CN113403642B - BiVO 4 /Co 1-X Preparation method and application of S composite photoelectrode - Google Patents
BiVO 4 /Co 1-X Preparation method and application of S composite photoelectrode Download PDFInfo
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Abstract
The invention belongs to the technical field of composite material preparation, relates to preparation of a photoelectric catalyst, and particularly relates to Co 1‑X S and BiVO 4 Composite photoelectrode (BiVO) 4 /Co 1‑X S) comprises the following steps: 50mL of deionized water is added into four beakers respectively, the numbers of the deionized water are 1, 2, 3 and 4, and 0.05-0.15 mmol of Co (NO) is dissolved in the No. 1 beaker 3 ) 2 ·6H 2 O, dissolving 0.05 to 0.15mmol of Na in No. 3 beaker 2 S; will be loaded with BiVO 4 The FTO sheets are soaked in the beakers according to the numbering sequence, taken out after circulating for 10-50 times, washed by deionized water and dried at room temperature to obtain BiVO 4 /Co 1‑X And S. The invention utilizes an electrodeposition method, a calcination method and an SILAR method to synthesize the BiVO 4 /Co 1‑X S，Co 1‑X S nano-particles are compounded in BiVO 4 Effectively improve BiVO on the surface 4 /Co 1‑X The S composite photoelectric catalyst has carrier migration rate, improves the problem of electron and hole recombination, and improves the photoelectric catalytic performance. The preparation process is simple, and the prepared BiVO 4 /Co 1‑X The S has good application prospect when being applied to hydrogen production by photoelectrocatalysis water decomposition, and can play a role in the fields of environment, energy and the like.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, relates to preparation of a photoelectric catalyst, and particularly relates to Co 1-X S and BiVO 4 Composite photoelectrode (BiVO) 4 /Co 1-X S) and the application thereof.
Background
H 2 As an ideal energy carrier, the composite material can be used in the fields of energy storage, transportation, fuel cells and the like. H 2 The energy provided in the combustion process is far higher than that of fossil fuel, the combustion product does not cause pollution to the environment, and the energy is one of important energy sources capable of replacing the fossil fuel, so that clean and efficient H is explored 2 The energy production mode is necessary to effectively promote the green sustainable development. Solar-driven hydrogen production by water splitting is an environmentally friendly process, where Photoelectrochemical (PEC) splitting of water is a mature and promising technology. However, in the PEC system, the performance impact of screening for suitable semiconductors is important, BiVO 4 There has been much interest in this area. BiVO 4 With a suitable band gap (2.4 eV), the conduction band is very close to H + /H 2 Thermodynamic redox potential of the reaction, which is responsible for the decomposition of water to produce H 2 Has obvious advantages and BiVO 4 The conversion efficiency of solar energy to hydrogen can be promoted to reach 9.3%. Furthermore, BiVO 4 Has the advantages of stable performance, low toxicity, excellent visible light response and the like.
However, BiVO is greatly limited by problems of slow carrier transport speed and oxidation kinetics, high electron-hole recombination efficiency, and the like 4 The use of (1). Researchers have tried many ways to solve these problems, such as element doping, heterojunction construction, synthesis of oxygen vacancies, etc., with great success. For example, BiVO by Ar-plasma etching technique 4 The film can generate controllable oxygen vacancy, and the photocurrent reaches 4.32 mA/cm 2 Is far higher than other pure BiVO 4 . This is mainly due to the fact that the activation of surface oxygen vacancies favours the separation and orientation of chargesTransfer of water oxidation reaction. In addition to the above-mentioned method, the modification with cocatalyst can also raise BiVO 4 General method of Performance. Transition metal compounds are generally used as Oxygen Evolution Reaction (OER) catalysts, and transition metal sulfides, for example, have the advantages of low cost, high thermal stability, weak M-S bond, and no toxicity, and are called ideal anode materials. It is noteworthy that transition metal sulfides have high electrical conductivity, since the low electronegativity of sulfur makes it react with metals to form elastic structures, which is very advantageous for the transport of electrons. Wherein Co 1-X S is a semiconductor material with a narrow band gap (1.25 eV), which reacts with BiVO 4 The energy band structures of the two-dimensional light-emitting diode are matched, and the two-dimensional light-emitting diode has strong visible light absorption capacity. Thus, Co 1-X S and BiVO 4 The combination of (a) will effectively separate the photogenerated electron-hole pairs, thereby improving PEC performance.
