CN111569896A - BiVO4-Ni/Co3O4Synthesis method of heterojunction and application of heterojunction to photoelectrolysis water - Google Patents

BiVO4-Ni/Co3O4Synthesis method of heterojunction and application of heterojunction to photoelectrolysis water Download PDF

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CN111569896A
CN111569896A CN202010423004.6A CN202010423004A CN111569896A CN 111569896 A CN111569896 A CN 111569896A CN 202010423004 A CN202010423004 A CN 202010423004A CN 111569896 A CN111569896 A CN 111569896A
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范伟强
俞立豪
白红叶
高杨
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Jiangsu University
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Abstract

The invention belongs to the technical field of nano composite materials, and relates to BiVO4‑Ni/Co3O4The heterogeneous combination method comprises growing a layer of BiOI nanoparticles on FTO substrate by electrodeposition, dropping vanadyl acetylacetonate solution on FTO surface, and calcining at high temperature to obtain bismuth vanadate (BiVO)4) Placing FTO obliquely on the surface of a substrate containing Co (NO) by continuous ion adsorption reaction3)2·6H2O、Ni(NO3)2·6H2O、C6H12N4、CH4N2O and NH4F, hydrothermal reaction at 120-200 ℃ in deionized water solutionTaking out the mixture for 2-5 h, washing the mixture with deionized water, annealing the mixture for 1.5-3 h at 300-500 ℃, and naturally cooling the mixture to room temperature to obtain the product. The invention also uses the prepared heterojunction as a photoelectrode to be applied to photoelectrochemical hydrolysis reaction. The method utilizes a simple electrodeposition method and a hydrothermal method, has simple operation and good repeatability, uses low material cost, has large reserve and no toxicity, and meets the environment-friendly requirement; the prepared material can obviously reduce the interface reaction potential barrier, effectively inhibit the charge recombination of a solid-liquid interface, accelerate the water oxidation reaction kinetics, and improve the photocurrent density, thereby better utilizing the solar energy.

Description

BiVO4-Ni/Co3O4Synthesis method of heterojunction and application of heterojunction to photoelectrolysis water
Technical Field
The invention belongs to the technical field of nano composite material synthesis, relates to heterosynthesis, and particularly relates to BiVO4-Ni/Co3O4A heterogeneous combination method and its application to the photo-electrolysis of water.
Background
The effective utilization of solar energy is always concerned, and due to the exhaustion of fossil fuels and the serious pollution caused by the exhaustion of fossil fuels, people have to search for new clean energy. The method for decomposing water by utilizing sunlight to generate hydrogen is a very good strategy and can meet the requirement of clean energy in the future.
In recent years, BiVO is adopted4The bismuth-based semiconductor represented by the above is widely used in the field of photoelectrochemical decomposition of water. It is favored by researchers because of its advantages of low cost, stable chemical properties, narrow band gap (2.4eV), etc. However, pure BiVO4The theoretical efficiency of photoelectrochemical decomposition of water to produce hydrogen is limited due to low charge separation efficiency and slow water oxidation kinetics leading to low photocurrent density.
For further development of BiVO4The strategies of the photoelectrocatalysis performance, heterojunction construction, morphology regulation, interface engineering, element doping and the like are researched and utilized. Co-based materials have been studied for their low cost, high storage capacity, and high functionality. P-type semiconductor Co as narrow band3O4(2.07eV), energy and BiVO4Coupled to form BiVO4-Ni/Co3O4The p-n heterojunction accelerates the electron-hole separation efficiency and improves the performance of photoelectrochemistry water decomposition. The introduction of Ni element further improves the conductivity. Ni/Co3O4The oxygen evolution promoter can reduce overpotential and obviously improve water oxidation kinetics.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a BiVO4-Ni/Co3O4A synthesis method of a heterojunction material.
