CN113684500A - Preparation method of composite photo-anode material - Google Patents
Preparation method of composite photo-anode material Download PDFInfo
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- 239000010405 anode material Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000011521 glass Substances 0.000 claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
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- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/067—Inorganic compound e.g. ITO, silica or titania
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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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/087—Photocatalytic compound
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a preparation method of a composite photo-anode material, which is characterized in that a compact granular seed layer material is introduced between an FTO (fluorine-doped tin oxide) glass substrate and a wormhole-shaped porous semiconductor material bismuth vanadate by improving the connection mode of the semiconductor material and the substrate, a brand-new composite photo-anode structure is reconstructed, the performance of an intrinsic semiconductor material BV (bismuth vanadate) is improved by 35-40% under the test condition without any catalyst promoter and is characterized and tested by ultraviolet, LSV, SPECM and IMPS analysis and test means, and the photo-anode material constructed by introducing the seed layer is proved to have better charge separation efficiency and increased intrinsic transmission dynamics, so that the photo-anode material with simple preparation, low cost and high efficiency has guiding significance for construction of a future photo-electrochemical material structure.
Description
Technical Field
The invention relates to the technical field of photoelectric anode materials, in particular to a preparation method of a composite photo-anode material.
Background
Considering the impact of global warming and the energy demand of fossil fuels, the production of valuable environmentally friendly fuels is a promising approach for clean energy utilization. Photoelectrochemical (PEC) water splitting is one of the promising approaches to sustainable energy conversion that artificially mimics natural photosynthesis.
The effectiveness of photocatalytic devices depends largely on three processes: light absorption, charge separation, and catalytic reactions at the semiconductor surface. The excellent semiconductor material is a prerequisite for establishing good and bad performance. The morphology of the material can be reasonably designed to obtain different specific surface areas by changing a synthesis method, so that the difference of intrinsic properties of the material is caused, the performance of the material is improved, and the monoclinic system BiVO with butterfly-shaped morphology is synthesized by adopting an alcohol-hydrothermal method4. With irregularly shaped BiVO4In contrast, butterfly BiVO4Has higher specific surface area and lower energy band width, and is favorable for promoting organic pollutants in BiVO4The surface adsorbs rapidly, energy absorption is reduced, and the light absorption range is increased.
Yet another process of particular importance is the separation and transport of pairs of photogenerated electrons. Some groups of subjects propose heating Ta by two-step flame2O5Precursor (TSFH-Ta)2O5) Nitridation to produce Ta with reduced surface defects3N5Photoanode (Reducing the surface defects of Ta)3N5A photoresist based enhanced photochemical water oxidation). Ta obtained by one-step flame heating method2O5(OSFH-Ta2O5) Compared with the method, the low-valence Ta species are reduced in Ta2O5The concentration at the surface reduces surface defects, thereby improving the charge separation and injection efficiency of the PEC water oxidation reaction. The photoelectric performance is improved. The photoelectric property of the material is improved by regulating and controlling the structure of the interface of the material and the catalyst so as to achieve the purpose of regulating and controlling charge transmission. However, so far, BiVO4(BV) achieves solar-hydrogen (STH) conversion efficiencies far below expectations due to the slow surface reaction kinetics and low electron-hole separation yields of this material. In order to improve BiVO4Performance, some research will focus on doping mainly, adopting layer-by-layer stacked loading, aiming at improving the poor electron transport performance. Other researches use an electron/hole sacrificial agent to inhibit recombination to the maximum extent on the basis of adopting a layer-by-layer supported catalyst and a cocatalyst, but a particularly critical factor is seldom concerned, namely an interface connection mode between an intrinsic semiconductor material and a substrate, which greatly influences the intrinsic electron-hole pair recombination condition of the material. In a solar cell, compared with a planar structure, the main reason for the higher performance of a nano-structure cell is the improvement of light absorption and charge separation efficiency, a nano-column structure and a porous structure are used for increasing light capture, and meanwhile, the specific surface area is enlarged, so that the material performance is improved, in the growth process of a nano-column, a seed layer plays the most critical role, the seed layer in the traditional sense has the great improvement effect on the growth of a nano-column array, because the seed layer is in lattice matching with an FTO substrate, the orientation of the array structure is enhanced due to the introduction of the seed layer, and whether the seed layer can play a certain role in the charge transmission process is deficient in related research at present. At the same time, there is also an important factor to be noted in this process, namely electronsThe separation efficiency of the hole pairs is not compatible with the increase in the specific surface area, and therefore, in the process, which factor has a dominant effect on the performance of the material, quantitative analysis and conclusive experimental evidence are still insufficient. Since the processes of charge separation and transport and specific surface area increase to increase the absorbance occur simultaneously, it is difficult to distinguish them, and it is impossible to determine the contribution of each factor, and previous studies only give some qualitative conclusions.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a method for preparing a composite photo-anode material.
