CN109092319B - WO (WO)3/BiVO4Ternary system composite material of/FeOOH and preparation method and application thereof - Google Patents
WO (WO)3/BiVO4Ternary system composite material of/FeOOH and preparation method and application thereof Download PDFInfo
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- CN109092319B CN109092319B CN201810678391.0A CN201810678391A CN109092319B CN 109092319 B CN109092319 B CN 109092319B CN 201810678391 A CN201810678391 A CN 201810678391A CN 109092319 B CN109092319 B CN 109092319B
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- 229910002588 FeOOH Inorganic materials 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910002915 BiVO4 Inorganic materials 0.000 claims abstract description 121
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 60
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 18
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229960000583 acetic acid Drugs 0.000 claims description 15
- 239000012362 glacial acetic acid Substances 0.000 claims description 15
- 238000010041 electrostatic spinning Methods 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 9
- 238000009987 spinning Methods 0.000 claims description 9
- 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 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 238000005286 illumination Methods 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 4
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- CSKRBHOAJUMOKJ-UHFFFAOYSA-N 3,4-diacetylhexane-2,5-dione Chemical compound CC(=O)C(C(C)=O)C(C(C)=O)C(C)=O CSKRBHOAJUMOKJ-UHFFFAOYSA-N 0.000 claims description 2
- FMEQFHHWMWVKLH-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[V+5].[V+5].CC(=O)CC(C)=O.CC(=O)CC(C)=O Chemical compound [O--].[O--].[O--].[O--].[O--].[V+5].[V+5].CC(=O)CC(C)=O.CC(=O)CC(C)=O FMEQFHHWMWVKLH-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 24
- 230000008569 process Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000010408 film Substances 0.000 description 15
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 238000002256 photodeposition Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910003091 WCl6 Inorganic materials 0.000 description 2
- 238000002083 X-ray spectrum Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B01J35/39—
-
- B01J35/60—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to WO3/BiVO4A/FeOOH ternary system composite material, a preparation method thereof and application thereof in photoelectrocatalysis belong to the field of photoelectrocatalysis. WO (WO)3/BiVO4The ternary system composite material of/FeOOH is mainly expressed in the form of monoclinic phase WO3Monoclinic BiVO4And amorphous FeOOH. WO3At the bottom layer, BiVO4Is covered in WO3FeOOH is coated on the outermost layer, wherein, BiVO4Has a mass of WO3/BiVO4The total mass of the/FeOOH ternary system composite material is 85-95%. WO of the invention3/BiVO4WO utilized by/FeOOH ternary system composite material3Porous BiVO4The high-efficiency heterojunction is constructed, FeOOH is used as a cocatalyst, the photoelectric catalytic performance is improved in many aspects, and the high-efficiency heterojunction can be effectively applied to photoelectric catalysis and has high efficiency and stability.
Description
Technical Field
The present invention relates to WO3/BiVO4A/FeOOH ternary system composite material, a preparation method thereof and application thereof in photoelectrocatalysis belong to the field of photoelectrocatalysis.
Background
The increasing social demand brings many challenges to electricity and energy, such as improving energy efficiency, developing new energy, and protecting the environment. Hydrogen energy is considered an ideal energy carrier because it is clean, renewable, widely available, and has a very high energy density. Semiconductor materials have attracted a wide range of attention for the conversion of solar energy into chemical energy by the decomposition of water energy by Photoelectrochemistry (PEC).
BiVO4The material has the advantages of narrow forbidden band width (2.4 eV), proper energy band structure, excellent stability and low cost, and has potential application in the aspects of photocatalytic degradation of organic pollutants, photocatalytic decomposition of water, photoelectrocatalysis, photoluminescence and the like. However, affect BiVO4The main factors of the conversion efficiency of the photoanode are the limited light absorption capacity, charge separation efficiency and surface charge transfer capacity, which greatly limit its application in photoelectrocatalysis. Researches show that the charge separation efficiency can be effectively improved by constructing a heterojunction, and meanwhile, the surface charge transfer capacity can be greatly improved by adding a cocatalyst on the surface, so that the water decomposition efficiency of photoelectrocatalysis is improved. Therefore, based on the above discussion, if an effective method for preparing heterojunction structure and cocatalyst can be found, it would be expected to solve the current single-phase BiVO4The main problems of the materials strongly promote the application of the photoelectrocatalysis technology in the field of solar energy conversion.