The invention first of allPreparing BiVO on FTO surface by adopting classical constant-voltage electrodeposition4Sequentially carrying out ultrasonic treatment on the FTO by using absolute ethyl alcohol, acetone and water, and drying for later use; selecting Co (NO)3)2·6H2O、Ni(NO3)2·6H2O、C6H12N4Urea (CH)4N2O) and NH4F and other reagents are prepared into a mixed solution, a hydrothermal method is adopted, a closed reaction kettle is placed in a high-temperature oven at 180 ℃ for reaction, the reaction kettle is taken out and washed by a large amount of deionized water, the reaction kettle is placed in a muffle furnace for high-temperature annealing, and finally a target product BiVO is obtained4-Ni/Co3O4。
BiVO4-Ni/Co3O4The synthesis method of the heterojunction comprises the following steps:
A. preparing 0.4mol/L KI solution, adding Bi (NO)3)3·5H2O to obtain a mixed aqueous solution, Bi (NO)3)3The concentration of the p-benzoquinone derivative is 0.04mol/L, the pH is adjusted to 1-3, preferably 1.7 by nitric acid, the p-benzoquinone ethanol solution is poured into the mixture, and the mixture is stirred for 10-20 min to obtain a BiOI precursor solution, wherein the volume ratio of the mixed aqueous solution to the p-benzoquinone ethanol solution is 5: 1-5: 3, preferably 5: 2; the concentration of the ethanol solution of the p-benzoquinone is 0.23 mol/L;
B. placing the precursor solution in a three-electrode system, taking FTO as a working electrode, Pt filaments as a counter electrode and Ag/AgCl as a reference electrode, performing electrodeposition for 3-6 min, preferably 5min under the bias of-0.1 Vvs Ag/AgCl, forming a uniform dark red BiOI thin film on the surface of the FTO, washing the FTO with ionized water, and drying at room temperature;
C. dropwise adding 0.2mol/L vanadyl acetylacetonate aqueous solution on the surface of the BiOI film, calcining and annealing FTO at 300-600 ℃ for 1.5-3 h, preferably annealing at 450 ℃ for 2h, taking out and naturally cooling to room temperature, soaking in NaOH solution to remove redundant V on the surface2O5Cleaning with deionized water, and drying to obtain FTO substrate with BiVO4A photo-anode;
D. adding Co (NO) to deionized water3)2·6H2O、Ni(NO3)2·6H2O、C6H12N4、CH4N2O and NH4F, ultrasonically stirring uniformly to obtain a mixed solution, wherein the Co (NO) is3)2·6H2O：Ni(NO3)2·6H2O：C6H12N4：CH4N2O：NH4F: deionized water in a solid-to-liquid ratio of 0.5-5 mM: 2.5 mM: 6 mM: 0.36 g: 0.195 g: 50mL, preferably 2.5 mM: 2.5 mM: 6 mM: 0.36 g: 0.195 g: 50 mL;
E. pouring the mixed solution into a hydrothermal reaction kettle to 60% of the volume, and growing BiVO on the prepared FTO substrate4And (3) placing the photoanode obliquely, heating at the reaction temperature of 120-200 ℃ for 2-5 h, preferably heating at 180 ℃ for 3h, naturally cooling to room temperature, taking out, washing with deionized water, annealing at the high temperature of 300-500 ℃ for 1.5-3 h, preferably annealing at the high temperature of 400 ℃ for 2h, and naturally cooling to room temperature to obtain the photoanode.
The FTO used in the invention needs pretreatment, namely, the FTO is sequentially treated by absolute ethyl alcohol, acetone and water by ultrasonic treatment and is dried for standby.
The phase, structure and performance characterization of the composite electrode synthesized by the invention are measured by an X-ray diffractometer.
Another object of the present invention is to apply the heterojunction material as a working electrode to a photoelectrochemical hydrolysis reaction.
BiVO4-Ni/Co3O4The method for testing the photocurrent of the heterojunction photoelectrode under the irradiation of the xenon lamp light source comprises the following steps:
in an electrochemical work station of CHI 852C type, 0.5mol/L sodium sulfate (Na) is added to the electrolytic cell2SO4) As electrolyte, silver chloride electrode as reference electrode, platinum electrode as counter electrode, BiVO4-Ni/Co3O4The heterojunction material is used as a working electrode to scan the I-V characteristic curve.
