CN114653383A - Indium zinc sulfide photocatalyst with surface modified by cobalt tungstate and cobaltosic oxide together and preparation method and application thereof - Google Patents
Indium zinc sulfide photocatalyst with surface modified by cobalt tungstate and cobaltosic oxide together and preparation method and application thereof Download PDFInfo
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- CN114653383A CN114653383A CN202210347897.XA CN202210347897A CN114653383A CN 114653383 A CN114653383 A CN 114653383A CN 202210347897 A CN202210347897 A CN 202210347897A CN 114653383 A CN114653383 A CN 114653383A
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- cobalt
- tungstate
- zinc sulfide
- indium zinc
- cobaltosic oxide
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 118
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 title claims abstract description 74
- OMAWWKIPXLIPDE-UHFFFAOYSA-N (ethyldiselanyl)ethane Chemical compound CC[Se][Se]CC OMAWWKIPXLIPDE-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 42
- -1 tungstate radical ion Chemical class 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 14
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 10
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 150000002471 indium Chemical class 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 150000003751 zinc Chemical class 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 claims description 2
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 2
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- DJZHPOJZOWHJPP-UHFFFAOYSA-N magnesium;dioxido(dioxo)tungsten Chemical compound [Mg+2].[O-][W]([O-])(=O)=O DJZHPOJZOWHJPP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 claims description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 24
- 238000005303 weighing Methods 0.000 description 20
- 239000004065 semiconductor Substances 0.000 description 18
- 238000000354 decomposition reaction Methods 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 238000003421 catalytic decomposition reaction Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 1
- 229910019408 CoWO4 Inorganic materials 0.000 description 1
- 229910002340 LaNiO3 Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005524 hole trap Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- C01B3/042—Decomposition of water
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Abstract
The invention discloses an indium zinc sulfide photocatalyst with a surface jointly modified by cobalt tungstate and cobaltosic oxide, a preparation method and application thereof; the preparation method of the indium zinc sulfide jointly modified by the cobalt tungstate and the cobaltosic oxide is divided into two steps, wherein the first step is an oil bath method, and the second step is a grinding method; the cobalt tungstate and the cobaltosic oxide are loaded on the surfaces of the indium zinc sulfide powder particles in a solid powder form; under visible light, when triethanolamine exists as a cavity sacrificial agent, compared with blank indium zinc sulfide, the catalytic effect of the indium zinc sulfide photocatalyst modified by cobalt tungstate for catalytically decomposing water to produce hydrogen is obviously improved, and the catalytic effect of the indium zinc sulfide photocatalyst modified by cobalt tungstate and cobaltosic oxide together is further improved; the invention has the advantages of cheap and easily obtained raw materials, simple preparation method and the like, and the cobalt tungstate and cobaltosic oxide jointly modified indium zinc sulfide photocatalyst has good circulation stability and can be repeatedly utilized.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, relates to a semiconductor photocatalysis surface modification method, and particularly provides an indium zinc sulfide photocatalyst with a surface modified by cobalt tungstate and cobaltosic oxide together, and a preparation method and application thereof.
Background
Since the 1970 s, the problems of continuously worsening environmental pollution and energy shortage have been increasingly appreciated. For sustainable development of human society, it is urgent to develop green and efficient environmental remediation and energy regeneration technologies. Solar energy, which is a renewable energy source, has the advantages of cleanliness, high efficiency and the like, and is one of the most preferable energy sources that can be exploited and utilized at present. On the other hand, hydrogen energy has high energy density, is environment-friendly and recyclable, and is an ideal energy carrier. Therefore, photocatalytic water decomposition by solar-driven semiconductors has a good application prospect, and is therefore of great interest to researchers.
To date, researchers have developed a variety of semiconductor photocatalysts with different forbidden band widths, conduction band potentials, and valence band potentials. The ternary sulfide indium zinc sulfide has the advantages of easily adjustable forbidden band width, good visible light response, and suitability for reduction and oxidation reactions of water due to the conduction band potential and the valence band potential, so that the ternary sulfide indium zinc sulfide becomes a research hotspot of a semiconductor material for producing hydrogen by photocatalytic decomposition of water.
