CN111215066A - Pt/BiVO4/Bi2O3Photo-assisted preparation method of catalyst and application of photo-assisted preparation method to photoelectrocatalysis - Google Patents
Pt/BiVO4/Bi2O3Photo-assisted preparation method of catalyst and application of photo-assisted preparation method to photoelectrocatalysis Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 229910002915 BiVO4 Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 102
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- 230000003647 oxidation Effects 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 229910052724 xenon Inorganic materials 0.000 abstract description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 46
- 239000002105 nanoparticle Substances 0.000 description 13
- 239000011941 photocatalyst Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 10
- 229910021397 glassy carbon Inorganic materials 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 238000005234 chemical deposition Methods 0.000 description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 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 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6482—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/33—
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—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
- C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
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- H01M4/90—Selection of catalytic material
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- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to a method for preparing Pt/BiVO by light irradiation4/Bi2O3A method for preparing the catalyst and application thereof in photoelectrocatalysis. The method specifically comprises the following steps: (1) firstly, preparing Pt/BiVO by adopting hydrogen impregnation reduction method4(ii) a (2) Mixing Pt/BiVO4Coating the Pt/BiVO on a conductive substrate, placing the Pt/BiVO in alkaline electrolyte, and using a xenon lamp as a light source4Irradiation oneTiming to obtain Pt/BiVO4/Bi2O3A catalyst. The invention has the advantages that the BiVO is generated under light irradiation4Surface capable of in-situ generation of Bi2O3To obtain BiVO4/Bi2O3The heterojunction has the characteristics of large interface area, tight interface contact and the like; the invention relates to Pt/BiVO4/Bi2O3Has good catalytic performance on the isoelectric catalytic oxidation and the photoelectrocatalysis oxidation of the methanol. In addition, the preparation process is simple and environment-friendly.
Description
Technical Field
The invention belongs to the field of photoelectric catalytic materials, and particularly relates to a bismuth vanadate/bismuth oxide (Pt/BiVO) loaded with noble metal platinum4/Bi2O3) A preparation method of the catalyst and application thereof in photoelectrocatalysis oxidation reaction.
Technical Field
The methanol electrocatalytic oxidation reaction is used as the anode reaction of the direct methanol fuel cell, and the reaction rate of the methanol electrocatalytic oxidation reaction has obvious influence on the discharge performance of the methanol fuel cell. The electrocatalytic oxidation of methanol to carbon dioxide involves 6-electron transfer, the kinetic process is slow, and the currently used platinum-based catalyst is easily poisoned by an intermediate species of methanol oxidation, namely, adsorbed carbon monoxide, so that the energy conversion efficiency of the methanol fuel cell is low. In recent years, it has been reported in the literature that the reaction efficiency of electrochemical oxidation of methanol can be effectively promoted by loading platinum nanoparticles on the surface of a semiconductor carrier having photoresponse under light irradiation. The literature (Journal of electroanalytical Chemistry,2014, 727, 135-140) makes use of WO3As a photocatalyst, Pt/WO (platinum/WO) is used for carrying platinum nano particles under the irradiation of visible light3The electrocatalytic oxidation performance on methanol is improved by 20 percent. Literature (electrochimica acta,2017,245, 863-871) utilizes CuI and TiO2Compared with the traditional electrocatalytic oxidation, the photocatalyst loads the platinum nano-particles, and the Pt-CuI/TiO nano-particles are prepared under the condition of illumination2The electrocatalytic activity for methanol oxidation is improved by 4 times. The literature (Journal of colloid and Interface Science,2019,552,179-185) utilizes two-dimensional ultra-thin bismuth tungstate (Bi)2WO6) The nano-sheet photocatalyst loads platinum nano-particles, and Pt/Bi is subjected to simulated solar radiation2WO6The electrocatalytic oxidation activity to methanol is 5.1 times that under dark field condition, and the excellent methanol oxidation performance is shown.