Using a solar simulator equipped with a monochromator, at incident light ranges of 300-540nm and 1.23VRHEUnder bias, the photoelectric conversion efficiency (IPCE) of the heterojunction photoanode was measured.
Advantageous effects
The invention prepares BiVO by utilizing a simple electrodeposition method and a hydrothermal synthesis method4-Ni/Co3O4The heterojunction photoelectrode has the advantages of good chemical stability and good photoelectrochemical performance, obviously reduces the interface reaction potential barrier, effectively inhibits the charge recombination of a solid-liquid interface, accelerates the water oxidation reaction kinetics, and improves the photocurrent density, thereby better utilizing the solar energy. The method has the advantages of simple operation, good repeatability, low cost of used materials, large reserves, no toxicity and environmental friendliness.
Drawings
FIG. 1.BiVO4、BiVO4/Co3O4And BiVO4-Ni/Co3O4X-ray powder diffraction pattern of the sample.
FIG. 2 BiVO in light and dark4、BiVO4/Co3O4And BiVO4-Ni/Co3O4The solid line and the broken line correspond to the photocurrent and the dark current, respectively.
FIG. 3 shows the photoelectric conversion efficiency (IPCE) of a heterojunction photoanode.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
BiVO4-Ni/Co3O4The synthesis method of the heterojunction comprises the following steps:
A. BiVO on FTO substrate4A photoanode, wherein BiVO is prepared on the FTO substrate4The photoanode comprises (1) dissolving 3.32g KI in 50mL deionized water, and mixing 0.9701g Bi (NO)3)3·5H2Adding the solution O into the solution, stirring for 10min, and dropwise adding nitric acid to adjust the pH value to 1.0 to form a stable mixed solution A;
(2) dissolving 0.4972g of p-benzoquinone in 20mL of absolute ethanol, sealing and stirring the beaker for 10min to obtain a solution B;
(3) slowly adding the solution B into the solution A and stirring for 10min to form a precursor solution C of the BiOI;
(4) a three-electrode system is adopted, wherein FTO is used as a working electrode, Pt wires are used as a counter electrode, and Ag/AgCl is used as a reference electrode. Under the bias voltage of-0.1V, electrodepositing for 3min to form a uniform dark red BiOI film on the FTO;
(5) and washing the FTO with ionized water and drying at room temperature. Dropwise adding quantitative 0.2mol/L vanadyl acetylacetonate on the surface of the BiOI film, placing the BiOI in a 300 ℃ muffle furnace for high-temperature annealing for 2h, and naturally cooling a sample to room temperature;
(6) finally, soaking the sample in 1mol/L NaOH solution for 20min to remove the redundant V on the surface of the electrode2O5。BiVO4The sample was rinsed with a large amount of deionized water and dried at room temperature to obtain pure BiVO4And a photo-anode.
B、BiVO4-Ni/Co3O4Preparing a photoelectrode:
(1) 0.5mM Co (NO)3)2·6H2O、2.5mM Ni(NO3)2·6H2O、6mM C6H12N40.36g of urea (CH)4N2O)、0.195g NH4Sequentially adding the F into 50mL of deionized water, and ultrasonically stirring for 15min to obtain a mixed solution D;
(2) adding 30mL of the mixed solution D into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, namely BiVO4The photo-anode is obliquely arranged in the reaction kettle. Placing the closed reaction kettle in a high-temperature oven at 120 ℃ for reaction for 3h, taking out a sample, washing the sample with a large amount of deionized water, placing the sample in a muffle furnace for high-temperature annealing at 400 ℃ for 2h to obtain a target product BiVO4-Ni/Co3O4。
The photoelectric conversion efficiency (IPCE), BiVO, of the heterojunction photoanode was measured4-Ni/Co3O4IPCE reached 25% at 380 nm.
