CN111530474A - Noble metal monoatomic regulation spinel array catalyst and preparation method and application thereof - Google Patents

Noble metal monoatomic regulation spinel array catalyst and preparation method and application thereof Download PDF

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CN111530474A
CN111530474A CN202010577622.6A CN202010577622A CN111530474A CN 111530474 A CN111530474 A CN 111530474A CN 202010577622 A CN202010577622 A CN 202010577622A CN 111530474 A CN111530474 A CN 111530474A
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noble metal
spinel
array
salt
chloride
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邢志财
杨秀荣
王德文
孟天
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • 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
    • B01J23/892—Nickel and noble metals
    • 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
    • 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
    • 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
    • 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

Abstract

The invention provides a noble metal monoatomic regulation spinel array catalyst, and a preparation method and application thereof, and belongs to the field of alkaline electrolytic cell water decomposition. The noble metal monatomic control spinel array catalyst is prepared by mixing a transition metal salt and a noble metal salt, and performing a hydrothermal reaction to prepare a spinel precursor array coated with noble metal; and then roasting the precursor array at high temperature to obtain the spinel array catalyst regulated and controlled by the noble metal monoatomic atom. The invention also provides the noble metal single-atom regulation spinel array catalyst prepared by the preparation method. The prepared noble metal monoatomic regulation spinel array catalyst is applied to an alkaline electrolytic cell, and has excellent electro-catalytic hydrogen evolution, oxygen evolution and full-electrolytic water performance.

