CN111302650B - Method for preparing bismuth vanadate photoelectric anode by spin coating of nanoparticle solution - Google Patents
Method for preparing bismuth vanadate photoelectric anode by spin coating of nanoparticle solution Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 166
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 166
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000004528 spin coating Methods 0.000 title claims abstract description 43
- 239000011248 coating agent Substances 0.000 claims abstract description 56
- 238000000576 coating method Methods 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 54
- 239000011521 glass Substances 0.000 claims abstract description 53
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 34
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 238000000137 annealing Methods 0.000 claims abstract description 24
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 19
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005642 Oleic acid Substances 0.000 claims abstract description 19
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 19
- RHGQOMYDGHIKFH-GNOQXXQHSA-K bis[[(z)-octadec-9-enoyl]oxy]bismuthanyl (z)-octadec-9-enoate Chemical compound [Bi+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O RHGQOMYDGHIKFH-GNOQXXQHSA-K 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 14
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000009987 spinning Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000004321 preservation Methods 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 239000002244 precipitate Substances 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 16
- 238000005119 centrifugation Methods 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 239000007853 buffer solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 10
- 229940057995 liquid paraffin Drugs 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 10
- 238000002310 reflectometry Methods 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 15
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 238000000151 deposition Methods 0.000 description 8
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- 239000000843 powder Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
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- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
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- 238000001429 visible spectrum Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 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 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910001451 bismuth ion Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 nitrate ions Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 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 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004070 electrodeposition 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
- 239000008236 heating water Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical group [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—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
- 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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- 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
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
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Abstract
The invention provides a method for preparing a bismuth vanadate photoelectric anode by spin coating of a nanoparticle solution, and relates to the technical field of preparation of bismuth vanadate photoelectric anodes. Mixing bismuth nitrate, oleic acid, oleylamine and a nonpolar solvent, and reacting in a nitrogen atmosphere at 170-175 ℃ to obtain a mixed solution of bismuth oleate and bismuth oleylamine; cooling the mixed solution of bismuth oleate and bismuth oleylamine to 130-140 ℃, mixing the cooled mixed solution with the mixed aqueous solution of ammonium metavanadate and ammonium paramolybdate, and reacting at the temperature of 90-100 ℃ to obtain molybdenum-doped bismuth vanadate nanoparticles; and dissolving the molybdenum-doped bismuth vanadate nano particles in chlorobenzene to obtain a molybdenum-doped bismuth vanadate nano particle solution, coating the molybdenum-doped bismuth vanadate nano particle solution on the surface of FTO conductive glass in a spinning mode, drying, and then annealing to obtain the bismuth vanadate photoelectric anode. The bismuth vanadate photoelectric anode prepared by the method has low reflectivity and high transmittance, the purity of the bismuth vanadate is high, and the obtained bismuth vanadate photoelectric anode has excellent photocatalytic performance.
Description
Technical Field
The invention relates to the technical field of bismuth vanadate photoelectric anode preparation, in particular to a method for preparing a bismuth vanadate photoelectric anode by utilizing a nano particle solution through spin coating.
Background
With the continuous consumption of fossil energy and the increasing energy demand of human beings, the development of various novel energy sources is urgently needed. Photoelectrochemical (PEC) water splitting to convert solar energy to hydrogen energy is a simple, low cost and efficient method of solar energy utilization. PEC devices typically include two photoelectrodes, a photoanode and a photocathode. Under illumination and bias, the photo-generated electrons and holes can separate and participate in the oxidation and reduction of water on the two electrodes. Thus, the quality of the photoelectrode directly affects the performance of the PEC device. Since the oxidation reaction occurring on the photoanode is more difficult than the reduction reaction occurring on the photocathode, a great deal of research has been conducted on the photoanode material.
Bismuth vanadate (BiVO)4) Has excellent lightCatalytically active, have been widely used as PEC photo-anode materials. BiVO calculated according to band gap4The theoretical maximum photocurrent density of the photoelectric anode under the illumination of standard sunlight (AM1.5G) can reach 7.5 milliamperes per square centimeter. At present, BiVO4The preparation of the photoanode generally employs two methods, including an electrochemical method and a metal organic decomposition method. The electrochemical method firstly obtains bismuth oxyiodide sheet-shaped structures on a substrate through an electrochemical deposition process, and then performs an ion exchange reaction with vanadyl acetylacetonate to obtain the bismuth vanadate photo-anode. The metal organic decomposition method is to directly mix and spin-coat precursors of bismuth and vanadium on a substrate and further anneal to obtain the bismuth vanadate photo-anode, although the method is simple and convenient to operate and the transmittance of the photo-anode is also improved, the vanadium source (usually vanadyl acetylacetonate) in the precursors has the possibility of volatilization or sublimation in the annealing process, so that impurities are generated, and the catalytic performance of the photo-anode is further influenced.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a bismuth vanadate photoanode by spin coating a nanoparticle solution. The bismuth vanadate photoelectric anode prepared by the method provided by the invention has low reflectivity and high transmittance, the purity of the bismuth vanadate is high, and the obtained bismuth vanadate photoelectric anode has excellent photocatalytic performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing a bismuth vanadate photo-anode by spin coating of a nanoparticle solution, which comprises the following steps:
(1) mixing bismuth nitrate with oleic acid, oleylamine and a nonpolar solvent, and reacting in a nitrogen atmosphere at 170-175 ℃ to obtain a mixed solution of bismuth oleate and bismuth oleylamine; the non-polar solvent is octadecene, benzyl ether or liquid paraffin; the dosage ratio of the bismuth nitrate to the oleic acid to the oleylamine is 1mmol: 1-3 mL;
(2) cooling the mixed solution of bismuth oleate and bismuth oleylamine to 130-140 ℃, mixing the cooled mixed solution with a mixed aqueous solution of ammonium metavanadate and ammonium paramolybdate, and reacting at the temperature of 90-100 ℃ to obtain molybdenum-doped bismuth vanadate nanoparticles;
(3) dissolving the molybdenum-doped bismuth vanadate nanoparticles in chlorobenzene to obtain a molybdenum-doped bismuth vanadate nanoparticle solution;
(4) and (3) coating the molybdenum-doped bismuth vanadate nanoparticle solution on the surface of FTO conductive glass in a spinning mode, drying, and annealing the obtained FTO conductive glass coating to obtain the bismuth vanadate photoelectric anode.