Example 2
BiVO4-Ni/Co3O4The synthesis method of the heterojunction comprises the following steps:
A. BiVO on FTO substrate4A photo-anode on the FTO groupBiVO is prepared on a chip4The photoanode comprises (1) dissolving 3.32g KI in 50mL deionized water, and mixing 0.9701g Bi (NO)3)3·5H2Adding the solution O into the solution, stirring for 10min, and dropwise adding nitric acid to adjust the pH value to 1.3 to form a stable mixed solution A;
(2) dissolving 0.4972g of p-benzoquinone in 20mL of absolute ethanol, sealing and stirring the beaker for 10min to obtain a solution B;
(3) slowly adding the solution B into the solution A and stirring for 10min to form a precursor solution C of the BiOI;
(4) adopting a three-electrode system, adopting FTO as a working electrode, Pt filaments as a counter electrode and Ag/AgCl as a reference electrode, and electrodepositing for 4min under the bias of-0.1V to form a uniform dark red BiOI film on the FTO;
(5) and washing the FTO with ionized water and drying at room temperature. Dropwise adding quantitative 0.2mol/L vanadyl acetylacetonate on the surface of the BiOI film, placing the BiOI in a 400 ℃ muffle furnace for high-temperature annealing for 2h, and naturally cooling a sample to room temperature;
(6) soaking the sample in 1mol/L NaOH solution for 20min to remove the redundant V on the surface of the electrode2O5，BiVO4The sample was rinsed with a large amount of deionized water and dried at room temperature to obtain pure BiVO4And a photo-anode.
B、BiVO4-Ni/Co3O4Preparing a photoelectrode:
(1) 1.5mM Co (NO)3)2·6H2O、2.5mM Ni(NO3)2·6H2O、6mM C6H12N40.36g of urea (CH)4N2O)、0.195g NH4Sequentially adding the F into 50mL of deionized water, and ultrasonically stirring for 15min to obtain a mixed solution D;
(2) then, 30mL of the mixed solution D was added to a 50mL polytetrafluoroethylene-lined stainless steel reaction vessel, BiVO4The photo-anode is obliquely arranged in the reaction kettle; placing the closed reaction kettle in a high-temperature oven at 160 ℃ for reaction for 3h, taking out a sample, washing the sample with a large amount of deionized water, placing the sample in a muffle furnace for high-temperature annealing at 400 ℃ for 2h to obtain a target product BiVO4-Ni/Co3O4。
The photoelectric conversion efficiency (IPCE), BiVO, of the heterojunction photoanode was measured4-Ni/Co3O4IPCE reached 26% at 380 nm.
Example 3
BiVO4-Ni/Co3O4The synthesis method of the heterojunction comprises the following steps:
A. BiVO on FTO substrate4A photoanode, wherein BiVO is prepared on the FTO substrate4The photoanode comprises (1) dissolving 3.32g KI in 50mL deionized water, and mixing 0.9701g Bi (NO)3)3·5H2Adding the solution O into the solution, stirring for 10min, and dropwise adding nitric acid to adjust the pH value to 1.7 to form a stable mixed solution A;
(2) dissolving 0.4972g of p-benzoquinone in 20mL of absolute ethanol, sealing and stirring the beaker for 10min to obtain a solution B;
(3) slowly adding the solution B into the solution A and stirring for 10min to form a precursor solution C of the BiOI;
(4) adopting a three-electrode system, adopting FTO as a working electrode, Pt filaments as a counter electrode and Ag/AgCl as a reference electrode, and electrodepositing for 5min under the bias of-0.1V to form a uniform dark red BiOI film on the FTO;
(5) washing the FTO with ionized water, drying at room temperature, dropwise adding quantitative 0.2mol/L vanadyl acetylacetonate on the surface of the BiOI film, placing the BiOI film in a muffle furnace at 450 ℃ for high-temperature annealing for 2h, and naturally cooling a sample to room temperature;
(6) soaking the sample in 1mol/L NaOH solution for 20min to remove the redundant V on the surface of the electrode2O5，BiVO4The sample was rinsed with a large amount of deionized water and dried at room temperature to obtain pure BiVO4And a photo-anode.