In order to improve photocatalytic efficiency, researchers have developed various strategies to extend the lifetime of photogenerated carriers or to accelerate surface reactions of semiconductors. One strategy to extend the lifetime of photogenerated carriers is to form heterojunctions with other semiconductors to achieve separation of the photogenerated electrons and holes. For example, indium zinc sulfide and CeO2、LaNiO3、Cu3The P material is compounded to form Z-type electron transfer so as to inhibit photoproduction electron hole recombination of the indium zinc sulfide, namely under the illumination condition, conduction band electrons of the compounded material are transferred to a valence band of the indium zinc sulfide and are compounded with holes in the indium zinc sulfide, and thus indium zinc sulfide electrons with reducing capability and holes of the compounded material with oxidizing capability are left.
In addition, the transition metal and the compound thereof can accelerate the surface reaction of the semiconductor and also can improve the hydrogen production efficiency of photocatalytic decomposition water. Researches find that the cobalt simple substance nano particles can be used as electron traps to accelerate the transfer of photoproduction electrons of the indium zinc sulfide to the cobalt simple substance nano particles and catalyze the reduction of protons in water, thereby accelerating the photocatalytic decomposition of the indium zinc sulfide to the water. In addition, the cobaltosic oxide nanoparticles can be used as a hole trap and a catalytic active site for oxidizing water, so that the photocatalytic oxidation of water by indium zinc sulfide is accelerated to generate oxygen. However, the use of cobalt tungstate for modifying indium zinc sulfide and the use of cobalt tungstate and cobaltosic oxide for modifying indium zinc sulfide in photocatalysis have been reported.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an indium zinc sulfide photocatalyst with a surface modified by cobalt tungstate and cobaltosic oxide together, and a preparation method and application thereof.
The invention firstly provides a preparation method of an indium zinc sulfide photocatalyst with a surface jointly modified by cobalt tungstate and cobaltosic oxide, which comprises the following steps:
1) adding cobalt salt serving as a cobalt source precursor into deionized water to prepare a cobalt ion solution;
2) adding tungstate serving as a tungstate ion precursor into deionized water to prepare a tungstate ion solution;
3) adding the tungstate radical ion solution obtained in the step 2) into the cobalt ion solution obtained in the step 1), or adding the cobalt ion solution obtained in the step 1) into the tungstate radical ion solution obtained in the step 2), wherein the molar ratio of tungstate radical ions to cobalt ions is 1-4:1, and stirring 1-3h h under the condition of keeping out of the sun to obtain a suspension;
4) adding the suspension obtained in the step 3) into a polytetrafluoroethylene lining stainless steel autoclave, and carrying out heating reaction at the temperature of 150 ℃ and 200 ℃ for 10-15h to obtain cobalt tungstate nanoparticle powder;
5) dispersing the cobalt tungstate nanoparticle powder obtained in the step 4) into deionized water by ultrasonic, adding ethylene glycol, and adding zinc salt, indium salt and sulfur-containing compounds serving as zinc source, indium source and sulfur source precursors, wherein the molar ratio of the zinc salt to the indium salt to the sulfur-containing compounds is (0.4-3.1) to (0.6-2.4) to 4;
6) heating the material obtained in the step 5) at 70-90 ℃ for reaction for 1-3h to obtain a precipitate material, and washing and drying to obtain cobalt tungstate modified indium zinc sulfide powder;
7) adding sodium hydroxide into the cobalt ion solution obtained by the same method as the step 1), wherein the molar ratio of cobalt salt to sodium hydroxide is 4-8:1, adding the obtained mixed material into a polytetrafluoroethylene lining stainless steel autoclave, heating and reacting at 150-180 ℃ for 5-8h, calcining at 400-600 ℃ for 2-5h in an air atmosphere, washing and drying to obtain cobaltosic oxide nanoparticle powder;
8) adding the cobalt tungstate modified indium zinc sulfide powder obtained in the step 6) into an agate mortar, adding ethanol, and then adding the cobaltosic oxide nanoparticle powder obtained in the step 7), wherein the mass ratio of the cobalt tungstate modified indium zinc sulfide powder to the cobaltosic oxide nanoparticle powder is 100: (1-9), grinding to obtain the indium zinc sulfide photocatalyst with the surface jointly modified by cobalt tungstate and cobaltosic oxide.
In a preferred embodiment of the present invention, the cobalt salt in step 1) is any one or more of cobalt chloride, cobalt nitrate, cobalt sulfate, and cobalt perchlorate.
