
  • a process of preparing a supported catalyst comprising the steps of: a) preparing a mixture comprising an organometallic compound of Ml, an organometallic compound of M2, an organometallic compound of TM, and SI, wherein:
  • M 1 and M2 are metals independently selected from the group consisting of Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb;
  • TM is a transition metal
  • S 1 is a support; wherein the weight ratio of M1:M2:TM is in the range of about 1 : 2-10 : 2-10; the weight ratio of (M1+M2):S1 is in the range of about 1 : 5-20; and
  • step (b) ball-milling the mixture of step (a) at a rotation speed of about 200 rpm to about 900 rpm for a duration of about 1 hour to about 5 hours to form a ball-milled mixture, and c) pyrolyzing the ball-milled mixture of step (b) at a temperature of about 300 °C to about 600 °C for a duration of about 1 hour to about 5 hours to form a pyrolyzed product.
  • the present disclosure provides for a robust and highly active catalyst that is produced through ball milling.
  • the presently disclosed catalysts are surprisingly stable in acidic media.
  • Ball-milling is both simple and environmentally friendly as it does not require significant energy input and does not require any solvent for mixing.
  • Ball-milling can also be fine-tuned to adjust metal-support interactions and produce strain and defects in the metal components, which cannot be accomplished by conventional methods such as impregnation, coprecipitation, sol-gel, etc.
  • the strain and/or defects introduced during the ball milling process may also enhance the interaction between the metals and the support, thus further improving the stability of catalysts produced by the method disclosed herein.
  • the presently disclosed method may also be easily scaled for large-scale synthesis. For example, ball-milling, pyrolysis and reduction may each be performed either in batch mode, or in flow-mode if necessary.
  • Current industrial infrastructure may also be easily and advantageously modified to fit the process requirements.
  • the presently disclosed method may comprise a reduction step.
  • the reduction step may comprise heating the product in a reductive atmosphere which may advantageously expose active sites that were previously covered by the oxide layer. Additionally, the reduction may also advantageously increase the porosity of the catalyst, further increasing its surface area and thus efficiency.
  • the presently disclosed method of producing the catalysts may also not require the use of any solvents, and thus advantageously reduces the amount of liquid waste that needs to be treated or disposed of. By avoiding the use of solvents, the problem of treating such toxic liquid waste is also thus advantageously eliminated.
  • the catalysts of the present invention may comprise expensive metals (such as iridium, ruthenium and palladium) in a much smaller weight% as compared to commercial and conventional catalysts which makes the catalyst of the present invention much more cost effective.
  • metal precursors are advantageously easier to handle as compared to the metallic elements themselves.
  • transition metal refers to a metal that is found in the d-block series of the periodic table.
  • support refers to any material which has good electron conductivity to which the catalyst is applied, and can support the same catalyst during reaction.
  • the support may provide a high surface area, as well as provide additional chemical and mechanical stability to the catalyst.
  • the phrase "at least,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements.
  • This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase "at least one" refers, whether related or unrelated to those elements specifically identified.
  • At least one of A and B can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
  • the term "about”, in the context of concentrations of components of the formulations, typically means +/- 10% of the stated value, more typically +/- 9% of the stated value, more typically +/- 8% of the stated value, more typically +/- 7% of the stated value, more typically +/- 6% of the stated value, more typically +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
  • range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • FIG. 1 A first figure.
  • Fig. 1 is a scheme depicting a general method of producing catalysts in accordance with an embodiment of the present invention.
  • Fig. 2a is a graph showing X-Ray Diffraction (XRD) patterns of various Ir R u-, based catalysts of the present invention, commercial catalysts, as well as those of WO3 and reduced WO3 (WO3-H2) as reference.
  • XRD X-Ray Diffraction
  • Fig. 2b is a Scanning Electron Microscopy (SEM) image of Iri RU3CO3-WO3-R from Example 1c.
  • Fig. 3 are spectra showing the X-ray Photoelectron Spectroscopy (XPS) of various catalysts of the present invention, (a) Survey, (b) O Is, (c) Ir 4f, (d) Ru 3d, (e) Co 2p and (f) W 4f.
  • XPS X-ray Photoelectron Spectroscopy
  • Fig. 4 are Transmission Electron Microscopy (TEM) and High-Resolution TEM (HR-TEM) images of the catalysts of the present invention, (a) 20 nm scale and (b) 2 nm scale for Iri RU3CO3-WO3; and (c) 20 nm scale and (d) 2 nm scale for hjRu3Co3-WC>3-R-450 °C.
  • TEM Transmission Electron Microscopy
  • HR-TEM High-Resolution TEM
  • Fig. 5a is a graph showing the Linear Sweep Voltammetry (LSV) curves of various catalysts of the present invention as well as that of a conventional catalyst as reference.
  • FIG. 5B is a graph showing the Linear Sweep Voltammetry (LSV) curves of various catalysts of the present invention as well as that of a conventional catalyst as reference.
  • Fig. 5b is a graph showing the corresponding Tafel plot of the results depicted in Fig. 5a.
  • Fig. 5c is a graph showing Linear Sweep Voltammetry (LSV) curves of various catalysts of the present invention as well as that of a conventional catalyst as reference, wherein values have been normalised to the mass of noble metal present.
  • LSV Linear Sweep Voltammetry
  • Fig. 5d is a graph showing the measured current density of the various catalysts of the present invention as well as that of a conventional catalyst at various overpotentials.
  • Fig. 6 is a graph showing the chronopotentiometric curves of a catalyst of the present invention, with that of a conventional catalyst as reference.
  • Ml precursor (100), M2 precursor (102), transition metal precursor (104) as well as support (106) undergo ball-milling (108).
  • the ball-milled mixture is then subjected to thermal treatment (110) to produce a supported catalyst (112) of the present invention.
  • an optional further reduction step to reduce the oxygen/oxide content of the supported catalyst.
  • the present disclosure provides for a supported catalyst comprising M 1 , M2, TM, and S 1 , wherein:
  • M 1 and M2 are metals independently selected from the group consisting of Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb;
  • TM is a transition metal
  • S 1 is a support; wherein the weight ratio of M1:M2:TM is in the range of about 1 : 2-10 : 2-10; the weight ratio of (M1+M2):S1 is in the range of about 1 : 5-20; and
  • Ml, M2, and TM are different.
  • Electron transport between the support and metals can affect the charge density and distribution of metal species, which will thus affect the catalytic properties of the catalyst.
  • Different supports can be used, for example, metal oxides such as TiOj, S11O2, WO3 amongst others, metal carbides such as TiC, WC, W2C, M02C amongst others, or metal nitrides such as TiN, TaN, amongst others.
  • the support (SI) may be a conductive support.
  • the support (SI) may be a thermally conductive support.
  • the support (SI) may be WO3, SiCL, AI2O3, carbon, TiCL, Z1O2, SiCh-AhCh, montmorillonite, SiOj-TiOj, tungstated ZrOj, zeolites, V2O5, MoOs, S11O2, TiC, WC, W2C, M02C, TiN, TaN, or mixtures and combinations thereof.
  • the support may be SiO2-
  • the weight ratio of the metals in the catalyst may comprise various ratios.
  • the weight ratio ofMl:M2:TM maybe inarange of about 1: 2-10: 2-10, about 1: 2-9: 2-10, about 1: 2-8: 2-10, about 1: 2-7: 2-10, about 1: 2-6: 2-10, about 1: 2-5: 2-10, about 1: 2-4: 2-10, about 1: 2-3: 2-10, about 1: 3- 10: 2-10, about 1: 4-10: 2-10, about 1: 5-10: 2-10, about 1: 6-10: 2-10, about 1: 7-10: 2-10, about 1: 8-10: 2-10, about 1: 9-10: 2-10, about 1: 2-10: 2-9, about 1: 2-10: 2-8, about 1: 2-10: 2-7, about 1: 2- 10: 2-6, about 1: 2-10: 2-5, about 1: 2-10: 2-4, about 1: 2-10: 2-3, about 1: 2-10: 3-10, about 1: 2-10: 4-10, about 1: 2-10:
  • the term “about” typically means +/- 10% of the stated value. This applies to all ranges mentioned herein. Hence, for example, when it is mentioned that the weight ratio of M1:M2:TM may be about 1:3 : 3, this includes a range of 0.9- 1.1 : 2.7-3.3 : 2.7-3.3.
  • the weight ratio of M1:M2:TM may be in the range of about 0.9- 1.1 : 2.7-3.3 : 2.7-3.3, about 1 : 2.7-3.2 : 2.7-3.2, 1 : 2.7-3.1 : 2.7-3.1, 1 : 2.7-3 : 2.7-3, 1 : 2.7-2.95 : 2.7-2.95, 1 : 2.7-2.94 : 2.7-2.94, 1 : 2.7-2.8 : 2.7-2.8, 1 : 2.7-2.9 : 2.7-2.9, about 1 : 2.8-3.3 : 2.8-3.3, about 1 : 2.8.2-3.3 : 2.8.2-3.3, about 1 : 2.85-3.3 : 2.85-3.3, about 1 : 2.9-3.3 : 2.9-3.3, about 1 : 2.94- 3.3 : 2.94-3.3, about 1 : 2.95-3.3 : 2.95-3.3, about 1 : 3-3.3 : 3-3.3, about 1 : 3.1-3.3 :
  • the weight ratio of M1:M2:TM may be from about 1 : 1 : 1 to about 1 : 10 : 1, from about 1 : 1 : 1 to about 1 :7: 1, from about 1 : 1 : 1 to about 1:5: 1, from about 1 : 1 : 1 to about 1:3: 1, from about 1 : 1 : 1 to about 1:2: 1, from about 1 : 2 : 1 to about 1 : 10 : 1, from about 1 : 2 : 1 to about 1:7: 1, from about 1:2: 1 to about 1:5: 1, from about 1 :2: 1 to about 1:3: 1, from about 1 : 3 : 1 to about 1 : 10 :
  • the weight ratio of M1:M2:TM may be at most about 1 : 1 : 1, at most about 1 : 2 : 1, at most about 1 : 3 : 1, at most about 1 : 5 : 1, at most about 1 : 7 : 1, at most about 1 : 10 : 1, at most about 1 : 1 :
  • the weight ratio of M1:M2:TM may be about 1 : 1 : 1, about 1 : 2: 1, about 1 : 3 : 1, about 1 :5 :
  • the present disclosure may provide for a catalyst wherein the content of the metal elements Ml, M2, and TM may be in the range of about 1 wt% to about 2 wt%, about 3 wt% to about 6 wt%, and about 3 wt% to 6 wt%, respectively.
  • the content of Ml may be in the range of about 1 wt% to about 2 wt%, about 1 wt% to about 1.9 wt%, about 1 wt% to about 1.8 wt%, about 1 wt% to about 1.7 wt%, about 1 wt% to about 1.6 wt%, about 1 wt% to about 1.5 wt%, about 1 wt% to about 1.4 wt%, about 1 wt% to about 1.3 wt%, about 1 wt% to about 1.2 wt%, about 1 wt% to about 1.1 wt%, about 1.1 wt% to about 2 wt%, about 1.2 wt% to about 2 wt%, about 1.3 wt% to about 2 wt%, about 1.4 wt% to about 2 wt%, about 1.5 wt% to about 2 wt%, about
  • 1.7 wt% or about 1 wt%, about 1.1 wt%, about 1.2 wt%, about 1.3 wt%, about 1.4 wt%, about 1.5 wt%, about 1.6 wt%, about 1.7 wt%, about 1.8 wt%, about 1.9 wt%, about 2 wt%, or any ranges or values therebetween.
  • the content of M2 may be in the range of about 3 wt% to about 6 wt%, about 3.5 wt% to about 6 wt%, about 4 wt% to about 6 wt%, about 4.5 wt% to about 6 wt%, about 4.8 wt% to about 6 wt%, about 5 wt% to about 6 wt%, about 5.5 wt% to about 6 wt%, about 3 wt% to about 5.5 wt%, about 3 wt% to about 5 wt%, about 3 wt% to about 4.8 wt%, about 3 wt% to about 4.5 wt%, about 3 wt% to about 4 wt%, about 3 wt% to about 3.5 wt%, about 3.5 wt% to about 5.5 wt%, about 4 wt% to about 5 wt%, or about 3 wt%, about 3.2 wt%, about 3.4 wt%
  • the content of M3 may be in the range of about 3 wt% to about 6 wt%, about 3.5 wt% to about 6 wt%, about 4 wt% to about 6 wt%, about 4.5 wt% to about 6 wt%, about 5 wt% to about 6 wt%, about 5.5 wt% to about 6 wt%, about 3 wt% to about 5.5 wt%, about 3 wt% to about 5 wt%, about 3 wt% to about
  • the present disclosure may provide for a catalyst, wherein the weight ratio of M1:M2:TM is in the range of about 1: 2-10 : 2-10.
  • the present disclosure may also provide for a catalyst, wherein the weight ratio of M1:M2:TM is in the range of about 1: 2-5 : 2-5.
  • the present disclosure may provide for a catalyst, wherein the weight ratio of M1:M2:TM is about 1: 3 : 3, or about 1: 2.82: 2.94.
  • the weight ratio of the metals M1+M2 in the catalyst may be related to the weight of the support (S I).
  • the weight ratio of (M1+M2):S1 may be at least about 1 : 3, at least about 1 : 5, at least about 1 : 10, at least about 1 : 15, at least about 1 : 20, at least about 1 : 30, at least about 1 : 50, or from about 1 : 3 to about 1 : 50, from about 1 : 3 to about 1 : 30, from about 1 : 3 to about 1 : 20, from about 1 : 3 to about 1 : 15, from about 1 : 3 to about 1 : 10, from about 1 : 3 to about 1 : 5, from about 1 : 5 to about 1 : 50, from about 1 : 5 to about 1 : 30, from about 1 : 5 to about 1 : 20, from about 1 :
  • the weight ratio of the support may be about 10 times
  • the weight ratio of (M1+M2):S1 may be about 1 : 5-20, about 1 : 5-18, about 1 : 5-16, about 1 : 5-14, about 1 : 5-12, about 1 : 5-10, about 1 : 5-8, about 1 : 8-20, about 1 : 10-20, about 1 : 12-20, about 1 : 14-20, about 1 : 16-20, about 1 : 18-20, or any ranges or values therebetween.
  • the weight ratio of (M1+M2):S1 may be from about 1:5 to about 1:20.
  • the weight ratio of (M1+M2):S1 may be from about 1:5 to about 1:15.
  • the weight ratio of (M1+M2):S1 may be about 1:10.
  • composition of the final products can be tuned by the ratio of metal elements to the support in the precursor mixture.
  • the composition of the metals and the support in the catalyst may also be expressed in terms of either a molar ratio, or a weight ratio.
  • the molar ratio of the metals and the support M1:M2:TM:S1 may be in a range of at least about 1 : 2 : 5: 10, at least about 1 : 3 : 5: 10, at least about 1 : 5.7 : 5: 10, at least about 1 : 6 : 5: 10, at least about 1 : 10 : 5: 10, at least about 1 : 2:5: 20, at least about 1 : 3 : 5: 20, at least about 1 : 5.7 : 5: 20, at least about 1 : 6: 5: 20, at least about 1 : 10 : 5: 20, at least about 1 : 2:5: 33.2, at least about 1 : 3 : 5: 33.2, at least about 1 : 5.7 : 5: 33.2, at least about 1 : 6: 5: 33.2, at least about 1 : 10 : 5: 33.2, at least about 1 :2:5: 34.6, at least about 1 : 3 :5: 34.6, at least about 1 : 3 :
  • the molar ratio of the metals and the support M1:M2:TM:S1 may be from about 1 : 2 : 5: 10 to about 1 : 10 : 5: 10, from about 1 :2:5: 10 to about 1 : 6 : 5: 10, from about 1 : 2 : 5: 10 to about 1 : 5.7 : 5: 10, from about 1 : 2 : 5: 10 to about 1 : 3 : 5: 10, from about 1 : 3 : 5: 10 to about 1 : 10 : 5: 10, from about 1 : 3 : 5: 10 to about 1 : 6 : 5: 10, from about 1 : 3 : 5: 10 to about 1 : 5.7 : 10: 10, from about 1 : 5.7 : 10 to about 1 : 10 : 5: 10, from about 1 : 5.7 : 10 to about 1 : 10 : 5: 10, from about 1 : 5.7 : 10 to about 1 : 10 : 5: 10, from about 1 : 5.7 : 10 to about
  • the molar ratio of the metals and the support M1:M2:TM:S1 may be at most about 1 : 2 : 5: 10, at most about 1 : 3 : 5: 10, at most about 1 : 5.7 : 5: 10, at most about 1 :6:5: 10, at most about 1 : 10 : 5: 10, at most about 1 :2:5: 20, at most about 1 : 3 :5: 20, at most about 1 : 5.7 : 5: 20, at most about 1 :6: 5: 20, at most about 1 : 10: 5: 20, at most about 1 :2:5: 33.2, at most about 1 : 3 : 5: 33.2, at most about 1 : 3 : 5: 33.2, at most about 1 : 3 : 5: 33.2, at most about
  • the molar ratio of the metals and the support M1:M2:TM:S1 may be about 1 : 2 : 5: 10, about 1 : 3 : 5: 10, about 1 : 5.7 : 5: 10, about 1 : 6 : 5: 10, about 1 : 10 : 5: 10, about 1 :2:5: 20, about 1 : 3 :5: 20, about 1 : 5.7 : 5: 20, about 1 :6:5: 20, about 1 : 10 : 5: 20, about 1 :2:5: 33.2, about 1 :3 :5: 33.2, about 1 : 5.7 : 5: 33.2, about 1 :6:5: 33.2, about 1 : 10 : 5: 33.2, about 1 : 2: 5: 34.6, about 1 : 3 :5: 34.6, about 1 : 5.7 : 5: 34.6, about 1 :6:5: 34.6, about 1 : 10 : 5: 34.6, about 1 :2:5: 50, about 1
  • the molar ratio of the metal elements and support in the catalyst may be about 1: 2-10 : 5-20 : 10- 100.
  • the molar ratio of the metal elements and support in the catalyst may be about 1 : 6 : 10 : 34.6.
  • the molar ratio of the metal elements and support in the catalyst may be about 1 : 5.7 : 9.77 : 33.2.
  • the content of the metal element in the support (S 1) may be in the range of about 40 wt% to about 60 wt%, about 45 wt% to about 60 wt%, about 50 wt% to about 60 wt%, about 55 wt% to about 60 wt%, about 40 wt% to about 55 wt%, about 40 wt% to about 50 wt%, about 40 wt% to about 45 wt%, about 45 wt% to about 55 wt%, about 50 wt% to about 55 wt%, or about 40 wt%, about 42 wt%, about 44 wt%, 46 wt%, about 48 wt%, about 50 wt%, about 52 wt%, about 54 wt%, about 56 wt%, about 58 wt%, about 60 wt%, or any ranges or values therebetween.
  • the catalysts of the present invention comprise these expensive metals in a much smaller weight% as compared to commercial and conventional catalysts.
  • the metals M1+M2 may make up the catalyst in a range of at least about 2 wt%, at least about 3 wt%, at least about 4 wt%, at least about 5 wt%, at least about 6 wt%, at least about 7 wt%, at least about 8 wt%, at least about 9 wt%, at least about 10 wt%, at least about 12 wt%, at least about 15 wt%, at least about 17 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, at least about 40 wt%, at least about 50 wt%; or from about 2 wt% to about 50 wt%, from about 2 wt% to about 40 wt%, from about 2 wt% to about 35 wt%, from about 2 wt% to about 30 wt%, from about 2 wt% to about 25 wt
  • 6 wt% to about 40 wt% from about 6 wt% to about 35 wt%, from about 6 wt% to about 30 wt%, from about 6 wt% to about 25 wt%, from about 6 wt% to about 20 wt%, from about 6 wt% to about 17 wt%, from about 6 wt% to about 15 wt%, from about 6 wt% to about 12 wt%, from about 6 wt% to about 10 wt%, from about 6 wt% to about 9 wt%, from about 6 wt% to about 8 wt%, from about 6 wt% to about 7 wt%, from about 7 wt% to about 50 wt%, from about 7 wt% to about 40 wt%, from about 7 wt% to about 35 wt%, from about 7 wt% to about 30 wt%, from about 7 wt% to about 25 wt%, from about
  • metals capable of catalyzing an OER reaction may be used.
  • metals like Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb may be used as Ml and M2 in the catalysts of the present invention.
  • the metals may be Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb.
  • the metals may be Ru, Pd, Ir, and Pt.
  • metal precursors may be used instead of providing the metals as-is for preparing the catalysts.
  • metal precursors advantageously allows for easier handling of the compounds, especially at micromolar or nanomolar scale. Additionally, precursors of the metals may make the reagents easier to weigh, and prevent unwanted metallic interactions during the preparation phase, for example, during ball-milling or pyrolysis. The use of such precursors also helps to improve the porosity and surface area of the catalysts after pyrolysis, as the salts are pyrolyzed from the mixture, leaving behind pure metals and empty spaces in the catalyst which increase surface area.
  • precursors can be used, like organometallic compounds of metals, such as metal carbonyl compounds, metal ethylene complexes, metal-acetylacetonates, metal-acetates, metal cyanide compounds, metal-bis(acetylacetonate)s, cyclopentadienyl metal compounds or mixtures and combinations thereof.
  • metals such as metal carbonyl compounds, metal ethylene complexes, metal-acetylacetonates, metal-acetates, metal cyanide compounds, metal-bis(acetylacetonate)s, cyclopentadienyl metal compounds or mixtures and combinations thereof.
  • Other precursors may also be used, as long as they can be removed cleanly during the pyrolysis step.
  • transition metals may be used, that instead of reducing the electrocatalytic properties of the catalyst, may instead enhance them. Such transition metals can also further adjust the catalytic performance of the prepared electrocatalysts.
  • the transition metal may be a Group III-XII transition metal.
  • the transition metal may be a Group IV- VII transition metal.
  • the transition metal may be a Group IV-V transition metal.
  • the transition metal may be Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au or Hg.
  • the transition metal may be Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag or Cd.
  • the transition metal may be Mn, Fe, Co, Ni or Cu.
  • the transition metal may be Co.
  • the catalysts of the present invention may have advantageously lower oxygen and/or oxide content after reduction in a reductive environment.
  • the chemical states of the surface metal elements can change from the oxidized state to either partially oxidized or even the pure metallic state.
  • Such reduced surface metal elements are particularly conducive and advantageously facilitate the OER process even more than other commercial catalysts.
  • the oxygen and/or oxide content in the catalyst before reduction may be in a range of at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, at least about 40 wt%, at least about 43 wt%, at least about 45 wt%, at least about 47 wt%, at least about 49 wt%, at least about 50 wt%, at least about 52 wt%, at least about 53 wt%, at least about 55 wt%, at least about 57 wt%, at least about 60 wt%, at least about 63 wt%, at least about 66 wt%, at least about 69 wt%, at least about 70 wt%; or from about 10 wt% to about 70 wt%, from about 10 wt% to about 69 wt%, from about 10 wt% to about
  • the catalyst has an oxygen and/or oxide content of less than about 60% before reduction. In some further preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 50% before reduction. In yet some other preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 49% before reduction. In some further preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 43% before reduction.
  • the oxygen and/or oxide content in the catalyst after reduction may be in a range of at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, at least about 40 wt%, at least about 43 wt%, at least about 45 wt%, at least about 47 wt%, at least about 49 wt%, at least about 50 wt%, at least about 52 wt%, at least about 53 wt%, at least about 55 wt%, at least about 57 wt%, at least about 60 wt%, at least about 63 wt%, at least about 66 wt%, at least about 69 wt%, at least about 70 wt%; or from about 10 wt% to about 70 wt%, from about 10 wt% to about 69 wt%, from about 10 wt% to about
  • the catalyst has an oxygen and/or oxide content of less than about 60% after reduction. In some further preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 50% after reduction. In yet some other preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 49% after reduction. In some further preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 43% after reduction.
  • the catalysts of the present disclosure may also be easily tuned by introducing various dopants (such as sulfur, selenium, or phosphorous) to adjust the various characteristics of the catalysts, such as the overpotential, pH stability in solution or conversion efficiency.
  • the dopant(s) may be added in an amount of about 0.1 wt% to about 5 wt%, about 0.5 wt% to about 5 wt%, about 1 wt% to about 5 wt%, about 2 wt% to about 5 wt%, about 3 wt% to about 5 wt%, about 4 wt% to about 5 wt%, about 0.1 wt% to about 4 wt%, 0.1 wt% to about 3 wt%, 0.1 wt% to about 2 wt%, 0.1 wt% to about 1 wt%, 0.1 wt% to about 0.5 wt%, or any ranges or values therebetween.
  • the present disclosure provides for a catalyst, wherein Ml is Ir, M2 is Ru, TM is Co, SI is WO3, the weight ratio of M1:M2:TM is about 1:3:3, and the weight ratio of (M1+M2):S1 is about 1:10, wherein the supported catalyst has an oxygen and/or oxide content of less than about 50%.
  • the present disclosure also provides for a process of preparing a supported catalyst, the process comprising the steps of: a) preparing a mixture comprising an organometallic compound of Ml, an organometallic compound of M2, an organometallic compound of TM, and SI, wherein:
  • Ml and M2 are metals independently selected from the group consisting of Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb;
  • TM is a transition metal
  • S 1 is a support; wherein the weight ratio of M1:M2:TM is in the range of about 1 : 2-10 : 2-10; the weight ratio of (M1+M2):S1 is in the range of about 1 : 5-20; and
  • step (b) ball-milling the mixture of step (a) at a rotation speed of about 200 rpm to about 900 rpm for a duration of about 1 hour to about 5 hours to form a ball-milled mixture, and c) pyrolyzing the ball-milled mixture of step (b) at a temperature of about 300 °C to about 600 °C for a duration of about 1 hour to about 5 hours to form a pyrolyzed product.
  • the mixture of metal (Ml, M2, TM) precursors as well as the support may be first ground into a homogenous mixture using ball-milling at different rotating speeds for different time durations under controlled ambient conditions, which could for example be reductive ambient or oxidizing ambient conditions.
  • milling balls may be used, for example zirconia balls, ceramic balls, alumina balls, steel balls, tungsten carbide balls, or agate balls.
  • jars may also be used, for example nylon jars.
  • zirconia balls are used in the ball milling step (b).
  • nylon jars are used in the ball milling step (b).
  • Ball-milling is a low energy process and allows the components in the mixture to mix uniformly, and be grounded as well to very fine nanoparticles.
  • tuning the parameters of the ball-milling process for example by adjusting the atmosphere of the ball-milling to either oxidizing or reducing, or by tuning other parameters of the process such as rotating speed, duration, ambient temperature, or by adding other materials, components and/or materials, the physiochemical properties of the ball-milled mixture can be tuned and adjusted. Further, various crystalline properties may even be imparted by the ball-milling process to the catalyst after ball-milling in combination with pyrolyis.
  • surfactants could also be introduced to tune or to further improve the interaction between the metal components and the support.
  • the present disclosure provides for a method of producing a catalyst, wherein ball-milling step (b) is performed in an oxidizing or reducing atmosphere.
  • the present disclosure also provides for a method of producing a catalyst, wherein ball-milling step (b) is performed in an oxidizing atmosphere.
  • the present disclosure further provides for a method of producing a catalyst, wherein ball-milling step (b) is performed in an reducing atmosphere.
  • the ball-milling step (b) may be performed at a rotation speed in a range of at least about 100 rpm, at least about 150 rpm, at least about 200 rpm, at least about 250 rpm, at least about 300 rpm, at least about 350 rpm, at least about 400 rpm, at least about 450 rpm, at least about 500 rpm, at least about 600 rpm, at least about 700 rpm, at least about 800 rpm, at least about 900 rpm, at least about 1000 rpm; or from about 100 rpm to about 1000 rpm, from about 100 rpm to about 900 rpm, from about 100 rpm to about 800 rpm, from about 100 rpm to about 700 rpm, from about 100 rpm to about 600 rpm, from about 100 rpm to about 500 rpm, from about 100 rpm to about 450 rpm, from about 100 rpm to about 400 rpm, from about 100 rpm to about 350 r
  • the ball-milling step (b) is performed for a duration range of at least about 0.5 hours, at least about 1 hour, at least about 1.5 hours, at least about 2 hours, at least about 2.5 hours, at least about 3 hours, at least about 3.5 hours, at least about 4 hours, at least about 4.5 hours, at least about 5 hours, at least about 6 hours, at least about 7 hours, at least about 8 hours, at least about 9 hours, at least about 10 hours; or from about 0.5 hours to about 10 hours, from about 0.5 hours to about 9 hours, from about 0.5 hours to about 8 hours, from about 0.5 hours to about 7 hours, from about 0.5 hours to about 6 hours, from about 0.5 hours to about 5 hours, from about 0.5 hours to about 4.5 hours, from about 0.5 hours to about 4 hours, from about 0.5 hours to about 3.5 hours, from about 0.5 hours to about 3 hours, from about 0.5 hours to about 2.5 hours, from about 0.5 hours to about 2 hours, from about 0.5 hours to about 1.5 hours, from about 0.5 hours to about 1 hour, from
  • the catalyst may have an average particle size in a range of at least about 0.5 nm, at least about 0.8 nm, at least about 1 nm, at least about 2 nm, at least about 3 nm, at least about 4 nm, at least about 5 nm, at least about 6 nm, at least about 7 nm, at least about 8 nm, at least about 9 nm, at least about 10 nm, at least about 12 nm, at least about 14 nm, at least about 15 nm, at least about 16 nm, at least about 18 nm, at least about 20 nm, at least about 25 nm, at least about 30 nm, at least about 40 nm, at least about 50 nm; or from about 0.5 nm to about 50 nm, from about 0.5 nm to about 40 nm, from about 0.5 nm to about 30 nm, from about 0.5 nm to about 25
  • the average particle size of the catalyst is from about
  • step (c) 2 nm to about 5 nm after the pyrolysis of step (c).
  • the present disclosure provides for a catalyst, wherein the catalyst has an average particle size of about 1 nm to about 10 nm.
  • the present disclosure also provides for a catalyst, wherein the catalyst has an average particle size of about 2 nm to about 5 nm.
  • the present disclosure further provides for a method of preparing a catalyst, wherein step (c) produces a product having an average particle size of about 1 nm to about 10 nm.
  • step (c) produces a product having an average particle size of about 2 nm to about 5 nm.
  • the mixture from step (b) may be subjected to a thermal treatment step, for example pyrolysis, to remove the salts from the metal precursors, in order to leave behind metals and support.
  • a thermal treatment step for example pyrolysis
  • the thermal treatment may also be adjusted to further tune the physiochemical properties of the mixture remaining after thermal treatment.
  • the thermal treatment step (c) may be performed at a temperature range of at least about 200 °C, at least about 250 °C, at least about 275 °C, at least about 300 °C, at least about 325 °C, at least about 350 °C, at least about 375 °C, at least about 400 °C, at least about 450 °C, at least about 500 °C, at least about 550 °C, at least about 600 °C, at least about 650 °C, at least about 700 °C, at least about 750 °C, at least about 800 °C, at least about 900 °C, at least about 1000 °C; or from about 200 °C to about 1000 °C, from about 200 °C to about 900 °C, from about 200 °C to about 800 °C, from about 200 °C to about 750 °C, from about 200 °C to about 700 °C, from about 200 °C to about 650 °C, from about 200
  • the thermal treatment step (c) may also be performed for a duration of at least about 0.5 hours, at least about 1 hour, at least about 1.5 hours, at least about 2 hours, at least about 2.5 hours, at least about 3 hours, at least about 3.5 hours, at least about 4 hours, at least about 4.5 hours, at least about 5 hours, at least about 6 hours, at least about 7 hours, at least about 8 hours, at least about 9 hours, at least about 10 hours; or from about 0.5 hours to about 10 hours, from about 0.5 hours to about 9 hours, from about 0.5 hours to about 8 hours, from about 0.5 hours to about 7 hours, from about 0.5 hours to about 6 hours, from about 0.5 hours to about 5 hours, from about 0.5 hours to about 4.5 hours, from about 0.5 hours to about 4 hours, from about 0.5 hours to about 3.5 hours, from about 0.5 hours to about 3 hours, from about 0.5 hours to about 2.5 hours, from about 0.5 hours to about 2 hours, from about 0.5 hours to about 1.5 hours, from about 0.5 hours to about 1 hour, from about
  • the ramping rate of the temperature during the thermal treatment can also be used to tune the physiochemical properties of the catalyst.