Disclosure of Invention
The present invention has been made to solve the above problems occurring in the prior art, and an object of the present invention is to provide a WO having high and stable catalytic activity3/BiVO4the/FeOOH ternary system composite material.
The purpose of the invention can be realized by the following technical scheme: WO (WO)3/BiVO4The ternary system composite material of/FeOOH, the main manifestation form of the composite material is monoclinic phase WO3Monoclinic BiVO4And amorphous FeOOH.
In the above-mentioned WO3/BiVO4In the ternary system composite material of/FeOOH, WO3At the bottom layer, BiVO4Is covered in WO3FeOOH is coated on the outermost layer of the film, wherein，BiVO4Has a mass of WO3/BiVO4The total mass of the/FeOOH ternary system composite material is 85-95%.
In the above-mentioned WO3/BiVO4In the ternary system composite material of/FeOOH, WO3WO with a particle size of 30-60nm3Films, WO3The thickness of the film is 30-50nm, BiVO4Is porous BiVO4The thickness of the porous BiVO is 300-1800nm, and the thickness of the FeOOH is 0.5-10 nm.
The present invention also provides the above WO3/BiVO4The preparation method of the/FeOOH ternary system composite material comprises the following steps:
tungsten hexachloride (WCl)6) Dissolving polyvinylpyrrolidone (PVP) in dimethyl formamide (DMF), stirring at room temperature to form spin coating liquid, coating the spin coating liquid on the conductive surface of the FTO conductive glass, drying, and annealing to form WO3A film substrate;
PVP, vanadium bis (acetylacetonate) (VO (acac))2) Dissolving bismuth nitrate pentahydrate and diisopropyl azodicarboxylate (DIPA) in absolute ethyl alcohol, glacial acetic acid and dimethyl formamide, stirring and mixing at room temperature to obtain spinning solution, using metal needle as anode, and using WO3Using the film substrate as a cathode, carrying out electrostatic spinning on the spinning solution to obtain a precursor film, and annealing the precursor film to obtain WO3Porous BiVO4；
In FeSO4·H2In O solution, WO3Porous BiVO4Working as a working electrode, Ag/AgCl (3M KCl) as a reference electrode, a platinum sheet counter electrode, a 300W xenon lamp and AM 1.5G under illumination, and carrying out light deposition at a potential of 0.5V vs. Ag/AgCl to obtain WO3/BiVO4the/FeOOH ternary system composite material.
The raw material used in the preparation of the ternary system composite material is WCl6、PVP、 DMF、Bi(NO3)3·5H2O、VO(acac)2And DIPA, absolute ethyl alcohol, glacial acetic acid, FeSO4·H2O, wherein PVP, DMF, absolute ethyl alcohol, glacial acetic acid and DIPA are decomposed and completely volatilized in the calcining treatment process; WCl6Providing a W sourceTo WO3，Bi (NO3)3·5H2O and VO (acac)2Separately provide a Bi source for BiVO4Synthesis of FeSO4·H2O provides a Fe source, and FeOOH is synthesized. Diisopropyl azodicarboxylate (DIPA) is added in the electrostatic spinning as a foaming agent, and is dissolved in spinning solution, and a large amount of gas is released in the later annealing process to form porous BiVO4。
In the above-mentioned WO3/BiVO4In the preparation method of the ternary system composite material of/FeOOH, vanadium oxide bis (acetylacetone) (VO (acac))2) The mass ratio of the bismuth nitrate pentahydrate to the bismuth nitrate pentahydrate is (1.5-2.5): 1.
in the above-mentioned WO3/BiVO4In the preparation method of the/FeOOH ternary system composite material, the mass ratio of absolute ethyl alcohol, glacial acetic acid and dimethylformamide in the electrostatic spinning solution is 1: (2.5-4): (1.5-2.5). The anhydrous ethanol, the glacial acetic acid and the dimethylformamide are used as solvents to dissolve the bismuth nitrate pentahydrate and the vanadium oxide bis (acetylacetone), and the yarns can be spun only by proportioning the anhydrous ethanol, the glacial acetic acid and the dimethylformamide according to the proportion in consideration of the volatilization rate of the solvents during spinning.
