CN116283287B - Quantum sheet anchored bismuth vanadate film, preparation method and application - Google Patents
Quantum sheet anchored bismuth vanadate film, preparation method and application Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 67
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 67
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 104
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 104
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 104
- 229940033123 tannic acid Drugs 0.000 claims abstract description 104
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 104
- 229920002258 tannic acid Polymers 0.000 claims abstract description 104
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000000725 suspension Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 150000003346 selenoethers Chemical class 0.000 claims abstract description 8
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000001699 photocatalysis Effects 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- 238000007146 photocatalysis Methods 0.000 claims abstract description 4
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- 229910004613 CdTe Inorganic materials 0.000 claims description 77
- 239000000084 colloidal system Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 238000002791 soaking Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000001338 self-assembly Methods 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 150000004767 nitrides Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 13
- 239000000969 carrier Substances 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 182
- 239000010409 thin film Substances 0.000 description 57
- 238000004873 anchoring Methods 0.000 description 50
- 239000000243 solution Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 24
- 229910052750 molybdenum Inorganic materials 0.000 description 18
- 238000002156 mixing Methods 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000001075 voltammogram Methods 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 11
- 238000004528 spin coating Methods 0.000 description 11
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 9
- 238000003917 TEM image Methods 0.000 description 9
- FSJSYDFBTIVUFD-XHTSQIMGSA-N (e)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O FSJSYDFBTIVUFD-XHTSQIMGSA-N 0.000 description 7
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 5
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000012430 stability testing Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
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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
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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
- C25B1/50—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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- 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
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/665—Local sintering, e.g. laser sintering
Abstract
The invention belongs to the technical field of photocatalysis and preparation and application of photocatalytic materials, and particularly relates to a quantum-sheet-anchored bismuth vanadate film, a preparation method and application thereof. The bismuth vanadate film comprises a bismuth vanadate film and a quantum sheet layer anchored on the bismuth vanadate film by tannic acid molecules; the quantum sheet layer is prepared by forming coordination bonds between dangling bonds on the surface of the quantum sheet and ortho-phenolic hydroxyl groups in tannic acid molecules; the quantum sheet is prepared by taking an original powder material of sulfide, selenide, telluride and the like of transition metal as a raw material and irradiating the raw material by a laser beam; the quantum sheet layer forms coordination bonds with metal suspension bonds on the surface of the bismuth vanadate film through ortho-phenolic hydroxyl groups in tannic acid molecules, and is anchored on the surface of the bismuth vanadate film. The quantum sheet anchored bismuth vanadate film not only effectively promotes the surface extraction of photo-generated carriers in the bismuth vanadate film, improves the photocurrent density of the film, but also effectively improves the working stability of the bismuth vanadate film.
Description
Technical Field
The invention belongs to the technical field of photocatalysis and preparation and application of photocatalytic materials, and particularly relates to a quantum-sheet-anchored bismuth vanadate film, a preparation method and application thereof.
Background
Photoelectrochemical water splitting hydrogen production technology (PEC) can directly convert solar energy into clean hydrogen, and provides an effective solution for the development and utilization of renewable clean energy. The photoelectrode material directly participates in the processes of photon absorption, photon-generated carrier transmission, photoelectrochemical reaction and the like of PEC reaction, and is the research focus of the technology. Wherein the metal oxide bismuth vanadate (BiVO 4 ) The light-absorbing material has great application potential due to the visible light absorption and the proper band edge position. However, the surface thereof serves as an important place where semiconductor-electrolyte interface (SCLJ) carrier extraction and photoelectrochemical reaction occur, and there is a problem of poor carrier surface extraction ability due to carrier recombination centers formed by surface defects. Meanwhile, poor extraction capacity of the carrier surface easily causes accumulation of the carrier on the film surface, further causes photo-corrosion of the film surface and seriously affects the working stability of the film. Therefore, how to solve BiVO 4 The problem of carrier extraction on the surface of the film becomes a very key problem of synchronous improvement of photoelectrochemical property and stability.
Forming stable oxides (e.g. NiO, co 3 O 4 、TiO 2 、SnO 2 、Rh:SrTiO 3 Etc.) surface heterojunction is a common method currently used to facilitate the surface extraction of carriers. However, most oxides are poor in conductivity and have limited carrier extraction from the thin film surface. Recently, biVO has been attempted to load non-metallic elemental materials (such as carbon dots, black phosphorus, etc.) with high conductivity and low dimensions 4 The surface extraction of the film carrier is improved. However, it can be used to improve BiVO at present 4 The high-conductivity low-dimensional material system for extracting the carriers on the surface of the film is very limited. In addition, the loading of the high-conductivity low-dimensional non-metallic simple substance material is realized only through simple physical deposition, so that the stability of the material is poor. Therefore, development and loading of high-conductivity low-dimensional materials with simple process and rich variety are used for improving BiVO 4 Carrier surface extraction, development of high photoelectrochemical property and high stability BiVO 4 Photoelectrodes are of importanceMeaning.
Disclosure of Invention
In view of the above-mentioned shortcomings of the background art, the present invention is directed to BiVO 4 The problem of poor extraction capability of the surface of a film carrier is solved, and a BiVO anchored by a quantum sheet is provided 4 Thin films, i.e. BiVO prepared in conventional manner 4 The quantum sheet is anchored on the film, and the anchoring of the quantum sheet can obviously improve BiVO 4 The carrier surface extraction efficiency, photoelectrochemical property and stability of the film; wherein the quantum sheet is prepared by liquid phase pulse laser irradiation technology, the quantum sheet is modified by self-assembly of tannic acid, and the tannic acid modified quantum sheet is anchored to BiVO by self-assembly 4 The surface of the film is anchored by a quantum sheet to obtain BiVO 4 A film. The method is simple to operate and has strong universality.
The first object of the present invention is to provide a BiVO with quantum sheet anchoring 4 The film comprises a bismuth vanadate film and a quantum sheet anchored on the bismuth vanadate film by tannic acid molecules;
the quantum sheet layer is prepared by forming coordination bonds between dangling bonds on the surface of the quantum sheet and ortho-phenolic hydroxyl groups in tannic acid molecules;
the quantum sheet is prepared by taking an original powder material of sulfide, selenide, telluride, carbide or nitride of transition metal as a raw material and irradiating the raw material by a laser beam;
the quantum sheet layer forms coordination bonds with metal dangling bonds on the surface of the bismuth vanadate film through ortho-phenolic hydroxyl groups in tannic acid molecules, and is anchored on the surface of the bismuth vanadate film.
Preferably, the sulfide is selected from WS 2 Or MoS 2 The selenide is selected from Sb 2 Se 3 、WSe 2 Or CdSe, the telluride is selected from CdTe, snTe or WTE 2 The carbide is selected from Mo 2 C or WC, the nitride being selected from W 2 N or MoN.