  • the ramping rate may be in a range of at least about 0.1 °C/min, at least about 0.2 °C/min, at least about 0.25 °C/min, at least about 0.5 °C/min, at least about 0.75 °C/min, at least about 1.0 °C/min, at least about 1.25 °C/min, at least about 1.5 °C/min, at least about 1.75 °C/min, at least about 2.0 °C/min, at least about 2.25 °C/min, at least about 2.5 °C/min, at least about 2.75 °C/min, at least about 3.0 °C/min, at least about 3.5 °C/min, at least about 4.0 °C/min, at least about 4.5 °C/min, at least about 5.0 °C/min, at least about 6.0 °C/min; or from about 0.1 °C/
  • the present disclosure provides for a method of producing a catalyst, comprising pyrolyzing the ball-milled mixture of step (b) at a temperature of about 300 °C to about 600 °C for a duration of about 1 hour to about 5 hours to form a pyrolyzed product.
  • the present disclosure provides for a method of producing a catalyst, comprising pyrolyzing the ball-milled mixture of step (b) at a temperature of about 450 °C for a duration of about 2 hours to form a pyrolyzed product.
  • the present disclosure also discloses a method for preparing a supported catalyst, further comprising step (d) reducing the pyrolyzed product of step (c) to form the supported catalyst.
  • the presently disclosed method may also disclose a further step (d) to reduce the pyrolyzed product from step (c) to form the supported catalyst.
  • Reducing the pyrolyzed product from step (c) advantageously reduces the oxygen and/or oxide content of the catalyst which may accordingly increase the amount of active sites available for catalysis. Reducing the product may also surprisingly open up more activation sites that were previously unavailable to due the previously present oxide layers. Reduction may also further improve the porosity and surface area of the catalyst thus further improving its catalytic and OER efficiency.
  • the product of step (d) may be lower in oxygen and/or oxide compared as compared to before step (d) was applied.
  • the reduction step (d) may be performed in a reductive atmosphere, at a temperature of at least about 200 °C, at least about 250 °C, at least about 300 °C, at least about 350 °C, at least about 375 °C, at least about 400 °C, at least about 425 °C, at least about 450 °C, at least about 475 °C, at least about 500 °C, at least about 525 °C, at least about 550 °C, at least about 575 °C, at least about 600 °C, at least about 625 °C, at least about 650 °C, at least about 700 °C, at least about 750 °C, at least about 800 °C; or from about
  • Step (d) may be performed in a reductive atmosphere for a duration of at least about 0.1 hours, at least about 0.25 hours, at least about 0.5 hours, at least about 0.75 hours, at least about 1 hour, at least about 1.5 hours, at least about 2 hours, at least about 2.5 hours, at least about 3 hours, at least about 3.5 hours, at least about 4 hours, at least about 4.5 hours, at least about 5 hours, at least about 6 hours, at least about 7 hours, at least about 8 hours, at least about 9 hours, at least about 10 hours; or from about 0.1 hours to about 10 hours, from about 0.1 hours to about 9 hours, from about 0.1 hours to about 8 hours, from about 0.1 hours to about 7 hours, from about 0.1 hours to about 6 hours, from about 0.1 hours to about 5 hours, from about 0.1 hours to about 4.5 hours, from about 0.1 hours to about 4 hours, from about 0.1 hours to about 3.5 hours, from about 0.1 hours to about 3 hours, from about 0.1 hours to about 2.5 hours, from about 0.1 hours to about 2
  • step (d) is performed in a reductive atmosphere at a temperature of about 300 °C to about 600 °C, for a duration of about 0.5 hours to about 3 hours.
  • the reductive atmosphere comprises in Ar, Hi in a range of at least about 0.1 vol%, at least about 0.2 vol%, at least about 0.4 vol%, at least about 0.6 vol%, at least about 0.8 vol%, at least about 1.0 vol%, at least about 1.25 vol%, at least about 1.5 vol%, at least about 1.75 vol%, at least about 2.0 vol%, at least about 2.5 vol%, at least about 3.0 vol%, at least about 4.0 vol%, at least about 5.0 vol%, at least about 6.0 vol%, at least about 7.0 vol%, at least about 8.0 vol%, at least about 9.0 vol%, at least about 10.0 vol%, at least about 12.0 vol%, at least about 15.0 vol%, at least about 20.0 vol%, at least about 25.0 vol%, at least about 30.0 vol%, at least about 35.0 vol%, at least about 40.0 vol%; or from about 0.1 vol% to about 40.0 vol%, from about 0.1 vol% to about 35.0 vol%, from about
  • the present disclosure provides for a method of producing a supported catalyst, wherein the reductive atmosphere comprises from about 1 vol% to about 10 vol% Hj in Ar.
  • the present disclosure also provides for a method of producing a supported catalyst, wherein the oxygen and/or oxide content of the supported catalyst of step (d) is lower than the oxygen and/or oxide content of the pyrolyzed product of step (c).
  • the oxygen and/or oxide content of the supported catalyst of step (d) may be lower than the oxygen and/or oxide content of the pyrolyzed product of step (c) in a range of at least about 0.1 wt%, at least about 0.2 wt%, at least about 0.5 wt%, at least about 1 wt%, at least about 2 wt%, at least about 3 wt%, at least about 5 wt%, at least about 7 wt%, at least about 9 wt%, at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%; or from about 0.1 wt% to about 40 wt%, from about 0.1 wt% to about 30 wt%, from about 0.1 wt% to about 20 wt%, from about 0.1 wt% to about 15 wt%, from about 0.1 wt% to about 10 wt
  • the presently disclosed method may be performed without using any solvents. This advantageously reduces the amount of liquid waste that needs to be treated or disposed of. By avoiding the use of solvents, the problem of treating such toxic liquid waste is also thus advantageously eliminated. Such a method is also advantageously more cost effective.
  • organometallic compounds of Ml, M2 and TM may comprise metal carbonyl compounds, metal ethylene complexes, metal-acetylacetonates, metal-acetates, metal cyanide compounds, metal-bis(acetylacetonate)s, and cyclopentadienyl metal compounds.
  • the present disclosure provides for a method, wherein the organometallic compound of Ml, M2 and TM is independently selected from the group consisting of metal carbonyl compounds, metal ethylene complexes, metal-acetylacetonates, metal-acetates, metal cyanide compounds, metal- bis(acetylacetonate)s, and cyclopentadienyl metal compounds.
  • the catalyst of the present invention may be used to advantageously drive a OER at a much higher efficiency as compared to other conventional catalysts.
  • the catalysts of the present invention may also advantageously require a much lower overpotential as compared to commercial catalysts to drive the OER, which results in lower energy costs, as well as increased safety, and increased energy efficiency.
  • the catalysts of the present invention may also exhibit unprecedented stability in acidic media. This is particularly pertinent as long-term operation of the catalysts in acidic conditions during hydrogen production and/or OER can result in degradation of the electrode, which thus requires the electrode to be regularly replaced. This results in increased operational costs. Instead, by providing catalysts that have unprecedented stability in acidic media, the electrodes formed from such catalysts are much more stable and thus require lower maintenance, resulting in advantageously lower operational costs in the long run.
  • the electrolytic production of hydrogen from water is also a concurrent process, comprising a Hydrogen Evolution Reaction (HER), as well as an Oxygen Evolution Reaction (OER).
  • HER Hydrogen Evolution Reaction
  • OER Oxygen Evolution Reaction
  • HER Hydrogen Evolution Reaction
  • OER Oxygen Evolution Reaction
  • (supported) catalysts are presently disclosed, for which they require a much lower overpotential as compared to commercial OER catalysts. Additionally, they also exhibit much better stability in acidic media as compared to commercial OER catalysts.
  • the catalysts of the present invention may also be advantageously used to produce hydrogen at much higher energy and cost efficiency as compared to commercial OER catalysts, with the concomitant release of oxygen in the process.
  • the present disclosure provides for a use of the catalyst disclosed herein for forming an electrode.
  • the present disclosure further provides for a use of the catalyst disclosed herein to produce oxygen.
  • the present disclosure also provides for a use of a supported catalyst disclosed herein to produce hydrogen.
  • the catalyst of the present invention may also be incorporated as an electrode into an electrochemical cell.
  • the catalyst of the present invention may also be incorporated as part of a system for producing hydrogen and/or oxygen.
  • the catalysts prepared by the methods described in the following examples exhibits enhanced intrinsic catalytic activity and stability during acidic water oxidation reactions, when compared to conventional pure IrO x catalysts.
  • the catalysts of the present invention may also provide up to 25 times higher catalytic activity while maintaining an enhanced catalytic stability.
  • the catalyst products may also be compatible with conventional processes for fabricating Polymer Electrolyte Membrane (PEM) water electrolyzers. Given the much lower loading of iridium and ruthenium, the catalysts and the methods for making such catalysts as disclosed in the present invention are expected to become a viable choice when fabricating PEM water electrolyzers.
  • PEM Polymer Electrolyte Membrane
  • a mixture of iridium-acetylacetonate (25.47 mg), ruthenium-acetylacetonate (118.26 mg), cobalt - acetylacetonate (Co(acac)j, 181.15 mg) and WO3 support (400 mg) were added into a Nylon jar.
  • the mixture comprised iridium, ruthenium and cobalt metals in a weight ratio of about 1:3:3 (Ir:Ru:Co), whereas the weight of WO3 added was 10 times the total weight of the metals (M1+M2; Ir+Ru) present.
  • the above mixture comprises Co metal (30 mg), Ir metal (10 mg), Ru metal (30 mg) and WO3 (400 mg) and the molar ratio of Ir:Ru:Co:W in the mixture is about 1 : 6 : 10 : 34.6.
  • the composition of the metals in the final mixture can be accordingly tuned by adjusting the ratio of the salts added to the mixture prior to ball-milling. Zirconia milling beads were further added to the mixture in the Nylon jar, after which the mixture was subjected to ball-milling with a rotating speed of 300 rpm for 3 hours.
  • Example la The ball-milled mixture from Example la was subjected to pyrolysis in air at 450 °C (25 °C to 450 °C at a ramping rate of 2.0 °C/min, maintaining at 450 °C for 2 h) in a muffle furnace (Carbolite, UK). After cooling down to room temperature, the product was collected and named as Ii iRmCo;,- WO 3 .
  • Example lb A portion of the product from Example lb was reduced in a reductive atmosphere at either 450 °C or 550 °C in 5 % FE/Ar for 1 h in a tubular furnace (Carbolite, UK) to obtain either hjRusCos- WO3-R-450 °C or IriRu 3 Co 3 -WO3-R-550 °C.
  • ICP Inductively Coupled Plasma
  • Fig. 2a shows the XRD patterns of the catalysts prepared from Examples lb and 1c, with some other catalysts as reference.
  • most of the diffraction signals originate from the WO3 support.
  • Example 1c hjRu3Co3-WO3-R-450 °C
  • a very weak diffraction peak appears at -45°, which can be assigned to the (101) diffraction of metallic Ru.
  • the weak diffraction intensity of noble metal related compounds again, agrees well with the low content of noble metals in the samples.
  • Fig. 2b showing the SEM image of the product from Example 1c (hjRu3Co3-WO3-R-450 °C), indicates aggregated nanoparticles with size of several hundred nanometers. No obvious structure segregation can be identified, suggesting that Ii'iRinCo? has been uniformly loaded on the WO3 support.
  • TEM images show that average particle size was in the range of 2-5 nm for the product from Example lb ( hi RinGn-WOd after the pyrolysis step. Moreover, the average size of particles did not change after further thermal treatment in reductive atmosphere at 450 °C in H2(5 %)/Ar for 1 h (Fig. 4c and 4d). This could suggest that the catalyst after pyrolysis comprises substantially either metals or their oxides thereof. The reduction of the catalyst without changing the average size could also indicate that the catalysts have become more porous after the reduction process.
  • the chemical states of samples were further examined by X-ray photoelectron spectroscopy (XPS) and shown in Figs. 3a to 3f.
  • XPS X-ray photoelectron spectroscopy
  • Fig. 3 shows the O Is, Ir 4f, Ru 3d, Co 2p and W 4f of the products from Examples lb and 1c (IriRusCos-WOs, IriRu3Co3-WO3-R-450 °C and IriRu3Co3-WO3-R-550 °C).
  • thermal treatment in reductive atmosphere was able to reduce the content of oxygen in samples.
  • the oxygen content decreased from about 52 % to 49% after the product from Example lb was reduced at 450 °C and decreased from about 52 % to 43 % after reduction at 550 °C.
  • Figs. 5a to 5d show the results of the Linear Sweep Voltammetry experiments, wherein the curves were recorded at a scan rate of 5 mV s -1 normalized to geometric area.
  • Fig. 5a compares the LSV curves, among which hjRusCos-WCL-R (produced at either reduction at 450 °C or 550 °C) displayed the best OER performance in the acidic medium with the lowest overpotential to reach 10 mA cm 2 catalytic current density (260 mV). This was in comparison to commercial IrO x catalyst requiring an overpotential of 290 mV.
  • the Tafel slope of hi RinC WCh-R (both 450 °C and 550 °C) were about 46 mV/dec, much lower than that of commercial IrO x (66 mV/dec).
  • the Ii'i RusCos-WOs-R exhibited much higher intrinsic water oxidation activity.
  • the mass- normalized current density of hi RinG)?- WO3-R as shown in Fig. 5c was about 250 mA/mgNobie-Metai, which is 25 times higher than that of the commercial IrO x catalyst.
  • the stability of the catalyst hjRu3Co3-WO3-R-450 °C from Example 1c was evaluated using chronopotentiometry experiments.
  • the mass loading of Ir+Ru for hjRu3Co3-WO3-R-450 °C and IrO x catalyst were 100 pg and 225 pg cm“ 2 gm , respectively.
  • the experiment was recorded in 0.5 M H2SO4 electrolyte at a current density of 10 mA cm“ 2 gm .
  • hjRu3Co3-WO3-R-450 °C is very stable in acidic conditions, which is likely due to the strong interaction between the metals ( Ii'iRinCo?) and the WO3 support.
  • the present invention relates to catalysts, in particular, catalysts for oxygen evolution reactions.
  • the catalysts of the present invention require a significantly lower overpotential to drive the OER as compared to currently known catalysts.
  • the catalysts of the present invention are also advantageously compatible with commercial fabrication processes of PEM water electrolyzers and other electrochemical devices, and hence may be easily taken up without any difficulty.
  • the catalysts of the present invention may thus also be advantageously used in producing hydrogen.
  • the present disclosure also refers to a method of producing such catalysts.
  • the method of the present invention may be easily scaled for large-scale synthesis. Current industrial infrastructure can also be easily modified to fit the process requirements.
  • the method of the present invention also does not use any solvents, and thus greatly reduces the amount of liquid waste that needs to be treated or disposed of, reducing environmental waste produced.
  • the method of the present invention accordingly also does not product liquid wastes of metals that are often toxic and/or environmentally hazardous, hence further reducing its environmental impact.
  • the method of the present invention also utilizes precursors that are advantageously easier to handle as compared to the metallic elements, and thus the method is easier to take up in industry. Thus this invention is capable of industrial applicability.

Abstract

The present disclosure refers to a supported catalyst comprising M1, M2, TM, and S1, wherein: M1 and M2 are metals independently selected from the group consisting of Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb; TM is a transition metal; S1 is a support; wherein the weight ratio of M1:M2:TM is in the range of about 1 : 2-10 : 2-10; the weight ratio of (M1+M2):S1 is in the range of about 1 : 5-20; and M1, M2, and TM are different. The present disclosure also refers to a process of preparing a supported catalyst, the process comprising the steps of: (a) preparing a mixture comprising an organometallic compound of M1, an organometallic compound of M2, an organometallic compound of TM, and S1, wherein: M1 and M2 are metals independently selected from the group consisting of Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb; TM is a transition metal; S1 is a support; wherein the weight ratio of M1:M2:TM is in the range of about 1 : 2-10 : 2-10; the weight ratio of (M1+M2):S1 is in the range of about 1 : 5-20; and M1, M2, and TM are different; (b) ball-milling the mixture of step (a) at a rotation speed of about 200 rpm to about 900 rpm for a duration of about 1 hour to about 5 hours to form a ball-milled mixture, and (c) pyrolyzing the ball-milled mixture of step (b) at a temperature of about 300 °C to about 600 °C for a duration of about 1 hour to about 5 hours to form a pyrolyzed product. The present disclosure also refers to a use of a supported catalyst disclosed herein to produce hydrogen.

Description

Title of Invention: Catalysts
Technical Field
The present disclosure generally relates to catalysts, in particular, catalysts for oxygen evolution reactions. The present disclosure also relates to a method of producing such catalysts. The present disclosure further relates to uses of such catalysts.
Background Art
The production of green hydrogen through proton exchange membrane (PEM) water electrolysis provides a promising strategy enabling storage, transportation and deployment of renewable electricity, and plays an important role in the transition towards a hydrogen economy. Water electrolysis systems usually consist of two half-reactions: a hydrogen evolution reaction (HER) at the cathode and oxygen evolution reaction (OER) at the anode.
In water electrolysis systems, the largest consumer of energy is the OER due to the high overpotential required by commercial catalysts, and thus most of the energy in such hydrogen production systems are accordingly dedicated to the OER half-cell process. Currently, the high cost of the OER anode catalyst is the main barrier that greatly restricts the large-scale application of the PEM water electrolysis technology for hydrogen gas.
IrOx has been commercially used as catalysts. However, Ir is an expensive metal, and such IrOx catalysts are not stable in acidic media, which is commonly found in PEM electrolyzers. Hence, commercial catalysts and electrodes comprising the same often need to be replaced frequently, further adding to the huge operational costs of the increased energy consumption. Other metals have been tested, however their costs are comparable to Ir, and thus the costs are hardly alleviated. Additionally, such catalysts formed with other metals still face the same problem of large overpotentials as well as instability in acidic media.
Thus, there is a need to find catalysts that ameliorates or solves at least one of the problems stated above.
Summary
In an aspect of the present disclosure, there is provided a supported catalyst comprising Ml, M2, TM, and SI, wherein:
M 1 and M2 are metals independently selected from the group consisting of Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb;
TM is a transition metal;
S 1 is a support; wherein the weight ratio of M1:M2:TM is in the range of about 1 : 2-10 : 2-10; the weight ratio of (M1+M2):S1 is in the range of about 1 : 5-20; and Ml, M2, and TM are different.
Advantageously, the catalysts of the present disclosure may contain strong interactions between the metals and the support, which results in an unprecedented stability in acidic media. This advantageously allows the catalysts to operate for a longer time and thus there is less need to replace the catalysts frequently.
The catalysts of the present disclosure may also require a significantly lower overpotential to drive the OER. This advantageously translates into both a better energy efficiency of the catalyst as well as lower energy costs.
The catalysts of the present disclosure may also be easily tuned by introducing various dopants to adjust the various characteristics of the catalysts, such as the overpotential, pH stability in solution or conversion efficiency.
The catalysts of the present disclosure may also be compatible with commercial fabrication processes of PEM water electrolyzers and other electrochemical devices, and hence may be easily and advantageously taken up and made use of in industry without any difficulty.
In another aspect of the present disclosure, there is provided a process of preparing a supported catalyst, the process comprising the steps of: a) preparing a mixture comprising an organometallic compound of Ml, an organometallic compound of M2, an organometallic compound of TM, and SI, wherein:
M 1 and M2 are metals independently selected from the group consisting of Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb;
TM is a transition metal;
S 1 is a support; wherein the weight ratio of M1:M2:TM is in the range of about 1 : 2-10 : 2-10; the weight ratio of (M1+M2):S1 is in the range of about 1 : 5-20; and
Ml, M2, and TM are different, b) ball-milling the mixture of step (a) at a rotation speed of about 200 rpm to about 900 rpm for a duration of about 1 hour to about 5 hours to form a ball-milled mixture, and c) pyrolyzing the ball-milled mixture of step (b) at a temperature of about 300 °C to about 600 °C for a duration of about 1 hour to about 5 hours to form a pyrolyzed product.
In a further aspect of the present disclosure, there is provided a use of a supported catalyst disclosed herein to produce hydrogen.
The present disclosure provides for a robust and highly active catalyst that is produced through ball milling. The presently disclosed catalysts are surprisingly stable in acidic media.
This is advantageous as ball-milling is both simple and environmentally friendly as it does not require significant energy input and does not require any solvent for mixing. Ball-milling can also be fine-tuned to adjust metal-support interactions and produce strain and defects in the metal components, which cannot be accomplished by conventional methods such as impregnation, coprecipitation, sol-gel, etc. Further advantageously, the strain and/or defects introduced during the ball milling process may also enhance the interaction between the metals and the support, thus further improving the stability of catalysts produced by the method disclosed herein.
The presently disclosed method may also be easily scaled for large-scale synthesis. For example, ball-milling, pyrolysis and reduction may each be performed either in batch mode, or in flow-mode if necessary. Current industrial infrastructure may also be easily and advantageously modified to fit the process requirements.
The presently disclosed method may comprise a reduction step. The reduction step may comprise heating the product in a reductive atmosphere which may advantageously expose active sites that were previously covered by the oxide layer. Additionally, the reduction may also advantageously increase the porosity of the catalyst, further increasing its surface area and thus efficiency.
The presently disclosed method of producing the catalysts may also not require the use of any solvents, and thus advantageously reduces the amount of liquid waste that needs to be treated or disposed of. By avoiding the use of solvents, the problem of treating such toxic liquid waste is also thus advantageously eliminated.
Also advantageously, the catalysts of the present invention may comprise expensive metals (such as iridium, ruthenium and palladium) in a much smaller weight% as compared to commercial and conventional catalysts which makes the catalyst of the present invention much more cost effective.
Further advantageously, metal precursors are advantageously easier to handle as compared to the metallic elements themselves.
Definitions
Unless otherwise defined herein, scientific and technical terms used in this application shall have the meanings that are commonly understood by those of ordinary skill in the art. Generally, nomenclature used in connection with, and techniques of, chemistry described herein, are those well- known and commonly used in the art.
Unless the context requires otherwise or specifically stated to the contrary, integers, steps, or elements of the invention recited herein as singular integers, steps or elements clearly encompass both singular and plural forms of the recited integers, steps or elements.
As used herein, the terms “catalyst” and “supported catalyst” are used interchangeably. As used herein, the term “transition metal” refers to a metal that is found in the d-block series of the periodic table.
As used herein, the term “support” refers to any material which has good electron conductivity to which the catalyst is applied, and can support the same catalyst during reaction. The support may provide a high surface area, as well as provide additional chemical and mechanical stability to the catalyst.
The word “substantially” does not exclude “completely” e.g. a composition which is “substantially free” from Y may be completely free from Y. Where necessary, the word “substantially” may be omitted from the definition of the invention.
As used herein in the specification and in the claims, the phrase "at least," in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase "at least one" refers, whether related or unrelated to those elements specifically identified. Thus, as a nonlimiting example, "at least one of A and B" (or, equivalently, "at least one of A or B," or, equivalently "at least one of A and/or B") can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
Unless specified otherwise, the terms "comprising" and "comprise", and grammatical variants thereof, are intended to represent "open" or "inclusive" language such that they include recited elements but also permit inclusion of additional, unrecited elements.
As used herein, the term "about", in the context of concentrations of components of the formulations, typically means +/- 10% of the stated value, more typically +/- 9% of the stated value, more typically +/- 8% of the stated value, more typically +/- 7% of the stated value, more typically +/- 6% of the stated value, more typically +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
Throughout this disclosure, certain embodiments may be disclosed in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
Certain embodiments may also be described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the disclosure. This includes the generic description of the embodiments with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.
Brief Description of Drawings
The accompanying drawings illustrate disclosed embodiments and serve to explain the principles of the disclosed embodiments. It is to be understood, however, that the drawings are designed for purposes of illustration only, and not as a definition of the limits of the invention.
FIG. 1
Fig. 1 is a scheme depicting a general method of producing catalysts in accordance with an embodiment of the present invention.
FIG. 2A
Fig. 2a is a graph showing X-Ray Diffraction (XRD) patterns of various Ir R u-, based catalysts of the present invention, commercial catalysts, as well as those of WO3 and reduced WO3 (WO3-H2) as reference.
FIG. 2B
Fig. 2b is a Scanning Electron Microscopy (SEM) image of Iri RU3CO3-WO3-R from Example 1c.
FIG. 3
Fig. 3 are spectra showing the X-ray Photoelectron Spectroscopy (XPS) of various catalysts of the present invention, (a) Survey, (b) O Is, (c) Ir 4f, (d) Ru 3d, (e) Co 2p and (f) W 4f.
FIG. 4
Fig. 4 are Transmission Electron Microscopy (TEM) and High-Resolution TEM (HR-TEM) images of the catalysts of the present invention, (a) 20 nm scale and (b) 2 nm scale for Iri RU3CO3-WO3; and (c) 20 nm scale and (d) 2 nm scale for hjRu3Co3-WC>3-R-450 °C.
FIG. 5A
Fig. 5a is a graph showing the Linear Sweep Voltammetry (LSV) curves of various catalysts of the present invention as well as that of a conventional catalyst as reference. FIG. 5B
Fig. 5b is a graph showing the corresponding Tafel plot of the results depicted in Fig. 5a.
FIG. 5C
Fig. 5c is a graph showing Linear Sweep Voltammetry (LSV) curves of various catalysts of the present invention as well as that of a conventional catalyst as reference, wherein values have been normalised to the mass of noble metal present.
FIG. 5D
Fig. 5d is a graph showing the measured current density of the various catalysts of the present invention as well as that of a conventional catalyst at various overpotentials.
FIG. 6
Fig. 6 is a graph showing the chronopotentiometric curves of a catalyst of the present invention, with that of a conventional catalyst as reference.
Detailed Disclosure of Drawings
Referring to Fig. 1, Ml precursor (100), M2 precursor (102), transition metal precursor (104) as well as support (106) undergo ball-milling (108). The ball-milled mixture is then subjected to thermal treatment (110) to produce a supported catalyst (112) of the present invention. Not depicted here is an optional further reduction step to reduce the oxygen/oxide content of the supported catalyst.
Detailed Disclosure of Embodiments
The present disclosure provides for a supported catalyst comprising M 1 , M2, TM, and S 1 , wherein:
M 1 and M2 are metals independently selected from the group consisting of Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb;
TM is a transition metal;
S 1 is a support; wherein the weight ratio of M1:M2:TM is in the range of about 1 : 2-10 : 2-10; the weight ratio of (M1+M2):S1 is in the range of about 1 : 5-20; and
Ml, M2, and TM are different.
Electron transport between the support and metals can affect the charge density and distribution of metal species, which will thus affect the catalytic properties of the catalyst. Different supports can be used, for example, metal oxides such as TiOj, S11O2, WO3 amongst others, metal carbides such as TiC, WC, W2C, M02C amongst others, or metal nitrides such as TiN, TaN, amongst others.
The support (SI) may be a conductive support. The support (SI) may be a thermally conductive support. The support (SI) may be WO3, SiCL, AI2O3, carbon, TiCL, Z1O2, SiCh-AhCh, montmorillonite, SiOj-TiOj, tungstated ZrOj, zeolites, V2O5, MoOs, S11O2, TiC, WC, W2C, M02C, TiN, TaN, or mixtures and combinations thereof. The support may be SiO2-
The weight ratio of the metals in the catalyst may comprise various ratios. The weight ratio ofMl:M2:TM maybe inarange of about 1: 2-10: 2-10, about 1: 2-9: 2-10, about 1: 2-8: 2-10, about 1: 2-7: 2-10, about 1: 2-6: 2-10, about 1: 2-5: 2-10, about 1: 2-4: 2-10, about 1: 2-3: 2-10, about 1: 3- 10: 2-10, about 1: 4-10: 2-10, about 1: 5-10: 2-10, about 1: 6-10: 2-10, about 1: 7-10: 2-10, about 1: 8-10: 2-10, about 1: 9-10: 2-10, about 1: 2-10: 2-9, about 1: 2-10: 2-8, about 1: 2-10: 2-7, about 1: 2- 10: 2-6, about 1: 2-10: 2-5, about 1: 2-10: 2-4, about 1: 2-10: 2-3, about 1: 2-10: 3-10, about 1: 2-10: 4-10, about 1: 2-10: 5-10, about 1: 2-10: 6-10, about 1: 2-10: 7-10, about 1: 2-10: 8-10, about 1: 2- 10: 9-10, about 1: 2-9: 2-9, about 1: 2-8: 2-8, about 1: 2-7: 2-7, about 1: 2-6: 2-6, about 1: 2-5: 2-5, about 1: 2-4: 2-4, about 1: 2-3: 2-3, or any ranges, ratios or values therebetween. The weight ratio of M1:M2:TM may be about 1: 3 : 3.
As mentioned in the definitions section above, as used herein, the term “about” typically means +/- 10% of the stated value. This applies to all ranges mentioned herein. Hence, for example, when it is mentioned that the weight ratio of M1:M2:TM may be about 1:3 : 3, this includes a range of 0.9- 1.1 : 2.7-3.3 : 2.7-3.3. Hence, the weight ratio of M1:M2:TM may be in the range of about 0.9- 1.1 : 2.7-3.3 : 2.7-3.3, about 1 : 2.7-3.2 : 2.7-3.2, 1 : 2.7-3.1 : 2.7-3.1, 1 : 2.7-3 : 2.7-3, 1 : 2.7-2.95 : 2.7-2.95, 1 : 2.7-2.94 : 2.7-2.94, 1 : 2.7-2.8 : 2.7-2.8, 1 : 2.7-2.9 : 2.7-2.9, about 1 : 2.8-3.3 : 2.8-3.3, about 1 : 2.8.2-3.3 : 2.8.2-3.3, about 1 : 2.85-3.3 : 2.85-3.3, about 1 : 2.9-3.3 : 2.9-3.3, about 1 : 2.94- 3.3 : 2.94-3.3, about 1 : 2.95-3.3 : 2.95-3.3, about 1 : 3-3.3 : 3-3.3, about 1 : 3.1-3.3 : 3.1-3.3, about 1 : 3.2-3.3 : 3.2-3.3, 1 : 2.8-3.1 : 2.8-3.1, 1 : 2.8-2.9 : 2.9-3, or 1: 2.75-2.95: 2.75-2.95, or 1: 2.8-2.9, 2.9-2.95, or 1: 2.82: 2.94.
