CN109778223B - ZnO modified WO3/BiVO4Preparation method of heterojunction and application of heterojunction in photoelectrocatalysis - Google Patents

ZnO modified WO3/BiVO4Preparation method of heterojunction and application of heterojunction in photoelectrocatalysis Download PDF

Info

Publication number
CN109778223B
CN109778223B CN201811419967.8A CN201811419967A CN109778223B CN 109778223 B CN109778223 B CN 109778223B CN 201811419967 A CN201811419967 A CN 201811419967A CN 109778223 B CN109778223 B CN 109778223B
Authority
CN
China
Prior art keywords
bivo
heterojunction
preparation
zno
modified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811419967.8A
Other languages
Chinese (zh)
Other versions
CN109778223A (en
Inventor
侯慧林
马自在
杨为佑
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo University of Technology
Original Assignee
Ningbo University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo University of Technology filed Critical Ningbo University of Technology
Priority to CN201811419967.8A priority Critical patent/CN109778223B/en
Publication of CN109778223A publication Critical patent/CN109778223A/en
Application granted granted Critical
Publication of CN109778223B publication Critical patent/CN109778223B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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 ZnO modified WO3/BiVO4A preparation method of heterojunction belongs to the technical field of material preparation. The method comprises the following steps: mixing WCl6Preparation of WO with PVP3A seed crystal layer; dissolving sodium tungstate in water, and sequentially adding hydrochloric acid and ammonium oxalate to obtain a transparent solution; adding the transparent solution with WO3Seed layer reaction to obtain WO3Array precursor, high-temperature annealing to obtain WO3An electrode; dissolving vanadium oxide bis (acetylacetone) and bismuth nitrate pentahydrate in glacial acetic acid, and adding ethyl cellulose to obtain BiVO4Precursor solution; BiVO (bismuth oxide) is added4Drop coating of precursor solution onto WO3Drying and annealing the electrode surface to obtain WO3/BiVO4A composite light anode; mixing WO3/BiVO4The composite photoanode is placed in an atomic layer deposition system, and the ZnO grows layer by layer after deposition circulation by using diethyl zinc and water, so that the ZnO modified WO with better high efficiency and stability in photoelectrocatalysis is obtained3/BiVO4A heterojunction.

