WO2018020356A1 - Matériaux à base de nitrure de carbone riche en azote à mésoporosité cubique tridimensionnelle à partir de diaminotétrazine - Google Patents

Matériaux à base de nitrure de carbone riche en azote à mésoporosité cubique tridimensionnelle à partir de diaminotétrazine Download PDF

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WO2018020356A1
WO2018020356A1 PCT/IB2017/054290 IB2017054290W WO2018020356A1 WO 2018020356 A1 WO2018020356 A1 WO 2018020356A1 IB 2017054290 W IB2017054290 W IB 2017054290W WO 2018020356 A1 WO2018020356 A1 WO 2018020356A1
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template
photocatalytic
mcn
carbon nitride
mesoporous
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Siddulu Naidu TALAPANENI
Ajayan Vinu
Ugo RAVON
Khalid Al-Bahily
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Sabic Global Technologies B.V.
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0605—Binary compounds of nitrogen with carbon
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
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    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/39—
    • B01J35/615—
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    • B01J35/635—
    • B01J35/638—
    • B01J35/647—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • 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

Definitions

  • the invention generally concerns a photocatalytic carbon nitride (CN) material.
  • the invention concerns a three-dimensional mesoporous carbon nitride matrix having an atomic nitrogen to atomic carbon (N:C) ratio of 1.8 to 2.1 and a band gap of 1.8 to 3 eV.
  • Vinu et al. reported the preparation of polyaniline based three-dimensional nitrogen doped mesoporous carbon with body centered cubic Ia3d structure using 3D mesoporous silica KIT-6 as a hard template with an aniline molecule as a precursor by using nanocasting for use in heterogeneous catalysis and sensing applications (Vinu et al., Micropor. Mesopor. Mater., 2008, 109:398; Talapaneni et al., J. Mater. Chem. , 2012, 22:9831 ; Mane et al, J. Mater. Chem. A, 2013, 1 :2913). Lee et al.
  • the solution is premised on a three dimensional photocatalytic CN material with a high nitrogen content and having a band gap of 1.8 to 3 eV.
  • this material is stable under photocatalytic conditions.
  • the methods and catalysts of the present invention provide an elegant way to tune the band gap of a carbon nitride material to allow optimization of the photon absorption relative to photon energy.
  • photocatalytic nitrogen rich mesoporous three dimensional (3-D) CN materials are described.
  • the photocatalytic 3-D material can include a three dimensional mesoporous CN matrix having an atomic nitrogen to atomic carbon (N:C) ratio of 1.8 to 2.1 and a band gap of 1.8 to 3 eV.
  • the CN matrix can be a C 3 N 6 diamino-s-tetrazine based material.
  • the mesoporous material can have an elemental N:C (C) ratio of 1.8 to 2.1.
  • the mesoporous material can have a pore volume of at least, at most, or about 0.2 to 1.5 cm 3 g _1 .
  • the mesoporous material is in the form of a powder.
  • the mesoporous material has a pore size of about 2 nm to 50 nm, or preferably 2 nm to 10 nm.
  • photocatalytic CN material of the present invention can have a specific surface area of 140 to 500 m 2 g _1 .
  • the photocatalytic CN material can further include a co-catalyst.
  • the co-catalyst can be a transition metal (e.g., platinum, titanium, nickel, palladium, rhodium, ruthenium, tungsten, molybdenum, gold, silver, copper, or combinations thereof, or alloys thereof).
  • the co- catalyst is platinum.
  • Co-catalysts can be added in amounts of 0.01 to 2.0 wt.% of the mesoporous material.
  • the co-catalyst is incorporated on or in the surface and/or pores of the carbon nitride materials.
  • Methods to prepare a photocatalytic CN material of the present invention can include one or more of the following steps: (a) contacting a mesoporous KIT-6 template having a selected porosity with an aminoguanidine hydrochloride solution forming, a template reactant mixture; and (b) heating the template reactant mixture, forming a carbon nitride material/KIT-6 composite (c) heating the template reactant mixture, forming a carbon nitride material/KIT-6 composite; and (e) removing the KIT-6 template from the mesoporous carbon nitride material/KIT-6 complex.
