CN114808013A - Tungsten trioxide/manganese tungstate/cobalt tungstate photoelectrode material and preparation method and application thereof - Google Patents
Tungsten trioxide/manganese tungstate/cobalt tungstate photoelectrode material and preparation method and application thereof Download PDFInfo
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- CN114808013A CN114808013A CN202210484532.1A CN202210484532A CN114808013A CN 114808013 A CN114808013 A CN 114808013A CN 202210484532 A CN202210484532 A CN 202210484532A CN 114808013 A CN114808013 A CN 114808013A
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title description 4
- OMAWWKIPXLIPDE-UHFFFAOYSA-N (ethyldiselanyl)ethane Chemical compound CC[Se][Se]CC OMAWWKIPXLIPDE-UHFFFAOYSA-N 0.000 title description 2
- CRLHSBRULQUYOK-UHFFFAOYSA-N dioxido(dioxo)tungsten;manganese(2+) Chemical compound [Mn+2].[O-][W]([O-])(=O)=O CRLHSBRULQUYOK-UHFFFAOYSA-N 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 150000003839 salts Chemical class 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001868 water Inorganic materials 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 23
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 20
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000002055 nanoplate Substances 0.000 claims abstract description 15
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 39
- 238000001354 calcination Methods 0.000 claims description 29
- 239000004065 semiconductor Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 6
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- 238000000926 separation method Methods 0.000 abstract description 22
- 239000000969 carrier Substances 0.000 abstract description 10
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- 238000002347 injection Methods 0.000 abstract description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 238000001035 drying Methods 0.000 description 15
- 238000012546 transfer Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
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- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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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
-
- 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
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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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
- 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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
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- C03C2217/23—Mixtures
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
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- 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 relates to the technical field of photoelectrode materials, and provides a WO 3 /MnWO 4 /CoWO 4 Photoelectrode material and preparation method and application thereof. The preparation method of the photoelectrode material provided by the invention comprises the following steps: mixing manganese acetate, cobalt acetate and water to obtain a metal salt mixed solution; mixing WO 3 Immersing the film in the mixed solution of the metal salt for in-situ hydrothermal reaction to obtain WO loaded with mixed metal salt 3 A film; said WO 3 The film comprises a substrate and WO loaded on the surface of the substrate 3 Nano-plate particles; WO of the loaded mixed metal salt 3 The film is washed, dried and calcined in sequence to obtain WO 3 /MnWO 4 /CoWO 4 And (3) a photoelectrode material. WO prepared by the invention 3 /MnWO 4 /CoWO 4 The photoelectrode material can realize effective separation of current carriers and rapid injection of interface charges, and greatly improves the MnWO 4 Water oxidation activity of the electrode.
Description
Technical Field
The invention relates to the technical field of photoelectrode materials, in particular to a WO 3 /MnWO 4 /CoWO 4 Photoelectrode material and a preparation method and application thereof.
Background
The heavy use of traditional fossil energy sources leads to atmospheric CO 2 The content is increasing, which requires the development of cleaner energy sources to gradually replace fossil energy sources. The semiconductor photoelectrocatalysis technology can realize the production of hydrogen by utilizing solar energy, and provides an effective way for the generation of clean energy. The principle of the photoelectrocatalysis technology is that light is utilized to excite a semiconductor material to generate an electron-hole pair, and under the action of a small amount of external bias voltage, the electron and the hole are effectively separated. The separated electrons and hydrogen ions in the solution undergo a reduction reaction to generate hydrogen, and the holes oxidize water molecules to generate oxygen. Hydrogen production compared to two-electron reaction (i.e. 2H) + +2e＝H 2 2 of H + Obtaining 2 electrons to form hydrogen gas), and generating hydrogen (namely 4e + 4H) by hole oxidation reaction with four electrons participating 2 O＝2H 2 +4OH - ,4OH - ＝2H 2 O+O 2 +4e) reacts more slowly kinetically. Therefore, slow water oxidation reactions hinder the practical application of semiconductor photoelectrocatalytic technology.