In the photo-assisted methanol electrocatalytic oxidation reaction, the energy band structure of the semiconductor photocatalyst has an important influence on the performance of the electrocatalytic oxidation reaction. Bismuth vanadate has a narrow band gap (2.4-2.8 eV) and a deep valence band position (2.78 eV), has high light absorption efficiency and strong oxidizing ability, and is often used as a photocatalyst or a photo-catalyst for oxidation reactions. However, photo-generated electron-spaceHoles are easy to recombine, the carrier transmission rate is low, and only minority photo-generated charges can be transferred to the surface of the catalyst to participate in catalytic reaction. In order to improve the efficiency of photo-generated charge separation and transmission, two photocatalysts are generally used to form a heterojunction, and a built-in electric field is used to drive photo-generated charge separation; for heterostructure photocatalysts, band matching and good contact interface are critical to photogenerated charge separation and transport efficiency. The document (Journal of Alloys and Compounds,2017,706,7-15) adopts bismuth nitrate and ammonium metavanadate as precursors, and prepares BiVO by regulating the proportion of the two precursors by a chemical deposition method4/Bi2O3Heterojunction, with BiVO4And Bi2O3BiVO, comparison of physically mixed samples4/Bi2O3The photocatalytic degradation capability of the heterojunction to the bisphenol A is obviously improved. However, BiVO prepared by the current physical mixing method and chemical deposition method4/Bi2O3The heterojunction has the problems of small interface area, insufficient contact and the like, so that the photoproduction charge separation efficiency and the transmission efficiency are still lower, and the development of the composite photocatalyst with energy band matching and good interface contact has important significance.
Disclosure of Invention
Aiming at BiVO prepared by the existing chemical deposition method and physical mixing method4/Bi2O3The invention provides a novel light irradiation in-situ generation BiVO (Bipolar-VO)4/Bi2O3Preparation technology of heterojunction and BiVO prepared by utilizing preparation technology4/Bi2O3The heterojunction interface area is large, and the photoelectric catalytic oxidation performance of the loaded platinum nanoparticles on methanol is good.
In one aspect, the invention provides a noble metal-loaded Pt/BiVO4/Bi2O3The preparation method of the heterojunction loads Pt nano particles to BiVO4In the above, BiVO is utilized4Can be decomposed into Bi under the irradiation of ultraviolet light2O3And V2O5At the same time V2O5Can be dissolved in alkaline electrolyte to obtain Pt/BiVO4/Bi2O3A photocatalyst. The method is characterized in that:
(1) mixing the chloroplatinic acid aqueous solution and BiVO4Uniformly mixing, drying, and then preserving the heat for 30 minutes at 180 ℃ in a hydrogen/argon mixed atmosphere to obtain Pt/BiVO4;
(2) Mixing Pt/BiVO4Coating the mixture on a conductive substrate, placing the conductive substrate in alkaline electrolyte, and irradiating the electrode for a certain time by adopting ultraviolet light to obtain Pt/BiVO4/Bi2O3A photocatalyst.
The conductive substrate can be at least one of carbon paper, carbon cloth, foamed nickel, foamed iron/foamed titanium or conductive glass;
the ultraviolet light irradiation time is 10 seconds to 120 minutes.
In still another aspect, the invention also provides Pt/BiVO4/Bi2O3The application of the photoelectric catalyst in the photoelectric catalytic oxidation reaction of methanol.
The preparation of Pt/BiVO mentioned in the invention4/Bi2O3The method of the photoelectric catalyst has the characteristics of simplicity, easiness in operation, environmental friendliness, low cost and the like. Pt/BiVO prepared by the invention4/Bi2O3The photoelectric catalyst is generated in situ and is in contact with BiVO4And Bi2O3Compared with a physically mixed sample, the method has the advantages of large interface area, high photoproduction charge transmission rate and high photoelectrocatalysis performance.