Preferably, the molar ratio of the ammonium metavanadate and the ammonium paramolybdate in the step (2) to the bismuth nitrate in the step (1) is 1-2: 0-0.0058: 1.
Preferably, after the reaction in the step (2), purifying the obtained reaction solution; the purification comprises the following steps:
(a) cooling the reaction liquid obtained in the step (2) to room temperature, then adding ethanol into the reaction liquid, standing and layering to obtain an upper organic phase and a lower aqueous phase, and removing the lower aqueous phase;
(b) adding acetone into the organic phase, and then carrying out first centrifugation to obtain a first precipitate;
(c) and sequentially adding chloroform and ethanol into the first precipitate, and then carrying out second centrifugation to obtain a second precipitate which is molybdenum-doped bismuth vanadate nano particles.
Preferably, the average particle size of the bismuth vanadate nanoparticles in the step (3) is 6 nm; the concentration of the bismuth vanadate nanoparticle solution is 100-200 mug/mL.
Preferably, the rotation speed of the spin coating in the step (4) is 1000-4000 r/min, the number of spin coating is 1-3, the time of each spin coating is 20-60 s, and the wet coating is dried after each spin coating.
Preferably, the drying temperature in the step (4) is 400 ℃, and the drying time is 2-10 min.
Preferably, the annealing treatment in the step (4) is performed by: heating the FTO conductive glass coating to 550 ℃ at a heating rate of 50 ℃/min, and carrying out first heat preservation; then heating the FTO conductive glass coating which is cooled to room temperature after the first heat preservation to 400-500 ℃ at the heating rate of 10 ℃/min, and carrying out second heat preservation; heating the FTO conductive glass coating cooled to room temperature after the second heat preservation to 300-400 ℃ at a heating rate of 10 ℃/min, and carrying out third heat preservation;
the first heat preservation time is 30-90 min, the second heat preservation time is 60-150 min, the third heat preservation time is 30-120 min, and the third heat preservation is carried out in a nitrogen atmosphere.
Preferably, the step (4) further comprises, after the annealing treatment:
and soaking the annealed FTO conductive glass coating in a phosphoric acid buffer solution of cobalt chloride, and then illuminating the FTO conductive glass coating soaked in the phosphoric acid buffer solution of cobalt chloride by using AM1.5 standard sunlight.
Preferably, the concentration of cobalt chloride in the phosphoric acid buffer solution of cobalt chloride is 0.1-0.5 mmol/L, and the concentration of phosphate radical is 0.1 mol/L; the pH value of the phosphoric acid buffer solution of the cobalt chloride is 7.2.
Preferably, the illumination time is 10-30 min.
The invention provides a method for preparing a bismuth vanadate photo-anode by spin coating of a nanoparticle solution, which comprises the following steps: (1) mixing bismuth nitrate with oleic acid, oleylamine and a nonpolar solvent, and reacting in a nitrogen atmosphere at 170-175 ℃ to obtain a mixed solution of bismuth oleate and bismuth oleylamine; the non-polar solvent is octadecene, benzyl ether or liquid paraffin; (2) cooling the mixed solution of bismuth oleate and bismuth oleylamine to 130-140 ℃, mixing the cooled mixed solution with a mixed aqueous solution of ammonium metavanadate and ammonium paramolybdate, and reacting at the temperature of 90-100 ℃ to obtain molybdenum-doped bismuth vanadate nanoparticles; (3) dissolving the molybdenum-doped bismuth vanadate nanoparticles in chlorobenzene to obtain a molybdenum-doped bismuth vanadate nanoparticle solution; (4) and (3) coating the molybdenum-doped bismuth vanadate nanoparticle solution on the surface of FTO conductive glass in a spinning mode, drying, and annealing the obtained FTO conductive glass coating to obtain the bismuth vanadate photoelectric anode. Firstly synthesizing a bismuth vanadate nanoparticle solution, then spin-coating the bismuth vanadate nanoparticle solution on FTO conductive glass, and carrying out annealing treatment to obtain the bismuth vanadate photoanode. According to the invention, a more smooth bismuth vanadate coating film can be obtained on the substrate by adopting a spin coating method, so that the obtained bismuth vanadate photo-anode has low reflectivity and high transmittance; because the synthesized bismuth vanadate nanoparticle solution is spin-coated, vanadium in the bismuth vanadate which is generated by reaction no longer has the possibility of volatilization or sublimation, and pure bismuth vanadate can be obtained after annealing treatment; and the spin coating method is simpler and more convenient to operate. The bismuth vanadate photoelectric anode prepared by the method provided by the invention has low reflectivity and high transmittance, the purity of the bismuth vanadate is high, and the obtained bismuth vanadate photoelectric anode has excellent photocatalytic performance.
