CN109621981B - Metal oxide-sulfide composite oxygen evolution electrocatalyst and preparation method and application thereof - Google Patents

Metal oxide-sulfide composite oxygen evolution electrocatalyst and preparation method and application thereof Download PDF

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CN109621981B
CN109621981B CN201811288260.8A CN201811288260A CN109621981B CN 109621981 B CN109621981 B CN 109621981B CN 201811288260 A CN201811288260 A CN 201811288260A CN 109621981 B CN109621981 B CN 109621981B
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nickel
sulfide
oxygen evolution
electrocatalyst
zinc
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CN109621981A (en
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李高仁
王辉
何序骏
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Sun Yat Sen University
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—
    • B01J35/396—
    • B01J35/61—
    • 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
    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • 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 discloses a metal oxide-sulfide composite oxygen evolution electrocatalyst and a preparation method and application thereof. The electrocatalyst is a composite material formed by coating zinc cobaltate nanowires with nickel cobalt sulfide nanosheets. The preparation method comprises the steps of firstly synthesizing zinc cobaltate nanowires by using a hydrothermal reaction, combining electrochemical deposition of sulfide nanosheets, and coating the zinc cobaltate nanowires with the nickel-cobalt sulfide nanosheets to prepare the metal oxide-sulfide composite oxygen evolution electrocatalyst with a core-shell coating structure. The electrocatalyst of the invention improves the active site and the surface area of the composite catalyst due to the specially designed chemical composition and microstructure, has higher oxygen evolution activity and stability compared with other oxide and sulfide electrocatalysts, has simple and convenient preparation method, adopts low-cost non-noble metal raw materials, is beneficial to the large-scale synthesis of the anode oxygen evolution catalyst required by electrolyzed water reaction, and has good popularization and application prospects.

Description

Metal oxide-sulfide composite oxygen evolution electrocatalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst materials. More particularly, relates to a metal oxide-sulfide composite oxygen evolution electrocatalyst, a preparation method and an application thereof.
Background
Energy and environment are two important factors for maintaining the sustainable development of human society. With the gradual depletion of traditional fossil energy and the air pollution and greenhouse effect generated along with the combustion of the fossil energy, the search for a clean renewable energy source to replace fossil fuel is urgent.
Hydrogen energy has attracted attention as a pollution-free, high energy density energy source. The hydrogen production by electrochemically decomposing water has the advantages of simple operation, high electrolytic conversion rate and no waste gas emission, and is expected to replace the high-energy-consumption steam reforming hydrogen production technology. However, the cost of hydrogen production by water electrolysis is far higher than that of the traditional catalytic hydrogen production technology, and the hydrogen production cost is mainly limited by a noble metal catalyst required by the hydrogen and oxygen evolution reaction of water electrolysis. The anodic oxygen evolution reaction is an electrode reaction which is unfavorable in thermodynamics and slow in kinetics, the overpotential of the anodic oxygen evolution reaction is far higher than that of the cathodic hydrogen evolution reaction, and a catalyst is needed to reduce the overpotential and improve the reaction rate, so that the efficiency of the electrolytic water reaction is integrally improved.
Currently, the most effective commercial oxygen evolution electrocatalysts are iridium dioxide and ruthenium dioxide, but these two noble metal catalysts limit the large scale application of the hydrogen production technology by water electrolysis due to their scarce reserves and high price. In addition, some cheap transition metal oxides, sulfides and other materials can be used as electrocatalysts for the anodic oxygen evolution reaction, but the performances of the materials are still a certain distance away from the performance of the noble metal catalysts.
Therefore, it is of great significance to develop an anodic oxygen evolution electrocatalyst that is low in cost and has both high activity and stability.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings of high cost, low activity and/or poor stability of the existing oxygen evolution electrocatalyst, and provide a metal oxide-sulfide composite anode oxygen evolution electrocatalyst with high oxygen evolution activity and stability, and a simple and convenient preparation method.
The invention aims to provide a metal oxide-sulfide composite oxygen evolution electrocatalyst.
The invention also aims to provide a preparation method of the composite oxygen evolution electrocatalyst.
The invention further aims to provide application of the composite oxygen evolution electrocatalyst.