The weight ratio of M1:M2:TM may be from about 1 : 1 : 1 to about 1 : 10 : 1, from about 1 : 1 : 1 to about 1 :7: 1, from about 1 : 1 : 1 to about 1:5: 1, from about 1 : 1 : 1 to about 1:3: 1, from about 1 : 1 : 1 to about 1:2: 1, from about 1 : 2 : 1 to about 1 : 10 : 1, from about 1 : 2 : 1 to about 1:7: 1, from about 1:2: 1 to about 1:5: 1, from about 1 :2: 1 to about 1:3: 1, from about 1 : 3 : 1 to about 1 : 10 :
1, from about 1 : 3 : 1 to about 1:7: 1, from about 1 : 3 : 1 to about 1:5: 1, from about 1 : 5 : 1 to about 1 : 10 : 1, from about 1 : 5 : 1 to about 1:7: 1, from about 1 : 7 : 1 to about 1 : 10 : 1, from about 1: 1:2 to about 1 : 10 : 2, from about 1 : 1 : 2 to about 1:7:2, from about 1 : 1 : 2 to about 1:5:2, from about 1 : 1 : 2 to about 1:3:2, from about 1 : 1 : 2 to about 1:2:2, from about 1 : 2 : 2 to about 1 : 10 : 2, from about 1 : 2 : 2 to about 1 :7:2, from about 1 : 2 : 2 to about 1 :5:2, from about 1 : 2 : 2 to about 1 :3:
2, from about 1 : 3 : 2 to about 1 : 10 : 2, from about 1 : 3 : 2 to about 1:7:2, from about 1 : 3 : 2 to about 1 :5:2, from about 1 : 5 : 2 to about 1 : 10 : 2, from about 1 : 5 : 2 to about 1 :7:2, from about 1:7:2 to about 1 : 10 : 2, from about 1 : 1 : 3 to about 1 : 10 : 3, from about 1 : 1 : 3 to about 1:7:3, from about 1 : 1 : 3 to about 1:5:3, from about 1 : 1 : 3 to about 1:3:3, from about 1 : 1 : 3 to about 1:2:3, from about 1 : 2 : 3 to about 1 : 10 : 3, from about 1 : 2 : 3 to about 1 :7:3, from about 1 : 2 : 3 to about 1:5:
3, from about 1 : 2 : 3 to about 1:3:3, from about 1 : 3 : 3 to about 1 : 10 : 3, from about 1 : 3 : 3 to about 1 :7:3, from about 1 : 3 : 3 to about 1 :5:3, from about 1 : 5 : 3 to about 1: 10:3, from about 1:5:3 to about 1:7:3, from about 1 : 7 : 3 to about 1 : 10 : 3, from about 1 : 1 : 4 to about 1 : 10 : 4, from about 1 : 1 : 4 to about 1:7:4, from about 1 : 1 : 4 to about 1:5:4, from about 1 : 1 : 4 to about 1:3:4, from about 1 : 1 : 4 to about 1 : 2:4, from about 1 : 2 : 4 to about 1 : 10 : 4, from about 1 : 2 : 4 to about 1 :7 :
4, from about 1 : 2 : 4 to about 1 :5 : 4, from about 1 : 2 : 4 to about 1 : 3 :4, from about 1 : 3 : 4 to about 1 : 10 : 4, from about 1 : 3 : 4 to about 1 : 7: 4, from about 1 : 3 : 4 to about 1 : 5 : 4, from about 1 : 5 : 4 to about 1 : 10 : 4, from about 1 : 5 : 4 to about 1 : 7:4, from about 1 : 7 : 4 to about 1 : 10 : 4, from about 1 : 1 : 5 to about 1 : 10 : 5, from about 1 : 1 : 5 to about 1 :7:5, from about 1 : 1 : 5 to about 1 :5 :5, from about 1 : 1 : 5 to about 1 : 3 :5, from about 1 : 1 : 5 to about 1 : 2: 5, from about 1 : 2 : 5 to about 1 : 10 :
5, from about 1 : 2 : 5 to about 1 :7: 5, from about 1 : 2 : 5 to about 1 : 5 :5, from about 1 : 2 : 5 to about 1 : 3 : 5, from about 1 : 3 : 5 to about 1 : 10 : 5, from about 1 : 3 : 5 to about 1 : 7: 5, from about 1 : 3 : 5 to about 1 : 5 : 5, from about 1 : 5 : 5 to about 1 : 10 : 5, from about 1 : 5 : 5 to about 1 : 7: 5, from about 1 : 7 : 5 to about 1 : 10 : 5, from about 1 : 1 : 7 to about 1 : 10 : 7, from about 1 : 1 : 7 to about 1 : 7 : 7, from about 1 : 1 : 7 to about 1 :5 :7, from about 1 : 1 : 7 to about 1 : 3 : 7, from about 1 : 1 : 7 to about 1 : 2 : 7, from about 1 : 2 : 7 to about 1 : 10 : 7, from about 1 : 2 : 7 to about 1 :7: 7, from about 1 : 2 : 7 to about 1 :5 :7, from about 1 : 2 : 7 to about 1 : 3 :7, from about 1 : 3 : 7 to about 1 : 10 : 7, from about 1 : 3 : 7 to about 1 :7 : 7, from about 1 : 3 : 7 to about 1 : 5 : 7, from about 1 : 5 : 7 to about 1 : 10: 7, from about 1 : 5 : 7 to about 1 :7:7, from about 1 : 7 : 7 to about 1 : 10 : 7, from about 1 : 1 : 10 to about 1 : 10 : 10, from about 1 : 1 : 10 to about 1 : 7 : 10, from about 1 : 1 : 10 to about 1 : 5 : 10, from about 1 : 1 : 10 to about 1 : 3 : 10, from about 1 : 1 : 10 to about 1 : 2 : 10, from about 1 : 2: 10 to about 1 : 10 : 10, from about 1 :2: 10 to about 1 : 7 : 10, from about 1 : 2 : 10 to about 1 : 5 : 10, from about 1 : 2 : 10 to about 1 : 3 : 10, from about 1 : 3 : 10 to about 1 : 10 : 10, from about 1 : 3 : 10 to about 1 : 7 : 10, from about 1 : 3 : 10 to about 1 : 5 : 10, from about 1 : 5 : 10 to about 1 : 10 : 10, from about 1 : 5 : 10 to about 1 : 7 : 10, from about 1 : 7 : 10 to about 1 : 10 : 10, or any ranges, ratios or values therebetween.
The weight ratio of M1:M2:TM may be at most about 1 : 1 : 1, at most about 1 : 2 : 1, at most about 1 : 3 : 1, at most about 1 : 5 : 1, at most about 1 : 7 : 1, at most about 1 : 10 : 1, at most about 1 : 1 :
2, at most about 1 : 2 : 2, at most about 1 : 3 : 2, at most about 1 : 5 : 2, at most about 1 : 7 : 2, at most about 1 : 10 : 2, at most about 1 : 1 : 3, at most about 1 : 2 : 3, at most about 1 : 3 : 3, at most about 1 :5 :
3, at most about 1 : 7 : 3, at most about 1 : 10 : 3, at most about 1 : 1 : 4, at most about 1 : 2 : 4, at most about 1 : 3 : 4, at most about 1 : 5 : 4, at most about 1 : 7 : 4, at most about 1 : 10 : 4, at most about 1 : 1 : 5, at most about 1 : 2 : 5, at most about 1 : 3 : 5, at most about 1 : 5 : 5, at most about 1 : 7 : 5, at most about 1 : 10 : 5, at most about 1 : 1 : 7, at most about 1 : 2 : 7, at most about 1 : 3 : 7, at most about 1 :5 : 7, at most about 1 : 7 : 7, at most about 1 : 10 : 7, at most about 1 : 1 : 10, at most about 1 : 2 : 10, at most about 1 : 3 : 10, at most about 1 : 5 : 10, at most about 1 : 7 : 10, at most about 1 : 10 : 10, or any ranges, ratios or values therebetween.
The weight ratio of M1:M2:TM may be about 1 : 1 : 1, about 1 : 2: 1, about 1 : 3 : 1, about 1 :5 :
1, about 1 : 7: 1, about 1 : 10 : 1, about 1 : 1 :2, about 1 :2:2, about 1 : 3 :2, about 1 : 5 :2, about 1 :7:
2, about 1 : 10 : 2, about 1 : 1 : 3, about 1 :2: 3, about 1 :3 : 3, about 1 :5 : 3, about 1 : 7: 3, about 1 : 10 : 3, about 1 : 1 :4, about 1 :2:4, about 1 : 3 :4, about 1 :5 :4, about 1 :7: 4, about 1 : 10 : 4, about 1 : 1 : 5, about 1 :2:5, about 1 : 3 :5, about 1 : 5 :5, about 1 :7:5, about 1 : 10 : 5, about 1 : 1 :7, about 1 : 2 : 7, about 1 : 3 :7, about 1 :5 : 7, about 1 :7 :7, about 1 : 10 : 7, about 1 : 1 : 10, about 1 : 2 : 10, about 1 : 3 : 10, about 1 : 5 : 10, about 1 : 7 : 10, about 1 : 10 : 10, or any ranges, ratios or values therebetween. The present disclosure may provide for a catalyst wherein the content of the metal elements Ml, M2, and TM may be in the range of about 1 wt% to about 2 wt%, about 3 wt% to about 6 wt%, and about 3 wt% to 6 wt%, respectively.
The content of Ml may be in the range of about 1 wt% to about 2 wt%, about 1 wt% to about 1.9 wt%, about 1 wt% to about 1.8 wt%, about 1 wt% to about 1.7 wt%, about 1 wt% to about 1.6 wt%, about 1 wt% to about 1.5 wt%, about 1 wt% to about 1.4 wt%, about 1 wt% to about 1.3 wt%, about 1 wt% to about 1.2 wt%, about 1 wt% to about 1.1 wt%, about 1.1 wt% to about 2 wt%, about 1.2 wt% to about 2 wt%, about 1.3 wt% to about 2 wt%, about 1.4 wt% to about 2 wt%, about 1.5 wt% to about 2 wt%, about
1.6 wt% to about 2 wt%, about 1.7 wt% to about 2 wt%, about 1.8 wt% to about 2 wt%, about 1.9 wt% to about 2 wt%, about 1.2 wt% to about 1.9 wt%, about 1.3 wt% to about 1.8 wt%, about 1.4 wt% to about
1.7 wt%, or about 1 wt%, about 1.1 wt%, about 1.2 wt%, about 1.3 wt%, about 1.4 wt%, about 1.5 wt%, about 1.6 wt%, about 1.7 wt%, about 1.8 wt%, about 1.9 wt%, about 2 wt%, or any ranges or values therebetween.
The content of M2 may be in the range of about 3 wt% to about 6 wt%, about 3.5 wt% to about 6 wt%, about 4 wt% to about 6 wt%, about 4.5 wt% to about 6 wt%, about 4.8 wt% to about 6 wt%, about 5 wt% to about 6 wt%, about 5.5 wt% to about 6 wt%, about 3 wt% to about 5.5 wt%, about 3 wt% to about 5 wt%, about 3 wt% to about 4.8 wt%, about 3 wt% to about 4.5 wt%, about 3 wt% to about 4 wt%, about 3 wt% to about 3.5 wt%, about 3.5 wt% to about 5.5 wt%, about 4 wt% to about 5 wt%, or about 3 wt%, about 3.2 wt%, about 3.4 wt%, about 3.5 wt%, about 3.6 wt%, about 3.8 wt%, about 4 wt%, about 4.2 wt%, about 4.4 wt%, about 4.5 wt%, about 4.6 wt%, about 4.8 wt%, about 5 wt%, about 5.2 wt%, about
5.4 wt%, about 5.6 wt%, about 5.8 wt%, about 6 wt%, or any ranges or values therebetween.
The content of M3 may be in the range of about 3 wt% to about 6 wt%, about 3.5 wt% to about 6 wt%, about 4 wt% to about 6 wt%, about 4.5 wt% to about 6 wt%, about 5 wt% to about 6 wt%, about 5.5 wt% to about 6 wt%, about 3 wt% to about 5.5 wt%, about 3 wt% to about 5 wt%, about 3 wt% to about
4.5 wt%, about 3 wt% to about 4 wt%, about 3 wt% to about 3.5 wt%, about 3.5 wt% to about 5.5 wt%, about 4 wt% to about 5 wt%, or about 3 wt%, about 3.2 wt%, about 3.4 wt%, about 3.5 wt%, about 3.6 wt%, about 3.8 wt%, about 4 wt%, about 4.2 wt%, about 4.4 wt%, about 4.5 wt%, about 4.6 wt%, about 5 wt%, about 5.2 wt%, about 5.4 wt%, about 5.6 wt%, about 5.8 wt%, about 6 wt%, or any ranges or values therebetween.
The present disclosure may provide for a catalyst, wherein the weight ratio of M1:M2:TM is in the range of about 1: 2-10 : 2-10. The present disclosure may also provide for a catalyst, wherein the weight ratio of M1:M2:TM is in the range of about 1: 2-5 : 2-5. In a further preferred embodiment, the present disclosure may provide for a catalyst, wherein the weight ratio of M1:M2:TM is about 1: 3 : 3, or about 1: 2.82: 2.94.
The weight ratio of the metals M1+M2 in the catalyst may be related to the weight of the support (S I). The weight ratio of (M1+M2):S1 may be at least about 1 : 3, at least about 1 : 5, at least about 1 : 10, at least about 1 : 15, at least about 1 : 20, at least about 1 : 30, at least about 1 : 50, or from about 1 : 3 to about 1 : 50, from about 1 : 3 to about 1 : 30, from about 1 : 3 to about 1 : 20, from about 1 : 3 to about 1 : 15, from about 1 : 3 to about 1 : 10, from about 1 : 3 to about 1 : 5, from about 1 : 5 to about 1 : 50, from about 1 : 5 to about 1 : 30, from about 1 : 5 to about 1 : 20, from about 1 :
5 to about 1 : 15, from about 1 : 5 to about 1 : 10, from about 1 : 10 to about 1 : 50, from about 1 : 10 to about 1 : 30, from about 1 : 10 to about 1 : 20, from about 1 : 10 to about 1 : 15, from about 1 : 15 to about 1 : 50, from about 1 : 15 to about 1 : 30, from about 1 : 15 to about 1 : 20, from about 1 : 20 to about 1 : 50, from about 1 : 20 to about 1 : 30, from about 1 : 30 to about 1 : 50, or at most about 1 : 3, at most about 1 : 5, at most about 1 : 10, at most about 1 : 15, at most about 1 : 20, at most about 1 : 30, at most about 1 : 50, or about 1 : 3, about 1 : 5, about 1 : 10, about 1 : 15, about 1 : 20, about 1 : 30, about 1 : 50, or any ranges or values therebetween. In an embodiment, the weight ratio of the support may be about 10 times that of the total mass of M1+M2.
The weight ratio of (M1+M2):S1 may be about 1 : 5-20, about 1 : 5-18, about 1 : 5-16, about 1 : 5-14, about 1 : 5-12, about 1 : 5-10, about 1 : 5-8, about 1 : 8-20, about 1 : 10-20, about 1 : 12-20, about 1 : 14-20, about 1 : 16-20, about 1 : 18-20, or any ranges or values therebetween.
The weight ratio of (M1+M2):S1 may be from about 1:5 to about 1:20. The weight ratio of (M1+M2):S1 may be from about 1:5 to about 1:15. The weight ratio of (M1+M2):S1 may be about 1:10.
The composition of the final products can be tuned by the ratio of metal elements to the support in the precursor mixture. The composition of the metals and the support in the catalyst may also be expressed in terms of either a molar ratio, or a weight ratio.
In some embodiments, the molar ratio of the metals and the support M1:M2:TM:S1 may be in a range of at least about 1 : 2 : 5: 10, at least about 1 : 3 : 5: 10, at least about 1 : 5.7 : 5: 10, at least about 1 : 6 : 5: 10, at least about 1 : 10 : 5: 10, at least about 1 : 2:5: 20, at least about 1 : 3 : 5: 20, at least about 1 : 5.7 : 5: 20, at least about 1 : 6: 5: 20, at least about 1 : 10 : 5: 20, at least about 1 : 2:5: 33.2, at least about 1 : 3 : 5: 33.2, at least about 1 : 5.7 : 5: 33.2, at least about 1 : 6: 5: 33.2, at least about 1 : 10 : 5: 33.2, at least about 1 :2:5: 34.6, at least about 1 : 3 :5: 34.6, at least about 1 : 5.7 : 5: 34.6, at least about 1 : 6: 5: 34.6, at least about 1 : 10 : 5: 34.6, at least about 1 : 2: 5: 50, at least about 1 : 3 : 5: 50, at least about 1 : 5.7 : 5: 50, at least about 1 : 6 : 5: 50, at least about 1 : 10 : 5: 50, at least about 1 :2: 5: 100, at least about 1 : 3 :5: 100, at least about 1 : 5.7 : 5: 100, at least about 1 :6:5: 100, at least about 1 : 10 : 5: 100, at least about 1 : 2 : 9.77: 10, at least about 1 : 3 : 9.77: 10, at least about 1 : 5.7 : 9.77: 10, at least about 1 : 6 : 9.77: 10, at least about 1 : 10 : 9.77: 10, at least about 1 : 2 : 9.77: 20, at least about 1 : 3 : 9.77: 20, at least about 1 : 5.7 : 9.77: 20, at least about 1 : 6 : 9.77: 20, at least about 1 : 10: 9.77: 20, at least about 1 :2: 9.77: 33.2, at least about 1 :3 : 9.77: 33.2, at least about 1 : 5.7 : 9.77: 33.2, at least about 1 :6: 9.77: 33.2, at least about 1 : 10: 9.77: 33.2, at least about 1 :2: 9.77: 34.6, at least about 1 : 3: 9.77: 34.6, at least about 1 : 5.7 : 9.77: 34.6, at least about 1 : 6: 9.77: 34.6, at least about 1 : 10 : 9.77: 34.6, at least about 1 : 2: 9.77: 50, at least about 1 : 3 : 9.77: 50, at least about 1 : 5.7 : 9.77: 50, at least about 1 :
6 : 9.77: 50, at least about 1 : 10 : 9.77: 50, at least about 1 :2: 9.77: 100, at least about 1 : 3 : 9.77: 100, at least about 1 : 5.7 : 9.77: 100, at least about 1 : 6 : 9.77: 100, at least about 1 : 10 : 9.77: 100, at least about 1 : 2 : 10 : 10, at least about 1 : 3 : 10 : 10, at least about 1 : 5.7 : 10 : 10, at least about 1 : 6 : 10 : 10, at least about 1 : 10 : 10 : 10, at least about 1 : 2 : 10 : 20, at least about 1 : 3 : 10: 20, at least about 1 : 5.7 : 10 : 20, at least about 1 : 6 : 10 : 20, at least about 1 : 10 : 10 : 20, at least about 1 :2: 10: 33.2, at least about 1 : 3 : 10: 33.2, at least about 1 : 5.7 : 10 : 33.2, at least about 1 : 6: 10 : 33.2, at least about 1 : 10 : 10 : 33.2, at least about 1 : 2 : 10 : 34.6, at least about 1 : 3 : 10 : 34.6, at least about 1 : 5.7 : 10 : 34.6, at least about 1 : 6 : 10 : 34.6, at least about 1 : 10 : 10 : 34.6, at least about 1 : 2: 10 : 50, at least about 1 : 3 : 10 : 50, at least about 1 : 5.7 : 10 : 50, at least about 1 : 6: 10 : 50, at least about 1 : 10 : 10 : 50, at least about 1 :2: 10 : 100, at least about 1 :3: 10: 100, at least about 1 : 5.7 : 10 : 100, at least about 1 : 6: 10 : 100, at least about 1 : 10 : 10 : 100, at least about 1 : 2 : 15 : 10, at least about 1 : 3 : 15 : 10, at least about 1 : 5.7 : 15 : 10, at least about 1 : 6 : 15 : 10, at least about 1 : 10 : 15 : 10, at least about 1 :2: 15 : 20, at least about 1 : 3 : 15 : 20, at least about 1 : 5.7 : 15 : 20, at least about 1 : 6 : 15 : 20, at least about 1 : 10 : 15 : 20, at least about 1 : 2 : 15 : 33.2, at least about 1 : 3 : 15 : 33.2, at least about 1 : 5.7 : 15 : 33.2, at least about 1 : 6 : 15 : 33.2, at least about 1 : 10 : 15 : 33.2, at least about 1 : 2 : 15 : 34.6, at least about 1 : 3 : 15: 34.6, at least about 1 : 5.7 : 15 : 34.6, at least about 1 : 6 : 15 : 34.6, at least about 1 : 10 : 15 : 34.6, at least about 1 : 2 : 15 : 50, at least about 1 : 3 : 15 : 50, at least about 1 : 5.7 : 15 : 50, at least about 1 : 6: 15 : 50, at least about 1 : 10 : 15 : 50, at least about 1 : 2 : 15 : 100, at least about 1 : 3 : 15 : 100, at least about 1 : 5.7 : 15 : 100, at least about 1 : 6 : 15 : 100, at least about 1 : 10 : 15 : 100, at least about 1 : 2 : 20 : 10, at least about 1 : 3 : 20 : 10, at least about 1 : 5.7 : 20 : 10, at least about 1 :6: 20 : 10, at least about 1 : 10 : 20 : 10, at least about 1 : 2 : 20 : 20, at least about 1 : 3 : 20 : 20, at least about 1 : 5.7 : 20 : 20, at least about 1 : 6 : 20 : 20, at least about 1 : 10 : 20 : 20, at least about 1 : 2 : 20 : 33.2, at least about 1 : 3 : 20 : 33.2, at least about 1 : 5.7 : 20 : 33.2, at least about 1 : 6 : 20 : 33.2, at least about 1 : 10 : 20 : 33.2, at least about 1 : 2 : 20 : 34.6, at least about 1 : 3 :20: 34.6, at least about 1 : 5.7 : 20 : 34.6, at least about 1 :6:20: 34.6, at least about 1 : 10 : 20 : 34.6, at least about 1 : 2 : 20 : 50, at least about 1 : 3 : 20 : 50, at least about 1 : 5.7 : 20 : 50, at least about 1 : 6 : 20 : 50, at least about 1 : 10 : 20 : 50, at least about 1 : 2 : 20 : 100, at least about 1 :3:20: 100, at least about 1 : 5.7 : 20 : 100, at least about 1 : 6 : 20 : 100, at least about 1 : 10 : 20 : 100, or any ranges, ratios, or values therebetween.
The molar ratio of the metals and the support M1:M2:TM:S1 may be from about 1 : 2 : 5: 10 to about 1 : 10 : 5: 10, from about 1 :2:5: 10 to about 1 : 6 : 5: 10, from about 1 : 2 : 5: 10 to about 1 : 5.7 : 5: 10, from about 1 : 2 : 5: 10 to about 1 : 3 : 5: 10, from about 1 : 3 : 5: 10 to about 1 : 10 : 5: 10, from about 1 : 3 : 5: 10 to about 1 : 6 : 5: 10, from about 1 : 3 : 5: 10 to about 1 : 5.7 : 5: 10, from about 1 : 5.7 : 5: 10 to about 1 : 10 : 5: 10, from about 1 : 5.7 : 5: 10 to about 1 : 6 : 5: 10, from about 1 :6:5: 10 to about 1 : 10: 5: 10, from about 1 : 2 : 5: 20 to about 1 : 10 : 5: 20, from about 1 : 2 : 5: 20 to about 1 :6:5: 20, from about 1 : 2 : 5: 20 to about 1 : 5.7 : 5: 20, from about 1 : 2 : 5: 20 to about 1 : 3 :5: 20, from about 1 : 3 : 5: 20 to about 1 : 10 : 5: 20, from about 1 : 3 : 5: 20 to about 1 : 6: 5: 20, from about 1 : 3 : 5: 20 to about 1 : 5.7 : 5: 20, from about 1 : 5.7 : 5: 20 to about 1 : 10 : 5: 20, from about 1 : 5.7 : 5: 20 to about 1 : 6 : 5: 20, from about 1 : 6 : 5: 20 to about 1 : 10 : 5: 20, from about 1 :2:5: 33.2 to about 1 : 10:5: 33.2, from about 1 : 2: 5: 33.2 to about 1 : 6: 5: 33.2, from about 1 :2: 5: 33.2 to about 1 : 5.7 : 5: 33.2, from about 1 : 2: 5: 33.2 to about 1 : 3 : 5: 33.2, from about 1 : 3 :5: 33.2 to about 1 : 10 : 5: 33.2, from about 1 : 3: 5: 33.2 to about 1 :6:5: 33.2, from about 1 : 3 :5: 33.2 to about 1 : 5.7 : 5: 33.2, from about 1 : 5.7 : 5: 33.2 to about 1 : 10 : 5: 33.2, from about 1 : 5.7 : 5: 33.2 to about 1 : 6: 5: 33.2, from about 1 : 6: 5: 33.2 to about 1 : 10 : 5: 33.2, from about 1 : 2: 5: 34.6 to about 1 : 10 : 5: 34.6, from about 1 : 2: 5: 34.6 to about 1 : 6 : 5: 34.6, from about 1 : 2 : 5: 34.6 to about 1 : 5.7 : 5: 34.6, from about 1 : 2 : 5: 34.6 to about 1 : 3 : 5: 34.6, from about 1 : 3 :5: 34.6 to about 1 : 10 : 5: 34.6, from about 1 : 3 :5: 34.6 to about 1 : 6 : 5: 34.6, from about 1 : 3 : 5: 34.6 to about 1 : 5.7 : 5: 34.6, from about 1 : 5.7 : 5: 34.6 to about 1 : 10 : 5: 34.6, from about 1 : 5.7 : 5: 34.6 to about 1 :6:5: 34.6, from about 1 :6:5: 34.6 to about 1 : 10 : 5: 34.6, from about 1 : 2 : 5: 50 to about 1 : 10 : 5: 50, from about 1 : 2 : 5: 50 to about 1:6:5: 50, from about 1 : 2 : 5: 50 to about 1 : 5.7 : 5: 50, from about 1 : 2 : 5: 50 to about 1 : 3 : 5: 50, from about 1 :3: 5: 50 to about 1 : 10 : 5: 50, from about 1 : 3 : 5: 50 to about 1 : 6 : 5: 50, from about 1 : 3 : 5: 50 to about
1 : 5.7 : 5: 50, from about 1 : 5.7 : 5: 50 to about 1 : 10 : 5: 50, from about 1 : 5.7 : 5: 50 to about 1:6:5: 50, from about 1 : 6 : 5: 50 to about 1 : 10 : 5: 50, from about 1 :2:5: 100 to about 1 : 10 : 5: 100, from about 1:2:5: 100 to about 1:6:5: 100, from about 1:2:5: 100 to about 1 : 5.7 : 5: 100, from about 1 :
2 : 5: 100 to about 1:3:5: 100, from about 1:3:5: 100 to about 1 : 10 : 5: 100, from about 1:3:5: 100 to about 1:6:5: 100, from about 1:3:5: 100 to about 1 : 5.7 : 5: 100, from about 1 : 5.7 : 5: 100 to about 1 : 10 : 5: 100, from about 1 : 5.7 : 5: 100 to about 1:6:5: 100, from about 1:6:5: 100 to about 1 : 10 : 5: 100, from about 1:2: 9.77: 10 to about 1 : 10 : 9.77: 10, from about 1:2: 9.77: 10 to about 1:6: 9.77: 10, from about 1 :2: 9.77: 10 to about 1 : 5.7 : 9.77: 10, from about 1 :2: 9.77: 10 to about 1 :3: 9.77: 10, from about 1 : 3 : 9.77: 10 to about 1 : 10 : 9.77: 10, from about 1 :3 : 9.77: 10 to about 1 :6: 9.77: 10, from about 1:3: 9.77: 10 to about 1 : 5.7 : 9.77: 10, from about 1 : 5.7 : 9.77: 10 to about 1 : 10 : 9.77: 10, from about 1 : 5.7 : 9.77: 10 to about 1:6: 9.77: 10, from about 1:6: 9.77: 10 to about 1 : 10 : 9.77: 10, from about 1 :2: 9.77: 20 to about 1 : 10 : 9.77: 20, from about 1 :2: 9.77: 20 to about 1 :6: 9.77:
20, from about 1 :2: 9.77: 20 to about 1 : 5.7 : 9.77: 20, from about 1 :2: 9.77: 20 to about 1 :3: 9.77:
20, from about 1 : 3 : 9.77: 20 to about 1 : 10 : 9.77: 20, from about 1 :3 : 9.77: 20 to about 1 :6: 9.77:
20, from about 1:3: 9.77: 20 to about 1 : 5.7 : 9.77: 20, from about 1 : 5.7 : 9.77: 20 to about 1 : 10 : 9.77:
20, from about 1 : 5.7 : 9.77: 20 to about 1:6: 9.77: 20, from about 1:6: 9.77: 20 to about 1 : 10 : 9.77: 20, from about 1 :2: 9.77: 33.2 to about 1 : 10 : 9.77: 33.2, from about 1 :2: 9.77: 33.2 to about 1 :6: 9.77: 33.2, from about 1:2: 9.77: 33.2 to about 1 : 5.7 : 9.77: 33.2, from about 1:2: 9.77: 33.2 to about 1 :3: 9.77: 33.2, from about 1 :3 : 9.77: 33.2 to about 1 : 10 : 9.77: 33.2, from about 1 :3: 9.77: 33.2 to about 1:6: 9.77: 33.2, from about 1:3: 9.77: 33.2 to about 1 : 5.7 : 9.77: 33.2, from about 1 : 5.7 : 9.77: 33.2 to about 1 : 10 : 9.77: 33.2, from about 1 : 5.7 : 9.77: 33.2 to about 1:6: 9.77: 33.2, from about 1 : 6 : 9.77: 33.2 to about 1 : 10 : 9.77: 33.2, from about 1:2: 9.77: 34.6 to about 1 : 10 : 9.77: 34.6, from about 1:2: 9.77: 34.6 to about 1:6: 9.77: 34.6, from about 1:2: 9.77: 34.6 to about 1 : 5.7 : 9.77: 34.6, from about 1:2: 9.77: 34.6 to about 1:3: 9.77: 34.6, from about 1:3: 9.77: 34.6 to about 1: 10: 9.77: 34.6, from about 1:3: 9.77: 34.6 to about 1:6: 9.77: 34.6, from about 1:3: 9.77: 34.6 to about 1 : 5.7 : 9.77: 34.6, from about 1 : 5.7 : 9.77: 34.6 to about 1 : 10 : 9.77: 34.6, from about 1 : 5.7 : 9.77: 34.6 to about 1 : 6 : 9.77: 34.6, from about 1:6: 9.77: 34.6 to about 1 : 10 : 9.77: 34.6, from about 1 :2: 9.77: 50 to about 1 : 10 : 9.77: 50, from about 1 :2: 9.77: 50 to about 1 :6: 9.77: 50, from about 1:2: 9.77: 50 to about 1 : 5.7 : 9.77: 50, from about 1:2: 9.77: 50 to about 1 :3: 9.77: 50, from about 1:3: 9.77: 50 to about 1 : 10 : 9.77: 50, from about 1 : 3 : 9.77: 50 to about 1 :6: 9.77: 50, from about 1 :3: 9.77: 50 to about 1 : 5.7 : 9.77: 50, from about 1 : 5.7 : 9.77: 50 to about 1 : 10 : 9.77: 50, from about 1 : 5.7 : 9.77: 50 to about 1 :6: 9.77: 50, from about 1 :6: 9.77: 50 to about 1 : 10 : 9.77: 50, from about 1:2: 9.77: 100 to about 1 : 10 : 9.77: 100, from about 1 : 2: 9.77: 100 to about 1 :6: 9.77: 100, from about 1 :2: 9.77: 100 to about 1 : 5.7 : 9.77: 100, from about 1:2: 9.77: 100 to about 1:3: 9.77: 100, from about 1:3: 9.77: 100 to about 1 : 10 : 9.77: 100, from about 1 :3: 9.77: 100 to about 1 :6: 9.77: 100, from about 1 :3: 9.77: 100 to about 1 : 5.7 : 9.77: 100, from about 1 : 5.7 : 9.77: 100 to about 1 : 10 : 9.77: 100, from about 1 : 5.7 : 9.77: 100 to about 1:6: 9.77: 100, from about 1:6: 9.77: 100 to about 1 : 10 : 9.77: 100, from about 1 :2: 10 : 10 to about 1 : 10 : 10 : 10, from about 1 :2: 10 : 10 to about 1 : 6 : 10 : 10, from about 1 :2: 10 : 10 to about 1 : 5.7 : 10 : 10, from about 1 : 2 : 10 : 10 to about 1 : 3 : 10 : 10, from about 1 : 3 : 10 : 10 to about 1 : 10 : 10 : 10, from about 1 : 3 : 10 : 10 to about 1 : 6 : 10 : 10, from about 1 : 3 : 10 : 10 to about 1 : 5.7 : 10 : 10, from about 1 : 5.7 : 10 : 10 to about 1 : 10 : 10 : 10, from about 1 : 5.7 : 10 : 10 to about 1 : 6 : 10 : 10, from about 1 : 6: 10 : 10 to about 1 : 10 : 10 : 10, from about 1 : 2: 10 : 20 to about 1 : 10 : 10 : 20, from about 1 : 2: 10 : 20 to about 1 :6: 10 : 20, from about 1 : 2: 10 : 20 to about 1 : 5.7 : 10 : 20, from about 1 : 2 : 10 : 20 to about 1 : 3 : 10 : 20, from about 1 : 3 : 10 : 20 to about 1 : 10 : 10 : 20, from about 1 : 3 : 10 : 20 to about 1 : 6 : 10 : 20, from about 1 : 3 : 10 : 20 to about 1 : 5.7 : 10 : 20, from about 1 : 5.7 : 10 : 20 to about 1 : 10 : 10 : 20, from about 1 : 5.7 : 10 : 20 to about 1 : 6 : 10 : 20, from about 1 : 6 : 10 : 20 to about 1 : 10 : 10 : 20, from about 1 : 2 : 10 : 33.2 to about 1 : 10 : 10 : 33.2, from about 1 : 2 : 10 : 33.2 to about 1 : 6 : 10 : 33.2, from about 1 : 2 : 10 : 33.2 to about 1 : 5.7 : 10 : 33.2, from about 1 : 2 : 10 : 33.2 to about 1 : 3 : 10 : 33.2, from about 1 : 3 : 10: 33.2 to about 1 : 10 : 10 : 33.2, from about 1 : 3 : 10 : 33.2 to about 1 : 6 : 10 : 33.2, from about 1 : 3 : 10 : 33.2 to about 1 : 5.7 : 10 : 33.2, from about 1 : 5.7 : 10 : 33.2 to about 1 : 10 : 10 : 33.2, from about 1 : 5.7 : 10 : 33.2 to about 1 : 6: 10 : 33.2, from about 1 : 6 : 10 : 33.2 to about 1 : 10 : 10 : 33.2, from about 1 : 2 : 10 : 34.6 to about 1 : 10 : 10