Preferably, the quantum sheet has a diameter of 5-20 nm and a thickness of 0.5-2 nm.
Preferably, the anchoring thickness of the quantum sheet layer is 5-20 nm.
A second object of the present invention is to provide BiVO with the above quantum sheet anchoring 4 The preparation method of the film comprises the following steps:
s1, preparation of quantum sheets: dispersing the original powder material of sulfide, selenide, telluride, carbide or nitride of transition metal in a liquid phase medium to obtain suspension of powder; under the anaerobic environment and the assistance of ultrasound, placing the suspension of the powder under a laser beam for irradiation to obtain a quantum sheet colloid solution;
s2, molecular modification of the quantum sheet: adding tannic acid into the quantum sheet colloid solution, and obtaining the tannic acid modified quantum sheet colloid solution through self-assembly;
S3、BiVO 4 preparation of the film: biVO preparation based on metal organic thermal decomposition method 4 Precursor solution, film making and sintering to obtain BiVO 4 A film;
s4, biVO anchored by quantum sheets 4 Preparation of the film: biVO prepared by S3 4 Soaking the film in the tannic acid modified quantum sheet colloid solution prepared in S2, and preparing the BiVO anchored to the quantum sheet through self-assembly 4 A film.
Preferably, in S1, the liquid medium is one or more of water, ethanol, acetone, dimethyl sulfoxide or ethyl acetate, and the suspension concentration of the powder is 0.01-0.5 mg/mL.
Preferably, in S1, the laser beam adopts unfocused pulse laser beam, the pulse frequency of the unfocused pulse laser beam is 10-30 Hz, the output wavelength is one of 266nm, 355nm, 532nm or 1064nm, the diameter of the output light spot is 5-20 mm, and the irradiation energy of the laser is 100-2000 mJ/cm 2 The irradiation time is 5-60 min.
Preferably, in S2, the concentration of tannic acid is 0.1-10 mg/ml, and the self-assembly is kept stand for 1-24 h.
Preferably, in S4, the self-assembly is to soak the bismuth vanadate thin film in the tannic acid modified quantum sheet colloid solution for 6-48 hours.
A third object of the present invention is to provide the aboveQuantum sheet anchored BiVO 4 The application of the film in photocatalysis or photoelectrocatalysis.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the quantum sheet anchored bismuth vanadate film, dangling bonds on the surface of the quantum sheet and orthophenolic hydroxyl groups in tannic acid molecules form coordination bonds, so that the tannic acid modified quantum sheet is prepared; the tannic acid modified quantum sheet is soaked only at normal temperature and normal pressure, and can form coordination bonds through orthophenolic hydroxyl groups in tannic acid molecules and dangling bonds on the surface of the bismuth vanadate film, so that the quantum sheet is anchored on the surface of the bismuth vanadate film by using the tannic acid molecules. The whole preparation process has simple process, convenient operation and obvious effect.
(2) The quantum sheet anchored BiVO prepared by the invention 4 The built-in electric field is introduced to the surface of the film, so that the surface extraction of photo-generated carriers in the bismuth vanadate film is effectively promoted, the photocurrent density of the film is improved, and the working stability of the bismuth vanadate film is effectively improved. Proved by experiments, the photoelectrode has high light current density and good stability, and is 1.23V RHE When the photocurrent density is from 1.97mA/cm 2 Increase to 4.09mA/cm 2 The stability is increased from less than 30h to 80h, thus greatly improving BiVO 4 The photocurrent density and stability of the film photoelectrode have very high practical application prospect.
(3) The invention adopts a pulse laser irradiation method, and utilizes an original powder material which is easy to purchase or synthesize, so that a plurality of quantum sheet materials which are difficult to synthesize by the traditional method, have a diameter of less than 10nm and a thickness of about 1nm can be directly obtained in one step.
Drawings
FIG. 1 is a schematic diagram of the structure of a quantum sheet anchored bismuth vanadate thin film provided by the invention;
FIG. 2 is a diagram showing Sb before pulse laser irradiation in example 1 2 Se 3 Original powder scanning electron microscope photo (a) and Sb after pulse laser irradiation 2 Se 3 A quantum sheet transmission electron micrograph (b) and an atomic force microscope photograph (c);
FIG. 3 is a chart showing modification of Sb with tannic acid in example 1 2 Se 3 Infrared spectrograms of the front and the back of the quantum sheet;
FIG. 4 is a chart showing the modification of Sb with tannic acid in example 1 2 Se 3 Quantum sheet in Mo/BiVO 4 Scanning electron microscope photograph and contact angle photograph before and after anchoring the surface of the film, wherein a is Mo: biVO 4 Scanning electron microscope photograph of film, b is Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 Scanning electron microscope photograph of film, c is Mo: biVO 4 Contact angle photograph of film, d is Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 A photograph of the contact angle of the film;
FIG. 5 is a graph of Mo-BiVO in comparative example 4 Thin film and Sb in example 1 2 Se 3 Linear voltammogram of quantum sheet anchored bismuth vanadate thin films;
FIG. 6 is a graph of Mo-BiVO in comparative example 4 Thin film and Sb in example 1 2 Se 3 Photocurrent density-time curve of quantum sheet anchored bismuth vanadate thin film;
FIG. 7 is a graph showing Sb after pulse laser irradiation in example 2 2 Se 3 Quantum sheet transmission electron microscope pictures;
FIG. 8 is a graph of Mo-BiVO in comparative example 4 Thin film and Sb in example 2 2 Se 3 Linear voltammogram of quantum sheet anchored bismuth vanadate thin films;
FIG. 9 is a graph showing Sb after pulse laser irradiation in example 3 2 Se 3 Quantum sheet transmission electron microscope pictures;
FIG. 10 is a graph of Mo-BiVO in comparative example 4 Thin film and Sb in example 3 2 Se 3 Linear voltammogram of quantum sheet anchored bismuth vanadate thin films;
FIG. 11 is a photograph of original CdTe powder before pulse laser irradiation (a) and a photograph of CdTe quantum sheet after pulse laser irradiation (b) and a photograph of atomic force microscope (c) in example 11;
FIG. 12 is an infrared spectrum of the front and rear of the tannic acid modified CdTe quantum sheet in example 11;