The above purpose of the invention is realized by the following technical scheme:
a metal oxide-sulfide composite oxygen evolution electrocatalyst is a composite material formed by coating zinc cobaltate nanowires with nickel-cobalt sulfide nanosheets.
Preferably, the diameter of the zinc cobaltate nanowire is 60 nm-120 nm.
More preferably, the zinc cobaltate nanowires have a diameter of 100 nm.
Preferably, the thickness of the nickel cobalt sulfide nanosheet is 100nm to 150 nm.
More preferably, the nickel cobalt sulphide nanosheets are 120nm thick.
In addition, the preparation method of the metal oxide-sulfide composite oxygen evolution electrocatalyst comprises the following steps: firstly synthesizing zinc cobaltate nanowires by using a hydrothermal reaction, combining electrochemical deposition of sulfide nanosheets, and coating the zinc cobaltate nanowires with the nickel-cobalt sulfide nanosheets to prepare the metal oxide-sulfide composite oxygen evolution electrocatalyst with a core-shell coating structure.
Specifically, the preparation method of the metal oxide-sulfide composite oxygen evolution electrocatalyst comprises the following steps:
s1, preparing a mixed aqueous solution of zinc nitrate, cobalt nitrate, ammonium fluoride and urea, transferring the mixed aqueous solution to a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, adding a piece of clean nickel foam, heating the mixture for 4 to 6 hours at 100 to 150 ℃ to obtain the nickel foam on which a precursor grows, taking out the nickel foam, cleaning and drying the nickel foam, and carrying out heat treatment for 1.5 to 3 hours at 350 to 500 ℃ in the air to obtain zinc cobaltate nanowires;
s2, electrochemically depositing nickel cobalt sulfide nanosheets in a three-electrode system by cyclic voltammetry: the foamed nickel with the zinc cobaltate nanosheets grown is used as a working electrode, the graphite rod is used as an auxiliary electrode, and the silver/silver chloride electrode is used as a reference electrode; the electrolyte is cobalt nitrate, nickel nitrate and thiourea; and after the reaction, taking out the foamed nickel, cleaning and drying to obtain the zinc cobaltate nanowire coated by the nickel-cobalt sulfide nanosheet, namely the metal oxide-sulfide composite oxygen evolution electrocatalyst.
Preferably, in the mixed aqueous solution in step S1, the molar ratio of zinc nitrate to cobalt nitrate is 1: 1 to 3.
More preferably, in the mixed aqueous solution in step S1, the molar ratio of zinc nitrate to cobalt nitrate is 1: 2.
preferably, in the mixed aqueous solution of step S1, the molar ratio of ammonium fluoride to urea is 1: 2 to 3.
More preferably, in the mixed aqueous solution of step S1, the molar ratio of ammonium fluoride to urea is 2: 5.
more preferably, in the mixed aqueous solution of step S1, the ratio of zinc nitrate: cobalt nitrate: ammonium fluoride: the molar ratio of urea is 1: 1-3: 2: 4 to 6.
More preferably, in the mixed aqueous solution of step S1, the ratio of zinc nitrate: cobalt nitrate: ammonium fluoride: the molar ratio of urea is 1: 2: 2: 5.
preferably, the concentration of the zinc nitrate in the step S1 is 0.01 mol/L-0.03 mol/L.
More preferably, the concentration of the zinc nitrate in the step S1 is 0.02 mol/L.
Preferably, the concentration of the cobalt nitrate in the step S1 is 0.03 mol/L-0.05 mol/L.
More preferably, the concentration of the cobalt nitrate in the step S1 is 0.04 mol/L.
Preferably, the concentration of the ammonium fluoride in the step S1 is 0.02 mol/L-0.06 mol/L.
More preferably, the concentration of the ammonium fluoride in the step S1 is 0.04 mol/L.
Preferably, the concentration of the urea in the step S1 is 0.05 mol/L-0.2 mol/L.
More preferably, the concentration of urea in step S1 is 0.1 mol/L.
Preferably, the area of the nickel foam in the step S1 is 2cm2-8cm2。
More preferably, the area of the nickel foam in the step S1 is 4 cm2。
Preferably, after the nickel foam is added in step S1, the mixture is heated at 100 to 150 ℃ for 4 to 6 hours to obtain the nickel foam with the precursor growing thereon, and the nickel foam is taken out, cleaned, dried and then heat-treated in the air at 350 to 500 ℃ for 1.5 to 3 hours to obtain the zinc cobaltate nanowire.