MnWO 4 Bandgap ofAbout 2.68eV, and recent studies have shown MnWO 4 Can be used for photocatalytic decomposition of organic pollutants or hydrogen production (CdS purified MnWO) 4 A new 0D-1D hybrid system for enhanced photonic hydrogen under natural light, YA Sethi, Nanoscale Advances, 2021/01/01). However, MnWO 4 The application in the field of photoelectrocatalysis has not been reported. Furthermore, simple MnWO 4 Still poor photocatalytic activity, because of MnWO 4 The photogenerated electron and hole pairs recombine faster and the interface charge transfers slower. Thus, MnWO 4 The photocatalytic activity of (A) needs to be further improved for practical use.
The construction of a nano-heterojunction by the combination of two semiconductors is an effective way to promote the separation of semiconductor carriers, but the quality of the interface between the two semiconductors has a great influence on the separation of photogenerated carriers. For example, if the crystal lattice mismatch of the two semiconductor interfaces results in an increase in interfacial resistance, it is difficult for carriers to be effectively separated at the interfaces. Therefore, simply coupling two semiconductor combinations does not necessarily improve the photocatalytic activity of the semiconductors. In addition, if the separated carriers are not efficiently transferred into the solution, they may also cause the final recombination of carriers. Thus, semiconductor modification is required not only to promote carrier separation, but also to accelerate charge transfer of carriers at the electrode/electrolyte interface. However, conventional heterojunction interfaces often have difficulty achieving both effective carrier separation and rapid interface charge injection.
Disclosure of Invention
In view of the above problems, it is an object of the present invention to provide a WO 3 /MnWO 4 /CoWO 4 Photoelectrode material, preparation method and application thereof, and WO prepared by using photoelectrode material 3 /MnWO 4 /CoWO 4 The photoelectrode material can realize effective separation of current carriers and rapid injection of interface charges, and greatly improves the MnWO 4 Water oxidation activity of the electrode.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a WO 3 /MnWO 4 /CoWO 4 The preparation method of the photoelectrode material comprises the following steps:
(1) mixing manganese acetate, cobalt acetate and water to obtain a metal salt mixed solution;
(2) mixing WO 3 Immersing the film in the mixed solution of the metal salt for in-situ hydrothermal reaction to obtain WO loaded with mixed metal salt 3 A film; said WO 3 The film comprises a substrate and WO loaded on the surface of the substrate 3 Nano-plate particles;
(3) WO of the loaded mixed metal salt 3 The film is washed, dried and calcined in sequence to obtain WO 3 /MnWO 4 /CoWO 4 And (3) a photoelectrode material.
Preferably, the molar ratio of the manganese acetate to the cobalt acetate is 50-100: 1; the concentration of manganese acetate in the metal salt mixed solution is 0.05-0.2 mol/L, and the concentration of cobalt acetate is 1-50 mmol/L.
Preferably, the temperature of the in-situ hydrothermal reaction is 100-140 ℃ and the time is 1-10 h.
Preferably, the calcining temperature is 400-800 ℃, the calcining time is 1-8 h, and the calcining is carried out in the air.
Preferably, the heating rate of heating to the calcining temperature is 1-5 ℃/min.
Preferably, after the calcination, the calcination product is soaked in an inorganic acid solution for 40-120 min.
The invention also provides WO prepared by the preparation method in the technical scheme 3 /MnWO 4 /CoWO 4 Photoelectrode material, said WO 3 /MnWO 4 /CoWO 4 The photoelectrode material comprises WO 3 /MnWO 4 /CoWO 4 A semiconductor heterojunction structure.
The invention also provides the WO of the technical scheme 3 /MnWO 4 /CoWO 4 The photoelectrode material is applied to the field of photoelectrocatalysis water decomposition.