In the above-mentioned WO3/BiVO4In the preparation method of the/FeOOH ternary system composite material, the mass ratio of absolute ethyl alcohol, glacial acetic acid and dimethylformamide in the electrostatic spinning solution is 1:3: 2.
In the above-mentioned WO3/BiVO4In the preparation method of the/FeOOH ternary system composite material, the distance between an anode and a cathode in electrostatic spinning is 12-18cm, the injection speed is 0.05-0.2mm/min, the pressure is 10-22kV, and the electrostatic spinning time is 5-18 min.
In the above-mentioned WO3/BiVO4In the preparation method of the/FeOOH ternary system composite material, the light deposition time is 5min-20 min. In the present application, if the deposition time is too short, less than 5min, the FeOOH content is too low to completely cover WO3Porous BiVO4The function of the cocatalyst cannot be fully exerted; if the deposition time is too long and is more than 20min, the excessive FeOOH can affect the light absorption of the electrode and the separation and transmission of photon-generated carriersThereby affecting the photocatalytic efficiency.
It is a third object of the present invention to provide the above WO3/BiVO4The application of the/FeOOH ternary system composite material in photoelectrocatalysis is implemented by mixing WO3/BiVO4the/FeOOH ternary system composite material is used as a working anode, Ag/AgCl (3M KCl) is used as a reference electrode, a platinum sheet counter electrode is used under the illumination of a xenon lamp and 0.5M Na2SO4And 0.5M Na2SO3The photocurrent density and the impedance of the mixed solution were measured by an electrochemical workstation.
The light source used for detecting the photocatalytic performance is xenon lamp simulated sunlight, and other types of light sources can also be used.
Compared with the prior art, the invention has the following advantages:
1. WO of the invention3/BiVO4WO utilized by/FeOOH ternary system composite material3Porous BiVO4An efficient heterojunction is constructed, FeOOH is used as a cocatalyst, and the photoelectric catalytic performance is improved in many aspects.
2. BiVO of the invention4The porous structure is formed by adding the DIPA foaming agent in the synthesis, so that the electrolyte can be conveniently infiltrated in the photoelectrocatalysis performance test, more active sites are manufactured, and the improvement of the photoelectrocatalysis performance is facilitated.
3. WO of the invention3/BiVO4the/FeOOH ternary system material can be effectively applied to photoelectrocatalysis and has high efficiency and stability.
4. WO of the invention3/BiVO4The preparation method of the/FeOOH ternary system photoelectric anode has simple and controllable process and good repeatability.