So far, there is no disclosure of successful application of BiVO by SILAR method 4 And Co 1-X S is compounded and used for photoelectrochemical water decomposition.
Disclosure of Invention
In order to solve BiVO 4 The invention discloses a Co-based organic electroluminescent device and a preparation method thereof, and solves the problems of low electron hole transmission speed, high recombination rate and slow interface reaction kinetics of a semiconductor 1-X S modified BiVO 4 Semiconductor (BiVO) 4 /Co 1-X S) preparation method.
The technical scheme is as follows:
potassium iodide, concentrated nitric acid and bismuth nitrate pentahydrate (Bi (NO) 3 ) 3 ·5H 2 O), p-benzoquinone and FTO glass sheets are used as raw materials, a BiOI film is obtained on the surface of the FTO by an electrodeposition method, and then the BiVO is synthesized by calcination treatment and SILAR 4 /Co 1-X S。
BiVO 4 /Co 1-X The preparation method of the S composite photoelectrode comprises the following steps:
A、BiVO 4 preparing a film: to 50mL of deionized water were added 3.32g of KI and 0.97g of Bi (NO) 3 ) 3 ∙5H 2 O, stirring and dissolving, and then adjusting the pH value to 1.7 by using concentrated nitric acid, namely a solution A; 0.4968g of p-benzoquinone are added into 20mL of ethanol and stirred until dissolved, and the solution is named as B solutionLiquid; mixing the solution A and the solution B, and uniformly stirring to obtain a precursor solution; electrodepositing on the surface of cleaned FTO to obtain a BiOI film, and calcining at 300-550 ℃ for 1-4 h, preferably at 450 ℃ for 2h after a vanadium source is dripped on the surface of the BiOI film to obtain BiVO 4 A film;
B、Co 1-X preparing an S precursor solution: 50mL of deionized water is added into the four beakers respectively, the numbers of the four beakers are 1, 2, 3 and 4, and 0.05-0.15 mmol of Co (NO) is dissolved in the No. 1 beaker 3 ) 2 ·6H 2 O, preferably 0.1mmol, and 0.05 to 0.15mmol of Na dissolved in No. 3 beaker 2 S, preferably 0.1 mmol;
C、BiVO 4 /Co 1-X s preparation: will be loaded with BiVO 4 The FTO sheets are soaked in the beakers according to the numbering sequence, are taken out after circulating for 10-50 times, preferably 30 times, are washed by deionized water and are dried at room temperature to obtain BiVO 4 /Co 1-X S。
In the preferred embodiment of the invention, the cleaned FTO glass sheet in step a is prepared by cleaning the surface of the FTO glass sheet, ultrasonic cleaning the FTO glass sheet in acetone, isopropanol and ethylene glycol for 0.5h, taking out, and air drying.
In the preferred embodiment of the invention, in the step A, the prepared sample is taken as a working electrode, Ag/AgCl and Pt are respectively taken as a reference electrode and a counter electrode, the working electrode and the counter electrode are connected with an electrochemical workstation, the bias voltage is set to be-0.1V vs. Ag/AgCl, and the time is 5 min.
In a preferred embodiment of the invention, the vanadium source in step A is a dimethyl sulfoxide solution containing 0.2M vanadyl acetylacetonate.
BiVO prepared according to the method disclosed by the invention 4 /Co 1-X S，BiVO 4 Exhibiting a worm-like structure, complex Co 1-X After S, BiVO 4 The surface has distinct nanoparticles.
Another purpose of the invention is to disclose BiVO prepared 4 /Co 1-X And S, applying to photoelectrocatalysis water decomposition hydrogen production.