B、BiVO4-Ni/Co3O4Preparing a photoelectrode:
(1) 2.5mM Co (NO)3)2·6H2O、2.5mM Ni(NO3)2·6H2O、6mM C6H12N40.36g of urea (CH)4N2O)、0.195g NH4F is added into 50mL of deionized water in sequence and stirred by ultrasonic for 15min to obtain a mixed solution D;
(2) adding 30mL of the mixed solution D into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, namely BiVO4Placing the photoanode in a reaction kettle in an inclined manner, placing the sealed reaction kettle in a high-temperature oven at 180 ℃ for reaction for 3h, taking out and washing with a large amount of deionized water, placing the reaction kettle in a muffle furnace for high-temperature annealing at 400 ℃ for 2h to obtain a target product BiVO4-Ni/Co3O4。
The photoelectric conversion efficiency (IPCE), BiVO, of the heterojunction photoanode was measured4-Ni/Co3O4IPCE reached 27% at 380 nm.
Example 4
BiVO4-Ni/Co3O4The synthesis method of the heterojunction comprises the following steps:
A. BiVO on FTO substrate4A photoanode, wherein BiVO is prepared on the FTO substrate4The photoanode comprises (1) dissolving 3.32g KI in 50mL deionized water, and mixing 0.9701g Bi (NO)3)3·5H2Adding the solution O into the solution, stirring for 10min, and dropwise adding nitric acid to adjust the pH to 2.5 to form a stable mixed solution A;
(2) dissolving 0.4972g of p-benzoquinone in 20mL of absolute ethanol, sealing and stirring the beaker for 10min to obtain a solution B;
(3) slowly adding the solution B into the solution A and stirring for 10min to form a precursor solution C of the BiOI;
(4) adopting a three-electrode system, adopting FTO as a working electrode, Pt filaments as a counter electrode and Ag/AgCl as a reference electrode, and electrodepositing for 5.5min under the bias of-0.1V to form a uniform dark red BiOI film on the FTO;
(5) washing the FTO with ionized water, drying at room temperature, dropwise adding quantitative 0.2mol/L vanadyl acetylacetonate on the surface of the BiOI film, annealing the BiOI film in a muffle furnace at 500 ℃ for 2 hours, and naturally cooling a sample to room temperature;
(6) soaking the sample in 1mol/L NaOH solution for 20min to remove the redundant V on the surface of the electrode2O5，BiVO4The sample was rinsed with a large amount of deionized water and dried at room temperature to obtain pure BiVO4And a photo-anode.
B、BiVO4-Ni/Co3O4Preparing a photoelectrode:
(1) 3.5mM Co (NO)3)2·6H2O、2.5mM Ni(NO3)2·6H2O、6mM C6H12N40.36g of urea (CH)4N2O)、0.195g NH4Sequentially adding the F into 50mL of deionized water, and ultrasonically stirring for 15min to obtain a mixed solution D;
(2) adding 30mL of the mixed solution D into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, namely BiVO4Placing the photoanode in a reaction kettle in an inclined manner, placing the sealed reaction kettle in a high-temperature oven at 190 ℃ for reaction for 3h, taking out a sample, washing the sample with a large amount of deionized water, placing the sample in a muffle furnace for high-temperature annealing at 400 ℃ for 2h to obtain a target product BiVO4-Ni/Co3O4。
The photoelectric conversion efficiency (IPCE), BiVO, of the heterojunction photoanode was measured4-Ni/Co3O4IPCE reached 25.5% at 380 nm.
Example 5
BiVO4-Ni/Co3O4The synthesis method of the heterojunction comprises the following steps:
A. BiVO on FTO substrate4A photoanode, wherein BiVO is prepared on the FTO substrate4The photoanode comprises (1) dissolving 3.32g KI in 50mL deionized water, and mixing 0.9701g Bi (NO)3)3·5H2Adding the solution O into the solution, stirring for 10min, and dropwise adding nitric acid to adjust the pH value to 3.0 to form a stable mixed solution A;
(2) dissolving 0.4972g of p-benzoquinone in 20mL of absolute ethanol, sealing and stirring the beaker for 10min to obtain a solution B;
(3) slowly adding the solution B into the solution A and stirring for 10min to form a precursor solution C of the BiOI;
(4) adopting a three-electrode system, adopting FTO as a working electrode, Pt filaments as a counter electrode and Ag/AgCl as a reference electrode, and electrodepositing for 6min under the bias of-0.1V to form a uniform dark red BiOI film on the FTO;
(5) washing the FTO with ionized water, drying at room temperature, dropwise adding quantitative 0.2mol/L vanadyl acetylacetonate on the surface of the BiOI film, placing the BiOI film in a 600 ℃ muffle furnace for high-temperature annealing for 2h, and naturally cooling a sample to room temperature;
(6) soaking the sample in 1mol/L NaOH solution for 20min to remove the redundant V on the surface of the electrode2O5，BiVO4The sample was rinsed with a large amount of deionized water and dried at room temperature to obtain pure BiVO4And a photo-anode.
