CN110565111B - Hexagonal column type WO3/Bi2WO6Preparation method of composite photoelectrode film - Google Patents
Hexagonal column type WO3/Bi2WO6Preparation method of composite photoelectrode film Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 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 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 5
- 238000013329 compounding Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims 2
- 241000135164 Timea Species 0.000 claims 1
- 238000003837 high-temperature calcination Methods 0.000 claims 1
- 238000010335 hydrothermal treatment Methods 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 30
- 239000010409 thin film Substances 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000000969 carrier Substances 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 239000002055 nanoplate Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 241000276425 Xiphophorus maculatus Species 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000012064 sodium phosphate buffer Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- 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 invention relates to a hexagonal column type WO3/Bi2WO6A preparation method of a composite photoelectrode film belongs to the technical field of material preparation. The prepared composite photoelectrode is novel in shape, regular in structure, high in separation efficiency of photon-generated carriers, excellent in photoelectric catalytic water decomposition performance and capable of realizing continuous and stable hydrogen production under visible light. The preparation method of the photo-anode film mainly comprises the following steps: sodium tungstate and ammonium oxalate are used as precursors, FTO conductive glass is used as a substrate, hydrothermal reaction is carried out for a period of time, and nano platy WO grows in situ on the FTO substrate3A film; the film is taken as a template, acetic acid aqueous solution of bismuth nitrate with a certain volume is dripped on the surface of the film, and the nano plate WO is calcined at high temperature3Thin film self-assembled into hexagonal column type WO3/Bi2WO6And (3) compounding the film. The composite photoelectrode is simple in preparation process, controllable in conditions, low in cost and wide in application prospect in the future energy field.
Description
Technical Field
The invention relates to a hexagonal column type WO3/Bi2WO6A preparation method of a composite photoelectrode film belongs to the technical field of material preparation, and particularly provides a hexagonal column WO with visible light response3/Bi2WO6The composite photoelectrode has the advantages of uniform size, large photocurrent, high carrier separation efficiency and stable hydrogen evolution.
Background
In the 21 st century, the economic development of human beings is severely restricted by energy and environmental problems. How to utilize solar energy, which is a renewable energy source, to realize light energy conversion is an important subject in front of researchers. The photoelectrocatalysis technology utilizes a semiconductor electrode to absorb solar energy, converts photons into electron and hole pairs, and realizes effective water decomposition into hydrogen with the assistance of electric energy. The process is carried out at normal temperature and normal pressure, the aim of continuously producing hydrogen can be achieved only by utilizing solar energy and water, and the method is a green way for solving the future energy crisis. However, the quantum efficiency of most of the semiconductors is low at present, which severely limits the practical application of the technology. Therefore, the development of a photoelectrode material with wide spectral absorption and high stability is the key to realizing the application of the technology.
In recent years, WO3The development of photoelectrode materials has attracted the attention of many researchers and enterprises because of WO3The band gap of the solar cell is 2.6eV, the visible light part in sunlight can be effectively captured, and further more photon-generated carriers can be generated. Furthermore, WO3Is positive (3.2eV, pH 0), the photogenerated holes have a strong oxidizing capacity, thermodynamically driving the water splitting reaction at the semiconductor/electrode interface to produce oxygen and hydrogen at the counter electrode. The hydrogen is an important green energy source in the future, and the combustion product is water, so that the environment is not polluted. And, WO3The preparation process is simple, the cost is low, and large-scale mass production is easy to realize. However, WO alone3The carrier separation efficiency of the electrode is low, so that the photoelectric conversion efficiency can not meet the requirement of practical application. Based on this, there is an urgent need to find an improved WO3A method of carrier separation efficiency. The built-in electric field can be generated by constructing the semiconductor heterojunction, so that the separation of carriers is promoted, the recombination of photon-generated carriers is reduced, and the problem of WO is hopefully solved3The separation efficiency of the photon-generated carriers is low. Bi2WO6The material is another visible light response type semiconductor photoelectrode material, the band gap of the material is 2.8eV, the material can absorb sunlight below 443nm, the conduction band potential and the valence band potential are respectively 0.46eV and 3.26eV, and the material is widely applied to the field of photocatalytic degradation of organic matters in recent years. WO3And Bi2WO6Position matching of the edges of the strips, when they are in contact, WO3Electrons in the conduction band can be transferred to Bi2WO6On a guide belt, and WO3Valence band holeTransferable to Bi2WO6And thus effective carrier separation. Thus, by constructing WO3/Bi2WO6The semiconductor heterojunction is expected to greatly improve WO3Photoelectric hydrogen production efficiency of the electrode. In addition, Bi2WO6The photoelectrode has better stability, Bi is added2WO6With WO3In combination, WO can be reduced3The contact area of the electrode and the solution is increased, thereby increasing WO3Stability of the electrodes, this for WO3The commercial application of electrodes is of great significance. To our knowledge, WO3/Bi2WO6The research of the composite photocatalyst for environmental management has been reported, but at present, hexagonal column type WO does not exist3/Bi2WO6Research report of composite photoelectrode shows that our preparation scheme will strongly promote WO3The development of photoelectrode promotes its application in the field of hydrogen production by photoelectrocatalysis.