In a preferred embodiment of the present invention, the tungstate in step 2) is a mixture of one or more of lithium tungstate, sodium tungstate, potassium tungstate, and magnesium tungstate.
In a preferred embodiment of the present invention, the zinc salt is any one or more of zinc chloride, zinc nitrate, zinc sulfate, and zinc perchlorate.
In a preferred embodiment of the present invention, the indium salt is a mixture of one or more of indium chloride, indium nitrate, and indium sulfate.
In a preferred embodiment of the present invention, the sulfur-containing compound is a mixture of any one or more of sodium sulfide, thioacetamide, and thiourea.
The invention also provides an indium zinc sulfide photocatalyst jointly modified by cobalt tungstate on the surface and cobaltosic oxide prepared by the method, wherein the loading rate of cobalt tungstate on the surface of indium zinc sulfide powder is 2.6-14.1 wt%, and further preferably, the cobalt tungstate has the best catalytic effect when the loading rate is 10.2 wt%. The load rate of the cobaltosic oxide on the surface of the indium zinc sulfide powder is 1-8 wt%.
The invention also provides application of the indium zinc sulfide photocatalyst with the surface modified by cobalt tungstate and cobaltosic oxide together, wherein the catalyst is used for generating hydrogen by photocatalytic decomposition of water in the presence of a hole sacrificial agent under visible light.
As a preferred embodiment of the present invention, the hole sacrificial agent is a mixture of sodium sulfide and sodium sulfite, methanol, lactic acid and triethanolamine; further preferably, the hole sacrificial agent is triethanolamine
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention aims to solve the other technical problem of providing the application of the indium zinc sulfide photocatalyst jointly modified by the surface cobalt tungstate and the cobaltosic oxide, which is used for producing hydrogen by photocatalytic decomposition of water in the presence of a hole sacrificial agent under visible light.
(2) The technical scheme adopted by the invention for solving the problems is as follows: the catalyst can be used for photocatalytic decomposition of water to produce hydrogen in the presence of triethanolamine under visible light.
(3) Compared with the prior art, the method has the advantages of cheap and easily obtained raw materials, simple preparation method and the like, compared with blank indium zinc sulfide, the cobalt tungstate modified indium zinc sulfide photocatalyst has obviously improved catalytic effect, the cobalt tungstate and cobaltosic oxide jointly modified indium zinc sulfide photocatalyst has further improved catalytic effect, and the cobalt tungstate and cobaltosic oxide jointly modified indium zinc sulfide photocatalyst has good circulation stability and can be repeatedly utilized.
Drawings
FIG. 1 is the indium zinc sulfide (ZnIn) prepared in example 12S4) Cobalt tungstate prepared in example 2 (CoWO)4) Tricobalt tetraoxide (Co) prepared in example 33O4) Indium zinc sulfide (Co) Co-modified with cobalt tungstate and cobaltosic oxide prepared in example 103O4/CoWO4/ZnIn2S4) X-ray diffraction pattern of (a).
FIG. 2 shows cobalt tungstate modified indium zinc sulfide (CoWO) prepared in example 64/ZnIn2S4) And tricobalt tetraoxide modified indium zinc sulfide (Co) prepared in example 93O4/ZnIn2S4) X-ray diffraction pattern of (a).
FIG. 3 is a graph of the hydrogen production versus time under visible light conditions and error for the products of examples 4-8.
FIG. 4 is a graph of the hydrogen production versus time under visible light conditions and error for the products of examples 1-3, 6, 9, and 10.
FIG. 5 is a graph of hydrogen production versus time for a cyclic experiment under visible light conditions for the products obtained in examples 1 and 10.
Wherein, the open circle in fig. 5 is indium zinc sulfide C1 corresponding to the right ordinate; the solid circle is indium zinc sulfide semiconductor powder B10 modified by 10.2 percent of cobalt tungstate and modified by 3 percent of cobaltosic oxide together, and corresponds to the left ordinate.