Preparation method of composite photo-anode material
The preparation method of the composite photo-anode material comprises the following steps:
(1) adding Bi (NO)3)3·5H2Adding O, ammonium metavanadate and citric acid into a dilute nitric acid solution, fully stirring, and adding polyvinyl alcohol and acetic acid after the solution turns blue to obtain a precursor solution. Wherein, Bi (NO)3)3·5H2The molar ratio of O, ammonium metavanadate and citric acid is 1:1: 1; the mass ratio of the citric acid to the polyvinyl alcohol is 1: 1.1; the mass-volume ratio of the polyvinyl alcohol to the acetic acid is 0.3-0.5 g/mL.
(2) Respectively ultrasonically cleaning an FTO conductive glass substrate for 20min through glass cleaning liquid-ultrapure water-acetone-ethanol, drying the FTO conductive glass substrate by using nitrogen, uniformly coating the precursor solution on the cleaned FTO conductive glass substrate by using a spin coating machine, controlling the rotating speed of the spin coating machine to be 1500-5000 r, rotating for 30-45 s, annealing at 450-550 ℃ for 2-4 hours, and successfully growing a compact bismuth vanadate seed layer on the FTO glass substrate to obtain FTO loaded with the seed layer; the thickness of the seed layer is 285-330 nm.
(3) Dissolving KI in ultrapure water, adding concentrated nitric acid to adjust the pH to 1.7-1.8, and adding Bi (NO)3)3·5H2O, stirring for 10-15 min, adding an absolute ethanol solution of p-benzoquinone, stirring for 25-35 min, uniformly mixing, performing electrodeposition by adopting a three-electrode system, and carrying out seed layer loading on the seed layer obtained in the step (2)And (3) taking the FTO as a working electrode, an Ag/AgCl electrode as a reference electrode, a Pt sheet electrode as a counter electrode, and performing electro-deposition for 150-1500 s by using a Chi-600e electrochemical workstation to obtain the BiOI. Wherein KI and Bi (NO)3)3·5H2The molar ratio of O is 9: 1-12: 1; p-benzoquinone and Bi (NO)3)3·5H2The molar ratio of O is 1: 1-1: 2; the concentration of the absolute ethanol solution of the p-benzoquinone is 0.1-0.2 mM.
(4) And (3) dripping a dimethyl sulfoxide solution of vanadyl acetylacetonate on the surface of the BiOI, annealing at 400-500 ℃ for 1-2 h, soaking the annealed sample in a 1M NaOH solution for 25-35 min, washing with ultrapure water, and drying to obtain the composite light anode material. Wherein the mass ratio of vanadyl acetylacetonate to KI is 1: 15-1: 16; the concentration of the absolute ethanol solution of the p-benzoquinone is 0.03-0.06 g/mL; the thickness of the composite photo-anode material is 1.5-1.7 mu m.
Second, structure and performance of photoelectric anode material
1. SEM characterization of photoanode materials
Fig. 1 is SEM images of different photo-anode materials, wherein a) is a front view of a seed layer material prepared by spin coating, and it can be seen that the seed layer prepared by the method is dense and uniform, and the nanoparticles are full; FIG. b) is a diagram of the preparation of BiVO by electrodeposition4The front surface of the semiconductor material is a porous sparse fluffy wormhole-shaped semiconductor material; graph c) and graph d) are BiVO with different thicknesses respectively4The BiVO can be clearly seen from the cross-sectional view of the semiconductor material grown on the seed layer4A semiconductor material is grown on the seed layer, wherein X represents the seed layer and D represents BiVO4A semiconductor material.
