CN106745474B - Preparation method of visible light response tungsten trioxide-bismuth vanadate heterojunction thin film electrode - Google Patents
Preparation method of visible light response tungsten trioxide-bismuth vanadate heterojunction thin film electrode Download PDFInfo
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Abstract
A preparation method of a visible-light-responsive tungsten trioxide-bismuth vanadate heterojunction thin-film electrode comprises the following steps: adding 1-3 g of Bi (NO)3)3·5H2Dissolving O in 100mL of 2mol/L acetic acid aqueous solution to obtain bismuth nitrate solution, and adding 0.2-1 g of NH4VO3Dissolving in 100mL of 50-200 mmol/L H2O2Obtaining peroxovanadic acid solution in water solution, then firstly spin-coating bismuth nitrate solution on WO3Coating the peroxyvanadic acid solution on the surface of the film by spinning3Repeating the spin coating process for 5-20 times, performing one-time heat treatment on the obtained film at 400-550 ℃ for 1-6 hours, and naturally cooling to obtain the WO3/BiVO4A heterojunction thin film electrode. The invention has the characteristics of simplicity, convenience, mildness and high efficiency, and the prepared WO3/BiVO4The heterojunction film electrode has good visible light absorption performance and good stability, high photoelectric efficiency and good effect of photoelectrocatalysis on degrading organic matters, and can be applied to the fields of photoelectrocatalysis hydrogen production, organic matter degradation, sensors and the like.
Description
Technical Field
The invention relates to a photoelectric catalytic electrode material, in particular to a preparation method of a visible-light-responsive tungsten trioxide-bismuth vanadate heterojunction thin-film electrode, and belongs to the field of nano materials.
Technical Field
The technology of organic matter degradation by sunlight, hydrogen production and sensors based on the photoelectrocatalysis technology is a new technology with application prospect. In the technology, the performance of the photocatalytic electrode directly influences the effect of a photoelectric catalysis system, so that the preparation of the photocatalytic electrode material is a hotspot of research in the field of photoelectric catalysis.
At present, BiVO is used4Modification of WO3WO3/BiVO4The heterojunction film is based on BiVO4Excellent visible light absorption (30% of sunlight can be absorbed) and based on WO3Excellent charge transport properties (12 cm)2V-1s-1) And the material has excellent photo-generated charge separation efficiency based on good energy level matching relationship between the two materials, and is a photocatalytic electrode material with great prospect. Are currently used in WO3BiVO modified on surface of thin film4Layer preparation of WO3/BiVO4The methods of the heterojunction film include a hydrothermal method, vapor deposition, a spin coating method and the like. Among them, the hydrothermal method requires a hydrothermal reactor to generate a high-temperature and high-pressure environment, and vapor deposition requires a high vacuum and complicated equipment, which limits the application of these methods.
The spin coating method becomes a method for preparing WO due to simple equipment and convenient operation3/BiVO4The mainstream method of the heterojunction thin film. The spin coating method reported at present is mainly based on heating and synthesizing BiVO by bismuth nitrate and ammonium metavanadate4The deposit-calcine method of (p.natl.acad.sci.usa,2012,109, 11564-. The process is first of all described in WO3The surface of the film is coated with a precursor solution containing bismuth nitrate and ammonium metavanadate in a spin coating manner, and then the precursor solution is calcined on a flat plate at the high temperature of 450 ℃ to obtain BiVO4And (3) a layer. The method needs repeated spin coating and repeated sintering to control BiVO4The thickness of the layer, namely the precursor solution of bismuth nitrate and ammonium metavanadate, needs to be sintered once every spin coating reaction, and is repeated to the thickness required by the heterojunction. The chemical reactions involved in the repeated sintering are:
although the method can be used for preparing BiVO on the surfaces of various substrates4Layer, but in the preparation process, WO3The film experiences moreThe repeated heating-cooling process can lead to WO3Repeated severe stress changes occur in the film, the internal structure of the substrate is damaged, and WO is increased3/BiVO4WO in heterojunction films3The substrate has structural defects, and thus there is a disadvantage in that the charge transport property of the electrode is degraded. In addition, the precursor solution containing bismuth nitrate and ammonium metavanadate can slowly generate BiVO4Precipitation and thus also has the disadvantage of being cost-effective.