: 34.6, from about 1 : 2 : 10 : 34.6 to about 1 : 6 : 10 : 34.6, from about 1 :2: 10 : 34.6 to about 1 : 5.7 : 10
: 34.6, from about 1 : 2 : 10 : 34.6 to about 1 : 3 : 10 : 34.6, from about 1 : 3 : 10 : 34.6 to about 1 : 10 : 10
: 34.6, from about 1 : 3 : 10 : 34.6 to about 1 : 6 : 10 : 34.6, from about 1 : 3 : 10 : 34.6 to about 1 : 5.7 : 10
: 34.6, from about 1 : 5.7 : 10 : 34.6 to about 1 : 10 : 10 : 34.6, from about 1 : 5.7 : 10 : 34.6 to about 1 : 6 : 10 : 34.6, from about 1 :6: 10 : 34.6 to about 1 : 10 : 10 : 34.6, from about 1 : 2 : 10 : 50 to about 1 : 10 : 10 : 50, from about 1 : 2 : 10 : 50 to about 1 : 6: 10 : 50, from about 1 : 2 : 10 : 50 to about 1 : 5.7 : 10 : 50, from about 1 : 2 : 10 : 50 to about 1 : 3 : 10 : 50, from about 1 : 3 : 10 : 50 to about 1 : 10 : 10 : 50, from about 1 : 3 : 10 : 50 to about 1 : 6 : 10 : 50, from about 1 : 3 : 10 : 50 to about 1 : 5.7 : 10 : 50, from about 1 : 5.7 : 10 : 50 to about 1 : 10 : 10 : 50, from about 1 : 5.7 : 10 : 50 to about 1 : 6 : 10 : 50, from about 1 : 6 : 10 : 50 to about 1 : 10 : 10 : 50, from about 1 : 2 : 10 : 100 to about 1 : 10 : 10 : 100, from about 1 : 2: 10 : 100 to about 1 : 6 : 10 : 100, from about 1 : 2 : 10 : 100 to about 1 : 5.7 : 10 : 100, from about 1 : 2 : 10 : 100 to about 1 : 3 : 10: 100, from about 1 : 3 : 10 : 100 to about 1 : 10 : 10 : 100, from about 1 : 3 : 10 : 100 to about 1 : 6 : 10 : 100, from about 1 : 3 : 10 : 100 to about 1 : 5.7 : 10 : 100, from about 1 : 5.7 : 10 : 100 to about 1 : 10 : 10 : 100, from about 1 : 5.7 : 10 : 100 to about 1 : 6 : 10 : 100, from about 1 : 6 : 10 : 100 to about 1 : 10 : 10 : 100, from about 1 : 2 : 15 : 10 to about 1 : 10 : 15 : 10, from about 1 : 2 : 15 : 10 to about 1 : 6 : 15 : 10, from about 1 : 2 : 15 : 10 to about 1 : 5.7 : 15 : 10, from about
1 : 2 : 15 : 10 to about 1 : 3 : 15 : 10, from about 1 : 3 : 15 : 10 to about 1 : 10 : 15 : 10, from about 1 : 3 : 15 : 10 to about 1 : 6 : 15 : 10, from about 1 : 3 : 15 : 10 to about 1 : 5.7 : 15 : 10, from about 1 : 5.7 : 15 : 10 to about 1 : 10 : 15 : 10, from about 1 : 5.7 : 15 : 10 to about 1 : 6 : 15 : 10, from about 1 : 6 : 15 : 10 to about 1 : 10 : 15 : 10, from about 1 :2: 15 : 20 to about 1 : 10 : 15 : 20, from about 1 : 2 : 15 : 20 to about 1 : 6 : 15 : 20, from about 1 : 2 : 15 : 20 to about 1 : 5.7 : 15 : 20, from about 1 : 2 : 15 : 20 to about 1 : 3 : 15 : 20, from about 1 : 3 : 15 : 20 to about 1 : 10 : 15 : 20, from about 1 : 3 : 15 : 20 to about 1 : 6 : 15 : 20, from about 1 : 3 : 15 : 20 to about 1 : 5.7 : 15 : 20, from about 1 : 5.7 : 15 : 20 to about 1 : 10 : 15 : 20, from about 1 : 5.7 : 15 : 20 to about 1 : 6 : 15 : 20, from about 1 :6: 15 : 20 to about 1 : 10 : 15 : 20, from about 1 : 2 : 15 : 33.2 to about 1 : 10 : 15 : 33.2, from about 1 : 2 : 15 : 33.2 to about 1 : 6 : 15 : 33.2, from about 1 : 2 : 15 : 33.2 to about 1 : 5.7 : 15 : 33.2, from about 1 : 2 : 15 : 33.2 to about 1 : 3 : 15 : 33.2, from about 1 : 3 : 15 : 33.2 to about 1 : 10 : 15 : 33.2, from about 1 : 3 : 15 : 33.2 to about 1 : 6 : 15 : 33.2, from about 1 : 3 : 15 : 33.2 to about 1 : 5.7 : 15 : 33.2, from about 1 : 5.7 : 15 : 33.2 to about 1 : 10 : 15 : 33.2, from about 1 : 5.7 : 15 : 33.2 to about 1 : 6: 15 : 33.2, from about 1 : 6 : 15 : 33.2 to about 1 : 10 : 15 : 33.2, from about 1 : 2 : 15 : 34.6 to about 1 : 10 : 15 : 34.6, from about 1 :2: 15 : 34.6 to about 1 : 6 : 15 : 34.6, from about 1 : 2 : 15 : 34.6 to about 1 : 5.7 : 15 : 34.6, from about 1 : 2 : 15 : 34.6 to about 1 : 3 : 15 : 34.6, from about 1 : 3 : 15 : 34.6 to about 1 : 10 : 15 : 34.6, from about 1 : 3 : 15 : 34.6 to about 1 : 6 : 15 : 34.6, from about 1 : 3 : 15 : 34.6 to about 1 : 5.7 : 15 : 34.6, from about 1 : 5.7 : 15 : 34.6 to about 1 : 10 : 15 : 34.6, from about 1 : 5.7 : 15 : 34.6 to about 1 : 6 : 15 : 34.6, from about 1 : 6 : 15 : 34.6 to about 1 : 10 : 15 : 34.6, from about 1 : 2 : 15 : 50 to about 1 : 10 : 15 : 50, from about 1 : 2 : 15 : 50 to about 1 : 6 : 15 : 50, from about 1 : 2 : 15 : 50 to about 1 : 5.7 : 15 : 50, from about 1 : 2 : 15 : 50 to about 1 : 3 : 15 : 50, from about 1 : 3 : 15 : 50 to about 1 : 10 : 15 : 50, from about 1 : 3 : 15 : 50 to about 1 : 6 : 15 : 50, from about 1 : 3 : 15 : 50 to about 1 : 5.7 : 15 : 50, from about 1 : 5.7 : 15 : 50 to about 1 : 10 : 15 : 50, from about 1 : 5.7 : 15 : 50 to about 1 : 6 : 15 : 50, from about 1 : 6 : 15 : 50 to about 1 : 10 : 15 : 50, from about 1 : 2 : 15 : 100 to about 1 : 10 : 15 : 100, from about 1 : 2 : 15 : 100 to about 1 : 6 : 15 : 100, from about 1 : 2 : 15 : 100 to about 1 : 5.7 : 15 : 100, from about 1 : 2 : 15 : 100 to about 1 : 3 : 15 : 100, from about 1 : 3 : 15 : 100 to about 1 : 10 : 15 : 100, from about 1 : 3 : 15 : 100 to about 1 : 6 : 15 : 100, from about 1 : 3 : 15 : 100 to about 1 : 5.7 : 15 : 100, from about 1 : 5.7 : 15 : 100 to about 1 : 10 : 15 : 100, from about 1 : 5.7 : 15 : 100 to about 1 : 6 : 15 : 100, from about 1 : 6 : 15 : 100 to about 1 : 10 : 15 : 100, from about 1 : 2 : 20 : 10 to about 1 : 10 : 20 : 10, from about 1 : 2 : 20 : 10 to about 1 : 6 : 20 : 10, from about 1 : 2 : 20 : 10 to about 1 : 5.7 : 20 : 10, from about 1 : 2 : 20 : 10 to about 1 : 3 : 20 : 10, from about 1 : 3 : 20 : 10 to about 1 : 10 : 20 : 10, from about 1 : 3 : 20 : 10 to about 1 : 6 : 20 : 10, from about 1 : 3 : 20 : 10 to about 1 : 5.7 : 20 : 10, from about 1 : 5.7 : 20 : 10 to about 1 : 10 : 20 : 10, from about 1 : 5.7 : 20 : 10 to about 1 : 6 : 20 : 10, from about 1 : 6 : 20 : 10 to about 1 : 10 : 20 : 10, from about 1 : 2 : 20 : 20 to about
1 : 10 : 20 : 20, from about 1 : 2 : 20 : 20 to about 1 : 6 : 20 : 20, from about 1 : 2 : 20 : 20 to about 1 : 5.7 : 20 : 20, from about 1 : 2 : 20 : 20 to about 1 : 3 : 20 : 20, from about 1 : 3 : 20 : 20 to about 1 : 10 : 20 : 20, from about 1 : 3 : 20 : 20 to about 1 : 6 : 20 : 20, from about 1 : 3 : 20 : 20 to about 1 : 5.7 : 20 : 20, from about 1 : 5.7 : 20 : 20 to about 1 : 10 : 20 : 20, from about 1 : 5.7 : 20 : 20 to about 1 : 6 : 20 : 20, from about 1 : 6 : 20 : 20 to about 1 : 10 : 20 : 20, from about 1 : 2 : 20 : 33.2 to about 1 : 10 : 20 : 33.2, from about 1 : 2 : 20 : 33.2 to about 1 : 6 : 20 : 33.2, from about 1 : 2 : 20 : 33.2 to about 1 : 5.7 : 20 : 33.2, from about 1 : 2 : 20 : 33.2 to about 1 : 3 : 20 : 33.2, from about 1 : 3 : 20 : 33.2 to about 1 : 10 : 20 : 33.2, from about 1 : 3 : 20 : 33.2 to about 1 : 6 : 20 : 33.2, from about 1 : 3 : 20 : 33.2 to about 1 : 5.7 : 20 : 33.2, from about 1 : 5.7 : 20 : 33.2 to about 1 : 10 : 20 : 33.2, from about 1 : 5.7 : 20 : 33.2 to about 1 : 6 : 20 :
33.2, from about 1 : 6 : 20 : 33.2 to about 1 : 10 : 20 : 33.2, from about 1 : 2 : 20 : 34.6 to about 1 : 10 : 20 : 34.6, from about 1 : 2 : 20 : 34.6 to about 1 : 6 : 20 : 34.6, from about 1 : 2 : 20 : 34.6 to about 1 : 5.7 : 20 : 34.6, from about 1 : 2 : 20 : 34.6 to about 1 : 3 : 20 : 34.6, from about 1 : 3 : 20 : 34.6 to about 1 : 10 : 20 : 34.6, from about 1 : 3 : 20 : 34.6 to about 1 : 6 : 20 : 34.6, from about 1 : 3 : 20 : 34.6 to about 1 : 5.7 : 20 : 34.6, from about 1 : 5.7 : 20 : 34.6 to about 1 : 10 : 20 : 34.6, from about 1 : 5.7 : 20 : 34.6 to about 1 : 6 : 20 : 34.6, from about 1 : 6 : 20 : 34.6 to about 1 : 10 : 20 : 34.6, from about 1 : 2 : 20 : 50 to about 1 : 10 : 20 : 50, from about 1 : 2 : 20 : 50 to about 1 : 6 : 20 : 50, from about 1 : 2 : 20 : 50 to about 1 : 5.7 : 20 : 50, from about 1 : 2 : 20 : 50 to about 1 : 3 : 20 : 50, from about 1 : 3 : 20 : 50 to about 1 : 10 : 20 : 50, from about 1 : 3 : 20 : 50 to about 1 : 6 : 20 : 50, from about 1 : 3 : 20 : 50 to about 1 : 5.7 : 20 : 50, from about 1 : 5.7 : 20 : 50 to about 1 : 10 : 20 : 50, from about 1 : 5.7 : 20 : 50 to about 1 : 6 : 20 : 50, from about 1 : 6 : 20 : 50 to about 1 : 10 : 20 : 50, from about 1 : 2 : 20 : 100 to about 1 : 10 : 20 : 100, from about 1 : 2 : 20 : 100 to about 1 : 6 : 20 : 100, from about 1 : 2 : 20 : 100 to about 1 : 5.7 : 20 : 100, from about 1 : 2 : 20 : 100 to about 1 : 3 : 20 : 100, from about 1 : 3 : 20 : 100 to about 1 : 10 : 20 : 100, from about 1 : 3 : 20 : 100 to about 1 : 6 : 20 : 100, from about 1 : 3 : 20 : 100 to about 1 : 5.7 : 20 : 100, from about 1 : 5.7 : 20 : 100 to about 1 : 10 : 20 : 100, from about 1 : 5.7 : 20 : 100 to about 1 :6:20: 100, from about 1 : 6 : 20 : 100 to about 1 : 10 : 20 : 100, or any ranges, ratios or values therebetween.
The molar ratio of the metals and the support M1:M2:TM:S1 may be at most about 1 : 2 : 5: 10, at most about 1 : 3 : 5: 10, at most about 1 : 5.7 : 5: 10, at most about 1 :6:5: 10, at most about 1 : 10 : 5: 10, at most about 1 :2:5: 20, at most about 1 : 3 :5: 20, at most about 1 : 5.7 : 5: 20, at most about 1 :6: 5: 20, at most about 1 : 10: 5: 20, at most about 1 :2:5: 33.2, at most about 1 : 3 : 5: 33.2, at most about
1 : 5.7 : 5: 33.2, at most about 1 :6:5: 33.2, at most about 1 : 10 : 5: 33.2, at most about 1 :2:5: 34.6, at most about 1 : 3 :5: 34.6, at most about 1 : 5.7 : 5: 34.6, at most about 1 : 6: 5: 34.6, at most about 1 : 10 : 5: 34.6, at most about 1 :2:5: 50, at most about 1 : 3 :5: 50, at most about 1 : 5.7 : 5: 50, at most about 1 : 6: 5: 50, at most about 1 : 10 : 5: 50, at most about 1 : 2: 5: 100, at most about 1 : 3 : 5: 100, at most about 1 : 5.7 : 5: 100, at most about 1 : 6: 5: 100, at most about 1 : 10 : 5: 100, at most about 1 :2: 9.77: 10, at most about 1 : 3 : 9.77: 10, at most about 1 : 5.7 : 9.77: 10, at most about 1 : 6 : 9.77: 10, at most about 1 : 10 : 9.77: 10, at most about 1 :2: 9.77: 20, at most about 1 : 3 : 9.77: 20, at most about 1 : 5.7 : 9.77: 20, at most about 1 : 6 : 9.77: 20, at most about 1 : 10 : 9.77: 20, at most about 1 : 2: 9.77: 33.2, at most about 1 : 3 : 9.77: 33.2, at most about 1 : 5.7 : 9.77: 33.2, at most about 1 : 6 : 9.77: 33.2, at most about 1 : 10 : 9.77: 33.2, at most about 1 : 2: 9.77: 34.6, at most about 1 : 3 : 9.77: 34.6, at most about 1 : 5.7 : 9.77: 34.6, at most about 1 :6: 9.77: 34.6, at most about 1 : 10 : 9.77: 34.6, at most about 1 :2: 9.77: 50, at most about 1 : 3 : 9.77: 50, at most about 1 : 5.7 : 9.77: 50, at most about 1 : 6 : 9.77: 50, at most about 1 : 10 : 9.77: 50, at most about 1 : 2: 9.77: 100, at most about 1 : 3 : 9.77: 100, at most about 1 : 5.7 : 9.77: 100, at most about 1 : 6: 9.77: 100, at most about 1 : 10 : 9.77: 100, at most about 1 : 2 : 10 : 10, at most about 1 : 3 : 10 : 10, at most about 1 : 5.7 : 10 : 10, at most about 1 : 6 : 10 : 10, at most about 1 : 10 : 10 : 10, at most about 1 : 2 : 10 : 20, at most about 1 : 3 : 10 : 20, at most about 1 : 5.7 : 10 : 20, at most about 1 : 6 : 10 : 20, at most about 1 : 10 : 10 : 20, at most about 1 : 2 : 10 : 33.2, at most about 1 : 3 : 10 : 33.2, at most about 1 : 5.7 : 10 : 33.2, at most about 1 : 6 : 10 : 33.2, at most about 1 : 10 : 10 : 33.2, at most about 1 :2: 10 : 34.6, at most about 1 : 3 : 10 : 34.6, at most about 1 : 5.7 : 10 : 34.6, at most about 1 :6: 10 : 34.6, at most about 1 : 10 : 10 : 34.6, at most about 1 :2: 10 : 50, at most about 1 : 3 : 10 : 50, at most about 1 : 5.7 : 10 : 50, at most about 1 : 6 : 10 : 50, at most about 1 : 10 : 10 : 50, at most about 1 :
2 : 10 : 100, at most about 1 : 3 : 10 : 100, at most about 1 : 5.7 : 10 : 100, at most about 1 : 6 : 10 : 100, at most about 1 : 10 : 10 : 100, at most about 1 : 2 : 15 : 10, at most about 1 : 3 : 15 : 10, at most about 1 : 5.7 : 15 : 10, at most about 1 : 6 : 15 : 10, at most about 1 : 10 : 15 : 10, at most about 1 : 2 : 15 : 20, at most about 1 : 3 : 15 : 20, at most about 1 : 5.7 : 15 : 20, at most about 1 : 6 : 15 : 20, at most about 1 : 10 : 15 : 20, at most about 1 : 2 : 15 : 33.2, at most about 1 : 3 : 15 : 33.2, at most about 1 : 5.7 : 15 : 33.2, at most about 1 : 6 : 15 : 33.2, at most about 1 : 10 : 15 : 33.2, at most about 1 : 2 : 15 : 34.6, at most about 1 : 3 : 15 : 34.6, at most about 1 : 5.7 : 15 : 34.6, at most about 1 : 6: 15 : 34.6, at most about 1 : 10 : 15 : 34.6, at most about 1 : 2 : 15 : 50, at most about 1 : 3 : 15 : 50, at most about 1 : 5.7 : 15 : 50, at most about 1 : 6 : 15 : 50, at most about 1 : 10 : 15 : 50, at most about 1 : 2 : 15 : 100, at most about 1 : 3 : 15 : 100, at most about 1 : 5.7 : 15 : 100, at most about 1 : 6 : 15 : 100, at most about 1 : 10 : 15 : 100, at most about 1 : 2 : 20 : 10, at most about 1 : 3 : 20 : 10, at most about 1 : 5.7 : 20 : 10, at most about 1 : 6 : 20 : 10, at most about 1 : 10 : 20 : 10, at most about 1 : 2 : 20 : 20, at most about 1 : 3 : 20 : 20, at most about 1 : 5.7 : 20 : 20, at most about 1 : 6 : 20 : 20, at most about 1 : 10 : 20 : 20, at most about 1 : 2 : 20 : 33.2, at most about 1 : 3 : 20 : 33.2, at most about 1 : 5.7 : 20 : 33.2, at most about 1 : 6 : 20 : 33.2, at most about 1 : 10 : 20 : 33.2, at most about 1 : 2 : 20 : 34.6, at most about 1 : 3 : 20 : 34.6, at most about 1 : 5.7 : 20 : 34.6, at most about 1 : 6 : 20 : 34.6, at most about 1 : 10 : 20 : 34.6, at most about 1 : 2 : 20 : 50, at most about 1 : 3 : 20 : 50, at most about 1 : 5.7 : 20 : 50, at most about 1 : 6 : 20 : 50, at most about 1 : 10 : 20 : 50, at most about 1 : 2 : 20 : 100, at most about 1 : 3 : 20 : 100, at most about 1 : 5.7 : 20 : 100, at most about 1 : 6 : 20 : 100, at most about 1 : 10 : 20 : 100, or any ranges, ratios or values therebetween.
The molar ratio of the metals and the support M1:M2:TM:S1 may be about 1 : 2 : 5: 10, about 1 : 3 : 5: 10, about 1 : 5.7 : 5: 10, about 1 : 6 : 5: 10, about 1 : 10 : 5: 10, about 1 :2:5: 20, about 1 : 3 :5: 20, about 1 : 5.7 : 5: 20, about 1 :6:5: 20, about 1 : 10 : 5: 20, about 1 :2:5: 33.2, about 1 :3 :5: 33.2, about 1 : 5.7 : 5: 33.2, about 1 :6:5: 33.2, about 1 : 10 : 5: 33.2, about 1 : 2: 5: 34.6, about 1 : 3 :5: 34.6, about 1 : 5.7 : 5: 34.6, about 1 :6:5: 34.6, about 1 : 10 : 5: 34.6, about 1 :2:5: 50, about 1 : 3 : 5: 50, about 1 : 5.7 : 5: 50, about 1 : 6 : 5: 50, about 1 : 10 : 5: 50, about 1 : 2: 5: 100, about 1 : 3 : 5: 100, about 1 : 5.7 : 5: 100, about 1 :6:5: 100, about 1 : 10 : 5: 100, about 1 :2: 9.77: 10, about 1 : 3 : 9.77: 10, about 1 : 5.7 : 9.77: 10, about 1 :6: 9.77: 10, about 1 : 10 : 9.77: 10, about 1 :2: 9.77: 20, about 1 : 3 : 9.77: 20, about 1 : 5.7 : 9.77: 20, about 1 :6: 9.77: 20, about 1 : 10: 9.77: 20, about 1 : 2: 9.77: 33.2, about 1 : 3 : 9.77: 33.2, about 1 : 5.7 : 9.77: 33.2, about 1 : 6 : 9.77: 33.2, about 1 : 10 : 9.77: 33.2, about 1 : 2 : 9.77: 34.6, about 1 : 3 : 9.77: 34.6, about 1 : 5.7 : 9.77: 34.6, about 1 :6: 9.77: 34.6, about 1 : 10 : 9.77: 34.6, about 1 : 2 : 9.77: 50, about 1 : 3 : 9.77: 50, about 1 : 5.7 : 9.77: 50, about 1 : 6: 9.77: 50, about 1 : 10 : 9.77: 50, about 1 : 2: 9.77: 100, about 1 : 3 : 9.77: 100, about 1 : 5.7 : 9.77: 100, about 1 : 6 : 9.77: 100, about 1 : 10 : 9.77: 100, about 1 : 2 : 10 : 10, about 1 : 3 : 10 : 10, about 1 : 5.7 : 10 : 10, about 1 : 6 : 10 : 10, about 1 : 10 : 10 : 10, about 1 : 2 : 10 : 20, about 1 : 3 : 10 : 20, about 1 : 5.7 : 10 : 20, about 1 : 6 : 10 : 20, about 1 : 10 : 10 : 20, about 1 : 2 : 10 : 33.2, about 1 : 3 : 10 : 33.2, about 1 : 5.7 : 10 : 33.2, about 1 : 6 : 10 : 33.2, about 1 : 10 : 10 : 33.2, about 1 : 2 : 10 : 34.6, about 1 : 3 : 10 : 34.6, about 1 : 5.7 : 10 : 34.6, about 1 : 6 : 10 : 34.6, about 1 : 10 : 10 : 34.6, about 1 : 2 : 10 : 50, about 1 : 3 : 10 : 50, about 1 : 5.7 : 10 : 50, about 1 : 6 : 10 : 50, about 1 : 10 : 10 : 50, about 1 :2: 10 : 100, about 1 : 3 : 10 : 100, about 1 : 5.7 : 10 : 100, about 1 : 6 : 10 : 100, about 1 : 10 : 10 : 100, about 1 : 2 : 15 : 10, about 1 : 3 : 15 : 10, about 1 : 5.7 : 15 : 10, about 1 : 6 : 15 : 10, about 1 : 10 : 15 : 10, about 1 : 2 : 15 : 20, about 1 : 3 : 15 : 20, about 1 : 5.7 : 15 : 20, about 1 : 6 : 15 : 20, about 1 : 10 : 15 : 20, about 1 : 2 : 15 : 33.2, about 1 : 3 : 15 : 33.2, about 1 : 5.7 : 15 : 33.2, about 1 : 6 : 15 : 33.2, about 1 : 10 : 15 : 33.2, about 1 : 2 : 15 : 34.6, about 1 : 3 : 15 : 34.6, about 1 : 5.7 : 15 : 34.6, about 1 : 6 : 15 : 34.6, about 1 : 10 : 15 : 34.6, about 1 : 2 : 15 : 50, about 1 : 3 : 15 : 50, about 1 : 5.7 : 15 : 50, about 1 :6: 15 : 50, about 1 : 10 : 15 : 50, about 1 : 2 : 15 : 100, about 1 : 3 : 15 : 100, about 1 : 5.7 : 15 : 100, about 1 : 6 : 15 : 100, about 1 : 10 : 15 : 100, about 1 : 2 : 20 : 10, about 1 : 3 : 20 : 10, about 1 : 5.7 : 20 : 10, about 1 : 6 : 20 : 10, about 1 : 10 : 20 : 10, about 1 : 2 : 20 : 20, about 1 : 3 : 20 : 20, about 1 : 5.7 : 20 : 20, about 1 : 6 : 20 : 20, about 1 : 10 : 20 : 20, about 1 : 2 : 20 : 33.2, about 1 : 3 : 20 : 33.2, about 1 : 5.7 : 20 : 33.2, about 1 : 6 : 20 : 33.2, about 1 : 10 : 20 : 33.2, about 1 : 2 : 20 : 34.6, about 1 : 3 : 20 : 34.6, about 1 : 5.7 : 20 : 34.6, about 1 : 6 : 20 : 34.6, about 1 : 10 : 20 : 34.6, about 1 : 2 : 20 : 50, about 1 : 3 : 20 : 50, about 1 : 5.7 : 20 : 50, about 1 : 6 : 20 : 50, about 1 : 10 : 20 : 50, about 1 : 2 : 20 : 100, about 1 : 3 : 20 : 100, about 1 : 5.7 : 20 : 100, about 1 : 6 : 20 : 100, about 1 : 10 : 20 : 100, or any ranges, ratios or values therebetween.
The molar ratio of the metal elements and support in the catalyst may be about 1: 2-10 : 5-20 : 10- 100. The molar ratio of the metal elements and support in the catalyst may be about 1 : 6 : 10 : 34.6. The molar ratio of the metal elements and support in the catalyst may be about 1 : 5.7 : 9.77 : 33.2. The content of the metal element in the support (S 1) may be in the range of about 40 wt% to about 60 wt%, about 45 wt% to about 60 wt%, about 50 wt% to about 60 wt%, about 55 wt% to about 60 wt%, about 40 wt% to about 55 wt%, about 40 wt% to about 50 wt%, about 40 wt% to about 45 wt%, about 45 wt% to about 55 wt%, about 50 wt% to about 55 wt%, or about 40 wt%, about 42 wt%, about 44 wt%, 46 wt%, about 48 wt%, about 50 wt%, about 52 wt%, about 54 wt%, about 56 wt%, about 58 wt%, about 60 wt%, or any ranges or values therebetween.
Metals like iridium, ruthenium or palladium and their oxides have been used as catalysts for the OER. However, as they are highly expensive, there is a commercial desire to reduce the amount of such metals in the catalysts to reduce costs. Advantageously, the catalysts of the present invention comprise these expensive metals in a much smaller weight% as compared to commercial and conventional catalysts.
The metals M1+M2 may make up the catalyst in a range of at least about 2 wt%, at least about 3 wt%, at least about 4 wt%, at least about 5 wt%, at least about 6 wt%, at least about 7 wt%, at least about 8 wt%, at least about 9 wt%, at least about 10 wt%, at least about 12 wt%, at least about 15 wt%, at least about 17 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, at least about 40 wt%, at least about 50 wt%; or from about 2 wt% to about 50 wt%, from about 2 wt% to about 40 wt%, from about 2 wt% to about 35 wt%, from about 2 wt% to about 30 wt%, from about 2 wt% to about 25 wt%, from about 2 wt% to about 20 wt%, from about 2 wt% to about 17 wt%, from about 2 wt% to about 15 wt%, from about 2 wt% to about 12 wt%, from about 2 wt% to about 10 wt%, from about 2 wt% to about 9 wt%, from about 2 wt% to about 8 wt%, from about 2 wt% to about 7 wt%, from about 2 wt% to about 6 wt%, from about 2 wt% to about 5 wt%, from about 2 wt% to about 4 wt%, from about
2 wt% to about 3 wt%, from about 3 wt% to about 50 wt%, from about 3 wt% to about 40 wt%, from about
3 wt% to about 35 wt%, from about 3 wt% to about 30 wt%, from about 3 wt% to about 25 wt%, from about 3 wt% to about 20 wt%, from about 3 wt% to about 17 wt%, from about 3 wt% to about 15 wt%, from about 3 wt% to about 12 wt%, from about 3 wt% to about 10 wt%, from about 3 wt% to about 9 wt%, from about 3 wt% to about 8 wt%, from about 3 wt% to about 7 wt%, from about 3 wt% to about 6 wt%, from about 3 wt% to about 5 wt%, from about 3 wt% to about 4 wt%, from about 4 wt% to about 50 wt%, from about 4 wt% to about 40 wt%, from about 4 wt% to about 35 wt%, from about 4 wt% to about 30 wt%, from about 4 wt% to about 25 wt%, from about 4 wt% to about 20 wt%, from about 4 wt% to about 17 wt%, from about 4 wt% to about 15 wt%, from about 4 wt% to about 12 wt%, from about 4 wt% to about 10 wt%, from about 4 wt% to about 9 wt%, from about 4 wt% to about 8 wt%, from about 4 wt% to about 7 wt%, from about 4 wt% to about 6 wt%, from about 4 wt% to about 5 wt%, from about 5 wt% to about 50 wt%, from about 5 wt% to about 40 wt%, from about 5 wt% to about 35 wt%, from about 5 wt% to about 30 wt%, from about 5 wt% to about 25 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 17 wt%, from about 5 wt% to about 15 wt%, from about 5 wt% to about 12 wt%, from about 5 wt% to about 10 wt%, from about 5 wt% to about 9 wt%, from about 5 wt% to about 8 wt%, from about
5 wt% to about 7 wt%, from about 5 wt% to about 6 wt%, from about 6 wt% to about 50 wt%, from about
6 wt% to about 40 wt%, from about 6 wt% to about 35 wt%, from about 6 wt% to about 30 wt%, from about 6 wt% to about 25 wt%, from about 6 wt% to about 20 wt%, from about 6 wt% to about 17 wt%, from about 6 wt% to about 15 wt%, from about 6 wt% to about 12 wt%, from about 6 wt% to about 10 wt%, from about 6 wt% to about 9 wt%, from about 6 wt% to about 8 wt%, from about 6 wt% to about 7 wt%, from about 7 wt% to about 50 wt%, from about 7 wt% to about 40 wt%, from about 7 wt% to about 35 wt%, from about 7 wt% to about 30 wt%, from about 7 wt% to about 25 wt%, from about 7 wt% to about 20 wt%, from about 7 wt% to about 17 wt%, from about 7 wt% to about 15 wt%, from about 7 wt% to about 12 wt%, from about 7 wt% to about 10 wt%, from about 7 wt% to about 9 wt%, from about 7 wt% to about 8 wt%, from about 8 wt% to about 50 wt%, from about 8 wt% to about 40 wt%, from about 8 wt% to about 35 wt%, from about 8 wt% to about 30 wt%, from about 8 wt% to about 25 wt%, from about 8 wt% to about 20 wt%, from about 8 wt% to about 17 wt%, from about 8 wt% to about 15 wt%, from about 8 wt% to about 12 wt%, from about 8 wt% to about 10 wt%, from about 8 wt% to about 9 wt%, from about 9 wt% to about 50 wt%, from about 9 wt% to about 40 wt%, from about 9 wt% to about 35 wt%, from about 9 wt% to about 30 wt%, from about 9 wt% to about 25 wt%, from about 9 wt% to about 20 wt%, from about 9 wt% to about 17 wt%, from about 9 wt% to about 15 wt%, from about 9 wt% to about 12 wt%, from about 9 wt% to about 10 wt%, from about 10 wt% to about 50 wt%, from about 10 wt% to about 40 wt%, from about 10 wt% to about 35 wt%, from about 10 wt% to about 30 wt%, from about 10 wt% to about 25 wt%, from about 10 wt% to about 20 wt%, from about 10 wt% to about 17 wt%, from about 10 wt% to about 15 wt%, from about 10 wt% to about 12 wt%, from about 12 wt% to about 50 wt%, from about 12 wt% to about 40 wt%, from about 12 wt% to about 35 wt%, from about 12 wt% to about 30 wt%, from about 12 wt% to about 25 wt%, from about 12 wt% to about 20 wt%, from about 12 wt% to about 17 wt%, from about 12 wt% to about 15 wt%, from about 15 wt% to about 50 wt%, from about 15 wt% to about 40 wt%, from about 15 wt% to about 35 wt%, from about 15 wt% to about 30 wt%, from about 15 wt% to about 25 wt%, from about 15 wt% to about 20 wt%, from about 15 wt% to about 17 wt%, from about 17 wt% to about 50 wt%, from about 17 wt% to about 40 wt%, from about 17 wt% to about 35 wt%, from about 17 wt% to about 30 wt%, from about 17 wt% to about 25 wt%, from about 17 wt% to about 20 wt%, from about 20 wt% to about 50 wt%, from about 20 wt% to about 40 wt%, from about 20 wt% to about 35 wt%, from about 20 wt% to about 30 wt%, from about 20 wt% to about 25 wt%, from about 25 wt% to about 50 wt%, from about 25 wt% to about 40 wt%, from about 25 wt% to about 35 wt%, from about 25 wt% to about 30 wt%, from about 30 wt% to about 50 wt%, from about 30 wt% to about 40 wt%, from about 30 wt% to about 35 wt%, from about 35 wt% to about 50 wt%, from about 35 wt% to about 40 wt%, from about 40 wt% to about 50 wt%; or at most about 2 wt%, at most about 3 wt%, at most about 4 wt%, at most about 5 wt%, at most about 6 wt%, at most about 7 wt%, at most about 8 wt%, at most about 9 wt%, at most about 10 wt%, at most about 12 wt%, at most about 15 wt%, at most about 17 wt%, at most about 20 wt%, at most about 25 wt%, at most about 30 wt%, at most about 35 wt%, at most about 40 wt%, at most about 50 wt%; or about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 12 wt%, about 15 wt%, about 17 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 50 wt%, or any ranges or values therebetween. In a preferred embodiment, the metals M1+M2 make up the catalyst in about 10 wt%.