Description

ZnO modified WO3/BiVO4Preparation method of heterojunction and application of heterojunction in photoelectrocatalysis
Technical Field
The invention relates to ZnO modified WO3/BiVO4Preparation method of heterojunction and prepared ZnO modified WO3/BiVO4The application of heterojunction in photoelectrocatalysis belongs to the technical field of material preparation.
Background
Energy is the basis of human survival and development, fossil energy consumption is continuously increased along with rapid development of economy, and people face increasingly serious problems of energy shortage and environmental destruction. Based on the method, the development of clean energy has important significance for guaranteeing energy safety, promoting environmental protection, reducing greenhouse gas emission and realizing national economy sustainable development. 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).
WO3And BiVO4Because of good physical and chemical stability and low costThe band structure is suitable and recognized as an attractive and promising photo-anode material. However, WO3Has relatively weak visible light response (< 460nm) and low absorption coefficient to photons. BiVO4The short lifetime and easy recombination of the mesogenic carriers limit their application in the field of photoelectrocatalysis. Research shows that BiVO is constructed4/WO3The II-type heterojunction can effectively improve the carrier separation efficiency. In addition, the carrier recombination on the surface of the photoelectrocatalysis photoanode is an important restriction factor for restricting the water-oxygen catalytic reaction on the surface of the photoelectrocatalysis photoanode. The surface recombination centers can be greatly reduced through the modification of the passivation layer, and the charge transfer capacity is improved, so that the water decomposition efficiency of photoelectrocatalysis is improved. Therefore, an effective preparation of the photoelectric anode is explored, and the application of the photoelectric catalysis technology in the field of solar energy conversion is powerfully promoted.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide ZnO modified WO3/BiVO4Preparation method of heterojunction and prepared ZnO modified WO3/BiVO4The heterojunction has better high efficiency and stability in photoelectrocatalysis.
The purpose of the invention can be realized by the following technical scheme: ZnO modified WO3/BiVO4A method of fabricating a heterojunction, said method comprising the steps of:
1) preparation of WO3Seed crystal layer: tungsten hexachloride (WCl)6) And Polyvinylpyrrolidone (PVP) are dissolved in dimethyl formamide (DMF), stirred and coated on the conductive surface of the FTO conductive glass at room temperature, dried and annealed to form WO3A seed crystal layer;
2) preparation of WO3Array: sodium tungstate (Na)2WO4) Dissolving in water, adding hydrochloric acid (HCl), stirring, and adding ammonium oxalate ((NH)4)2C2O4) Stirring to obtain a transparent solution; adding the transparent solution with WO3Carrying out reaction in FTO reaction kettle of seed crystal layer to obtain WO3Array precursor, annealing at high temperature in sintering furnace to obtain WO3Electrode for electrochemical cell；
3) Preparation of BiVO4Precursor solution: bis (acetylacetonato) vanadia (VO (acac)2) And bismuth nitrate pentahydrate (Bi (NO))3·5H2O) in glacial acetic acid (CH)3COOH), adding ethyl cellulose, stirring and mixing to obtain BiVO4Precursor solution;
4) preparation of WO3/BiVO4A composite light anode: BiVO (bismuth oxide) is added4Drop coating of precursor solution onto WO3Drying and annealing the electrode surface to obtain WO3/BiVO4A composite light anode;
5) preparation of ZnO modified WO3/BiVO4Heterojunction: mixing WO3/BiVO4Placing a composite photoanode in an atomic layer deposition system, and using diethyl zinc (Zn (C)2H5)2) Taking water as raw material, depositing and circulating ZnO to grow layer by layer to obtain ZnO modified WO3/BiVO4A heterojunction.
ZnO-modified WO in the invention3/BiVO4Heterojunctions with WO in the previous patent3/BiVO4The ternary system of/FeOOH composites are completely different, WO3/BiVO4The structure of the/FeOOH ternary system composite material is a layered structure from bottom to top, and ZnO in the invention modifies WO3/BiVO4The heterojunction is a structure from inside to outside.
The raw material used by the invention is WCl6、PVP、DMF、Bi(NO3)3·5H2O、VO(acac)2And glacial acetic acid, ethyl cellulose, diethyl zinc and water, wherein the PVP, the glacial acetic acid and the ethyl cellulose are decomposed and completely volatilized in the calcining treatment process; WCl6Synthesis of WO by providing a W source3，Bi(NO3)3·5H2O and VO (acac)2Separately providing a Bi source and a V source for BiVO4And (3) synthesizing, wherein diethyl zinc provides a Zn source, and ZnO is synthesized.
In the above-mentioned ZnO-modified WO3/BiVO4In the preparation method of the heterojunction, the mass ratio of the tungsten hexachloride to the polyvinylpyrrolidone in the step 1) is 20:1-30: 1. Tungsten hexachloride provides a tungsten source for producing tungsten oxide, and polyvinylpyrrolidone isSlightly viscosity of the solution, and controlling the mass ratio of the tungsten hexachloride to the polyvinylpyrrolidone to be 20:1-30:1 can make the spin coating liquid spin-coat more uniformly.
In the above-mentioned ZnO-modified WO3/BiVO4In the preparation method of the heterojunction, sodium tungstate (Na) in the step 2)2WO4) With ammonium oxalate ((NH)4)2C2O4) The mass ratio of (A) to (B) is 1:1-3: 1. Sodium tungstate provides a tungsten source in hydrothermal reaction, ammonium oxalate serves as a ligand, and sodium tungstate (Na)2WO4) With ammonium oxalate ((NH)4)2C2O4) Too large or too small a mass ratio of (b) may affect the morphology of the tungsten oxide.