Disclosure of Invention
The invention aims to provide a hexagonal column type WO3/Bi2WO6The invention discloses a preparation method of a composite photoelectrode film, which comprises the step of firstly adopting a hydrothermal method to dope SnO with fluorine2Growth of WO on transparent conductive glass (FTO)3The nano-plate electrode is then coated with WO3The nano plate electrode is used as a template, the surface of the nano plate electrode is dripped with an acetic acid aqueous solution of nickel nitrate, the nickel nitrate is decomposed into nickel oxide at high temperature, and then the nickel oxide is mixed with WO3Reaction to produce WO3/Bi2WO6And (4) compounding photoelectrodes. Interestingly, the presence of acetic acid allows the WO to be calcined at high temperatures3The nanoplates spontaneously assemble into a hexagonal-cylindrical structure. The hexagonal-prism-shaped composite photoelectrode can realize effective water decomposition to produce hydrogen under simulated solar illumination, and has a single photocurrent compared with WO3The electrode is higher, the stability is better, and the method has wide application prospect in the field of photoelectrocatalysis water decomposition.
The aim of the invention is realized by the following operation steps:
1) respectively preparing 15ml of sodium tungstate with the concentration of 20-30mmol/L and ammonium oxalate aqueous solution with the concentration of 40-60mmol/L at normal temperature, and slowly dripping 5ml of hydrochloric acid solution (3mol/L)Adding into sodium tungstate solution, adjusting pH to 2-8 to obtain white emulsion; adding an ammonium oxalate solution into the emulsion, stirring for 30min, transferring to a hydrothermal reaction kettle, putting FTO conductive glass into the reaction kettle, enabling the FTO conductive surface to be downward, carrying out hydrothermal reaction at the constant temperature of 140 ℃ for 6h, cooling, washing with ultrapure water for three times, drying at room temperature, calcining at the temperature of 450 ℃ and 600 ℃ for 1-6h, and obtaining the WO3A thin film electrode;
2) weighing a certain amount of bismuth nitrate solid, and adding the bismuth nitrate solid into an acetic acid aqueous solution with the concentration of 1-5mol/L, wherein the concentration of bismuth nitrate is controlled to be 0.01-0.5 mmol/L; transferring 10-300 μ L of Bi (NO)3)3WO of solution to 1cm × 2.5cm3Drying the surface of the thin film electrode at room temperature, calcining the surface of the thin film electrode in air at the temperature of 400-800 ℃ for 1-10h, cooling the surface of the thin film electrode, and then using HNO with the concentration of 0.5-1mol/l3Soaking for 15h to remove Bi on the surface2O3To obtain WO3/Bi2WO6A film.
The invention has the beneficial effects that: the preparation process is simple, the conditions are controllable, the cost is low, the repeatability is high, and the method is suitable for large-scale preparation of the photoelectrode film. The hexagonal column WO prepared3/Bi2WO6The film is uniformly distributed, can keep better photostability and photoelectrocatalysis water oxidation activity under long-time irradiation, and has wide application prospect in the field of utilization of future hydrogen energy.
