CN108408776A - A kind of pucherite photo-anode film and preparation method thereof - Google Patents
A kind of pucherite photo-anode film and preparation method thereof Download PDFInfo
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- CN108408776A CN108408776A CN201810523892.1A CN201810523892A CN108408776A CN 108408776 A CN108408776 A CN 108408776A CN 201810523892 A CN201810523892 A CN 201810523892A CN 108408776 A CN108408776 A CN 108408776A
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- doping
- thin film
- pucherite
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- bismuth thin
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000010409 thin film Substances 0.000 claims abstract description 72
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 71
- 239000010408 film Substances 0.000 claims abstract description 58
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 53
- 239000011733 molybdenum Substances 0.000 claims abstract description 53
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 22
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 17
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-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-SUKNRPLKSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 15
- CTHCTLCNUREAJV-UHFFFAOYSA-N heptane-2,4,6-trione Chemical compound CC(=O)CC(=O)CC(C)=O CTHCTLCNUREAJV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 18
- 238000004544 sputter deposition Methods 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000004528 spin coating Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- SWXQKHHHCFXQJF-UHFFFAOYSA-N azane;hydrogen peroxide Chemical compound [NH4+].[O-]O SWXQKHHHCFXQJF-UHFFFAOYSA-N 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 229910002915 BiVO4 Inorganic materials 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000224 chemical solution deposition Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- 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
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
A kind of high-performance pucherite photo-anode film of present invention offer and preparation method thereof.Photo-anode film is made of the NiO superthin section catalyst of the Fe2O3 doping on the pucherite thin-film light-absorbing layer of gradient molybdenum doping and its surface.Preparation process includes：1) in FTO electro-conductive glass deposition on substrate bismuth thin films；2) undoped vanadic acid bismuth thin film is obtained by the reaction with vanadyl acetylacetonate in bismuth thin film under 450 degrees Celsius；3) it uses vanadyl acetylacetonate and diacetyl acetone oxidation molybdenum to be doped processing to vanadic acid bismuth thin film, obtains the vanadic acid bismuth thin film of gradient molybdenum doping；4) Ni (OH) for adulterating Fe2Superthin section is spin-coated on the vanadic acid bismuth thin film of molybdenum doping, and after heat treatment obtaining load has the pucherite photo-anode film of NiO catalyst of Fe2O3 doping.The pucherite photo-anode film of the easy environmental protection of the method for the present invention, preparation effectively promotes separation of charge and transmission, and has good visible absorption performance and the aqueous energy of photoelectric decomposition.
Description
Technical field
The present invention relates to inorganic non-metallic material manufacturing technology field, specially a kind of pucherite photo-anode film.
Background technology
Global energy crisis and problem of environmental pollution are the great challenges that sustainable development faces.With science and technology
Development is expected to become the important technological means solved these problems using solar photoelectric hydrogen production by water decomposition technology.Light
The selectable material of electrolysis water hydrogen manufacturing has very much, such as common metal oxide semiconductor, nitride or sulfide.Can
Under light-exposed irradiation, semiconductor can excite, detach charge, and redox reaction further occurs to prepare hydrogen.Pucherite
(BiVO4) it is used as good visible light-responded material, it has nontoxic, inexpensive, band gap suitable (2.4eV), property stabilization etc. excellent
Point, usually can be as the light anode material in hydrogen production by water decomposition system.In addition, pucherite material is in degradation of contaminant, the sun
The fields such as energy battery are also widely used.