In the above-mentioned ZnO-modified WO3/BiVO4In the preparation method of the heterojunction, the reaction temperature in the step 2) is 100-130 ℃, and the reaction time is 10-15 h. The growth of tungsten oxide is affected by the temperature of the reaction being too high or too low.
In the above-mentioned ZnO-modified WO3/BiVO4In the preparation method of the heterojunction, vanadium bis (acetylacetonate) oxide (VO (acac) in the step 3)2) And bismuth nitrate pentahydrate (Bi (NO))3·5H2O) is 0.8:1 to 1.2: 1.
In the above-mentioned ZnO-modified WO3/BiVO4In the preparation method of the heterojunction, the annealing temperature in the step 4) is 450-500 ℃, and the annealing time is 0.5-2 h.
In the above-mentioned ZnO-modified WO3/BiVO4In the method for preparing the heterojunction, the number of deposition cycles in the step 5) is 30-100. If the number of deposition cycles is too small, the effect is insignificant, but if the number of deposition cycles is too large, the recombination of photogenerated carriers is accelerated, and the performance is reduced.
The invention also provides the ZnO modified WO3/BiVO4Application of heterojunction in photoelectrocatalysis, namely ZnO modified WO3/BiVO4Heterojunction as working anode, Ag/AgCl as reference electrode, platinum sheet as counter electrode, and Na under xenon lamp illumination2SO4The photocurrent density and impedance were measured using an electrochemical workstation.
The light source used for detecting the photoelectric catalytic 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. the invention deposits ZnO on WO by an atomic layer deposition technology3/BiVO4The surface and deposition thickness are accurate and controllable, so that the separation and passivation of surface carriers in a photoelectrocatalysis performance test are facilitated, and the improvement of photoelectrocatalysis performance is facilitated.
2. ZnO modified WO of the invention3/BiVO4The preparation method of the heterojunction has simple and controllable process and good repeatability.
3. ZnO modified WO of the invention3/BiVO4Heterojunction using WO3/BiVO4The high-efficiency heterojunction is constructed, ZnO is used as a passivation layer, the photoelectric catalysis performance is improved in many aspects, and the high-efficiency heterojunction is applied to photoelectric catalysis and has high efficiency and stability.
Drawings
FIG. 1 shows WO obtained in example 1 of the present invention3A seed layer Scanning Electron Micrograph (SEM);
FIG. 2 shows WO obtained in example 1 of the present invention3Nanosheet electrode Scanning Electron Microscopy (SEM);
FIG. 3 shows WO obtained in example 1 of the present invention3Scanning Electron Microscope (SEM) of the cross section of the nanosheet array electrode;
FIG. 4 shows WO obtained in example 1 of the present invention3/BiVO4Scanning Electron Micrographs (SEM) of the composite photoanode;
FIG. 5 shows WO obtained in example 1 of the present invention3/BiVO4Electrode WO3/BiVO4Scanning Electron Microscope (SEM) images of the cross section of the composite photoanode;
FIG. 6 shows 50C ZnO modified WO obtained in example 1 of the present invention3/BiVO4Scanning Electron Micrographs (SEM) of the heterojunction;
FIG. 7 shows 50C ZnO modified WO obtained in example 1 of the present invention3/BiVO4Cross-sectional Scanning Electron Micrographs (SEM) of the heterojunction;
FIG. 8 shows 50C ZnO modified WO obtained in example 1 of the present invention3/BiVO4An X-ray diffraction pattern (XRD) of the heterojunction photoanode;
FIG. 9 shows 50C ZnO modified WO obtained in example 1 of the present invention3/BiVO4Transmission Electron Microscopy (TEM) of the heterojunction photoanode;
FIG. 10 shows the 30C ZnO modified WO obtained in example 2 of the present invention3/BiVO4Scanning Electron Micrographs (SEM) of the heterojunction photoelectrocatalytic anode material;
FIG. 11 shows 100C ZnO modified WO obtained in example 2 of the present invention3/BiVO4Scanning Electron Micrographs (SEM) of the heterojunction photoelectrocatalytic anode material;
FIG. 12 shows WO obtained in comparative example 1 of the present invention3An X-ray diffraction pattern (XRD) of the nanosheet array photoelectrocatalysis anode material;
FIG. 13 shows BiVO obtained in comparative example 2 of the present invention4Scanning Electron Micrographs (SEM);
FIG. 14 shows BiVO obtained in comparative example 2 of the present invention4X-ray diffraction pattern (XRD);
FIG. 15 shows WO obtained in comparative example 3 of the present invention3/BiVO4X-ray diffraction pattern (XRD);
FIG. 16 shows that the 30C ZnO modified WO of the present invention3/BiVO4Heterojunction, 50C ZnO modified WO3/BiVO4Heterojunction, 100C ZnO modified WO3/BiVO4A photo current density contrast graph of the heterojunction photo anode under different bias voltages;
FIG. 17 shows WO of the present invention3、BiVO4、WO3/BiVO4And 50C ZnO modified WO3/BiVO4A photo current density contrast graph of the heterojunction photo anode under different bias voltages;
FIG. 18 shows 50C ZnO modified WO of the present invention3/BiVO4And (3) a stability test chart of the heterojunction photoelectric anode.
FIG. 19 shows WO of the present invention3、BiVO4、WO3/BiVO4And 50C ZnO modified WO3/BiVO4Impedance of heterojunction photoanode versus graph.
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 PVP and 2g WCl were weighed separately6Dissolved in 10mL of DMF, and stirred at room temperature for 1 hour to obtain a spin-on solution. Coating 20 μ L of the mixture on an FTO glass conductive surface at 4000 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 seed layer. FIG. 1 shows the WO obtained3Scanning Electron Microscopy (SEM) pictures of the seed layer, it can be seen from the very fine WO3The particles are formed and densely covered on the FTO conductive surface.