The example result shows that the bismuth vanadate photoelectric anode prepared by the method has high transparency, the reflectivity of the bismuth vanadate photoelectric anode to a visible spectrum is 20-30%, the transmissivity of the bismuth vanadate photoelectric anode in a long wavelength region can reach 60-70%, and the current densities of sodium sulfite oxide and water oxide under the applied voltage of 1.23V relative to a standard hydrogen electrode can respectively reach 4.15 milliampere per square centimeter and 2.50 milliampere per square centimeter.
Drawings
FIG. 1 is a transmission electron micrograph of bismuth vanadate nanoparticles obtained in example 1;
FIG. 2 is an XRD spectrum of bismuth vanadate nanoparticles obtained in example 1;
FIG. 3 is a room light photograph of the bismuth vanadate photoanode obtained in example 1;
FIG. 4 is an XRD spectrum of a bismuth vanadate photoanode obtained in example 1;
FIG. 5 is a scanning electron micrograph of a bismuth vanadate photoanode obtained in example 1;
FIG. 6 is a scanning electron micrograph of a cross section of a bismuth vanadate photoanode obtained in example 1;
FIG. 7 is a reflection spectrum of a bismuth vanadate photoanode obtained in example 1;
FIG. 8 is a transmission spectrum of a bismuth vanadate photoanode obtained in example 1;
FIG. 9 is a graph of current density vs. voltage curves for sodium sulfite oxide and water oxide of the bismuth vanadate photoanode obtained in example 1.
Detailed Description
The invention provides a method for preparing a bismuth vanadate photo-anode by spin coating of a nanoparticle solution, which comprises the following steps:
(1) mixing bismuth nitrate with oleic acid, oleylamine and a nonpolar solvent, and reacting in a nitrogen atmosphere at 170-175 ℃ to obtain a mixed solution of bismuth oleate and bismuth oleylamine; the non-polar solvent is octadecene, benzyl ether or liquid paraffin;
(2) cooling the mixed solution of bismuth oleate and bismuth oleylamine to 130-140 ℃, mixing the cooled mixed solution with an aqueous solution of ammonium metavanadate and ammonium paramolybdate, and reacting at the temperature of 90-100 ℃ to obtain molybdenum-doped bismuth vanadate nanoparticles;
(3) dissolving the molybdenum-doped bismuth vanadate nanoparticles in chlorobenzene to obtain a molybdenum-doped bismuth vanadate nanoparticle solution;
(4) and (3) coating the molybdenum-doped bismuth vanadate nanoparticle solution on the surface of FTO conductive glass in a spinning mode, drying, and annealing the obtained FTO conductive glass coating to obtain the bismuth vanadate photoelectric anode.
Mixing bismuth nitrate, oleic acid, oleylamine and a nonpolar solvent, and reacting in a nitrogen atmosphere at 170-175 ℃ to obtain a mixed solution of bismuth oleate and bismuth oleylamine; the non-polar solvent is octadecene, benzyl ether or liquid paraffin. In the invention, the dosage ratio of the bismuth nitrate to the oleic acid to the oleylamine is 1mmol: 1-3 mL, preferably 1mmol:2mL:2 mL; the dosage ratio of the bismuth nitrate to the nonpolar solvent is preferably 1mmol: 5-20 mL, and more preferably 1mmol:10 mL. The present invention does not require any particular source for the bismuth nitrate, the nonpolar solvent, the oleic acid, and the oleylamine, and commercially available products well known to those skilled in the art may be used. At the temperature of 170-175 ℃, bismuth nitrate reacts with oleic acid and oleylamine to generate bismuth oleate and bismuth oleylamine, and the bismuth oleate and the bismuth oleylamine are further dissolved in nonpolar solvents such as octadecene, benzyl ether or liquid paraffin.