FIG. 13 shows the result of the tannic acid modification of CdTe quantum sheet in the embodiment 11 in the form of Mo: biVO 4 Scanning electron microscope photograph and contact angle photograph before and after anchoring the surface of the film, wherein a is Mo: biVO 4 Scanning electron microscope photograph of film, b is CdTe quantum sheet anchored Mo: biVO 4 Scanning electron microscope photograph of film, c is Mo: biVO 4 Contact angle photograph of film, d is CdTe quantum sheet anchored Mo: biVO 4 A photograph of the contact angle of the film;
FIG. 14 shows the ratio of Mo to BiVO in the comparative example 4 Linear voltammograms of the films and CdTe quantum sheet anchored bismuth vanadate films in example 11;
FIG. 15 shows the ratio of Mo to BiVO in the comparative example 4 Photocurrent density versus time curves for the films and CdTe quantum sheet-anchored bismuth vanadate films in example 11;
FIG. 16 is a transmission electron micrograph of a CdTe quantum sheet after pulsed laser irradiation in example 12;
FIG. 17 is a graph of Mo-BiVO in comparative example 4 Linear voltammograms of the films and CdTe quantum sheet anchored bismuth vanadate films in example 12;
FIG. 18 is a transmission electron micrograph of a CdTe quantum plate after pulsed laser irradiation in example 13;
FIG. 19 is a graph of Mo BiVO in comparative example 4 Linear voltammograms of the films and CdTe quantum sheet anchored bismuth vanadate films in example 13;
FIG. 20 is Sb in example 16 2 Se 3 Quantum sheet anchored bismuth vanadate thin film and comparative Mo BiVO 4 Long-term stability testing of the films;
FIG. 21 shows the CdTe quantum sheet-anchored bismuth vanadate thin film of example 17 and the Mo: biVO of comparative example 4 Long-term stability testing of the films;
reference numerals illustrate:
1. transparent glass; 2. a fluorine doped tin dioxide layer; 3. bismuth vanadate film (BiVO) 4 ) A layer; 4. a quantum sheet; 5. quantum sheets.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to the specific examples and the accompanying drawings, but the examples are not intended to be limiting. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a BiVO anchored by a quantum sheet 4 Thin film comprising BiVO 4 Thin film, tannic acid molecule for anchoring quantum sheet, and anchoring on BiVO using tannic acid molecule 4 Quantum sheets on the film. The quantum sheet is prepared by taking an original powder material of sulfide, selenide or telluride of transition metal and the like as a raw material through pulse laser irradiation; the quantum sheet forms coordination bonds with ortho-phenolic hydroxyl groups in tannic acid molecules through surface dangling bonds; the quantum sheet layer passes through tannic acid and BiVO 4 The metal suspension bond on the surface of the film forms a coordination bond and is anchored on the BiVO 4 The surface of the film.
BiVO used in the present invention 4 The film is BiVO which is undoped, molybdenum doped or tungsten doped 4 BiVO in one of the films 4 The film is prepared by one of a drop coating method, a spray coating method, a pulling method or a spin coating method. For the purpose of detailed description, biVO in the following examples 4 The film is made of Mo and BiVO 4 And is prepared by spin coating.
The experimental methods in the embodiments of the invention are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
Example 1
Sb (Sb) 2 Se 3 Quantum sheet anchored Mo, biVO 4 As shown in FIG. 1, the thin film comprises Mo, biVO 4 Thin film for anchoring Sb 2 Se 3 Tannic acid molecules of quantum sheet and anchoring of tannic acid molecules to Mo/BiVO 4 Sb on film 2 Se 3 Quantum sheets. Sb (Sb) 2 Se 3 Quantum sheet layer on Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The thickness of the film surface was 10nm.
The Sb is as follows 2 Se 3 Quantum sheet anchored Mo, biVO 4 The specific preparation method of the film comprises the following steps:
s1, 1mg Sb 2 Se 3 Dispersing the powder in 10ml of acetone, and performing ultrasonic treatment for 10min to obtain suspension; placing the suspension in an anaerobic environment, under the assistance of ultrasound, using pulse frequency of 10Hz, output wavelength of 1064nm, output spot diameter of 10mm, and single pulse energy of 900mJ/cm 2 Is irradiated by unfocused pulse laser for 10min to prepare Sb with concentration of 0.1mg/ml, diameter of about 10nm and thickness of about 1nm 2 Se 3 A quantum sheet;
s2, dissolving 0.5mg of tannic acid in the quantum sheet colloid solution prepared in the step S1, and standing for 12 hours to obtain the tannic acid modified Sb 2 Se 3 A quantum sheet;
s3, preparing Mo (BiVO) by adopting a spin coating method 4 Film: bi (NO) 3 ) 3 ·5H 2 O and MoO 2 (acac) 2 Adding into a mixed solution composed of 3ml of ethylene glycol and 4ml of acetic acid, and uniformly mixing; further adding VO (acac) 2 And mixing uniformly; finally, adding 0.5g of block copolymer F-108 (pore-forming agent) into the mixed solution, and uniformly mixing to obtain the Mo/BiVO with the concentration of 0.3mol/L 4 A precursor solution; wherein Mo is BiVO 4 Bi (NO 3) in the precursor solution 3 ·5H 2 The concentration of O is 0.3mol/L, moO 2 (acac) 2 The mass concentration is 2%, VO (acac) 2 The concentration of (2) is 0.6mol/L; mo: biVO 4 Spin-coating the precursor solution onto FTO glass, heat-treating at 200deg.C for 15min, and further heat-treating at 500deg.C in a muffle furnace for 1 hr to obtain Mo/BiVO with film thickness of about 200nm 4 A film;
s4, preparing Mo (BiVO) from S3 4 Soaking the film in S2 to obtain tannic acid modified Sb 2 Se 3 Soaking in quantum sheet colloid solution for 16 hr to obtain Sb 2 Se 3 Sb with a quantum sheet thickness of about 10nm 2 Se 3 Quantum sheet anchored Mo, biVO 4 A film.
Example 2
Sb (Sb) 2 Se 3 Quantum sheet anchored Mo, biVO 4 Thin film comprising Mo, biVO 4 Thin film for anchoring Sb 2 Se 3 Tannic acid molecules of quantum sheet and anchoring of tannic acid molecules to Mo/BiVO 4 Sb on film 2 Se 3 Quantum sheets. Sb (Sb) 2 Se 3 Quantum sheet layer on Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The thickness of the film surface was 10nm.
Specific preparation method and example 1 were different in that 2.5mg of Sb in S1 of example 2 2 Se 3 Dispersing the powder in a mixed solvent consisting of 5ml of water and 5ml of ethanol, and carrying out ultrasonic treatment for 10min to obtain a suspension; placing the suspension in an anaerobic environment, under the assistance of ultrasound, using pulse frequency of 10Hz, output wavelength of 1064nm, output spot diameter of 10mm, and single pulse energy of 900mJ/cm 2 Is irradiated by unfocused pulse laser for 10min to prepare Sb with concentration of 0.1mg/ml, diameter of about 10nm and thickness of about 1nm 2 Se 3 A quantum sheet; the amount of tannic acid added in S2 of example 2 was 1.5mg, and the standing time was 8 hours; the soaking time in S4 of example 2 was 24h.