0.25g of Na2WO4Dissolved in 30mL of water, 6mL of 3M HCl was added, and after stirring well, 0.2g (NH) was added4)2C2O4Water was added to 70mL and stirred until a clear solution formed. Taking 28mL of the prepared solution, adding and placing WO3And reacting the seed crystal layer in an FTO reaction kettle at 120 ℃ for 12 h. After the reaction is finished and cooled, the surface of the electrode is cleaned by deionized water and ethanol, and then the electrode is placed into a muffle furnace to be annealed at 500 ℃ for 30 min to obtain WO3A nanosheet array electrode. FIG. 2 shows the WO obtained3The nano-sheet array Scanning Electron Microscope (SEM) is composed of nano-sheets which are 800nm long and 100nm thick and are vertical to the FTO conductive glass; FIG. 3 is WO3Scanning Electron Microscope (SEM) of the cross section of the nanosheet array electrode.
Will (VO (acac)2) And Bi (NO)3·5H2O is prepared by mixing the following components in a molar ratio of 1:1 mu.M each was dissolved in 10mL of glacial acetic acid, followed by addition of 0.1g of ethyl cellulose for increasing the viscosity, followed by mixing with stirring at room temperature to give BiVO4And (3) precursor solution.
Taking prepared BiVO4Dripping 10 mu L of precursor solution to 1cm2Drying the surface of tungsten oxide electrode at 80 deg.C for 3 hr, and annealing at 450 deg.C for 1 hr to obtain WO3/BiVO4A composite light anode; FIG. 4 shows the WO obtained3/BiVO4Typical of electrodesScanning Electron Microscopy (SEM), showing BiVO4The layers being uniformly covered in WO3And (3) the surface of the nanosheet. FIG. 5 shows the WO obtained3/BiVO4The cross section of the electrode is shown by a Scanning Electron Microscope (SEM) picture, and the thickness of the electrode is not obviously increased, which shows that BiVO4Is thin and uniform in the WO3A surface.
Mixing WO3/BiVO4Placing a composite photoanode in an atomic layer deposition system, and using diethyl zinc (Zn (C)2H5)2) Taking water as raw material, depositing and circulating for 50 times, and growing ZnO layer by layer to obtain ZnO modified WO3/BiVO4A heterojunction. FIG. 6 shows 50C ZnO modified WO3/BiVO4Scanning Electron Microscope (SEM) images of the heterojunction show that the surface of the electrode has no obvious change after ZnO is deposited, which indicates that the ZnO layer is extremely thin. FIG. 7 shows the obtained 50C ZnO modified WO3/BiVO4The cross-sectional Scanning Electron Microscope (SEM) image of the heterojunction can be seen from WO3/BiVO4There is no significant difference. FIG. 8 shows the prepared 50C ZnO modified WO3/BiVO4The X-ray diffraction pattern of the heterojunction shows that the corresponding WO which is obvious in the photoelectrocatalysis anode3、BiVO4And no obvious characteristic peak can be detected due to the extremely thin ZnO. FIG. 9 shows the WO thus obtained3/BiVO4The transmission electron microscope image of the/50C photo-anode shows that the zinc oxide layer is well crystallized and has the thickness of about 15 nm.
Example 2
Only 30 deposition cycles are performed on the ZnO layer, which is different from example 1, and other processes are the same as example 1 and are not described herein again. The cross-sectional Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is shown in figure 10, the surface appearance is not obviously changed, and the ZnO layer is very thin.
Example 3
Only the deposition cycle of the ZnO layer is 100 times different from that of embodiment 1, and other processes are the same as those of embodiment 1 and are not described herein again. The cross-sectional Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is shown in figure 11, and the surface appearance is not obviously changed.
Example 4
Only the deposition cycle of the ZnO layer was 40 times as different from that of example 1, and other processes are the same as those of example 1 and are not described herein again. The surface appearance of the cross section Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is not obviously changed.
Example 5
Only the deposition cycle of the ZnO layer is 60 times as different from that of the embodiment 1, and other processes are the same as the embodiment 1 and are not described again. The surface appearance of the cross section Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is not obviously changed.
Example 6
Only the deposition cycle of the ZnO layer was 80 times different from that of example 1, and other processes are the same as those of example 1 and are not described herein again. The surface appearance of the cross section Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is not obviously changed.
Example 7
Only 20 deposition cycles are performed on the ZnO layer, which is different from example 1, and other processes are the same as example 1 and are not described herein again. The surface appearance of the cross section Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is not obviously changed.
Example 8
Only the deposition cycle of the ZnO layer is 120 times as different from that of the embodiment 1, and other processes are the same as the embodiment 1 and are not described again. The cross section Scanning Electron Microscope (SEM) surface of the prepared photoelectrocatalysis anode material is uniformly and densely covered with a layer of thin film on WO3/BiVO4A surface.
Example 9
The difference from example 1 is that only 2.5g of tungsten hexachloride is added, and the other processes are the same as example 1 and are not repeated herein. The surface appearance of the cross section Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is not obviously changed.
Example 10
The difference from example 1 is that only 3g of tungsten hexachloride is added, and the other processes are the same as example 1 and are not repeated herein. The surface appearance of the cross section Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is not obviously changed.