Pucherite method for manufacturing thin film has chemical solution deposition, sol-gel method, biomimetic method, electrochemical deposition at present
Method, hydro-thermal method, sputtering method etc..Patent CN 201310033856.4 is using Bi (NO3)3·5H2O and NH3VO3With citric acid, second
Acid, ethanol amine are secondary solvent, are prepared into precursor solution, vanadium is obtained on conducting glass substrate using chemical solution deposition
Sour bismuth thin film.Patent CN201210107811.2 discloses a kind of sol-gel method on FTO to obtain the skill of vanadic acid bismuth thin film
Art.Patent CN103173753A uses Bi (NO3)3·5H2It is prepared by the acetylacetone,2,4-pentanedione solution of O- acetic acid solutions and vanadyl acetylacetonate
Pucherite colloid, be spin-coated on ITO electro-conductive glass, a nanometer vanadic acid bismuth thin film obtained by roasting.Patent
CN201710203262.1 adjusts NH using nitric acid, boric acid4VO3With Bi (NO3)3·5H2O mixed liquors, pass through electrostatic on substrate
It adsorbs self assembly and laminated assembling technology forms amorphous BiVO4Film.Patent 201610033268.4 uses vanadium oxide and oxidation
Bismuth mixing target grows to obtain large area vanadic acid bismuth thin film by rf magnetron sputtering.Patent CN201610033270.1 is then adopted
It is target with bismuth metal and vanadium metal, magnetically controlled DC sputtering is carried out in oxidizing atmosphere and obtains vanadic acid bismuth thin film.Patent CN
201610977924.6 first deposit bismuth oxyiodide (BiOI) film on the glass substrate using electro-deposition method, then utilize hydro-thermal
Method obtains vanadic acid bismuth thin film with ammonium metavanadate solution reacting drying at 180 DEG C.(the Science 2014,343,990- such as Kim
994) BiOI films are obtained using electrochemical deposition method, it is small then under 450 degree to react 2 with it by vanadyl acetylacetonate solution
When obtain undoped pucherite light anode.Patent CN201710550371.0 discloses a kind of three-electrode method on electro-conductive glass
Deposition obtains bismuth oxyiodide, then obtains pucherite with vanadyl acetylacetonate pyroreaction；Further obtained using electrochemical deposition
To ferronickel oxyhydroxide.Patent CN201710497490.4 discloses a kind of method that hydro-thermal method prepares pucherite, and passes through
Fast electrochemical sedimentation deposits iron-based double-metal hydroxide on surface, and iron-based double-metal hydroxide/vanadic acid is prepared
Bismuth light anode material.Patent CN201710235859.4 on conductive substrates surface by preparing Mo：BiVO4Film, then in table
If face prepares dried layer Mo:BiVO4Film obtains Mo:BiVO4/Co:BiVO4Optoelectronic pole.
The preparation of above-mentioned pucherite photo-anode film is all substantially undoped or single doped structure, moreover, pucherite is still
So have the shortcomings that, such as separation of charge/transmission is slower, charge mobility is low, poor oxidation kinetics etc..
Invention content
The present invention provides a kind of high-performance pucherite photo-anode films and preparation method thereof.The photo-anode film is by ladder
Spend the pucherite thin-film light-absorbing layer of molybdenum doping and its NiO superthin section catalyst composition of the Fe2O3 doping on surface.Prepared
Film crystal quality is high, uniform, good with substrate adhesion.
The present invention can be achieved through the following technical solutions：
A kind of pucherite photo-anode film, the membrane structure include light absorbing layer, and the light absorbing layer upper surface is equipped with
The lower surface of oxygen-separating catalyst layer, the light absorbing layer is equipped with substrate, and the light absorbing layer is that the pucherite of gradient molybdenum doping is thin
Film, the oxygen-separating catalyst layer are the NiO ultrathin nanometer pieces of Fe2O3 doping, and the substrate is FTO electro-conductive glass.The gradient molybdenum is mixed
Miscellaneous vanadic acid bismuth thin film is high surface levels molybdenum doping.The doping concentration of the vanadic acid bismuth thin film of the gradient molybdenum doping is rubbed for 5%
That ratio.