Drawings
FIG. 1 shows WO obtained in example 1 of the present invention3Scanning Electron Microscope (SEM) images of thin film substrates;
FIG. 2 shows WO obtained in example 1 of the present invention3Scanning Electron Microscope (SEM) images of the cross section of the thin film substrate;
FIG. 3 shows WO obtained in example 1 of the present invention3Porous BiVO4Scanning Electron Microscope (SEM) images of (a);
FIG. 4 shows WO obtained in example 1 of the present invention3Porous BiVO4Cross-sectional Scanning Electron Microscope (SEM) images of (a);
FIG. 5 shows WO obtained in example 1 of the present invention3/BiVO4A Scanning Electron Microscope (SEM) picture of/FeOOH;
FIG. 6 shows WO obtained in example 1 of the present invention3/BiVO4A cross-sectional Scanning Electron Microscope (SEM) image of/FeOOH;
FIG. 7 shows WO obtained in example 1 of the present invention3/BiVO4X-ray diffraction patterns (XRD) of a/FeOOH photoanode;
FIG. 8 shows WO obtained in example 1 of the present invention3/BiVO4Raman spectrum (Raman) of FeOOH photo-anode;
FIG. 9 shows WO obtained in example 2 of the present invention3/BiVO4A cross section Scanning Electron Microscope (SEM) image of the/FeOOH ternary system composite material;
FIG. 10 shows WO obtained in example 3 of the present invention3/BiVO4A cross section Scanning Electron Microscope (SEM) image of the/FeOOH ternary system composite material;
FIG. 11 is a high resolution TEM image of the material obtained in example 4 of the present invention;
FIG. 12 shows WO obtained in comparative example 1 of the present invention3Raman spectra (Raman) of thin films;
FIG. 13 shows BiVO without DIPA obtained in comparative example 2 of the present invention4Scanning Electron Microscope (SEM) images;
FIG. 14 shows BiVO without DIPA obtained in comparative example 2 of the present invention4X-ray diffraction pattern (XRD);
FIG. 15 shows BiVO with added DIPA obtained in comparative example 3 of the present invention4Scanning Electron Microscope (SEM) images;
FIG. 16 shows BiVO with added DIPA obtained in comparative example 3 of the present invention4X-ray diffraction pattern (XRD);
FIG. 17 shows WO of the present invention3Film, BiVO4Porous BiVO4、WO3Porous BiVO4And WO3/BiVO4A photocurrent density comparison graph of the/FeOOH ternary system composite material under different bias voltages;
FIG. 18 shows WO of the present invention3Film, BiVO4Porous BiVO4、WO3Porous BiVO4And WO3/BiVO4A transient photocurrent density contrast diagram of the/FeOOH ternary system composite material along with the prolonging of illumination time;
FIG. 19 shows WO of the present invention3Film, BiVO4Porous BiVO4、WO3Porous BiVO4And WO3/BiVO4Impedance comparison graph of ternary system composite material of/FeOOH.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1
0.1g of polyvinylpyrrolidone (PVP) and 0.02g of tungsten hexachloride (WCl) were weighed out separately6) Dissolved in 10ml of Dimethylformamide (DMF), and stirred at room temperature for 1 hour to obtain a spin-on solution. Coating 20 microliter of the obtained product on the conductive surface of FTO conductive glass at 2000 rpm, drying at 80 deg.C for 3 hr, and annealing at 500 deg.C in a muffle furnace for 1 hr to obtain WO3A film substrate. FIG. 1 shows the WO obtained3Scanning Electron Microscope (SEM) pictures of thin film substrates, it can be seen that WO3The particles are about 50nm and densely cover the FTO conductive surface. FIG. 2 shows the WO obtained3Cross-sectional Scanning Electron Microscopy (SEM) of thin film substrates, demonstrating WO3The thickness of the thin film substrate was about 35 nm.
0.5g of PVP, 2.468g of Bi (NO)3)3·5H2O、1.337g VO(acac)2And 1g of DIPA was dissolved in 2g of DMF, 3g of glacial acetic acid and 1g of absolute ethanol, and stirred at room temperature to be mixed into a spinning solution, 3mL of which was taken out and injected into a plastic syringe, and the plastic syringe was placed on an electrostatic spinning machine, with the injection speed set at 0.1 mm/min. A metal needle as an anode, the previously prepared WO3Using a film substrate as a cathode, fixing the distance between the anode and the cathode to be 15cm, carrying out electrostatic spinning at 20kV and high pressure for 15 minutes to obtain a precursor film, and annealing at 450 ℃ for 1 hour in a muffle furnaceThen, WO is obtained3Porous BiVO4A material. FIG. 3 shows the WO obtained3Porous BiVO4Typical Scanning Electron Micrographs (SEM) of BiVO under the action of a foaming agent DIPA4The layer is porous and FIG. 4 shows the WO obtained3Porous BiVO4Cross-sectional Scanning Electron Micrograph (SEM) of (B) illustrating BiVO4The thickness of the layer is about 700 nm.