Disclosure of Invention
The invention aims to provide a visible light response WO aiming at overcoming the defects of the prior art3/BiVO4The preparation method of the heterojunction thin film electrode has the characteristics of simplicity, convenience, mildness and high efficiency, and the prepared WO3/BiVO4The heterojunction film electrode has good visible light absorption performance and good stability, high photoelectric efficiency and good effect of photoelectrocatalysis on degrading organic matters, and can be applied to the fields of photoelectrocatalysis hydrogen production, organic matter degradation, sensors and the like.
The invention is realized by the following technical scheme:
visible light response WO3/BiVO4Preparation method of heterojunction film electrode by using bismuth nitrate and peroxovanadic acid in WO3Reacting the surface of the film to generate bismuth peroxovanadate, and repeatedly spin-coating a bismuth nitrate solution and a bismuth peroxovanadate solution in sequence to obtain the bismuth peroxovanadate-modified WO3A film is sintered at one time to obtain the WO3/BiVO4A heterojunction thin film electrode.
The technical scheme of the invention is as follows:
adding 1-3 g of Bi (NO)3)3·5H2Dissolving O in 100mL of 2mol/L acetic acid aqueous solution to obtain bismuth nitrate solution, and adding 0.2-1 g of NH4VO3Dissolving in 100mL of 50-200 mmol/L H2O2Obtaining peroxovanadic acid solution in water solution, then firstly spin-coating bismuth nitrate solution on WO3Coating the peroxyvanadic acid solution on the surface of the film by spinning3Repeating the spin coating process for 5-20 times on the surface of the film, and then performing one-step coating on the obtained film at 400-550 DEG CCarrying out heat treatment for 1-6 h, and naturally cooling to obtain the WO3/BiVO4A heterojunction thin film electrode.
Further, said WO3The film can be a nano-structured WO prepared by a hydrothermal method, a chemical bath method or an anodic oxidation method in the prior art3A film.
Further, said WO3/BiVO4The heterojunction film electrode can be applied to the fields of organic pollutant treatment, water decomposition and hydrogen production, sensors and the like.
Visible light responsive WO according to the invention3/BiVO4The preparation method of the heterojunction film electrode has the characteristics of simplicity, convenience, mildness and high efficiency, and the bismuth peroxyvanadate is generated by utilizing the direct reaction of the bismuth nitrate and the bismuth peroxyvanadate to replace the repeated high-temperature sintering reaction of the bismuth nitrate and the ammonium metavanadate in the traditional method, so that the defects in the traditional deposition-calcination method are overcome. The invention can be based on the need to modify the thickness, as described in WO3The reaction times of bismuth nitrate and vanadic peroxide are repeatedly carried out on the film substrate. Because the reaction is carried out under the condition of normal temperature and does not involve a sintering process, repeated and violent stress changes can not be generated to cause the substrate WO3Defects in the thin film crystals. This step involves the following reaction scheme:
when the repeated reaction times meet the requirements, the heterojunction film can be prepared only by one-time sintering. The reactions involved in the sintering process are:
experimental data show that the WO prepared by the invention3/BiVO4The heterojunction film electrode has good visible light absorption performance and high photoelectric efficiency, and the effect of photoelectrocatalysis on degrading organic matters is good. In addition, the invention adopts stable bismuth nitrate solution and peroxyvanadate solution,also overcomes the defect that the bismuth nitrate and the ammonium metavanadate in the precursor liquid can slowly act to generate BiVO in the traditional deposition-calcination method4Insufficient precipitation.
The invention has the characteristics of simplicity, convenience, mildness and high efficiency, and the prepared WO3/BiVO4The heterojunction film electrode has good visible light absorption performance and good stability, high photoelectric efficiency and good effect of photoelectrocatalysis on degrading organic matters, and can be applied to the fields of photoelectrocatalysis hydrogen production, organic matter degradation, sensors and the like.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the present invention.
FIG. 2 shows WO obtained in example 13Film and WO3/BiVO4XRD pattern of the heterojunction thin film electrode.
FIG. 3 shows WO obtained in example 13/BiVO4The electron microscope picture of the heterojunction film electrode, the picture inserted is its section electron microscope photograph;
FIG. 4 shows WO obtained in example 13Film and WO3/BiVO4Ultraviolet-visible absorption spectrum of the heterojunction thin film electrode.
FIG. 5 shows WO obtained in example 13Film and WO3/BiVO4Voltammograms of heterojunction thin film electrodes.