Experiment for photoelectrocatalysis water decomposition
(1) Prepared into 50mL of solution with the concentration of0.1～1.0 mol·L -1 Na (b) of 2 SO 4 The solution is placed in the dark, preferably 0.5 mol.L -1 ；
(2) The BiVO treated by different soaking times 4 /Co 1-X S samples are respectively placed in a photoelectrocatalysis device, and prepared Na is added 2 SO 4 And (5) turning on a light source to perform a hydrogen production experiment by photoelectrocatalysis water decomposition.
The invention has the characteristics that:
(1) introduction of Co 1-X S forms BiVO 4 /Co 1-X The S-shaped photoelectrode effectively promotes carrier migration and inhibits electron hole pair recombination;
(2) introduction of Co 1-X S forming BiVO 4 /Co 1-X The S photoelectrode enables the photoelectrocatalysis to decompose water to achieve higher hydrogen production efficiency.
BiVO prepared by the invention 4 /Co 1-X The S-shaped photoelectrode utilizes instruments such as X-ray diffraction (XRD), a Scanning Electron Microscope (SEM), X-ray photoelectron spectroscopy (XPS) and the like to analyze the appearance structure and the composition of a product, an ultraviolet-visible spectrophotometer is used for measuring absorbance, and a standard three-electrode electrochemical workstation is used for measuring transient photocurrent and stability so as to evaluate the photoelectrocatalysis activity of the S-shaped photoelectrode.
The reagent used in the invention is commercially available.
Advantageous effects
The invention utilizes an electrodeposition method, a calcination method and an SILAR method to synthesize BiVO 4 /Co 1-X S，Co 1-X S nano-particles are compounded in BiVO 4 Effectively improve BiVO on the surface 4 /Co 1-X The S composite photoelectric catalyst has carrier migration rate, improves the problem of electron and hole recombination, and improves the photoelectric catalytic performance. The preparation process is simple, and the prepared BiVO 4 /Co 1-X The S has good application prospect when being applied to hydrogen production by photoelectrocatalysis water decomposition, and can play a role in the fields of environment, energy and the like.
Drawings
FIG. 1. BiVO prepared in example 1 4 /Co 1-X XRD diffraction spectrum of S photoelectrode;
FIG. 2 BiVO prepared in example 1 4 /Co 1-X XPS plot of S photoelectrode;
FIG. 3 BiVO prepared in example 1 4 /Co 1-X A Scanning Electron Microscope (SEM) image of the S-photo electrode;
FIG. 4 BiVO prepared in example 1 4 /Co 1-X A UV-vis spectrogram of an S-ray electrode;
FIG. 5 BiVO prepared in example 1 4 /Co 1-X A Linear Sweep Voltammetry (LSV) plot of the S-ray electrode;
FIG. 6 BiVO prepared in example 1 4 /Co 1-X Stability (i-t) diagram of S-photoelectrode.
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.
The surfaces of the FTO glass sheets used in the following examples were cleaned, then ultrasonically cleaned in acetone, isopropanol and ethylene glycol for 0.5h, removed and dried.
The electrodeposition process conditions are that a prepared sample is taken as a working electrode, Ag/AgCl and Pt are respectively taken as a reference electrode and a counter electrode, the reference electrode and the counter electrode are connected with an electrochemical workstation, the bias voltage is set to be-0.1V vs. Ag/AgCl, and the time is 5 min.