Example 11
The difference from example 1 is that only 2.5g of tungsten hexachloride is added, and the other processes are the same as example 1 and are not repeated herein. The surface appearance of the cross section Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is not obviously changed.
Example 12
The difference from example 1 is that 0.2g sodium tungstate is added, and the other processes are the same as example 1 and are not repeated here. The surface appearance of the cross section Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is not obviously changed.
Example 13
The difference from example 1 is that 0.6g sodium tungstate is added, and the other processes are the same as example 1 and are not repeated here. The surface appearance of the cross section Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is not obviously changed.
Example 14
The difference from example 1 is only that the reaction temperature is 100 ℃, the reaction time is 15h, other processes are the same as example 1, and the description is omitted. The surface appearance of the cross section Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is not obviously changed.
Example 15
The difference from example 1 is that the reaction temperature is 30 ℃, the reaction time is 10h, other processes are the same as example 1, and the description is omitted. The surface appearance of the cross section Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is not obviously changed.
Example 16
Differs from example 1 only in (VO (acac)2) And Bi (NO)3·5H2The molar ratio of O is 0.8:1, other processes are the same as those of the embodiment 1, and are not described again here. The surface appearance of the cross section Scanning Electron Microscope (SEM) of the prepared photoelectrocatalysis anode material is not obviously changed.
Example 17
Differs from example 1 only in (VO (acac)2) And Bi (NO)3·5H2The molar ratio of O is 1.2:1, other processes are the same as those of the embodiment 1, and are not described again here. Of the prepared photoelectrocatalytic anode materialThe surface appearance of the cross section Scanning Electron Microscope (SEM) is not obviously changed.
Comparative example 1
In contrast to example 1, in which only WO is prepared3The other processes of the nanosheet array electrode are the same as those in embodiment 1, and are not described herein again. The X-ray diffraction pattern (XRD) of the prepared photoelectrocatalysis anode material is shown in figure 12, which shows that the prepared material is WO3。
Comparative example 2
The difference from example 1 is that BiVO is prepared only on FTO conductive glass4Other processes of the layer and the layer are the same as those of embodiment 1, and are not described again here. FIG. 13 is BiVO4Scanning Electron Micrographs (SEM) are a uniform layer of small particle, non-dense film. 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 only WO is prepared3/BiVO4Other processes of the layer and the layer are the same as those of embodiment 1, and are not described again here. FIG. 15 is an X-ray spectrum (XRD) of the electrode material, showing that the material prepared is WO3、BiVO4。
Application examples 1 to 3
WO was modified with ZnO prepared in examples 1 to 3, respectively3/BiVO4Heterojunction as working anode, Ag/AgCl as reference electrode, platinum sheet as counter electrode, 0.5M L-1Na2SO4As electrolyte, an electrolytic cell with a quartz glass window was chosen. The photocurrent density of the samples at different biases was tested by an electrochemical workstation with a 300W xenon lamp equipped with an AM 1.5G filter as a simulated light source.
Comparative application examples 1 to 3
WO prepared in comparative examples 1 to 3, respectively3、BiVO4、WO3/BiVO4For the photo-anode, other processes and test procedures are the same as those in application example 1, and will not be described herein again.
FIG. 16 shows that the 30C ZnO modified WO of the present invention3/BiVO4Heterojunction, 50C ZnO modified WO3/BiVO4Heterojunction100CZnO modified WO3/BiVO4The comparison graph of the photocurrent density of the heterojunction photo-anode under different bias voltages shows that the 50C ZnO modified WO prepared by the invention3/BiVO4The heterojunction has more excellent photoelectrocatalysis performance as a photoelectric anode, namely ZnO deposited for 50 cycles has better performance.
FIG. 17 shows WO of the present invention3、BiVO4、WO3/BiVO4And 50C ZnO modified WO3/BiVO4The comparison graph of the photocurrent density of the heterojunction photo-anode under different bias voltages shows that the 50C ZnO modified WO prepared by the invention3/BiVO4Heterojunction as photo-anode ratio WO3、BiVO4、WO3/BiVO4The photoelectric anode material has more excellent photoelectric catalytic performance, and ZnO surface modification can improve the photoelectric catalytic performance.
FIG. 18 shows 50C ZnO modified WO of the present invention3/BiVO4The stability test of the heterojunction as a photoelectric anode can show that the prepared 50C ZnO modified WO3/BiVO4The heterojunction photoelectric anode material still keeps stable performance for 6 hours under illumination without obvious attenuation.
FIG. 19 shows WO of the present invention3、BiVO4、WO3/BiVO4And 50C ZnO modified WO3/BiVO4Impedance comparison graph of heterojunction photoelectric anode illustrates 50C ZnO modified WO prepared by the invention3/BiVO4The heterojunction serving as the photoelectrocatalysis anode material has more excellent charge conduction performance, and the fact that the 50C ZnO modified WO prepared by the invention is proved again3/BiVO4The heterojunction has more excellent photoelectrocatalysis performance when being used as a photoelectrocatalysis anode material.
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 (7)