Drawings
FIG. 1 shows WO prepared in example one3/Bi2WO6An X-ray diffraction pattern of the thin film electrode;
FIG. 2 shows WO prepared in example II3And WO3/Bi2WO6(ii) the ultraviolet-visible diffuse reflectance spectrum of the film;
FIG. 3 shows WO prepared in example III3And WO3/Bi2WO6A photocurrent and potential curve graph of the thin film electrode under the irradiation of simulated sunlight;
FIG. 4 shows WO prepared in example four3/Bi2WO6Scanning electron microscope image of the film electrode;
FIG. 5 shows WO prepared in example four3/Bi2WO6High power scanning electron microscope image of thin film electrode.
Detailed Description
For a better understanding of the present invention, the following examples and drawings are included to further illustrate the present invention, but the present invention is not limited to the following examples.
Example one
Hexagonal column type WO3/Bi2WO6The preparation method of the composite photoelectrode film comprises the following specific steps:
respectively preparing 15ml of 25mmol/L sodium tungstate and 55mmol/L ammonium oxalate aqueous solution at normal temperature, slowly dropwise adding 5ml of hydrochloric acid solution (3mol/L) into the sodium tungstate solution, uniformly stirring, mixing with the ammonium oxalate solution, and stirring for 30 min; then transferring the mixed solution into a hydrothermal reaction kettle, inserting FTO conductive glass, placing the mixture into a constant-temperature air-blast drying oven at 140 ℃ for reaction for 6 hours, cooling, washing with water, drying, and calcining at 550 ℃ for 2.5 hours to obtain WO3Cutting the electrode into pieces of 1cm × 2.5.5 cm, adding 150 μ L of 0.1mmol/L bismuth nitrate in acetic acid water solution, drying at room temperature, calcining at 550 deg.C for 6 hr, cooling, and adding 0.5mol/L HNO3Soaking for 15h to remove Bi on the surface2O3To obtain WO3/Bi2WO6A film.
FIG. 1 is WO prepared3/Bi2WO6The X-ray diffraction pattern of the thin-film electrode can be found by searching MDI Jade software, and the diffraction peaks in figure 1 correspond to two substances which are respectively monoclinic WO3(PDF card No. 20-1324) and Bi2WO6(PDF card number 39-0256). This illustrates the WO prepared beforehand3After the electrode is dripped with bismuth nitrate solution, the bismuth nitrate solution can be partially converted into Bi by high-temperature treatment2WO6Thereby obtaining WO3/Bi2WO6And (4) compounding photoelectrodes.
Example two
Hexagonal column type WO3/Bi2WO6Preparation method of composite photoelectrode film, WO3The preparation steps of the film are carried out in the same wayExample I, WO was prepared3After the thin film electrode, 50ml of 0.1mmol/L aqueous bismuth nitrate solution was prepared, and concentrated acetic acid was added to adjust the pH to 0.6. Then, 100. mu.L of the solution was transferred to WO3Drying the surface of the film electrode at room temperature, calcining at 650 ℃ for 6h, cooling, and then adding 0.8mol/L HNO3Soaking for 15h to remove Bi on the surface2O3De WO3/Bi2WO6A film.
FIG. 2 shows WO prepared3And WO3/Bi2WO6The diffuse reflection pattern of the thin film electrode in the UV-visible spectrum is evident, with decreasing wavelength, WO3And WO3/Bi2WO6The absorbance of the thin film electrode gradually increases, WO3Band edge absorption at 470nm, and WO3/Bi2WO6The absorption of the thin film electrode in the visible region is increased because bismuth tungstate can also absorb visible light.
EXAMPLE III
Hexagonal column type WO3/Bi2WO6Preparation method of composite photoelectrode film, WO3The film was prepared in the same manner as in example one, and WO was prepared3After the thin film electrode, 50ml of 0.02mmol/L aqueous bismuth nitrate solution was prepared, and concentrated acetic acid was added to adjust the pH to 0.5. Thereafter, 200. mu.L of the solution was transferred to WO3Drying the surface of the film electrode at room temperature, calcining at 600 ℃ for 4h, cooling, and then adding 0.5mol/l HNO3Soaking for 15h to remove Bi on the surface2O3De WO3/Bi2WO6A film.