Example 1
BiVO 4 /Co 1-X The preparation method of the S composite photoelectrode comprises the following steps:
A、BiVO 4 preparing a film: to 50mL of deionized water were added 3.32g of KI and 0.97g of Bi (NO) 3 ) 3 ∙5H 2 O, stirring and dissolving, then adjusting the pH value to 1.7 by using concentrated nitric acid, and naming the solution as A solution; 0.4968g of p-benzoquinone is added into 20mL of ethanol and stirred until the p-benzoquinone is dissolved, and the solution is named as solution B; mixing the solution A and the solution B, and uniformly stirring to obtain a precursor solution; electrodepositing on the surface of cleaned FTO to obtain a BiOI film, dripping a vanadium source on the surface of the BiOI film, and calcining for 2 hours at 450 ℃ in a muffle furnace to obtain BiVO 4 A film;
B、Co 1-X preparing an S precursor solution: four 50mL beakers were prepared, numbered 1, 2, 3, and 4, respectively. In a No. 1 beaker, 0.1mmol Co (NO) 3 ) 2 ·6H 2 O was dissolved in 50mL of deionized water, and 0.1mmol of Na was added to No. 3 beaker 2 S to 50mL of aqueous solution, the beakers 2 and 4 are pure deionized water;
C、BiVO 4 /Co 1-X s preparation: will be loaded with BiVO 4 The FTO sheet is soaked in four beakers containing different solutions in turn, namely the SILAR method, the FTO sheet is taken out after 30 times of circulation, washed by deionized water and dried at room temperature to obtain BiVO 4 /Co 1-X S。
Experiment for photoelectrocatalysis water decomposition
(1) 50mL of the solution was prepared at a concentration of 0.5 mol. L -1 Na of (2) 2 SO 4 A solution;
(2) taking BiVO with different soaking times 4 /Co 1-X S samples are respectively placed in a photoelectrocatalysis device, and prepared Na is added 2 SO 4 And (5) turning on a light source to perform a hydrogen production experiment by photoelectrocatalysis water decomposition.
BiVO 4 /Co 1-X Characterization of S-ray electrode
As shown in FIG. 1, Co 1-X S nanoparticle loaded BiVO 4 The XRD patterns before and after the detection show that Co is not found 1-X The characteristic peak of S is due to low content;
as shown in FIG. 2, the XPS chart containing the existence of Bi, O, V, S and Co elements and corresponding valence states proves that Co is effectively prepared 1-X S；
BiVO, as shown in FIG. 3 4 Vermicular morphology of and Co 1-X S nano-particles are uniformly attached to BiVO 4 A surface;
as shown in fig. 4, pure BiVO 4 And BiVO 4 /Co 1-X S shows a steeper absorption edge at 510 nm, BiVO 4 /Co 1-X The absorbance of the S-shaped photoelectrode in a visible light area is improved to a certain extent;
BiVO, as shown in FIG. 5 4 /Co 1-X Linear Sweep Voltammetry (LSV) testing of S-photoelectrode maximum photocurrent of 2.9 mA/cm at different soak times treatments 2 （1.23 V vs RHE）；
BiVO, as shown in FIG. 6 4 /Co 1-X The S-shaped photoelectrode has good stability.
Example 2
BiVO 4 /Co 1-X The preparation method of the S composite photoelectrode comprises the following steps:
A、BiVO 4 preparing a film: to 50mL of deionized water were added 3.32g of KI and 0.97g of Bi (NO) 3 ) 3 ∙5H 2 O, stirring and dissolving, then adjusting the pH value to 1.7 by using concentrated nitric acid, and naming the solution as A solution; 0.4968g of p-benzoquinone is added into 20mL of ethanol and stirred until the p-benzoquinone is dissolved, and the solution is named as solution B; mixing the solution A and the solution B, and uniformly stirring to obtain a precursor solution; electrodepositing on the surface of cleaned FTO to obtain a BiOI film, dripping a vanadium source on the surface of the BiOI film, and calcining for 3 hours at 350 ℃ in a muffle furnace to obtain BiVO 4 A film;
B、Co 1-X preparing an S precursor solution: four 50mL beakers were prepared, numbered 1, 2, 3, and 4, respectively. In a No. 1 beaker, 0.05 mmol Co (NO) 3 ) 2 ·6H 2 O was dissolved in 50mL of deionized water, and 0.05 mmol of Na was added to No. 3 beaker 2 S to 50mL of aqueous solution, beakers 2 and 4 are pure deionized water;
C、BiVO 4 /Co 1-X s preparation: will be loaded with BiVO 4 The FTO sheet is soaked in four beakers containing different solutions in turn, namely the SILAR method, the FTO sheet is taken out after 10 times of circulation, washed by deionized water and dried at room temperature to obtain BiVO 4 /Co 1-X S。
Experiment for photoelectrocatalysis water decomposition
(1) 50mL of the solution was prepared at a concentration of 0.5 mol. L -1 Na of (2) 2 SO 4 A solution;
(2) taking BiVO with different soaking times 4 /Co 1-X S samples are respectively placed in a photoelectrocatalysis device and added with the preparedNa 2 SO 4 And (5) turning on a light source to perform a hydrogen production experiment by photoelectrocatalysis water decomposition.