  • Step (b) heating can include (i) heating the template reactant mixture at a predetermined first temperature for a first time interval; and (ii) raising the temperature to a second temperature for a second time interval.
  • the first temperature is 90 to 1 10 °C. In one particular aspect, the first temperature is about 100 °C.
  • the first time interval can be 4 to 8 hours. In certain aspects, the first time interval can be about 6 hours.
  • the second temperature can be 150 to 170 °C. In certain aspects, the second temperature is about 160 °C.
  • the second time interval can be 4 to 8 hours. In certain aspects, the second time interval is about 6 hours.
  • the CN/KIT-6 composite can be heated under nitrogen flow to temperature at a rate of about 3 °C per minute.
  • the nitrogen flow can be at about 50 to 150 ml per minute.
  • the CN/KIT-6 composite can be heated in step (c) at about 400 C°.
  • the CN/KIT-6 composite is heated under an inert conditions (e.g., a nitrogen flow) at the desired temperature for about 5 hours.
  • the KIT-6 template can be removed by contacting the CN/KIT-6 composite hydrofluoric acid or similar solvents.
  • the method can further include collecting the 3-D mesoporous CN material by filtration.
  • the filtered material can be ground to a powder.
  • Certain embodiments are directed to methods of producing the KIT-6 template by (a) mixing an amphiphilic triblock copolymer dispersed in an aqueous hydrogen chloride solution with 1-butanol and tetraethyl orthosilicate (TEOS) to form a polymerization mixture; (b) heating the polymerization mixture at a predetermined synthesis temperature to form a KIT-6 template, where the predetermined temperature determines the pore size of the KIT-6 template; and (c) calcining the KIT-6 template by heating the KIT-6 template to about 540 °C.
  • the polymerization mixture can be heated at a temperature of about 90 °C to 200 °C. In certain aspects, the polymerization mixture can be heated at a temperature of about 100 °C, 130 °C, or 150 °C. In certain aspects, the polymerization mixture is heated at a temperature of about 150 °C.
  • Certain embodiments are directed to photocatalytic processes that include using the photocatalytic CN material of the present invention in a water splitting process.
  • the process can include contacting the photocatalytic mesoporous 3-D CN material of the present invention with water under conditions sufficient to produce hydrogen from the water.
  • photocatalytic mesoporous 3-D CN material includes a platinum co- catalyst.
  • wt.% refers to a weight percentage of a component, a volume percentage of a component, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component.
  • 10 grams of component in 100 grams of the material is 10 wt.% of component.
  • the catalysts of the present invention can "comprise,” “consist essentially of,” or “consist of particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phase “consisting essentially of,” in one non- limiting aspect, a basic and novel characteristic of the catalysts of the present invention are their abilities to catalyze water-splitting reactions.
  • FIG. 1 Schematic representation for the preparation of diamino-s-tetrazine based 3D cubic mesoporous carbon nitride (c-MCN) of the present invention using KIT-6.
  • FIG. 2 Lower angle and wide angle (insert) powder X-ray diffraction (XRD) patterns of (a) c-MCN -100 (b) c-MCN-130 and (c) c-MCN-150 of the present invention prepared by using different pore diameters of KIT-6 silica templates. [0027] FIG. 3.
  • FIG. 5 High resolution transmission electron microscopy (HRTEM) images of (a, b) c-MCN-100, (c, d) c-MCN-130 and (e, f) c-MCN-150 of the present invention at 50 nm and 20 nm resolution, respectively.
  • FIG. 6 High resolution scanning electron microscopy (HRSEM) images of (a, b) c-MCN-100, (c, d) c-MCN-130 and (e, f) c-MCN-150 samples of the present invention at 3 and 1 micron magnifications, respectively.
  • FIG. 7 Electron energy loss spectra (EELS) of diamino-s-tetrazine based 3D cubic mesoporous carbon nitride (c-MCN) materials of the present invention with various textural parameters prepared from KIT-6-X templates: (a) c-MCN-100, (b) c-MCN-130, and (c) c-MCN-150.