2. Performance of the photoanode material
FIG. 2 shows different photoanode materials in 0.5M Na2SO4LSV photoelectrochemical scanning curves under sunlight source conditions were simulated in the solution. Wherein, the graph a) is an LSV photoelectrochemical scanning curve of the composite photo-anode material under different seed layer thicknesses, the composite photo-anode material is prepared under the conditions of different seed layer thicknesses and the same deposition time (300S), and the timeliness of the seed layer thickness being 300nm can be seenThe optimum performance is achieved, so that the thickness of the seed layer is controlled to be 300nm in subsequent material tests; figure b) shows the variation of the performance of the composite photo-anode material (X + D) along with the thickness, wherein the numbers 1-6 are respectively corresponding to the thicknesses of the composite photo-anode material (X + D) from large to small, namely 1.6 mu m, 850nm, 730nm, 2.3 mu m, 500nm and 2.7 mu m; graph c) is BiVO directly grown on FTO conductive glass substrate4The performance of the semiconductor material changes along with the thickness, and the deposition time is 150-1200s and corresponds to the thickness of 600nm, 1.16 μm, 2.7 μm and 3.2 μm respectively; from the graphs b) and c), it can be clearly seen that the change trends of the two photoelectrodes are approximately the same, and the photocurrent shows the effect of increasing first and then decreasing with the increase of the thickness. The light absorption efficiency is low due to the fact that the material is thin at the beginning, the specific surface area of the material is small, the specific surface area participating in the reaction is increased along with the thickness of the material, the performance of the material is improved, when the thickness of the material reaches a certain degree, the electron hole pairs of the body are seriously compounded, the positive influence brought by absorbance is mutually offset, and therefore the subsequent current performance is reduced. In addition, it can be obviously seen that the photoelectric property of the composite photo-anode material is more directly grown on BiVO on the FTO conductive glass substrate4The semiconductor material is improved by 35-40%, so that the effect is considerable without using any sacrificial agent or catalyst, and the application prospect is wide; and D) the composite photo-anode material (X + D) and the pure semiconductor material BiVO are prepared under the condition that the thickness of the seed layer is 300nm4(D) And a comparison graph of the seed layer (X), wherein the graph shows that the performance of the composite photo-anode material is outstanding under the condition of the same thickness, and the current density is also changed from showing a rapid descending trend (60%) to a slow trend (15%), which shows that the recombination phenomenon of electron-hole pairs is also greatly improved.
FIG. 3 shows BiVO of pure semiconductor materials with different thicknesses4The solid ultraviolet characterization of the composite photo-anode material (the left picture) and the composite photo-anode material (the right picture) proves that the ultraviolet spectrum is good, the specific surface area of the material is increased along with the increase of the thickness, the absorbance is enhanced, the result is consistent with the LSV display result, the longitudinal comparison of the two pictures shows that the integral light absorption difference is not large, and the introduction of the visible seed layer to the light absorption methodThe influence of the facets is not very large.
FIG. 4 shows BiVO for the seed layer (X), pure semiconductor material4(D) The SPECM approximation curve fitting of the composite photo-anode material (X + D1/2/3 is the composite photo-anode material obtained under the conditions that the seed layer thickness is 300nm and the deposition time is different) (the left graph is the graph with the curves from top to bottom being X + D1, X + D2, X + D3 and D, X in sequence), and the kinetic constant change calculated according to the approximation curve fitting (the right graph). From the left picture, we can clearly see the kinetic fitting result, which is consistent with the LSV result, and the charge transfer kinetics of the composite photo-anode material is more pure semiconductor material BiVO4(D) And the seed layer is significantly larger and attenuates downwards in sequence, and the increase of the kinetic constant of the right graph is more intuitive.