After the mixed solution of bismuth oleate and bismuth oleylamine is obtained, the mixed solution of bismuth oleate and bismuth oleylamine is cooled to 130-140 ℃, then mixed with the mixed aqueous solution of ammonium metavanadate and ammonium paramolybdate, and reacted at the temperature of 90-100 ℃ to obtain the molybdenum-doped bismuth vanadate nanoparticles. In the present invention, the cooling method is preferably natural cooling. In the invention, the molar ratio of the ammonium metavanadate and ammonium paramolybdate to the bismuth nitrate is preferably 1-2: 0-0.0058: 1, and more preferably 2:0.0029: 1. In the present invention, the aqueous solution of ammonium metavanadate and ammonium paramolybdate is preferably prepared by the following method: heating water to boiling, adding ammonium metavanadate powder and ammonium paramolybdate powder into the water, continuously heating and shaking for a plurality of minutes until the powder is completely dissolved, and then cooling to room temperature; the dosage ratio of the water to the ammonium metavanadate is preferably 5 mL:1 mmol. Because the aqueous solution of ammonium metavanadate and ammonium paramolybdate is a room-temperature aqueous solution, and is added into the mixed solution of bismuth oleate and bismuth oleylamine at the temperature of 130-140 ℃, the temperature of the mixed solution is rapidly reduced to 80-90 ℃, and therefore the mixed solution needs to be reheated, so that the temperature of the mixed solution reaches the reaction temperature of 90-100 ℃. In the present invention, the reaction time is preferably 5 min. Reacting partial vanadate acid radicals and secondary molybdate acid radicals in the solution with bismuth ions at 90-100 ℃ to generate molybdenum-doped bismuth vanadate nano particles, wherein carrier concentration can be improved by doping molybdenum so as to improve carrier mobility and enhance electrode catalytic performance; in addition, the invention uses excessive oleic acid and oleylamine as ligands, the carboxylate radical and ammonium radical of the oleic acid and oleylamine can be complexed on the surface of the bismuth vanadate nano particle, and the hydrophobic long alkyl chain faces outwards, so that the obtained bismuth vanadate nano particle has very excellent solubility in a low-polarity oil phase solvent, and a completely clear nano particle solution can be obtained.
After the reaction of the metavanadate radical, the secondary molybdate radical and the bismuth ions is finished, the invention preferably carries out post-treatment on the obtained reaction liquid; the post-treatment preferably comprises the steps of:
(a) cooling the obtained reaction liquid to room temperature, then adding ethanol into the reaction liquid, standing for layering to obtain an upper organic phase and a lower aqueous phase, and removing the lower aqueous phase;
(b) adding acetone into the organic phase, and then carrying out first centrifugation to obtain a first precipitate;
(c) and sequentially adding chloroform and ethanol into the first precipitate, and then carrying out second centrifugation to obtain a second precipitate which is molybdenum-doped bismuth vanadate nano particles.
The invention cools the obtained reaction liquid to room temperature, then adds ethanol into the reaction liquid, stands and stratifies to obtain an upper organic phase and a lower aqueous phase. In the present invention, the volume ratio of the reaction solution to ethanol is preferably 1: 0.5 to 1. In the invention, the main components of the upper organic phase are molybdenum-doped bismuth vanadate nano particles, octadecene (dibenzyl ether or liquid paraffin), redundant free oleic acid and oleylamine; the main components of the lower water phase are nitrate ions and ammonium ions; the lower aqueous phase was removed to give the upper organic phase.
After the upper organic phase is obtained, acetone is added into the obtained organic phase, and then first centrifugation is carried out to obtain a first precipitate. In the present invention, the volume ratio of the organic phase to acetone is preferably 1: 1. in the present invention, the acetone is preferably added slowly, and since the solubility of the molybdenum-doped bismuth vanadate nanoparticles having the surfaces complexed with the oleic acid and the oleylamine ligand is poor in a highly polar solvent such as acetone, the solution gradually becomes turbid during the addition of the acetone to generate a precipitate, and the precipitate is separated by a first centrifugation process. In the present invention, the speed of the first centrifugation is preferably 6000r/min, and the time is preferably 3 min. Removing supernatant after first centrifugation to obtain a first precipitate; the supernatant is mainly acetone, octadecene (dibenzyl ether or liquid paraffin), redundant free oleic acid and oleylamine, and the first precipitate is mainly molybdenum-doped bismuth vanadate nano particles.
After the first precipitate is obtained, chloroform and ethanol are sequentially added into the first precipitate, and then second centrifugation is carried out to obtain a second precipitate which is molybdenum-doped bismuth vanadate nano particles. In the present invention, the volume ratio of chloroform to ethanol is preferably 1: 1. In the present invention, chloroform is added to the first precipitate, the first precipitate is completely dissolved in chloroform, ethanol is further added to the resulting solution, the solution is precipitated, and the precipitate is separated by a second centrifugation process. In the present invention, the speed of the second centrifugation is preferably 6000r/min, and the time is preferably 3 min. After second centrifugation, removing supernatant to obtain a second precipitate; the supernatant was mainly chloroform, ethanol, residual octadecene (dibenzyl ether or liquid paraffin), free oleic acid and oleylamine. After the second precipitate is obtained, the invention preferably further repeats the above-mentioned mixing with chloroform and ethanol, and then performs the centrifugation operation to obtain the molybdenum-doped bismuth vanadate nanoparticles. According to the invention, through the processes of washing and centrifuging for many times, relatively pure molybdenum-doped bismuth vanadate nano ions are separated from the reaction liquid. In the present invention, the average particle size of the molybdenum-doped bismuth vanadate nanoparticles is preferably 6 nm.
After the molybdenum-doped bismuth vanadate nano particles are obtained, the molybdenum-doped bismuth vanadate nano ions are dissolved in chlorobenzene to obtain a molybdenum-doped bismuth vanadate nano particle solution. In the invention, the concentration of the molybdenum-doped bismuth vanadate nanoparticle solution is preferably 100-200 mug/mL, and more preferably 100-150 mug/mL. In the present invention, once molybdenum-doped nanoparticles are obtained, they need to be dissolved in chlorobenzene to obtain a clear nanoparticle solution.