FIG. 6 shows WO obtained in example 23/BiVO4Heterojunction thin film electrode and DA-WO prepared by traditional deposition-calcination (DA) method3/BiVO4A comparison graph of modulated photocurrent spectra (IMPS) of the heterojunction thin film electrodes;
FIG. 7 shows WO obtained in example 33/BiVO4A photocurrent curve of water decomposed by the heterojunction film electrode through photoelectrocatalysis and a hydrogen production and oxygen production rate curve.
FIG. 8 shows WO obtained in example 43/BiVO4And (3) a degradation curve of phenol by photoelectrocatalytic degradation of the heterojunction film electrode.
FIG. 9 shows WO obtained in example 53/BiVO4And (3) a degradation curve of the Congo red by photoelectrocatalytic degradation of the heterojunction film electrode.
FIG. 10 shows WO obtained in example 63/BiVO4The degradation curve of the heterojunction film electrode in 6 repeated photoelectrocatalysis degradation tetracycline hydrochloride.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings, but the scope of the present invention should not be limited thereto.
Referring first to FIG. 1, FIG. 1 shows a visible light response WO according to the present invention3/BiVO4Schematic preparation process of heterojunction thin film electrode, and visible light responsive WO of the invention3/BiVO4The heterojunction thin film electrode is prepared by the method disclosed in WO3Repeatedly and alternately spin coating bismuth nitrate solution and peroxyvanadate solution on the surface of the film, and using the bismuth nitrate and the peroxyvanadate in WO3The surface of the film directly reacts to obtain bismuth peroxovanadate, and the WO is obtained by sintering the film at one time3/BiVO4A heterojunction thin film electrode. The method specifically comprises the following steps:
adding 1-3 g of Bi (NO)3)3·5H2Dissolving O in 100mL of 2mol/L acetic acid aqueous solution to obtain bismuth nitrate solution, and adding 0.2-1 g of NH4VO3Dissolving in 100mL of 50-200 mmol/L H2O2Obtaining peroxovanadic acid solution in water solution, then firstly spin-coating bismuth nitrate solution on WO3Coating the peroxyvanadic acid solution on the surface of the film by spinning3Repeating the spin coating process for 5-20 times on the surface of the film, carrying out one-time heat treatment on the obtained film at the temperature of 400-550 ℃ for 1-6 h, and naturally cooling to obtain the WO3/BiVO4A heterojunction thin film electrode.
Said WO3The film can be WO with a nano structure prepared by adopting a hydrothermal method, a chemical bath method, an anodic oxidation method and other public methods3A film.
The present invention will be described in detail with reference to examples.
Example 1
Firstly, the chemical bath method in the prior art is adopted to prepare WO3Nanosheet film (Zhou Bao, et al, WO)3Nanosheet arrayThe preparation method and the application research of the film, the Chinese patent application number: 201510724443. X): in the presence of 0.4g Na2WO4·2H2O, 0.15g ammonium oxalate 9mL 37% hydrochloric acid, 8mL 37% H2O2And 30mL of ethanol in 30mL of deionized water, performing water bath at 85 ℃ for 200min to obtain a tungstic acid film on a conductive glass substrate, and performing heat treatment at 500 ℃ for 2h to obtain WO3A nanosheet film.
2.4gBi (NO)3)3·5H2O was dissolved in 100mL of a 2mol/L aqueous acetic acid solution to obtain a bismuth nitrate solution, and 0.58g of NH was added4VO3100mmol/L H dissolved in 100mL2O2Obtaining peroxovanadic acid solution in water solution, then spin coating bismuth nitrate solution on the above WO3Coating the peroxyvanadic acid solution on the surface of the nano-sheet film by spinning3Repeating the spin coating process for 15 times on the surface of the nano-sheet film, carrying out one-step heat treatment on the obtained film at the temperature of 450 ℃ for 3h, and naturally cooling to obtain WO3/BiVO4A heterojunction thin film electrode.
FIG. 2 shows the example WO3Nanosheet film and WO3/BiVO4XRD pattern of the heterojunction thin film electrode, indicating that the WO3WO with pure monoclinic nano-sheet film3Having a relatively weak (002) plane diffraction peak and a relatively strong (200) plane diffraction peak, the WO3/BiVO4The heterojunction film electrode presents monoclinic BiVO4。
FIG. 3 shows the WO of this example3/BiVO4The surface of the heterojunction film is in a micro-shape, and the surface of the heterojunction film is porous BiVO4Layer covering WO3The thickness of the film on the surface of the nano sheet is about 980 nm.