Example 3
Sb (Sb) 2 Se 3 Quantum sheet anchored Mo, biVO 4 Thin film comprising Mo, biVO 4 Thin film for anchoring Sb 2 Se 3 Tannic acid molecules of quantum sheet and anchoring of tannic acid molecules to Mo/BiVO 4 Sb on film 2 Se 3 Quantum sheets. Sb (Sb) 2 Se 3 Quantum sheet layer on Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The thickness of the film surface was 10nm.
The specific preparation method is different from example 1 in that: 5mg of Sb in step 1 of example 3 2 Se 3 Dispersing the powder in 10ml of ethyl acetate to obtain a mixed solution; in S2 of example 3, the addition amount of tannic acid was 2.5mg and the standing time was 10 hours; the soaking time in S4 of example 3 was 18h.
Example 4
Sb (Sb) 2 Se 3 Quantum sheet anchored Mo, biVO 4 Thin film comprising Mo, biVO 4 Thin film for anchoring Sb 2 Se 3 Tannic acid molecules of quantum sheet and anchoring of tannic acid molecules to Mo/BiVO 4 Sb on film 2 Se 3 Quantum sheets. Sb (Sb) 2 Se 3 Quantum sheet layer on Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The thickness of the film surface was 10nm.
The specific preparation method is different from example 1 in that S1 is different, specifically: will 0.1mg Sb 2 Se 3 Dispersing the powder in 10ml of acetone, and performing ultrasonic treatment for 10min to obtain suspension; the suspension is placed in an anhydrous and anaerobic environment, under the assistance of ultrasound, the pulse frequency is 10Hz, the output wavelength is 266nm, the diameter of an output light spot is 10mm, and the single pulse energy is 900mJ/cm 2 Is irradiated by unfocused pulse laser for 10min to prepare Sb with concentration of 0.1mg/ml, diameter of about 10nm and thickness of about 1nm 2 Se 3 Quantum sheets.
Example 5
Sb (Sb) 2 Se 3 Quantum sheet anchored Mo, biVO 4 Thin film comprising Mo, biVO 4 Thin film for anchoring Sb 2 Se 3 Tannic acid molecules of quantum sheet and anchoring of tannic acid molecules to Mo/BiVO 4 Sb on film 2 Se 3 Quantum sheets. Sb (Sb) 2 Se 3 Quantum sheet layer on Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The thickness of the film surface was 10nm.
The specific preparation method and example 1 differ in that the laser irradiation parameters in S1 are different, specifically: the pulse frequency is 10Hz, the output wavelength is 1064nm, the diameter of the output light spot is 20mm, and the single pulse energy is 100mJ/cm 2 Is irradiated by unfocused pulse laser for 60min to prepare Sb with the concentration of 0.1mg/ml, the diameter of about 10nm and the thickness of about 1nm 2 Se 3 Quantum sheets.
Example 6
Sb (Sb) 2 Se 3 Quantum sheet anchored Mo, biVO 4 Thin film comprising Mo, biVO 4 Thin film for anchoring Sb 2 Se 3 Tannic acid molecules of quantum sheet and anchoring of tannic acid molecules to Mo/BiVO 4 Sb on film 2 Se 3 Quantum sheets. Sb (Sb) 2 Se 3 Quantum sheet layer on Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The thickness of the film surface was 10nm.
The specific preparation method and example 1 differ in that the laser irradiation parameters in S1 are different, specifically: the pulse frequency is 10Hz, the output wavelength is 1064nm, the diameter of the output light spot is 5mm, and the single pulse energy is 2000mJ/cm 2 Is irradiated by unfocused pulse laser for 5min to prepare Sb with concentration of 0.1mg/ml, diameter of about 10nm and thickness of about 1nm 2 Se 3 Quantum sheets.
Example 7
Sb (Sb) 2 Se 3 Quantum sheet anchored Mo, biVO 4 Thin film comprising Mo, biVO 4 Thin film for anchoring Sb 2 Se 3 Tannic acid molecules of quantum sheet and anchoring of tannic acid molecules to Mo/BiVO 4 Sb on film 2 Se 3 Quantum sheets. Sb (Sb) 2 Se 3 Quantum sheet layer on Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The thickness of the film surface was 10nm.
The specific preparation method is different from example 1 in that S2 is different, specifically: dissolving 0.5mg of tannic acid in the quantum sheet colloid solution prepared in the step S1, and standing for 24 hours to obtain the tannic acid modified Sb 2 Se 3 Quantum sheets.
Example 8
Sb (Sb) 2 Se 3 Quantum sheet anchored Mo, biVO 4 Thin film comprising Mo, biVO 4 Thin film for anchoring Sb 2 Se 3 Tannic acid molecules of quantum sheet and anchoring of tannic acid molecules to Mo/BiVO 4 Sb on film 2 Se 3 Quantum sheets. Sb (Sb) 2 Se 3 Quantum sheet layer on Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The thickness of the film surface was 10nm.
Specific preparation method and example 1The S2 is different, and specifically comprises the following steps: dissolving 0.5mg of tannic acid in the quantum sheet colloid solution prepared in the step S1, and standing for 1h to obtain the tannic acid modified Sb 2 Se 3 Quantum sheets.
Example 9
Sb (Sb) 2 Se 3 Quantum sheet anchored Mo, biVO 4 Thin film comprising Mo, biVO 4 Thin film for anchoring Sb 2 Se 3 Tannic acid molecules of quantum sheet and anchoring of tannic acid molecules to Mo/BiVO 4 Sb on film 2 Se 3 Quantum sheets. Sb (Sb) 2 Se 3 Quantum sheet layer on Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The thickness of the film surface was 10nm.
The specific preparation method is different from example 1 in that S4 is different, specifically: mo from S3 BiVO 4 Soaking the film in S2 to obtain tannic acid modified Sb 2 Se 3 Soaking in quantum sheet colloid solution for 6 hr to obtain Sb 2 Se 3 Sb with a quantum sheet thickness of about 10nm 2 Se 3 Quantum sheet anchored Mo, biVO 4 A film.
Example 10
Sb (Sb) 2 Se 3 Quantum sheet anchored Mo, biVO 4 Thin film comprising Mo, biVO 4 Thin film for anchoring Sb 2 Se 3 Tannic acid molecules of quantum sheet and anchoring of tannic acid molecules to Mo/BiVO 4 Sb on film 2 Se 3 Quantum sheets. Sb (Sb) 2 Se 3 Quantum sheet layer on Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The thickness of the film surface was 10nm.
The specific preparation method is different from example 1 in that S4 is different, specifically: mo from S3 BiVO 4 Soaking the film in S2 to obtain tannic acid modified Sb 2 Se 3 Soaking in quantum sheet colloid solution for 48 hr to obtain Sb 2 Se 3 Sb with a quantum sheet thickness of about 10nm 2 Se 3 Quantum sheet anchored Mo, biVO 4 A film.