BiVO 4 /Co 1-X Maximum photocurrent of 1.79 mA/cm for Linear Sweep Voltammetry (LSV) test of S-photo electrode 2 （1.23 V vs RHE）。
Example 3
BiVO 4 /Co 1-X The preparation method of the S composite photoelectrode comprises the following steps:
A、BiVO 4 preparing a film: to 50mL of deionized water were added 3.32g of KI and 0.97g of Bi (NO) 3 ) 3 ∙5H 2 O, stirring and dissolving, then adjusting the pH value to 1.7 by using concentrated nitric acid, and naming the solution as A solution; 0.4968g of p-benzoquinone is added into 20mL of ethanol and stirred until the p-benzoquinone is dissolved, and the solution is named as solution B; mixing the solution A and the solution B, and uniformly stirring to obtain a precursor solution; electrodepositing on the surface of cleaned FTO to obtain a BiOI film, dripping a vanadium source on the surface of the BiOI film, and calcining for 2 hours at 350 ℃ in a muffle furnace to obtain BiVO 4 A film;
B、Co 1-X preparing an S precursor solution: four 50mL beakers were prepared, numbered 1, 2, 3, and 4, respectively. In a No. 1 beaker, 0.15mmol Co (NO) 3 ) 2 ·6H 2 O was dissolved in 50mL of deionized water, and 0.15mmol of Na was added to No. 3 beaker 2 S to 50mL of aqueous solution, the beakers 2 and 4 are pure deionized water;
C、BiVO 4 /Co 1-X s preparation: will be loaded with BiVO 4 The FTO sheet is soaked in four beakers containing different solutions in turn, namely the SILAR method, the FTO sheet is taken out after circulating for 20 times, is washed by deionized water and is dried at room temperature, and BiVO can be obtained 4 /Co 1-X S。
Experiment for photoelectrocatalysis water decomposition
(1) 50mL of the solution was prepared at a concentration of 0.5 mol. L -1 Na of (2) 2 SO 4 A solution;
(2) taking BiVO with different soaking times 4 /Co 1-X S samples are respectively placed in a photoelectrocatalysis device, and prepared Na is added 2 SO 4 And (5) turning on a light source to perform a hydrogen production experiment by photoelectrocatalysis water decomposition.