After the molybdenum-doped bismuth vanadate nanoparticle solution is obtained, the molybdenum-doped bismuth vanadate nanoparticle solution is coated on the surface of FTO conductive glass in a spinning mode, and after drying, the obtained FTO conductive glass coating is subjected to annealing treatment to obtain the bismuth vanadate photoelectric anode. The FTO (fluorine doped tin oxide) conductive glass has no special requirement, and the FTO conductive glass well known to those skilled in the art can be adopted. In the invention, the rotation speed of the spin coating is preferably 1000-4000 r/min, more preferably 2000-3000 r/min; the number of spin coating is preferably 1-3, more preferably 2-3; the time of each spin coating is preferably 20-60 s, and more preferably 30-50 s; the invention has no special requirement on the solution amount of each spin coating, and can completely cover the substrate. The coating film obtained by spin coating is not completely dried, the solution is directly spin-coated on the surface of the coating film again, and a solvent in the solution can dissolve and damage the previous coating film, so that the wet coating is preferably dried after each spin coating so as to quickly volatilize the residual solvent in the coating film; the drying temperature is preferably 400 ℃, and the drying time is preferably 2-10 min.
After drying, the FTO conductive glass coating is annealed. In the present invention, the annealing treatment method is preferably: heating the FTO conductive glass coating to 550 ℃ at a heating rate of 50 ℃/min, and carrying out first heat preservation; then heating the FTO conductive glass coating which is cooled to room temperature after the first heat preservation to 400-500 ℃ at the heating rate of 10 ℃/min, and carrying out second heat preservation; and heating the FTO conductive glass coating cooled to room temperature after the second heat preservation to 300-400 ℃ at a heating rate of 10 ℃/min, and carrying out third heat preservation. In the present invention, the first heat preservation is preferably performed on a heating table, and the time of the first heat preservation is preferably 30 to 90min, and more preferably 40 to 60 min. In the present invention, the second heat preservation is preferably performed in a tube furnace (under an air atmosphere), and the time of the second heat preservation is preferably 60 to 150min, and more preferably 70 to 90 min. In the invention, the third heat preservation is preferably carried out in a tube furnace, the time of the third heat preservation is preferably 30-120 min, more preferably 90-110 min, and the third heat preservation is preferably carried out in a nitrogen atmosphere. The first heat preservation process and the second heat preservation process of the annealing treatment are high-temperature heat preservation steps, oleic acid and oleylamine ligands which are complexed on the surfaces of the nano particles in the FTO conductive glass coating can be fully removed, adjacent small nano particles can be gradually gathered and grown into larger grains, the size of the grains can reach 100-200 nm, and the large grains are beneficial to carrier transmission and further beneficial to improvement of the catalytic performance of the photoelectric anode; the third heat preservation process of the annealing treatment is to dope a small amount of nitrogen atoms at a relatively low temperature to improve the performance of the photo-anode.
After annealing treatment, the invention also preferably soaks the annealed FTO conductive glass coating in phosphoric acid buffer solution of cobalt chloride, and then irradiates the FTO conductive glass coating soaked in phosphoric acid buffer solution of cobalt chloride with AM1.5 standard sunlight. In the invention, the concentration of cobalt chloride in the phosphoric acid buffer solution of cobalt chloride is preferably 0.1-0.5 mmol/L, and the concentration of phosphate radical is preferably 0.1 mol/L; the pH value of the phosphoric acid buffer solution of cobalt chloride is preferably 7.2. In the invention, the illumination time is preferably 10-30 min. According to the invention, through the processes of soaking and illumination, the cobalt phosphate cocatalyst can be loaded on the surface of the FTO conductive glass coating, so that the improvement of the water oxidation kinetics process of the bismuth vanadate surface is facilitated, and the catalytic performance of water oxidation is facilitated.
After soaking and illumination, the invention preferably carries out deionized water washing and drying on the FTO conductive glass coating loaded with the cocatalyst in sequence to obtain the bismuth vanadate photoelectric anode. The present invention does not require any particular temperature or time for drying, and can remove water sufficiently.
The bismuth vanadate photoelectric anode prepared by the method provided by the invention has low reflectivity and high transmittance, the purity of the bismuth vanadate is high, and the obtained bismuth vanadate photoelectric anode has excellent photocatalytic performance. The reflectivity of the bismuth vanadate photoelectric anode prepared by the method disclosed by the invention to a visible spectrum is 20-30%, the transmittance in a long wavelength region can reach 60-70%, and the current densities of sodium sulfite oxide and water oxide under an applied voltage of 1.23V relative to a standard hydrogen electrode can reach 4.15 milliampere per square centimeter and 2.50 milliampere per square centimeter respectively.