Description

Noble metal monoatomic regulation spinel array catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of water decomposition of alkaline electrolytic cells, in particular to a noble metal monatomic regulation spinel array catalyst, and a preparation method and application thereof.
Background
Electrochemical water decomposition is an important means for effectively preparing hydrogen and further realizing industrialization thereof, and further plays a key role in solving the increasingly serious problems of energy crisis and environmental pollution energy [ chem.soc.rev.2015,44,5148; adv. mater.2020,32,1806326 ]. Despite the tremendous efforts of scientists in developing non-noble metal catalysts, they still exhibit relatively poor electrochemical performance compared to noble metal catalysts, namely a higher overpotential [ nat. commun.2014,5,3783; nat. mater.2012,11,802 ]. Catalysts based on noble metals have been widely used in industrial applications, but their reserves are scarce, raising the production costs of the related industries. The dispersion of noble metals into ultrafine nanoparticles is an effective strategy to improve their efficiency and catalytic reactivity [ nat. nanotech.2018,13,856 ]. In recent years, monatomic catalysts (SACs) comprise atomically dispersed active metal sites supported on a carrier, and have wide application prospects in the field of catalysis due to unique catalytic performance as a novel catalytic material. In order to construct SACs having precise structures and high density of monoatomic sites and prevent the monoatomic sites from polymerizing into nanoparticles, the catalyst can have excellent activity and selectivity in various catalytic reactions by regulating the distribution and chemical bonding of active sites on a carrier [ adv.mater.2019,31,1902031 ].
Spinel (formula AB is abbreviated to2O4Where a and B are metal ions) play an important role in data storage, biotechnology, electronics, laser, sensors, conversion reactions and energy storage/conversion due to their magnetic, optical, conductive and catalytic properties, which depend to a large extent on their precise structure and composition [ chem]. Spinel not only has the advantages of abundant storage and cheap raw materials, but also shows excellent catalytic activity and stability in alkaline solution, so that spinel is used for Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) as the most promising non-noble metal electrocatalyst, and further receives extensive attention of researchers. In recent years, there have been some spinel composites [ j.am.chem.soc.2015,137,2688]Is used to accelerate Hydrogen Evolution Reaction (HER), but its catalytic performance and stability are relatively poor. However, it is worth mentioning that noble metals have been used so farThe research of using the single-atom regulating spinel array material for high-efficiency water electrolysis reaction is not reported. In conclusion, the spinel array catalyst regulated and controlled by the noble metal monoatomic condition can become an effective full-electrolysis water catalyst.
Disclosure of Invention
The invention aims to solve the technical problems of low catalytic activity and relatively poor stability of the existing spinel hydrogen evolution catalyst, and provides a noble metal single-atom regulation spinel array catalyst, and a preparation method and application thereof.
The invention firstly provides a preparation method of a noble metal monoatomic regulation spinel array catalyst, which comprises the following steps:
the method comprises the following steps: preparing a spinel precursor array coated with noble metal;
step two: and (3) placing the spinel precursor array obtained in the step one in a tubular furnace, and heating for 0.5-4 h at 300-600 ℃ to prepare the noble metal monoatomic regulation spinel array catalyst.
Preferably, the preparation method of the precious metal-coated spinel precursor array comprises the following steps: fully dissolving metal salt in water in a reaction kettle, then cleaning a conductive substrate by using dilute hydrochloric acid, ethanol and deionized water, and obliquely inserting the conductive substrate into the reaction kettle; sealing the reaction kettle, and then placing the reaction kettle into a blast oven to react for 6 hours at the temperature of 80-200 ℃; and after natural cooling, repeatedly washing with ethanol and deionized water to obtain the precious metal-coated spinel precursor array.
Preferably, the metal salt is two of cobalt salt, nickel salt, iron salt, manganese salt and zinc salt.
Preferably, the metal salt is two of nickel chloride, cobalt chloride, ferrous chloride, zinc chloride, nickel nitrate, cobalt nitrate or ferric nitrate.
Preferably, the metal salt is a mixture of nickel chloride and cobalt chloride, and the molar ratio of the nickel chloride to the cobalt chloride is 1: 2.
Preferably, the noble metal salt is ruthenium salt, iridium salt or rhodium salt.
Preferably, the noble metal salt is ruthenium chloride, iridium chloride, rhodium chloride or chloroplatinic acid.
Preferably, the molar ratio of the metal in the metal salt to the noble metal in the noble metal salt is 3: (0.1-1).
The invention also provides the noble metal single-atom regulation spinel array catalyst prepared by the preparation method.
The invention also provides application of the noble metal monatomic control spinel array catalyst in an alkaline electrolytic cell.
The invention has the advantages of
The invention provides a noble metal monatomic control spinel array catalyst and a preparation method and application thereof, wherein the catalyst is prepared by preparing a spinel precursor array coated with noble metal; and then preparing the precursor array obtained in the step one into a noble metal single-atom regulating spinel array by high-temperature roasting. The preparation method is simple and can be used for large-scale production, and the prepared array catalyst is applied to an alkaline electrolytic cell and has excellent electro-catalytic hydrogen evolution and oxygen evolution and full-electrolytic water performance.
Drawings
FIG. 1 is a scanning electron micrograph of an array of Ru-coated Ni-Co-O precursors prepared in example 1;
FIG. 2 is a scanning electron micrograph of the Ru atom-mediated Ni-Co-O array catalyst prepared in example 2;
FIG. 3 is a photograph of a TEM image of the Ru atom-mediated Ni-Co-O array catalyst prepared in example 2;
FIG. 4 is a hydrogen evolution polarization curve diagram of the Ru atom-regulated Ni-Co-O array catalyst prepared in example 2 under alkaline conditions;