BiVO 4 /Co 1-X Maximum photocurrent of 1.95 mA/cm for Linear Sweep Voltammetry (LSV) test of S-photo electrode 2 （1.23 V vs RHE）。
Example 4
BiVO 4 /Co 1-X The preparation method of the S composite photoelectrode comprises the following steps:
A、BiVO 4 preparing a film: to 50mL of deionized water were added 3.32g of KI and 0.97g of Bi (NO) 3 ) 3 ∙5H 2 O, stirring and dissolving, then adjusting the pH value to 1.7 by using concentrated nitric acid, and naming the solution as A solution; 0.4968g of p-benzoquinone is added into 20mL of ethanol and stirred until the p-benzoquinone is dissolved, and the solution is named as solution B; mixing the solution A and the solution B, and uniformly stirring to obtain a precursor solution; electrodepositing on the surface of cleaned FTO to obtain a BiOI film, dripping a vanadium source on the surface of the BiOI film, and calcining for 3 hours at 450 ℃ in a muffle furnace to obtain BiVO 4 A film;
B、Co 1-X preparing an S precursor solution: four 50mL beakers were prepared, numbered 1, 2, 3, and 4, respectively. In a No. 1 beaker, 0.1mmol Co (NO) 3 ) 2 ·6H 2 O was dissolved in 50mL of deionized water, and 0.1mmol of Na was added to No. 3 beaker 2 S to 50mL of aqueous solution, the beakers 2 and 4 are pure deionized water;
C、BiVO 4 /Co 1-X s preparation: will be loaded with BiVO 4 The FTO sheet is soaked in four beakers containing different solutions in turn, namely the SILAR method, the FTO sheet is taken out after circulating for 40 times, is washed by deionized water and is dried at room temperature, and BiVO can be obtained 4 /Co 1-X S。
Experiment for photoelectrocatalysis water decomposition
(1) 50mL of the solution was prepared at a concentration of 0.5 mol. L -1 Na of (2) 2 SO 4 A solution;
(2) taking BiVO with different soaking times 4 /Co 1-X S samples are respectively placed in a photoelectrocatalysis device, and prepared Na is added 2 SO 4 And (5) turning on a light source to perform a hydrogen production experiment by photoelectrocatalysis water decomposition.
BiVO 4 /Co 1-X Maximum photocurrent of 2.06 mA/cm for Linear Sweep Voltammetry (LSV) test of S-photo electrode 2 （1.23 V vs RHE）。
Example 5
BiVO 4 /Co 1-X The preparation method of the S composite photoelectrode comprises the following steps:
A、BiVO 4 preparing a film: to 50mL of deionized water were added 3.32g of KI and 0.97g of Bi (NO) 3 ) 3 ∙5H 2 O, stirring and dissolving, then adjusting the pH value to 1.7 by using concentrated nitric acid, and naming the solution as A solution; 0.4968g of p-benzoquinone is added into 20mL of ethanol and stirred until the p-benzoquinone is dissolved, and the solution is named as solution B; mixing the solution A and the solution B, and uniformly stirring to obtain a precursor solution; electrodepositing on the surface of cleaned FTO to obtain a BiOI film, dripping a vanadium source on the surface of the BiOI film, and calcining for 4 hours at 350 ℃ in a muffle furnace to obtain BiVO 4 A film;
B、Co 1-X preparing an S precursor solution: four 50mL beakers were prepared, numbered 1, 2, 3, and 4, respectively. In a No. 1 beaker, 0.05 mmol Co (NO) 3 ) 2 ·6H 2 O was dissolved in 50mL of deionized water, and 0.05 mmol of Na was added to No. 3 beaker 2 S to 50mL of aqueous solution, the beakers 2 and 4 are pure deionized water;
C、BiVO 4 /Co 1-X s preparation: will be loaded with BiVO 4 The FTO sheet is soaked in four beakers containing different solutions in turn, namely the SILAR method, the FTO sheet is taken out after circulating for 50 times, is washed by deionized water and is dried at room temperature, and the BiVO can be obtained 4 /Co 1-X S。
Photoelectrocatalysis water decomposition experiment
(1) 50mL of the solution was prepared at a concentration of 0.5 mol. L -1 Na of (2) 2 SO 4 A solution;
(2) taking BiVO with different soaking times 4 /Co 1-X S samples are respectively placed in a photoelectrocatalysis device, and prepared Na is added 2 SO 4 Solution, turn on lightAnd performing a hydrogen production experiment by decomposing water through photoelectrocatalysis.