FIG. 4 shows the WO of this example3Nanosheet film and WO3/BiVO4UV-visible absorption spectra of heterojunction thin film electrodes, which indicate the WO3The nano-sheet film can only emit light with a wavelength less than 471nm, and WO3/BiVO4The absorption band edge of the heterojunction film electrode is increased to 518nm, and the heterojunction film electrode has good absorption to visible light and ultraviolet lightAnd (4) performance recovery.
FIG. 5 shows the WO of this example3Nanosheet film and WO3/BiVO4The heterojunction film electrode is used as a working electrode, the platinum electrode is used as a counter electrode, the Saturated Calomel Electrode (SCE) is used as a reference electrode, and 0.1M Na is used2SO4The solution is electrolyte, and can be used for simulating the sunlight AM1.5(100 mW/cm)2) Under the irradiation condition, the scanning speed is 0.005V/s. Show WO3/BiVO4The heterojunction thin film electrode has a structure higher than WO3The photocurrent density of the nano-sheet film at 1.5V vs. SCE is 5.2mA/cm2About WO3Nanosheet film (2.1 mA/cm)2) 2.5 times of the total weight of the powder.
Example 2
Firstly, the prior art anodic oxidation method is adopted to prepare WO3Nanoporous films (J.solid State electrochem.2014,18, 157-161): anodizing the tungsten piece in an aqueous solution containing 0.1M sodium sulfate and 0.5% HF at 35 ℃ under 50V voltage for 30min, and then heat-treating at 500 ℃ for 2h to obtain WO3A nanoporous film.
1g of Bi (NO)3)3·5H2Dissolving O in 100mL of 2mol/L acetic acid aqueous solution to obtain bismuth nitrate solution, adding 0.2g NH4VO3Dissolved in 100mL of 50mmol/L H2O2Obtaining peroxovanadic acid solution in water solution, and then spin-coating bismuth nitrate solution on obtained WO3Coating the surface of the nano-pore film with peroxyvanadic acid solution3Repeating the spin coating process for 20 times on the surface of the nano-pore film, performing one-time heat treatment on the obtained film at the temperature of 400 ℃ for 6h, and naturally cooling to obtain the WO3/BiVO4A heterojunction thin film electrode. The electrode can be used for pH and CH4、NO2And a sensor for detecting COD.
As a control, the conventional deposition-calcination (DA) method (P.Natl.Acad.Sci.USA,2012,109, 11564-3Nano-pore film modified BiVO4Layer formation to DA-WO3/BiVO4Heterojunction thin-film electrode: 1.45gBi (NO)3)3·5H2O and 0.35gNH4VO3Dissolving in 10mL of 2mol/L nitric acid aqueous solution to obtain a precursor solution, and spin-coating the precursor solution on the obtained WO3Heating the surface of the nano-pore film on a heating plate at 450 ℃ for 20min, naturally cooling, repeating the spin coating-heat treatment process for 4 times, heat-treating the obtained film at 400 ℃ for 6h, and naturally cooling to obtain DA-WO3/BiVO4A heterojunction thin film electrode.
Subjecting said WO to3/BiVO4Heterojunction thin film electrode or DA-WO3/BiVO4The heterojunction film electrode is used as a working electrode, the platinum electrode is used as a counter electrode, the Saturated Calomel Electrode (SCE) is used as a reference electrode, and 0.1M Na is used2SO4The solution was electrolyte and the bias voltage was 1Vvs. SCE, the WO being tested3/BiVO4Heterojunction thin film electrode or DA-WO3/BiVO4A modulated photocurrent profile (IMPS) of the heterojunction thin film electrode.