Any metals capable of catalyzing an OER reaction may be used. For example, metals like Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb may be used as Ml and M2 in the catalysts of the present invention. The metals may be Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb. The metals may be Ru, Pd, Ir, and Pt.
Instead of providing the metals as-is for preparing the catalysts, metal precursors may be used instead. Using metal precursors advantageously allows for easier handling of the compounds, especially at micromolar or nanomolar scale. Additionally, precursors of the metals may make the reagents easier to weigh, and prevent unwanted metallic interactions during the preparation phase, for example, during ball-milling or pyrolysis. The use of such precursors also helps to improve the porosity and surface area of the catalysts after pyrolysis, as the salts are pyrolyzed from the mixture, leaving behind pure metals and empty spaces in the catalyst which increase surface area.
Various precursors can be used, like organometallic compounds of metals, such as metal carbonyl compounds, metal ethylene complexes, metal-acetylacetonates, metal-acetates, metal cyanide compounds, metal-bis(acetylacetonate)s, cyclopentadienyl metal compounds or mixtures and combinations thereof. Other precursors may also be used, as long as they can be removed cleanly during the pyrolysis step.
Various transition metals may be used, that instead of reducing the electrocatalytic properties of the catalyst, may instead enhance them. Such transition metals can also further adjust the catalytic performance of the prepared electrocatalysts. The transition metal may be a Group III-XII transition metal. The transition metal may be a Group IV- VII transition metal. The transition metal may be a Group IV-V transition metal. The transition metal may be Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au or Hg. The transition metal may be Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag or Cd. The transition metal may be Mn, Fe, Co, Ni or Cu. The transition metal may be Co.
The catalysts of the present invention may have advantageously lower oxygen and/or oxide content after reduction in a reductive environment. Under reduction, the chemical states of the surface metal elements can change from the oxidized state to either partially oxidized or even the pure metallic state. Such reduced surface metal elements are particularly conducive and advantageously facilitate the OER process even more than other commercial catalysts.
The oxygen and/or oxide content in the catalyst before reduction may be in a range of at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, at least about 40 wt%, at least about 43 wt%, at least about 45 wt%, at least about 47 wt%, at least about 49 wt%, at least about 50 wt%, at least about 52 wt%, at least about 53 wt%, at least about 55 wt%, at least about 57 wt%, at least about 60 wt%, at least about 63 wt%, at least about 66 wt%, at least about 69 wt%, at least about 70 wt%; or from about 10 wt% to about 70 wt%, from about 10 wt% to about 69 wt%, from about 10 wt% to about 66 wt%, from about 10 wt% to about 63 wt%, from about 10 wt% to about 60 wt%, from about 10 wt% to about 57 wt%, from about 10 wt% to about 55 wt%, from about 10 wt% to about 53 wt%, from about 10 wt% to about 52 wt%, from about 10 wt% to about 50 wt%, from about 10 wt% to about 49 wt%, from about 10 wt% to about 47 wt%, from about 10 wt% to about 45 wt%, from about 10 wt% to about 43 wt%, from about 10 wt% to about 40 wt%, from about 10 wt% to about 35 wt%, from about 10 wt% to about 30 wt%, from about 10 wt% to about 25 wt%, from about 10 wt% to about 20 wt%, from about 10 wt% to about 15 wt%, from about 15 wt% to about 70 wt%, from about 15 wt% to about 69 wt%, from about 15 wt% to about 66 wt%, from about 15 wt% to about 63 wt%, from about 15 wt% to about 60 wt%, from about 15 wt% to about 57 wt%, from about 15 wt% to about 55 wt%, from about 15 wt% to about 53 wt%, from about 15 wt% to about 52 wt%, from about 15 wt% to about 50 wt%, from about 15 wt% to about 49 wt%, from about 15 wt% to about 47 wt%, from about 15 wt% to about 45 wt%, from about 15 wt% to about 43 wt%, from about 15 wt% to about 40 wt%, from about 15 wt% to about 35 wt%, from about 15 wt% to about 30 wt%, from about 15 wt% to about 25 wt%, from about 15 wt% to about 20 wt%, from about 20 wt% to about 70 wt%, from about 20 wt% to about 69 wt%, from about 20 wt% to about 66 wt%, from about 20 wt% to about 63 wt%, from about 20 wt% to about 60 wt%, from about 20 wt% to about 57 wt%, from about 20 wt% to about 55 wt%, from about 20 wt% to about 53 wt%, from about 20 wt% to about 52 wt%, from about 20 wt% to about 50 wt%, from about 20 wt% to about 49 wt%, from about 20 wt% to about 47 wt%, from about 20 wt% to about 45 wt%, from about 20 wt% to about 43 wt%, from about 20 wt% to about 40 wt%, from about 20 wt% to about 35 wt%, from about 20 wt% to about 30 wt%, from about 20 wt% to about 25 wt%, from about 25 wt% to about 70 wt%, from about 25 wt% to about 69 wt%, from about 25 wt% to about 66 wt%, from about 25 wt% to about 63 wt%, from about 25 wt% to about 60 wt%, from about 25 wt% to about 57 wt%, from about 25 wt% to about 55 wt%, from about 25 wt% to about 53 wt%, from about 25 wt% to about 52 wt%, from about 25 wt% to about 50 wt%, from about 25 wt% to about 49 wt%, from about 25 wt% to about 47 wt%, from about 25 wt% to about 45 wt%, from about 25 wt% to about 43 wt%, from about 25 wt% to about 40 wt%, from about 25 wt% to about 35 wt%, from about 25 wt% to about 30 wt%, from about 30 wt% to about 70 wt%, from about 30 wt% to about 69 wt%, from about 30 wt% to about 66 wt%, from about 30 wt% to about 63 wt%, from about 30 wt% to about 60 wt%, from about 30 wt% to about 57 wt%, from about 30 wt% to about 55 wt%, from about 30 wt% to about 53 wt%, from about 30 wt% to about 52 wt%, from about 30 wt% to about 50 wt%, from about 30 wt% to about 49 wt%, from about 30 wt% to about 47 wt%, from about 30 wt% to about 45 wt%, from about 30 wt% to about 43 wt%, from about 30 wt% to about 40 wt%, from about 30 wt% to about 35 wt%, from about 35 wt% to about 70 wt%, from about 35 wt% to about 69 wt%, from about 35 wt% to about 66 wt%, from about 35 wt% to about 63 wt%, from about 35 wt% to about 60 wt%, from about 35 wt% to about 57 wt%, from about 35 wt% to about 55 wt%, from about 35 wt% to about 53 wt%, from about 35 wt% to about 52 wt%, from about 35 wt% to about 50 wt%, from about 35 wt% to about 49 wt%, from about 35 wt% to about 47 wt%, from about 35 wt% to about 45 wt%, from about 35 wt% to about 43 wt%, from about 35 wt% to about 40 wt%, from about 40 wt% to about 70 wt%, from about 40 wt% to about 69 wt%, from about 40 wt% to about 66 wt%, from about 40 wt% to about 63 wt%, from about 40 wt% to about 60 wt%, from about 40 wt% to about 57 wt%, from about 40 wt% to about 55 wt%, from about 40 wt% to about 53 wt%, from about 40 wt% to about 52 wt%, from about 40 wt% to about 50 wt%, from about 40 wt% to about 49 wt%, from about 40 wt% to about 47 wt%, from about 40 wt% to about 45 wt%, from about 40 wt% to about 43 wt%, from about 43 wt% to about 70 wt%, from about 43 wt% to about 69 wt%, from about 43 wt% to about 66 wt%, from about 43 wt% to about 63 wt%, from about 43 wt% to about 60 wt%, from about 43 wt% to about 57 wt%, from about 43 wt% to about 55 wt%, from about 43 wt% to about 53 wt%, from about 43 wt% to about 52 wt%, from about 43 wt% to about 50 wt%, from about 43 wt% to about 49 wt%, from about 43 wt% to about 47 wt%, from about 43 wt% to about 45 wt%, from about 45 wt% to about 70 wt%, from about 45 wt% to about 69 wt%, from about 45 wt% to about 66 wt%, from about 45 wt% to about 63 wt%, from about 45 wt% to about 60 wt%, from about 45 wt% to about 57 wt%, from about 45 wt% to about 55 wt%, from about 45 wt% to about 53 wt%, from about 45 wt% to about 52 wt%, from about 45 wt% to about 50 wt%, from about 45 wt% to about 49 wt%, from about 45 wt% to about 47 wt%, from about 47 wt% to about 70 wt%, from about 47 wt% to about 69 wt%, from about 47 wt% to about 66 wt%, from about 47 wt% to about 63 wt%, from about 47 wt% to about 60 wt%, from about 47 wt% to about 57 wt%, from about 47 wt% to about 55 wt%, from about 47 wt% to about 53 wt%, from about 47 wt% to about 52 wt%, from about 47 wt% to about 50 wt%, from about 47 wt% to about 49 wt%, from about 49 wt% to about 70 wt%, from about 49 wt% to about 69 wt%, from about 49 wt% to about 66 wt%, from about 49 wt% to about 63 wt%, from about 49 wt% to about 60 wt%, from about 49 wt% to about 57 wt%, from about 49 wt% to about 55 wt%, from about 49 wt% to about 53 wt%, from about 49 wt% to about 52 wt%, from about 49 wt% to about 50 wt%, from about 50 wt% to about 70 wt%, from about 50 wt% to about 69 wt%, from about 50 wt% to about 66 wt%, from about 50 wt% to about 63 wt%, from about 50 wt% to about 60 wt%, from about 50 wt% to about 57 wt%, from about 50 wt% to about 55 wt%, from about 50 wt% to about 53 wt%, from about 50 wt% to about 52 wt%, from about 52 wt% to about 70 wt%, from about 52 wt% to about 69 wt%, from about 52 wt% to about 66 wt%, from about 52 wt% to about 63 wt%, from about 52 wt% to about 60 wt%, from about 52 wt% to about 57 wt%, from about 52 wt% to about 55 wt%, from about 52 wt% to about 53 wt%, from about 53 wt% to about 70 wt%, from about 53 wt% to about 69 wt%, from about 53 wt% to about 66 wt%, from about 53 wt% to about 63 wt%, from about 53 wt% to about 60 wt%, from about 53 wt% to about 57 wt%, from about 53 wt% to about 55 wt%, from about 55 wt% to about 70 wt%, from about 55 wt% to about 69 wt%, from about 55 wt% to about 66 wt%, from about 55 wt% to about 63 wt%, from about 55 wt% to about 60 wt%, from about 55 wt% to about 57 wt%, from about 57 wt% to about 70 wt%, from about 57 wt% to about 69 wt%, from about 57 wt% to about 66 wt%, from about 57 wt% to about 63 wt%, from about 57 wt% to about 60 wt%, from about 60 wt% to about 70 wt%, from about 60 wt% to about 69 wt%, from about 60 wt% to about 66 wt%, from about 60 wt% to about 63 wt%, from about 63 wt% to about 70 wt%, from about 63 wt% to about 69 wt%, from about 63 wt% to about 66 wt%, from about 66 wt% to about 70 wt%, from about 66 wt% to about 69 wt%, from about 69 wt% to about 70 wt%; or at most about 10 wt%, at most about 15 wt%, at most about 20 wt%, at most about 25 wt%, at most about 30 wt%, at most about 35 wt%, at most about 40 wt%, at most about 43 wt%, at most about 45 wt%, at most about 47 wt%, at most about 49 wt%, at most about 50 wt%, at most about 52 wt%, at most about 53 wt%, at most about 55 wt%, at most about 57 wt%, at most about 60 wt%, at most about 63 wt%, at most about 66 wt%, at most about 69 wt%, at most about 70 wt%; or about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 43 wt%, about 45 wt%, about 47 wt%, about 49 wt%, about 50 wt%, about 52 wt%, about 53 wt%, about 55 wt%, about 57 wt%, about 60 wt%, about 63 wt%, about 66 wt%, about 69 wt%, about 70 wt%, or any ranges or values therebetween. In some preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 60% before reduction. In some further preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 50% before reduction. In yet some other preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 49% before reduction. In some further preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 43% before reduction.
The oxygen and/or oxide content in the catalyst after reduction may be in a range of at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, at least about 40 wt%, at least about 43 wt%, at least about 45 wt%, at least about 47 wt%, at least about 49 wt%, at least about 50 wt%, at least about 52 wt%, at least about 53 wt%, at least about 55 wt%, at least about 57 wt%, at least about 60 wt%, at least about 63 wt%, at least about 66 wt%, at least about 69 wt%, at least about 70 wt%; or from about 10 wt% to about 70 wt%, from about 10 wt% to about 69 wt%, from about 10 wt% to about 66 wt%, from about 10 wt% to about 63 wt%, from about 10 wt% to about 60 wt%, from about 10 wt% to about 57 wt%, from about 10 wt% to about 55 wt%, from about 10 wt% to about 53 wt%, from about 10 wt% to about 52 wt%, from about 10 wt% to about 50 wt%, from about 10 wt% to about 49 wt%, from about 10 wt% to about 47 wt%, from about 10 wt% to about 45 wt%, from about 10 wt% to about 43 wt%, from about 10 wt% to about 40 wt%, from about 10 wt% to about 35 wt%, from about 10 wt% to about 30 wt%, from about 10 wt% to about 25 wt%, from about 10 wt% to about 20 wt%, from about 10 wt% to about 15 wt%, from about 15 wt% to about 70 wt%, from about 15 wt% to about 69 wt%, from about 15 wt% to about 66 wt%, from about 15 wt% to about 63 wt%, from about 15 wt% to about 60 wt%, from about 15 wt% to about 57 wt%, from about 15 wt% to about 55 wt%, from about 15 wt% to about 53 wt%, from about 15 wt% to about 52 wt%, from about 15 wt% to about 50 wt%, from about 15 wt% to about 49 wt%, from about 15 wt% to about 47 wt%, from about 15 wt% to about 45 wt%, from about 15 wt% to about 43 wt%, from about 15 wt% to about 40 wt%, from about 15 wt% to about 35 wt%, from about 15 wt% to about 30 wt%, from about 15 wt% to about 25 wt%, from about 15 wt% to about 20 wt%, from about 20 wt% to about 70 wt%, from about 20 wt% to about 69 wt%, from about 20 wt% to about 66 wt%, from about 20 wt% to about 63 wt%, from about 20 wt% to about 60 wt%, from about 20 wt% to about 57 wt%, from about 20 wt% to about 55 wt%, from about 20 wt% to about 53 wt%, from about 20 wt% to about 52 wt%, from about 20 wt% to about 50 wt%, from about 20 wt% to about 49 wt%, from about 20 wt% to about 47 wt%, from about 20 wt% to about 45 wt%, from about 20 wt% to about 43 wt%, from about 20 wt% to about 40 wt%, from about 20 wt% to about 35 wt%, from about 20 wt% to about 30 wt%, from about 20 wt% to about 25 wt%, from about 25 wt% to about 70 wt%, from about 25 wt% to about 69 wt%, from about 25 wt% to about 66 wt%, from about 25 wt% to about 63 wt%, from about 25 wt% to about 60 wt%, from about 25 wt% to about 57 wt%, from about 25 wt% to about 55 wt%, from about 25 wt% to about 53 wt%, from about 25 wt% to about 52 wt%, from about 25 wt% to about 50 wt%, from about 25 wt% to about 49 wt%, from about 25 wt% to about 47 wt%, from about 25 wt% to about 45 wt%, from about 25 wt% to about 43 wt%, from about 25 wt% to about 40 wt%, from about 25 wt% to about 35 wt%, from about 25 wt% to about 30 wt%, from about 30 wt% to about 70 wt%, from about 30 wt% to about 69 wt%, from about 30 wt% to about 66 wt%, from about 30 wt% to about 63 wt%, from about 30 wt% to about 60 wt%, from about 30 wt% to about 57 wt%, from about 30 wt% to about 55 wt%, from about 30 wt% to about 53 wt%, from about 30 wt% to about 52 wt%, from about 30 wt% to about 50 wt%, from about 30 wt% to about 49 wt%, from about 30 wt% to about 47 wt%, from about 30 wt% to about 45 wt%, from about 30 wt% to about 43 wt%, from about 30 wt% to about 40 wt%, from about 30 wt% to about 35 wt%, from about 35 wt% to about 70 wt%, from about 35 wt% to about 69 wt%, from about 35 wt% to about 66 wt%, from about 35 wt% to about 63 wt%, from about 35 wt% to about 60 wt%, from about 35 wt% to about 57 wt%, from about 35 wt% to about 55 wt%, from about 35 wt% to about 53 wt%, from about 35 wt% to about 52 wt%, from about 35 wt% to about 50 wt%, from about 35 wt% to about 49 wt%, from about 35 wt% to about 47 wt%, from about 35 wt% to about 45 wt%, from about 35 wt% to about 43 wt%, from about 35 wt% to about 40 wt%, from about 40 wt% to about 70 wt%, from about 40 wt% to about 69 wt%, from about 40 wt% to about 66 wt%, from about 40 wt% to about 63 wt%, from about 40 wt% to about 60 wt%, from about 40 wt% to about 57 wt%, from about 40 wt% to about 55 wt%, from about 40 wt% to about 53 wt%, from about 40 wt% to about 52 wt%, from about 40 wt% to about 50 wt%, from about 40 wt% to about 49 wt%, from about 40 wt% to about 47 wt%, from about 40 wt% to about 45 wt%, from about 40 wt% to about 43 wt%, from about 43 wt% to about 70 wt%, from about 43 wt% to about 69 wt%, from about 43 wt% to about 66 wt%, from about 43 wt% to about 63 wt%, from about 43 wt% to about 60 wt%, from about 43 wt% to about 57 wt%, from about 43 wt% to about 55 wt%, from about 43 wt% to about 53 wt%, from about 43 wt% to about 52 wt%, from about 43 wt% to about 50 wt%, from about 43 wt% to about 49 wt%, from about 43 wt% to about 47 wt%, from about 43 wt% to about 45 wt%, from about 45 wt% to about 70 wt%, from about 45 wt% to about 69 wt%, from about 45 wt% to about 66 wt%, from about 45 wt% to about 63 wt%, from about 45 wt% to about 60 wt%, from about 45 wt% to about 57 wt%, from about 45 wt% to about 55 wt%, from about 45 wt% to about 53 wt%, from about 45 wt% to about 52 wt%, from about 45 wt% to about 50 wt%, from about 45 wt% to about 49 wt%, from about 45 wt% to about 47 wt%, from about 47 wt% to about 70 wt%, from about 47 wt% to about 69 wt%, from about 47 wt% to about 66 wt%, from about 47 wt% to about 63 wt%, from about 47 wt% to about 60 wt%, from about 47 wt% to about 57 wt%, from about 47 wt% to about 55 wt%, from about 47 wt% to about 53 wt%, from about 47 wt% to about 52 wt%, from about 47 wt% to about 50 wt%, from about 47 wt% to about 49 wt%, from about 49 wt% to about 70 wt%, from about 49 wt% to about 69 wt%, from about 49 wt% to about 66 wt%, from about 49 wt% to about 63 wt%, from about 49 wt% to about 60 wt%, from about 49 wt% to about 57 wt%, from about 49 wt% to about 55 wt%, from about 49 wt% to about 53 wt%, from about 49 wt% to about 52 wt%, from about 49 wt% to about 50 wt%, from about 50 wt% to about 70 wt%, from about 50 wt% to about 69 wt%, from about 50 wt% to about 66 wt%, from about 50 wt% to about 63 wt%, from about 50 wt% to about 60 wt%, from about 50 wt% to about 57 wt%, from about 50 wt% to about 55 wt%, from about 50 wt% to about 53 wt%, from about 50 wt% to about 52 wt%, from about 52 wt% to about 70 wt%, from about 52 wt% to about 69 wt%, from about 52 wt% to about 66 wt%, from about 52 wt% to about 63 wt%, from about 52 wt% to about 60 wt%, from about 52 wt% to about 57 wt%, from about 52 wt% to about 55 wt%, from about 52 wt% to about 53 wt%, from about 53 wt% to about 70 wt%, from about 53 wt% to about 69 wt%, from about 53 wt% to about 66 wt%, from about 53 wt% to about 63 wt%, from about 53 wt% to about 60 wt%, from about 53 wt% to about 57 wt%, from about 53 wt% to about 55 wt%, from about 55 wt% to about 70 wt%, from about 55 wt% to about 69 wt%, from about 55 wt% to about 66 wt%, from about 55 wt% to about 63 wt%, from about 55 wt% to about 60 wt%, from about 55 wt% to about 57 wt%, from about 57 wt% to about 70 wt%, from about 57 wt% to about 69 wt%, from about 57 wt% to about 66 wt%, from about 57 wt% to about 63 wt%, from about 57 wt% to about 60 wt%, from about 60 wt% to about 70 wt%, from about 60 wt% to about 69 wt%, from about 60 wt% to about 66 wt%, from about 60 wt% to about 63 wt%, from about 63 wt% to about 70 wt%, from about 63 wt% to about 69 wt%, from about 63 wt% to about 66 wt%, from about 66 wt% to about 70 wt%, from about 66 wt% to about 69 wt%, from about 69 wt% to about 70 wt%; or at most about 10 wt%, at most about 15 wt%, at most about 20 wt%, at most about 25 wt%, at most about 30 wt%, at most about 35 wt%, at most about 40 wt%, at most about 43 wt%, at most about 45 wt%, at most about 47 wt%, at most about 49 wt%, at most about 50 wt%, at most about 52 wt%, at most about 53 wt%, at most about 55 wt%, at most about 57 wt%, at most about 60 wt%, at most about 63 wt%, at most about 66 wt%, at most about 69 wt%, at most about 70 wt%; or about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 43 wt%, about 45 wt%, about 47 wt%, about 49 wt%, about 50 wt%, about 52 wt%, about 53 wt%, about 55 wt%, about 57 wt%, about 60 wt%, about 63 wt%, about 66 wt%, about 69 wt%, about 70 wt%, or any ranges or values therebetween. In some preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 60% after reduction. In some further preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 50% after reduction. In yet some other preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 49% after reduction. In some further preferred embodiments, the catalyst has an oxygen and/or oxide content of less than about 43% after reduction. The catalysts of the present disclosure may also be easily tuned by introducing various dopants (such as sulfur, selenium, or phosphorous) to adjust the various characteristics of the catalysts, such as the overpotential, pH stability in solution or conversion efficiency. The dopant(s) may be added in an amount of about 0.1 wt% to about 5 wt%, about 0.5 wt% to about 5 wt%, about 1 wt% to about 5 wt%, about 2 wt% to about 5 wt%, about 3 wt% to about 5 wt%, about 4 wt% to about 5 wt%, about 0.1 wt% to about 4 wt%, 0.1 wt% to about 3 wt%, 0.1 wt% to about 2 wt%, 0.1 wt% to about 1 wt%, 0.1 wt% to about 0.5 wt%, or any ranges or values therebetween.
In a preferred embodiment, the present disclosure provides for a catalyst, wherein Ml is Ir, M2 is Ru, TM is Co, SI is WO3, the weight ratio of M1:M2:TM is about 1:3:3, and the weight ratio of (M1+M2):S1 is about 1:10, wherein the supported catalyst has an oxygen and/or oxide content of less than about 50%.
The present disclosure also provides for a process of preparing a supported catalyst, the process comprising the steps of: a) preparing a mixture comprising an organometallic compound of Ml, an organometallic compound of M2, an organometallic compound of TM, and SI, wherein:
Ml and M2 are metals independently selected from the group consisting of Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb;
TM is a transition metal;
S 1 is a support; wherein the weight ratio of M1:M2:TM is in the range of about 1 : 2-10 : 2-10; the weight ratio of (M1+M2):S1 is in the range of about 1 : 5-20; and
Ml, M2, and TM are different, b) ball-milling the mixture of step (a) at a rotation speed of about 200 rpm to about 900 rpm for a duration of about 1 hour to about 5 hours to form a ball-milled mixture, and c) pyrolyzing the ball-milled mixture of step (b) at a temperature of about 300 °C to about 600 °C for a duration of about 1 hour to about 5 hours to form a pyrolyzed product.
In the present invention, the mixture of metal (Ml, M2, TM) precursors as well as the support may be first ground into a homogenous mixture using ball-milling at different rotating speeds for different time durations under controlled ambient conditions, which could for example be reductive ambient or oxidizing ambient conditions.
Various milling balls may be used, for example zirconia balls, ceramic balls, alumina balls, steel balls, tungsten carbide balls, or agate balls. Various jars may also be used, for example nylon jars. In some embodiments, zirconia balls are used in the ball milling step (b). In some other embodiments, nylon jars are used in the ball milling step (b).
Ball-milling is a low energy process and allows the components in the mixture to mix uniformly, and be grounded as well to very fine nanoparticles. By tuning the parameters of the ball-milling process, for example by adjusting the atmosphere of the ball-milling to either oxidizing or reducing, or by tuning other parameters of the process such as rotating speed, duration, ambient temperature, or by adding other materials, components and/or materials, the physiochemical properties of the ball-milled mixture can be tuned and adjusted. Further, various crystalline properties may even be imparted by the ball-milling process to the catalyst after ball-milling in combination with pyrolyis. In some embodiments, surfactants could also be introduced to tune or to further improve the interaction between the metal components and the support.
The present disclosure provides for a method of producing a catalyst, wherein ball-milling step (b) is performed in an oxidizing or reducing atmosphere. The present disclosure also provides for a method of producing a catalyst, wherein ball-milling step (b) is performed in an oxidizing atmosphere. The present disclosure further provides for a method of producing a catalyst, wherein ball-milling step (b) is performed in an reducing atmosphere.
The ball-milling step (b) may be performed at a rotation speed in a range of at least about 100 rpm, at least about 150 rpm, at least about 200 rpm, at least about 250 rpm, at least about 300 rpm, at least about 350 rpm, at least about 400 rpm, at least about 450 rpm, at least about 500 rpm, at least about 600 rpm, at least about 700 rpm, at least about 800 rpm, at least about 900 rpm, at least about 1000 rpm; or from about 100 rpm to about 1000 rpm, from about 100 rpm to about 900 rpm, from about 100 rpm to about 800 rpm, from about 100 rpm to about 700 rpm, from about 100 rpm to about 600 rpm, from about 100 rpm to about 500 rpm, from about 100 rpm to about 450 rpm, from about 100 rpm to about 400 rpm, from about 100 rpm to about 350 rpm, from about 100 rpm to about 300 rpm, from about 100 rpm to about 250 rpm, from about 100 rpm to about 200 rpm, from about 100 rpm to about 150 rpm, from about 150 rpm to about 1000 rpm, from about 150 rpm to about 900 rpm, from about 150 rpm to about 800 rpm, from about 150 rpm to about 700 rpm, from about 150 rpm to about 600 rpm, from about 150 rpm to about 500 rpm, from about 150 rpm to about 450 rpm, from about 150 rpm to about 400 rpm, from about 150 rpm to about 350 rpm, from about 150 rpm to about 300 rpm, from about 150 rpm to about 250 rpm, from about 150 rpm to about 200 rpm, from about 200 rpm to about 1000 rpm, from about 200 rpm to about 900 rpm, from about 200 rpm to about 800 rpm, from about 200 rpm to about 700 rpm, from about 200 rpm to about 600 rpm, from about 200 rpm to about 500 rpm, from about 200 rpm to about 450 rpm, from about 200 rpm to about 400 rpm, from about 200 rpm to about 350 rpm, from about 200 rpm to about 300 rpm, from about 200 rpm to about 250 rpm, from about 250 rpm to about 1000 rpm, from about 250 rpm to about 900 rpm, from about 250 rpm to about 800 rpm, from about 250 rpm to about 700 rpm, from about 250 rpm to about 600 rpm, from about 250 rpm to about 500 rpm, from about 250 rpm to about 450 rpm, from about 250 rpm to about 400 rpm, from about 250 rpm to about 350 rpm, from about 250 rpm to about 300 rpm, from about 300 rpm to about 1000 rpm, from about 300 rpm to about 900 rpm, from about 300 rpm to about 800 rpm, from about 300 rpm to about 700 rpm, from about 300 rpm to about 600 rpm, from about 300 rpm to about 500 rpm, from about 300 rpm to about 450 rpm, from about 300 rpm to about 400 rpm, from about 300 rpm to about 350 rpm, from about 350 rpm to about 1000 rpm, from about 350 rpm to about 900 rpm, from about 350 rpm to about 800 rpm, from about 350 rpm to about 700 rpm, from about 350 rpm to about 600 rpm, from about 350 rpm to about 500 rpm, from about 350 rpm to about 450 rpm, from about 350 rpm to about 400 rpm, from about 400 rpm to about 1000 rpm, from about 400 rpm to about 900 rpm, from about 400 rpm to about 800 rpm, from about 400 rpm to about 700 rpm, from about 400 rpm to about 600 rpm, from about 400 rpm to about 500 rpm, from about 400 rpm to about 450 rpm, from about 450 rpm to about 1000 rpm, from about 450 rpm to about 900 rpm, from about 450 rpm to about 800 rpm, from about 450 rpm to about 700 rpm, from about 450 rpm to about 600 rpm, from about 450 rpm to about 500 rpm, from about 500 rpm to about 1000 rpm, from about 500 rpm to about 900 rpm, from about 500 rpm to about 800 rpm, from about 500 rpm to about 700 rpm, from about 500 rpm to about 600 rpm, from about 600 rpm to about 1000 rpm, from about 600 rpm to about 900 rpm, from about 600 rpm to about 800 rpm, from about 600 rpm to about 700 rpm, from about 700 rpm to about 1000 rpm, from about 700 rpm to about 900 rpm, from about 700 rpm to about 800 rpm, from about 800 rpm to about 1000 rpm, from about 800 rpm to about 900 rpm, from about 900 rpm to about 1000 rpm; or at most about 100 rpm, at most about 150 rpm, at most about 200 rpm, at most about 250 rpm, at most about 300 rpm, at most about 350 rpm, at most about 400 rpm, at most about 450 rpm, at most about 500 rpm, at most about 600 rpm, at most about 700 rpm, at most about 800 rpm, at most about 900 rpm, at most about 1000 rpm; or about 100 rpm, about 150 rpm, about 200 rpm, about 250 rpm, about 300 rpm, about 350 rpm, about 400 rpm, about 450 rpm, about 500 rpm, about 600 rpm, about 700 rpm, about 800 rpm, about 900 rpm, about 1000 rpm. In some preferred embodiments, the ball-milling step (b) is performed at a rotation speed of about 200 pm to about 900 rpm. In some further preferred embodiments, the ball-milling step is performed at a rotation speed of about 300 rpm.