A kind of preparation method of pucherite photo-anode film, includes the following steps,
The first step is first deposited one layer of metal bismuth thin film in FTO Conducting Glass by vacuum sputtering；
Second step, the preparation of undoped vanadic acid bismuth thin film：On above-mentioned metal bismuth thin film, even application contains levulinic
The DMSO solution of ketone vanadyl, being to slowly warm up to 450 degrees Celsius after dry, the reaction was continued 4~6 hours, after natural cooling, then rubs through 1
You/liter NaOH solution impregnate 20~30 minutes and distilled water flushing, dry to obtain undoped vanadic acid bismuth thin film；
Third walks, the preparation of the pucherite photo-anode film of gradient molybdenum doping：On above-mentioned undoped vanadic acid bismuth thin film
Even application contains the DMSO solution of vanadyl acetylacetonate and diacetyl acetone oxidation molybdenum, and it is Celsius to be to slowly warm up to 500 after dry
Degree reaction 2~4 hours, NaOH solution after natural cooling, then through 1 mol/L is impregnated 20~30 minutes and distilled water flushing, dries in the air
The dry vanadic acid bismuth thin film for obtaining gradient molybdenum doping；
4th step, the Ni (OH) of Fe doping2The preparation of dispersion liquid：Take the Ni (NO of 0.1 mol/L3)2Solution is added dropwise
To in the NaOH solution of 1 mol/L and stir 10 minutes, obtained Ni (OH)2Precipitation, by repeatedly centrifuging, washing redisperse
To obtaining Ni (OH) in distilled water2Dispersion liquid；Under ultrasonic disperse state, 1 mol/L Fe is added dropwise again to above-mentioned dispersion liquid
(NO3)3Solution continues ultrasound and carries out within 2 hours being centrifuged repeatedly again after ion exchange, wash to remove excess ions, is re-dispersed into
The Ni (OH) of Fe doping is obtained in distilled water2Dispersion liquid；
5th step, load have the pucherite photo-anode film of the NiO nanometer sheet catalyst of ultra-thin Fe doping：Take 50 microlitres of Fe
The Ni (OH) of doping2Dispersion liquid is spin-coated on the vanadic acid bismuth thin film of gradient molybdenum doping, then passes through 300 DEG C of heat treatments in air
2 hours, obtained load had the pucherite photo-anode film of the NiO nanometer sheet catalyst of ultra-thin Fe doping.
Preferential, the cleaning step of FTO Conducting Glass, the cleaning process are first carried out before the above-mentioned first step
For：Using 1:1:Mixture and distilled water the difference supersound washing of 1 hydrogen peroxide-ammonium hydroxide-distilled water 2~3 hours, then in sky
It spontaneously dries, is dried, clean FTO conductive substrates in gas.
It is preferential, in the above-mentioned first step using vacuum ion sputtering instrument in FTO Conducting Glass sputtering sedimentation
Metal bismuth thin film, and pass through crystal microbalance monitoring and controlling film thickness.
Preferential, the sputtering current of metal bismuth thin film is 25 milliamperes in the above-mentioned first step, and sputtering time is 30 seconds, the gold
The film thickness for belonging to bismuth thin film is 40~120 nanometers.
Preferential, the metal bismuth thin film of the DMSO solution coated with vanadyl acetylacetonate is 80~100 in above-mentioned second step
It is dry in DEG C baking oven to be placed on 450 DEG C of Muffle furnaces and react 4~6 hours；It is coated with vanadyl acetylacetonate and two in above-mentioned third step
The drying in 80~100 DEG C of baking ovens of the vanadic acid bismuth thin film of the DMSO solution of acetylacetone,2,4-pentanedione molybdenum oxide is placed in 500 DEG C of Muffle furnaces
Reaction 2~4 hours.
Preferential, the molar ratio of above-mentioned second step and vanadyl acetylacetonate and diacetyl acetone oxidation molybdenum in third step is equal
It is 5%.
Preferential, the NiO nanometer sheet catalyst of ultra-thin Fe doping, spin coating speed are applied in above-mentioned 5th step using spin-coating method
3000 revs/min of rate, spin-coating time are 30 seconds.