FIG. 6 shows the WO obtained in this example3/BiVO4Heterojunction thin film electrode or DA-WO3/BiVO4Comparison of IMPS for heterojunction thin film electrodes. The corresponding frequencies of the lowest points of the two curves are respectively 7.15Hz and 3.39Hz according to the formula taud＝(2π·fmin(IMPS))-1(wherein τ)dThe mean migration time of the majority carriers (electrons) in the photocatalytic electrode under test to the conductive substrate, fmin(IMPS) is the frequency value corresponding to the lowest point in the IMPS curve), and the WO is obtained through calculation3/BiVO4The average migration time of the photo-generated electrons in the heterojunction thin film electrode is 22.27ms, and the DA-WO3/BiVO4The mean migration time of the photo-generated electrons in the heterojunction thin-film electrode was 46.97 ms. Showing WO obtained by the present invention3/BiVO4The mobility rate of photogenerated carriers in the heterojunction film electrode is higher than that of DA-WO (digital-to-analog) obtained by the traditional deposition-calcination method3/BiVO4The mobility rate of photogenerated carriers in the heterojunction thin-film electrode. WO mentioned in this description3/BiVO4The structural defects of the heterojunction film electrode are less than those of DA-WO (digital-analog-to-digital) obtained by the traditional deposition-calcination method3/BiVO4A heterojunction thin film electrode.
Example 3
Firstly, the chemical bath method in the prior art is adopted to prepare WO3Nanosheet film (Zhou Bao, et al, WO)3The preparation method and the application research of the nano-sheet array film are as follows: 201510724443. X): in the presence of 0.4g Na2WO4·2H2O, 0.15g ammonium oxalate 9mL 37% hydrochloric acid, 8mL 37% H2O2And 30mL of ethanol in 30mL of deionized water, performing water bath at 85 ℃ for 200min to obtain a tungstic acid film on a conductive glass substrate, and performing heat treatment at 500 ℃ for 2h to obtain WO3A nanosheet film.
3gBi (NO)3)3·5H2Dissolving O in 100mL of 2mol/L acetic acid aqueous solution to obtain bismuth nitrate solution, and adding 1g of NH4VO3Dissolved in 100mL of 200mmol/L H2O2Obtaining peroxovanadic acid solution in water solution, then spin coating bismuth nitrate solution on the above WO3Coating the peroxyvanadic acid solution on the surface of the nano-sheet film by spinning3Repeating the spin coating process for 10 times on the surface of the nanosheet film, performing one-time heat treatment on the obtained film at the temperature of 550 ℃ for 1h, and naturally cooling to obtain WO3/BiVO4A heterojunction thin film electrode.
Subjecting said WO to3/BiVO4The heterojunction film electrode is used as a working electrode, the platinum electrode is used as a counter electrode, the Saturated Calomel Electrode (SCE) is used as a reference electrode, and the K of 0.5M is used2SO4The solution is electrolyte, and can be used for simulating the sunlight AM1.5(100 mW/cm)2) Under illumination conditions, the bias voltage was 1Vvs. SCE, and the WO was tested3/BiVO4The photoelectrocatalysis water decomposition performance of the heterojunction film electrode.
FIG. 7 shows the WO of the present embodiment3/BiVO4The photocurrent-time curves of the heterojunction thin film electrode in the above test and the production rate curves of hydrogen and oxygen. Shows the WO3/BiVO4The photocurrent of the heterojunction film electrode is basically kept stable in the 180min test process, and the current density is about 5.28mA/cm2Hydrogen production rate of about 94.7μmol h-1cm-2The oxygen generation rate was about 46.5. mu. mol h-1cm-2. Shows that said WO3/BiVO4The heterojunction film electrode has stable and efficient photoelectrocatalysis water decomposition performance.
Example 4
Firstly, the prior art hydrothermal method is adopted to prepare WO3A nano-sheet film (Zhou Bao Xue, etc., a tungsten-based tungsten trioxide film, a preparation method and application thereof, Chinese patent No. CN 102674463B): an aqueous solution containing 30mM sodium tungstate and 10% polyethylene glycol 300 at a pH of 2.5 was used as a precursor solution, and the heat-treated tungsten piece was placed therein and hydrothermally treated at 180 ℃ for 2 hours. The obtained film is subjected to heat treatment at 500 ℃ for 2 hours to obtain WO3A nanosheet film.
1.5gBi (NO)3)3·5H2Dissolving O in 100mL of 2mol/L acetic acid aqueous solution to obtain bismuth nitrate solution, adding 0.4g NH4VO3100mmol/L H dissolved in 100mL2O2Obtaining peroxovanadic acid solution in water solution, then spin coating bismuth nitrate solution on the above WO3Coating the peroxyvanadic acid solution on the surface of the nano-sheet film by spinning3Repeating the spin coating process for 15 times on the surface of the nanosheet film, performing one-step heat treatment on the obtained film at the temperature of 500 ℃ for 3 hours, and naturally cooling to obtain WO3/BiVO4A heterojunction thin film electrode.