Detailed Description
The invention will be further illustrated and described with reference to specific embodiments. The described embodiments are merely exemplary of the disclosure and are not intended to limit the scope thereof. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
The cobalt tungstate and cobaltosic oxide co-modified indium zinc sulfide photocatalyst is prepared by loading cobalt tungstate and cobaltosic oxide on the surface of indium zinc sulfide semiconductor powder together, wherein the preferred loading rate (mass ratio) of cobalt tungstate is 2.6-14.1%. More preferably, the cobalt tungstate has the best catalytic effect when the loading rate (mass ratio) is 10.2%. The preferred loading (mass ratio) of the cobaltosic oxide is 3%. Referring to the attached figures 1 and 2, the XRD patterns of the photocatalyst respectively load cobalt tungstate and cobaltosic oxide or jointly load cobalt tungstate and cobaltosic oxide, the crystal structure of indium zinc sulfide is not influenced, and characteristic peaks of the loaded cobalt tungstate or cobaltosic oxide can be obviously seen in the XRD patterns.
Compared with blank indium zinc sulfide, the physical properties such as crystallinity, crystalline phase composition, average particle size, pore structure and specific surface area of the composite photocatalyst are not changed, but the activity of catalyzing water decomposition to produce hydrogen is obviously improved in the presence of triethanolamine under visible light.
The cobalt tungstate, cobaltosic oxide and indium zinc sulfide are prepared by self, and the specific measures are as follows: cobalt salt is used as a cobalt source, tungstate is used as a tungstate source, water is used as a solvent, and cobalt tungstate nanopowder is obtained through hydrothermal reaction. Cobalt salt is used as a cobalt source, sodium hydroxide is used as one of raw materials, water is used as a solvent, and the cobaltosic oxide nano powder is obtained through hydrothermal reaction. The preparation method of the indium zinc sulfide jointly modified by the cobalt tungstate and the cobaltosic oxide is divided into two steps, wherein the first step is an oil bath method, and the second step is a grinding method. The concrete measures are as follows: firstly, dispersing cobalt tungstate nanoparticle powder into deionized water by ultrasonic, adding ethylene glycol, adding zinc salt, indium salt and sulfur-containing compounds serving as zinc source, indium source and sulfur source precursors, and reacting under an oil bath condition to obtain cobalt tungstate modified indium zinc sulfide powder; secondly, adding the obtained cobalt tungstate modified indium zinc sulfide powder into an agate mortar, adding ethanol, adding the obtained cobaltosic oxide nano-particle powder, and grinding to obtain the cobalt tungstate and cobaltosic oxide co-modified indium zinc sulfide powder photocatalyst.
Example 1
Step one, respectively weighing 68mg of zinc chloride, 221mg of indium chloride and 150mg of thioacetamide, weighing 2mL of ethylene glycol, putting into 16mL of deionized water, and performing ultrasonic treatment for 5 minutes to dissolve the ethylene glycol and the deionized water to obtain a material A1.
Step two, adding the material A1 into a 20ml reaction tube at room temperature, and heating and reacting in an oil bath at 80 ℃ for 2h to obtain a material pale yellow precipitate B1;
and step three, centrifugally washing and drying the material B1 obtained in the step two for multiple times, and drying in an oven at the temperature of 60 ℃ for 12 hours to obtain the indium zinc sulfide C1.
Example 2
Step one, 915mg of cobalt nitrate and 1470mg of sodium tungstate are respectively weighed, put into 50mL of deionized water, dissolved by ultrasonic treatment for 5 minutes, and stirred for 1 hour to obtain a material A2.
Step two, adding the material A2 into a 100ml reaction kettle at room temperature, placing the reaction kettle in an oven, and heating and reacting for 12 hours at 180 ℃ to obtain a material dark blue precipitate B2;
and step three, centrifugally washing and drying the material B2 obtained in the step two for multiple times, and drying in an oven at the temperature of 60 ℃ for 12 hours to obtain cobalt tungstate C2.
Example 3
Step one, 7320mg of cobalt nitrate and 400mg of sodium hydroxide are respectively weighed and put into 40mL of deionized water, and the materials are dissolved by ultrasonic treatment for 5 minutes to obtain a material A3.
Step two, adding the material A3 into a 100ml reaction kettle at room temperature, placing the reaction kettle in an oven, and heating and reacting for 5 hours at 180 ℃ to obtain a material black precipitate B3;
and step three, centrifugally washing and drying the material B3 obtained in the step two for multiple times, and drying in an oven at the temperature of 60 ℃ for 12 hours to obtain the cobaltosic oxide C3.
Example 4
Step one, weighing 5mg of C2, putting into 16mL of deionized water, and carrying out ultrasonic treatment for 5 minutes to uniformly disperse the C2 to obtain a material A4.