The ball-milling step (b) is performed for a duration range of at least about 0.5 hours, at least about 1 hour, at least about 1.5 hours, at least about 2 hours, at least about 2.5 hours, at least about 3 hours, at least about 3.5 hours, at least about 4 hours, at least about 4.5 hours, at least about 5 hours, at least about 6 hours, at least about 7 hours, at least about 8 hours, at least about 9 hours, at least about 10 hours; or from about 0.5 hours to about 10 hours, from about 0.5 hours to about 9 hours, from about 0.5 hours to about 8 hours, from about 0.5 hours to about 7 hours, from about 0.5 hours to about 6 hours, from about 0.5 hours to about 5 hours, from about 0.5 hours to about 4.5 hours, from about 0.5 hours to about 4 hours, from about 0.5 hours to about 3.5 hours, from about 0.5 hours to about 3 hours, from about 0.5 hours to about 2.5 hours, from about 0.5 hours to about 2 hours, from about 0.5 hours to about 1.5 hours, from about 0.5 hours to about 1 hour, from about 1 hour to about 10 hours, from about 1 hour to about 9 hours, from about 1 hour to about 8 hours, from about 1 hour to about 7 hours, from about 1 hour to about 6 hours, from about 1 hour to about 5 hours, from about 1 hour to about 4.5 hours, from about 1 hour to about 4 hours, from about 1 hour to about 3.5 hours, from about 1 hour to about 3 hours, from about 1 hour to about 2.5 hours, from about 1 hour to about 2 hours, from about 1 hour to about 1.5 hours, from about 1.5 hours to about 10 hours, from about 1.5 hours to about 9 hours, from about 1.5 hours to about 8 hours, from about 1.5 hours to about 7 hours, from about 1.5 hours to about 6 hours, from about 1.5 hours to about 5 hours, from about 1.5 hours to about 4.5 hours, from about 1.5 hours to about 4 hours, from about 1.5 hours to about 3.5 hours, from about 1.5 hours to about 3 hours, from about 1.5 hours to about 2.5 hours, from about 1.5 hours to about 2 hours, from about 2 hours to about 10 hours, from about 2 hours to about 9 hours, from about 2 hours to about 8 hours, from about 2 hours to about 7 hours, from about 2 hours to about 6 hours, from about 2 hours to about 5 hours, from about 2 hours to about 4.5 hours, from about 2 hours to about 4 hours, from about 2 hours to about 3.5 hours, from about 2 hours to about 3 hours, from about 2 hours to about 2.5 hours, from about 2.5 hours to about 10 hours, from about 2.5 hours to about 9 hours, from about 2.5 hours to about 8 hours, from about 2.5 hours to about 7 hours, from about 2.5 hours to about 6 hours, from about 2.5 hours to about 5 hours, from about 2.5 hours to about 4.5 hours, from about 2.5 hours to about 4 hours, from about 2.5 hours to about 3.5 hours, from about 2.5 hours to about 3 hours, from about 3 hours to about 10 hours, from about 3 hours to about 9 hours, from about 3 hours to about 8 hours, from about 3 hours to about 7 hours, from about 3 hours to about 6 hours, from about 3 hours to about 5 hours, from about 3 hours to about 4.5 hours, from about 3 hours to about 4 hours, from about 3 hours to about 3.5 hours, from about 3.5 hours to about 10 hours, from about 3.5 hours to about 9 hours, from about 3.5 hours to about 8 hours, from about 3.5 hours to about 7 hours, from about 3.5 hours to about 6 hours, from about 3.5 hours to about 5 hours, from about 3.5 hours to about 4.5 hours, from about 3.5 hours to about 4 hours, from about 4 hours to about 10 hours, from about 4 hours to about 9 hours, from about 4 hours to about 8 hours, from about 4 hours to about 7 hours, from about 4 hours to about 6 hours, from about 4 hours to about 5 hours, from about 4 hours to about 4.5 hours, from about 4.5 hours to about 10 hours, from about 4.5 hours to about 9 hours, from about 4.5 hours to about 8 hours, from about 4.5 hours to about 7 hours, from about 4.5 hours to about 6 hours, from about 4.5 hours to about 5 hours, from about 5 hours to about 10 hours, from about 5 hours to about 9 hours, from about 5 hours to about 8 hours, from about 5 hours to about 7 hours, from about 5 hours to about 6 hours, from about 6 hours to about 10 hours, from about 6 hours to about 9 hours, from about 6 hours to about 8 hours, from about 6 hours to about 7 hours, from about 7 hours to about 10 hours, from about 7 hours to about 9 hours, from about 7 hours to about 8 hours, from about 8 hours to about 10 hours, from about 8 hours to about 9 hours, from about 9 hours to about 10 hours; or at most about 0.5 hours, at most about 1 hour, at most about 1.5 hours, at most about 2 hours, at most about 2.5 hours, at most about 3 hours, at most about 3.5 hours, at most about 4 hours, at most about 4.5 hours, at most about 5 hours, at most about 6 hours, at most about 7 hours, at most about 8 hours, at most about 9 hours, at most about 10 hours; or about 0.5 hours, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, about 4 hours, about 4.5 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, or any ranges or values therebetween. In some preferred embodiments, the ball-milling step (b) is performed for a duration of about 1 hour to about 5 hours. In some further preferred embodiments, the ball-milling step (b) is performed for a duration of about 3 hours.
After the pyrolysis of step (c), the catalyst may have an average particle size in a range of at least about 0.5 nm, at least about 0.8 nm, at least about 1 nm, at least about 2 nm, at least about 3 nm, at least about 4 nm, at least about 5 nm, at least about 6 nm, at least about 7 nm, at least about 8 nm, at least about 9 nm, at least about 10 nm, at least about 12 nm, at least about 14 nm, at least about 15 nm, at least about 16 nm, at least about 18 nm, at least about 20 nm, at least about 25 nm, at least about 30 nm, at least about 40 nm, at least about 50 nm; or from about 0.5 nm to about 50 nm, from about 0.5 nm to about 40 nm, from about 0.5 nm to about 30 nm, from about 0.5 nm to about 25 nm, from about 0.5 nm to about 20 nm, from about 0.5 nm to about 18 nm, from about 0.5 nm to about 16 nm, from about 0.5 nm to about 15 nm, from about 0.5 nm to about 14 nm, from about 0.5 nm to about 12 nm, from about 0.5 nm to about 10 nm, from about 0.5 nm to about 9 nm, from about 0.5 nm to about 8 nm, from about 0.5 nm to about 7 nm, from about 0.5 nm to about 6 nm, from about 0.5 nm to about 5 nm, from about 0.5 nm to about 4 nm, from about 0.5 nm to about 3 nm, from about 0.5 nm to about 2 nm, from about 0.5 nm to about 1 nm, from about 0.5 nm to about 0.8 nm, from about 0.8 nm to about 50 nm, from about 0.8 nm to about 40 nm, from about 0.8 nm to about 30 nm, from about 0.8 nm to about 25 nm, from about 0.8 nm to about 20 nm, from about 0.8 nm to about 18 nm, from about 0.8 nm to about 16 nm, from about 0.8 nm to about 15 nm, from about 0.8 nm to about 14 nm, from about 0.8 nm to about 12 nm, from about 0.8 nm to about 10 nm, from about 0.8 nm to about 9 nm, from about 0.8 nm to about 8 nm, from about 0.8 nm to about 7 nm, from about 0.8 nm to about 6 nm, from about 0.8 nm to about 5 nm, from about 0.8 nm to about 4 nm, from about 0.8 nm to about 3 nm, from about 0.8 nm to about 2 nm, from about 0.8 nm to about 1 nm, from about 1 nm to about 50 nm, from about 1 nm to about 40 nm, from about 1 nm to about 30 nm, from about 1 nm to about 25 nm, from about 1 nm to about 20 nm, from about 1 nm to about 18 nm, from about
1 nm to about 16 nm, from about 1 nm to about 15 nm, from about 1 nm to about 14 nm, from about 1 nm to about 12 nm, from about 1 nm to about 10 nm, from about 1 nm to about 9 nm, from about 1 nm to about 8 nm, from about 1 nm to about 7 nm, from about 1 nm to about 6 nm, from about 1 nm to about 5 nm, from about 1 nm to about 4 nm, from about 1 nm to about 3 nm, from about 1 nm to about 2 nm, from about 2 nm to about 50 nm, from about 2 nm to about 40 nm, from about 2 nm to about 30 nm, from about
2 nm to about 25 nm, from about 2 nm to about 20 nm, from about 2 nm to about 18 nm, from about 2 nm to about 16 nm, from about 2 nm to about 15 nm, from about 2 nm to about 14 nm, from about 2 nm to about 12 nm, from about 2 nm to about 10 nm, from about 2 nm to about 9 nm, from about 2 nm to about 8 nm, from about 2 nm to about 7 nm, from about 2 nm to about 6 nm, from about 2 nm to about 5 nm, from about 2 nm to about 4 nm, from about 2 nm to about 3 nm, from about 3 nm to about 50 nm, from about 3 nm to about 40 nm, from about 3 nm to about 30 nm, from about 3 nm to about 25 nm, from about
3 nm to about 20 nm, from about 3 nm to about 18 nm, from about 3 nm to about 16 nm, from about 3 nm to about 15 nm, from about 3 nm to about 14 nm, from about 3 nm to about 12 nm, from about 3 nm to about 10 nm, from about 3 nm to about 9 nm, from about 3 nm to about 8 nm, from about 3 nm to about 7 nm, from about 3 nm to about 6 nm, from about 3 nm to about 5 nm, from about 3 nm to about 4 nm, from about 4 nm to about 50 nm, from about 4 nm to about 40 nm, from about 4 nm to about 30 nm, from about
4 nm to about 25 nm, from about 4 nm to about 20 nm, from about 4 nm to about 18 nm, from about 4 nm to about 16 nm, from about 4 nm to about 15 nm, from about 4 nm to about 14 nm, from about 4 nm to about 12 nm, from about 4 nm to about 10 nm, from about 4 nm to about 9 nm, from about 4 nm to about 8 nm, from about 4 nm to about 7 nm, from about 4 nm to about 6 nm, from about 4 nm to about 5 nm, from about 5 nm to about 50 nm, from about 5 nm to about 40 nm, from about 5 nm to about 30 nm, from about 5 nm to about 25 nm, from about 5 nm to about 20 nm, from about 5 nm to about 18 nm, from about
5 nm to about 16 nm, from about 5 nm to about 15 nm, from about 5 nm to about 14 nm, from about 5 nm to about 12 nm, from about 5 nm to about 10 nm, from about 5 nm to about 9 nm, from about 5 nm to about 8 nm, from about 5 nm to about 7 nm, from about 5 nm to about 6 nm, from about 6 nm to about 50 nm, from about 6 nm to about 40 nm, from about 6 nm to about 30 nm, from about 6 nm to about 25 nm, from about 6 nm to about 20 nm, from about 6 nm to about 18 nm, from about 6 nm to about 16 nm, from about 6 nm to about 15 nm, from about 6 nm to about 14 nm, from about 6 nm to about 12 nm, from about
6 nm to about 10 nm, from about 6 nm to about 9 nm, from about 6 nm to about 8 nm, from about 6 nm to about 7 nm, from about 7 nm to about 50 nm, from about 7 nm to about 40 nm, from about 7 nm to about 30 nm, from about 7 nm to about 25 nm, from about 7 nm to about 20 nm, from about 7 nm to about 18 nm, from about 7 nm to about 16 nm, from about 7 nm to about 15 nm, from about 7 nm to about 14 nm, from about 7 nm to about 12 nm, from about 7 nm to about 10 nm, from about 7 nm to about 9 nm, from about 7 nm to about 8 nm, from about 8 nm to about 50 nm, from about 8 nm to about 40 nm, from about
8 nm to about 30 nm, from about 8 nm to about 25 nm, from about 8 nm to about 20 nm, from about 8 nm to about 18 nm, from about 8 nm to about 16 nm, from about 8 nm to about 15 nm, from about 8 nm to about 14 nm, from about 8 nm to about 12 nm, from about 8 nm to about 10 nm, from about 8 nm to about
9 nm, from about 9 nm to about 50 nm, from about 9 nm to about 40 nm, from about 9 nm to about 30 nm, from about 9 nm to about 25 nm, from about 9 nm to about 20 nm, from about 9 nm to about 18 nm, from about 9 nm to about 16 nm, from about 9 nm to about 15 nm, from about 9 nm to about 14 nm, from about 9 nm to about 12 nm, from about 9 nm to about 10 nm, from about 10 nm to about 50 nm, from about 10 nm to about 40 nm, from about 10 nm to about 30 nm, from about 10 nm to about 25 nm, from about 10 nm to about 20 nm, from about 10 nm to about 18 nm, from about 10 nm to about 16 nm, from about 10 nm to about 15 nm, from about 10 nm to about 14 nm, from about 10 nm to about 12 nm, from about 12 nm to about 50 nm, from about 12 nm to about 40 nm, from about 12 nm to about 30 nm, from about 12 nm to about 25 nm, from about 12 nm to about 20 nm, from about 12 nm to about 18 nm, from about 12 nm to about 16 nm, from about 12 nm to about 15 nm, from about 12 nm to about 14 nm, from about 14 nm to about 50 nm, from about 14 nm to about 40 nm, from about 14 nm to about 30 nm, from about 14 nm to about 25 nm, from about 14 nm to about 20 nm, from about 14 nm to about 18 nm, from about 14 nm to about 16 nm, from about 14 nm to about 15 nm, from about 15 nm to about 50 nm, from about 15 nm to about 40 nm, from about 15 nm to about 30 nm, from about 15 nm to about 25 nm, from about 15 nm to about 20 nm, from about 15 nm to about 18 nm, from about 15 nm to about 16 nm, from about 16 nm to about 50 nm, from about 16 nm to about 40 nm, from about 16 nm to about 30 nm, from about 16 nm to about 25 nm, from about 16 nm to about 20 nm, from about 16 nm to about 18 nm, from about 18 nm to about 50 nm, from about 18 nm to about 40 nm, from about 18 nm to about 30 nm, from about 18 nm to about 25 nm, from about 18 nm to about 20 nm, from about 20 nm to about 50 nm, from about 20 nm to about 40 nm, from about 20 nm to about 30 nm, from about 20 nm to about 25 nm, from about 25 nm to about 50 nm, from about 25 nm to about 40 nm, from about 25 nm to about 30 nm, from about 30 nm to about 50 nm, from about 30 nm to about 40 nm, from about 40 nm to about 50 nm; or at most about 0.5 nm, at most about 0.8 nm, at most about 1 nm, at most about 2 nm, at most about 3 nm, at most about 4 nm, at most about 5 nm, at most about 6 nm, at most about 7 nm, at most about 8 nm, at most about 9 nm, at most about 10 nm, at most about 12 nm, at most about 14 nm, at most about 15 nm, at most about 16 nm, at most about 18 nm, at most about 20 nm, at most about 25 nm, at most about 30 nm, at most about 40 nm, at most about 50 nm; or about 0.5 nm, about 0.8 nm, about 1 nm, about 2 nm, about 3 nm, about 4 nm, about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, about 10 nm, about 12 nm, about 14 nm, about 15 nm, about 16 nm, about 18 nm, about 20 nm, about 25 nm, about 30 nm, about 40 nm, about 50 nm, or any ranges or values therebetween. The average particle size of the catalyst may be from about
1 nm to about 10 nm after the pyrolysis of step (c). The average particle size of the catalyst is from about
2 nm to about 5 nm after the pyrolysis of step (c).
The present disclosure provides for a catalyst, wherein the catalyst has an average particle size of about 1 nm to about 10 nm. The present disclosure also provides for a catalyst, wherein the catalyst has an average particle size of about 2 nm to about 5 nm. The present disclosure further provides for a method of preparing a catalyst, wherein step (c) produces a product having an average particle size of about 1 nm to about 10 nm. The present disclosure also provides for a method of preparing a catalyst, wherein step (c) produces a product having an average particle size of about 2 nm to about 5 nm.
The mixture from step (b) may be subjected to a thermal treatment step, for example pyrolysis, to remove the salts from the metal precursors, in order to leave behind metals and support. The thermal treatment may also be adjusted to further tune the physiochemical properties of the mixture remaining after thermal treatment. The thermal treatment step (c) may be performed at a temperature range of at least about 200 °C, at least about 250 °C, at least about 275 °C, at least about 300 °C, at least about 325 °C, at least about 350 °C, at least about 375 °C, at least about 400 °C, at least about 450 °C, at least about 500 °C, at least about 550 °C, at least about 600 °C, at least about 650 °C, at least about 700 °C, at least about 750 °C, at least about 800 °C, at least about 900 °C, at least about 1000 °C; or from about 200 °C to about 1000 °C, from about 200 °C to about 900 °C, from about 200 °C to about 800 °C, from about 200 °C to about 750 °C, from about 200 °C to about 700 °C, from about 200 °C to about 650 °C, from about 200 °C to about 600 °C, from about 200 °C to about 550 °C, from about 200 °C to about 500 °C, from about 200 °C to about 450 °C, from about 200 °C to about 400 °C, from about 200 °C to about 375 °C, from about 200 °C to about 350 °C, from about 200 °C to about 325 °C, from about 200 °C to about 300 °C, from about 200 °C to about 275 °C, from about 200 °C to about 250 °C, from about 250 °C to about 1000 °C, from about 250 °C to about 900 °C, from about 250 °C to about 800 °C, from about 250 °C to about 750 °C, from about 250 °C to about 700 °C, from about 250 °C to about 650 °C, from about 250 °C to about 600 °C, from about 250 °C to about 550 °C, from about 250 °C to about 500 °C, from about 250 °C to about 450 °C, from about 250 °C to about 400 °C, from about 250 °C to about 375 °C, from about 250 °C to about 350 °C, from about 250 °C to about 325 °C, from about 250 °C to about 300 °C, from about 250 °C to about 275 °C, from about 275 °C to about 1000 °C, from about 275 °C to about 900 °C, from about 275 °C to about 800 °C, from about 275 °C to about 750 °C, from about 275 °C to about 700 °C, from about 275 °C to about 650 °C, from about 275 °C to about 600 °C, from about 275 °C to about 550 °C, from about 275 °C to about 500 °C, from about 275 °C to about 450 °C, from about 275 °C to about 400 °C, from about 275 °C to about 375 °C, from about 275 °C to about 350 °C, from about 275 °C to about 325 °C, from about 275 °C to about 300 °C, from about 300 °C to about 1000 °C, from about 300 °C to about 900 °C, from about 300 °C to about 800 °C, from about 300 °C to about 750 °C, from about 300 °C to about 700 °C, from about 300 °C to about 650 °C, from about 300 °C to about 600 °C, from about 300 °C to about 550 °C, from about 300 °C to about 500 °C, from about 300 °C to about 450 °C, from about 300 °C to about 400 °C, from about 300 °C to about 375 °C, from about 300 °C to about 350 °C, from about 300 °C to about 325 °C, from about 325 °C to about 1000 °C, from about 325 °C to about 900 °C, from about 325 °C to about 800 °C, from about 325 °C to about 750 °C, from about 325 °C to about 700 °C, from about 325 °C to about 650 °C, from about 325 °C to about 600 °C, from about 325 °C to about 550 °C, from about 325 °C to about 500 °C, from about 325 °C to about 450 °C, from about 325 °C to about 400 °C, from about 325 °C to about 375 °C, from about 325 °C to about 350 °C, from about 350 °C to about 1000 °C, from about 350 °C to about 900 °C, from about 350 °C to about 800 °C, from about 350 °C to about 750 °C, from about 350 °C to about 700 °C, from about 350 °C to about 650 °C, from about 350 °C to about 600 °C, from about 350 °C to about 550 °C, from about 350 °C to about 500 °C, from about 350 °C to about 450 °C, from about 350 °C to about 400 °C, from about 350 °C to about 375 °C, from about 375 °C to about 1000 °C, from about 375 °C to about 900 °C, from about 375 °C to about 800 °C, from about 375 °C to about 750 °C, from about 375 °C to about 700 °C, from about 375 °C to about 650 °C, from about 375 °C to about 600 °C, from about 375 °C to about 550 °C, from about 375 °C to about 500 °C, from about 375 °C to about 450 °C, from about 375 °C to about 400 °C, from about 400 °C to about 1000 °C, from about 400 °C to about 900 °C, from about 400 °C to about 800 °C, from about 400 °C to about 750 °C, from about 400 °C to about 700 °C, from about 400 °C to about 650 °C, from about 400 °C to about 600 °C, from about 400 °C to about 550 °C, from about 400 °C to about 500 °C, from about 400 °C to about 450 °C, from about 450 °C to about 1000 °C, from about 450 °C to about 900 °C, from about 450 °C to about 800 °C, from about 450 °C to about 750 °C, from about 450 °C to about 700 °C, from about 450 °C to about 650 °C, from about 450 °C to about 600 °C, from about 450 °C to about 550 °C, from about 450 °C to about 500 °C, from about 500 °C to about 1000 °C, from about 500 °C to about 900 °C, from about 500 °C to about 800 °C, from about 500 °C to about 750 °C, from about 500 °C to about 700 °C, from about 500 °C to about 650 °C, from about 500 °C to about 600 °C, from about 500 °C to about 550 °C, from about 550 °C to about 1000 °C, from about 550 °C to about 900 °C, from about 550 °C to about 800 °C, from about 550 °C to about 750 °C, from about 550 °C to about 700 °C, from about 550 °C to about 650 °C, from about 550 °C to about 600 °C, from about 600 °C to about 1000 °C, from about 600 °C to about 900 °C, from about 600 °C to about 800 °C, from about 600 °C to about 750 °C, from about 600 °C to about 700 °C, from about 600 °C to about 650 °C, from about 650 °C to about 1000 °C, from about 650 °C to about 900 °C, from about 650 °C to about 800 °C, from about 650 °C to about 750 °C, from about 650 °C to about 700 °C, from about 700 °C to about 1000 °C, from about 700 °C to about 900 °C, from about 700 °C to about 800 °C, from about 700 °C to about 750 °C, from about 750 °C to about 1000 °C, from about 750 °C to about 900 °C, from about 750 °C to about 800 °C, from about 800 °C to about 1000 °C, from about 800 °C to about 900 °C, from about 900 °C to about 1000 °C; or at most about 200 °C, at most about 250 °C, at most about 275 °C, at most about 300 °C, at most about 325 °C, at most about 350 °C, at most about 375 °C, at most about 400 °C, at most about 450 °C, at most about 500 °C, at most about 550 °C, at most about 600 °C, at most about 650 °C, at most about 700 °C, at most about 750 °C, at most about 800 °C, at most about 900 °C, at most about 1000 °C; or about 200 °C, about 250 °C, about 275 °C, about 300 °C, about 325 °C, about 350 °C, about 375 °C, about 400 °C, about 450 °C, about 500 °C, about 550 °C, about 600 °C, about 650 °C, about 700 °C, about 750 °C, about 800 °C, about 900 °C, about 1000 °C, or any ranges or values therebetween. The thermal treatment step (c) may be performed at a temperature of about 300 °C to about 600 °C. The thermal treatment step (c) may be performed at 450 °C.
The thermal treatment step (c) may also be performed for a duration of at least about 0.5 hours, at least about 1 hour, at least about 1.5 hours, at least about 2 hours, at least about 2.5 hours, at least about 3 hours, at least about 3.5 hours, at least about 4 hours, at least about 4.5 hours, at least about 5 hours, at least about 6 hours, at least about 7 hours, at least about 8 hours, at least about 9 hours, at least about 10 hours; or from about 0.5 hours to about 10 hours, from about 0.5 hours to about 9 hours, from about 0.5 hours to about 8 hours, from about 0.5 hours to about 7 hours, from about 0.5 hours to about 6 hours, from about 0.5 hours to about 5 hours, from about 0.5 hours to about 4.5 hours, from about 0.5 hours to about 4 hours, from about 0.5 hours to about 3.5 hours, from about 0.5 hours to about 3 hours, from about 0.5 hours to about 2.5 hours, from about 0.5 hours to about 2 hours, from about 0.5 hours to about 1.5 hours, from about 0.5 hours to about 1 hour, from about 1 hour to about 10 hours, from about 1 hour to about 9 hours, from about 1 hour to about 8 hours, from about 1 hour to about 7 hours, from about 1 hour to about 6 hours, from about 1 hour to about 5 hours, from about 1 hour to about 4.5 hours, from about 1 hour to about 4 hours, from about 1 hour to about 3.5 hours, from about 1 hour to about 3 hours, from about 1 hour to about 2.5 hours, from about 1 hour to about 2 hours, from about 1 hour to about 1.5 hours, from about 1.5 hours to about 10 hours, from about 1.5 hours to about 9 hours, from about 1.5 hours to about 8 hours, from about 1.5 hours to about 7 hours, from about 1.5 hours to about 6 hours, from about 1.5 hours to about 5 hours, from about 1.5 hours to about 4.5 hours, from about 1.5 hours to about 4 hours, from about 1.5 hours to about 3.5 hours, from about 1.5 hours to about 3 hours, from about 1.5 hours to about 2.5 hours, from about 1.5 hours to about 2 hours, from about 2 hours to about 10 hours, from about 2 hours to about 9 hours, from about 2 hours to about 8 hours, from about 2 hours to about 7 hours, from about 2 hours to about 6 hours, from about 2 hours to about 5 hours, from about 2 hours to about 4.5 hours, from about 2 hours to about 4 hours, from about 2 hours to about 3.5 hours, from about 2 hours to about 3 hours, from about 2 hours to about 2.5 hours, from about 2.5 hours to about 10 hours, from about 2.5 hours to about 9 hours, from about 2.5 hours to about 8 hours, from about 2.5 hours to about 7 hours, from about 2.5 hours to about 6 hours, from about 2.5 hours to about 5 hours, from about 2.5 hours to about 4.5 hours, from about 2.5 hours to about 4 hours, from about 2.5 hours to about 3.5 hours, from about 2.5 hours to about 3 hours, from about 3 hours to about 10 hours, from about 3 hours to about 9 hours, from about 3 hours to about 8 hours, from about 3 hours to about 7 hours, from about 3 hours to about 6 hours, from about 3 hours to about 5 hours, from about 3 hours to about 4.5 hours, from about 3 hours to about 4 hours, from about 3 hours to about 3.5 hours, from about 3.5 hours to about 10 hours, from about 3.5 hours to about 9 hours, from about 3.5 hours to about 8 hours, from about 3.5 hours to about 7 hours, from about 3.5 hours to about 6 hours, from about 3.5 hours to about 5 hours, from about 3.5 hours to about 4.5 hours, from about 3.5 hours to about 4 hours, from about 4 hours to about 10 hours, from about 4 hours to about 9 hours, from about 4 hours to about 8 hours, from about 4 hours to about 7 hours, from about 4 hours to about 6 hours, from about 4 hours to about 5 hours, from about 4 hours to about 4.5 hours, from about 4.5 hours to about 10 hours, from about 4.5 hours to about 9 hours, from about 4.5 hours to about 8 hours, from about 4.5 hours to about 7 hours, from about 4.5 hours to about 6 hours, from about 4.5 hours to about 5 hours, from about 5 hours to about 10 hours, from about 5 hours to about 9 hours, from about 5 hours to about 8 hours, from about 5 hours to about 7 hours, from about 5 hours to about 6 hours, from about 6 hours to about 10 hours, from about 6 hours to about 9 hours, from about 6 hours to about 8 hours, from about 6 hours to about 7 hours, from about 7 hours to about 10 hours, from about 7 hours to about 9 hours, from about 7 hours to about 8 hours, from about 8 hours to about 10 hours, from about 8 hours to about 9 hours, from about 9 hours to about 10 hours; or at most about 0.5 hours, at most about 1 hour, at most about 1.5 hours, at most about 2 hours, at most about 2.5 hours, at most about 3 hours, at most about 3.5 hours, at most about 4 hours, at most about 4.5 hours, at most about 5 hours, at most about 6 hours, at most about 7 hours, at most about 8 hours, at most about 9 hours, at most about 10 hours; or about 0.5 hours, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, about 4 hours, about 4.5 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, or any ranges or values therebetween. The thermal treatment step (c) may be performed for a duration of about 1 hour to about 5 hours. The thermal treatment step (c) may be performed for a duration of about 2 hours.