The method for preparing a bismuth vanadate photoanode by using nanoparticle solution spin coating according to the present invention is described in detail below with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
(1) Preparing a bismuth vanadate nanoparticle solution:
firstly, adding 10ml of deionized water into a weighing bottle, heating the mixture to boiling by using a heating table, then adding powder of 2 millimole of ammonium metavanadate and 2.9 micromole of ammonium paramolybdate into the mixture, continuing heating the mixture and shaking the mixture for a plurality of minutes until the powder is completely dissolved, and calling the solution A;
1mmol of bismuth nitrate, 10ml of octadecene, 2ml of oleic acid and 2ml of oily ammonia are added to a three-necked flask, and the mixture is heated to 175 ℃ under nitrogen until the solution is completely clear, which is called solution B;
stopping heating, naturally cooling the solution B, and adding the solution A into the solution B when the solution B is cooled to 140 ℃; then reheating to 100 ℃ for 5 minutes, stopping heating and cooling to room temperature to terminate the reaction;
adding 10ml of ethanol into the mixture after reaction, standing for layering, and removing a lower layer; adding 10ml of acetone into the upper layer, centrifuging for 3 minutes at 6000 rpm, and removing the supernatant; dissolving the precipitate in 10ml of chloroform, adding 10ml of ethanol, centrifuging at 6000 rpm for 3 minutes, and removing the supernatant, wherein the step needs to be repeated for 1 time; the final precipitate, bismuth vanadate nanoparticles, was dissolved in 2mL of chlorobenzene (100. mu.g/mL) to obtain a bismuth vanadate nanoparticle solution.
(2) Preparing a bismuth vanadate photoelectric anode:
(2.1) spin coating: spin-coating a chlorobenzene solution of bismuth vanadate nano particles on FTO conductive glass at the spin-coating speed of 2000 rpm for 20 seconds; heating the mixture on a heating table at 400 ℃ for 2 minutes, and repeating the spin coating process, wherein the total spin coating times are 3;
(2.2) annealing: annealing the FTO conductive glass coating, comprising the following steps: placing the FTO conductive glass coating on a heating table, raising the temperature to 550 ℃ at a speed of 50 ℃ per minute, keeping the temperature for 30 minutes, and cooling to room temperature; then, in the air atmosphere, placing the FTO conductive glass coating in a tube furnace, raising the temperature to 450 ℃ at the speed of 10 ℃ per minute, keeping the temperature for 90 minutes, and cooling to room temperature; then, under the nitrogen atmosphere, raising the temperature of the tube furnace to 375 ℃ at the speed of 10 ℃ per minute, keeping the temperature for 120 minutes, and then cooling the tube furnace to room temperature;
(2.3) deposition of surface promoter, comprising the following steps: and soaking the annealed FTO conductive glass coating in a phosphoric acid buffer solution containing 0.5 millimole per liter of cobalt chloride and 0.1 millimole per liter of phosphate radical and having a pH value of 7.2, using standard sunlight (AM1.5G) as a light source for illumination for 10 minutes, and fully washing and drying the coating by using deionized water to obtain the bismuth vanadate photoelectric anode.
Fig. 1 and fig. 2 are a transmission electron microscope image and an XRD spectrogram of the obtained bismuth vanadate nanoparticles, respectively, from fig. 1, it can be seen that small bismuth vanadate nanoparticles were successfully synthesized in this example, and it can be seen that the synthesized bismuth vanadate nanoparticles are monoclinic type by comparing fig. 2 with a standard card.
Fig. 3 is a room light photograph of the obtained bismuth vanadate photoanode, which shows that the bismuth vanadate photoanode has good transparency.
Fig. 4 is an XRD spectrogram of the obtained bismuth vanadate photo-anode, which is compared with a standard card to show that the bismuth vanadate photo-anode is monoclinic.
FIG. 5 is a scanning electron microscope image of the obtained bismuth vanadate photoanode, which shows that the bismuth vanadate thin film in the photoanode is formed by connecting about 100-200 nm crystal grains.
FIG. 6 is a scanning electron microscope image of the cross section of the obtained bismuth vanadate photoanode, which shows that the thickness of the bismuth vanadate thin film in the photoanode is about 306 nm.
FIG. 7 shows the reflectance of the obtained bismuth vanadate photoanode in the visible spectrum of about 20 to 30%.
Fig. 8 shows the transmittance of the obtained bismuth vanadate photoanode, which indicates that the transmittance of the bismuth vanadate photoanode in the long wavelength region can be 60 to 70%.
The photocatalytic performance of the obtained bismuth vanadate photoelectric anode is tested, and the photocatalytic performance of the obtained photoelectric anode is measured by the current density of sodium sulfite oxide and water oxide under the applied voltage of 1.23V relative to a standard hydrogen electrode, wherein the test method comprises the following steps: a special photoelectrocatalysis electrolytic cell and a three-electrode system are used for carrying out a catalytic performance test, wherein a bismuth vanadate photoelectrode is a working electrode, a platinum electrode is a counter electrode, a silver/silver chloride electrode is a reference electrode, 0.1mol/L phosphoric acid buffer solution with the pH value of 7.2 (when testing sodium sulfite oxide, 1mol/L sodium sulfite is added) is used as electrolyte, and standard sunlight (AM1.5G) is used as a light source; keeping light on the photoelectrode, measuring a linear voltammetry curve by using an electrochemical workstation, and converting the linear voltammetry curve into a current density-voltage curve according to the light area (0.196 square centimeter). Fig. 9 is a measured current density-voltage curve of sodium sulfite oxide and water oxide of a bismuth vanadate photoanode, the upper curve in fig. 9 is a current density-voltage curve of sodium sulfite oxide of a bismuth vanadate photoanode, and the lower curve is a current density-voltage curve of water oxide of a bismuth vanadate photoanode. As can be seen from fig. 9, the current densities of sodium sulfite oxide and water oxide of the obtained bismuth vanadate photo-anode under an applied voltage of 1.23V relative to the standard hydrogen electrode can reach 4.15 milliamperes per square centimeter and 2.50 milliamperes per square centimeter respectively.