At 0.1M FeSO4·H2In O solution, WO3Porous BiVO4Making working electrode, making reference electrode of Ag/AgCl (3M KCl), making counter electrode of platinum sheet, and performing photo-deposition at 0.5V vs. Ag/AgCl potential for 10min under illumination of 300W xenon lamp and AM 1.5G to obtain WO3/BiVO4the/FeOOH ternary system composite material. FIG. 5 shows WO3/BiVO4Scanning Electron Microscope (SEM) of the ternary system composite material/FeOOH shows that the surface of the material becomes rougher after FeOOH is deposited. FIG. 6 is WO3/BiVO4The cross section Scanning Electron Microscope (SEM) of the ternary system composite material of/FeOOH can show that the thickness of the electrode is almost unchanged after FeOOH is deposited. FIG. 7 shows the WO thus obtained3/BiVO4The X-ray diffraction pattern of the FeOOH photoelectrode shows that the photoelectrocatalysis anode material is prepared from WO3、BiVO4And FeOOH. FIG. 8 is WO3/BiVO4Raman spectra (Raman) of the/FeOOH ternary system composites, again confirmed by WO3、BiVO4And FeOOH.
Example 2
The only difference from example 1 is that BiVO in this example4The spinning time of the layer was 10 minutes, and the other processes were the same as in example 1 and will not be described again. WO prepared3/BiVO4The cross-sectional Scanning Electron Microscope (SEM) of the/FeOOH ternary system composite material is shown in FIG. 9, which shows BiVO4Is 300 nm.
Example 3
The only difference from example 1 is that BiVO in this example4The spinning time of the layer was 20 minutes, and the other processes were the same as in example 1 and will not be described again. WO prepared3/BiVO4Ternary body of/FeOOHThe cross-sectional Scanning Electron Microscope (SEM) of the composite material is shown in FIG. 10, which shows BiVO4Is 1800 nm.
Example 4
The difference from embodiment 1 is only that the time of the photo-deposition in this embodiment is 5min, and other processes are the same as those in embodiment 1 and are not described herein again. A high resolution TEM image of the material produced in this example is shown in figure 11. As can be seen from FIG. 11, FeOOH has a thickness of about 5nm and is porous BiVO in the material4Is the main body material and is about 92 percent.
Example 5
The difference from embodiment 1 is only that the time of the photo-deposition in this embodiment is 15min, and other processes are the same as those in embodiment 1 and are not described herein again.
Example 6
The difference from embodiment 1 is only that the time of the photo-deposition in this embodiment is 20min, and other processes are the same as those in embodiment 1 and are not described herein again.
Example 7
The difference from example 1 is only that the mass of the absolute ethyl alcohol, the glacial acetic acid and the dimethylformamide in the electrospinning solution in this example is 1g, 2.5g and 1.5g respectively, that is, the ratio of the absolute ethyl alcohol, the glacial acetic acid and the dimethylformamide is 1: 2.5: 1.5, the other processes are the same as example 1 and are not repeated herein.
Example 8
The difference from example 1 is only that the mass of the absolute ethyl alcohol, the glacial acetic acid and the dimethylformamide in the electrospinning solution in this example is 1g, 4g and 2.5g respectively, that is, the ratio of the absolute ethyl alcohol, the glacial acetic acid and the dimethylformamide is 1: 4: 2.5, the other processes are the same as in example 1 and are not described again here.
Example 9
The only difference from example 1 is that the mass ratio of vanadium bis (acetylacetonate) oxide (vo (acac)2) to bismuth nitrate pentahydrate in this example is 1.5: 1, other processes are the same as those of the embodiment 1, and are not described again here.
Example 10
The only difference from example 1 is that the mass ratio of vanadium bis (acetylacetonate) oxide (vo (acac)2) to bismuth nitrate pentahydrate in this example is 2.5: 1, other processes are the same as those of the embodiment 1, and are not described again here.