Example 11
CdTe quantum sheet anchored Mo BiVO 4 Thin film comprising Mo, biVO 4 Film, tannic acid molecule for anchoring CdTe quantum sheet and anchoring on Mo/BiVO using tannic acid molecule 4 CdTe quantum sheets on the film. Mo of CdTe quantum sheet anchored in CdTe quantum sheet, biVO 4 The thickness of the film surface was 15nm.
The preparation method comprises the following steps:
s1, dispersing 1mg of CdTe powder in 10ml of acetone, and carrying out ultrasonic treatment for 10min to obtain a suspension; the suspension is placed in an anhydrous and anaerobic environment, under the assistance of ultrasound, the pulse frequency is 30Hz, the output wavelength is 1064nm, the diameter of an output light spot is 8mm, and the single pulse energy is 1500mJ/cm 2 The non-focusing pulse laser of (2) is irradiated for 7min to prepare CdTe quantum plates with the concentration of 0.15mg/ml, the diameter of about 8nm and the thickness of about 1 nm;
s2, dissolving 0.8mg of tannic acid in the quantum sheet colloid solution prepared in the step S1, and standing for 12 hours to obtain a tannic acid modified CdTe quantum sheet;
s3, preparing Mo (BiVO) by adopting a spin coating method 4 Film: the preparation method is the same as in example 1;
s4, preparing Mo (BiVO) from S3 4 Soaking the film in the colloid solution of the CdTe quantum sheet modified by tannic acid prepared by S2 for 16h at normal temperature and normal pressure to obtain anchored Mo of CdTe quantum sheet with the thickness of CdTe quantum sheet of about 15nm, wherein BiVO is a crystal structure of the CdTe quantum sheet 4 A film.
Example 12
CdTe quantum sheet anchored Mo BiVO 4 Thin film comprising Mo, biVO 4 Film, tannic acid molecule for anchoring CdTe quantum sheet and anchoring on Mo/BiVO using tannic acid molecule 4 CdTe quantum sheets on the film. Mo of CdTe quantum sheet anchored in CdTe quantum sheet, biVO 4 The thickness of the film surface was 15nm.
The specific preparation method is different from example 4 in that 2.5mg of CdTe powder in S1 of example 5 is dispersed in 10ml of dimethyl sulfoxide to obtain a mixed solution; in S2 of example 5, the addition amount of tannic acid was 1.5mg and the standing time was 10 hours; the soaking time in S4 of example 5 was 18h.
Example 13
CdTe quantum sheet anchored Mo BiVO 4 Thin film comprising Mo, biVO 4 Film, tannic acid molecule for anchoring CdTe quantum sheet and anchoring on Mo/BiVO using tannic acid molecule 4 CdTe quantum sheets on the film. Mo of CdTe quantum sheet anchored in CdTe quantum sheet, biVO 4 The thickness of the film surface was 15nm.
The specific preparation method is different from example 4 in that 7.5mg of CdTe powder in S1 of example 5 is dispersed in a mixed solvent of 5ml of dimethyl sulfoxide, 5ml of ethyl acetate and 5ml of acetone to obtain a mixed solution; in S2 of example 5, the addition amount of tannic acid was 3mg and the standing time was 15 hours; the soaking time in S4 of example 5 was 20h.
Example 14
Mo (molybdenum) 2 Mo/BiVO anchored by C quantum sheet 4 Thin film comprising Mo, biVO 4 Film for anchoring Mo 2 Tannic acid molecule of C quantum sheet and anchoring of tannic acid molecule to Mo/BiVO 4 Mo on film 2 And C quantum sheets. Mo (Mo) 2 C quantum sheet layer in Mo 2 Mo/BiVO anchored by C quantum sheet 4 The thickness of the film surface was 20nm.
The Mo is 2 Mo/BiVO anchored by C quantum sheet 4 The specific preparation method of the film comprises the following steps:
s1, 1mg Mo 2 Dispersing the powder C in 10ml of acetone, and performing ultrasonic treatment for 10min to obtain a suspension; placing the suspension in an anaerobic environment, under the assistance of ultrasound, using pulse frequency of 10Hz, output wavelength of 1064nm, output spot diameter of 10mm, and single pulse energy of 900mJ/cm 2 Is irradiated by unfocused pulse laser for 10min to prepare Mo with the concentration of 0.12mg/ml, the diameter of about 20nm and the thickness of about 0.5nm 2 C quantum sheets;
s2, dissolving 0.5mg of tannic acid in the quantum sheet colloid solution prepared in the step S1, and standing for 12 hours to obtain tannic acid modified Mo 2 C quantum sheets;
s3, preparing Mo (BiVO) by adopting a spin coating method 4 Film:bi (NO) 3 ) 3 ·5H 2 O and MoO 2 (acac) 2 Adding into a mixed solution composed of 3ml of ethylene glycol and 4ml of acetic acid, and uniformly mixing; further adding VO (acac) 2 And mixing uniformly; finally, adding 0.5g of block copolymer F-108 (pore-forming agent) into the mixed solution, and uniformly mixing to obtain the Mo/BiVO with the concentration of 0.3mol/L 4 A precursor solution; wherein Mo is BiVO 4 Bi (NO) in precursor solution 3 ) 3 ·5H 2 The concentration of O is 0.3mol/L, moO 2 (acac) 2 The mass concentration is 2%, VO (acac) 2 The concentration of (2) is 0.6mol/L; mo: biVO 4 Spin-coating the precursor solution onto FTO glass, heat-treating at 200deg.C for 15min, and further heat-treating at 500deg.C in a muffle furnace for 1 hr to obtain Mo/BiVO with film thickness of about 200nm 4 A film;
s4, preparing Mo (BiVO) from S3 4 Soaking the film in S2 to obtain tannic acid modified Mo 2 Soaking in C quantum sheet colloid solution for 16 hr to obtain Mo 2 Mo with thickness of C quantum sheet layer about 20nm 2 Mo/BiVO anchored by C quantum sheet 4 A film.
Example 15
W (W) 2 N quantum sheet anchored Mo BiVO 4 Thin film comprising Mo, biVO 4 Film for anchoring W 2 Tannic acid molecule of N quantum sheet and anchoring of tannic acid molecule to Mo/BiVO 4 W on film 2 N quantum sheets. W (W) 2 N quantum sheet layer is at W 2 N quantum sheet anchored Mo BiVO 4 The thickness of the film surface was 5nm.