More preferably, after adding the nickel foam in step S1, heating the mixture at 120 ℃ for 5 hours to obtain the nickel foam with the precursor growing thereon, taking out the nickel foam, washing, drying, and then performing heat treatment at 400 ℃ in the air for 2 hours to obtain the zinc cobaltate nanowires.
Preferably, the potential sweep range of the cyclic voltammetry in step S2 is-1.2V-0.2V (relative to a reference electrode), and the sweep rate is 4-6 mV/S.
More preferably, the scanning speed of step S2 is 5 mV/S.
Preferably, the number of scanning cycles of the cyclic voltammetry in step S2 is 10-20 cycles.
More preferably, the number of scanning cycles of the cyclic voltammetry in step S2 is 15.
Preferably, in the electrolyte of step S2, the ratio of cobalt nitrate: nickel nitrate: the molar ratio of thiourea is 1: 1-2: 10 to 50.
More preferably, in the electrolyte of step S2, the ratio of cobalt nitrate: nickel nitrate: the molar ratio of thiourea is 1: 1.5: 20.
preferably, in the electrolyte of step S2, the concentration of cobalt nitrate is 0.005 mol/L-0.02 mol/L.
More preferably, in the electrolyte of step S2, the concentration of cobalt nitrate is 0.01 mol/L.
In addition, the metal oxide-sulfide composite oxygen evolution electrocatalyst prepared by the method and the application thereof in the aspect of hydrogen production by water electrolysis are also within the protection scope of the invention. In particular, the method is mainly applied to the anodic oxygen evolution reaction of the water electrolysis device.
The invention has the following beneficial effects:
(1) the invention synthesizes an oxide-sulfide composite electrocatalyst by combining hydrothermal reaction and an electrochemical deposition method, and the chemical composition, the micro-morphology and the size of the composite electrocatalyst can be conveniently adjusted by controlling reaction conditions, so that the performance of the catalyst can be adjusted and controlled.
(2) The composite catalyst has a special core-shell coating structure, and can grow on a porous foam nickel current collector with good conductivity in situ, so that the catalyst has excellent stability and high specific surface area, and can generate more catalytic active sites.
(3) Compared with other reported catalysts, the catalyst provided by the invention has the advantages of simple and controllable synthesis method, low cost and high catalytic activity, can effectively reduce the overpotential of the anodic oxygen evolution reaction, is beneficial to large-scale preparation on a current collector, and has industrial application potential.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the electrocatalyst obtained in example 1.
FIG. 2 is a TEM photograph of the electrocatalyst obtained in example 1, wherein (a), (b) and (c) are TEM photographs of low power and high power, respectively.
FIG. 3 is a graph of the electrocatalytic performance of the electrocatalyst obtained in example 1, wherein (a) is the linear sweep voltammogram of the catalyst and (b) is the Tafel plot of the electrocatalyst.
Fig. 4 is a graph of the stability of the electrocatalyst obtained in example 1.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
1. The preparation of the metal oxide-sulfide composite oxygen evolution electrocatalyst
(1) 30mL of mixed aqueous solution of 0.02mol/L zinc nitrate, 0.04 mol/L cobalt nitrate, 0.04 mol/L ammonium fluoride and 0.1 mol/L urea is prepared, the mixed aqueous solution is transferred to a 40 mL stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, a piece of clean nickel foam is added, and the area of the nickel foam is 4 cm2. The hydrothermal reaction kettle is placed in an oven and heated at 120 ℃ for 5 hours. And taking out the foamed nickel with the precursor, cleaning, drying, and then carrying out heat treatment in the air at 400 ℃ for 2 hours to obtain the foamed nickel with the zinc cobaltate nanowires.