B、BiVO4-Ni/Co3O4Preparing a photoelectrode:
(1) 5mM Co (NO)3)2·6H2O、2.5mM Ni(NO3)2·6H2O、6mM C6H12N40.36g of urea (CH)4N2O)、0.195g NH4Sequentially adding the F into 50mL of deionized water, and ultrasonically stirring for 15min to obtain a mixed solution D;
(2) adding 30mL of the mixed solution D into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, namely BiVO4Placing the photoanode in a reaction kettle in an inclined manner, placing the sealed reaction kettle in a high-temperature oven at 200 ℃ for reaction for 3h, taking out a sample, washing the sample with a large amount of deionized water, placing the sample in a muffle furnace for high-temperature annealing at 400 ℃ for 2h to obtain a target product BiVO4-Ni/Co3O4。
The photoelectric conversion efficiency (IPCE), BiVO, of the heterojunction photoanode was measured4-Ni/Co3O4IPCE reached 26% at 380 nm.
The characteristic diffraction peaks at 18.3 °, 28.1 ° and 29.9 ° in fig. 1 correspond to BiVO, respectively4The (011), (121) and (040) crystal planes of (JCPDS card No. 14-0688), proving BiVO4Successful preparation; a single diffraction peak at 36.8 deg. was designated as Co3O4(311) diffraction of (JCPDS chip No. 42-1467) indicating Co3O4Was successfully synthesized.
It can be seen in fig. 2 that all samples had essentially zero dark current and increased photocurrent to various degrees, with BiVO being the best effect4-Ni/Co3O4Description of BiVO4-Ni/Co3O4The photoelectrochemical properties of (a) are the best. BiVO4-Ni/Co3O4At 1.23VRHEThe photocurrent density under bias reaches 2.23mA/cm2It is the original BiVO44.4 times of the total weight of the powder.
BiVO in FIG. 34-Ni/Co3O4The light absorption intensity is obviously stronger than that of the original BiVO4. And BiVO4(5%) BiVO4-Ni/Co3O4The IPCE value reached 27% at 380nm, which is about 5 times higher than the former. This indicates that Ni/Co is3O4The oxygen evolution catalyst inhibits the recombination of interface charges at a semiconductor/electrolyte interface, reduces the potential barrier of water oxidation reaction and improves the efficiency.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims (9)

1.BiVO4-Ni/Co3O4The synthesis method of the heterojunction is characterized by comprising the following steps:
A. preparing 0.4mol/L KI solution, adding Bi (NO)3)3·5H2O to obtain a mixed aqueous solution, Bi (NO)3)3Adjusting the pH value to 1-3 with nitric acid, pouring an ethanol solution of p-benzoquinone, and stirring for 10-20 min to obtain a BiOI precursor solution, wherein the volume ratio of the mixed aqueous solution to the ethanol solution of p-benzoquinone is 5: 1-5: 3; the concentration of the ethanol solution of the p-benzoquinone is 0.23 mol/L;
B. placing the precursor solution in a three-electrode system, performing electrodeposition for 3-6 min under the bias of-0.1 Vvs Ag/AgCl by taking FTO as a working electrode, Pt filaments as a counter electrode and Ag/AgCl as a reference electrode, forming a uniform dark red BiOI film on the surface of the FTO, washing the FTO with ionized water, and drying at room temperature;
C. dropwise adding 0.2mol/L vanadyl acetylacetonate aqueous solution on the surface of the BiOI film, calcining and annealing FTO at 300-600 ℃ for 1.5-3 h, and taking outNaturally cooling to room temperature, soaking in NaOH solution to remove excessive V on the surface2O5Cleaning with deionized water, and drying to obtain FTO substrate with BiVO4A photo-anode;