Example 2
The bismuth vanadate photoanode was prepared according to the scheme of example 1, except that the annealed FTO conductive glass coating in this example was not subjected to deposition of a surface promoter.
The current densities of sodium sulfite oxide and water oxide of the finally obtained bismuth vanadate photo-anode under the external voltage of 1.23V relative to the standard hydrogen electrode can respectively reach 4.15 milliampere per square centimeter and 1.61 milliampere per square centimeter.
Example 3
The method for preparing the bismuth vanadate photoanode adopts the scheme of the embodiment 1, except that the spin coating step of the embodiment is as follows: performing spin coating by using chlorobenzene solution of bismuth vanadate nano particles, wherein the concentration is 100 mu g/mL, the spin coating rotating speed is 2000 rpm, the spin coating time is 20 seconds, and then heating the bismuth vanadate nano particles on a heating table at 400 ℃ for 2 minutes, wherein the total spin coating times are 1 time; and the annealed FTO conductive glass coating does not undergo surface promoter deposition.
The current density of the sodium sulfite oxide of the finally obtained bismuth vanadate photo-anode under the external voltage of 1.23V relative to the standard hydrogen electrode can reach 2.64 milliampere per square centimeter.
Example 4
The method for preparing the bismuth vanadate photoanode adopts the scheme of the embodiment 1, except that the spin coating step of the embodiment is as follows: performing spin coating by using chlorobenzene solution of bismuth vanadate nano particles, wherein the concentration is 100 mu g/mL, the spin coating rotating speed is 2000 rpm, the spin coating time is 20 seconds, heating the bismuth vanadate nano particles on a heating table at 400 ℃ for 2 minutes, and then repeating the spin coating process, wherein the total spin coating times are 2 times; and the annealed FTO conductive glass coating does not undergo surface promoter deposition.
The current density of the sodium sulfite oxide of the finally obtained bismuth vanadate photo-anode under the external voltage of 1.23V relative to the standard hydrogen electrode can reach 3.63 milliamperes per square centimeter.
Example 5
The method for preparing the bismuth vanadate photoanode adopts the scheme of the embodiment 1, except that the annealing step of the embodiment is as follows: raising the FTO conductive glass coating to 550 ℃ on a heating table at the speed of 50 ℃ per minute, keeping for 30 minutes, and cooling to room temperature; then raising the FTO conductive glass coating to 450 ℃ in a tube furnace at the speed of 10 ℃ per minute in the air atmosphere, keeping the temperature for 90 minutes, and cooling to room temperature; then, under the nitrogen atmosphere, raising the temperature of the tube furnace to 375 ℃ at the speed of 10 ℃ per minute, keeping the temperature for 120 minutes, and then cooling the tube furnace to room temperature; and the annealed FTO conductive glass coating does not undergo surface promoter deposition.
The current density of the sodium sulfite oxide of the finally obtained bismuth vanadate photo-anode under the applied voltage of 1.23V relative to the standard hydrogen electrode can reach 3.41 milliampere per square centimeter.
Example 6
The method for preparing the bismuth vanadate photoanode adopts the scheme of the embodiment 1, except that the annealing step of the embodiment is as follows: raising the FTO conductive glass coating to 550 ℃ on a heating table at the speed of 50 ℃ per minute, keeping for 30 minutes, and cooling to room temperature; then raising the FTO conductive glass coating to 475 ℃ in a tube furnace at the speed of 10 ℃ per minute in the air atmosphere, keeping the temperature for 90 minutes, and cooling to room temperature; then, under the nitrogen atmosphere, raising the temperature of the tube furnace to 375 ℃ at the speed of 10 ℃ per minute, keeping the temperature for 120 minutes, and then cooling the tube furnace to room temperature; and the annealed FTO conductive glass coating does not undergo surface promoter deposition.
The current density of the sodium sulfite oxide of the finally obtained bismuth vanadate photo-anode under the external voltage of 1.23V relative to the standard hydrogen electrode can reach 3.95 milliamperes per square centimeter.
Example 7
The method for preparing the bismuth vanadate photoanode adopts the scheme of the embodiment 1, except that the annealing step of the embodiment is as follows: raising the FTO conductive glass coating to 550 ℃ on a heating table at the speed of 50 ℃ per minute, keeping for 30 minutes, and cooling to room temperature; then raising the FTO conductive glass coating to 450 ℃ in a tube furnace at the speed of 10 ℃ per minute in the air atmosphere, keeping for 60 minutes, and cooling to room temperature; then, under the nitrogen atmosphere, raising the temperature of the tube furnace to 375 ℃ at the speed of 10 ℃ per minute, keeping the temperature for 120 minutes, and then cooling the tube furnace to room temperature; and the annealed FTO conductive glass coating does not undergo surface promoter deposition.
The current density of the sodium sulfite oxide of the finally obtained bismuth vanadate photo-anode under the external voltage of 1.23V relative to the standard hydrogen electrode can reach 3.96 milliampere per square centimeter.