(2) Electrochemically depositing nickel cobalt sulfide nanosheets in a three-electrode system by cyclic voltammetry: the foamed nickel with zinc cobaltate nanowires is used as a working electrode, a graphite rod is used as an auxiliary electrode, a silver/silver chloride electrode is used as a reference electrode, the potential scanning range is-1.2V-0.2V (relative to the reference electrode), the scanning speed is 5mV/s, and the number of scanning turns is 15. The electrolyte is 0.01 mol/L cobalt nitrate, 0.015 mol/L nickel nitrate and 0.2mol/L thiourea aqueous solution. And after the reaction, taking out the foamed nickel, cleaning and drying to obtain the zinc cobaltate nanowire coated by the nickel-cobalt sulfide nanosheet, namely the metal oxide-sulfide composite oxygen evolution electrocatalyst.
2. Structural analysis
The X-ray powder diffraction pattern of the obtained electrocatalyst is shown in figure 1, and the comparison of the standard pattern shows that the chemical composition of the prepared electrocatalyst is zinc cobaltate (ZnCo)2O4) And nickel cobalt sulfide (CoNi)2S4）。
The transmission electron microscope photo of the obtained electrocatalyst is shown in fig. 2, and the low magnification photo shows that the electrocatalyst has a special core-shell coating structure, wherein the inner layer is a zinc cobaltate nanowire, and the outer layer is a nickel-cobalt sulfide nanosheet. The diameter of the zinc oxide nanowire is 100nm, and the height of the nickel cobalt sulfide nanosheet coating is 120 nm. From the high magnification photograph, the lattice width of the inner zinc cobaltate nanowire corresponds to the (220) and (331) crystal faces thereof, and the lattice width of the outer nickel cobalt sulfide nanosheet corresponds to the (400) and (331) crystal faces thereof.
From the above results, the prepared electrocatalyst is composed of zinc cobaltate nanowires coated with nickel cobalt sulfide nanosheets.
3. Performance testing
The zinc cobaltate nanowires and the nickel cobalt sulfide nanosheet catalyst with the single components are synthesized by the same method for comparison.
And (3) respectively taking each catalyst as a working electrode, a graphite rod as an auxiliary electrode and a saturated calomel electrode as a reference electrode to form a three-electrode system for testing the oxygen evolution reaction performance of the anode of the catalyst, wherein the electrolyte is a 1 mol/L potassium hydroxide aqueous solution.
Structures asFIG. 3, a in FIG. 3, shows a composite electrocatalyst (ZnCo)2O4@ Ni-Co-S), zinc cobaltate nanowire and nickel cobalt sulfide nanosheet single component catalyst (ZnCo)2O4And Ni-Co-S), when the current density is 10mA/cm2In the process, the overpotential of the prepared composite electrocatalyst is only 300mV, which is lower than that of the zinc cobaltate nanowire and the nickel cobalt sulfide nanosheet which are independently composed.
In FIG. 3, the b diagram is a Tafel curve of three groups, wherein the Tafel slope of the composite electrocatalyst is only 30 mV/dec, which is lower than that of the zinc cobaltate nanowire and the nickel cobalt sulfide nanosheet.
From the above results, it is found that the composite electrocatalyst has excellent catalytic activity for oxygen evolution reaction.
4. Stability testing of composite electrocatalysts
Further by chronopotentiometry at 10mA/cm2The relationship between the potential required for the oxygen evolution reaction and the time is measured at the current density of (1), as shown in fig. 4, and the overpotential is increased by only 20mV after the reaction for a long time of 10 hours, indicating that the composite electrocatalyst has high stability.
In conclusion, compared with the existing catalyst, the composite electrocatalyst provided by the invention has very excellent catalytic activity and stability in the anodic oxygen evolution reaction, and has application potential for replacing a noble metal catalyst.
Example 2
The preparation method is basically the same as the preparation method of the embodiment 1, except that the number of turns of the electrochemical deposition of the nickel-cobalt sulfide nanosheet is changed from 15 turns to 20 turns, and the composition of the obtained composite catalyst is basically the same as that of the embodiment. At 10mA/cm2The overpotential required for the oxygen evolution reaction was measured at a current density of 320 mV.
Example 3
The preparation method is basically the same as the preparation method of the embodiment 1, except that the number of turns of the electrochemical deposition nickel cobalt sulfide nano sheet is changed from 15 turns to 10 turns, and the composition of the obtained composite catalyst is basically the same as the components of the embodiment. At 10mA/cm2The overpotential required for the oxygen evolution reaction was measured at a current density of 335 mV.