Step two, respectively weighing 68mg of zinc chloride, 221mg of indium chloride and 150mg of thioacetamide at room temperature, weighing 2mL of ethylene glycol, adding the ethylene glycol into the material A4, and heating and reacting for 2 hours at 80 ℃ in an oil bath to obtain a precipitate B4;
and step three, centrifugally washing and drying the material B4 obtained in the step two for multiple times, and drying in an oven at the temperature of 60 ℃ for 12 hours to obtain the indium zinc sulfide C4 modified by 2.6% of cobalt tungstate.
Example 5
Step one, weighing 10mg of C2, putting into 16mL of deionized water, and carrying out ultrasonic treatment for 5 minutes to uniformly disperse the C2 to obtain a material A5.
Step two, respectively weighing 68mg of zinc chloride, 221mg of indium chloride and 150mg of thioacetamide at room temperature, weighing 2mL of ethylene glycol, adding the ethylene glycol into the material A5, and heating and reacting for 2 hours at 80 ℃ in an oil bath to obtain a precipitate B5;
and step three, centrifugally washing and drying the material B5 obtained in the step two for multiple times, and drying in an oven at the temperature of 60 ℃ for 12 hours to obtain the indium zinc sulfide C5 modified by 5.8% of cobalt tungstate.
Example 6
Step one, weighing 15mg of C2, putting into 16mL of deionized water, and carrying out ultrasonic treatment for 5 minutes to uniformly disperse the C2 to obtain a material A6.
Step two, respectively weighing 68mg of zinc chloride, 221mg of indium chloride and 150mg of thioacetamide at room temperature, weighing 2mL of ethylene glycol, adding the ethylene glycol into the material A6, and heating and reacting for 2 hours at 80 ℃ in an oil bath to obtain a precipitate B6;
and step three, centrifugally washing and drying the material B6 obtained in the step two for multiple times, and drying in an oven at the temperature of 60 ℃ for 12 hours to obtain the indium zinc sulfide C6 modified by 10.2% of cobalt tungstate.
Example 7
Step one, weighing 20mg of C2, putting into 16mL of deionized water, and performing ultrasonic treatment for 5 minutes to uniformly disperse the C2 to obtain a material A7.
Step two, respectively weighing 68mg of zinc chloride, 221mg of indium chloride and 150mg of thioacetamide at room temperature, weighing 2mL of ethylene glycol, adding the ethylene glycol into the material A7, and heating and reacting for 2 hours at 80 ℃ in an oil bath to obtain a precipitate B7;
and step three, centrifugally washing and drying the material B7 obtained in the step two for multiple times, and drying in an oven at the temperature of 60 ℃ for 12 hours to obtain the indium zinc sulfide C7 modified by 11.8% of cobalt tungstate.
Example 8
Step one, weighing 25mg of C2, putting into 16mL of deionized water, and carrying out ultrasonic treatment for 5 minutes to uniformly disperse the C2 to obtain a material A8.
Step two, respectively weighing 68mg of zinc chloride, 221mg of indium chloride and 150mg of thioacetamide at room temperature, weighing 2mL of ethylene glycol, adding the ethylene glycol into the material A8, and heating and reacting for 2 hours at 80 ℃ in an oil bath to obtain a precipitate B8;
and step three, centrifugally washing and drying the material B8 obtained in the step two for multiple times, and drying in an oven at the temperature of 60 ℃ for 12 hours to obtain the indium zinc sulfide C8 modified by 14.1% of cobalt tungstate.
Example 9
Step one, 50mg of C1 is weighed and added into an agate mortar, and 0.5mL of ethanol is dripped to obtain a material A9.
And step two, weighing 1.5mg of C3, putting into the material A9, and grinding for 10min at room temperature to obtain the indium zinc sulfide B9 modified by the cobaltosic oxide with the concentration of 3%.
Example 10
Step one, weighing 50mg of C6, adding into an agate mortar, and dropwise adding 0.5mL of ethanol to obtain a material A10.
And step two, weighing 1.5mg of C3, putting into the material A10, and grinding for 10min at room temperature to obtain indium zinc sulfide B10B10 jointly modified by 10.2% of cobalt tungstate and 3% of cobaltosic oxide.