BiVO 4 /Co 1-X Maximum photocurrent of 1.94 mA/cm for Linear Sweep Voltammetry (LSV) test of S-photo electrode 2 （1.23 V vs RHE）。
Example 6
BiVO 4 /Co 1-X The preparation method of the S composite photoelectrode comprises the following steps:
A、BiVO 4 preparing a film: to 50mL of deionized water were added 3.32g of KI and 0.97g of Bi (NO) 3 ) 3 ∙5H 2 O, stirring and dissolving, then adjusting the pH value to 1.7 by using concentrated nitric acid, and naming the solution as A solution; 0.4968g of p-benzoquinone is added into 20mL of ethanol and stirred until the p-benzoquinone is dissolved, and the solution is named as solution B; mixing the solution A and the solution B, and uniformly stirring to obtain a precursor solution; electrodepositing on the surface of cleaned FTO to obtain a BiOI film, dripping a vanadium source on the surface of the BiOI film, and calcining for 1 h at 550 ℃ in a muffle furnace to obtain BiVO 4 A film;
B、Co 1-X preparing an S precursor solution: four 50mL beakers were prepared, numbered 1, 2, 3, and 4, respectively. In a No. 1 beaker, 0.15mmol Co (NO) 3 ) 2 ·6H 2 O was dissolved in 50mL of deionized water, and 0.15mmol of Na was added to No. 3 beaker 2 S to 50mL of aqueous solution, the beakers 2 and 4 are pure deionized water;
C、BiVO 4 /Co 1-X s preparation: will be loaded with BiVO 4 The FTO sheet is soaked in four beakers containing different solutions in turn, namely the SILAR method, the FTO sheet is taken out after 10 times of circulation, washed by deionized water and dried at room temperature to obtain BiVO 4 /Co 1-X S。
Experiment for photoelectrocatalysis water decomposition
(1) 50mL of the solution was prepared at a concentration of 0.5 mol. L -1 Na of (2) 2 SO 4 A solution;
(2) taking BiVO with different soaking times 4 /Co 1-X S samples are respectively placed in a photoelectrocatalysis device, and prepared Na is added 2 SO 4 Solution, turning on light source, and performing lightExperiment for hydrogen production by electrocatalysis water decomposition.
BiVO 4 /Co 1-X Maximum photocurrent of 2.32 mA/cm for Linear Sweep Voltammetry (LSV) test of S-photo electrode 2 （1.23 V vs RHE）。
Example 7
BiVO 4 /Co 1-X The preparation method of the S composite photoelectrode comprises the following steps:
A、BiVO 4 preparation of the film: to 50mL of deionized water were added 3.32g of KI and 0.97g of Bi (NO) 3 ) 3 ∙5H 2 O, stirring and dissolving, then adjusting the pH value to 1.7 by using concentrated nitric acid, and naming the solution as A solution; 0.4968g of p-benzoquinone is added into 20mL of ethanol and stirred until the p-benzoquinone is dissolved, and the solution is named as solution B; mixing the solution A and the solution B, and uniformly stirring to obtain a precursor solution; electrodepositing on the surface of cleaned FTO to obtain a BiOI film, dripping a vanadium source on the surface of the BiOI film, and calcining for 2 hours at 550 ℃ in a muffle furnace to obtain BiVO 4 A film;
B、Co 1-X preparing an S precursor solution: four 50mL beakers were prepared, numbered 1, 2, 3, and 4, respectively. In a No. 1 beaker, 0.1mmol Co (NO) 3 ) 2 ·6H 2 O was dissolved in 50mL of deionized water, and 0.1mmol of Na was added to No. 3 beaker 2 S to 50mL of aqueous solution, the beakers 2 and 4 are pure deionized water;
C、BiVO 4 /Co 1-X s preparation: will be loaded with BiVO 4 The FTO sheet is soaked in four beakers containing different solutions in turn, namely the SILAR method, the FTO sheet is taken out after circulating for 20 times, is washed by deionized water and is dried at room temperature, and BiVO can be obtained 4 /Co 1-X S。
Experiment for photoelectrocatalysis water decomposition
(1) 50mL of the solution was prepared at a concentration of 0.5 mol. L -1 Na of (2) 2 SO 4 A solution;
(2) taking BiVO with different soaking times 4 /Co 1-X S samples are respectively placed in a photoelectrocatalysis device, and prepared Na is added 2 SO 4 The solution is turned on to carry out photoelectrocatalysis water decompositionAnd (3) hydrogen production experiment.