FIG. 5 is a graph of oxygen evolution polarization of the Ru atom-regulated NiCo-O array catalyst prepared in example 2 under alkaline conditions;
fig. 6 is a polarization curve diagram of the ruthenium atom-regulated nickel-cobalt-oxygen array catalyst prepared in example 2 under the alkaline condition in a two-electrode system.
Detailed Description
The method comprises the following steps: preparing a spinel precursor array coated with noble metal;
step two: and (3) placing the spinel precursor array obtained in the step one in a tubular furnace, and heating for 0.5-4 h at 300-600 ℃ to prepare the noble metal monoatomic regulation spinel array catalyst.
According to the invention, a precious metal-coated spinel precursor array is prepared, and the preparation method of the precious metal-coated precursor array is not particularly limited, and a hydrothermal method and a solvothermal method which are well known to those skilled in the art can be adopted, and the hydrothermal method is preferred.
The hydrothermal method preferably includes fully dissolving metal salt and noble metal salt in water in a reaction kettle, preferably adding a precipitator in the preparation process for better controlling the appearance of spinel, wherein the precipitator is determined according to the type of spinel, preferably urea, hexamethylenetetramine and ammonium fluoride, the addition amount of the precipitator is not particularly limited, preferably 2-9 times the mass of the noble metal salt, and then cleaning a conductive substrate with dilute hydrochloric acid, ethanol and deionized water and obliquely inserting the conductive substrate into the reaction kettle; and sealing the reaction kettle, putting the reaction kettle into a blast oven, reacting for 6 hours at the temperature of 80-200 ℃, preferably at the temperature of 120 ℃, and repeatedly washing the reaction kettle with ethanol and deionized water after natural cooling to obtain the precious metal coated spinel precursor array.
According to the invention, the metal salt is preferably one or more of cobalt salt, nickel salt, iron salt, manganese salt and zinc salt, more preferably two of nickel chloride, cobalt chloride, ferrous chloride, zinc chloride, nickel nitrate, cobalt nitrate and ferric nitrate, most preferably a mixture of nickel chloride and cobalt chloride, and the molar ratio of the nickel chloride to the cobalt chloride is preferably 1: 2.
according to the present invention, the noble metal salt is preferably a ruthenium salt, an iridium salt, or a rhodium salt, more preferably ruthenium chloride, iridium chloride, rhodium chloride, or chloroplatinic acid, and the molar ratio of the metal in the metal salt to the noble metal in the noble metal salt is preferably 3: (0.1-1), more preferably 3: 0.6.
according to the invention, the conductive substrate is preferably a nickel mesh, carbon paper, titanium mesh or titanium sheet.
According to the invention, the prepared spinel precursor array coated with the noble metal is placed in a magnetic boat and is roasted at high temperature to prepare the noble metal monatomic regulation spinel array catalyst; specifically, it is preferable that: and placing the obtained spinel precursor array coated with the noble metal in a magnetic boat, placing the magnetic boat in a tubular furnace, reacting for 2 hours at the temperature of 300-600 ℃, preferably at the temperature of 400-500 ℃, and taking out after cooling to obtain the noble metal monatomic control spinel array catalyst. The noble metal is ruthenium, iridium, rhodium and platinum.
The invention also provides a noble metal monoatomic regulation spinel array catalyst prepared by the method, wherein the noble metal monoatomic regulation spinel array catalyst is preferably monoatomic ruthenium, monoatomic iridium, monoatomic rhodium and monoatomic platinum; the spinel is preferably nickel-cobalt-oxygen, nickel-ferrite, cobalt-ferrite, iron-cobalt-oxygen, iron-nickel-oxygen, cobalt-nickel-oxygen, zinc-cobalt-oxygen, zinc-ferrite, zinc-nickel-oxygen, nickel-manganese-oxygen, cobalt-manganese-oxygen, nickel-chromium-oxygen, iron-chromium-oxygen, cobalt-chromium-oxygen, and the like.
The invention also provides the application of the noble metal monatomic control spinel array catalyst in the aspect of alkaline electrolytic cells, the noble metal monatomic control spinel array catalyst is used as a cathode, an anode or a cathode and anode to be assembled into a full cell, and the electro-catalytic hydrogen evolution, oxygen evolution and full electrolysis performance of the noble metal monatomic control spinel array catalyst in alkaline electrolyte is tested by utilizing a CHI660E type electrochemical workstation.
The present invention is further illustrated by the following examples, in which the starting materials are all commercially available.
Example 1
Nickel chloride (0.475 g), cobalt chloride (0.666 g), ruthenium chloride (0.249 g) and urea (0.725 g) were dispersed in 37.5 ml of deionized water and stirred for 20 minutes to completely dissolve the solution. The above solution was transferred to a 50 ml reaction vessel, and then a nickel mesh (2 cm. times.4 cm) treated with dilute hydrochloric acid and deionized water was inserted obliquely into the reaction vessel, sealed, and placed in a forced air oven to react at 120 ℃ for 6 hours. And after natural cooling, repeatedly washing and drying by using ethanol and deionized water to obtain the ruthenium-coated nickel-cobalt-oxygen precursor array.
Fig. 1 is a scanning electron micrograph of the ruthenium coated nickel-cobalt-oxygen precursor array prepared in example 1, wherein a is a scanning electron micrograph on a 5 micron scale, and b is a scanning electron micrograph on a 1 micron scale, which shows that the nickel mesh is completely covered by the nanowire array, the nanowires having a length of about 2 microns and a diameter of about 200 nm.
Example 2
And (3) putting the precursor array coated with ruthenium obtained in the example 1 into a porcelain boat, heating the precursor array at 450 ℃ for 2 hours under the protection of argon, and cooling the precursor array to room temperature to obtain the ruthenium monatomic controlled nickel-cobalt-oxygen spinel array.
Fig. 2 is a scanning electron micrograph of the ruthenium monatomic-controlled nickel-cobalt-oxygen spinel array prepared in example 2, wherein fig. a is a scanning electron micrograph on a 5-micrometer scale, and fig. b is a scanning electron micrograph on a 1-micrometer scale, and the scanning electron micrograph shows that the nickel mesh is completely covered by the nanosheet array, and the nanowires are changed from the smooth surface in fig. 1 into a rough surface with a large number of nanopores.