Subjecting said WO to3/BiVO4The heterojunction thin film electrode was used as a working electrode, a platinum electrode as a counter electrode, a Saturated Calomel Electrode (SCE) as a reference electrode, and 0.1M Na containing 10mg/L phenol2SO4The solution is simulated organic wastewater, and the simulated sunlight AM1.5(100 mW/cm)2) Under irradiation conditions, the bias voltage was 1vvs. sce, and changes in phenol concentration were tested.
FIG. 8 shows phenol in WO3/BiVO4The degradation of the heterojunction thin-film electrode is 72% after 3h under the photoelectrocatalysis condition, and the direct photolysis efficiency as a contrast is only 3%. The film material can also be used as a photocatalytic electrode for preparing hydrogen by photoelectrocatalysis or degrading organic matters, and a photocatalytic waste water fuel cell.
Example 5
Firstly, the prior art hydrothermal method is adopted to prepare WO3A nano-rod film (Zhou Bao Xue, etc., a tungsten-based tungsten trioxide film, a preparation method and an application thereof, Chinese patent No. CN 102674463B): an aqueous solution containing 20mM sodium tungstate and 10% polyethylene glycol 300 at a pH of 2.5 was used as a precursor, and the heat-treated tungsten piece was placed therein and heated at 180 ℃ for 6 hours. The obtained film is subjected to heat treatment at 500 ℃ for 2 hours to obtain WO3A nanorod film.
2gBi (NO)3)3·5H2Dissolving O in 100mL of 2mol/L acetic acid aqueous solution to obtain bismuth nitrate solution, and adding 0.6g NH4VO3160mmol/L H dissolved in 100mL2O2Obtaining peroxovanadic acid solution in water solution, then spin coating bismuth nitrate solution on the above WO3Coating the peroxyvanadic acid solution on the surface of the nano-sheet film by spinning3Repeating the spin coating process for 10 times on the surface of the nanosheet film, performing one-step heat treatment on the obtained film at the temperature of 450 ℃ for 4h, and naturally cooling to obtain WO3/BiVO4A heterojunction thin film electrode.
Subjecting said WO to3/BiVO4The heterojunction film electrode is used as working electrode, platinum electrode as counter electrode, Saturated Calomel Electrode (SCE) as reference electrode, and 0.1M Na containing 10mg/L Congo red2SO4The solution is simulated organic wastewater, and the simulated sunlight AM1.5(100 mW/cm)2) Under irradiation conditions, the bias voltage was 1vvs. sce, and changes in phenol concentration were tested.
FIG. 9 shows Congo red in WO3/BiVO4The degradation of the heterojunction film electrode is 97 percent after 3 hours under the condition of photoelectrocatalysis. While the direct photolysis efficiency as a control is only 12%.
Example 6
Firstly, the chemical bath method in the prior art is adopted to prepare WO3Nanosheet film (Zhou Bao, et al, WO)3The preparation method and the application research of the nano-sheet array film are as follows: 201510724443. X): in the presence of 0.4g Na2WO4·2H2O, 0.15g ammonium oxalate9mL of 37% hydrochloric acid, 8mL of 37% H2O2And 30mL of ethanol in 30mL of deionized water, performing water bath at 85 ℃ for 200min to obtain a tungstic acid film on a conductive glass substrate, and performing heat treatment at 500 ℃ for 2h to obtain WO3A nanosheet film.
3gBi (NO)3)3·5H2Dissolving O in 100mL of 2mol/L acetic acid aqueous solution to obtain bismuth nitrate solution, and adding 1g of NH4VO3Dissolved in 100mL of 200mmol/L H2O2Obtaining peroxovanadic acid solution in water solution, then spin coating bismuth nitrate solution on the above WO3Coating the peroxyvanadic acid solution on the surface of the nano-sheet film by spinning3Repeating the spin coating process for 5 times on the surface of the nanosheet film, performing one-time heat treatment on the obtained film at the temperature of 550 ℃ for 1h, and naturally cooling to obtain WO3/BiVO4A heterojunction thin film electrode.