The W is 2 N quantum sheet anchored Mo BiVO 4 The specific preparation method of the film comprises the following steps:
s1, 1mg W 2 Dispersing N powder in 10ml acetone, and performing ultrasonic treatment for 10min to obtain suspension; placing the suspension in an anaerobic environment, under the assistance of ultrasound, using pulse frequency of 10Hz, output wavelength of 1064nm, output spot diameter of 10mm, and single pulse energy of 900mJ/cm 2 Is irradiated by unfocused pulse laser for 10min to obtain a concentration of 0.12mg/ml, a diameter of about 5nm, and a thicknessW of about 0.5nm 2 An N quantum sheet;
s2, dissolving 0.5mg of tannic acid in the quantum sheet colloid solution prepared in the step S1, and standing for 12 hours to obtain tannic acid modified W 2 An N quantum sheet;
s3, preparing Mo (BiVO) by adopting a spin coating method 4 Film: bi (NO) 3 ) 3 ·5H 2 O and MoO 2 (acac) 2 Adding into a mixed solution composed of 3ml of ethylene glycol and 4ml of acetic acid, and uniformly mixing; further adding VO (acac) 2 And mixing uniformly; finally, adding 0.5g of block copolymer F-108 (pore-forming agent) into the mixed solution, and uniformly mixing to obtain the Mo/BiVO with the concentration of 0.3mol/L 4 A precursor solution; wherein Mo is BiVO 4 Bi (NO 3) in the precursor solution 3 ·5H 2 The concentration of O is 0.3mol/L, moO 2 (acac) 2 The mass concentration is 2%, VO (acac) 2 The concentration of (2) is 0.6mol/L; mo: biVO 4 Spin-coating the precursor solution onto FTO glass, heat-treating at 200deg.C for 15min, and further heat-treating at 500deg.C in a muffle furnace for 1 hr to obtain Mo/BiVO with film thickness of about 200nm 4 A film;
s4, preparing Mo (BiVO) from S3 4 Soaking the film in S2 at normal temperature and pressure to obtain tannic acid modified W 2 Soaking in N quantum sheet colloid solution for 16 hr to obtain W 2 W with a thickness of about 20nm 2 N quantum sheet anchored Mo BiVO 4 A film.
Comparative example
Preparation of Mo/BiVO by spin coating 4 Film: first, 0.3mol/L Bi (NO) 3 ) 3 ·5H 2 O and MoO with mass concentration of 2% 2 (acac) 2 Adding into a mixed solution composed of 3ml of ethylene glycol and 4ml of acetic acid, and uniformly mixing; further adding 0.6mol/L VO (acac) 2 And mixing uniformly; finally, adding 0.5g of block copolymer F-108 (pore-forming agent) into the mixed solution, and uniformly mixing to obtain the Mo/BiVO with the concentration of 0.3mol/L 4 A precursor solution; mo: biVO 4 Spin-coating the precursor solution onto FTO glass, heat-treating at 200deg.C for 15min, and further heat-treating at 500deg.C in muffle furnace for 1 hr to obtain M film with thickness of about 200nmo:BiVO 4 A film.
Since the properties of the quantum sheet-anchored bismuth vanadate thin films prepared in examples 1 to 15 are substantially the same, the effect of the properties of the thin films will be described below by taking examples 1 to 3 and examples 11 to 13 as examples.
BiVO of Mo provided in examples 1-3, examples 11-13 and comparative example 4 KH of 1mol/L film 2 PO 4 Photocurrent density was measured in solution. The specific results are shown in Table 1.
TABLE 1 photocurrent Density
As can be seen from Table 1, the photocurrent densities of the films obtained in examples 1 to 3 and examples 11 to 13 were higher than those of the films of the comparative examples. The photocurrent densities of examples 1-3 and examples 11-13 were increased by 89.8%, 58.4%, 7.1%, 107.6%, 82.7% and 42.6%, respectively, as compared to the comparative examples.
To illustrate the effect of the present invention, the present invention also characterizes and tests the properties of the raw materials and the prepared products in examples 1 to 3, examples 11 to 13 and comparative examples, and the specific results are shown in fig. 2 to 19.
FIG. 2 is a diagram showing Sb before pulse laser irradiation in example 1 2 Se 3 Original powder scanning electron microscope photo (a) and Sb after pulse laser irradiation 2 Se 3 Quantum sheet transmission electron micrographs (b) and atomic force microscope micrographs (c). As can be seen from a, sb 2 Se 3 The original powder is distributed in a layered structure, and the grain diameter is more than 20 mu m; as can be seen from b, after pulsed laser irradiation, sb 2 Se 3 The quantum sheets are distributed in a monodispersed way, and the size is smaller than 10nm; as can be seen from c, sb 2 Se 3 The quantum sheet was about 1nm.
FIG. 3 is a sheet of example 1Niacin modified Sb 2 Se 3 Infrared spectrograms before and after the quantum sheet. As can be seen from the graph, the H-O stretching vibration peak in the raw tannic acid is 3317cm -1 Nearby, and tannic acid modifies Sb 2 Se 3 After quantum sheet, H-O stretching vibration peak shifts to 3435cm toward larger wave number -1 Nearby, illustrate the hydroxyl functionality and Sb 2 Se 3 The metal hanging bond on the surface is effectively coordinated to form the Sb anchored by tannic acid 2 Se 3 Quantum sheets.
FIG. 4 is a chart showing the modification of Sb with tannic acid in example 1 2 Se 3 Quantum sheet in Mo/BiVO 4 Scanning electron microscope photograph and contact angle photograph before and after anchoring the surface of the film, wherein a is Mo: biVO 4 Scanning electron microscope photograph of film, b is Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 Scanning electron microscope photograph of film, c is Mo: biVO 4 Contact angle photograph of film, d is Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 Contact angle photograph of the film. As can be seen from the figure, sb 2 Se 3 The morphology of the film is worm-shaped porous structure before and after the quantum sheet is anchored, the morphology is similar, but Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The film has dispersed grains with grain size smaller than 10nm and anchored to Mo/BiVO 4 Sb on the surface of the film 2 Se 3 Quantum sheets. And the contact angle of the film is from Sb 2 Se 3 The 48.1 DEG of the quantum sheet before anchoring is reduced to Sb 2 Se 3 18℃after quantum sheet anchoring, sb is explained in view of good hydrophilicity of tannic acid 2 Se 3 The quantum sheet is effectively anchored in Mo BiVO 4 The surface of the film.
FIG. 5 is a graph of Mo-BiVO in comparative example 4 Thin film and Sb in example 1 2 Se 3 Linear voltammogram of quantum sheet anchored bismuth vanadate thin films. As can be seen from the figure, sb 2 Se 3 After the quantum sheet is anchored, sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The photocurrent density of the film is obviously improved at 1.23V RHE The photocurrent density was improved by about 89.8%.
FIG. 6 is a graph of Mo-BiVO in comparative example 4 Thin film and Sb in example 1 2 Se 3 Photocurrent density versus time curve for quantum sheet anchored bismuth vanadate thin films. As can be seen from the figure, sb 2 Se 3 After the quantum sheet is anchored, sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The stability of the film is obviously enhanced, and the photocurrent density can be maintained to be 72.6% of the initial current density after 60min.