  • EELS Electron energy loss spectra
  • FIG. 8. Energy dispersive X-ray spectroscopy (EDX) images of (a) c-MCN-100, (b) c-MCN-130, and (c) c-MCN-150 of the present invention.
  • FIG. 9. (A) X-ray photon spectroscopy (XPS) survey spectra, (B) CI s XPS survey spectra, and (C) Nls XPS survey spectra of c-MCN-150 of the present invention.
  • XPS X-ray photon spectroscopy
  • FIG. 10 Fourier transform infrared (FTIR) spectra from (a) c-MCN-100, (b) c- MCN-130, and (c) c-MCN-150 of the present invention.
  • FTIR Fourier transform infrared
  • FIG. 11 Band gap data and ultraviolet and visible (UV-Vis) spectra (inset) of (a) c-MCN-100, (b) c-MCN-130 and (c) c-MCN-150 of the present invention.
  • FIG. 12 Elemental mappings of (a) c-MCN- 100, (b) c-MCN- 130 and (c) c-MCN- 150 of the present invention.
  • FIG. 13 Thermal gravimetric (TG) curve of c-MCN-150 of the present invention.
  • FIG. 14 Graphs of H 2 gas evolution using c-MCN photocatalyst of the present invention (circles) as a function of time, with reference to non-porous CN (squares).
  • Described herein are 3-D mesoporous carbon nitride materials that provide the appropriate characteristics for photocatalytic water-splitting.
  • the band gap of the CN material can be tuned in order to optimize the photon absorption relative to photon energy.
  • tuning a CN is accomplished by controlling the pore size and other dimensions of the CN material.
  • Certain embodiments are directed to a nitrogen rich mesoporous material.
  • a nitrogen rich mesoporous material can have a 3-D body-centered cubic structure and have a general formula of C 3 N 6 , which is designated as c-MCN throughout the specification.
  • the c-MCN can be a 3-D matrix structure based on diamino-s-tetrazine having a pore size of 2, 5, 10, or 20 to 10, 20, 30, 40, or 50 nm.
  • the mesoporous material can have an atomic N:C ratio of 1.8 to 2.1, or 1.8, 1.9, 2.0, or 2.1, or any range or value there between.
  • the pore volume of the mesoporous material can range from 0.1 to 1, or 0.3 to 0.8, or 0.3 to 0.65 cm 3 g _1 , or any value or range there between (e.g., 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.5, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65, 0.67, 0.68, 0.69, 0.70, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, or 1.0 cm 3 g -1
  • the c-MCN material is tuned to a band gap of 1.8 to 3 eV, or 2.0 to 2.8 eV, 2.2 to 2.5 eV, or 1.8, 1.9, 2.0, 2.2, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0 eV.
  • the photocatalytic reaction of c-MCN materials of the present invention can be increased by the addition of metals, which can serve as a co-catalyst in a water splitting reaction.
  • the co-catalyst is or comprises titanium, nickel, palladium, platinum, rhodium, ruthenium, tungsten, molybdenum, gold, silver, or copper metal.
  • the c- MCN material can include 0.01, 0.10, 0.15 to 2.0 wt.% of the co-catalyst.
  • the co-catalyst is incorporated on the surface of or embedded in the carbon nitride matrix.
  • the photon energy necessary to split water is greater than 1.23 eV, thus tuning the band gap of the mesoporous CN material can allow for more water splitting than recombination. Without wishing to be bound by theory, it is believed that tuning the CN band gap reduces the likelihood that an excited electron will spontaneously revert to its non-excited state (i.e., the electron-hole recombination rate can be reduced or suppressed).
  • an electron can move from a given valence band (VB) to a given conduction (CB) (e.g., excitation through absorption of light), the electron will be restrained from spontaneously moving back to the VB, as the spontaneous emission of a photon that is typically associated with such a move from the CB to the VB would be at a frequency that is restricted due to the material's photonic band gap.
  • the electron can remain in the CB for a longer period of time, which can result in use of said electron to split water rather than moving back to its VB (i.e., the electron-hole pair remains in existence for a longer period of time).
  • co-catalyst electrically conductive material deposited on the photoactive material, provides for a more efficient use of the excited electrons in water-splitting applications.