FIG. 3 is WO3And WO3/Bi2WO6The linear sweep voltammetry curve chart of the film electrode has the sweep speed of 20mV/s and the xenon lamp light source output intensity of 100mW/cm2The supporting electrolyte is a sodium phosphate buffer solution with pH equal to 7 and the concentration is 0.1 mol/L. Under these conditions, WO is a function of the applied potential3The photocurrent of the thin film gradually increases, which corresponds to the oxidation of water. As can be seen from the figure, WO3The initial potential for aqueous oxidation of the film was approximately 0.1V (vs. Ag/AgCl). Interestingly, WO3/Bi2WO6The photocurrent of the photoanode is obviously higher than that of pure WO3The current at the electrode is large and the initial potential for water splitting is significantly shifted negatively, which indicates WO3/Bi2WO6The composite electrode is added with WO3Performance of photoelectrocatalysis water decomposition.
Example four
Hexagonal column type WO3/Bi2WO6Preparation method of composite photoelectrode film, WO3The film was prepared in the same manner as in example one, and WO was prepared3After the thin film electrode, 50ml of 0.2mmol/L aqueous bismuth nitrate solution was prepared, and concentrated acetic acid was added to adjust the pH to 0.54. Then, 80. mu.L of the solution was transferred to WO3Drying the surface of the thin film electrode at room temperature, calcining at 550 ℃ for 6h, cooling, and then adding 0.5mol/L HNO3Soaking for 15h to remove Bi on the surface2O3De WO3/Bi2WO6A film.
FIGS. 4 and 5 are WO3/Bi2WO6Scanning electron micrographs of low power and high power of the composite photoelectrode film, it can be seen from the figure that WO prepared3/Bi2WO6Is in a hexagonal column shape and is well dispersed on the FTO substrate. The surface of the hexagonal column is rough, the middle part of the hexagonal column is sunken inwards, and the side length of the hexagonal column is about 5.5 mu m.
Claims (6)
1. Hexagonal column type WO3/Bi2WO6The preparation method of the composite photoelectrode film is characterized by comprising the following steps:
1) preparing aqueous solution of sodium tungstate and ammonium oxalate, and adjusting the pH value of the solution by using concentrated hydrochloric acid; then mixing the two solutions, stirring uniformly, pouring the mixed solution into a reaction kettle, inserting FTO conductive glass, and carrying out hydrothermal reaction for 6 hours at 140 ℃; calcining the product after hydrothermal treatment in air at the temperature of 450-600 ℃ for 1-6h to obtain WO3A film;
2) dissolving the bismuth nitrate solid in an acetic acid aqueous solution to completely dissolve the bismuth nitrate solid; transferring a certain volume of bismuth nitrate solution, and dropwise adding into the WO3Drying the surface of the film electrode at room temperature, and calcining the dried film electrode in a muffle furnace for a certain timeA (c) is added; the bismuth oxide produced during the high temperature calcination process can be removed by HNO3Removing the solution by soaking and dissolving to finally obtain WO3/Bi2WO6And (3) compounding the photoelectrode film.
2. Hexagonal prism type WO according to claim 13/Bi2WO6The preparation method of the composite photoelectrode film is characterized in that the concentration of the bismuth nitrate aqueous solution in the step 2) is 0.01-0.5 mmol/L.
3. Hexagonal prism type WO according to claim 13/Bi2WO6The preparation method of the composite photoelectrode film is characterized in that the concentration of the acetic acid in the step 2) is 1-5 mol/L.
4. Hexagonal prism type WO according to claim 13/Bi2WO6The preparation method of the composite photoelectrode film is characterized in that the volume of the dropwise added bismuth nitrate solution in the step 2) is 10-300 mu L.
5. Hexagonal prism type WO according to claim 13/Bi2WO6The preparation method of the composite photoelectrode film is characterized in that the calcination temperature in the muffle furnace in the step 2) is 400-800 ℃, and the calcination time is 1-10 h.
6. Hexagonal prism type WO according to claim 13/Bi2WO6The preparation method of the composite photoelectrode film is characterized in that the bismuth oxide obtained in the step 2) can pass through HNO3Soaking in solution to dissolve and remove HNO in the solution3The concentration of the solution is 0.5-1 mol/l.
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| CN113293383B (en) * | 2020-11-03 | 2023-03-17 | 台州学院 | Bismuth tungstate/indium oxyhydroxide composite photoelectrode and preparation method and application thereof |
| CN112588303B (en) * | 2020-11-23 | 2022-09-13 | 安徽大学 | Preparation method of selenium-bismuth oxide nanosheet and heterojunction type photoelectrode based on selenium-bismuth oxide nanosheet |
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