The invention provides a WO 3 /MnWO 4 /CoWO 4 Photovoltaic deviceThe preparation method of the pole material comprises the following steps: (1) mixing manganese acetate, cobalt acetate and water to obtain a metal salt mixed solution; (2) mixing WO 3 Immersing the film in the mixed solution of the metal salt for in-situ hydrothermal reaction to obtain WO loaded with mixed metal salt 3 A film; said WO 3 The film comprises a substrate and WO loaded on the surface of the substrate 3 Nano-plate particles; (3) WO of the loaded mixed metal salt 3 The film is washed, dried and calcined in sequence to obtain WO 3 /MnWO 4 /CoWO 4 And (3) a photoelectrode material. Firstly, manganese acetate and cobalt acetate nanosheets are uniformly dispersed and firmly anchored in WO by in-situ hydrothermal reaction 3 The surface of the nano-plate is then calcined to make manganese acetate, cobalt acetate and WO 3 A solid phase reaction takes place, part of WO 3 Conversion to MnWO 4 And CoWO 4 To finally obtain WO 3 /MnWO 4 /CoWO 4 The composite photoelectrode material is prepared from MnWO 4 And CoWO 4 Common WO 3 As template for the reaction, the resulting MnWO 4 And CoWO 4 Sharing WO 4 2- Ions enable the interfaces of the two to be better matched, and efficient separation of photo-generated charges can be achieved. Meanwhile, WO 3 And MnWO 4 A heterojunction also exists between the two, and MnWO can be promoted 4 Separation of photogenerated carriers. WO prepared in the present invention 3 /MnWO 4 /CoWO 4 Among the photoelectrode materials, CoWO 4 Can be used as semiconductor material, and MnWO 4 Forming a semiconductor heterojunction structure to accelerate the separation of carriers; meanwhile, CoWO 4 The photocatalyst can also be used as a cocatalyst for water oxidation reaction, so that the interfacial water oxidation activity of photogenerated holes after separation is accelerated, and the interfacial charge transfer is accelerated. Thus, WO 3 /MnWO 4 /CoWO 4 The photoelectrode material can realize the synchronous promotion of carrier separation and interface charge transfer, and greatly improves the MnWO 4 Water oxidation activity of the electrode.
Drawings
FIG. 1 shows WO prepared in example 1 3 Scanning electron micrographs of the film;
FIG. 2 is a graph showing a preparation process of comparative example 1WO prepared 3 /MnWO 4 And WO prepared in example 1 3 /MnWO 4 /CoWO 4 Ultraviolet-visible absorption spectrogram of the photoelectrode material;
FIG. 3 shows WO of example 1 for supporting mixed metal salts 3 Scanning electron micrographs of the film;
FIG. 4 shows WO prepared in example 1 3 /MnWO 4 /CoWO 4 Scanning electron microscope images of photoelectrode materials;
FIG. 5 shows WO prepared in comparative example 2 3 /MnWO 4 WO prepared in example 2 3 /MnWO 4 /CoWO 4 A current-time curve graph of the photoelectrode material under the irradiation of interstitial sunlight;
FIG. 6 is WO prepared in comparative example 3 3 /MnWO 4 WO prepared in example 3 3 /MnWO 4 /CoWO 4 The carrier separation efficiency of the photoelectrode material under different potentials;
FIG. 7 shows WO prepared in comparative example 3 3 /MnWO 4 WO prepared in example 3 3 /MnWO 4 /CoWO 4 And the carrier transfer efficiency of the photoelectrode material under different potentials.
Detailed Description
The invention provides a WO 3 /MnWO 4 /CoWO 4 The preparation method of the photoelectrode material comprises the following steps:
(1) mixing manganese acetate, cobalt acetate and water to obtain a metal salt mixed solution;
(2) mixing WO 3 Immersing the film in the mixed solution of the metal salt for in-situ hydrothermal reaction to obtain WO loaded with mixed metal salt 3 A film; said WO 3 The film comprises a substrate and WO loaded on the surface of the substrate 3 Nano-plate particles;
(3) WO of the loaded mixed metal salt 3 The film is washed, dried and calcined in sequence to obtain WO 3 /MnWO 4 /CoWO 4 And (3) a photoelectrode material.