1. ZnO modified WO3/BiVO4The preparation method of the heterojunction is characterized by comprising the following steps:
1) preparation of WO3Seed crystal layer: tungsten hexachloride (WCl)6) And Polyvinylpyrrolidone (PVP) are dissolved in dimethyl formamide (DMF), stirred and coated on the conductive surface of the FTO conductive glass at room temperature, dried and annealed to form WO3A seed crystal layer;
2) preparation of WO3Array: sodium tungstate (Na)2WO4) Dissolving in water, adding hydrochloric acid (HCl), stirring, and adding ammonium oxalate ((NH)4)2C2O4) Stirring to obtain a transparent solution; adding the transparent solution with WO3Carrying out reaction in FTO reaction kettle of seed crystal layer to obtain WO3Array precursor, annealing at high temperature in sintering furnace to obtain WO3An array;
3) preparation of BiVO4Precursor solution: bis (acetylacetonato) vanadia (VO (acac)2) And bismuth nitrate pentahydrate (Bi (NO))3·5H2O) in glacial acetic acid (CH)3COOH), adding ethyl cellulose, stirring and mixing to obtain BiVO4Precursor solution;
4) preparation of WO3/BiVO4A composite light anode: BiVO (bismuth oxide) is added4Drop coating of precursor solution onto WO3Drying and annealing the array surface to obtain WO3/BiVO4A composite light anode;
5) preparation of ZnO modified WO3/BiVO4Heterojunction: mixing WO3/BiVO4Placing a composite photoanode in an atomic layer deposition system, and using diethyl zinc (Zn (C)2H5)2) Taking water as raw material, depositing and circulating ZnO to grow layer by layer to obtain ZnO modified WO3/BiVO4A heterojunction.
2. ZnO modified WO according to claim 13/BiVO4The preparation method of the heterojunction is characterized in that the mass ratio of the tungsten hexachloride to the polyvinylpyrrolidone in the step 1) is 20:1-30: 1.
3. ZnO modified WO according to claim 13/BiVO4The preparation method of the heterojunction is characterized in that sodium tungstate (Na) in the step 2)2WO4) With ammonium oxalate ((NH)4)2C2O4) The mass ratio of (A) to (B) is 1:1-3: 1.
4. ZnO modified WO according to claim 13/BiVO4The preparation method of the heterojunction is characterized in that the reaction temperature in the step 2) is 100-130 ℃, and the reaction time is 10-15 h.
5. ZnO modified WO according to claim 13/BiVO4The preparation method of the heterojunction is characterized in that in the step 3), vanadium bis (acetylacetonate) oxide (VO (acac)2) And bismuth nitrate pentahydrate (Bi (NO))3·5H2O) in a molar ratio of 0.8:1 to 1.2: 1.
6. ZnO modified WO according to claim 13/BiVO4The preparation method of the heterojunction is characterized in that the annealing temperature in the step 4) is 450-500 ℃, and the annealing time is 0.5-2 h.
7. ZnO modified WO according to claim 13/BiVO4A method for preparing a heterojunction, comprising the steps ofThe number of deposition cycles in step 5) is 30-100.
CN201811419967.8A 2018-11-26 2018-11-26 ZnO modified WO3/BiVO4Preparation method of heterojunction and application of heterojunction in photoelectrocatalysis Active CN109778223B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811419967.8A CN109778223B (en) 2018-11-26 2018-11-26 ZnO modified WO3/BiVO4Preparation method of heterojunction and application of heterojunction in photoelectrocatalysis