Drawings
FIGS. 1(a) and (b) are Pt/BiVO prepared in example 14Transmission electron microscope and high resolution transmission electron microscope images;
FIGS. 1(c) and (d) are Pt/BiVO prepared in example 14/Bi2O3Transmission electron microscope and high resolution transmission electron microscope images of the photocatalyst;
FIG. 2 is a comparison of cyclic voltammograms of the catalysts prepared in examples 1, 2 and 3 and of a comparative example for the electrocatalytic oxidation of methanol;
FIG. 3 is a comparison of cyclic voltammograms of the catalysts prepared in examples 1, 2 and 3 and of the comparative example for the electrocatalytic oxidation of methanol under light irradiation.
Detailed Description
The invention is further illustrated below with reference to specific examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The method comprises the following steps: 2.428 g of pentahydrate bismuth nitrate is weighed and dissolved in 10 ml of 4.0 mol/L nitric acid water solution, and then 0.255 g of sodium dodecyl benzene sulfonate is added and stirred evenly; 0.589 g of ammonium metavanadate is weighed and dissolved in 10 ml of 2.0 mol/L sodium hydroxide aqueous solution, and the two solutions are mixed and stirred uniformly. Then, a 2.0 mol/l aqueous solution of sodium hydroxide was added dropwise to the mixed solution until the pH of the mixed solution was 7.0. Pouring the mixed solution into a 100 ml high-pressure reaction kettle, preserving the heat for 90 minutes at 200 ℃, cooling to room temperature, centrifugally separating yellow precipitate, and washing with absolute ethyl alcohol and deionized water. Then drying for 12 hours at 60 ℃ in a vacuum drying oven to obtain BiVO4And (3) powder.
Step two: weighing 190 mg of BiVO obtained in the first step4Adding the powder into 30 ml of ultrapure water, performing ultrasonic dispersion for 10 minutes, adding 2.705 ml of a 3.7 mg/ml chloroplatinic acid aqueous solution, uniformly mixing, and evaporating water in a rotary evaporator to dryness to obtain orange powder; putting the yellow powder in a quartz boat, placing the quartz boat in a tube furnace, introducing hydrogen/argon mixed gas, treating the quartz boat for 30 minutes at 180 ℃, taking out a sample after the temperature is reduced to room temperature, washing the sample with deionized water for a plurality of times, and finally drying the sample in a vacuum drying oven for 12 hours at 60 ℃ to obtain Pt/BiVO4And (3) sampling.
Step three: 5 mg of Pt/BiVO obtained in the second step4And 1 mg of activated carbon powder, adding 1 ml of absolute ethyl alcohol, uniformly dispersing by ultrasonic, adding 30 microliters of 5% naphthol solution, forming uniform slurry by ultrasonic dispersion, taking 10 microliters of slurry to drop-coat a glassy carbon electrode with the diameter of 5 mm, drying, placing the glassy carbon electrode coated with the catalyst in 1 mol/l potassium hydroxide aqueous solution, and irradiating the glassy carbon electrode coated with the catalyst by using xenon ultraviolet light for 20 minutes to obtain Pt/BiVO4/Bi2O3And (3) sampling.
Example 2
The first step and the second step are the same as the first step and the second step in the embodiment 1.
Step three: 5 mg of Pt/BiVO obtained in the second step4And 1 mg of activated carbon powder, adding 1 ml of absolute ethyl alcohol, uniformly dispersing by ultrasonic, adding 30 microliters of 5% naphthol solution, forming uniform slurry by ultrasonic dispersion, taking 10 microliters of slurry to drop-coat on a glassy carbon electrode with the diameter of 5 mm, drying, placing the glassy carbon electrode coated with the catalyst in 1 mol/l potassium hydroxide aqueous solution, and irradiating the glassy carbon electrode coated with the catalyst by using xenon ultraviolet light for 40 minutes to obtain Pt/BiVO4/Bi2O3And (3) sampling.
Example 3
The first step and the second step are the same as the first step and the second step in the embodiment 1.
Step three: 5 mg of Pt/BiVO obtained in the second step4And 1 mg of activated carbon powder, adding 1 ml of absolute ethyl alcohol, uniformly dispersing by ultrasonic, adding 30 microliters of 5% naphthol solution, forming uniform slurry by ultrasonic dispersion, taking 10 microliters of slurry to drop-coat a glassy carbon electrode with the diameter of 5 mm, drying, placing the glassy carbon electrode coated with the catalyst in 1 mol/l potassium hydroxide aqueous solution, and irradiating the glassy carbon electrode coated with the catalyst by using xenon ultraviolet light for 60 minutes to obtain Pt/BiVO4/Bi2O3And (3) sampling.