FIG. 5 shows BiVO for the seed layer (X), pure semiconductor material4(D) IMPS scan curve (left) of the composite photoanode material (X + D) and the corresponding charge transport time (right). The lowest point frequency in the left graph is X from top to bottom in sequence>D>And X + D indirectly shows the improvement of the charge transmission efficiency of the composite photo-anode material (X + D), and the reduction of the transmission time of the composite photo-anode material (X + D) in the right picture more powerfully proves that the charge separation transmission efficiency is effectively improved by the introduction of the seed layer.
The invention has the beneficial effects that:
according to the invention, by improving the connection mode of the semiconductor material and the substrate, a compact granular seed layer material is introduced between the FTO glass substrate and the wormhole-shaped porous semiconductor material bismuth vanadate, a brand-new composite light anode material is reconstructed, and the seed layer and the wormhole-shaped porous semiconductor material bismuth vanadate have similar crystallinity and impurity concentration, so that the purpose of tighter connection between the porous semiconductor material and the substrate can be achieved, and the porous BiVO is weakened4The bulk is compounded, so that the charge transmission efficiency is improved, and the intrinsic reaction kinetics is improved. The invention improves the interface contact between the material and the substrate by introducing the seed layer, the intrinsic composite effect is obviously weakened, the photoelectric property is greatly improved, and no catalyst or cocatalyst is usedUnder the condition of no electronic sacrificial agent, the performance of the intrinsic composite photo-anode material is improved by 35-40%; the synthesis method is simple, avoids the use of a series of complex and expensive catalysts and cocatalysts, has strong practicability and wide application range, and has guiding significance for the construction of the photoelectrode of the semiconductor material in the future.
Drawings
FIG. 1 is an SEM image of different photo-anode materials;
FIG. 2 shows different photoanode materials in 0.5M Na2SO4Simulating an LSV photoelectrochemical scanning curve in the solution under the condition of a sunlight source;
FIG. 3 shows BiVO of pure semiconductor materials with different thicknesses4(left panel) and solid uv characterization of composite photoanode material (right panel);
FIG. 4 shows BiVO for the seed layer (X), pure semiconductor material4(D) Fitting a SPECM approximation curve of the composite photo-anode material (X + D) (left graph) and calculating the change of the kinetic constant according to the approximation curve fitting (right graph);
FIG. 5 shows BiVO for the seed layer (X), pure semiconductor material4(D) IMPS scan curve (left) of the composite photoanode material (X + D) and the corresponding charge transport time (right).
Detailed Description
The preparation of the composite photoanode material of the present invention is further illustrated by the following specific examples.
Examples
(1) Adding 500 μ l concentrated nitric acid into 10ml ultrapure water, diluting, stirring, adding 3mM Bi (NO)3)3·5H2O, 3mM ammonium metavanadate and 1.101g of citric acid are sequentially added into a dilute nitric acid solution, the mixture is fully stirred, after the solution turns blue, 1.23g of polyvinyl alcohol and 3ml of acetic acid are added, and the polyvinyl alcohol is completely dissolved to obtain a precursor solution.
(2) Respectively ultrasonically cleaning an FTO conductive glass substrate for 20min by using glass cleaning liquid-ultrapure water-acetone-ethanol, uniformly coating a precursor solution on the cleaned FTO conductive glass substrate by using a spin coater, annealing for 3 hours at 500 ℃ to obtain the FTO loaded with a bismuth vanadate seed layer, and controlling the rotation speed of the spin coater to be 2500r/s and the thickness of the seed layer to be 300nm in 35 s.
(3) Adding 3.32g KI in ultrapure water as solvent, ultrasonic dissolving, adding concentrated nitric acid, adjusting pH to 1.75 with pH meter, and slowly adding 5mM Bi (NO)3)3·5H2O, fully stirring for 10 minutes to ensure that the solution turns orange, the precipitate completely disappears, adding an absolute ethyl alcohol solution of p-benzoquinone (3 mM of p-benzoquinone is dissolved in 20ml of absolute ethyl alcohol and stirred until the absolute ethyl alcohol solution of p-benzoquinone is completely dissolved), continuously stirring for 30 minutes, performing electrodeposition by adopting a three-electrode system, taking the FTO loaded with the seed layer obtained in the step (2) as a working electrode, an Ag/AgCl electrode as a reference electrode, a Pt sheet electrode as a counter electrode, and using a Chi-600e electrochemical workstation to obtain the BiOI, wherein the electrodeposition time is 300 s;
(4) 0.2121g of vanadyl acetylacetonate was dissolved in 4ml of dimethyl sulfoxide to obtain a solution of vanadyl acetylacetonate in dimethyl sulfoxide, which was dropped on the surface of the above BiOI (150. mu.l) and annealed at 450 ℃ for 1 hour using a muffle furnace. And soaking the annealed sample in a 1M NaOH solution for 30 minutes, washing the sample with ultrapure water, and drying the sample in an oven to obtain the composite light anode material (X + D) with the thickness of 1.6 microns. The performance of the composite photo-anode material is shown in FIG. 2 (b).