Application example 1
The indium zinc sulfide semiconductor powder modified by cobalt tungstate on the surface obtained in the example 4-5 and corresponding blank indium zinc sulfide are used as photocatalysts, visible light catalytic decomposition water is carried out to produce hydrogen under the condition that triethanolamine is used as a cavity sacrificial agent in nitrogen atmosphere, the influence of different cobalt tungstate loading rates on the water and hydrogen decomposition of indium zinc sulfide is examined (see attached figure 3), the hydrogen production rate of water through photocatalytic decomposition is firstly improved and then reduced along with the improvement of the cobalt tungstate loading rate, and when the cobalt tungstate loading rate reaches 10.2%, the effect of hydrogen production through photocatalytic decomposition water is optimal.
Application example 2
The blank indium zinc sulfide obtained in example 1, the blank cobalt tungstate obtained in example 2 and the 10.2% cobalt tungstate modified indium zinc sulfide semiconductor powder obtained in example 6 are used as photocatalysts, visible light catalytic decomposition water hydrogen production is carried out under the condition that triethanolamine is used as a hole sacrificial agent in a nitrogen atmosphere, the influence of photocatalytic decomposition water hydrogen production of cobalt tungstate per se is examined (see attached figure 4), and the fact that the cobalt tungstate per se cannot be used for photocatalytic decomposition water hydrogen production when triethanolamine is used as a hole sacrificial agent under visible light is found out, and the cobalt tungstate per se can only be used as a cocatalyst to improve the photocatalytic performance of semiconductors.
Application example 3
The blank indium zinc sulfide obtained in example 1, the blank cobaltosic oxide obtained in example 3 and the indium zinc sulfide semiconductor powder modified by 3% of cobaltosic oxide obtained in example 9 are used as photocatalysts, visible light catalytic decomposition water hydrogen production is carried out under the condition that triethanolamine is used as a hole sacrificial agent in nitrogen atmosphere, the influence of the cobaltosic oxide on the photocatalytic decomposition water hydrogen production is examined (see figure 4), and the fact that the cobaltosic oxide cannot be used for photocatalytic decomposition water hydrogen production when the triethanolamine is used as the hole sacrificial agent under the visible light condition is found out, and the cobaltosic oxide can only be used as a cocatalyst to improve the photocatalytic performance of the semiconductor.
Application example 4
By using the blank indium zinc sulfide obtained in example 1, 10.2% cobalt tungstate modified indium zinc sulfide semiconductor powder obtained in example 6, 3% cobaltosic oxide modified indium zinc sulfide semiconductor powder obtained in example 9 and 10.2% cobalt tungstate and 3% cobaltosic oxide co-modified indium zinc sulfide semiconductor powder obtained in example 10 are used as corresponding photocatalysts, visible light catalytic decomposition of water to produce hydrogen is performed under the condition that triethanolamine is used as a cavity sacrificial agent in a nitrogen atmosphere, the influence of photocatalytic decomposition of water on the cobalt tungstate and cobaltosic oxide co-modified indium zinc sulfide semiconductor powder is examined (see attached figure 4), and the effect of photocatalytic decomposition of water to produce hydrogen is found to be optimal when the cobalt tungstate and cobaltosic oxide co-modified indium zinc sulfide is used under visible light and the triethanolamine is used as a cavity sacrificial agent.
