CN113684500B - Preparation method of composite photo-anode material - Google Patents
Preparation method of composite photo-anode material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000010405 anode material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 15
- 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 21
- 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
- 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
- 238000004070 electrodeposition 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 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
- 238000004528 spin coating Methods 0.000 claims description 3
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Classifications
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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
-
- 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
-
- 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
- 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 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, under the condition of no catalyst promoter, the performance of an intrinsic semiconductor material BV (bismuth vanadate) is improved by 35-40% under the test condition without any electron sacrificial agent, and the characteristic test is carried out on the intrinsic semiconductor material BV by an ultraviolet and LSV, SPECM, IMPS analysis test means, so that the photo-anode material formed by introducing the seed layer is proved to have better charge separation efficiency and increased intrinsic transmission dynamics.
Description
Technical Field
The invention relates to the technical field of photoelectric anode materials, in particular to a preparation method of a composite photoelectric anode material.
Background
Given the impact of global warming and the energy demand of fossil fuels, the production of valuable environmentally friendly fuels is a promising approach to 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 a photocatalytic device depends largely on three processes: light absorption, charge separation, and catalytic reaction of the semiconductor surface. Excellent semiconductor materials are a prerequisite for laying down good performance. The morphology of the material can be reasonably designed to obtain different specific surface areas by changing the synthesis method, so that the difference of the intrinsic performance of the material is caused, the material performance is improved, and a monoclinic BiVO with butterfly morphology is synthesized by an alcohol-hydrothermal method 4 . BiVO with irregular shape 4 In contrast, butterfly BiVO 4 Has higher specific surface area and lower energy band width, and promotes organic pollutants in BiVO 4 The rapid adsorption of the surface reduces the energy absorption and increases the absorption range.
Yet another process of particular importance is the separation and transport of the photogenerated electron pairs. Some groups have proposed Ta heated by a two-step flame 2 O 5 Precursor (TSFH-Ta) 2 O 5 ) Nitriding to produce Ta with reduced surface defects 3 N 5 Photoanode (Reducing the surface defects of Ta) 3 N 5 photoanode towards enhanced photoelectrochemical water oxidation). Ta obtained by one-step flame heating 2 O 5 (OSFH-Ta 2 O 5 ) Compared with the low-valence Ta species in Ta 2 O 5 The concentration of the surface reduces surface defects, thereby improving the charge separation and injection efficiency of PEC water oxidation reactions. The photoelectric performance is improved. The photoelectric property of the material is improved by adjusting and controlling the structure of the interface between the material and the catalyst so as to achieve the purpose of adjusting and controlling charge transmission. However, to date, biVO 4 The solar-to-hydrogen (STH) conversion efficiency achieved By (BV) is far lower than expected due to the slow surface reaction kinetics of this material, electron-holeThe isolation yield is low. To improve BiVO 4 Performance, some studies have focused mainly on doping, with layer-by-layer stacking loading, with the aim of improving their poor electron transport properties. Other researches use electron/hole sacrificial agents to inhibit recombination to the greatest extent on the basis of adopting layer-by-layer supported catalysts and cocatalysts, but one of the particularly critical factors is seldom concerned, namely the interface connection mode between the intrinsic semiconductor material and the substrate, which greatly influences the intrinsic electron hole pair recombination condition of the material. In the solar cell, compared with a planar structure, the nano-structure cell has higher performance mainly due to the improvement of light absorption and charge separation efficiency, the nano-pillar structure and the porous structure are used for increasing light capture and enlarging specific surface area so as to improve material performance, the seed layer plays the most critical role in the nano-pillar during the growth process of the nano-pillar, the seed layer in the traditional sense has great improvement effect on the growth of the nano-pillar array, and the orientation of the array structure is enhanced due to the fact that the seed layer is in lattice matching with the FTO substrate, and the seed layer can play a certain role in the charge transmission process. At the same time, an important factor is concerned in the process, namely that the separation efficiency of electron hole pairs is not compatible with the increase of specific surface area, so that experimental evidence of quantitative analysis and validation is still lacking in the process as to which factor plays a dominant role in the performance of the material. Since charge separation transport takes place simultaneously with the increase of specific surface area, which leads to an increase of absorbance, it is difficult to distinguish it from each other, it is impossible to determine the magnitude of the contribution of each factor, and previous studies have only given qualitative conclusions.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for preparing a composite photoanode material.