The ramping rate of the temperature during the thermal treatment can also be used to tune the physiochemical properties of the catalyst. The ramping rate may be in a range of at least about 0.1 °C/min, at least about 0.2 °C/min, at least about 0.25 °C/min, at least about 0.5 °C/min, at least about 0.75 °C/min, at least about 1.0 °C/min, at least about 1.25 °C/min, at least about 1.5 °C/min, at least about 1.75 °C/min, at least about 2.0 °C/min, at least about 2.25 °C/min, at least about 2.5 °C/min, at least about 2.75 °C/min, at least about 3.0 °C/min, at least about 3.5 °C/min, at least about 4.0 °C/min, at least about 4.5 °C/min, at least about 5.0 °C/min, at least about 6.0 °C/min; or from about 0.1 °C/min to about 6.0 °C/min, from about 0.1 °C/min to about 5.0 °C/min, from about 0.1 °C/min to about 4.5 °C/min, from about 0.1 °C/min to about 4.0 °C/min, from about 0.1 °C/min to about 3.5 °C/min, from about 0.1 °C/min to about 3.0 °C/min, from about 0.1 °C/min to about 2.75 °C/min, from about 0.1 °C/min to about 2.5 °C/min, from about 0.1 °C/min to about 2.25 °C/min, from about 0.1 °C/min to about 2.0 °C/min, from about 0.1 °C/min to about 1.75 °C/min, from about 0.1 °C/min to about 1.5 °C/min, from about 0.1 °C/min to about 1.25 °C/min, from about 0.1 °C/min to about 1.0 °C/min, from about 0.1 °C/min to about 0.75 °C/min, from about 0.1 °C/min to about 0.5 °C/min, from about 0.1 °C/min to about 0.25 °C/min, from about 0.1 °C/min to about 0.2 °C/min, from about 0.2 °C/min to about 6.0 °C/min, from about 0.2 °C/min to about 5.0 °C/min, from about 0.2 °C/min to about 4.5 °C/min, from about 0.2 °C/min to about 4.0 °C/min, from about 0.2 °C/min to about 3.5 °C/min, from about 0.2 °C/min to about 3.0 °C/min, from about 0.2 °C/min to about 2.75 °C/min, from about 0.2 °C/min to about 2.5 °C/min, from about 0.2 °C/min to about 2.25 °C/min, from about 0.2 °C/min to about 2.0 °C/min, from about 0.2 °C/min to about 1.75 °C/min, from about 0.2 °C/min to about 1.5 °C/min, from about 0.2 °C/min to about 1.25 °C/min, from about 0.2 °C/min to about 1.0 °C/min, from about 0.2 °C/min to about 0.75 °C/min, from about 0.2 °C/min to about 0.5 °C/min, from about 0.2 °C/min to about 0.25 °C/min, from about 0.25 °C/min to about 6.0 °C/min, from about 0.25 °C/min to about 5.0 °C/min, from about 0.25 °C/min to about 4.5 °C/min, from about 0.25 °C/min to about 4.0 °C/min, from about 0.25 °C/min to about 3.5 °C/min, from about 0.25 °C/min to about 3.0 °C/min, from about 0.25 °C/min to about 2.75 °C/min, from about 0.25 °C/min to about 2.5 °C/min, from about 0.25 °C/min to about
2.25 °C/min, from about 0.25 °C/min to about 2.0 °C/min, from about 0.25 °C/min to about 1.75 °C/min, from about 0.25 °C/min to about 1.5 °C/min, from about 0.25 °C/min to about 1.25 °C/min, from about 0.25 °C/min to about 1.0 °C/min, from about 0.25 °C/min to about 0.75 °C/min, from about 0.25 °C/min to about 0.5 °C/min, from about 0.5 °C/min to about 6.0 °C/min, from about 0.5 °C/min to about 5.0 °C/min, from about 0.5 °C/min to about 4.5 °C/min, from about 0.5 °C/min to about 4.0 °C/min, from about 0.5 °C/min to about 3.5 °C/min, from about 0.5 °C/min to about 3.0 °C/min, from about 0.5 °C/min to about 2.75 °C/min, from about 0.5 °C/min to about 2.5 °C/min, from about 0.5 °C/min to about 2.25 °C/min, from about 0.5 °C/min to about 2.0 °C/min, from about 0.5 °C/min to about 1.75 °C/min, from about 0.5 °C/min to about 1.5 °C/min, from about 0.5 °C/min to about 1.25 °C/min, from about 0.5 °C/min to about 1.0 °C/min, from about 0.5 °C/min to about 0.75 °C/min, from about 0.75 °C/min to about 6.0 °C/min, from about 0.75 °C/min to about 5.0 °C/min, from about 0.75 °C/min to about 4.5 °C/min, from about 0.75 °C/min to about 4.0 °C/min, from about 0.75 °C/min to about 3.5 °C/min, from about 0.75 °C/min to about 3.0 °C/min, from about 0.75 °C/min to about 2.75 °C/min, from about 0.75 °C/min to about 2.5 °C/min, from about 0.75 °C/min to about 2.25 °C/min, from about 0.75 °C/min to about 2.0 °C/min, from about 0.75 °C/min to about 1.75 °C/min, from about 0.75 °C/min to about 1.5 °C/min, from about 0.75 °C/min to about 1.25 °C/min, from about 0.75 °C/min to about 1.0 °C/min, from about 1.0 °C/min to about 6.0 °C/min, from about 1.0 °C/min to about 5.0 °C/min, from about 1.0 °C/min to about 4.5 °C/min, from about 1.0 °C/min to about 4.0 °C/min, from about 1.0 °C/min to about 3.5 °C/min, from about 1.0 °C/min to about 3.0 °C/min, from about 1.0 °C/min to about 2.75 °C/min, from about 1.0 °C/min to about 2.5 °C/min, from about 1.0 °C/min to about 2.25 °C/min, from about 1.0 °C/min to about 2.0 °C/min, from about 1.0 °C/min to about 1.75 °C/min, from about 1.0 °C/min to about 1.5 °C/min, from about 1.0 °C/min to about 1.25 °C/min, from about 1.25 °C/min to about 6.0 °C/min, from about 1.25 °C/min to about 5.0 °C/min, from about 1.25 °C/min to about 4.5 °C/min, from about 1.25 °C/min to about 4.0 °C/min, from about 1.25 °C/min to about 3.5 °C/min, from about 1.25 °C/min to about 3.0 °C/min, from about 1.25 °C/min to about 2.75 °C/min, from about 1.25 °C/min to about 2.5 °C/min, from about 1.25 °C/min to about 2.25 °C/min, from about 1.25 °C/min to about 2.0 °C/min, from about 1.25 °C/min to about 1.75 °C/min, from about
1.25 °C/min to about 1.5 °C/min, from about 1.5 °C/min to about 6.0 °C/min, from about 1.5 °C/min to about 5.0 °C/min, from about 1.5 °C/min to about 4.5 °C/min, from about 1.5 °C/min to about 4.0 °C/min, from about 1.5 °C/min to about 3.5 °C/min, from about 1.5 °C/min to about 3.0 °C/min, from about 1.5 °C/min to about 2.75 °C/min, from about 1.5 °C/min to about 2.5 °C/min, from about 1.5 °C/min to about 2.25 °C/min, from about 1.5 °C/min to about 2.0 °C/min, from about 1.5 °C/min to about 1.75 °C/min, from about 1.75 °C/min to about 6.0 °C/min, from about 1.75 °C/min to about 5.0 °C/min, from about 1.75 °C/min to about 4.5 °C/min, from about 1.75 °C/min to about 4.0 °C/min, from about 1.75 °C/min to about 3.5 °C/min, from about 1.75 °C/min to about 3.0 °C/min, from about 1.75 °C/min to about 2.75 °C/min, from about 1.75 °C/min to about 2.5 °C/min, from about 1.75 °C/min to about 2.25 °C/min, from about
1.75 °C/min to about 2.0 °C/min, from about 2.0 °C/min to about 6.0 °C/min, from about 2.0 °C/min to about 5.0 °C/min, from about 2.0 °C/min to about 4.5 °C/min, from about 2.0 °C/min to about 4.0 °C/min, from about 2.0 °C/min to about 3.5 °C/min, from about 2.0 °C/min to about 3.0 °C/min, from about 2.0 °C/min to about 2.75 °C/min, from about 2.0 °C/min to about 2.5 °C/min, from about 2.0 °C/min to about 2.25 °C/min, from about 2.25 °C/min to about 6.0 °C/min, from about 2.25 °C/min to about 5.0 °C/min, from about 2.25 °C/min to about 4.5 °C/min, from about 2.25 °C/min to about 4.0 °C/min, from about 2.25 °C/min to about 3.5 °C/min, from about 2.25 °C/min to about 3.0 °C/min, from about 2.25 °C/min to about
2.75 °C/min, from about 2.25 °C/min to about 2.5 °C/min, from about 2.5 °C/min to about 6.0 °C/min, from about 2.5 °C/min to about 5.0 °C/min, from about 2.5 °C/min to about 4.5 °C/min, from about 2.5 °C/min to about 4.0 °C/min, from about 2.5 °C/min to about 3.5 °C/min, from about 2.5 °C/min to about 3.0 °C/min, from about 2.5 °C/min to about 2.75 °C/min, from about 2.75 °C/min to about 6.0 °C/min, from about 2.75 °C/min to about 5.0 °C/min, from about 2.75 °C/min to about 4.5 °C/min, from about 2.75 °C/min to about 4.0 °C/min, from about 2.75 °C/min to about 3.5 °C/min, from about 2.75 °C/min to about 3.0 °C/min, from about 3.0 °C/min to about 6.0 °C/min, from about 3.0 °C/min to about 5.0 °C/min, from about 3.0 °C/min to about 4.5 °C/min, from about 3.0 °C/min to about 4.0 °C/min, from about 3.0 °C/min to about 3.5 °C/min, from about 3.5 °C/min to about 6.0 °C/min, from about 3.5 °C/min to about 5.0 °C/min, from about 3.5 °C/min to about 4.5 °C/min, from about 3.5 °C/min to about 4.0 °C/min, from about 4.0 °C/min to about 6.0 °C/min, from about 4.0 °C/min to about 5.0 °C/min, from about 4.0 °C/min to about 4.5 °C/min, from about 4.5 °C/min to about 6.0 °C/min, from about 4.5 °C/min to about 5.0 °C/min, from about 5.0 °C/min to about 6.0 °C/min; or at most about 0.1 °C/min, at most about 0.2 °C/min, at most about 0.25 °C/min, at most about 0.5 °C/min, at most about 0.75 °C/min, at most about 1.0 °C/min, at most about 1.25 °C/min, at most about 1.5 °C/min, at most about 1.75 °C/min, at most about 2.0 °C/min, at most about 2.25 °C/min, at most about 2.5 °C/min, at most about 2.75 °C/min, at most about 3.0 °C/min, at most about 3.5 °C/min, at most about 4.0 °C/min, at most about 4.5 °C/min, at most about 5.0 °C/min, at most about 6.0 °C/min; or about 0.1 °C/min, about 0.2 °C/min, about 0.25 °C/min, about 0.5 °C/min, about 0.75 °C/min, about 1.0 °C/min, about 1.25 °C/min, about 1.5 °C/min, about 1.75 °C/min, about 2.0 °C/min, about 2.25 °C/min, about 2.5 °C/min, about 2.75 °C/min, about 3.0 °C/min, about 3.5 °C/min, about 4.0 °C/min, about 4.5 °C/min, about 5.0 °C/min, about 6.0 °C/min, or any ranges or values therebetween. The ramping rate in thermal treatment step (c) is about 2.0 °C/min.
The present disclosure provides for a method of producing a catalyst, comprising pyrolyzing the ball-milled mixture of step (b) at a temperature of about 300 °C to about 600 °C for a duration of about 1 hour to about 5 hours to form a pyrolyzed product. The present disclosure provides for a method of producing a catalyst, comprising pyrolyzing the ball-milled mixture of step (b) at a temperature of about 450 °C for a duration of about 2 hours to form a pyrolyzed product. The present disclosure also discloses a method for preparing a supported catalyst, further comprising step (d) reducing the pyrolyzed product of step (c) to form the supported catalyst. The presently disclosed method may also disclose a further step (d) to reduce the pyrolyzed product from step (c) to form the supported catalyst. Reducing the pyrolyzed product from step (c) advantageously reduces the oxygen and/or oxide content of the catalyst which may accordingly increase the amount of active sites available for catalysis. Reducing the product may also surprisingly open up more activation sites that were previously unavailable to due the previously present oxide layers. Reduction may also further improve the porosity and surface area of the catalyst thus further improving its catalytic and OER efficiency. As such, the product of step (d) may be lower in oxygen and/or oxide compared as compared to before step (d) was applied.
The reduction step (d) may be performed in a reductive atmosphere, at a temperature of at least about 200 °C, at least about 250 °C, at least about 300 °C, at least about 350 °C, at least about 375 °C, at least about 400 °C, at least about 425 °C, at least about 450 °C, at least about 475 °C, at least about 500 °C, at least about 525 °C, at least about 550 °C, at least about 575 °C, at least about 600 °C, at least about 625 °C, at least about 650 °C, at least about 700 °C, at least about 750 °C, at least about 800 °C; or from about
200 °C to about 800 °C, from about 200 °C to about 750 °C, from about 200 °C to about 700 °C, from about 200 °C to about 650 °C, from about 200 °C to about 625 °C, from about 200 °C to about 600 °C, from about 200 °C to about 575 °C, from about 200 °C to about 550 °C, from about 200 °C to about 525 °C, from about 200 °C to about 500 °C, from about 200 °C to about 475 °C, from about 200 °C to about 450 °C, from about 200 °C to about 425 °C, from about 200 °C to about 400 °C, from about 200 °C to about 375 °C, from about 200 °C to about 350 °C, from about 200 °C to about 300 °C, from about 200 °C to about 250 °C, from about 250 °C to about 800 °C, from about 250 °C to about 750 °C, from about 250 °C to about 700 °C, from about 250 °C to about 650 °C, from about 250 °C to about 625 °C, from about 250 °C to about 600 °C, from about 250 °C to about 575 °C, from about 250 °C to about 550 °C, from about 250 °C to about 525 °C, from about 250 °C to about 500 °C, from about 250 °C to about 475 °C, from about 250 °C to about 450 °C, from about 250 °C to about 425 °C, from about 250 °C to about 400 °C, from about 250 °C to about 375 °C, from about 250 °C to about 350 °C, from about 250 °C to about 300 °C, from about 300 °C to about 800 °C, from about 300 °C to about 750 °C, from about 300 °C to about 700 °C, from about 300 °C to about 650 °C, from about 300 °C to about 625 °C, from about 300 °C to about 600 °C, from about 300 °C to about 575 °C, from about 300 °C to about 550 °C, from about 300 °C to about 525 °C, from about 300 °C to about 500 °C, from about 300 °C to about 475 °C, from about 300 °C to about 450 °C, from about 300 °C to about 425 °C, from about 300 °C to about 400 °C, from about 300 °C to about 375 °C, from about 300 °C to about 350 °C, from about 350 °C to about 800 °C, from about 350 °C to about 750 °C, from about 350 °C to about 700 °C, from about 350 °C to about 650 °C, from about 350 °C to about 625 °C, from about 350 °C to about 600 °C, from about 350 °C to about 575 °C, from about 350 °C to about 550 °C, from about 350 °C to about 525 °C, from about 350 °C to about 500 °C, from about 350 °C to about 475 °C, from about 350 °C to about 450 °C, from about 350 °C to about 425 °C, from about 350 °C to about 400 °C, from about 350 °C to about 375 °C, from about 375 °C to about 800 °C, from about 375 °C to about 750 °C, from about 375 °C to about 700 °C, from about 375 °C to about 650 °C, from about 375 °C to about 625 °C, from about 375 °C to about 600 °C, from about 375 °C to about 575 °C, from about 375 °C to about 550 °C, from about 375 °C to about 525 °C, from about 375 °C to about 500 °C, from about 375 °C to about 475 °C, from about 375 °C to about 450 °C, from about 375 °C to about 425 °C, from about 375 °C to about 400 °C, from about 400 °C to about 800 °C, from about 400 °C to about 750 °C, from about 400 °C to about 700 °C, from about 400 °C to about 650 °C, from about 400 °C to about 625 °C, from about 400 °C to about 600 °C, from about 400 °C to about 575 °C, from about 400 °C to about 550 °C, from about 400 °C to about 525 °C, from about 400 °C to about 500 °C, from about 400 °C to about 475 °C, from about 400 °C to about 450 °C, from about 400 °C to about 425 °C, from about 425 °C to about 800 °C, from about 425 °C to about 750 °C, from about 425 °C to about 700 °C, from about 425 °C to about 650 °C, from about 425 °C to about 625 °C, from about 425 °C to about 600 °C, from about 425 °C to about 575 °C, from about 425 °C to about 550 °C, from about 425 °C to about 525 °C, from about 425 °C to about 500 °C, from about 425 °C to about 475 °C, from about 425 °C to about 450 °C, from about 450 °C to about 800 °C, from about 450 °C to about 750 °C, from about 450 °C to about 700 °C, from about 450 °C to about 650 °C, from about 450 °C to about 625 °C, from about 450 °C to about 600 °C, from about 450 °C to about 575 °C, from about 450 °C to about 550 °C, from about 450 °C to about 525 °C, from about 450 °C to about 500 °C, from about 450 °C to about 475 °C, from about 475 °C to about 800 °C, from about 475 °C to about 750 °C, from about 475 °C to about 700 °C, from about 475 °C to about 650 °C, from about 475 °C to about 625 °C, from about 475 °C to about 600 °C, from about 475 °C to about 575 °C, from about 475 °C to about 550 °C, from about 475 °C to about 525 °C, from about 475 °C to about 500 °C, from about 500 °C to about 800 °C, from about 500 °C to about 750 °C, from about 500 °C to about 700 °C, from about 500 °C to about 650 °C, from about 500 °C to about 625 °C, from about 500 °C to about 600 °C, from about 500 °C to about 575 °C, from about 500 °C to about 550 °C, from about 500 °C to about 525 °C, from about 525 °C to about 800 °C, from about 525 °C to about 750 °C, from about 525 °C to about 700 °C, from about 525 °C to about 650 °C, from about 525 °C to about 625 °C, from about 525 °C to about 600 °C, from about 525 °C to about 575 °C, from about 525 °C to about 550 °C, from about 550 °C to about 800 °C, from about 550 °C to about 750 °C, from about 550 °C to about 700 °C, from about 550 °C to about 650 °C, from about 550 °C to about 625 °C, from about 550 °C to about 600 °C, from about 550 °C to about 575 °C, from about 575 °C to about 800 °C, from about 575 °C to about 750 °C, from about 575 °C to about 700 °C, from about 575 °C to about 650 °C, from about 575 °C to about 625 °C, from about 575 °C to about 600 °C, from about 600 °C to about 800 °C, from about 600 °C to about 750 °C, from about 600 °C to about 700 °C, from about 600 °C to about 650 °C, from about 600 °C to about 625 °C, from about 625 °C to about 800 °C, from about 625 °C to about 750 °C, from about 625 °C to about 700 °C, from about 625 °C to about 650 °C, from about 650 °C to about 800 °C, from about 650 °C to about 750 °C, from about 650 °C to about 700 °C, from about 700 °C to about 800 °C, from about 700 °C to about 750 °C, from about 750 °C to about 800 °C; or at most about 200 °C, at most about 250 °C, at most about 300 °C, at most about 350 °C, at most about 375 °C, at most about 400 °C, at most about 425 °C, at most about 450 °C, at most about 475 °C, at most about 500 °C, at most about 525 °C, at most about 550 °C, at most about 575 °C, at most about 600 °C, at most about 625 °C, at most about 650 °C, at most about 700 °C, at most about 750 °C, at most about 800 °C; or about 200 °C, about 250 °C, about 300 °C, about 350 °C, about 375 °C, about 400 °C, about 425 °C, about 450 °C, about 475 °C, about 500 °C, about 525 °C, about 550 °C, about 575 °C, about 600 °C, about 625 °C, about 650 °C, about 700 °C, about 750 °C, about 800 °C, or any ranges or values therebetween. Step (d) may be performed in a reductive atmosphere at a temperature of about 300 °C to about 600 °C.
Step (d) may be performed in a reductive atmosphere for a duration of at least about 0.1 hours, at least about 0.25 hours, at least about 0.5 hours, at least about 0.75 hours, at least about 1 hour, at least about 1.5 hours, at least about 2 hours, at least about 2.5 hours, at least about 3 hours, at least about 3.5 hours, at least about 4 hours, at least about 4.5 hours, at least about 5 hours, at least about 6 hours, at least about 7 hours, at least about 8 hours, at least about 9 hours, at least about 10 hours; or from about 0.1 hours to about 10 hours, from about 0.1 hours to about 9 hours, from about 0.1 hours to about 8 hours, from about 0.1 hours to about 7 hours, from about 0.1 hours to about 6 hours, from about 0.1 hours to about 5 hours, from about 0.1 hours to about 4.5 hours, from about 0.1 hours to about 4 hours, from about 0.1 hours to about 3.5 hours, from about 0.1 hours to about 3 hours, from about 0.1 hours to about 2.5 hours, from about 0.1 hours to about 2 hours, from about 0.1 hours to about 1.5 hours, from about 0.1 hours to about 1 hour, from about 0.1 hours to about 0.75 hours, from about 0.1 hours to about 0.5 hours, from about 0.1 hours to about 0.25 hours, from about 0.25 hours to about 10 hours, from about 0.25 hours to about 9 hours, from about 0.25 hours to about 8 hours, from about 0.25 hours to about 7 hours, from about 0.25 hours to about 6 hours, from about 0.25 hours to about 5 hours, from about 0.25 hours to about 4.5 hours, from about 0.25 hours to about 4 hours, from about 0.25 hours to about 3.5 hours, from about 0.25 hours to about 3 hours, from about 0.25 hours to about 2.5 hours, from about 0.25 hours to about 2 hours, from about 0.25 hours to about 1.5 hours, from about 0.25 hours to about 1 hour, from about 0.25 hours to about 0.75 hours, from about 0.25 hours to about 0.5 hours, from about 0.5 hours to about 10 hours, from about 0.5 hours to about 9 hours, from about 0.5 hours to about 8 hours, from about 0.5 hours to about 7 hours, from about 0.5 hours to about 6 hours, from about 0.5 hours to about 5 hours, from about 0.5 hours to about 4.5 hours, from about 0.5 hours to about 4 hours, from about 0.5 hours to about 3.5 hours, from about 0.5 hours to about 3 hours, from about 0.5 hours to about 2.5 hours, from about 0.5 hours to about 2 hours, from about 0.5 hours to about 1.5 hours, from about 0.5 hours to about 1 hour, from about 0.5 hours to about 0.75 hours, from about 0.75 hours to about 10 hours, from about 0.75 hours to about 9 hours, from about 0.75 hours to about
8 hours, from about 0.75 hours to about 7 hours, from about 0.75 hours to about 6 hours, from about 0.75 hours to about 5 hours, from about 0.75 hours to about 4.5 hours, from about 0.75 hours to about 4 hours, from about 0.75 hours to about 3.5 hours, from about 0.75 hours to about 3 hours, from about 0.75 hours to about 2.5 hours, from about 0.75 hours to about 2 hours, from about 0.75 hours to about 1.5 hours, from about 0.75 hours to about 1 hour, from about 1 hour to about 10 hours, from about 1 hour to about 9 hours, from about 1 hour to about 8 hours, from about 1 hour to about 7 hours, from about 1 hour to about 6 hours, from about 1 hour to about 5 hours, from about 1 hour to about 4.5 hours, from about 1 hour to about 4 hours, from about 1 hour to about 3.5 hours, from about 1 hour to about 3 hours, from about 1 hour to about 2.5 hours, from about 1 hour to about 2 hours, from about 1 hour to about 1.5 hours, from about 1.5 hours to about 10 hours, from about 1.5 hours to about 9 hours, from about 1.5 hours to about 8 hours, from about 1.5 hours to about 7 hours, from about 1.5 hours to about 6 hours, from about 1.5 hours to about 5 hours, from about 1.5 hours to about 4.5 hours, from about 1.5 hours to about 4 hours, from about 1.5 hours to about 3.5 hours, from about 1.5 hours to about 3 hours, from about 1.5 hours to about 2.5 hours, from about 1.5 hours to about 2 hours, from about 2 hours to about 10 hours, from about 2 hours to about
9 hours, from about 2 hours to about 8 hours, from about 2 hours to about 7 hours, from about 2 hours to about 6 hours, from about 2 hours to about 5 hours, from about 2 hours to about 4.5 hours, from about 2 hours to about 4 hours, from about 2 hours to about 3.5 hours, from about 2 hours to about 3 hours, from about 2 hours to about 2.5 hours, from about 2.5 hours to about 10 hours, from about 2.5 hours to about 9 hours, from about 2.5 hours to about 8 hours, from about 2.5 hours to about 7 hours, from about 2.5 hours to about 6 hours, from about 2.5 hours to about 5 hours, from about 2.5 hours to about 4.5 hours, from about 2.5 hours to about 4 hours, from about 2.5 hours to about 3.5 hours, from about 2.5 hours to about 3 hours, from about 3 hours to about 10 hours, from about 3 hours to about 9 hours, from about 3 hours to about 8 hours, from about 3 hours to about 7 hours, from about 3 hours to about 6 hours, from about 3 hours to about 5 hours, from about 3 hours to about 4.5 hours, from about 3 hours to about 4 hours, from about 3 hours to about 3.5 hours, from about 3.5 hours to about 10 hours, from about 3.5 hours to about 9 hours, from about 3.5 hours to about 8 hours, from about 3.5 hours to about 7 hours, from about 3.5 hours to about 6 hours, from about 3.5 hours to about 5 hours, from about 3.5 hours to about 4.5 hours, from about 3.5 hours to about 4 hours, from about 4 hours to about 10 hours, from about 4 hours to about 9 hours, from about 4 hours to about 8 hours, from about 4 hours to about 7 hours, from about 4 hours to about 6 hours, from about 4 hours to about 5 hours, from about 4 hours to about 4.5 hours, from about 4.5 hours to about 10 hours, from about 4.5 hours to about 9 hours, from about 4.5 hours to about 8 hours, from about 4.5 hours to about 7 hours, from about 4.5 hours to about 6 hours, from about 4.5 hours to about 5 hours, from about 5 hours to about 10 hours, from about 5 hours to about 9 hours, from about 5 hours to about 8 hours, from about 5 hours to about 7 hours, from about 5 hours to about 6 hours, from about 6 hours to about 10 hours, from about 6 hours to about 9 hours, from about 6 hours to about 8 hours, from about 6 hours to about 7 hours, from about 7 hours to about 10 hours, from about 7 hours to about 9 hours, from about 7 hours to about 8 hours, from about 8 hours to about 10 hours, from about 8 hours to about 9 hours, from about 9 hours to about 10 hours; or at most about 0.1 hours, at most about 0.25 hours, at most about 0.5 hours, at most about 0.75 hours, at most about 1 hour, at most about 1.5 hours, at most about 2 hours, at most about 2.5 hours, at most about 3 hours, at most about 3.5 hours, at most about 4 hours, at most about 4.5 hours, at most about 5 hours, at most about 6 hours, at most about 7 hours, at most about 8 hours, at most about 9 hours, at most about 10 hours; or about 0.1 hours, about 0.25 hours, about 0.5 hours, about 0.75 hours, about 1 hour, about 1.5 hours, about 2 hours, about 2.5 hours, about 3 hours, about 3.5 hours, about 4 hours, about 4.5 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours, about 10 hours, or any ranges or values therebetween. Step (d) may be performed in a reductive atmosphere for a duration of about 0.5 hours to about 3 hours.
In an embodiment, the present disclosure discloses a process, wherein step (d) is performed in a reductive atmosphere at a temperature of about 300 °C to about 600 °C, for a duration of about 0.5 hours to about 3 hours.