D. adding Co (NO) to deionized water3)2·6H2O、Ni(NO3)2·6H2O、C6H12N4、CH4N2O and NH4F, ultrasonically stirring uniformly to obtain a mixed solution, wherein the Co (NO) is3)2·6H2O：Ni(NO3)2·6H2O：C6H12N4：CH4N2O：NH4F: deionized water in a solid-to-liquid ratio of 0.5-5 mM: 2.5 mM: 6 mM: 0.36 g: 0.195 g: 50 mL;
E. pouring the mixed solution into a hydrothermal reaction kettle to 60% of the volume, and growing BiVO on the prepared FTO substrate4And (3) placing the photoanode obliquely, heating for 2-5 h at the reaction temperature of 120-200 ℃, naturally cooling to room temperature, taking out, washing with deionized water, annealing at the high temperature of 300-500 ℃ for 1.5-3 h, and naturally cooling to room temperature to obtain the photoanode.
2. BiVO according to claim 14-Ni/Co3O4The synthesis method of the heterojunction is characterized in that: the pH was adjusted to 1.7 with nitric acid as described in step A.
3. BiVO according to claim 14-Ni/Co3O4The synthesis method of the heterojunction is characterized in that: the volume ratio of the mixed aqueous solution to the ethanol solution of the p-benzoquinone in the step A is 5: 2.
4. BiVO according to claim 14-Ni/Co3O4The synthesis method of the heterojunction is characterized in that: electrodeposition was carried out for 5min under the bias of-0.1 Vvs Ag/AgCl described in step B.
5. BiVO according to claim 14-Ni/Co3O4Heterogeneous natureThe synthesis method of the junction is characterized in that: in the step C, the FTO is calcined and annealed at 450 ℃ for 2 h.
6. BiVO according to claim 14-Ni/Co3O4The synthesis method of the heterojunction is characterized in that: co (NO) as described in step C3)2·6H2O：Ni(NO3)2·6H2O：C6H12N4：CH4N2O：NH4F: deionized water at a solid-to-liquid ratio of 2.5 mM: 2.5 mM: 6 mM: 0.36 g: 0.195 g: 50 mL.
7. BiVO according to claim 14-Ni/Co3O4The synthesis method of the heterojunction is characterized in that: d, pouring the mixed solution into a hydrothermal reaction kettle to 60% of the volume, wherein BiVO grows on the prepared FTO substrate4The photo-anode is obliquely placed, the reaction temperature is 180 ℃, and the heating is carried out for 3 hours.
8. BiVO according to claim 14-Ni/Co3O4The synthesis method of the heterojunction is characterized in that: and D, annealing at 400 ℃ for 2 h.
9. BiVO synthesized according to any one of claims 1 to 84-Ni/Co3O4Use of a heterojunction, characterized in that: the electrode is used as a working electrode for photoelectrochemical hydrolysis reaction.
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CN113398944A (en) * 2021-05-24 2021-09-17 苏州科技大学 Composite material of bismuth vanadate surface modified nickel cobaltate spinel and preparation and application thereof
CN113403642A (en) * 2021-05-24 2021-09-17 江苏大学 BiVO4/Co1-XPreparation method and application of S composite photoelectrode
CN113398944B (en) * 2021-05-24 2022-02-22 苏州科技大学 Composite material of bismuth vanadate surface modified nickel cobaltate spinel and preparation and application thereof
CN113403642B (en) * 2021-05-24 2022-09-16 江苏大学 BiVO 4 /Co 1-X Preparation method and application of S composite photoelectrode
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CN115261869A (en) * 2022-08-03 2022-11-01 中国石油大学(北京) Preparation method and application of bismuth vanadate-based photoproduction cathode protection coating

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