1. Preparation method of composite photo-anode material
The preparation method of the composite photo-anode material comprises the following steps:
(1) Bi (NO) 3 ) 3 ·5H 2 Adding 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 ·5H 2 The mol 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 by nitrogen, uniformly coating the precursor solution on the cleaned FTO conductive glass substrate by using a spin coating method through a spin coater, controlling the rotating speed of the spin coater to be 1500-5000 r, rotating for 30-45 s, annealing for 2-4 hours at 450-550 ℃, and successfully growing a compact bismuth vanadate seed layer on the FTO glass substrate to obtain the FTO carrying 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 ·5H 2 And (3) after stirring 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, taking an Ag/AgCl electrode as a reference electrode, taking 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. Wherein KI and Bi (NO 3 ) 3 ·5H 2 The mol ratio of O is 9:1-12:1; p-benzoquinone and Bi (NO) 3 ) 3 ·5H 2 The molar ratio of O is 1:1-1:2; the concentration of the absolute ethyl alcohol solution of the p-benzoquinone is 0.1-0.2 mM.
(4) And (3) dripping dimethyl sulfoxide solution of vanadyl acetylacetonate on the surface of the BiOI, annealing for 1-2 hours at 400-500 ℃, soaking the annealed sample in 1M NaOH solution for 25-35 minutes, washing with ultrapure water, and drying to obtain the composite photo-anode material. Wherein the mass ratio of the vanadyl acetylacetonate to the 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; the thickness of the composite photo-anode material is 1.5-1.7 mu m.
2. Structure and performance of photo-anode material
1. SEM characterization of photoanode materials
FIG. 1 is an SEM image of different photoanode materials, wherein FIG. a) is a front view of a spin-coating process for preparing a seed layer material, which can be seen to prepare a seed layer that is dense and uniform and has plump nanoparticles; FIG. b) preparation of BiVO by electrodeposition 4 A front view of the semiconductor material, which can be seen to be a porous sparse and fluffy worm-hole-shaped semiconductor material; panel c) and panel d) are respectively bivos of different thickness 4 The cross-section of the semiconductor material grown on the seed layer can clearly see BiVO 4 A semiconductor material is grown on the seed layer, wherein X represents the seed layer and D represents BiVO 4 A semiconductor material.
2. Performance of photoanode materials
FIG. 2 shows the difference of 0.5M Na for various photo-anode materials 2 SO 4 LSV photoelectrochemical scanning curve under the condition of simulating sunlight light source in the solution. Wherein, figure a) is LSV photoelectrochemical scanning curve of composite photo-anode material under different seed layer thickness, the composite photo-anode material prepared under different seed layer thickness, the same deposition time (300S) condition, can see that the performance is best when the seed layer thickness is 300nm, therefore, the subsequent material test, all control the seed layer thickness to be 300nm; FIG. b) shows the variation of the properties of the composite photo-anode material (X+D) with the thickness, wherein the numbers 1 to 6 correspond to the thicknesses of the composite photo-anode material (X+D) from 1.6 μm, 850nm, 730nm, 2.3 μm, 500nm and 2.7 μm respectively according to the properties from large to small; FIG. c) BiVO grown directly on FTO conductive glass substrate 4 The performance of the semiconductor material changes along with the thickness, and the deposition time is 150-1200s, which respectively corresponds to the thickness of 600nm, 1.16 mu m, 2.7 mu m and 3.2 mu m; it is clear from the figures b) and c) that the change trend of the two photoelectrodes is approximately the same, and the photocurrent shows the effect of increasing and then decreasing with the increase of the thickness. This is because the material is thin at the beginning, the specific surface area of the material is small, the light absorption efficiency is low, the specific surface area participating in the reaction is increased along with the thickness of the material, and the material is causedAnd when the thickness of the material reaches a certain degree, the electron hole pair of the body is seriously compounded, and the positive influence caused by absorbance is counteracted, so that the subsequent current performance is reduced. In addition, it can be obviously seen that the photoelectric property of the composite photo-anode material is higher than that of BiVO directly grown on the FTO conductive glass substrate 4 The semiconductor material is improved by 35% -40%, the effect is considerable under the condition that no sacrificial agent or catalyst is used, and the application prospect is wide; FIG. D) is a composite photo-anode material (X+D) and a pure semiconductor material BiVO under the condition that the thickness of the seed layer is 300nm 4 (D) And a comparative graph of the seed layer (X), from which it is known that the performance of the composite photoanode material is prominent and the current density also transitions from exhibiting a "fast" decreasing trend (60%) to a "slow" (15%) trend, indicating that the recombination phenomenon of electron-hole pairs is also greatly improved.