BiVO 4 /Co 1-X Maximum photocurrent of 2.41 mA/cm for Linear Sweep Voltammetry (LSV) test of S-photo electrode 2 （1.23 V vs RHE）。
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. BiVO 4 /Co 1-X The preparation method of the S composite photoelectrode is characterized by comprising the following steps:
A. to 50mL of deionized water were added 3.32g of KI and 0.97g of Bi (NO) 3 ) 3 ·5H 2 O, stirring and dissolving, and then adjusting the pH value to 1.7 by using concentrated nitric acid, namely a solution A; 0.4968g of p-benzoquinone is added into 20mL of ethanol and stirred until the p-benzoquinone is dissolved, and the solution is named as solution B; mixing the solution A and the solution B, and uniformly stirring to obtain a precursor solution; electrodepositing on the surface of cleaned FTO to obtain a BiOI film, dropwise adding a vanadium source on the surface of the BiOI film, and calcining at 300-550 ℃ for 1-4 h to obtain BiVO 4 The thin film is formed by electrodeposition, wherein FTO is used as a working electrode, Ag/AgCl and Pt are used as a reference electrode and a counter electrode respectively, the thin film is connected with an electrochemical workstation, the bias voltage is set to be minus 0.1V vs. Ag/AgCl, and the time is 5 min;
B. 50mL of deionized water is added into the four beakers respectively, the numbers of the four beakers are 1, 2, 3 and 4, and 0.05-0.15 mmol of Co (NO) is dissolved in the No. 1 beaker 3 ) 2 ·6H 2 O, dissolving 0.05-0.15 mmol of Na in No. 3 beaker 2 S；
C. Will be loaded with BiVO 4 The FTO sheets are soaked in the beaker according to the serial number sequence, taken out after circulating for 10-50 times, washed by deionized water and dried at room temperature to obtain BiVO 4 /Co 1-X S。
2. BiVO according to claim 1 4 /Co 1-X The preparation method of the S composite photoelectrode is characterized in thatIn the following steps: a, after a vanadium source is dripped on the surface of the mixture obtained in the step A, calcining the mixture for 2 hours at 450 ℃ to obtain BiVO 4 A film.
3. BiVO according to claim 1 4 /Co 1-X The preparation method of the S composite photoelectrode is characterized by comprising the following steps: and B, cleaning the surface of the cleaned FTO glass sheet, respectively ultrasonically cleaning the FTO glass sheet in acetone, isopropanol and ethylene glycol for 0.5h, taking out and airing.
4. BiVO according to claim 1 4 /Co 1-X The preparation method of the S composite photoelectrode is characterized by comprising the following steps: and the vanadium source in the step A is dimethyl sulfoxide solution containing 0.2M vanadyl acetylacetonate.
5. BiVO according to claim 1 4 /Co 1-X The preparation method of the S composite photoelectrode is characterized by comprising the following steps: step B dissolving 0.1mmol Co (NO) in No. 1 beaker 3 ) 2 ·6H 2 O。
6. BiVO according to claim 1 4 /Co 1-X The preparation method of the S composite photoelectrode is characterized by comprising the following steps: step B dissolving 0.1mmol of Na in No. 3 beaker 2 S。
7. BiVO according to claim 1 4 /Co 1-X The preparation method of the S composite photoelectrode is characterized by comprising the following steps: step C said will load BiVO 4 The FTO sheets are soaked in the beakers according to the numbering sequence, and are taken out after 30 times of circulation.
8. BiVO prepared by the method of any one of claims 1 to 7 4 /Co 1-X The S composite photoelectrode is characterized in that: BiVO in the composite photoelectrode 4 Exhibit a worm-like structure, compounding with Co 1-X After S, BiVO 4 The surface has distinct nanoparticles.
9.BiVO according to claim 8 4 /Co 1-X The application of the S composite photoelectrode is characterized in that: the method is applied to photoelectrocatalysis decomposition of water to prepare hydrogen.
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