Comparative example procedure the first and second procedure were as in example 1.
Step two: 4 mmol of bismuth nitrate pentahydrate was dissolved in 50 ml of dimethylformamide solution, and after stirring for 2 hours, the mixed solution was poured into 100 ml of high-pressure reactionAnd (5) preserving the heat for 12 hours at 180 ℃ in the kettle. After cooling to room temperature, the dark gray precipitate was centrifuged and washed clean with absolute ethanol and deionized water. Drying at 60 ℃ for 12 hours in a vacuum drying oven, loading the black and gray powder into a quartz boat, placing the quartz boat in a muffle furnace, and treating at 400 ℃ for 2 hours to obtain Bi2O3And (3) powder.
Step three: weighing 87 mg of bismuth vanadate powder obtained in the first step and 8 mg of bismuth oxide powder obtained in the second step, adding the bismuth vanadate powder and the bismuth oxide powder into 30 ml of ultrapure water, performing ultrasonic dispersion for 10 minutes, adding 1.355 ml of a 3.7 mg/ml chloroplatinic acid aqueous solution, uniformly mixing, and evaporating water in a rotary evaporator to dryness to obtain orange powder; placing the yellow powder in a quartz boat, placing the quartz boat in a tubular furnace, introducing hydrogen/argon mixed gas, treating the quartz boat for 30 minutes at 180 ℃, taking out a sample after the temperature is reduced to room temperature, and performing suction filtration and washing on the sample in a Buchner funnel for several times by using deionized water; finally, drying the obtained filter cake in a vacuum drying oven at 60 ℃ for 12 hours to obtain Pt-loaded BiVO4And Bi2O3The samples were physically mixed.
Effect example 1
Pt/BiVO obtained in examples 1, 2, 3 and comparative examples in an electrochemical three-electrode system using the Shanghai Chenghua electrochemical workstation (CHI604E)4/Bi2O3The catalyst was tested for its electrocatalytic oxidation properties on methanol. The working electrode was prepared by dispersing 5 mg of the catalyst in 1 ml of absolute ethanol, adding 30. mu.l of naphthol solution (5%, DuPont corporation) as a binder, ultrasonically dispersing for 15 minutes, coating 10. mu.l of the solution on the surface of a glassy carbon electrode (diameter: 5 mm), and drying in air to obtain the working electrode. The counter electrode was a graphite rod, the reference electrode was mercury/mercury oxide (0.951 volts vs. reversible hydrogen electrode), and the electrolyte was a mixed aqueous solution of 1 mol/l potassium hydroxide and 1 mol/l methanol. The potential window for electrochemical scanning ranged from 0.151 volts to 1.251 volts (versus a reversible hydrogen electrode), the scan rate was 20 millivolts/second, and the current-potential curve was recorded. The results are shown in FIG. 2.
Effect example 2
Pt/BiVO obtained in examples 1, 2, 3 and comparative examples in an electrochemical three-electrode system with a light window using the Shanghai Chenghua electrochemical workstation (CHI604E)4/Bi2O3The catalyst is used for testing the electrocatalytic oxidation performance of the methanol under the irradiation of light. The working electrode of example 1 was prepared, and the counter electrode, reference electrode, electrolyte and test methods were the same as those of example 1. Except that the catalyst coated working electrode was irradiated with xenon uv light while performing the electrochemical scan. The total output power of the xenon lamp is 50 watts, and the wavelength range is 320-2500 nanometers. The current-potential curve of the electrochemical scan was recorded. The results are shown in FIG. 3.