Manganese acetate, cobalt acetate and water are mixed to obtain a metal salt mixed solution. In the invention, the molar ratio of the manganese acetate to the cobalt acetate is preferably 50-100: 1, and more preferably 50-70: 1; the concentration of manganese acetate in the metal salt mixed solution is preferably 0.05-0.2 mol/L, more preferably 0.05-0.15 mol/L, and further preferably 0.05-0.1 mol/L; the concentration of the cobalt acetate in the metal salt mixed solution is preferably 1 to 50mmol/L, more preferably 1 to 40mmol/L, and further preferably 1 to 25 mmol/L. The cobalt acetate and manganese acetate are conventional commercial products in the field. The mixing method is not particularly limited, as long as the uniform mixing can be achieved.
After obtaining the metal salt mixed solution, the invention uses WO 3 Immersing the film in the mixed solution of the metal salt for in-situ hydrothermal reaction to obtain WO loaded with mixed metal salt 3 A film. In the present invention, the WO 3 The film preferably comprises a substrate and WO supported on the surface of the substrate 3 Nano-plate particles; the temperature of the in-situ hydrothermal reaction is preferably 100-140 ℃, and more preferably 120-140 ℃; the time of the in-situ hydrothermal reaction is preferably 1-10 h, more preferably 1-5 h, and further preferably 2-4 h; said WO 3 The film is preferably placed in the metal salt mixed solution with the conductive surface facing downwards; the equipment for the in-situ hydrothermal reaction has no special requirements and is a conventional hydrothermal reaction kettle in the field.
The present invention is directed to said WO 3 The thickness and the production method of the film are not particularly limited, and a method known to those skilled in the art may be used. In a specific embodiment of the present invention, said WO 3 The process for preparing the film preferably comprises the following steps:
mixing a sodium tungstate solution with a hydrochloric acid solution to obtain a first mixed solution;
mixing an ammonium oxalate solution with the first mixed solution to obtain a second mixed solution;
immersing the FTO glass with the conductive surface facing downwards into the second mixed solution for hydrothermal reaction, and growing WO on the surface of the FTO glass 3 A nanoparticle;
will grow with WO 3 The nano-particle FTO glass is dried and calcined in sequence (denoted as second calcination) to obtain WO 3 A film.
In the invention, the concentration of the sodium tungstate solution is preferably 0.01-0.05 mol/L, more preferably 0.01-0.014 mol/L, the concentration of the ammonium oxalate is preferably 0.03-0.05 mol/L, more preferably 0.03-0.0315 mol/L, and the concentration of the hydrochloric acid is preferably 1-5 mol/L, more preferably 1-3 mol/L; the volume ratio of the sodium tungstate solution to the hydrochloric acid solution to the ammonium oxalate solution is preferably (2-4): (2-4): 1, more preferably (3-4): (3-4): 1, the first mixed solution is a white suspension; the second mixed solution is a clear solution; the temperature of the hydrothermal reaction is preferably 100-150 ℃, and more preferably 140-150 ℃; the time of the hydrothermal reaction is preferably 2-5 h, and more preferably 4-5 h; before the hydrothermal reaction, preferably cleaning the FTO glass, wherein the cleaning comprises respectively cleaning with ethanol, acetone and ultrapure water for three times; before the drying, it is also preferable to include WO on the growth with water 3 Cleaning the FTO glass of the nanoparticles, wherein the single time of cleaning is preferably 15 min; the invention has no special requirement on the drying mode, and the drying mode is only required to be dry, and the drying mode is preferably natural drying in a room temperature environment; in the invention, the temperature of the second calcination is preferably 400-600 ℃, and more preferably 400-500 ℃; the second calcining time is preferably 1-3 h, and more preferably 2-3 h; the second calcination is preferably carried out in air; the heating rate of heating to the second calcining temperature is preferably 1-3 ℃/min, and more preferably 3 ℃/min; the apparatus for the second calcination is preferably a muffle furnace.