FIG. 3 shows the pure semiconductor material BiVO of different thickness 4 Solid ultraviolet characterization of (left) and composite photo-anode materials (right) the ultraviolet spectrum well demonstrates that as the specific surface area of the materials increases with increasing thickness, the absorbance increases, which is consistent with the LSV display results, and the longitudinal comparison of the two figures shows that the difference in overall light absorption is not great, and the introduction of a seed layer is not greatly affected in light absorption.
FIG. 4 shows the preparation of a seed layer (X), pure semiconductor material BiVO 4 (D) The SPECM approximation curve fitting (left graph, curves from top to bottom are X+D1, X+D2, X+D3, D, X) of the composite photo-anode material (X+D1/2/3 is the same seed layer thickness 300nm, the composite photo-anode material is obtained under different deposition times), and the kinetic constant change (right graph) is calculated according to the approximation curve fitting. From the left graph, the dynamics fitting result is obvious, and is consistent with the LSV result, and the charge transfer dynamics of the composite photo-anode material is relatively pure semiconductor material BiVO 4 (D) And the seed layer is obviously larger and sequentially decays downwards, so that the dynamic constant of the right graph is more visual.
FIG. 5 shows a seed layer (X), pure semiconductorMaterial BiVO 4 (D) An IMPS scan curve (left graph) of the composite photo-anode material (x+d) and a charge transfer time corresponding thereto (right graph). The lowest point frequency in the left graph is sequentially X from top to bottom>D>X+D indirectly illustrates the improvement of the charge transmission efficiency of the composite photo-anode material (X+D), and the shortening of the transmission time of the composite photo-anode material (X+D) in the right graph proves that the introduction of the seed layer effectively improves the charge separation transmission efficiency.
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 photo-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 more tightly connecting the porous semiconductor material and the substrate can be achieved, and the porous BiVO is weakened 4 The bulk recombination of the polymer improves the charge transmission efficiency and the intrinsic reaction kinetics. According to the invention, by introducing the seed layer, the interface contact between the material and the substrate is well improved, the intrinsic composite effect is obviously weakened, the photoelectric performance is greatly improved, and under the condition that no catalyst or cocatalyst is used, the performance of the intrinsic composite photo-anode material is improved by 35-40% under the condition that no electronic sacrificial agent is used; the synthesis method is simple, avoids the use of a series of complex and expensive catalysts and cocatalysts, has strong practicability and wider application range, and has guiding significance for the construction of the semiconductor material photoelectrode in the future.
Drawings
FIG. 1 is an SEM image of a different photoanode material;
FIG. 2 shows the difference of 0.5M Na for various photo-anode materials 2 SO 4 Simulating an LSV photoelectrochemical scanning curve under the condition of a sunlight source in the solution;
FIG. 3 shows the pure semiconductor material BiVO of different thickness 4 Solid uv characterization of (left panel) and composite photo-anode material (right panel);
FIG. 4 shows the preparation of a seed layer (X), pure semiconductor material BiVO 4 (D) SPECM approximated curve fitting (left plot) of the composite photoanode material (X+D), and kinetic constant variation (right plot) calculated from the approximated curve fitting;
FIG. 5 shows the process of forming a seed layer (X), a pure semiconductor material BiVO 4 (D) An IMPS scan curve (left graph) of the composite photo-anode material (x+d) and a charge transfer time corresponding thereto (right graph).
Detailed Description
The preparation of the composite photoanode material of the present invention is further illustrated by the following specific examples.
Examples
(1) 500. Mu.l of concentrated nitric acid was added to 10ml of ultra pure water, diluted and stirred well, and 3mM Bi (NO 3 ) 3 ·5H 2 O, 3mM ammonium metavanadate and 1.101g citric acid are sequentially added into a dilute nitric acid solution, the solution is fully stirred, after the solution turns blue, 1.23g polyvinyl alcohol and 3ml acetic acid are added, and the polyvinyl alcohol is completely dissolved, so that a precursor solution is obtained.