  • the co-catalyst can be an electron sink and/or promote H 2 production from water instead of electron-hole (e " -h + ) recombination events during the photocatalytic water-splitting reaction.
  • the c-MCN material can be formed by nanocasting methodology using a template.
  • Nanocasting is a technique to form periodic mesoporous framework using a hard template to produce a negative replica of the hard template structure.
  • a molecular precursor can be infiltrated into the pores of the hard template and subsequently polymerized within the pores of the hard template at elevated temperatures. Then the hard template can be removed by a suitable method. This nanocasting route is advantageous because no cooperative assembly processes between the template and the precursors are needed.
  • a hard template can be a mesoporous silica.
  • Template 10 (e.g., calcined KIT-6) can include canal 12 and pores 14. Canal 12 is representative of the pore volume of template 10. Pores 14 can be filled corresponding carbon nitride precursor material 16 to form a tempi ate/carb on nitride precursor material.
  • an aqueous solution of an amine salt e.g., aminoguanidine hydrochloride
  • an amine salt e.g., aminoguanidine hydrochloride
  • the tempi ate/carb on nitride precursor material can undergo a thermal treatment to polymerize the precursor inside the pore of the material to form template/CN composite 16 having canal 12 and polymerized CN material 18.
  • Template/CN composite 16 can be subjected to conditions sufficient to dissolve the template 10 (e.g., KIT-6), and form the mesoporous carbon nitride material 20 of the present invention.
  • the template 10 can be dissolved using an HF treatment, a very high alkaline solution, or any other dissolution agent capable of removing the template and not dissolving the CN framework.
  • the kind of template and the CN precursor used influence the characteristics of the final material.
  • various KIT-6 with various pore diameters can be used as templates.
  • the pore size of the KIT-6 template can be tuned and a diamino-s-tetrazine CN precursor (e.g., aminoguanidine hydrochloride) can be used to produce a high nitrogen content.
  • a diamino-s-tetrazine CN precursor e.g., aminoguanidine hydrochloride
  • step one of a non-limiting method of preparing the nitrogen rich mesoporous material of the present invention can include contacting a calcined mesoporous KIT-6 template having a selected porosity with an CN precursor material (e.g., aqueous aminoguanidine hydrochloride) solution to form a template reactant mixture.
  • the template reactant mixture is a gel.
  • the template reactant mixture can be heated to a first temperature of 90 to 1 10 °C or 95 to 105 °C, or 100 °C for a desired amount of time (e.g., 4 to 8 hours or 5 to 7 hours, or 4, 5, 6, 7, or 8 hours).
  • the temperature of the templating reactant mixture can be increased to a second temperature (e.g., 150 to 170 °C, or 155 to 165 °C, or 150 °C, 155 °C, 160 °C, 165 °C, or 170 °C) and held (incubated) at the second temperature for a desired amount of time (e.g., 4 to 8 hours or 5 to 7 hours, or 4, 5, 6, 7, or 8 hours) to form an s-tetrazine/KIT-6 composite.
  • the incremental heating can facilitate filling of pores of the KIT-6 material by the CN precursor gel to form a CN/KIT-6 composite.
  • Step 4 of the method can include polymerization of the s-tetrazine/KIT-6 composite.
  • the s-tetrazine /KIT-6 composite can be heated in a nitrogen flow to about 350 to 450 °C, or 375 °C to 425 °C , or 400 °C for about 3 to 7 hours, 3, 4, 5, 6, to 7 hours, or until polymerization of the tetrazine is complete, forming a cubic mesoporous carbon nitride material/KIT-6 complex.
  • the CN/KIT-6 composite can be heated under an inert gaseous (e.g., nitrogen, argon, helium) atmosphere.
  • CN/KIT-6 composite can be heated under a nitrogen flow to temperature at a rate of about 1, 2, 3, 4, 5, or 6 °C per minute.
  • the nitrogen flow can be at about 50, 60, or 70 to 100, 120, or 150 mL per minute, including all values and ranges there between while the CN/KIT-6 composite is heated at about 400 C°.