Claims (8)
1. A preparation method of the composite photo-anode material comprises the following steps:
(1) adding Bi (NO)3)3·5H2Adding O, ammonium metavanadate and citric acid into a dilute nitric acid solution, fully stirring, and adding polyvinyl alcohol and acetic acid after the solution turns blue to obtain a precursor solution;
(2) respectively ultrasonically cleaning an FTO conductive glass substrate for 20min through glass cleaning liquid-ultrapure water-acetone-ethanol, drying the FTO conductive glass substrate by using nitrogen, uniformly coating the precursor solution on the cleaned FTO conductive glass substrate by using a spin coating machine, controlling the rotating speed of the spin coating machine to be 1500-5000 r, rotating for 30-45 s, annealing at 450-550 ℃ for 2-4 hours, and successfully growing a compact bismuth vanadate seed layer on the FTO glass substrate to obtain FTO loaded with the seed layer;
(3) dissolving KI in ultrapure water, adding concentrated nitric acid to adjust the pH to 1.7-1.8, and adding Bi (NO)3)3·5H2Stirring O for 10-15 min, adding an absolute ethanol solution of p-benzoquinone, stirring for 25-35 min, uniformly mixing, performing electrodeposition by adopting a three-electrode system, taking the FTO loaded with the seed layer obtained in the step (2) as a working electrode, an Ag/AgCl electrode as a reference electrode, a Pt sheet electrode as a counter electrode, and performing electrodeposition for 150-1500 s by using a Chi-600e electrochemical workstation to obtain the BiOI;
(4) and (3) dripping a dimethyl sulfoxide solution of vanadyl acetylacetonate on the surface of the BiOI, annealing at 400-500 ℃ for 1-2 h, soaking the annealed sample in a 1M NaOH solution for 25-35 min, washing with ultrapure water, and drying to obtain the composite light anode material.
2. The method for preparing the composite photo-anode material as claimed in claim 1, wherein: in step (1), Bi (NO)3)3·5H2The molar ratio of O, ammonium metavanadate and citric acid is 1:1: 1.
3. The method for preparing the composite photo-anode material as claimed in claim 1, wherein: in the step (1), the mass ratio of citric acid to polyvinyl alcohol is 1: 1.1; the mass-volume ratio of the polyvinyl alcohol to the acetic acid is 0.3-0.5 g/mL.
4. The method for preparing the composite photo-anode material as claimed in claim 1, wherein: in the step (2), the thickness of the seed layer is 285-330 nm.
5. The method for preparing the composite photo-anode material as claimed in claim 1, wherein: in step (3), KI and Bi (NO)3)3·5H2The molar ratio of O is 9: 1-12: 1.
6. According to claim 1The preparation method of the composite photo-anode material is characterized by comprising the following steps: in the step (3), p-benzoquinone and Bi (NO)3)3·5H2The molar ratio of O is 1: 1-1: 2; the concentration of the absolute ethanol solution of the p-benzoquinone is 0.1-0.2 mM.
7. The method for preparing the composite photo-anode material as claimed in claim 1, wherein: in the step (4), the mass ratio of vanadyl acetylacetonate to KI is 1: 15-1: 16; the concentration of the absolute ethyl alcohol solution of the p-benzoquinone is 0.03-0.06 g/mL.
8. The method for preparing the composite photo-anode material as claimed in claim 1, wherein: in the step (4), the thickness of the composite photo-anode material is 1.5-1.7 μm.
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