As can be seen from the transmission electron microscope and high resolution transmission electron microscope images of the sample of example 1 in FIG. 1, the Pt nanoparticles are distributed relatively uniformly in the BiVO4On the nano sheet, the lattice spacing of nano particles generated on the surface is 0.231 nm, and the nano particles belong to a Pt (111) crystal face; the lattice spacing of the substrate is 0.473 nm, and the substrate is BiVO4(110) A crystal plane. As can be seen from the transmission electron microscope and high resolution transmission electron microscope images of FIGS. 1(c) and (d), Bi2O3Nanoparticles and BiVO4The nano sheets are overlapped in an interlaced way, the lattice spacing of the nano particles generated on the surface is 0.346 nanometer, and the nano particles are assigned as Bi2O3(002) A crystal face; the lattice spacing of the substrate is 0.303 nm, and the substrate is BiVO4(121) A crystal plane. Thus, it was confirmed that light irradiation of Pt/BiVO was performed4After the surface, Pt/BiVO is formed in situ4/Bi2O3A heterojunction. The heterojunction formed by the method has the characteristics of large interface area and tight contact.
As can be seen from fig. 2, the peak current for the electrocatalytic oxidation of methanol was gradually increased for the catalyst samples of example 1, example 2 and example 3, and reached 3.9 ma/cm for the electrocatalytic oxidation of methanol for the sample of example 3. This is due to BiVO with increasing light irradiation time during catalyst preparation4Surface in situ generated Bi2O3Increased BiVO4/Bi2O3The interface area between the two is increased, and the promotion is thatThe charge transfer in the electrochemical oxidation process is realized, so that the electrocatalytic oxidation performance of the methanol is improved. BiVO in comparative sample4/Bi2O3The interfacial contact between them is not tight enough and thus the performance for electrocatalytic oxidation of methanol is intermediate between the samples of example 1 and example 2. Therefore, the Pt/BiVO prepared by the invention4/Bi2O3The heterojunction catalyst has excellent methanol electrocatalytic oxidation performance.
As can be seen from fig. 3, under the irradiation of ultraviolet light, the peak current of the catalyst samples of example 1, example 2 and example 3 for the electrocatalytic oxidation of methanol gradually increases, and the sample of example 3 has the highest peak current for the photoelectrocatalytic oxidation of methanol, reaching 4.6 milliamperes per square centimeter. The comparative sample has a performance for methanol oxidation that is intermediate between the samples of example 1 and example 2. Effect example 1, example 2, example 3 and comparative example all showed significant increases in methanol oxidation current, 44.4%, 207.7%, 17.9% and 68.8%, respectively, compared to the methanol oxidation current measured in no light irradiation in example 1. Therefore, the Pt/BiVO prepared by the invention4/Bi2O3The catalyst has excellent photoelectrocatalysis performance when being used for photo-assisted methanol electrocatalysis oxidation.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (6)
1. Pt/BiVO4/Bi2O3The preparation method of the catalyst is that Pt/BiVO is mixed4Irradiating with light in alkaline solution for a certain time at Pt/BiVO4Surface in situ generation of Bi2O3Thereby obtaining Pt/BiVO4/Bi2O3A catalyst.
2. As claimed inSolution of the Pt/BiVO of claim 14The method is characterized in that the loading amount of Pt can be 0.1-10%.