Chemical reagent used in the present invention is all that analysis is pure, is purchased from Shanghai pharmaceutical reagent company or AlfaAesar company.
Characterization method used in the present invention：Confocal microscope (Reinshaw inViaReflex) is used for the crystal of judgement sample
Eigen vibration confirms that the crystal structure of film is pucherite with x-ray diffractometer (Brooker D8Advance, copper target), uses X-
The doping of X-ray photoelectron spectroscopy X instrument (the silent winged generation that Escalab 250Xi of match) detection Mo elements, with UV Diffuse Reflectance Spectroscopy (peace
Prompt human relations Cary 5000) characterization film visible absorption performance, with high-resolution-ration transmission electric-lens (FEI Tecnai G2F20) confirm
The crystal structure of the NiO of Fe doping.The nickel oxide of Fe2O3 doping is confirmed with atomic force microscope (Brooker Dimension Icon)
For super-thin sheet-shaped structure, the performance of optoelectronic pole is proved with light current -voltage curve.
Pucherite photo-anode film of the present invention and preparation method thereof has following advantageous effect：
The first, the present invention synthesizes the vanadic acid bismuth thin film of molybdenum doping using two-step method：The first step synthesizes to obtain undoped with vanadic acid
Bismuth thin film, second step synthesize to obtain the vanadic acid bismuth thin film of gradient molybdenum doping, the film crystal quality prepared by this kind of two-step method is high,
Uniformly, good with substrate adhesion, there is preferable PhotoelectrocatalytiPerformance Performance compared to previous molybdenum doping vanadic acid bismuth thin film.
The second, the present invention uses vacuum ion sputtering technology, and target is bismuth source, the bismuth metal film thickness deposited is controllable,
It uniformly, and can large area preparation.
The ion exchange technique of third, ultrasonic wave added of the present invention can prepare the Ni of ultra-thin Fe2O3 doping
(OH)2Nanometer sheet.
4th, the present invention modifies the NiO ultrathin nanometer piece catalyst of Fe2O3 doping, side using spin-coating method on vanadic acid bismuth thin film
Method simply ensures efficiently separating and transmitting in charge again.
5th, the vanadic acid bismuth thin film of the gradient molybdenum doping of the NiO modifications of the Fe2O3 doping prepared by the present invention is in alkaline solution
In with higher photoelectrocatalysis decompose water activity.
Description of the drawings
Attached drawing 1 is the layer structure chart of pucherite photo-anode film of the present invention；
Attached drawing 2 is the optical photograph figure of 1,2,3 product of the embodiment of the present invention；
Attached drawing 3 is the XRD diagram of 1 metal bismuth thin film of the embodiment of the present invention；
Attached drawing 4 is the XRD diagram of 1 undoped vanadic acid bismuth thin film of the embodiment of the present invention；
Attached drawing 5 is the XRD diagram of the vanadic acid bismuth thin film of 2 uniform molybdenum doping of the embodiment of the present invention；
Attached drawing 6 is the XRD diagram of the vanadic acid bismuth thin film of 3 gradient molybdenum doping of the embodiment of the present invention；
Attached drawing 7 is the Raman figure of the vanadic acid bismuth thin film of 3 gradient molybdenum doping of the embodiment of the present invention；
Attached drawing 8 is the xps energy spectrum figure of the vanadic acid bismuth thin film of 3 gradient molybdenum doping of the embodiment of the present invention；
Attached drawing 9 is the UV-vis figures of the vanadic acid bismuth thin film of 3 gradient molybdenum doping of the embodiment of the present invention；
Attached drawing 10 is the SEM figures of the vanadic acid bismuth thin film of 3 gradient molybdenum doping of the embodiment of the present invention；
Attached drawing 11 is the Ni (OH) of 4 Fe2O3 doping of present example2It is super with the NiO of Fe2O3 doping
The XRD diagram of thin nanometer sheet；
Attached drawing 12 is the high-resolution-ration transmission electric-lens figure of the NiO of 4 Fe2O3 doping of the embodiment of the present invention；
Attached drawing 13 is the atomic force microscopy figure of the NiO of 4 Fe2O3 doping of the embodiment of the present invention；
14 present invention of attached drawing implements the performance chart of the light anode oxidation water of 1,2,3 products；
15 present invention of attached drawing implements the performance chart of the light anode oxidation water of 3,4,5,6 products.