Obtaining WO loaded with Mixed Metal salts 3 After film formation, the invention will load the WO with mixed metal salts 3 The film is washed, dried and calcined in sequence to obtain WO 3 /MnWO 4 /CoWO 4 And (3) a photoelectrode material. In the invention, the calcination temperature is preferably 400-800 ℃, more preferably 600-800 ℃, and further preferably 600-700 ℃; the calcination time is preferably 1-8 h, more preferably 1-6 h, and further preferably 1-4 h; the calcination is preferably carried out in air; the heating rate of the temperature to the calcining temperature is preferably 1-5 ℃/min, and more preferably 1-3 ℃/min. In the inventionPreferably, the washing is performed by deionized water, and the number of washing is preferably 3 to 4. The present invention has no special requirement on the drying mode, and the drying mode is preferably natural drying in a room temperature environment.
In the present invention, the substrate is preferably FTO glass, and there is no particular requirement in the present invention for the area of the substrate and the volume of the second mixed solution in the hydrothermal reaction as long as the substrate can be immersed in the second mixed solution, resulting in WO 3 After film formation, the WO is 3 Cutting the edge of the film, and then carrying out in-situ hydrothermal reaction after cutting; in the in-situ hydrothermal reaction, the invention has no special requirements on the area of the substrate and the volume of the metal salt mixed solution, as long as the substrate can be immersed in the metal salt mixed solution; in a particular embodiment of the invention, the area of the original substrate is preferably 5X 2.5cm 2 The area of the substrate after cutting is preferably 3X 2.5cm 2 。
In the invention, after the calcination, the calcination product is preferably soaked in an inorganic acid solution, the inorganic acid is preferably hydrochloric acid or nitric acid, and the soaking time is preferably 40-120 min, more preferably 40-60 min, and most preferably 60 min; when the inorganic acid solution is a hydrochloric acid solution, the concentration of the hydrochloric acid solution is preferably 0.2-3 mol/L; when the inorganic acid solution is a nitric acid solution, the concentration of the nitric acid solution is preferably 0.2-3 mol/L. In the invention, because manganese oxide and cobalt oxide are generated after manganese acetate and cobalt acetate are calcined at high temperature, the inorganic acid solution can dissolve part of manganese oxide and cobalt oxide, thereby improving the purity of the photoelectrode material.
The invention also provides WO prepared by the preparation method in the technical scheme 3 /MnWO 4 /CoWO 4 Photoelectrode material, wherein MnWO 4 And CoWO 4 Sharing WO 4 2- Ions to form WO 3 /MnWO 4 /CoWO 4 A semiconductor heterojunction structure; said WO 3 /MnWO 4 /CoWO 4 The photoelectrode material is arranged at the intensity of sunlight (100 mW/cm) 2 ) The current density at the lower part is 0.46mA/cm 2 The maximum carrier separation efficiency was 45.5%.
The invention also provides the WO of the technical scheme 3 /MnWO 4 /CoWO 4 The photoelectrode material is applied to the field of photoelectrocatalysis water decomposition. The present invention is directed to said WO 3 /MnWO 4 /CoWO 4 The specific use method of the photoelectrode material is not particularly limited, and a conventional use method of the photoelectrode material may be adopted.
To further illustrate the present invention, the following example is provided to illustrate one of the WO's of the present invention 3 /MnWO 4 /CoWO 4 The photoelectrode material, the method of preparation and the use thereof are described in detail, but they should not be construed as limiting the scope of the invention.
Example 1
Preparation of WO 3 Film formation: 0.1237g of sodium tungstate is weighed and dissolved in 30mL of water to prepare a sodium tungstate solution; 0.1172g of ammonium oxalate is weighed and dissolved in 30mL of water to prepare an ammonium oxalate solution; and then adding 10mL of hydrochloric acid solution with the concentration of 3mol/L into the prepared sodium tungstate solution, magnetically stirring until the solution forms white suspension, adding the prepared ammonium oxalate solution, and recovering the solution into a clear solution. The clear solution was transferred to a 100mL reaction vessel having an area of 5X 2.5cm 2 The FTO is respectively cleaned by ethanol, acetone and ultrapure water for three times, the cleaned FTO is completely immersed into a clear solution in the inner liner of the reaction kettle with the conductive surface facing downwards, and then the high-pressure reaction kettle is sealed and is subjected to hydrothermal treatment at the temperature of 140 ℃ for 4 hours. After the reaction kettle is cooled, taking out the WO 3 The film, wiped off 7mm edges, washed three times in immersion water, each time for 15min, then dried at room temperature. Finally, drying the WO 3 Placing the film in a muffle furnace for calcining, raising the temperature to 500 ℃ at the heating rate of 3 ℃/min, and calcining for 2.5 hours to obtain WO 3 A film.