3. The alkaline solution of claim 1, wherein the alkaline solution is 0.01-5 mol/L KOH, NaOH or NaHCO3And the like.
4. The method of claim 1, wherein the wavelength of light used is greater than 320 nm.
5. The light irradiation time of claim 1 may be 10 seconds to 120 minutes.
6. The Pt/BiVO of claim 14/Bi2O3Can be used as an electrocatalytic methanol oxidation catalyst and a photoelectrocatalytic methanol oxidation catalyst.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111751414A (en) * | 2020-06-10 | 2020-10-09 | 西安电子科技大学 | Preparation method and application of irradiation modified bismuth vanadate aptamer photoelectrochemical sensor |
CN113571717A (en) * | 2021-07-23 | 2021-10-29 | 中国人民解放军军事科学院军事医学研究院 | High-efficiency photoelectrode and preparation method and application thereof |
KR20220157075A (en) * | 2021-05-20 | 2022-11-29 | 성균관대학교산학협력단 | Method for manufacturing photoelectrode |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106450508A (en) * | 2016-11-30 | 2017-02-22 | 湘潭大学 | Bismuth vanadium/nickel hydroxide secondary alkaline battery and preparation method thereof |
CN106898780A (en) * | 2017-01-22 | 2017-06-27 | 天津大学 | One kind has multilayer BiVO4Electrode, its preparation method and its purposes in photoelectrocatalysis |
CN107042103A (en) * | 2016-02-05 | 2017-08-15 | 高丽大学校产学协力团 | The photochemical catalyst of bioxin is removed, the method that the method and photoactivation agent for preparing photochemical catalyst handle bioxin contaminated soil |
CN108273492A (en) * | 2018-04-01 | 2018-07-13 | 云南大学 | A kind of bismuth oxide/bismuth tetroxide heterojunction photocatalyst and its preparation method and purposes |
CN110354840A (en) * | 2019-08-02 | 2019-10-22 | 重庆大学 | It is a kind of to prepare β-Bi2O3/BiVO4The new method of composite photocatalyst material |
CN110791777A (en) * | 2019-10-29 | 2020-02-14 | 天津大学 | Bismuth vanadate electrode rich in surface oxygen vacancies and preparation method and application thereof |
-
2020
- 2020-02-22 CN CN202010109394.XA patent/CN111215066B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107042103A (en) * | 2016-02-05 | 2017-08-15 | 高丽大学校产学协力团 | The photochemical catalyst of bioxin is removed, the method that the method and photoactivation agent for preparing photochemical catalyst handle bioxin contaminated soil |
CN106450508A (en) * | 2016-11-30 | 2017-02-22 | 湘潭大学 | Bismuth vanadium/nickel hydroxide secondary alkaline battery and preparation method thereof |
CN106898780A (en) * | 2017-01-22 | 2017-06-27 | 天津大学 | One kind has multilayer BiVO4Electrode, its preparation method and its purposes in photoelectrocatalysis |
CN108273492A (en) * | 2018-04-01 | 2018-07-13 | 云南大学 | A kind of bismuth oxide/bismuth tetroxide heterojunction photocatalyst and its preparation method and purposes |
CN110354840A (en) * | 2019-08-02 | 2019-10-22 | 重庆大学 | It is a kind of to prepare β-Bi2O3/BiVO4The new method of composite photocatalyst material |
CN110791777A (en) * | 2019-10-29 | 2020-02-14 | 天津大学 | Bismuth vanadate electrode rich in surface oxygen vacancies and preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
JIAYUE HU,ET AL: ""Enhanced electrocatalytic ethanol oxidation reaction in alkaline media over Pt on a 2D BiVO4-modified electrode under visible light irradiation"", 《CATAL. SCI. TECHNOL.》 * |
R. MIRABAL-ROJAS,ET AL: ""Effect of the KOH chemical treatment on the optical and photocatalytic properties of BiVO4 thin films"", 《APPL. PHYS. A》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111751414A (en) * | 2020-06-10 | 2020-10-09 | 西安电子科技大学 | Preparation method and application of irradiation modified bismuth vanadate aptamer photoelectrochemical sensor |
CN111751414B (en) * | 2020-06-10 | 2022-01-28 | 西安电子科技大学 | Irradiation modified bismuth vanadate aptamer photoelectrochemical sensor |
KR20220157075A (en) * | 2021-05-20 | 2022-11-29 | 성균관대학교산학협력단 | Method for manufacturing photoelectrode |
KR102609275B1 (en) | 2021-05-20 | 2023-12-04 | 성균관대학교산학협력단 | Method for manufacturing photoelectrode |
CN113571717A (en) * | 2021-07-23 | 2021-10-29 | 中国人民解放军军事科学院军事医学研究院 | High-efficiency photoelectrode and preparation method and application thereof |
CN113571717B (en) * | 2021-07-23 | 2024-03-19 | 中国人民解放军军事科学院军事医学研究院 | Efficient photoelectrode and preparation method and application thereof |
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