Specific implementation mode
In order that those skilled in the art will better understand the technical solution of the present invention, with reference to embodiment and attached drawing
Product of the present invention is described in further detail.
Embodiment 1
As shown in Figure 1, a kind of pucherite photo-anode film, the membrane structure include light absorbing layer, the light absorbing layer
Upper surface is equipped with oxygen-separating catalyst layer, and the lower surface of the light absorbing layer is equipped with substrate, and the light absorbing layer is gradient molybdenum doping
Vanadic acid bismuth thin film, the oxygen-separating catalyst layer be Fe2O3 doping NiO ultrathin nanometer pieces, the substrate be FTO electro-conductive glass.Institute
The vanadic acid bismuth thin film for stating gradient molybdenum doping is high surface levels molybdenum doping.The doping of the vanadic acid bismuth thin film of the gradient molybdenum doping is dense
Degree is 5% molar ratio.
Steps are as follows for undoped pucherite film preparation：
1) use high vacuum ion sputtering instrument in drying, clean length and width for the FTO electro-conductive glass bases of 2 centimetres of 1 cm x
On piece sputters bismuth thin film；Sputtering current is 25 milliamperes, and sputtering time is 30 seconds, and sputtering thickness is 20-120 nanometers, and preferably 40 receive
Rice.
2) 50 microlitres of DMSO solutions containing the vanadyl acetylacetonate that molar ratio is 0.5 mol/L are dropped evenly into gold
Belong on bismuth thin film, it is dry in 80~100 DEG C of baking ovens to be placed on Muffle furnace and be warming up to 450 DEG C with 2 DEG C/min of speed and keep
4 hours, after natural cooling, then brown film passed through distilled water and rushes through 1 mol/L NaOH solution immersion treatment 20-30 minutes
It washes away except foreign ion, dry to obtain undoped vanadic acid bismuth thin film.Its optical photograph is shown in No. 1 film in attached drawing 2.Fig. 3 is institute
The XRD diagram of the bismuth metal of deposition, wherein F are labeled as the SnO of F doping2Substrate.Fig. 4 is prepared undoped vanadic acid bismuth thin film,
The XRD illustrates that film is monocline BiVO4Structure.
In Figure 13 example 1 be this sample prepared by light anode aoxidize water performance curve, electrolyte used be 1 mole/
Rise NaOH solution.
Embodiment 2
Similar to Example 1 to use sputtering method deposited metal bismuth thin film, above, 50 microlitres of content ratios of even application are
19/1 vanadyl acetylacetonate and the molar ratio of diacetyl acetone oxidation molybdenum are the DMSO solution of 0.5 mol/L, by with implementation
Example 1 such as similarly dries, is heat-treated, impregnating, cleaning, drying at the processes, obtains the vanadic acid bismuth thin film of uniform molybdenum doping.Its optics shines
Piece is shown in No. 2 films in attached drawing 2.Fig. 5 is the vanadic acid bismuth thin film of uniform molybdenum doping, and all XRD diffraction maximums can be classified as respectively
BiVO4Mutually SnO is adulterated with F2Substrate.Example 2 is the performance curve of the light anode oxidation water prepared by this sample in Figure 13.