Example 4
The preparation method is basically the same as that of the example 1, except that the hydrothermal reaction kettle is placed in an oven and heated at 120 ℃ for 10 hours, and the composition of the finally obtained composite catalyst is basically the same as that of the example. The overpotential required for the oxygen evolution reaction was measured at a current density of 10mA/cm2 to be 345 mV.
Example 5
The preparation method is basically the same as the preparation method of the embodiment 1, except that the foamed nickel with the precursor is taken out, cleaned, dried and then thermally treated in the air at 400 ℃ for 2 hours to obtain the zinc cobaltate nanowire, and the composition of the finally obtained composite catalyst is basically the same as that of the embodiment. The overpotential required for the oxygen evolution reaction was measured at a current density of 10mA/cm2 and was 352 mV.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. The metal oxide-sulfide composite oxygen evolution electrocatalyst is characterized by comprising nickel cobalt sulfide CoNi2S4The preparation method of the composite material is that the zinc cobaltate nanowire is firstly synthesized by using hydrothermal reaction, the nickel cobalt sulfide nanosheet is combined with electrochemical deposition sulfide nanosheet, and the zinc cobaltate nanowire is coated by the nickel cobalt sulfide nanosheet, so that the metal oxide-sulfide composite oxygen evolution electrocatalyst with a core-shell coating structure is prepared;
the diameter of the zinc cobaltate nanowire is 60 nm-120 nm, and the thickness of the nickel-cobalt sulfide nanosheet is 100 nm-150 nm.
2. The preparation method of the composite oxygen evolution electrocatalyst according to claim 1, characterized in that a hydrothermal reaction is used to firstly synthesize zinc cobaltate nanowires, and then a nickel cobalt sulfide nanosheet is used to coat the zinc cobaltate nanowires in combination with an electrochemical deposition of sulfide nanosheet, so as to prepare the metal oxide-sulfide composite oxygen evolution electrocatalyst with a core-shell coating structure.
3. The method of claim 2, comprising the steps of:
s1, preparing a mixed aqueous solution of zinc nitrate, cobalt nitrate, ammonium fluoride and urea, transferring the mixed aqueous solution to a hydrothermal reaction container, adding a clean nickel foam, heating the mixture for 4 to 24 hours at the temperature of 100 to 150 ℃ to obtain the nickel foam on which a precursor grows, taking out the nickel foam, cleaning, drying the nickel foam, and performing heat treatment for 1.5 to 24 hours at the temperature of 350 to 500 ℃ in the air to obtain zinc cobaltate nanowires;
s2, electrochemically depositing nickel cobalt sulfide nanosheets in a three-electrode system by using cyclic voltammetry: the foamed nickel grown with the zinc cobaltate nanosheets obtained in the step S1 is used as a working electrode, a graphite rod is used as an auxiliary electrode, and a silver/silver chloride electrode is used as a reference electrode; the electrolyte is cobalt nitrate, nickel nitrate and thiourea; and after the reaction, taking out the foamed nickel, cleaning and drying to obtain the zinc cobaltate nanowire coated by the nickel-cobalt sulfide nanosheet, namely the metal oxide-sulfide composite oxygen evolution electrocatalyst.
4. The method according to claim 3, wherein in the mixed aqueous solution of step S1, the molar ratio of zinc nitrate to cobalt nitrate is 1: 1-3; in the mixed aqueous solution, the molar ratio of ammonium fluoride to urea is 1: 2 to 3.
5. The method according to claim 3, wherein in the mixed aqueous solution of step S1, the ratio of zinc nitrate: cobalt nitrate: ammonium fluoride: the molar ratio of urea is 1: 1-3: 2: 4 to 6.
6. The preparation method according to claim 3, wherein the potential sweep range of the cyclic voltammetry in step S2 is-1.2V-0.2V, the sweep rate is 4-6 mV/S, and the number of sweep cycles is 10-20 cycles; in the electrolyte, cobalt nitrate: nickel nitrate: the molar ratio of thiourea is 1: 1-2: 10 to 50.
7. An electrocatalyst prepared according to any one of claims 2 to 6.
8. The use of the metal oxide-sulfide composite oxygen evolution electrocatalyst according to claim 1 in the aspect of hydrogen production by electrolysis of water.
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