Weighing 0.5g of manganese acetate, 0.01g of cobalt acetate and 30mL of water, mixing, stirring and dissolving to obtain a metal salt mixed solution; cutting the area to 3 × 2.5cm 2 WO 3 Immersing the film in the mixed solution of metal salt with the conductive surface facing downwards, and carrying out in-situ hydrothermal reaction for 2h at the temperature of 120 ℃ to obtain WO loaded with mixed metal salt 3 Film ofWO after loading with mixed metal salts 3 Washing the film with deionized water for 3 times, naturally drying at room temperature, calcining at a heating rate of 1 deg.C/min to 600 deg.C for 2 hr in air atmosphere, naturally cooling, soaking in concentrated hydrochloric acid solution for 60min, washing with water, and drying to obtain WO 3 /MnWO 4 /CoWO 4 And (3) a photoelectrode material.
Comparative example 1
Preparation of WO according to the procedure of example 1 3 /MnWO 4 The procedure of example 1 was followed except that cobalt acetate was not added throughout the experiment.
FIG. 1 shows WO prepared in example 1 3 Scanning Electron microscopy of the film, it can be seen from FIG. 1 that WO was obtained by hydrothermal reaction 3 The nano plate is in a shape of a nano plate, the thickness of the nano plate is 200-400nm, the length and the width of the nano plate are in the range of 600-1400nm, the surface of the nano plate is rough, partial cracks exist, and most of the nano plate is vertical to the substrate.
FIG. 2 shows WO prepared in comparative example 1 3 /MnWO 4 And WO prepared in example 1 3 /MnWO 4 /CoWO 4 The ultraviolet-visible absorption spectrum of the photoelectrode material is shown in WO 3 /MnWO 4 The film was able to absorb light having a wavelength of 480nm or less, confirming WO 3 /MnWO 4 Has visible light absorption capability; when CoWO is used 4 When present, WO 3 /MnWO 4 /CoWO 4 The light absorption capacity of (2) is improved to a small extent.
FIG. 3 shows WO of example 1 for supporting mixed metal salts 3 The scanning electron microscope image of the film shows that after the in-situ hydrothermal reaction, manganese acetate and cobalt acetate nano-sheets directly grow in WO 3 The surface of the nano-plate is well covered with WO 3 And (4) a bottom layer of the nano plate.
FIG. 4 shows WO prepared in example 1 3 /MnWO 4 /CoWO 4 The scanning electron microscope image of the photoelectrode material shows that after calcination, MnWO 4 And CoWO 4 Can maintain the nano flake shape.
Example 2
Preparation of WO 3 Film formation:the same as in example 1.
Weighing 0.5g of manganese acetate, 0.01g of cobalt acetate and 30mL of water, mixing, stirring and dissolving to obtain a metal salt mixed solution; cutting the area to 3 × 2.5cm 2 WO 3 Immersing the film in a metal salt mixed solution with a conductive surface facing downwards, and carrying out in-situ hydrothermal reaction for 4 hours at the temperature of 130 ℃ to obtain WO loaded with mixed metal salt 3 Film, then the WO loaded with mixed metal salt 3 Washing the film with deionized water for 3 times, naturally drying at room temperature, calcining, heating to 650 deg.C at a heating rate of 3 deg.C/min, calcining in air atmosphere for 3h, naturally cooling, soaking in concentrated hydrochloric acid solution for 60min, washing with water, and drying to obtain WO 3 /MnWO 4 /CoWO 4 And (3) a photoelectrode material.