Embodiment 3
The pucherite film preparation step of gradient molybdenum doping：On the 1 undoped vanadic acid bismuth thin film of gained of embodiment, it is added dropwise
The molar ratio of vanadyl acetylacetonate and diacetyl acetone oxidation molybdenum that 50 microlitres of content ratios are 19/1 is 0.5 mol/L
DMSO solution；Dry be placed in Muffle furnace is first warming up to 450 DEG C with 2 DEG C/min of rates and heats up again in 80~100 DEG C of baking ovens
2 hours are kept the temperature to 500 DEG C and at 500 DEG C；After natural cooling, gained brown film is through 1 mol/L NaOH solution immersion treatment 20
~30 minutes, and through distilled water flushing removal foreign ion, dry to obtain the vanadic acid bismuth thin film of gradient molybdenum doping.Its optical photograph
See No. 3 films in attached drawing 2.
Fig. 6 is the vanadic acid bismuth thin film of gradient molybdenum doping, and all XRD diffraction maximums can be attributed to BiVO respectively4Mutually mixed with F
Miscellaneous SnO2Substrate.Fig. 7 illustrates sample characteristic Raman signal (325,368,711 and 826cm-1) be molybdenum doping pucherite knot
Structure.Fig. 8 is that xps energy spectrum illustrates to mainly contain Bi, Mo and V element in film.Fig. 9 UV-vis can calculate the vanadium of gradient molybdenum doping
About 500 nanometers of sour bismuth ABSORPTION EDGE, band gap about 2.48eV.Figure 10 show for gradient molybdenum doping pucherite film surface and
Cross-section cutaway view.Example 3 is the performance curve of the light anode oxidation water prepared by this sample in Figure 14, shows that this sample ratio is not mixed
The pucherite of miscellaneous or uniform molybdenum doping has the aqueous energy of preferable photoelectric decomposition.
Embodiment 4
The preparation process of the NiO ultrathin nanometer pieces of Fe doping：Under magnetic stirring by the Ni of 25 milliliter of 0.1 mol/L
(NO3)2Solution is added dropwise in the NaOH solution of 6 milliliter of 1 mol/L and continues stirring 10 minutes, obtained light green color Ni
(OH)2Precipitation；The precipitation removes foreign ion by repeatedly centrifugation, washing, and Ni is obtained in redisperse to 20 milliliters of distilled water
(OH)2Dispersion liquid；Under the conditions of ultrasonic disperse, to above-mentioned Ni (OH)2300 microlitres of 1M Fe (NO are added in dispersion liquid3)3It is molten
Liquid continues ultrasound and carries out ion exchange in 2 hours；Gained brown precipitate removes excess ions through being centrifuged repeatedly, washing, and divides again
It is scattered to the Ni (OH) that Fe doping is obtained in distilled water2Dispersion liquid (solid content 120ppm)；The Ni for taking 50 microlitres of Fe to adulterate
(OH)2Dispersion liquid is with 3000 revs/min of spin speed, the vanadium of spin coating 30 seconds obtained gradient molybdenum dopings in embodiment 3
On sour bismuth thin film, then the film passes through 300 DEG C and is heat-treated 2 hours in air, and obtaining load has the NiO of Fe doping is ultra-thin to urge
The pucherite photo-anode film of the gradient molybdenum doping of agent.
Figure 11 bottom curves are the Ni (OH) of Fe2O3 doping2The XRD of ultrathin nanometer piece；Upper graph is that the NiO of Fe doping is super
The XRD diagram of thin nanometer sheet, structure are cube centroid structure NiO.Figure 12, which is the bright Fe-NiO of high-resolution-ration transmission electric-lens chart, to be had
Highly crystalline structure.Figure 13 is atomic force microscopy figure, shows that the two-dimensional of sample is 40-80 nanometers, thickness is 2-5 nanometers.
In Figure 15 example 4 be this sample prepared by light anode aoxidize water performance curve, electrolyte used be 1 mole/
Rise NaOH solution.
Embodiment 5
This example provides a kind of side of the NiO ultrathin nanometer pieces modification pucherite photo-anode film preparation of a small amount of Fe2O3 doping
Method, specific implementation process with embodiment 3, the difference is that：The Ni (OH) of used Fe doping2Dispersion liquid it is a concentration of
12ppm。
Example 5 is the performance curve of the light anode oxidation water prepared by this sample in Figure 15, illustrates NiO points of Fe- doping
When a concentration of 12ppm of dispersion liquid, the pucherite for the gradient molybdenum doping modified has the aqueous energy of highest photoelectric decomposition.