Subjecting said WO to3/BiVO4The heterojunction film electrode is used as working electrode, platinum electrode as counter electrode, Saturated Calomel Electrode (SCE) as reference electrode, and 0.1M Na containing 10mg/L tetracycline hydrochloride2SO4The solution is simulated organic wastewater, and the simulated sunlight AM1.5(100 mW/cm)2) Under the irradiation condition, the bias voltage was 1Vvs. SCE, and the change in the concentration of tetracycline hydrochloride was tested. After 3h of degradation, the WO was added3/BiVO4The heterojunction thin film electrode was rinsed clean and dried, and then the above photoelectrocatalytic degradation experiment was repeated for 6 times.
FIG. 10 is a graph of the change in tetracycline hydrochloride concentration during these 6 degradations, showing that tetracycline hydrochloride is able to degrade by more than 83% in 3 hours and that the performance is essentially unchanged after repeated testing, illustrating the WO3/BiVO4The heterojunction film electrode has good photoelectrocatalysis stability.
In summary, the visible light response WO of the present invention3/BiVO4The preparation method of the heterojunction thin film electrode has the characteristics of simplicity, convenience, mildness and high efficiency, and the prepared WO3/BiVO4The heterojunction film electrode has good visible light absorption performance and stability, high photoelectric efficiency, and reduced photoelectrocatalysisThe effect of organic matter decomposition is good. Compared with the prior art, the method has good technical effect and has important significance for the development of the photoelectrocatalysis technology.
Claims (3)
1. Visible light response WO3/BiVO4The preparation method of the heterojunction film electrode is characterized by comprising the following steps:
1) adding 1-3 g of Bi (NO)3)3·5H2Dissolving O in 100mL of 2mol/L acetic acid aqueous solution to obtain bismuth nitrate solution, and adding 0.2-1 g of NH4VO3Dissolving in 100mL of 50-200 mmol/L H2O2Obtaining peroxyvanadic acid solution in the water solution;
2) then the bismuth nitrate solution is coated on WO in a spinning way3Coating the peroxyvanadic acid solution on the surface of the film by spinning3Repeating the spin coating process for 5-20 times on the surface of the thin film,
3) carrying out one-time heat treatment on the obtained film at the temperature of 400-550 ℃ for 1-6 hours, and naturally cooling to obtain the WO3/BiVO4A heterojunction thin film electrode.
2. Visible light responsive WO according to claim 13/BiVO4The preparation method of the heterojunction film electrode is characterized in that the WO3The film is WO with a nano structure prepared by a hydrothermal method, a chemical bath method or an anodic oxidation method3A film.
3. Visible light responsive WO according to claim 13/BiVO4A method for preparing a heterojunction thin film electrode, characterized in that said WO3/BiVO4A heterojunction film electrode is applied to the fields of organic pollutant treatment, water decomposition and hydrogen production or sensors.
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| CN109092319B (en) * | 2018-06-27 | 2022-04-26 | 宁波工程学院 | WO (WO)3/BiVO4Ternary system composite material of/FeOOH and preparation method and application thereof |
| CN110042409A (en) * | 2019-05-09 | 2019-07-23 | 苏州大学 | Tungsten oxide/pucherite heterojunction photovoltaic anode preparation method and self-powered photoelectrolysis water system |
| CN111979561B (en) * | 2019-05-21 | 2022-08-26 | 南京理工大学 | SnOx/BiVO 4 Electrode, preparation method thereof and application of electrode in photoelectrocatalysis hydrogen peroxide synthesis |
| CN112408556B (en) * | 2020-11-25 | 2022-11-15 | 南京工程学院 | Dispersed built-in electric field tungsten-bismuth-based array for water oxidation and preparation method thereof |
| CN114573031B (en) * | 2022-03-21 | 2023-07-25 | 安徽大学 | Preparation of sheet-shaped WO 3 Is used for electrocatalytic conversion of methane to ethanol |
| CN114703500B (en) * | 2022-04-18 | 2023-06-30 | 台州学院 | Tungsten trioxide-bismuth vanadate-organic acid composite photoelectrode and preparation method and application thereof |
| CN115672307A (en) * | 2022-09-29 | 2023-02-03 | 上海第二工业大学 | Tungsten oxide-based photoelectric catalytic material growing on FTO (fluorine-doped tin oxide), preparation method and application thereof |
| CN117434129B (en) * | 2023-10-31 | 2024-07-23 | 重庆师范大学 | Oxygen vacancy regulation bismuth vanadate photoelectrode for detecting tetracycline hydrochloride and preparation method thereof |
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