(2) Respectively ultrasonically cleaning an FTO conductive glass substrate for 20min through 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 the bismuth vanadate seed layer, controlling the rotating speed of the spin coater to 2500r/s, and controlling the thickness of the seed layer to 300nm by 35 s.
(3) Under the condition that ultrapure water is used as a solvent, 3.32g of KI is added, ultrasonic treatment is carried out until the KI is dissolved, concentrated nitric acid is added, the pH value is adjusted to 1.75 by using a pH meter, and 5mM Bi (NO) is slowly added 3 ) 3 ·5H 2 O, fully stirring for 10 minutes, turning the solution into orange color, completely disappearing the precipitate, adding an absolute ethanol solution of p-benzoquinone (3 mM of p-benzoquinone is taken and dissolved in 20ml of absolute ethanol, and stirring until the absolute ethanol solution of p-benzoquinone is completely dissolved), continuously stirring for 30 minutes, electrodepositing by adopting a three-electrode system, taking the FTO loaded with the seed layer obtained in the step (2) as a working electrode, taking an Ag/AgCl electrode as a reference electrode, and taking a Pt sheet as an electrodeThe electrodes are counter electrodes, a Chi-600e electrochemical workstation is used, and the electrodeposition time is 300s, so that BiOI is obtained;
(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 onto the surface (150. Mu.l) of the above BiOI and annealed at a high temperature of 450℃for 1 hour using a muffle furnace. The annealed sample was immersed in a 1M NaOH solution for 30 minutes, rinsed with ultra pure water, and dried in an oven to obtain a composite photoanode material (x+d) having a thickness of 1.6 μm. The performance of the composite photoanode material is shown in fig. 2 (b).
Claims (7)
1. A preparation method of a composite photo-anode material comprises the following steps:
(1) Bi (NO) 3 ) 3 ·5H 2 Adding 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 by nitrogen, uniformly coating the precursor solution on the cleaned FTO conductive glass substrate by using a spin coating method through a spin coater, controlling the rotating speed of the spin coater to be 1500-5000 r, rotating for 30-45 s, annealing for 2-4 hours at 450-550 ℃, and successfully growing a compact bismuth vanadate seed layer on the FTO glass substrate to obtain the FTO carrying the seed layer; the thickness of the seed layer is 300nm;
(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 ·5H 2 After stirring O for 10-15 min, adding 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, taking an Ag/AgCl electrode as a reference electrode, taking a Pt sheet electrode as a counter electrode, and performing electrodeposition for 150-1500 s by using a Chi-600e electrochemical workstation to obtain BiOI;
(4) And (3) dripping dimethyl sulfoxide solution of vanadyl acetylacetonate on the surface of the BiOI, annealing for 1-2 hours at 400-500 ℃, soaking the annealed sample in 1M NaOH solution for 25-35 minutes, washing with ultrapure water, and drying to obtain the composite photo-anode material.
2. The method for preparing the composite photo-anode material according to claim 1, wherein the method comprises the following steps: in step (1), bi (NO) 3 ) 3 ·5H 2 The mol ratio of O, ammonium metavanadate and citric acid is 1:1:1.
3. The method for preparing the composite photo-anode material according to claim 1, wherein the method comprises the following steps: in the step (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.
4. The method for preparing the composite photo-anode material according to claim 1, wherein the method comprises the following steps: in step (3), KI and Bi (NO) 3 ) 3 ·5H 2 The molar ratio of O is 9:1-12:1.
5. The method for preparing the composite photo-anode material according to claim 1, wherein the method comprises the following steps: in step (3), p-benzoquinone and Bi (NO 3 ) 3 ·5H 2 The molar ratio of O is 1:1-1:2; the concentration of the absolute ethyl alcohol solution of the p-benzoquinone is 0.1-0.2 mM.
6. The method for preparing the composite photo-anode material according to claim 1, wherein the method comprises the following steps: in the step (4), the mass ratio of the vanadyl acetylacetonate to the 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.
7. The method for preparing the composite photo-anode material according to claim 1, wherein the method comprises the following steps: in the step (4), the thickness of the composite photo-anode material is 1.5-1.7 μm.
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