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811419967.8A CN109778223B (en) 2018-11-26 2018-11-26 ZnO modified WO3/BiVO4Preparation method of heterojunction and application of heterojunction in photoelectrocatalysis

Publications (2)

Publication Number Publication Date
CN109778223A CN109778223A (en) 2019-05-21
CN109778223B true CN109778223B (en) 2020-06-23

Family

ID=66496428

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811419967.8A Active CN109778223B (en) 2018-11-26 2018-11-26 ZnO modified WO3/BiVO4Preparation method of heterojunction and application of heterojunction in photoelectrocatalysis

Country Status (1)

Country Link
CN (1) CN109778223B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110373680A (en) * 2019-08-20 2019-10-25 河南师范大学 A kind of preparation method for the ZnO/BiVO4 hetero-junctions light anode composite material decomposing water for optical electro-chemistry
CN114016039A (en) * 2021-09-25 2022-02-08 西北师范大学 Semiconductor composite light anode, preparation method and application
CN114180630A (en) * 2021-12-27 2022-03-15 南京理工大学 Multilayer nano plate-shaped WO3 and preparation method and application thereof
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
CN115007137B (en) * 2022-07-14 2023-07-28 南大恩洁优环境技术(江苏)股份公司 Catalyst for purifying dioxin and preparation method 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
CN115845832A (en) * 2022-11-24 2023-03-28 百色学院 ZIF-8-derivatized ZnO/BiVO 4 Preparation method and application of heterojunction compound