Fig. 3 is a transmission electron micrograph of the ruthenium monatomic control nickel-cobalt-oxygen spinel array prepared in example 2, which is a transmission electron micrograph under a 200 nm scale, and shows that the nanowires are composed of nanopores and a rough surface.
Fig. 4 shows the hydrogen evolution polarization curve of the ruthenium monatomic controlled nickel-cobalt-oxygen spinel array catalyst under alkaline conditions (1 mol potassium hydroxide, pH 14). Compared with a single nickel-cobalt-oxygen spinel array and a bare nickel net, the nickel-cobalt-oxygen spinel array regulated by the ruthenium single atom shows very excellent hydrogen evolution energy, and can drive 100 milliamperes/cm by 57 millivolts of overpotential2Current density of up to 1.2A/cm2. It is worth mentioning that the ruthenium monatomic tuned nickel-cobalt-oxygen spinel array catalyst has superior hydrogen evolution performance over platinum carbon at high current densities compared to commercial platinum carbon.
Fig. 5 is a graph of oxygen evolution polarization of the ruthenium monatomic controlled nickel-cobalt-oxygen spinel array catalyst under alkaline conditions (1 mole potassium hydroxide, pH 14). FIG. 6 illustrates that the oxygen evolution performance of the catalyst is significantly better than the control Ni-Co-O spinel and bare nickel mesh, and is significantly better than commercial ruthenium dioxide, requiring 260 mV overpotential to drive 100 mCAmpere/cm2Current density of up to 1.6A/cm2。
FIG. 6 is a polarization curve diagram of the ruthenium monatomic controlled Ni-Co-O spinel array catalyst under the alkaline condition in a two-electrode system, and the ruthenium monatomic controlled Ni-Co-O spinel array catalyst can reach 10 milliamperes/cm only by potentials of 1.33 volts and 1.70 volts2And 100 milliamps/cm2The current density of (1).
Example 3
Nickel chloride (0.475 g), cobalt chloride (0.666 g), iridium chloride (0.358 g) and urea (0.725 g) were dispersed in 37.5 ml of deionized water and stirred for 20 minutes to completely dissolve the solution. The above solution was transferred to a 50 ml reaction vessel, and then a nickel mesh (2 cm. times.4 cm) treated with dilute hydrochloric acid and deionized water was inserted obliquely into the reaction vessel, sealed, and placed in a forced air oven to react at 120 ℃ for 6 hours. And after natural cooling, repeatedly washing and drying by using ethanol and deionized water to obtain the iridium-coated nickel-cobalt-oxygen precursor array.
And (3) putting the iridium-coated precursor array into a porcelain boat, heating the porcelain boat for 2 hours at 450 ℃ under the protection of argon, and cooling the porcelain boat to room temperature to obtain the iridium monatomic controlled nickel-cobalt-oxygen spinel array.
Example 4
Nickel chloride (0.475 g), cobalt chloride (0.666 g), rhodium chloride (0.251 g) and urea (0.725 g) were dispersed in 37.5 ml of deionized water and stirred for 20 minutes to completely dissolve the solution. The above solution was transferred to a 50 ml reaction vessel, and then a nickel mesh (2 cm. times.4 cm) treated with dilute hydrochloric acid and deionized water was inserted obliquely into the reaction vessel, sealed, and placed in a forced air oven to react at 120 ℃ for 6 hours. And after natural cooling, repeatedly washing and drying by using ethanol and deionized water to obtain the rhodium-coated nickel-cobalt-oxygen precursor array.
And (3) putting the rhodium-coated precursor array into a porcelain boat, heating the porcelain boat for 2 hours at 450 ℃ under the protection of argon, and cooling the porcelain boat to room temperature to obtain the rhodium monoatomic control nickel-cobalt-oxygen spinel array.
Example 5
Nickel nitrate (0.582 g), cobalt nitrate (1.164 g), ruthenium chloride (0.249 g) and urea (0.725 g) were dispersed in a mixture of 40 ml of ethanol and water (volume ratio 1:1), and stirred for 20 minutes to completely dissolve the solution. The solution was transferred to a 50 ml reaction vessel, and then a titanium mesh (2 cm. times.4 cm) treated with dilute hydrochloric acid and deionized water was inserted obliquely into the reaction vessel, sealed, and placed in a forced air oven to react at 85 ℃ for 8 hours. And after natural cooling, repeatedly washing and drying by using ethanol and deionized water to obtain the ruthenium-coated nickel-cobalt-oxygen precursor array.
And (3) putting the coated ruthenium precursor array prepared by using the nitrate into a porcelain boat, heating the porcelain boat for 2 hours at 400 ℃ under the protection of argon, and cooling the porcelain boat to room temperature to obtain the ruthenium monatomic controlled nickel-cobalt-oxygen spinel array.
Example 6
Nickel nitrate (0.582 g), cobalt nitrate (1.164 g), iridium chloride (0.358 g) and urea (0.725 g) were dispersed in 40 ml of a mixture of ethanol and water (volume ratio 1:1), and the solution was completely dissolved by stirring for 20 minutes. The solution was transferred to a 50 ml reaction vessel, and then a titanium mesh (2 cm. times.4 cm) treated with dilute hydrochloric acid and deionized water was inserted obliquely into the reaction vessel, sealed, and placed in a forced air oven to react at 85 ℃ for 8 hours. And after natural cooling, repeatedly washing and drying by using ethanol and deionized water to obtain the iridium-coated nickel-cobalt-oxygen precursor array.
And (3) putting the coated iridium precursor array prepared by using the nitrate into a porcelain boat, heating the porcelain boat for 2 hours at 400 ℃ under the protection of argon, and cooling the porcelain boat to room temperature to obtain the iridium monatomic controlled nickel-cobalt-oxygen spinel array.
Example 7
Iron nitrate (0.808 g), cobalt nitrate (1.164 g), iridium chloride (0.358 g), hexamethylenetetramine (2.803 g) and ammonium fluoride (0.296 g) were dispersed in 40 ml of water, and the solution was stirred for 20 minutes to completely dissolve. The above solution was transferred to a 50 ml reaction vessel, and then a nickel mesh (2 cm. times.4 cm) treated with dilute hydrochloric acid and deionized water was inserted obliquely into the reaction vessel, sealed, and placed in a forced air oven to react at 120 ℃ for 12 hours. And after natural cooling, repeatedly washing and drying by using ethanol and deionized water to obtain the iridium-coated iron-cobalt-oxygen precursor array.
And (3) putting the iridium-coated iron-cobalt-oxygen precursor array into a porcelain boat, heating the porcelain boat for 2 hours at 400 ℃ under the protection of argon, and cooling the porcelain boat to room temperature to obtain the iridium-monatomic-controlled iron-cobalt-oxygen spinel array.