  • the KIT-6 can be removed by dissolving the KIT-6 template from the cubic mesoporous carbon nitride material/KIT-6 complex to form the c-MCN of the present invention having a desired pore size.
  • hydrofluoric acid or other suitable solvent or treatment can be used that dissolves the KIT-6 without dissolving the CN framework.
  • the method can further comprise collecting the cubic mesoporous carbon nitride material of the present invention by filtration.
  • the filtered material can be ground to a powder.
  • the c-MCN compound includes a metal or metal alloy as a co- catalyst.
  • the metal or metal alloys can be obtained from a variety of commercial sources in a variety of forms (e.g., particles, rods, films, etc.) and sizes (e.g., Nano scale or Micro scale).
  • each of Sigma- Aldrich® Co. LLC and Alfa Aesar GmbH & Co KG offer such products.
  • the metal containing c-MCN can be prepared using co- precipitation or deposition-precipitation methods. The metal can be deposited on the c-MCN material prior to or during a photochemical reactions.
  • a metal precursor e.g., a metal nitrate or metal halide
  • a metal salt can absorb on the surface of the c-MCN material.
  • the metal ions can be converted to the active metal species (i.e., zero valance).
  • a KIT-6 template can be produced by (a) mixing an amphiphilic triblock copolymer dispersed in an aqueous hydrogen chloride solution with 1-butanol and tetraethyl orthosilicate (TEOS) to form a polymerization mixture; (b) heating the polymerization mixture at a predetermined synthesis temperature to form a KIT-6 template, where the predetermined temperature determines the pore size of the KIT-6 template; and (c) calcining the KIT-6 template by heating the KIT-6 template to about 480, 500, 520, 540, 560, or 580 °C.
  • TEOS tetraethyl orthosilicate
  • the polymerization mixture can be heated at a temperature of about 75 °C, 100 °C, or 125 °C to 150 °C, 175 °C, or 200 °C or any value or range there between. In certain aspects, the polymerization mixture can be incubated at a synthesis temperature of about 100 °C, 130 °C, or 150 °C or any value or range there between.
  • the 3-D diamino-s-tetrazine based mesoporous carbon nitride matrix material of the present invention with or without a co-catalyst can be used as a photocatalyst in water- splitting reactions.
  • an aqueous reactant mixture that includes a photocatalytic 3-D mesoporous CN material of the present invention that includes platinum can be irradiated with light (e.g., visible light) to form a product stream that includes hydrogen and oxygen.
  • the hydrogen product can be collected.
  • a sacrificial agent can be added to the reactant mixture.
  • the presence of the sacrificial agent can increase the efficiency of the photosystem by further reducing the likelihood of hole/electron recombination via oxidation of the sacrificial agent by the hole rather than recombination with the excited electron and/or assist in photodeposition of the co-catalyst on the c-MCN surface.
  • Non-limiting examples of sacrificial agents that can be used in the methods of the present invention include ethanolamines, alcohols, diols, polyols, dioic acids, or any combination thereof.
  • a non- limiting example of particular sacrificial agent includes triethanolamine.
  • TEOS Tetraethyl orthosilicate
  • aminoguanidine hydrochloride triblock copolymer poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol)
  • Pluronic PI 23 molecular weight 5800 g mol "1 , EO 20 PO 70 EO 20 )
  • Sigma-Aldrich® U.S. A
  • Ethanol and hydrofluoric acid (HF) were purchased from Wako Pure Chemical Industries (U.S.A.). All the chemicals were used without further purification. Doubly deionized water has been used throughout the synthesis process.
  • KIT-6 having different pore diameters was synthesized by using a P123 and n- butanol mixture as the structure directing agent at different synthesis temperatures.
  • P123 (4.0 g) was dispersed in a water (144 g) and HC1 solution (7.9 g), and stirred for 4 h to obtain an aqueous P123 homogeneous solution.
  • 1-butanol (4.0 g) and TEOS (8.6 g) were added at once to the aqueous P123 homogeneous solution under stirring, and stirring was continued at 35 °C for 24 hours to produce a reaction mixture. Subsequently, the reaction mixture was aged at 100 °C for 24 h under static conditions.