Comparative example 1
In contrast to example 1, this example only produces WO3The other processes of the film are the same as those of embodiment 1, and are not described herein again. The Raman (Raman) spectrum of the obtained material is shown in FIG. 12, which shows that the obtained material is WO3。
Comparative example 2
The difference from example 1 is that this example only produces BiVO4Layer, no foaming agent DIPA was added, and the other processes were the same as in example 1 and are not repeated herein. FIG. 13 shows BiVO without DIPA4Scanning Electron Micrographs (SEM) show fewer pores on the surface of the electrode material. FIG. 14 is an X-ray spectrum (XRD) of the electrode material, which shows that the prepared material is BiVO4。
Comparative example 3
The difference from example 1 is that this example only produces BiVO4Other processes of the layer and the layer are the same as those of embodiment 1, and are not described again here. FIG. 15 shows BiVO with DIPA added4Scanning Electron Micrograph (SEM) FIG. 15 further demonstrates that the addition of DIPA serves a foaming effect to form porous BiVO4. FIG. 16 is an X-ray spectrum (XRD) of the material, showing that the prepared material is BiVO4。
Comparative example 4
The difference from example 1 is that this example only produces WO3And porous BiVO4Other processes of the layer and the layer are the same as those of embodiment 1, and are not described again here.
Application example 1
Photoelectrocatalysis performance test adopts a three-electrode system, and WO prepared in example 1 is used respectively3/BiVO4the/FeOOH ternary system composite material is used as a working electrode, the platinum sheet is used as a counter electrode, the Ag/AgCl is used as a reference electrode, and the concentration of the Ag/AgCl is 0.5M L-1Na2SO4And 0.5M L-1Na2SO3As electrolyte, an electrolytic cell with a quartz glass window was chosen. 300W xenon lamp equipped with AM1.5 filteringThe sheet was used as a simulated light source to test the photocurrent density of the samples at different biases through the electrochemical workstation.
Application example 2
Only distinction from application example 1 is made between WO prepared in example 2 at the working electrode used3/BiVO4the/FeOOH ternary system composite material is used as a working electrode, and other processes and test procedures are the same as those in application example 1 and are not described in a repeated manner here.
Application example 3
Only difference from application example 1 was made in the working electrode used as WO prepared in example 33/BiVO4the/FeOOH ternary system composite material is used as a working electrode, and other processes and test procedures are the same as those in application example 1 and are not described in a repeated manner here.
Application example 4
Only difference from application example 1 was made in the working electrode used, that is, WO prepared in example 43/BiVO4the/FeOOH ternary system composite material is used as a working electrode, and other processes and test procedures are the same as those in application example 1 and are not described in a repeated manner here.
Comparative application example 1
WO prepared in comparative example 1, differing only in the working electrode used in application example 13The thin film material, other processes and test procedures were the same as those in application example 1 and will not be described again here.
Comparative application example 2
BiVO prepared in comparative example 2 is distinguished from application example 1 only in that the working electrode used4The materials, other processes and testing procedures are the same as those in the first embodiment and will not be described again here.
Comparative application example 3
Porous BiVO prepared in comparative example 3 was used as a working electrode only to distinguish from application example 14Other processes and test procedures are the same as those in application example 1, and will not be described again here.
Comparative application example 4
WO prepared in comparative example 4 as working electrode only distinguished from application example 13Porous BiVO4Other processes and test procedures are the same as those in application example 1, and will not be described again here.
The WO prepared in the invention3、BiVO4Porous BiVO4、WO3Porous BiVO4And WO3/BiVO4The ternary system composite material of/FeOOH is tested, and the photocurrent density of the ternary system composite material under different bias voltages is shown in a comparison graph in FIG. 17. WO prepared according to the invention is illustrated in FIG. 173/BiVO4Pure WO with FeOOH ternary system composite material as photo-anode ratio3Film, BiVO4Porous BiVO4Porous WO3/BiVO4The material has more excellent photoelectric catalytic performance.
WO obtained in the present invention3、BiVO4Porous BiVO4、WO3Porous BiVO4And WO3/BiVO4The transient photocurrent density of the/FeOOH ternary system composite material along with the prolonging of the illumination time is shown in a comparison graph in FIG. 18. FIG. 18 further illustrates WO prepared according to the present invention3/BiVO4The photoelectric catalytic performance of the/FeOOH ternary system composite material is superior.