Claims (10)

1. A preparation method of a noble metal monatomic control spinel array catalyst is characterized by comprising the following steps:
the method comprises the following steps: preparing a spinel precursor array coated with noble metal;
step two: and (3) placing the spinel precursor array obtained in the step one in a tubular furnace, and heating for 0.5-4 h at 300-600 ℃ to prepare the noble metal monoatomic regulation spinel array catalyst.
2. The preparation method of the noble metal monatomic control spinel array catalyst according to claim 1, wherein the preparation method of the noble metal-coated spinel precursor array comprises the following steps: fully dissolving metal salt in water in a reaction kettle, then cleaning a conductive substrate by using dilute hydrochloric acid, ethanol and deionized water, and obliquely inserting the conductive substrate into the reaction kettle; sealing the reaction kettle, and then placing the reaction kettle into a blast oven to react for 6 hours at the temperature of 80-200 ℃; and after natural cooling, repeatedly washing with ethanol and deionized water to obtain the precious metal-coated spinel precursor array.
3. The method for preparing a noble metal monatomic control spinel array catalyst according to claim 2, wherein the metal salt is two of a cobalt salt, a nickel salt, an iron salt, a manganese salt, and a zinc salt.
4. The method for preparing a noble metal monatomic control spinel array catalyst according to claim 3, wherein the metal salt is two of nickel chloride, cobalt chloride, ferrous chloride, zinc chloride, nickel nitrate, cobalt nitrate, or ferric nitrate.
5. The method for preparing a noble metal monatomic control spinel array catalyst according to claim 4, wherein the metal salt is a mixture of nickel chloride and cobalt chloride, and the molar ratio of nickel chloride to cobalt chloride is 1: 2.
6. The method for preparing a noble metal monatomic control spinel array catalyst according to claim 2, wherein the noble metal salt is a ruthenium salt, an iridium salt, or a rhodium salt.
7. The method for preparing a noble metal monatomic control spinel array catalyst according to claim 6, wherein the noble metal salt is ruthenium chloride, iridium chloride, rhodium chloride, or chloroplatinic acid.
8. The method for preparing a noble metal monatomic control spinel array catalyst according to claim 2, wherein the molar ratio of the metal in the metal salt to the noble metal in the noble metal salt is 3: (0.1-1).
9. A noble metal monatomic control spinel array catalyst obtained by the production method according to any one of claims 1 to 8.
10. Use of the noble metal monatomic control spinel array catalyst of claim 9 in an alkaline electrolytic cell.
CN202010577622.6A 2020-06-23 2020-06-23 Noble metal monoatomic regulation spinel array catalyst and preparation method and application thereof Pending CN111530474A (en)