Example 8
The method for preparing the bismuth vanadate photoanode adopts the scheme of the embodiment 1, except that the annealing step of the embodiment is as follows: raising the FTO conductive glass coating to 550 ℃ on a heating table at the speed of 50 ℃ per minute, keeping for 30 minutes, and cooling to room temperature; then raising the FTO conductive glass coating to 450 ℃ in a tube furnace at the speed of 10 ℃ per minute in the air atmosphere, keeping the temperature for 120 minutes, and cooling to room temperature; then, under the nitrogen atmosphere, raising the temperature of the tube furnace to 375 ℃ at the speed of 10 ℃ per minute, keeping the temperature for 120 minutes, and then cooling the tube furnace to room temperature; and the annealed FTO conductive glass coating does not undergo surface promoter deposition.
The current density of the sodium sulfite oxide of the finally obtained bismuth vanadate photo-anode under the external voltage of 1.23V relative to the standard hydrogen electrode can reach 4.15 milliampere per square centimeter.
It can be seen from the above examples that the bismuth vanadate photoanode prepared by the method provided by the invention has low reflectivity and high transmittance, and since the bismuth vanadate nanoparticle solution is synthesized by spin coating, vanadium in the bismuth vanadate generated by reaction no longer has the possibility of volatilization or sublimation, and high-purity bismuth vanadate is obtained after annealing treatment, and the obtained bismuth vanadate photoanode has excellent photocatalytic performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A method for preparing a bismuth vanadate photoelectric anode by utilizing nano particle solution spin coating comprises the following steps:
(1) mixing bismuth nitrate with oleic acid, oleylamine and a nonpolar solvent, and reacting in a nitrogen atmosphere at 170-175 ℃ to obtain a mixed solution of bismuth oleate and bismuth oleylamine; the non-polar solvent is octadecene, benzyl ether or liquid paraffin; the dosage ratio of the bismuth nitrate to the oleic acid to the oleylamine is 1mmol: 1-3 mL;
(2) cooling the mixed solution of bismuth oleate and bismuth oleylamine to 130-140 ℃, mixing the cooled mixed solution with a mixed aqueous solution of ammonium metavanadate and ammonium paramolybdate, and reacting at the temperature of 90-100 ℃ to obtain molybdenum-doped bismuth vanadate nanoparticles;
(3) dissolving the molybdenum-doped bismuth vanadate nanoparticles in chlorobenzene to obtain a molybdenum-doped bismuth vanadate nanoparticle solution;
(4) the molybdenum-doped bismuth vanadate nanoparticle solution is coated on the surface of FTO conductive glass in a spinning mode, and after drying, the obtained FTO conductive glass coating is subjected to annealing treatment to obtain a bismuth vanadate photoelectric anode;
the annealing treatment method comprises the following steps: heating the FTO conductive glass coating to 550 ℃ at a heating rate of 50 ℃/min, and carrying out first heat preservation; then heating the FTO conductive glass coating which is cooled to room temperature after the first heat preservation to 400-500 ℃ at the heating rate of 10 ℃/min, and carrying out second heat preservation; heating the FTO conductive glass coating cooled to room temperature after the second heat preservation to 300-400 ℃ at a heating rate of 10 ℃/min for third heat preservation;
the first heat preservation time is 30-90 min, the second heat preservation time is 60-150 min, the third heat preservation time is 30-120 min, and the third heat preservation is carried out in a nitrogen atmosphere.
2. The method according to claim 1, wherein the molar ratio of ammonium metavanadate and ammonium paramolybdate in the step (2) to bismuth nitrate in the step (1) is 1-2: 0-0.0058: 1.
3. The method according to claim 1 or 2, wherein after the reaction in step (2), the method further comprises purifying the obtained reaction solution; the purification comprises the following steps:
(a) cooling the reaction liquid obtained in the step (2) to room temperature, then adding ethanol into the reaction liquid, standing and layering to obtain an upper organic phase and a lower aqueous phase, and removing the lower aqueous phase;
(b) adding acetone into the organic phase, and then carrying out first centrifugation to obtain a first precipitate;
(c) and sequentially adding chloroform and ethanol into the first precipitate, and then carrying out second centrifugation to obtain a second precipitate which is molybdenum-doped bismuth vanadate nano particles.
4. The method according to claim 1, wherein the molybdenum-doped bismuth vanadate nanoparticles in step (3) have an average particle size of 6 nm; the concentration of the molybdenum-doped bismuth vanadate nanoparticle solution is 100-200 mug/mL.
5. The method according to claim 1, wherein the spin coating in the step (4) is performed at a rotation speed of 1000 to 4000r/min for 1 to 3 times, each spin coating is performed for 20 to 60s, and the wet coating is dried after each spin coating.
6. The method according to claim 1 or 5, wherein the drying temperature in the step (4) is 400 ℃, and the drying time is 2-10 min.
7. The method of claim 1, wherein the step (4) further comprises, after the annealing process:
and soaking the annealed FTO conductive glass coating in a phosphoric acid buffer solution of cobalt chloride, and then illuminating the FTO conductive glass coating soaked in the phosphoric acid buffer solution of cobalt chloride by using AM1.5 standard sunlight.
8. The method according to claim 7, wherein the concentration of cobalt chloride in the phosphoric acid buffer solution of cobalt chloride is 0.1-0.5 mmol/L, and the concentration of phosphate is 0.1 mol/L; the pH value of the phosphoric acid buffer solution of the cobalt chloride is 7.2.
9. The method according to claim 7, wherein the illumination time is 10-30 min.
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