  • KIT-6 silica template materials with different pore diameters were synthesized at the synthesis temperatures of 100, 130, and 150 °C.
  • the samples were labeled KIT-6-X, for which X denotes the synthesis temperature.
  • the CN/KIT-6-X composite was heated in a nitrogen flow of 100 mL per minute to 400 °C with a heating rate of 3 °C min "1 and kept under these conditions for 5 hours for polymerization.
  • the c-MCN-X material e.g., cMCN-100, cMCN-130 and cMCN-150
  • X represents the temperature used for formation of the KIT-6 material was recovered after dissolution of the silica framework in 5 wt.% hydrofluoric acid by filtration, washed several times with ethanol, and dried at 100 °C.
  • Nonporous CN was prepared using the above conditions except for the addition of the mesoporous silica template in the synthesis mixture.
  • FIG. 2 shows lower angle and wide (inset) angle powder XRD patterns of (a) c-MCN -100 (b) c-MCN-130 and
  • Textural parameters Textural parameters and mesoscale ordering (d (211 > spacing, unit cell size, surface area, pore volume and pore diameter) of the KIT-6-X compounds of Example 1 and the Example 2 catalysts was determined from nitrogen adsorption-desorption isotherms using a Quantachrome Instruments (U.S.A.) sorption analyzer at -196 °C. All samples were out-gassed for 12 hrs at high temperatures under vacuum (p ⁇ l > ⁇ 10-5 h.Pa) in the degas port of the adsorption analyzer. The specific surface area was calculated using the Brunauer-Emmett-Teller (BET) method.
  • BET Brunauer-Emmett-Teller
  • FIG. 3 shows the nitrogen adsorption-desorption isotherms and shows the BJH pore- size distributions for c-MCN-100 (circles), c-MCN-130 (diamonds) and c-MCN-150 (squares).
  • FIG. 4 shows nitrogen adsorption-desorption isotherms and BJH pore-size distributions of c-MCN-100 and KIT-6-100 silica template.
  • HRTEM and EELS HRTEM and EEL images of the Example 2 catalysts were obtained using a high-resolution transmission electron microscope JEOL-3100FEF, (JOEL, U.S.A.) equipped with a Gatan-766 electron energy-loss spectrometer (EELS).
  • the preparation of the samples for HRTEM analysis involved sonication in ethanol for 5 min and deposition on a copper grid.
  • the accelerating voltage of the electron beam was 200 kV.
  • FIG. 5. are HRTEM images of (a,b) c-MCN-100, (c,d) c-MCN-130 and (e,f) c-MCN-150 of the present invention at 50 and 20 nm magnifications, respectively FIG.
  • FIG. 6 are HRSEM images of (a,b) c-MCN-100, (c,d) c-MCN-130 and (e,f) c-MCN-150 at 3 and 2 micron magnifications, respectively.
  • FIG. 7 shows EEL spectra of Example 2 catalysts: (a) c-MCN-100, (b) c-MCN- 130, and (c) c-MCN-150.
  • FESEM and EDX Morphology of the Example 2 catalysts was observed on a Hitachi S-4800 (U.S.A.) field emission scanning electron microscope (FE-SEM). The machine is equipped with energy dispersive X-ray (EMAX) elemental analyzer. Prior to observation, all the samples were sputtered with Pt for 20 sec by using ion coater. Samples were measured under the accelerating voltage of 5-10 kV, emission current around 10 mA and condensed lens of 5 Megapixel. For SEM, objective aperture 2 was used with a working distance around 8 mm while during elemental analysis (EDX), aperture number 1 with working distance around 15 mm was used.
  • EMAX energy dispersive X-ray
  • EDX EDX along with elemental mapping were recorded on the same machine using accelerating voltage of 15 kV.
  • EDX spectra of the Example 2 catalysts were obtained.
  • FIG. 8 shown energy dispersive X-ray spectroscopy (EDX) images of (a) c-MCN-100, (b) c-MCN-130, and (c) c-MCN-150 of the present invention.