In some other embodiments, the reductive atmosphere comprises in Ar, Hi in a range of at least about 0.1 vol%, at least about 0.2 vol%, at least about 0.4 vol%, at least about 0.6 vol%, at least about 0.8 vol%, at least about 1.0 vol%, at least about 1.25 vol%, at least about 1.5 vol%, at least about 1.75 vol%, at least about 2.0 vol%, at least about 2.5 vol%, at least about 3.0 vol%, at least about 4.0 vol%, at least about 5.0 vol%, at least about 6.0 vol%, at least about 7.0 vol%, at least about 8.0 vol%, at least about 9.0 vol%, at least about 10.0 vol%, at least about 12.0 vol%, at least about 15.0 vol%, at least about 20.0 vol%, at least about 25.0 vol%, at least about 30.0 vol%, at least about 35.0 vol%, at least about 40.0 vol%; or from about 0.1 vol% to about 40.0 vol%, from about 0.1 vol% to about 35.0 vol%, from about 0.1 vol% to about 30.0 vol%, from about 0.1 vol% to about 25.0 vol%, from about 0.1 vol% to about 20.0 vol%, from about 0.1 vol% to about 15.0 vol%, from about 0.1 vol% to about 12.0 vol%, from about 0.1 vol% to about 10.0 vol%, from about 0.1 vol% to about 9.0 vol%, from about 0.1 vol% to about 8.0 vol%, from about 0.1 vol% to about 7.0 vol%, from about 0.1 vol% to about 6.0 vol%, from about 0.1 vol% to about 5.0 vol%, from about 0.1 vol% to about 4.0 vol%, from about 0.1 vol% to about 3.0 vol%, from about 0.1 vol% to about 2.5 vol%, from about 0.1 vol% to about 2.0 vol%, from about 0.1 vol% to about 1.75 vol%, from about 0.1 vol% to about 1.5 vol%, from about 0.1 vol% to about 1.25 vol%, from about 0.1 vol% to about 1.0 vol%, from about 0.1 vol% to about 0.8 vol%, from about 0.1 vol% to about 0.6 vol%, from about 0.1 vol% to about 0.4 vol%, from about 0.1 vol% to about 0.2 vol%, from about 0.2 vol% to about 40.0 vol%, from about 0.2 vol% to about 35.0 vol%, from about 0.2 vol% to about 30.0 vol%, from about 0.2 vol% to about 25.0 vol%, from about 0.2 vol% to about 20.0 vol%, from about 0.2 vol% to about 15.0 vol%, from about 0.2 vol% to about 12.0 vol%, from about 0.2 vol% to about 10.0 vol%, from about 0.2 vol% to about 9.0 vol%, from about 0.2 vol% to about 8.0 vol%, from about 0.2 vol% to about 7.0 vol%, from about 0.2 vol% to about 6.0 vol%, from about 0.2 vol% to about 5.0 vol%, from about 0.2 vol% to about 4.0 vol%, from about 0.2 vol% to about 3.0 vol%, from about 0.2 vol% to about 2.5 vol%, from about 0.2 vol% to about 2.0 vol%, from about 0.2 vol% to about 1.75 vol%, from about 0.2 vol% to about 1.5 vol%, from about 0.2 vol% to about 1.25 vol%, from about 0.2 vol% to about 1.0 vol%, from about 0.2 vol% to about 0.8 vol%, from about 0.2 vol% to about 0.6 vol%, from about 0.2 vol% to about 0.4 vol%, from about 0.4 vol% to about 40.0 vol%, from about 0.4 vol% to about 35.0 vol%, from about 0.4 vol% to about 30.0 vol%, from about 0.4 vol% to about 25.0 vol%, from about 0.4 vol% to about 20.0 vol%, from about 0.4 vol% to about 15.0 vol%, from about 0.4 vol% to about 12.0 vol%, from about 0.4 vol% to about 10.0 vol%, from about 0.4 vol% to about 9.0 vol%, from about 0.4 vol% to about 8.0 vol%, from about 0.4 vol% to about 7.0 vol%, from about 0.4 vol% to about 6.0 vol%, from about 0.4 vol% to about 5.0 vol%, from about 0.4 vol% to about 4.0 vol%, from about 0.4 vol% to about 3.0 vol%, from about 0.4 vol% to about 2.5 vol%, from about 0.4 vol% to about 2.0 vol%, from about 0.4 vol% to about 1.75 vol%, from about 0.4 vol% to about 1.5 vol%, from about 0.4 vol% to about 1.25 vol%, from about 0.4 vol% to about 1.0 vol%, from about 0.4 vol% to about 0.8 vol%, from about 0.4 vol% to about 0.6 vol%, from about 0.6 vol% to about 40.0 vol%, from about 0.6 vol% to about 35.0 vol%, from about 0.6 vol% to about 30.0 vol%, from about 0.6 vol% to about 25.0 vol%, from about 0.6 vol% to about 20.0 vol%, from about 0.6 vol% to about 15.0 vol%, from about 0.6 vol% to about 12.0 vol%, from about 0.6 vol% to about 10.0 vol%, from about 0.6 vol% to about 9.0 vol%, from about 0.6 vol% to about 8.0 vol%, from about 0.6 vol% to about 7.0 vol%, from about 0.6 vol% to about 6.0 vol%, from about 0.6 vol% to about 5.0 vol%, from about 0.6 vol% to about 4.0 vol%, from about 0.6 vol% to about 3.0 vol%, from about 0.6 vol% to about 2.5 vol%, from about 0.6 vol% to about 2.0 vol%, from about 0.6 vol% to about 1.75 vol%, from about 0.6 vol% to about 1.5 vol%, from about 0.6 vol% to about 1.25 vol%, from about 0.6 vol% to about 1.0 vol%, from about 0.6 vol% to about 0.8 vol%, from about 0.8 vol% to about 40.0 vol%, from about 0.8 vol% to about 35.0 vol%, from about 0.8 vol% to about 30.0 vol%, from about 0.8 vol% to about 25.0 vol%, from about 0.8 vol% to about 20.0 vol%, from about 0.8 vol% to about 15.0 vol%, from about 0.8 vol% to about 12.0 vol%, from about 0.8 vol% to about 10.0 vol%, from about 0.8 vol% to about 9.0 vol%, from about 0.8 vol% to about 8.0 vol%, from about 0.8 vol% to about 7.0 vol%, from about 0.8 vol% to about 6.0 vol%, from about 0.8 vol% to about 5.0 vol%, from about 0.8 vol% to about 4.0 vol%, from about 0.8 vol% to about 3.0 vol%, from about 0.8 vol% to about 2.5 vol%, from about 0.8 vol% to about 2.0 vol%, from about 0.8 vol% to about 1.75 vol%, from about 0.8 vol% to about 1.5 vol%, from about 0.8 vol% to about 1.25 vol%, from about 0.8 vol% to about 1.0 vol%, from about 1.0 vol% to about 40.0 vol%, from about 1.0 vol% to about 35.0 vol%, from about 1.0 vol% to about 30.0 vol%, from about 1.0 vol% to about 25.0 vol%, from about 1.0 vol% to about 20.0 vol%, from about 1.0 vol% to about 15.0 vol%, from about 1.0 vol% to about 12.0 vol%, from about 1.0 vol% to about 10.0 vol%, from about 1.0 vol% to about 9.0 vol%, from about 1.0 vol% to about 8.0 vol%, from about 1.0 vol% to about 7.0 vol%, from about 1.0 vol% to about 6.0 vol%, from about 1.0 vol% to about 5.0 vol%, from about 1.0 vol% to about 4.0 vol%, from about 1.0 vol% to about 3.0 vol%, from about 1.0 vol% to about 2.5 vol%, from about 1.0 vol% to about 2.0 vol%, from about 1.0 vol% to about 1.75 vol%, from about 1.0 vol% to about 1.5 vol%, from about 1.0 vol% to about 1.25 vol%, from about 1.25 vol% to about 40.0 vol%, from about 1.25 vol% to about 35.0 vol%, from about 1.25 vol% to about 30.0 vol%, from about 1.25 vol% to about 25.0 vol%, from about 1.25 vol% to about 20.0 vol%, from about 1.25 vol% to about 15.0 vol%, from about 1.25 vol% to about 12.0 vol%, from about 1.25 vol% to about 10.0 vol%, from about 1.25 vol% to about 9.0 vol%, from about 1.25 vol% to about 8.0 vol%, from about 1.25 vol% to about 7.0 vol%, from about 1.25 vol% to about 6.0 vol%, from about 1.25 vol% to about 5.0 vol%, from about 1.25 vol% to about 4.0 vol%, from about 1.25 vol% to about 3.0 vol%, from about 1.25 vol% to about 2.5 vol%, from about 1.25 vol% to about 2.0 vol%, from about 1.25 vol% to about 1.75 vol%, from about 1.25 vol% to about 1.5 vol%, from about 1.5 vol% to about 40.0 vol%, from about 1.5 vol% to about 35.0 vol%, from about 1.5 vol% to about 30.0 vol%, from about 1.5 vol% to about 25.0 vol%, from about
1.5 vol% to about 20.0 vol%, from about 1.5 vol% to about 15.0 vol%, from about 1.5 vol% to about 12.0 vol%, from about 1.5 vol% to about 10.0 vol%, from about 1.5 vol% to about 9.0 vol%, from about 1.5 vol% to about 8.0 vol%, from about 1.5 vol% to about 7.0 vol%, from about 1.5 vol% to about 6.0 vol%, from about 1.5 vol% to about 5.0 vol%, from about 1.5 vol% to about 4.0 vol%, from about 1.5 vol% to about 3.0 vol%, from about 1.5 vol% to about 2.5 vol%, from about 1.5 vol% to about 2.0 vol%, from about 1.5 vol% to about 1.75 vol%, from about 1.75 vol% to about 40.0 vol%, from about 1.75 vol% to about 35.0 vol%, from about 1.75 vol% to about 30.0 vol%, from about 1.75 vol% to about 25.0 vol%, from about 1.75 vol% to about 20.0 vol%, from about 1.75 vol% to about 15.0 vol%, from about 1.75 vol% to about 12.0 vol%, from about 1.75 vol% to about 10.0 vol%, from about 1.75 vol% to about 9.0 vol%, from about 1.75 vol% to about 8.0 vol%, from about 1.75 vol% to about 7.0 vol%, from about 1.75 vol% to about 6.0 vol%, from about 1.75 vol% to about 5.0 vol%, from about 1.75 vol% to about 4.0 vol%, from about 1.75 vol% to about 3.0 vol%, from about 1.75 vol% to about 2.5 vol%, from about 1.75 vol% to about 2.0 vol%, from about 2.0 vol% to about 40.0 vol%, from about 2.0 vol% to about 35.0 vol%, from about 2.0 vol% to about 30.0 vol%, from about 2.0 vol% to about 25.0 vol%, from about 2.0 vol% to about 20.0 vol%, from about 2.0 vol% to about 15.0 vol%, from about 2.0 vol% to about 12.0 vol%, from about 2.0 vol% to about 10.0 vol%, from about 2.0 vol% to about 9.0 vol%, from about 2.0 vol% to about 8.0 vol%, from about 2.0 vol% to about 7.0 vol%, from about 2.0 vol% to about 6.0 vol%, from about 2.0 vol% to about 5.0 vol%, from about 2.0 vol% to about 4.0 vol%, from about 2.0 vol% to about 3.0 vol%, from about 2.0 vol% to about 2.5 vol%, from about 2.5 vol% to about 40.0 vol%, from about 2.5 vol% to about 35.0 vol%, from about 2.5 vol% to about 30.0 vol%, from about 2.5 vol% to about 25.0 vol%, from about 2.5 vol% to about 20.0 vol%, from about 2.5 vol% to about 15.0 vol%, from about 2.5 vol% to about 12.0 vol%, from about 2.5 vol% to about 10.0 vol%, from about 2.5 vol% to about 9.0 vol%, from about
2.5 vol% to about 8.0 vol%, from about 2.5 vol% to about 7.0 vol%, from about 2.5 vol% to about 6.0 vol%, from about 2.5 vol% to about 5.0 vol%, from about 2.5 vol% to about 4.0 vol%, from about 2.5 vol% to about 3.0 vol%, from about 3.0 vol% to about 40.0 vol%, from about 3.0 vol% to about 35.0 vol%, from about 3.0 vol% to about 30.0 vol%, from about 3.0 vol% to about 25.0 vol%, from about 3.0 vol% to about 20.0 vol%, from about 3.0 vol% to about 15.0 vol%, from about 3.0 vol% to about 12.0 vol%, from about 3.0 vol% to about 10.0 vol%, from about 3.0 vol% to about 9.0 vol%, from about 3.0 vol% to about 8.0 vol%, from about 3.0 vol% to about 7.0 vol%, from about 3.0 vol% to about 6.0 vol%, from about 3.0 vol% to about 5.0 vol%, from about 3.0 vol% to about 4.0 vol%, from about 4.0 vol% to about 40.0 vol%, from about 4.0 vol% to about 35.0 vol%, from about 4.0 vol% to about 30.0 vol%, from about 4.0 vol% to about 25.0 vol%, from about 4.0 vol% to about 20.0 vol%, from about 4.0 vol% to about 15.0 vol%, from about 4.0 vol% to about 12.0 vol%, from about 4.0 vol% to about 10.0 vol%, from about 4.0 vol% to about 9.0 vol%, from about 4.0 vol% to about 8.0 vol%, from about 4.0 vol% to about 7.0 vol%, from about 4.0 vol% to about 6.0 vol%, from about 4.0 vol% to about 5.0 vol%, from about 5.0 vol% to about 40.0 vol%, from about 5.0 vol% to about 35.0 vol%, from about 5.0 vol% to about 30.0 vol%, from about 5.0 vol% to about 25.0 vol%, from about 5.0 vol% to about 20.0 vol%, from about 5.0 vol% to about 15.0 vol%, from about 5.0 vol% to about 12.0 vol%, from about 5.0 vol% to about 10.0 vol%, from about 5.0 vol% to about 9.0 vol%, from about 5.0 vol% to about 8.0 vol%, from about 5.0 vol% to about 7.0 vol%, from about 5.0 vol% to about 6.0 vol%, from about 6.0 vol% to about 40.0 vol%, from about 6.0 vol% to about 35.0 vol%, from about 6.0 vol% to about 30.0 vol%, from about 6.0 vol% to about 25.0 vol%, from about 6.0 vol% to about 20.0 vol%, from about 6.0 vol% to about 15.0 vol%, from about 6.0 vol% to about 12.0 vol%, from about 6.0 vol% to about 10.0 vol%, from about 6.0 vol% to about 9.0 vol%, from about 6.0 vol% to about 8.0 vol%, from about 6.0 vol% to about 7.0 vol%, from about 7.0 vol% to about 40.0 vol%, from about 7.0 vol% to about 35.0 vol%, from about 7.0 vol% to about 30.0 vol%, from about 7.0 vol% to about 25.0 vol%, from about 7.0 vol% to about 20.0 vol%, from about 7.0 vol% to about 15.0 vol%, from about 7.0 vol% to about 12.0 vol%, from about 7.0 vol% to about 10.0 vol%, from about 7.0 vol% to about 9.0 vol%, from about 7.0 vol% to about 8.0 vol%, from about 8.0 vol% to about 40.0 vol%, from about 8.0 vol% to about 35.0 vol%, from about 8.0 vol% to about 30.0 vol%, from about 8.0 vol% to about 25.0 vol%, from about 8.0 vol% to about 20.0 vol%, from about 8.0 vol% to about 15.0 vol%, from about 8.0 vol% to about 12.0 vol%, from about 8.0 vol% to about 10.0 vol%, from about 8.0 vol% to about 9.0 vol%, from about 9.0 vol% to about 40.0 vol%, from about 9.0 vol% to about 35.0 vol%, from about 9.0 vol% to about 30.0 vol%, from about 9.0 vol% to about 25.0 vol%, from about 9.0 vol% to about 20.0 vol%, from about 9.0 vol% to about 15.0 vol%, from about 9.0 vol% to about 12.0 vol%, from about 9.0 vol% to about 10.0 vol%, from about 10.0 vol% to about 40.0 vol%, from about 10.0 vol% to about 35.0 vol%, from about 10.0 vol% to about 30.0 vol%, from about 10.0 vol% to about 25.0 vol%, from about 10.0 vol% to about 20.0 vol%, from about 10.0 vol% to about 15.0 vol%, from about 10.0 vol% to about 12.0 vol%, from about 12.0 vol% to about 40.0 vol%, from about 12.0 vol% to about 35.0 vol%, from about 12.0 vol% to about 30.0 vol%, from about 12.0 vol% to about 25.0 vol%, from about 12.0 vol% to about 20.0 vol%, from about 12.0 vol% to about 15.0 vol%, from about 15.0 vol% to about 40.0 vol%, from about 15.0 vol% to about 35.0 vol%, from about 15.0 vol% to about 30.0 vol%, from about 15.0 vol% to about 25.0 vol%, from about 15.0 vol% to about 20.0 vol%, from about 20.0 vol% to about 40.0 vol%, from about 20.0 vol% to about 35.0 vol%, from about 20.0 vol% to about 30.0 vol%, from about 20.0 vol% to about 25.0 vol%, from about 25.0 vol% to about 40.0 vol%, from about 25.0 vol% to about 35.0 vol%, from about 25.0 vol% to about 30.0 vol%, from about 30.0 vol% to about 40.0 vol%, from about 30.0 vol% to about 35.0 vol%, from about 35.0 vol% to about 40.0 vol%; or at most about 0.1 vol%, at most about 0.2 vol%, at most about 0.4 vol%, at most about 0.6 vol%, at most about 0.8 vol%, at most about 1.0 vol%, at most about 1.25 vol%, at most about 1.5 vol%, at most about 1.75 vol%, at most about 2.0 vol%, at most about 2.5 vol%, at most about 3.0 vol%, at most about 4.0 vol%, at most about 5.0 vol%, at most about 6.0 vol%, at most about 7.0 vol%, at most about 8.0 vol%, at most about 9.0 vol%, at most about 10.0 vol%, at most about 12.0 vol%, at most about 15.0 vol%, at most about 20.0 vol%, at most about 25.0 vol%, at most about 30.0 vol%, at most about 35.0 vol%, at most about 40.0 vol%; or about 0.1 vol%, about 0.2 vol%, about 0.4 vol%, about 0.6 vol%, about 0.8 vol%, about 1.0 vol%, about 1.25 vol%, about 1.5 vol%, about 1.75 vol%, about 2.0 vol%, about 2.5 vol%, about 3.0 vol%, about 4.0 vol%, about 5.0 vol%, about 6.0 vol%, about 7.0 vol%, about 8.0 vol%, about 9.0 vol%, about 10.0 vol%, about 12.0 vol%, about 15.0 vol%, about 20.0 vol%, about 25.0 vol%, about 30.0 vol%, about 35.0 vol%, about 40.0 vol%, or any ranges or values therebetween. The reductive atmosphere may comprise about 1 vol% to about 10 vol% Hi in Ar. The reductive atmosphere may comprise about 5 vol% Hj in Ar.
In an embodiment, the present disclosure provides for a method of producing a supported catalyst, wherein the reductive atmosphere comprises from about 1 vol% to about 10 vol% Hj in Ar. The present disclosure also provides for a method of producing a supported catalyst, wherein the oxygen and/or oxide content of the supported catalyst of step (d) is lower than the oxygen and/or oxide content of the pyrolyzed product of step (c).
The oxygen and/or oxide content of the supported catalyst of step (d) may be lower than the oxygen and/or oxide content of the pyrolyzed product of step (c) in a range of at least about 0.1 wt%, at least about 0.2 wt%, at least about 0.5 wt%, at least about 1 wt%, at least about 2 wt%, at least about 3 wt%, at least about 5 wt%, at least about 7 wt%, at least about 9 wt%, at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%; or from about 0.1 wt% to about 40 wt%, from about 0.1 wt% to about 30 wt%, from about 0.1 wt% to about 20 wt%, from about 0.1 wt% to about 15 wt%, from about 0.1 wt% to about 10 wt%, from about 0.1 wt% to about 9 wt%, from about 0.1 wt% to about 7 wt%, from about 0.1 wt% to about 5 wt%, from about 0.1 wt% to about 3 wt%, from about 0.1 wt% to about 2 wt%, from about 0.1 wt% to about 1 wt%, from about 0.1 wt% to about 0.5 wt%, from about 0.1 wt% to about 0.2 wt%, from about 0.2 wt% to about 40 wt%, from about 0.2 wt% to about 30 wt%, from about 0.2 wt% to about 20 wt%, from about 0.2 wt% to about 15 wt%, from about 0.2 wt% to about 10 wt%, from about 0.2 wt% to about 9 wt%, from about 0.2 wt% to about 7 wt%, from about 0.2 wt% to about 5 wt%, from about 0.2 wt% to about 3 wt%, from about 0.2 wt% to about 2 wt%, from about 0.2 wt% to about 1 wt%, from about 0.2 wt% to about 0.5 wt%, from about 0.5 wt% to about 40 wt%, from about 0.5 wt% to about 30 wt%, from about 0.5 wt% to about 20 wt%, from about 0.5 wt% to about 15 wt%, from about 0.5 wt% to about 10 wt%, from about 0.5 wt% to about 9 wt%, from about 0.5 wt% to about 7 wt%, from about 0.5 wt% to about 5 wt%, from about 0.5 wt% to about 3 wt%, from about 0.5 wt% to about 2 wt%, from about 0.5 wt% to about 1 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 30 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 15 wt%, from about 1 wt% to about 10 wt%, from about 1 wt% to about 9 wt%, from about 1 wt% to about 7 wt%, from about 1 wt% to about 5 wt%, from about 1 wt% to about 3 wt%, from about 1 wt% to about 2 wt%, from about 2 wt% to about 40 wt%, from about 2 wt% to about 30 wt%, from about 2 wt% to about 20 wt%, from about 2 wt% to about 15 wt%, from about 2 wt% to about 10 wt%, from about 2 wt% to about 9 wt%, from about 2 wt% to about 7 wt%, from about 2 wt% to about 5 wt%, from about 2 wt% to about 3 wt%, from about 3 wt% to about 40 wt%, from about 3 wt% to about 30 wt%, from about 3 wt% to about 20 wt%, from about 3 wt% to about 15 wt%, from about 3 wt% to about 10 wt%, from about 3 wt% to about 9 wt%, from about 3 wt% to about 7 wt%, from about 3 wt% to about 5 wt%, from about 5 wt% to about 40 wt%, from about 5 wt% to about 30 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 15 wt%, from about 5 wt% to about 10 wt%, from about 5 wt% to about 9 wt%, from about 5 wt% to about 7 wt%, from about 7 wt% to about 40 wt%, from about 7 wt% to about 30 wt%, from about 7 wt% to about 20 wt%, from about 7 wt% to about 15 wt%, from about 7 wt% to about 10 wt%, from about 7 wt% to about 9 wt%, from about 9 wt% to about 40 wt%, from about 9 wt% to about 30 wt%, from about 9 wt% to about 20 wt%, from about 9 wt% to about 15 wt%, from about 9 wt% to about 10 wt%, from about 10 wt% to about 40 wt%, from about 10 wt% to about 30 wt%, from about 10 wt% to about 20 wt%, from about 10 wt% to about 15 wt%, from about 15 wt% to about 40 wt%, from about 15 wt% to about 30 wt%, from about 15 wt% to about 20 wt%, from about 20 wt% to about 40 wt%, from about 20 wt% to about 30 wt%, from about 30 wt% to about 40 wt%; or at most about 0.1 wt%, at most about 0.2 wt%, at most about 0.5 wt%, at most about 1 wt%, at most about 2 wt%, at most about 3 wt%, at most about 5 wt%, at most about 7 wt%, at most about 9 wt%, at most about 10 wt%, at most about 15 wt%, at most about 20 wt%, at most about 30 wt%, at most about 40 wt%; or about 0.1 wt%, about 0.2 wt%, about 0.5 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 5 wt%, about 7 wt%, about 9 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 30 wt%, about 40 wt%, or any ranges or values therebetween. The oxygen and/or oxide content of the catalyst of step (d) may be at least about 2 wt% lower than the oxygen and/or oxide content of the pyrolyzed product of step (c).
The presently disclosed method may be performed without using any solvents. This advantageously reduces the amount of liquid waste that needs to be treated or disposed of. By avoiding the use of solvents, the problem of treating such toxic liquid waste is also thus advantageously eliminated. Such a method is also advantageously more cost effective.
In some embodiments of the presently disclosed method, organometallic compounds of Ml, M2 and TM may comprise metal carbonyl compounds, metal ethylene complexes, metal-acetylacetonates, metal-acetates, metal cyanide compounds, metal-bis(acetylacetonate)s, and cyclopentadienyl metal compounds. The present disclosure provides for a method, wherein the organometallic compound of Ml, M2 and TM is independently selected from the group consisting of metal carbonyl compounds, metal ethylene complexes, metal-acetylacetonates, metal-acetates, metal cyanide compounds, metal- bis(acetylacetonate)s, and cyclopentadienyl metal compounds.
The catalyst of the present invention may be used to advantageously drive a OER at a much higher efficiency as compared to other conventional catalysts. The catalysts of the present invention may also advantageously require a much lower overpotential as compared to commercial catalysts to drive the OER, which results in lower energy costs, as well as increased safety, and increased energy efficiency.
The catalysts of the present invention may also exhibit unprecedented stability in acidic media. This is particularly pertinent as long-term operation of the catalysts in acidic conditions during hydrogen production and/or OER can result in degradation of the electrode, which thus requires the electrode to be regularly replaced. This results in increased operational costs. Instead, by providing catalysts that have unprecedented stability in acidic media, the electrodes formed from such catalysts are much more stable and thus require lower maintenance, resulting in advantageously lower operational costs in the long run.
The electrolytic production of hydrogen from water is also a concurrent process, comprising a Hydrogen Evolution Reaction (HER), as well as an Oxygen Evolution Reaction (OER). By increasing the efficiency of either process, it will be possible to design and create a process for producing hydrogen that is much more energy and cost-efficient than the current commercial processes. In the present invention, (supported) catalysts are presently disclosed, for which they require a much lower overpotential as compared to commercial OER catalysts. Additionally, they also exhibit much better stability in acidic media as compared to commercial OER catalysts. Hence, the catalysts of the present invention may also be advantageously used to produce hydrogen at much higher energy and cost efficiency as compared to commercial OER catalysts, with the concomitant release of oxygen in the process.
The present disclosure provides for a use of the catalyst disclosed herein for forming an electrode. The present disclosure further provides for a use of the catalyst disclosed herein to produce oxygen. The present disclosure also provides for a use of a supported catalyst disclosed herein to produce hydrogen.
The catalyst of the present invention may also be incorporated as an electrode into an electrochemical cell. The catalyst of the present invention may also be incorporated as part of a system for producing hydrogen and/or oxygen.
Examples
The catalysts prepared by the methods described in the following examples exhibits enhanced intrinsic catalytic activity and stability during acidic water oxidation reactions, when compared to conventional pure IrOx catalysts. The catalysts of the present invention may also provide up to 25 times higher catalytic activity while maintaining an enhanced catalytic stability. The catalyst products may also be compatible with conventional processes for fabricating Polymer Electrolyte Membrane (PEM) water electrolyzers. Given the much lower loading of iridium and ruthenium, the catalysts and the methods for making such catalysts as disclosed in the present invention are expected to become a viable choice when fabricating PEM water electrolyzers.
Non-limiting examples of the invention and comparative examples will be further described in greater detail by reference to specific examples, which should not be construed as in any way limiting the scope of the invention.
Example 1: Procedure for Preparing Catalyst
Example la: Ball-milling
A mixture of iridium-acetylacetonate (25.47 mg), ruthenium-acetylacetonate (118.26 mg), cobalt - acetylacetonate (Co(acac)j, 181.15 mg) and WO3 support (400 mg) were added into a Nylon jar. The mixture comprised iridium, ruthenium and cobalt metals in a weight ratio of about 1:3:3 (Ir:Ru:Co), whereas the weight of WO3 added was 10 times the total weight of the metals (M1+M2; Ir+Ru) present. Hence, the above mixture comprises Co metal (30 mg), Ir metal (10 mg), Ru metal (30 mg) and WO3 (400 mg) and the molar ratio of Ir:Ru:Co:W in the mixture is about 1 : 6 : 10 : 34.6. The composition of the metals in the final mixture can be accordingly tuned by adjusting the ratio of the salts added to the mixture prior to ball-milling. Zirconia milling beads were further added to the mixture in the Nylon jar, after which the mixture was subjected to ball-milling with a rotating speed of 300 rpm for 3 hours.
Example lb: Pyrolysis
The ball-milled mixture from Example la was subjected to pyrolysis in air at 450 °C (25 °C to 450 °C at a ramping rate of 2.0 °C/min, maintaining at 450 °C for 2 h) in a muffle furnace (Carbolite, UK). After cooling down to room temperature, the product was collected and named as Ii iRmCo;,- WO3.
Example 1c: Reduction
A portion of the product from Example lb was reduced in a reductive atmosphere at either 450 °C or 550 °C in 5 % FE/Ar for 1 h in a tubular furnace (Carbolite, UK) to obtain either hjRusCos- WO3-R-450 °C or IriRu3Co3-WO3-R-550 °C.
Example 2: Characterizing the catalyst
Inductively Coupled Plasma (ICP) analysis of the product from Example lb showed that content of metal elements (Ir, Ru, Co and W) was about 1.7 wt%, 4.8 wt%, 5 wt% and 52 wt% respectively. This indicates further that the catalysts of the present invention contain advantageously low amounts of expensive metals, meaning they can be produced far more cheaply as compared to commercial catalysts.
Fig. 2a shows the XRD patterns of the catalysts prepared from Examples lb and 1c, with some other catalysts as reference. In all the XRD patterns, most of the diffraction signals originate from the WO3 support. For the catalyst from Example 1c (hjRu3Co3-WO3-R-450 °C), a very weak diffraction peak appears at -45°, which can be assigned to the (101) diffraction of metallic Ru. The weak diffraction intensity of noble metal related compounds again, agrees well with the low content of noble metals in the samples.
Fig. 2b, showing the SEM image of the product from Example 1c (hjRu3Co3-WO3-R-450 °C), indicates aggregated nanoparticles with size of several hundred nanometers. No obvious structure segregation can be identified, suggesting that Ii'iRinCo? has been uniformly loaded on the WO3 support.
TEM images (Figs. 4a and 4b) show that average particle size was in the range of 2-5 nm for the product from Example lb ( hi RinGn-WOd after the pyrolysis step. Moreover, the average size of particles did not change after further thermal treatment in reductive atmosphere at 450 °C in H2(5 %)/Ar for 1 h (Fig. 4c and 4d). This could suggest that the catalyst after pyrolysis comprises substantially either metals or their oxides thereof. The reduction of the catalyst without changing the average size could also indicate that the catalysts have become more porous after the reduction process. The chemical states of samples were further examined by X-ray photoelectron spectroscopy (XPS) and shown in Figs. 3a to 3f.
Fig. 3 shows the O Is, Ir 4f, Ru 3d, Co 2p and W 4f of the products from Examples lb and 1c (IriRusCos-WOs, IriRu3Co3-WO3-R-450 °C and IriRu3Co3-WO3-R-550 °C). As shown in Fig. 3, thermal treatment in reductive atmosphere was able to reduce the content of oxygen in samples. For example, the oxygen content decreased from about 52 % to 49% after the product from Example lb was reduced at 450 °C and decreased from about 52 % to 43 % after reduction at 550 °C. The reduction of the metals in the catalyst was also confirmed by the presence of new peaks in the XPS spectra indicating either a partially oxidized or pure metallic state after thermal treatment in reductive atmosphere. This is particularly advantageous, as such metals in either the partially oxidized or pure metallic state have higher propensity towards oxidation and thus would catalyst the OER reaction at much higher efficiency than other commercial catalysts.
Example 3: Determining OER performance
To prepare the catalyst ink for the OER testing, 5 mg of catalyst as prepared from either Examples lb or 1c and 25 pl of 5% Nation 117 solution (DuPont) were introduced into 975 pl of 1: 1 water/isopropanol solution, after which the mixture was sonicated for 3 hours.
The OER performance of the catalysts was examined on a rotating disk electrode (RDE, Pine Research, PHYCHEMi, US) at 25 °C in an 0.5 M H2SO4 solution, at a scan rate of 5 mV s-1 and a rotation speed of 1600 rpm. For the OER test, a catalyst loading of 0.15 mg cm-2 was applied onto the test electrode. A saturated calomel electrode (SCE) was used as the reference electrode. All potentials were calibrated with respect to the RHE scale according to the Nernst equation:
(ERHE = ESCE + 0.059 x pH + 0.243 V).
Figs. 5a to 5d show the results of the Linear Sweep Voltammetry experiments, wherein the curves were recorded at a scan rate of 5 mV s-1 normalized to geometric area. Fig. 5a compares the LSV curves, among which hjRusCos-WCL-R (produced at either reduction at 450 °C or 550 °C) displayed the best OER performance in the acidic medium with the lowest overpotential to reach 10 mA cm2 catalytic current density (260 mV). This was in comparison to commercial IrOx catalyst requiring an overpotential of 290 mV. This result is surprising, especially since commercial IrOx catalyst comprise up to 70 wt% of Ir, while the catalyst of the present invention only comprises about 10 wt% of the expensive metals. These results further show the advantages of the catalysts of the present invention, only needing a far lower overpotential in order to drive the same OER reaction. This directly relates into both lower energy costs, as well as better operational life of the electrode comprising the catalysts of the present invention.
As shown in Fig. 5b, the Tafel slope of hi RinC WCh-R (both 450 °C and 550 °C) were about 46 mV/dec, much lower than that of commercial IrOx (66 mV/dec). Furthermore, the Ii'i RusCos-WOs-R exhibited much higher intrinsic water oxidation activity. For example, at 300 mV overpotential, the mass- normalized current density of hi RinG)?- WO3-R as shown in Fig. 5c was about 250 mA/mgNobie-Metai, which is 25 times higher than that of the commercial IrOx catalyst. These results are further shown in Fig. 5d, where the current density was measured for the different catalysts at various overpotential values. As shown in Fig. 5d, hj RU3CO3-WO3-R possess a far higher current density at the same overpotential as the commercial IrOx catalyst, while maintaining at least 3 times the current density at the same overpotential as InRu3Co3-WO3 of the present invention. This higher current density indicates a far better transfer and conversion of energy and thus better efficiency of the catalysts of the present invention.
Example 4: Assessing stability of catalyst
The stability of the catalyst hjRu3Co3-WO3-R-450 °C from Example 1c was evaluated using chronopotentiometry experiments. The mass loading of Ir+Ru for hjRu3Co3-WO3-R-450 °C and IrOx catalyst were 100 pg and 225 pg cm“2 gm, respectively. The experiment was recorded in 0.5 M H2SO4 electrolyte at a current density of 10 mA cm“2 gm.
As shown in Fig. 6, hjRu3Co3-WO3-R-450 °C is very stable in acidic conditions, which is likely due to the strong interaction between the metals ( Ii'iRinCo?) and the WO3 support. These results indicate that the catalysts of the present invention are far more stable in acidic conditions, and thus have better operational lifespan as well as requiring lesser maintenance, translating in lower operational and maintenance costs.
Industrial Applicability
The present invention relates to catalysts, in particular, catalysts for oxygen evolution reactions. The catalysts of the present invention require a significantly lower overpotential to drive the OER as compared to currently known catalysts. The catalysts of the present invention are also advantageously compatible with commercial fabrication processes of PEM water electrolyzers and other electrochemical devices, and hence may be easily taken up without any difficulty. The catalysts of the present invention may thus also be advantageously used in producing hydrogen.
The present disclosure also refers to a method of producing such catalysts. The method of the present invention may be easily scaled for large-scale synthesis. Current industrial infrastructure can also be easily modified to fit the process requirements. The method of the present invention also does not use any solvents, and thus greatly reduces the amount of liquid waste that needs to be treated or disposed of, reducing environmental waste produced. The method of the present invention accordingly also does not product liquid wastes of metals that are often toxic and/or environmentally hazardous, hence further reducing its environmental impact. The method of the present invention also utilizes precursors that are advantageously easier to handle as compared to the metallic elements, and thus the method is easier to take up in industry. Thus this invention is capable of industrial applicability.
It will be apparent that various other modifications and adaptations of the invention will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the spirit and scope of the invention and it is intended that all such modifications and adaptations come within the scope of the appended claims.

Claims

48 Claims
1. A supported catalyst comprising Ml, M2, TM, and SI, wherein:
M 1 and M2 are metals independently selected from the group consisting of Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb;
TM is a transition metal;
S 1 is a support; wherein the weight ratio of M1:M2:TM is in the range of about 1 : 2-10 : 2-10; the weight ratio of (M1+M2):S1 is in the range of about 1 : 5-20; and Ml, M2, and TM are different.
2. The supported catalyst of claim 1, wherein S 1 is selected from the group consisting of WO3, SiOz, AI2O3, carbon, TiOz, Z1O2, SiOz-AbOz, montmorillonite, SiOz-TiOz, tungstated Z1O2, zeolites, V2O5, MOO3, S11O2, TiC, WC, W2C, Mo2C, TiN, TaN, and mixtures thereof.
3. The supported catalyst of claim 1 or 2, wherein the weight ratio of M1:M2:TM is in the range of about 1: 2-5 : 2-5.
4. The supported catalyst of any one of claims 1-3, wherein the weight ratio of (M1+M2):S 1 is in the range of about 1: 5-15.
5. The supported catalyst of any one of claims 1-4, wherein Ml and M2 are independently selected from the group consisting of Ru, Pd, Ir, and Pt.
6. The supported catalyst of any one of claims 1-5, wherein TM is selected from the group consisting of Mn, Fe, Co, Ni, and Cu.
7. The supported catalyst of any one of claims 1-6, wherein the supported catalyst has an oxygen and/or oxide content of less than about 60% .
8. The supported catalyst of any one of claims 1-7 wherein the supported catalyst has an oxygen and/or oxide content of less than about 50%.
9. The supported catalyst of any one of claims 1-8, wherein the supported catalyst has an average particle size of about 1 nm to about 10 nm.
10. The supported catalyst of any one of claims 1-9, wherein Ml is Ir, M2 is Ru, TM is Co, SI is WO3, the weight ratio of M1:M2:TM is about 1:3:3, and the weight ratio of (M1+M2):S1 is about 1: 10, wherein the supported catalyst has an oxygen and/or oxide content of less than about 50%.
11. A process of preparing a supported catalyst, the process comprising the steps of: a) preparing a mixture comprising an organometallic compound of Ml, an organometallic compound of M2, an organometallic compound of TM, and SI, wherein: 49
Ml and M2 are metals independently selected from the group consisting of Ru, Pd, Ir, Pt, Au, Os, Re, Rh, Ag, Mo, Tc, and Nb;
TM is a transition metal;
S 1 is a support; wherein the weight ratio of M1:M2:TM is in the range of about 1 : 2-10 : 2-10; the weight ratio of (M1+M2):S1 is in the range of about 1 : 5-20; and
Ml, M2, and TM are different, b) ball-milling the mixture of step (a) at a rotation speed of about 200 rpm to about 900 rpm for a duration of about 1 hour to about 5 hours to form a ball-milled mixture, and c) pyrolyzing the ball-milled mixture of step (b) at a temperature of about 300 °C to about 600 °C for a duration of about 1 hour to about 5 hours to form a pyrolyzed product.
12. The process of claim 11, wherein the pyrolyzed product of step (c) is crystalline.
13. The process of claim 11 or 12, wherein step (b) is performed in an oxidizing or reducing atmosphere.
14. The process of any one of claims 11-13, further comprising step (d) reducing the pyrolyzed product of step (c) to form the supported catalyst.
15. The process of claim 14, wherein step (d) is performed in a reductive atmosphere at a temperature of about 300 °C to about 600 °C, for a duration of about 0.5 hours to about 3 hours.
16. The process of claim 15, wherein the reductive atmosphere comprises from about 1% to about 10% H2 in Ar.
17. The process of any one of claims 14-16, wherein the oxygen and/or oxide content of the supported catalyst of step (d) is lower than the oxygen and/or oxide content of the pyrolyzed product of step
(c).
18. The process of claim 17, wherein the oxygen and/or oxide content of the supported catalyst of step
(d) is at least about 2 wt% lower than the oxygen and/or oxide content of the pyrolyzed product of step (c).
19. The process of any one of claims 11-18, wherein the organometallic compound of Ml, M2 and TM is independently selected from the group consisting of metal carbonyl compounds, metal ethylene complexes, metal-acetylacetonates, metal-acetates, metal cyanide compounds, metal- bis(acetylacetonate)s, and cyclopentadienyl metal compounds.
20. The process of any one of claims 11-19, wherein the process is a solvent-free process.
21. Use of a supported catalyst of any one of claims 1-10 to produce hydrogen.
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