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Cited By (2)

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CN114959767A (en) * 2021-02-26 2022-08-30 蓝星(北京)化工机械有限公司 Nickel-based active cathode and preparation method thereof
CN114990565A (en) * 2022-05-13 2022-09-02 深圳大学 Preparation method and application of ruthenium-doped rod-like lithium manganese spinel electrocatalyst

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CN108598502A (en) * 2018-03-23 2018-09-28 广东工业大学 A kind of Ni-Co metal oxides air cell electrode catalyst and its preparation method and application
CN109806879A (en) * 2019-02-28 2019-05-28 北京化工大学 A kind of CeO2-NiCo2O4/ NF composite electro catalytic material and its preparation method and application
CN111054391A (en) * 2019-12-15 2020-04-24 南京星宁环保科技有限公司 Novel Pd-type NiCo loaded with noble metal2O4Preparation method of spinel catalyst

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DE2911042A1 (en) * 1979-03-21 1980-10-02 Bosch Gmbh Robert ELECTROCHEMICAL PROBE FOR DETERMINING THE OXYGEN CONCENTRATION AND METHOD FOR THE PRODUCTION THEREOF
CN101410180A (en) * 2006-03-30 2009-04-15 大发工业株式会社 Catalyst composition
CN108598502A (en) * 2018-03-23 2018-09-28 广东工业大学 A kind of Ni-Co metal oxides air cell electrode catalyst and its preparation method and application
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114959767A (en) * 2021-02-26 2022-08-30 蓝星(北京)化工机械有限公司 Nickel-based active cathode and preparation method thereof
CN114959767B (en) * 2021-02-26 2024-03-19 蓝星(北京)化工机械有限公司 Nickel-based active cathode and preparation method thereof
CN114990565A (en) * 2022-05-13 2022-09-02 深圳大学 Preparation method and application of ruthenium-doped rod-like lithium manganese spinel electrocatalyst
CN114990565B (en) * 2022-05-13 2023-05-12 深圳大学 Preparation method and application of ruthenium-doped rod-shaped lithium manganese spinel electrocatalyst

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