Embodiment 6
This example provides a kind of side of the NiO ultrathin nanometer pieces modification pucherite photo-anode film preparation of a small amount of Fe2O3 doping
Method, specific implementation process with embodiment 3, the difference is that：The Ni (OH) of used Fe doping2Dispersion liquid it is a concentration of
1.2ppm。
Example 6 is the performance curve of the light anode oxidation water prepared by this sample in Figure 15, illustrates NiO points of Fe- doping
When a concentration of 1.2ppm of dispersion liquid, the photoelectric decomposition of the pucherite for the gradient molybdenum doping modified is aqueous to improve unobvious.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the present invention in any form；It is all
The those of ordinary skill of the industry can be shown in by specification attached drawing and described above and swimmingly implement the present invention；But it is all
Those skilled in the art without departing from the scope of the present invention, using disclosed above technology contents
The equivalent variations for a little variation, modification and evolution made are the equivalent embodiment of the present invention；Meanwhile it is all according to the present invention
Substantial technological to the variation, modification and evolution etc. of any equivalent variations made by above example, still fall within the present invention's
Within the protection domain of technical solution.
Claims (10)
1. a kind of pucherite photo-anode film, it is characterised in that:The membrane structure includes light absorbing layer, on the light absorbing layer
Surface is equipped with oxygen-separating catalyst layer, and the lower surface of the light absorbing layer is equipped with substrate, and the light absorbing layer is gradient molybdenum doping
Vanadic acid bismuth thin film, the oxygen-separating catalyst layer are the NiO ultrathin nanometer pieces of Fe2O3 doping, and the substrate is FTO electro-conductive glass.
2. pucherite photo-anode film according to claim 1, it is characterised in that：The pucherite of the gradient molybdenum doping is thin
Film is high surface levels molybdenum doping.
3. pucherite photo-anode film according to claim 2, it is characterised in that：The pucherite of the gradient molybdenum doping is thin
The doping concentration of film is 5% molar ratio.
4. the preparation method of the pucherite photo-anode film described in a kind of any one of claims 1 to 3 claim, feature exist
In：Include the following steps,
The first step is first deposited one layer of metal bismuth thin film in FTO Conducting Glass by vacuum sputtering；
Second step, the preparation of undoped vanadic acid bismuth thin film：On above-mentioned metal bismuth thin film, even application contains acetylacetone,2,4-pentanedione oxygen
The DMSO solution of vanadium, being to slowly warm up to 450 degrees Celsius after dry, the reaction was continued 4~6 hours, after natural cooling, then through 1 mole/
The NaOH solution risen impregnates 20~30 minutes and distilled water flushing, dries to obtain undoped vanadic acid bismuth thin film；
Third walks, the preparation of the pucherite photo-anode film of gradient molybdenum doping：On above-mentioned undoped vanadic acid bismuth thin film uniformly
The DMSO solution containing vanadyl acetylacetonate and diacetyl acetone oxidation molybdenum is applied, 500 degrees Celsius are to slowly warm up to after dry instead
It answers 2~4 hours, after natural cooling, then NaOH solution through 1 mol/L is impregnated 20~30 minutes and distilled water flushing, dries
To the vanadic acid bismuth thin film of gradient molybdenum doping；
4th step, the Ni (OH) of Fe doping2The preparation of dispersion liquid：Take the Ni (NO of 0.1 mol/L3)2Solution is added dropwise to 1 and rubs
You/liter NaOH solution in and stir 10 minutes, obtained Ni (OH)2Precipitation, by repeatedly centrifuging, washing redisperse to distillation
Ni (OH) is obtained in water2Dispersion liquid；Under ultrasonic disperse state, 1 mol/L Fe (NO are added dropwise again to above-mentioned dispersion liquid3)3Solution,
Continue ultrasound to carry out within 2 hours being centrifuged repeatedly again after ion exchange, wash to remove excess ions, is re-dispersed into distilled water and obtains
The Ni (OH) adulterated to Fe2Dispersion liquid；
5th step, load have the pucherite photo-anode film of the NiO nanometer sheet catalyst of ultra-thin Fe doping：Take 50 microlitres of Fe doping
Ni (OH)2Dispersion liquid is spin-coated on the vanadic acid bismuth thin film of gradient molybdenum doping, and it is small then to pass through 300 DEG C of heat treatments 2 in air
When, obtained load has the pucherite photo-anode film of the NiO nanometer sheet catalyst of ultra-thin Fe doping.