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2812031A1 (en) * 2010-09-10 2012-03-15 Geoffrey A. Ozin Photoactive material
CN107316748B (en) * 2017-07-17 2019-02-01 宁波工程学院 High-purity ZnO/BiVO4Application of the heterogeneous nucleocapsid micro belt in photoelectrocatalysis
CN107190362B (en) * 2017-07-17 2019-11-19 宁波工程学院 A kind of high-purity ZnO/BiVO4The preparation method of heterogeneous micro belt

Also Published As

Publication number Publication date
CN109778223A (en) 2019-05-21

Similar Documents

Publication Publication Date Title
CN109778223B (en) ZnO modified WO3/BiVO4Preparation method of heterojunction and application of heterojunction in photoelectrocatalysis
JP4714844B2 (en) Method for producing precursor for forming porous zinc oxide film, method for producing porous zinc oxide film
CN108842169B (en) Metal oxide loaded bismuth vanadate composite material and preparation and application thereof
CN102107850B (en) Method for preparing nuclear-shell-structured rutile monocrystal titanium dioxide nanowire array with surface-cladding carbon layer
CN108579765B (en) Preparation of copper sulfide/bismuth vanadate double-layer film composite material and application of copper sulfide/bismuth vanadate double-layer film composite material as photoelectric anode
CN108611653B (en) Magnetic nanoparticle-loaded bismuth vanadate composite material and preparation and application thereof
Ahmad et al. Three dimensional rosette-rod TiO2/Bi2S3 heterojunction for enhanced photoelectrochemical water splitting
CN109092319B (en) WO (WO)3/BiVO4Ternary system composite material of/FeOOH and preparation method and application thereof
Guo et al. Hierarchical TiO 2–CuInS 2 core–shell nanoarrays for photoelectrochemical water splitting
CN105986292B (en) Preparation method of cobalt-nickel double-layer hydroxide modified titanium dioxide nanotube array and application of photoelectrochemical hydrolysis hydrogen production
Wei et al. Cooperation effect of heterojunction and co-catalyst in BiVO 4/Bi 2 S 3/NiOOH photoanode for improving photoelectrochemical performances
Han et al. Photostable 3D heterojunction photoanode made of ZnO nanosheets coated onto TiO 2 nanowire arrays for photoelectrochemical solar hydrogen generation
CN108511198B (en) Ni-doped BiVO4Thin-film photoelectric anode, preparation method and application thereof
Xin et al. Construction of BiVO4 nanosheets@ WO3 arrays heterojunction photoanodes by versatile phase transformation strategy
Nien et al. Investigation of Dye-Sensitized Solar Cell With Photoanode Modified by TiO₂-ZnO Nanofibers
CN113481546B (en) Zinc oxide/zinc sulfide composite film photoelectrode and recovery device for solar photo-deposited noble metal
CN113293404B (en) Heterojunction photo-anode material and preparation method and application thereof
KR102218173B1 (en) Electrode for photoelectrochemical cell, Method of manufacturing the same, and Photoelectrochemical cell comprising the same
CN109518213B (en) NiB auxiliary agent modified bismuth vanadate nano porous film electrode and preparation method and application thereof
CN111821972A (en) Bismuth vanadate thin film electrode formed by oriented growth crystal array and preparation and application thereof
CN111755256B (en) Preparation method of three-dimensional ZnO/CuO nano heterogeneous hierarchical structure photoelectrode
KR102099644B1 (en) Photoanode with Tungsten oxide film and preparing method of the same
CN114592212A (en) Heterojunction MoO3Preparation method and application of/ZnO photoelectrode film
CN110359058B (en) Preparation method of lead zirconate titanate modified hematite nanorod array photoanode
CN113745410A (en) Based on P type CuNiO2Preparation method of thin film perovskite solar cell

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant