CN109402656B - Preparation method of cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode - Google Patents

Preparation method of cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode Download PDF

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CN109402656B
CN109402656B CN201811540907.1A CN201811540907A CN109402656B CN 109402656 B CN109402656 B CN 109402656B CN 201811540907 A CN201811540907 A CN 201811540907A CN 109402656 B CN109402656 B CN 109402656B
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photoelectrode
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bismuth vanadate
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刘长海
罗恒
陈智栋
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Changzhou University
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Abstract

The invention discloses a preparation method of a cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode, which comprises the steps of firstly preparing a bismuth oxyiodide photoelectrode on the surface of conductive glass by adopting a deposition method, dropwise adding a vanadium source and a molybdenum source solution on the bismuth oxyiodide photoelectrode, annealing and cleaning to obtain a molybdenum-doped bismuth vanadate photoelectrode, and then carrying out photo-assisted electrodeposition of cobalt phosphide on the surface of the molybdenum-doped bismuth vanadate photoelectrode in a three-electrode system to obtain the prepared novel bismuth vanadate photoelectrode. The photoelectrode prepared by the invention is used for preparing hydrogen by decomposing water through photoelectrocatalysis, the molybdenum doping can effectively increase the concentration of current carriers and increase the photocurrent, and the electrodeposition of cobalt and phosphorus can effectively delay the recombination loss in the photoelectrode, prolong the service life of the photon-generated current carriers and promote the oxygen precipitation reaction on the surface of the photoelectrode, thereby improving the solar energy hydrogen conversion efficiency of the semiconductor photoelectrode.

Description

Preparation method of cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a preparation method of a cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode and application of the cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode in photoelectrocatalysis decomposition water.
Background
In order to realize the strategy of sustainable development, the development and utilization of renewable energy industry has become an important strategic target in countries of the world. The solar energy is taken as a clean renewable energy source, and the storage capacity of the solar energy is tens of thousands of times of that of other renewable energy sources; meanwhile, the solar energy hardly releases greenhouse gases in the using process, which is beneficial to relieving environmental pollution caused by using a large amount of petroleum and environmental problems such as greenhouse effect caused by fuel combustion and the like, and the solar energy occupies an important position in the renewable energy industry.
The semiconductor photoelectric functional material has photoconduction and photovoltaic effects, and the photoelectric misstatement spark is determined by the behavior characteristic that the semiconductor material generates photon-generated carriers after being excited by enough energy light, so that the possibility is provided for the utilization of solar energy. The semiconductor photoelectric functional material is used for converting solar energy into chemical energy, and has important research significance and practical value for solving the current energy crisis and environmental problems.
The photoelectric functional materials mainly researched at present comprise non-oxide materials and oxide materials, the preparation cost of the non-oxide materials is high, the photo-corrosion phenomenon is serious, and little attention is paid to the materials. The oxide material is generally stable in electrode, simple in preparation method and low in cost, is widely concerned by people, and mainly focuses on titanium dioxide, zinc oxide, ferric oxide, bismuth vanadate and the like. Wherein bismuth vanadate (BiVO)4) Has the characteristics of abundant reserves and good stability in neutral solution, has a valence band edge of 2.4V relative to a standard hydrogen electrode, can be well used for catalyzing and decomposing water, has a narrow band gap of 2.4eV, and can absorb visible light below 516nmSunlight. The theoretical photolytic efficiency of bismuth vanadate is 9.2 percent, which is equivalent to the photocurrent density of 7.5mA cm-2However, the actual water photolysis efficiency of bismuth vanadate is far lower than the theoretical efficiency, and the current density of the intrinsic bismuth vanadate photoelectrode is only 0.42mA cm-2This is caused by the following three aspects: firstly, 60-80% of charges are compounded due to poor electron transport and high surface defects; ② the dynamic process of oxygen precipitation is slow; and the conduction band edge is slightly lower than the reversible hydrogen potential.
In order to solve the above three problems, researchers have combined bismuth vanadate with other semiconductors in order to improve the separation efficiency of photogenerated carriers, and modified a promoter on the surface of bismuth vanadate by a sputtering method, a hydrothermal synthesis method, a photo-assisted electrodeposition method, or the like. Therefore, the doping to improve the concentration of the photon-generated carriers and the electrodeposition composite promoter is expected to improve the photocurrent density of the bismuth vanadate and promote the photocatalytic water decomposition efficiency of the bismuth vanadate.
Disclosure of Invention
In order to promote the photocatalytic decomposition efficiency of water by the bismuth vanadate photoelectrode, the invention aims to provide a preparation method of a cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode, and the photocurrent of the photoelectrode is improved by a cobalt-phosphorus cocatalyst and doped molybdenum.
The invention also provides a preparation method of the cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode and application of the cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode in photoelectrocatalysis decomposition of water.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode comprises the following steps:
(1) preparing a bismuth oxyiodide photoelectrode by an electrodeposition method by taking conductive glass as a substrate;
(2) dripping dimethyl sulfoxide solution of molybdenum acetylacetonate and vanadyl acetylacetonate on the bismuth oxyiodide electrode obtained in the step (1), heating to 400-500 ℃, keeping the temperature for 1.5-2.5 hours at constant temperature, cooling to room temperature, soaking in alkali solution, cleaning and drying to obtain a molybdenum-doped bismuth vanadate photoelectrode;
(3) and (3) taking the molybdenum-doped bismuth vanadate photoelectricity obtained in the step (2) as a working electrode, a platinum sheet as a counter electrode and an Ag/AgCl electrode as a reference electrode to form a three-electrode system, taking an aqueous solution containing 4-6 mmol/L of cobalt nitrate and 0.075-0.15 mol/L of sodium phosphate as an electrolyte, assisting by simulated sunlight irradiation, adopting a potentiostatic method and 0.35-0.45V as a constant potential, taking the deposition time to be 120-140 s, taking out the working electrode after deposition, washing and drying to obtain the molybdenum-doped bismuth vanadate photoelectricity.
Preferably, in the step (2), the concentration of the molybdenum acetylacetonate in the molybdenum acetylacetonate dimethyl sulfoxide solution is 2-3 mmol/L, and the concentration of the vanadyl acetylacetonate in the molybdenum acetylacetonate dimethyl sulfoxide solution is 0.15-0.25 mol/L.
Preferably, the heating in the step (2) is to directly dropwise add 150-400 μ L of dimethyl sulfoxide solution to the surface of bismuth oxyiodide and then heat in a muffle furnace, wherein the heating rate is controlled to be 1.5-3 ℃/min.
Preferably, the simulated solar radiation in step (3) is provided with a solar radiation intensity of 1.5 AM.
Preferably, the deposition time adopted in the step (3) is stopped after the cobalt-phosphorus deposition time is 120-140 s.
The cobalt-phosphorus modified molybdenum-doped bismuth vanadate (CoPi/Mo/BiVO) prepared by the method4) And a photoelectrode.
BiVO is synthesized by the invention4Growing to the surface of FTO conductive glass, doping molybdenum element while growing, and then attaching CoPi to the surface of BiVO4 to form a uniform promoter layer. Modifying Mo/BiVO by CoPi4The photoelectrode is used for preparing hydrogen by decomposing water through photoelectrocatalysis, can effectively delay self-recombination of photon-generated carriers and increase the density of the photon-generated carriers, thereby promoting precipitation reaction on the surface of the photoelectrode.
Drawings
FIG. 1 shows the CoPi/Mo/BiVO4Scanning electron microscope photographs of the photoelectrode;
FIG. 2 shows the resulting CoPi/Mo/BiVO4High-definition transmission electron microscope photographs of the photoelectrode;
FIG. 3 shows the CoPi/Mo/BiVO4Linear scanning voltammetry curves of the photoelectrode and the contrast electrode under illumination;
FIG. 4 shows the CoPi/Mo/BiVO4Mott Schottky curves and fitted straight lines of the photoelectrode and the contrast electrode.
Detailed Description
In order to make the technical purpose, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention are further described with reference to specific examples, which are intended to explain the present invention and are not to be construed as limiting the present invention, and those who do not specify a specific technique or condition in the examples follow the techniques or conditions described in the literature in the art or follow the product specification.
A preparation method of a cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode comprises the following steps:
(1) using FTO conductive glass as a working electrode, a platinum sheet as a counter electrode, and an Ag/AgCl electrode (saturated KCl solution) as a reference electrode to form a three-electrode system, mixing an acidic solution containing bismuth nitrate and potassium iodide with an ethanol solution of p-benzoquinone to serve as an electrolyte, depositing the electrolyte with a constant potential of-0.1V (vs. Ag/AgCl) for 180s, taking out the working electrode, washing the working electrode with deionized water, and drying to obtain a bismuth oxyiodide photoelectrode;
(2) dropwise adding 400 mu L of dimethyl sulfoxide solution containing 0.2M vanadyl acetylacetonate and 2.5mM molybdenum acetylacetonate on the surface of bismuth oxyiodide of the bismuth oxyiodide electrode obtained in the step (1) to uniformly spread the dimethyl sulfoxide solution of the molybdenum acetylacetonate and the vanadyl acetylacetonate on the surface of the bismuth oxyiodide material, then placing the bismuth oxyiodide material into a muffle furnace for heating, raising the temperature to 450 ℃ at the speed of 2 ℃/min, keeping the constant temperature for 2 hours, and naturally cooling to room temperature to obtain the Mo/BiVO-loaded bismuth oxide electrode4An electrode of the thin film; will load Mo/BiVO4The electrode of the film is placed in 1mol/L NaOH aqueous solution and stirred for 30 minutes to remove the loaded Mo/BiVO4Residual V of electrode surface of thin film2O5Then washed by deionized water and dried to obtain Mo/BiVO4And an electrode.
(3) Taking the molybdenum-doped bismuth vanadate photoelectricity obtained in the step (2) as a working electrode, a platinum sheet as a counter electrode, and an Ag/AgCl electrode as a reference electrode to form a three-electrode system, taking an aqueous solution containing 5mmol/L cobalt nitrate and 0.1mol/L sodium phosphate as an electrolyte, assisting in simulated sunlight irradiation with 1.5AM light intensity, adopting a potentiostatic method, taking 0.4V as a constant potential, and depositing the charge of 0.07C, taking out the working electrode after deposition, washing and drying to obtain the CoPi/Mo/BiVO4And a photoelectrode.
Wherein the electrolyte in the step (1) is prepared by uniformly mixing an acidic aqueous solution containing bismuth nitrate and potassium iodide with an ethanol solution of p-benzoquinone according to the volume ratio of 5: 2; wherein the concentration of bismuth nitrate in the acidic aqueous solution containing bismuth nitrate and potassium iodide is 0.04M, the concentration of potassium iodide is 0.4M, the pH of the mixed solution of bismuth nitrate and potassium iodide is adjusted to 1.7 by using 5wt% of dilute nitric acid, and the concentration of p-benzoquinone in the ethanol solution of p-benzoquinone is 0.23M.
FIG. 1 is CoPi/Mo/BiVO4The scanning electron micrograph of the structure on the photoelectrode is magnified by 30000 times and is obviously visible, and the prepared CoPi/Mo/BiVO4The tissue is a rod-shaped structure, the size is uniform, and the diameter of the rod-shaped tissue is 100-200 nm. FIG. 2 is CoPi/Mo/BiVO4Microstructure of the structure, it is obvious that the deposited CoPi is distributed on the surface of the substrate doped with the molybdenum bismuth vanadate in a dense cellular shape.
To help understand BiVO4And CoPi/Mo/BiVO4The difference in the photoelectrocatalytic properties of (A) is shown in FIG. 3, which is BiVO4、Mo/BiVO4、CoPi/BiVO4And CoPi/Mo/BiVO4From the linear sweep voltammogram under the illumination condition, CoPi/Mo/BiVO was observed at a voltage of 1.23V vs. RHE (0.6V vs. Ag/AgCl)4The photocurrent of the light source is up to 2.38mA cm-22.975 times the photocurrent of BiVO 4.
In order to verify that molybdenum is successfully doped into a bismuth vanadate matrix in the doping process, BiVO is tested4、Mo/BiVO4、CoPi/BiVO4And CoPi/Mo/BiVO4The mott schottky curve of the photoelectrode is shown in fig. 4. As can be seen from FIG. 4, the photo-generated carrier density of the photoelectrode doped with molybdenum element is obviously higher than that of the photoelectrode not doped with molybdenum elementThe larger the impurity, the smaller the slope of the line to which the mott schottky curve fits. The increase of the density of the photogenerated carriers means that the photocurrent density under the same degree of illumination is higher, and the precipitation reaction of the action is stronger.
Finally, the parameters for preparing the composite photo-electrode can be adjusted in a corresponding range, and the obviously increased fluid, the semiconductor material and the cocatalyst can be correspondingly replaced and modified. The above embodiments are merely intended to illustrate the technical solution of the present invention and not to limit the same, and although the present invention has been described with reference to preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.

Claims (8)

1. A preparation method of a cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode is characterized by comprising the following steps:
(1) preparing a bismuth oxyiodide photoelectrode by using a-0.1V constant potential electrodeposition method by using conductive glass FTO as a substrate, a platinum sheet as a counter electrode, an Ag/AgCl electrode as a reference electrode and an acidic solution containing bismuth nitrate and potassium iodide and an ethanol solution of p-benzoquinone as electrolyte;
(2) dropwise adding dimethyl sulfoxide solutions of molybdenum acetylacetonate and vanadyl acetylacetonate on the bismuth oxyiodide electrode obtained in the step (1), heating to 450 ℃, keeping the temperature for 1.5-2.5 hours at a constant temperature, cooling to room temperature, soaking in an alkali solution, cleaning, and drying to obtain a molybdenum-doped bismuth vanadate photoelectrode;
(3) and (3) taking the molybdenum-doped bismuth vanadate photoelectrode obtained in the step (2) as a working electrode, a platinum sheet as a counter electrode and an Ag/AgCl electrode as a reference electrode to form a three-electrode system, taking an aqueous solution containing 4-6 mmol/L of metal cobalt salt and 0.075-0.15 mol/L of phosphate as an electrolyte, depositing by adopting a potentiostatic method under the irradiation of simulated sunlight, taking the deposition time between 120-140 s, taking out the working electrode after deposition, washing by deionized water and drying to obtain the cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode.
2. The method for preparing a cobalt phosphide-modified molybdenum-doped bismuth vanadate photoelectrode according to claim 1, which is characterized in that: in the step (2), the concentration of the molybdenum acetylacetonate in the dimethyl sulfoxide solution of the molybdenum acetylacetonate is 2-3 mmol/L, and the concentration of the vanadyl acetylacetonate in the dimethyl sulfoxide solution of the vanadyl acetylacetonate is 0.15-0.25 mol/L.
3. The method for preparing a cobalt phosphide-modified molybdenum-doped bismuth vanadate photoelectrode according to claim 1, which is characterized in that: in the step (2), the temperature raising treatment condition is 450 ℃ in the air atmosphere, and the temperature is kept for 1.5-2.5 hours.
4. The method for preparing a cobalt phosphide-modified molybdenum-doped bismuth vanadate photoelectrode according to claim 1, which is characterized in that: the temperature rise rate in the step (2) is controlled to be 1.5-3 ℃/min.
5. The method for preparing a cobalt phosphide-modified molybdenum-doped bismuth vanadate photoelectrode according to claim 1, which is characterized in that: the alkali solution in the step (2) is one of sodium hydroxide solution and potassium hydroxide solution.
6. The method for preparing a cobalt phosphide-modified molybdenum-doped bismuth vanadate photoelectrode according to claim 1, which is characterized in that: the metal cobalt salt in the step (3) is one of cobalt nitrate, cobalt sulfate and cobalt chloride, and the concentration is 5 mmol/L.
7. The method for preparing a cobalt phosphide-modified molybdenum-doped bismuth vanadate photoelectrode according to claim 1, which is characterized in that: the phosphate in the step (3) is one of sodium phosphate and potassium phosphate, and the concentration is 0.1 mmol/L.
8. The method for preparing a cobalt phosphide-modified molybdenum-doped bismuth vanadate photoelectrode according to claim 1, which is characterized in that: the constant potential in the step (3) is any potential between 0.35V and 0.45V, and the deposition time is 120-140 s.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112266045A (en) * 2020-09-21 2021-01-26 华南理工大学 Photoanode for retarding corrosion in photoelectrocatalysis wastewater treatment process by utilizing amorphous cobalt phosphate Co-Pi and preparation method and application thereof

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