Comparative example 2
Preparation of WO according to the procedure of example 2 3 /MnWO 4 The procedure of example 2 was followed except that cobalt acetate was not added throughout the experiment.
Testing of photoelectrode Water splitting Performance Using an electrochemical workstation, specifically WO 3 /MnWO 4 Or WO 3 /MnWO 4 /CoWO 4 The photoelectrode material is a working electrode, Ag/AgCl is a reference electrode, a Pt sheet is a counter electrode, and the simulated sunlight (100mW cm) is transmitted by an optical fiber -2 ) Introducing into electrode surface, and measuring WO by linear sweep voltammetry 3 /MnWO 4 Or WO 3 /MnWO 4 /CoWO 4 The current density of the photoelectrode in a dark state or under illumination is 0.1mol/L KHCO 3 The pH value of the solution is 9. The test results are shown in FIG. 5, and FIG. 5 shows WO prepared in comparative example 2 3 /MnWO 4 WO prepared in example 2 3 /MnWO 4 /CoWO 4 Current-time curve of photoelectrode material under intermittent sunlight irradiation. As can be seen from FIG. 5, in the dark state, WO 3 /MnWO 4 Or WO 3 /MnWO 4 /CoWO 4 No obvious current density was observed at either photoelectrode, indicating that neither electrode could achieve water oxidation in the dark state; after illumination, the current densities of the two electrodes are significantly increased, WO 3 /MnWO 4 The photocurrent density of the electrode reaches 0.3mA/cm 2 And WO to 3 /MnWO 4 /CoWO 4 The current density of the electrode was increased to 0.46mA/cm 2 This result shows WO 3 /MnWO 4 And CoWO 4 The compounding can effectively improve MnWO 4 Water splitting efficiency of the electrode. Thus, construction of WO 3 /MnWO 4 /CoWO 4 Improvement of nano heterojunction pair WO 3 /MnWO 4 The photoelectrocatalysis water decomposition activity has great promotion effect.
Example 3
Preparation of WO 3 Film formation: the same as in example 1.
Weighing 1.038g of manganese acetate, 0.015g of cobalt acetate and 30mL of water, mixing, stirring and dissolving to obtain a metal salt mixed solution; cutting the area to 3 × 2.5cm 2 WO 3 Immersing the film in the mixed solution of metal salt with the conductive surface facing downwards, and carrying out in-situ hydrothermal reaction for 4h at the temperature of 140 ℃ to obtain WO loaded with mixed metal salt 3 Film, then the WO loaded with mixed metal salt 3 Washing the film with deionized water for 3 times, naturally drying at room temperature, calcining at a heating rate of 2 ℃/min to 700 ℃, calcining for 1h in air atmosphere, naturally cooling, soaking in concentrated hydrochloric acid solution for 60min, washing with water, and drying to obtain WO 3 /MnWO 4 /CoWO 4 And (3) a photoelectrode material.
Comparative example 3
Preparation of WO according to the procedure of example 3 3 /MnWO 4 The procedure of example 3 was followed except that cobalt acetate was not added throughout the experiment.
For the test of the carrier separation efficiency at different potentials and the carrier transfer efficiency at different potentials, CHI660E electrochemical workstation, in particular, WO, was used 3 /MnWO 4 Or WO 3 /MnWO 4 /CoWO 4 Is a working electrode, Ag/AgCl is a reference electrode, a Pt sheet is a counter electrode, and simulated sunlight (100mW cm) is transmitted through an optical fiber -2 ) Introducing into electrode surface, and measuring WO by linear sweep voltammetry 3 /MnWO 4 Or WO 3 /MnWO 4 /CoWO 4 Photoelectrode is at0.1mol/L KHCO 3 Solution or 0.1mol/L KHCO 3 +0.1mol/L Na 2 SO 3 The photocurrent density in the solution and the pH value of the solution were both 9.