Application example 5
Cycling experiments of visible light catalytic decomposition water hydrogen production under nitrogen atmosphere and with triethanolamine as a hole sacrificial agent were performed on the blank indium zinc sulfide obtained in example 1, the indium zinc sulfide co-modified with 10.2% cobalt tungstate and 3% cobaltosic oxide obtained in example 8, respectively, and the stability of the indium zinc sulfide co-modified with cobalt tungstate and cobaltosic oxide in the photocatalytic process was examined (see fig. 5). After five cycles of circulation, the hydrogen yield of blank indium zinc sulfide is reduced by 25%, while the hydrogen yield of indium zinc sulfide modified by cobalt tungstate and cobaltosic oxide in the photocatalysis process is reduced by 4%, and the stability of the indium zinc sulfide is obviously improved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (9)
1. A preparation method of indium zinc sulfide photocatalyst with surface modified by cobalt tungstate and cobaltosic oxide is characterized by comprising the following steps:
1) adding cobalt salt serving as a cobalt source precursor into deionized water to prepare a cobalt ion solution;
2) adding tungstate serving as a tungstate ion precursor into deionized water to prepare a tungstate ion solution;
3) adding the tungstate radical ion solution obtained in the step 2) into the cobalt ion solution obtained in the step 1), or adding the cobalt ion solution obtained in the step 1) into the tungstate radical ion solution obtained in the step 2), wherein the molar ratio of tungstate radical ions to cobalt ions is 1-4:1, and stirring for 1-3 hours under the condition of keeping out of the sun to obtain a suspension;
4) adding the suspension obtained in the step 3) into a polytetrafluoroethylene lining stainless steel autoclave, and carrying out heating reaction at the temperature of 150 ℃ and 200 ℃ for 10-15h to obtain cobalt tungstate nanoparticle powder;
5) dispersing the cobalt tungstate nano-particle powder obtained in the step 4) into deionized water by ultrasonic, adding ethylene glycol, and adding zinc salt, indium salt and sulfur-containing compound serving as zinc source, indium source and sulfur source precursors, wherein the molar ratio of the zinc salt, the indium salt and the sulfur-containing compound is (0.4-3.1): (0.6-2.4): 4)
6) Heating the material obtained in the step 5) at 70-90 ℃ for reaction for 1-3h to obtain a precipitate material, and washing and drying to obtain cobalt tungstate modified indium zinc sulfide powder;
7) adding sodium hydroxide into the cobalt ion solution obtained by the same method as the step 1), wherein the molar ratio of cobalt salt to sodium hydroxide is 4-8:1, adding the obtained mixed material into a polytetrafluoroethylene lining stainless steel autoclave, heating and reacting for 5-8h at the temperature of 150-;
8) adding the cobalt tungstate modified indium zinc sulfide powder obtained in the step 6) into an agate mortar, adding ethanol, and then adding the cobaltosic oxide nanoparticle powder obtained in the step 7), wherein the mass ratio of the cobalt tungstate modified indium zinc sulfide powder to the cobaltosic oxide nanoparticle powder is 100: (1-9), grinding to obtain the indium zinc sulfide photocatalyst with the surface jointly modified by cobalt tungstate and cobaltosic oxide.
2. The method for preparing the indium zinc sulfide photocatalyst with the surface jointly modified by the cobalt tungstate and the cobaltosic oxide as claimed in claim 1, wherein the cobalt salt in the step 1) is any one or a mixture of cobalt chloride, cobalt nitrate, cobalt sulfate and cobalt perchlorate.
3. The method for preparing the indium zinc sulfide photocatalyst jointly modified by the cobalt tungstate and the cobaltosic oxide on the surface as claimed in claim 1, wherein the tungstate in the step 2) is any one or a mixture of more of lithium tungstate, sodium tungstate, potassium tungstate and magnesium tungstate.
4. The method for preparing the indium zinc sulfide photocatalyst with the surface jointly modified by cobalt tungstate and cobaltosic oxide as claimed in claim 1, wherein the zinc salt is any one or more of zinc chloride, zinc nitrate, zinc sulfate and zinc perchlorate.
5. The method for preparing the indium zinc sulfide photocatalyst with the surface jointly modified by the cobalt tungstate and the cobaltosic oxide as claimed in claim 1, wherein the indium salt is any one or a mixture of indium chloride, indium nitrate and indium sulfate.
6. The method for preparing the indium zinc sulfide photocatalyst with the surface jointly modified by the cobalt tungstate and the cobaltosic oxide as claimed in claim 1, wherein the sulfur-containing compound is any one or a mixture of sodium sulfide, thioacetamide and thiourea.
7. An indium zinc sulfide photocatalyst with a surface modified by cobaltous tungstate and cobaltosic oxide prepared by any one of the methods in claims 1-6, wherein the loading rate of the cobaltous tungstate on the surface of the indium zinc sulfide powder is 2.6-14.1 wt%, and the loading rate of the cobaltosic oxide on the surface of the indium zinc sulfide powder is 1-8 wt%.
8. Use of the indium zinc sulfide photocatalyst co-modified with surface cobalt tungstate and cobaltosic oxide as claimed in claim 7, wherein the photocatalyst is used for decomposing water to generate hydrogen in the presence of a hole sacrificial agent under visible light.
9. Use according to claim 8, wherein the cavitating sacrificial agent is a mixture of sodium sulphide and sodium sulphite, methanol, lactic acid or triethanolamine.
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