  • UV-VIS UV-Vis absorption spectra of the Example 2 catalysts were recorded by using LAMBDA 750 UV/VIS/NIR spectrophotometer (190 nm-3300 nm) from Perkin Elmer (U.S.A.). Instrument is equipped with a diffuse reflectance integrating sphere coated with BaS04, which serve as a standard. Thickness of the quartz optical cell was 5 mm. The band gap of the materials were calculated using Tauc Plot method. Band gap data was determined using UV-Vis spectra of the Example 2 catalysts was obtained.
  • FIG. 10 shows the UV spectra (insert) and the band gap data for (a) c-MCN-100, (b) c-MCN-130 and (c) c-MCN- [0060]
  • FTIR FTIR spectra of the Example 2 catalysts were recorded by using Perkin Elmer (U.S.A.) spectrum 100 series, bench top model equipped with the optical system that gives the data collection over the range of 7800 to 370 cm-1. The spectra were recorded by averaging 200 scans with a resolution of 2 cm-1, measuring in transmission mode using the KBr self-supported pellet technique. The spectrometer chamber was continuously purged with dry air to remove water vapor.
  • FIG. 11 shows spectra of (a) c-MCN-100, (b) c-MCN- 130, and (c) c-MCN-150 samples.
  • Elemental Mapping Elemental mapping of the Example 2 catalysts was obtained during EDX analysis.
  • FIG. 12 shows the results of elemental mappings of carbon (C) and nitrogen (N) of the (a) c-MCN-100, (b) c-MCN-130, and (c) c-MCN-150 samples.
  • TGA Thermo-gravimetric analysis (TGA) of the c-MCN-150 sample was performed on an SII Nano Technology TG/DTA 6200 instrument (Hitachi High Tech Science Corporation, JAPAN) using pure nitrogen as a carrier gas in with different heating rates. TG analysis was performed.
  • FIG. 13 shows the results of thermogravimetric (TG) analysis of the c-MCN-150 sample.
  • Photocatalytic reactions were carried out in a Pyrex top irradiation reaction vessel connected to a glass closed gas circulation system.
  • Hydrogen (H 2 ) production was performed by dispersing 0.1 g well ground catalyst powder in an aqueous solution (100 mL) containing triethanolamine (10 vol.%) as sacrificial electron donor.
  • Platinum (Pt) was photodeposited on the catalysts using H 2 PtCl 6 dissolved in the reactant solution.
  • the reactant solution was evacuated several times to remove air completely prior to irradiation under a 300 W Xe lamp and a water cooling filter.
  • the wavelength of the incident light was controlled by using an appropriate long pass cut-off filter.
  • FIG. 14 shows the time course of H 2 gas evolution using c-MCN photocatalyst of Examples 2 referenced to non-porous CN.
  • c-MCN three dimensional diamino-s-tetrazine based mesoporous carbon nitride materials
  • H 2 NNHCNHNH 2 .HC1 nitrogen enriched aminoguanidine hydrochloride
  • the c-MCN shows moderate activity for photochemical reduction of water with visible light in the presence of Pt as a co-catalyst and electron donors. This material is stable under experimental conditions.

Abstract

Des modes de réalisation concernent des matériaux à base de nitrure de carbone qui fournissent des caractéristiques appropriées pour la séparation photocatalytique de l'eau. Les matériaux à base de nitrure de carbone présentent un matériau CN tridimensionnel à teneur élevée en azote qui est stable dans des conditions photocatalytiques. Un procédé de production d'un matériau de CN photocatalytique comprend (a) la mise en contact d'une matrice mésoporeuse ayant une porosité sélectionnée avec une solution de chlorhydrate d'aminoguanidine, formant un mélange de réactifs de matrice; et (b) à chauffer le mélange de réactifs de matrice, formant un composite de matériau/matrice de nitrure de carbone; (c) à chauffer le composite CN/matrice dans une atmosphère de gaz inerte à une température comprise entre environ 350 °C et 450 °C, à former un complexe matériau/matrice de nitrure de carbone mésoporeux cubique; et d) à retirer la matrice du complexe matériau/matrice de nitrure de carbone mésoporeux. La matrice d'azote de carbone est basée de C3N6diamino-s-tétrazine.
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