5. the preparation method of pucherite photo-anode film according to claim 4, it is characterised in that：The above-mentioned first step it
The preceding cleaning step for also having a step FTO Conducting Glass, the cleaning process are：Using 1:1:1 hydrogen peroxide-ammonium hydroxide-steaming
Mixture and distilled water the difference supersound washing of distilled water 2~3 hours, then spontaneously dries in air.
6. the preparation method of pucherite photo-anode film according to claim 5, it is characterised in that：It is adopted in the above-mentioned first step
It is vacuum ion sputtering instrument sputtering sedimentation metal bismuth thin film in FTO Conducting Glass, and is supervised by crystal microbalance
Observing and controlling made membrane thickness.
7. the preparation method of pucherite photo-anode film according to claim 6, it is characterised in that：It is golden in the above-mentioned first step
The sputtering current for belonging to bismuth thin film is 25 milliamperes, and sputtering time is 30 seconds, and the film thickness of the metal bismuth thin film is received for 40~120
Rice.
8. the preparation method of pucherite photo-anode film according to claim 4, it is characterised in that：It is applied in above-mentioned second step
It is covered with the drying in 80~100 DEG C of baking ovens of the metal bismuth thin film of the DMSO solution of vanadyl acetylacetonate and is placed on 450 DEG C of Muffle furnaces
Reaction 4~6 hours；
The vanadic acid bismuth thin film of the DMSO solution coated with vanadyl acetylacetonate and diacetyl acetone oxidation molybdenum exists in above-mentioned third step
Dry be placed in 500 DEG C of Muffle furnaces is reacted 2~4 hours in 80~100 DEG C of baking ovens.
9. the preparation method of pucherite photo-anode film according to claim 4, it is characterised in that：Above-mentioned second step and
The molar ratio of vanadyl acetylacetonate and diacetyl acetone oxidation molybdenum in three steps is 5%.
10. the preparation method of pucherite photo-anode film according to claim 4, it is characterised in that：In above-mentioned 5th step
The NiO nanometer sheet catalyst of ultra-thin Fe doping is applied using spin-coating method, 3000 revs/min of spin coating rate, spin-coating time is 30 seconds.
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| CN113398944B (en) * | 2021-05-24 | 2022-02-22 | 苏州科技大学 | Composite material of bismuth vanadate surface modified nickel cobaltate spinel and preparation and application thereof |
| CN115007137A (en) * | 2022-07-14 | 2022-09-06 | 南大恩洁优环境技术(江苏)股份公司 | Catalyst for purifying dioxin and preparation method thereof |
| CN115007137B (en) * | 2022-07-14 | 2023-07-28 | 南大恩洁优环境技术(江苏)股份公司 | Catalyst for purifying dioxin and preparation method thereof |
| CN116283287A (en) * | 2023-03-20 | 2023-06-23 | 西北工业大学 | Quantum sheet anchored bismuth vanadate film, preparation method and application |
| CN116283287B (en) * | 2023-03-20 | 2024-04-05 | 西北工业大学 | Quantum sheet anchored bismuth vanadate film, preparation method and application |
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| CN109440126A (en) | 2019-03-08 |
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