FIG. 7 is a graph showing Sb after pulse laser irradiation in example 2 2 Se 3 Quantum sheet transmission electron micrographs. As can be seen from the figure, after pulse laser irradiation, sb 2 Se 3 The quantum sheets are distributed in a monodispersed mode, and the size of the quantum sheets is smaller than 10nm.
FIG. 8 is a graph of Mo-BiVO in comparative example 4 Thin film and Sb in example 2 2 Se 3 Linear voltammogram of quantum sheet anchored bismuth vanadate thin films. As can be seen from the figure, sb 2 Se 3 After the quantum sheet is anchored, sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The photocurrent density of the film is increased by 1.23V RHE The photocurrent density was improved by about 58.4%.
FIG. 9 is a graph showing Sb after pulse laser irradiation in example 3 2 Se 3 Quantum sheet transmission electron micrographs. As can be seen from the figure, after pulse laser irradiation, sb 2 Se 3 The quantum sheets are in monodisperse distribution and have a size of about 20nm.
FIG. 10 is a graph of Mo-BiVO in comparative example 4 Thin film and Sb in example 3 2 Se 3 Linear voltammogram of quantum sheet anchored bismuth vanadate thin films. As can be seen from the figure, sb 2 Se 3 After the quantum sheet is anchored, sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The photocurrent density of the film is slightly improved at 1.23V RHE The photocurrent density was improved by about 7.1%.
Fig. 11 is a scanning electron micrograph (a) of original CdTe powder before pulse laser irradiation and a transmission electron micrograph (b) and an atomic force micrograph (c) of CdTe quantum sheet after pulse laser irradiation in example 11. As can be seen from a, the particle size of CdTe original powder is larger than 5 μm; b, after pulse laser irradiation, cdTe quantum plates are in monodisperse distribution, and the size is smaller than 10nm; as can be seen from c, the CdTe quantum plate is about 1nm.
Fig. 12 is an infrared spectrum of the front and rear of the tannic acid modified CdTe quantum sheet in example 11. As can be seen from the graph, the H-O stretching vibration peak in the raw tannic acid is 3317cm -1 Nearby, after the tannic acid modifies the CdTe quantum sheet, the H-O stretching vibration peak shifts to 3445cm towards a larger wave number direction -1 Nearby, it is indicated that the hydroxyl functional group is effectively coordinated with the metal dangling bond on the CdTe surface, so as to form the tannic acid anchored CdTe quantum sheet.
FIG. 13 shows the result of the tannic acid modification of CdTe quantum sheet in the embodiment 11 in the form of Mo: biVO 4 Scanning electron microscope photograph and contact angle photograph before and after anchoring the surface of the film, wherein a is Mo: biVO 4 Scanning electron microscope photograph of film, b is CdTe quantum sheet anchored Mo: biVO 4 Scanning electron microscope photograph of film, c is Mo: biVO 4 Contact angle photograph of film, d is CdTe quantum sheet anchored Mo: biVO 4 Contact angle photograph of the film. As can be seen from the figure, the morphology of the film is worm-shaped porous structure before and after the anchorage of the CdTe quantum sheet, but the morphology is similar, but the Mo of the anchorage of the CdTe quantum sheet is BiVO 4 The film has dispersed grains with grain size smaller than 10nm and anchored to Mo/BiVO 4 CdTe quantum plate on film surface. And the contact angle of the film is from Sb 2 Se 3 51.3 reduction to Sb before quantum sheet anchoring 2 Se 3 19.4 degrees after the quantum sheets are anchored, and considering the good hydrophilicity of tannic acid, the CdTe quantum sheets are effectively anchored in Mo/BiVO 4 The surface of the film.
FIG. 14 shows the ratio of Mo to BiVO in the comparative example 4 Linear voltammograms of the films and CdTe quantum sheet anchored bismuth vanadate films in example 11. As can be seen from the figure, after the CdTe quantum sheet is anchored, the CdTe quantum sheet is anchored with Mo, biVO 4 The photocurrent density of the film is obviously improved at 1.23V RHE The photocurrent density was improved by about 107.6%.
FIG. 15 shows the ratio of Mo to BiVO in the comparative example 4 Thin film and CdTe quantum sheet anchored bismuth vanadate thin in example 11Photocurrent density versus time curve of the film. As can be seen from the figure, after the CdTe quantum sheet is anchored, the CdTe quantum sheet is anchored with Mo, biVO 4 The stability of the film is obviously enhanced, and the photocurrent density can maintain 81.7% of the initial current density after 60min.
FIG. 16 is a transmission electron micrograph of the CdTe quantum plate after pulsed laser irradiation in example 12. As can be seen from the figure, after the pulse laser is irradiated, the CdTe quantum plates are in monodisperse distribution, and the size is smaller than 15nm.
FIG. 17 is a graph of Mo-BiVO in comparative example 4 Linear voltammograms of the films and CdTe quantum sheet anchored bismuth vanadate films in example 12. As can be seen from the figure, after the CdTe quantum sheet is anchored, the CdTe quantum sheet is anchored with Mo, biVO 4 The photocurrent density of the film is obviously improved at 1.23V RHE The photocurrent density was increased by about 82.7%.
Fig. 18 is a transmission electron micrograph of the CdTe quantum sheet after pulsed laser irradiation in example 13. As can be seen from the figure, after the pulse laser is irradiated, the CdTe quantum plates are in monodisperse distribution, and the size is smaller than 20nm.
FIG. 19 is a graph of Mo BiVO in comparative example 4 Linear voltammograms of the films and CdTe quantum sheet anchored bismuth vanadate films in example 13. As can be seen from the figure, after the CdTe quantum sheet is anchored, the CdTe quantum sheet is anchored with Mo, biVO 4 The photocurrent density of the film is obviously improved at 1.23V RHE The photocurrent density was increased by about 42.6%.
The Mo/BiVO provided by the invention 4 The film can make the promoter FeNiOOH load on the surface of the film, thereby further improving the stability of the film.
Example 16
Sb (Sb) 2 Se 3 Quantum sheet anchored Mo, biVO 4 Thin film comprising Mo, biVO 4 Thin film for anchoring Sb 2 Se 3 Tannic acid molecules of quantum sheet and anchoring of tannic acid molecules to Mo/BiVO 4 Sb on film 2 Se 3 Quantum sheets. Sb (Sb) 2 Se 3 Quantum sheet layer on Sb 2 Se 3 Quantum sheet anchored Mo, biVO 4 The thickness of the film surface was 10nm.