The carrier separation efficiency and carrier transfer efficiency were calculated using the following formulas:
J H2O ＝J abs ×Φ sep ×Φ cat (1)
J Na2SO3 ＝J abs ×Φ sep (2)
wherein J H2O Is the photocurrent density of water oxidation; phi sep Carrier separation efficiency, meaning the yield of photogenerated holes reaching the electrode/electrolyte surface; phi cat The yield of photogenerated holes injected into the solution is reflected for carrier transfer efficiency. Due to Na 2 SO 3 As a commonly used hole trapping agent, the hole oxidation speed is very high, and the surface charge transfer efficiency is almost phi cat 100%. The presence or absence of Na in the electrolyte was determined 2 SO 3 As the photocurrent density under the hole trapping agent, the carrier separation and transfer efficiency was further calculated from equations (1) and (2), and the results are shown in fig. 6 and 7.
FIG. 6 is WO prepared in comparative example 3 3 /MnWO 4 WO prepared in example 3 3 /MnWO 4 /CoWO 4 The carrier separation efficiency of the photoelectrode material under different potentials; as can be seen from FIG. 6, WO 3 /MnWO 4 /CoWO 4 WO with relatively simple carrier separation efficiency of photoelectrode material 3 /MnWO 4 The electrode is greatly improved, MnWO 4 The maximum carrier separation efficiency of (1) is only 26.8%, whereas WO 3 /MnWO 4 /CoWO 4 The maximum carrier separation efficiency of the photoelectrode material can reach 45.5%, and the result fully shows that WO 3 /MnWO 4 /CoWO 4 The photoelectrode material can effectively improve the carrier separation efficiency, thereby greatly promoting the water decomposition activity.
FIG. 7 shows MnWO prepared in comparative example 3 4 WO prepared in example 3 3 /MnWO 4 /CoWO 4 Carrying of photoelectrode materials at different potentials(ii) a streamer transfer efficiency; as can be seen from FIG. 7, WO 3 /MnWO 4 /CoWO 4 The carrier transfer efficiency of the photoelectrode material is higher than that of the pure WO 3 /MnWO 4 Electrodes, which demonstrate CoWO 4 Can indeed act as a water oxidation catalyst, accelerating the efficiency of interfacial hole transfer, thus maintaining the faster water splitting efficiency of the interface.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. WO (WO) 3 /MnWO 4 /CoWO 4 The preparation method of the photoelectrode material is characterized by comprising the following steps:
(1) mixing manganese acetate, cobalt acetate and water to obtain a metal salt mixed solution;
(2) WO (International patent application) 3 Immersing the film in the mixed solution of the metal salt for in-situ hydrothermal reaction to obtain WO loaded with mixed metal salt 3 A film; said WO 3 The film comprises a substrate and WO loaded on the surface of the substrate 3 Nano-plate particles;
(3) WO of the loaded mixed metal salt 3 The film is washed, dried and calcined in sequence to obtain WO 3 /MnWO 4 /CoWO 4 A photoelectrode material.
2. The preparation method according to claim 1, wherein the molar ratio of the manganese acetate to the cobalt acetate is 50-100: 1; the concentration of manganese acetate in the metal salt mixed solution is 0.05-0.2 mol/L, and the concentration of cobalt acetate is 1-50 mmol/L.
3. The preparation method according to claim 1, wherein the temperature of the in-situ hydrothermal reaction is 100-140 ℃ and the time is 1-10 h.
4. The preparation method of claim 1, wherein the calcination is carried out at a temperature of 400 to 800 ℃ for 1 to 8 hours in air.
5. The method according to claim 4, wherein the rate of temperature increase to the calcination temperature is 1 to 5 ℃/min.
6. The preparation method according to claim 5, wherein after the calcination, the method further comprises soaking the calcined product in an inorganic acid solution for 40-120 min.
7. WO obtained by the production method according to any one of claims 1 to 6 3 /MnWO 4 /CoWO 4 Photoelectrode material, said WO 3 /MnWO 4 /CoWO 4 The photoelectrode material comprises WO 3 /MnWO 4 /CoWO 4 Semiconductor heterojunction structures.
8. WO as defined in claim 7 3 /MnWO 4 /CoWO 4 The photoelectrode material is applied to the field of photoelectrocatalysis water decomposition.
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