WO obtained in the present invention3、BiVO4Porous BiVO4、WO3Porous BiVO4And WO3/BiVO4The impedance comparison graph of the/FeOOH ternary system composite material is shown in FIG. 19. FIG. 19 illustrates WO prepared according to the present invention3/BiVO4the/FeOOH ternary system composite material has more excellent charge conduction performance. It was confirmed again that WO prepared according to the present invention3/BiVO4the/FeOOH ternary system composite material has more excellent photoelectric catalytic performance.
The technical scope of the invention claimed by the embodiments herein is not exhaustive and new solutions formed by equivalent replacement of single or multiple technical features in the embodiments are also within the scope of the invention, and all parameters involved in the solutions of the invention do not have mutually exclusive combinations if not specifically stated.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (5)
1. WO (WO)3/BiVO4The ternary system composite material of/FeOOH is characterized in that the main manifestation form in the composite material is monoclinic phase WO3Monoclinic BiVO4And amorphous FeOOH; WO3At the bottom layer, BiVO4Is covered in WO3FeOOH is coated on the outermost layer, wherein, BiVO4Has a mass of WO3/BiVO4The total mass of the/FeOOH ternary system composite material is 85-95%; WO3WO with a particle size of 30-60nm3Films, WO3The thickness of the film is 30-50nm, BiVO4Is porous BiVO4The thickness of the porous BiVO is 300-1800nm, and the thickness of the FeOOH is 0.5-10 nm;
the preparation method of the ternary system composite material comprises the following steps:
dissolving tungsten hexachloride and polyvinylpyrrolidone in dimethylformamide, stirring uniformly at room temperature to form spin coating liquid, coating the spin coating liquid on the conductive surface of FTO conductive glass, drying, and annealing to form WO3A film substrate;
dissolving PVP, vanadium oxide bis (acetylacetone), bismuth nitrate pentahydrate and diisopropyl azodicarboxylate in anhydrous ethanol, glacial acetic acid and dimethylformamide, stirring and mixing at room temperature to obtain spinning solution, using metal needle as anode, and WO3Using the film substrate as a cathode, carrying out electrostatic spinning on the spinning solution to obtain a precursor film, and annealing the precursor film to obtain WO3Porous BiVO4；
In FeSO4·H2In O solution, WO3Porous BiVO4Performing light deposition under the illumination of a 300W xenon lamp and an AM 1.5G at a potential of 0.5V vs. Ag/AgCl to obtain WO3/BiVO4The ternary system composite material of/FeOOH;
the mass ratio of the vanadium oxide bis (acetylacetone) to the bismuth nitrate pentahydrate is (1.5-2.5): 1;
the mass ratio of the absolute ethyl alcohol to the glacial acetic acid to the dimethylformamide in the electrostatic spinning solution is 1: (2.5-4): (1.5-2.5).
2. WO according to claim 13/BiVO4the/FeOOH ternary system composite material is characterized in that the mass ratio of absolute ethyl alcohol, glacial acetic acid and dimethylformamide in the electrostatic spinning solution is 1:3: 2.
3. WO according to claim 13/BiVO4the/FeOOH ternary system composite material is characterized in that the distance between an anode and a cathode in electrostatic spinning is 12-18cm, the injection speed is 0.05-0.2mm/min, the pressure is 10-22kV, and the electrostatic spinning time is 5-18 min.
4. WO according to claim 13/BiVO4The ternary system composite material of/FeOOH is characterized in that the light deposition time is 5min-20 min.
5. WO as defined in claim 13/BiVO4The application of the/FeOOH ternary system composite material in photoelectrocatalysis is characterized in that WO is added3/BiVO4the/FeOOH ternary system composite material is used as a working anode, Ag/AgCl is used as a reference electrode, a platinum sheet counter electrode is used under the illumination of a xenon lamp and 0.5M Na2SO4And 0.5M Na2SO3The photocurrent density and the impedance of the mixed solution were measured by an electrochemical workstation.