The Sb is as follows 2 Se 3 Quantum sheet anchored Mo, biVO 4 The specific preparation method of the film is different from that of the embodiment 1 in that S4 is different, specifically: mo from S3 BiVO 4 Soaking the film in S2 to obtain tannic acid modified Sb 2 Se 3 Soaking in quantum sheet colloid solution for 16 hr to obtain Sb 2 Se 3 Sb with a quantum sheet thickness of about 10nm 2 Se 3 Quantum sheet anchored Mo, biVO 4 And finally adding FeNiOOH as a cocatalyst into the film. Wherein, the cocatalyst FeNiOOH is prepared by the following steps: feSO with concentration of 0.01M 4 And Ni (NO) 3 ) 2 Mixing the water solutions at a volume ratio of 1:2, and soaking at 30deg.C for 5 hr.
Example 17
CdTe quantum sheet anchored Mo BiVO 4 Thin film comprising Mo, biVO 4 Film, tannic acid molecule for anchoring CdTe quantum sheet and anchoring on Mo/BiVO using tannic acid molecule 4 CdTe quantum sheets on the film. Mo of CdTe quantum sheet anchored in CdTe quantum sheet, biVO 4 The thickness of the film surface was 10nm.
Mo of the CdTe quantum sheet anchoring BiVO 4 The specific preparation method of the film is different from that of example 16 in that the preparation method of the cocatalyst FeNiOOH is different, specifically: feSO at 0.5M concentration 4 And Ni (NO) 3 ) 2 Mixing the water solutions at a volume ratio of 1:10, and soaking at 50deg.C for 36 hr.
Long-term stability testing was performed on the films provided in examples 16-17 and comparative examples. The results are shown in FIGS. 20 to 21. As can be seen from the figure, sb 2 Se 3 After the quantum sheet or CdTe quantum sheet is anchored, the stability of the film is obviously enhanced, and the stability is increased from less than 30h to 80h of the foundation.
In summary, the invention adopts the liquid phase pulse laser irradiation technology to obtain a plurality of quantum sheet materials which are difficult to synthesize by the traditional method, have the diameter of less than 10nm and the thickness of about 1nm in one step, and the method is simple and efficient; then by means of tannic acid molecules, onlySoaking at normal temperature and normal pressure, the orthophenolic hydroxyl groups in tannic acid molecules can form coordination bonds with dangling bonds on the quantum sheets and dangling bonds on the surfaces of the bismuth vanadate thin films, and the coordination bonds are anchored on the surfaces of the bismuth vanadate thin films, so that the whole preparation process is simple in process, convenient to operate and remarkable in effect; the quantum sheet is adopted for anchoring, a built-in electric field is introduced to the surface of the film, so that the surface extraction of carriers is promoted, and meanwhile, the anchoring agent tannic acid molecules protect the surface of the film and prevent the surface of the film from photo-corrosion. The film photocurrent density and stability were tested to find BiVO relative to unanchored quantum sheets 4 The photocurrent density of the film was from 1.97mA/cm of the base 2 Is increased to 4.09mA/cm 2 The stability is increased from less than 30h to 80h, and the photoelectric performance and stability are obviously improved.
The present invention describes preferred embodiments and effects thereof. Additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The quantum sheet anchored bismuth vanadate film is characterized by comprising a bismuth vanadate film and a quantum sheet layer anchored on the bismuth vanadate film by tannic acid molecules;
the quantum sheet layer is prepared by forming coordination bonds between dangling bonds on the surface of the quantum sheet and ortho-phenolic hydroxyl groups in tannic acid molecules;
the quantum sheet is prepared by taking an original powder material of sulfide, selenide, telluride, carbide or nitride of transition metal as a raw material and irradiating the raw material by a laser beam;
the quantum sheet layer forms coordination bonds with metal dangling bonds on the surface of the bismuth vanadate film through ortho-phenolic hydroxyl groups in tannic acid molecules, and is anchored on the surface of the bismuth vanadate film.
2. The quantum sheet anchored bismuth vanadate film according to claim 1, wherein the sulfide is selected from WS 2 Or MoS 2 The selenide is selected from Sb 2 Se 3 、WSe 2 Or CdSe, the telluride is selected from CdTe, snTe or WTE 2 The carbide is selected from Mo 2 C or WC, the nitride being selected from W 2 N or MoN.
3. The quantum sheet anchored bismuth vanadate film according to claim 1, wherein the quantum sheet has a diameter of 5-20 nm and a thickness of 0.5-2 nm.
4. The quantum sheet anchored bismuth vanadate film according to claim 1, wherein the quantum sheet layer has an anchor thickness of 5-20 nm.
5. A method for preparing a quantum sheet anchored bismuth vanadate film as claimed in any one of claims 1 to 4, wherein the method is carried out according to the following steps:
s1, preparation of quantum sheets: dispersing the original powder material of sulfide, selenide, telluride, carbide or nitride of transition metal in a liquid phase medium to obtain suspension of powder; under the anaerobic environment and the assistance of ultrasound, placing the suspension of the powder under a laser beam for irradiation to obtain a quantum sheet colloid solution;
s2, molecular modification of the quantum sheet: adding tannic acid into the quantum sheet colloid solution, and obtaining the tannic acid modified quantum sheet colloid solution through self-assembly;
s3, preparing a bismuth vanadate film: preparing bismuth vanadate precursor solution based on a metal organic thermal decomposition method, preparing a film, and sintering to obtain a bismuth vanadate film;
s4, preparing a quantum sheet anchored bismuth vanadate film: and (3) soaking the bismuth vanadate film prepared in the step (S3) in the tannic acid modified quantum sheet colloid solution prepared in the step (S2), and preparing the quantum sheet anchored bismuth vanadate film through self-assembly.
6. The preparation method of the quantum-sheet-anchored bismuth vanadate film according to claim 5, wherein in S1, the liquid phase medium is one or more of water, ethanol, acetone, dimethyl sulfoxide or ethyl acetate, and the suspension concentration of the powder is 0.01-0.5 mg/mL.
7. The method for preparing a quantum-anchored bismuth vanadate film according to claim 6, wherein in S1, the laser beam is a non-focused pulse laser beam, the pulse frequency of the non-focused pulse laser beam is 10-30 Hz, the output wavelength is one of 266nm, 355nm, 532nm or 1064nm, the diameter of the output light spot is 5-20 mm, and the irradiation energy of the laser is 100-2000 mJ/cm 2 The irradiation time is 5-60 min.
8. The method for producing a quantum sheet anchored bismuth vanadate film according to claim 7, wherein in S2, the concentration of tannic acid is 0.1 to 10mg/ml, and the self-assembly is allowed to stand for 1 to 24 hours.
9. The method for preparing a quantum-sheet-anchored bismuth vanadate film according to claim 5, wherein in S4, the self-assembly is performed by immersing the bismuth vanadate film in the tannic-modified quantum-sheet colloid solution for 6 to 48 hours.
10. Use of a quantum sheet anchored bismuth vanadate film as claimed in any of the claims 1-4 in the field of photocatalysis or photoelectrocatalysis.
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