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| CN110441372B (en) * | 2019-08-27 | 2021-06-04 | 济南大学 | Preparation method and application of hydroxyl iron oxide composite material photoelectrochemical sensor with polyoxometallate as electron donor |
| CN111762880B (en) * | 2020-07-22 | 2021-12-10 | 南京理工大学 | Method for biologically and intensively treating refractory organic pollutants based on light-excited holes as electron acceptors |
| CN113145136A (en) * | 2021-03-31 | 2021-07-23 | 天津城建大学 | WO for photoelectrocatalytic degradation of pollutants3/CdS/MoS2Preparation method of composite film |
| CN113385200B (en) * | 2021-07-07 | 2022-05-20 | 浙江大学 | Full-spectrum oxygen production CeF without sacrificial agent3alpha-FeOOH photocatalyst and preparation method thereof |
| CN114452969B (en) * | 2022-01-21 | 2023-05-30 | 山东大学 | Double-cocatalyst-supported photocatalyst and preparation method and application thereof |
| CN114657588A (en) * | 2022-03-16 | 2022-06-24 | 福建师范大学泉港石化研究院 | Novel ternary WO3/BiVO4Three-step synthesis method of/NiOOH composite photo anode |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266783A (en) * | 2011-06-23 | 2011-12-07 | 浙江大学 | Iron-doped tungsten trioxide photocatalyst and preparation method thereof |
| CN105435774A (en) * | 2015-12-17 | 2016-03-30 | 宁波工程学院 | BiVO4 full-mesoporous fiber material efficient photocatalyst |
| CN105923656A (en) * | 2016-05-10 | 2016-09-07 | 上海大学 | BiVO4/WO3/rGO ternary nanocomposite material and preparation method thereof |
| CN106076314A (en) * | 2016-06-20 | 2016-11-09 | 宁波工程学院 | A kind of BiVO4full mesoporous nano belt high efficiency photocatalyst and its preparation method and application |
| CN106745474A (en) * | 2017-01-20 | 2017-05-31 | 上海交通大学 | Visible light-responded tungstic acid pucherite hetero-junction thin-film electrode preparation method |
| CN107190362A (en) * | 2017-07-17 | 2017-09-22 | 宁波工程学院 | A kind of high-purity ZnO/BiVO4The preparation method of heterogeneous micro belt |
-
2018
- 2018-06-27 CN CN201810678391.0A patent/CN109092319B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266783A (en) * | 2011-06-23 | 2011-12-07 | 浙江大学 | Iron-doped tungsten trioxide photocatalyst and preparation method thereof |
| CN105435774A (en) * | 2015-12-17 | 2016-03-30 | 宁波工程学院 | BiVO4 full-mesoporous fiber material efficient photocatalyst |
| CN105923656A (en) * | 2016-05-10 | 2016-09-07 | 上海大学 | BiVO4/WO3/rGO ternary nanocomposite material and preparation method thereof |
| CN106076314A (en) * | 2016-06-20 | 2016-11-09 | 宁波工程学院 | A kind of BiVO4full mesoporous nano belt high efficiency photocatalyst and its preparation method and application |
| CN106745474A (en) * | 2017-01-20 | 2017-05-31 | 上海交通大学 | Visible light-responded tungstic acid pucherite hetero-junction thin-film electrode preparation method |
| CN107190362A (en) * | 2017-07-17 | 2017-09-22 | 宁波工程学院 | A kind of high-purity ZnO/BiVO4The preparation method of heterogeneous micro belt |
Non-Patent Citations (3)
| Title |
|---|
| Enhanced photoelectrocatalytic activity of FTO/WO3/BiVO4 electrode modified with gold nanoparticles for water oxidation under visible light irradiation;Ponchio Chatchai et al;《Electrochimica Acta》;20090915;第55卷;第592-596页 * |
| Transparent Nanoparticulate FeOOH Improves the Performance of a WO3 Photoanode in a Tandem Water-Splitting Device;Wai Ling Kwong et al;《J. Phys. Chem. C. 》;20160506;第120卷;第10941-10950页 * |
| Ultrathin FeOOH Nanolayers with Abundant Oxygen Vacancies on BiVO4 Photoanodes for Efficient Water Oxidation;Beibei Zhang et al，;《Angew. Chem. Int. Ed.》;20180201;第57卷;第592-596页 * |
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