CN109650493B - VS with hierarchical structure2Synthesis method of nanosheet array electrode material - Google Patents
VS with hierarchical structure2Synthesis method of nanosheet array electrode material Download PDFInfo
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Abstract
VS with hierarchical structure2The synthesis method of the nano-sheet array electrode material adopts an electrochemical anodic oxidation method to carry out carbon clothProcessing; then adding a vanadium source and a sulfur source into deionized water under stirring to obtain a suspension A; adding dodecyl dimethyl amine oxide into the suspension A and uniformly stirring to obtain a solution B; putting the solution B and the treated carbon cloth into a high-pressure reaction kettle, and then putting the high-pressure reaction kettle into a reaction oven for hydrothermal reaction; after the reaction is finished, cooling the reaction kettle to room temperature, alternately washing the product with deionized water and ethanol for a plurality of times, and then drying in vacuum to obtain VS with a hierarchical structure2A nanosheet array electrode material. The method adopts a high-efficiency, simple and low-cost one-step hydrothermal method to prepare the vanadium disulfide nanosheet array electrocatalyst on the carbon cloth, and effectively improves the hydrogen evolution performance of electrolyzed water.
Description
Technical Field
The invention belongs to the field of electrolytic water catalysis, relates to preparation of an electrolytic water catalysis electrode material, and particularly relates to VS with a hierarchical structure2A synthesis method of a nano-sheet array electrode material.
Background
With the increase of global population and the rapid development of economy, a series of problems such as large energy demand, serious waste, exhaustion of fossil fuel, carbon emission, greenhouse effect and the like are forcing the global energy to carry out a thorough energy revolution. Practice proves that the energy structure mainly based on fossil fuel can not meet the requirements of human social development. Therefore, the search for clean, efficient, renewable energy sources and energy carriers is the focus of discussion and research in today's society. Hydrogen energy is a green sustainable energy of a new generation, and people hope for it. The electrocatalytic water decomposition technology is one of the effective ways for producing hydrogen.
The transition metal sulfide has the advantages of rich content, low cost and the like, and has wide application in the aspect of electrocatalytic water crackingAnd (4) foreground. Wherein VS2The intrinsic metal characteristics and the advantage of low price of the material are widely concerned. Research shows that vanadium has flexible valence state (+3, +4, +5) and excellent reaction activity, and the combination of the catalyst and the conducting substrate can promote charge transmission effectively and raise the catalytic activity and stability obviously.
Disclosure of Invention
The invention aims to provide a VS with a hierarchical structure2The synthesis method of the nanosheet array electrode material is simple to operate, mild in reaction condition, short in time consumption, low in cost, high in purity of the prepared vanadium disulfide product, uniform in appearance and size, and excellent in electrocatalytic hydrogen evolution performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
1) treating the carbon cloth by adopting an electrochemical anodic oxidation method, wherein the selected electrolyte is 3-5 mol/L ammonium dihydrogen phosphate, the electrolytic current is 0.2-0.6A, and then, drying in vacuum;
2) according to the following steps: (3-6) taking a vanadium source and a sulfur source according to the molar ratio, and adding the vanadium source and the sulfur source into 25-40 ml of deionized water under stirring to enable the concentration of the vanadium source to be 15-30 mol/L to obtain suspension A;
3) adding 0.002-0.02 g of dodecyl dimethyl amine oxide into the suspension A, and uniformly stirring to obtain a solution B;
4) putting the solution B and the carbon cloth treated in the step 1) into a high-pressure reaction kettle, and then putting the high-pressure reaction kettle into a reaction oven for hydrothermal reaction;
5) after the reaction is finished, cooling the reaction kettle to room temperature, alternately washing the product with deionized water and ethanol for a plurality of times, and then drying in vacuum to obtain VS with a hierarchical structure2A nanosheet array electrode material.
The vacuum drying temperature in the step 1) is 40-60 ℃, and the drying time is 4-12 h.
The vanadium source in the step 2) is one or a mixture of more than one of vanadium acetylacetonate, sodium metavanadate or sodium vanadate dodecahydrate in any proportion.
The sulfur source in the step 2) is one or a mixture of more than one of thiourea, thioacetamide and sodium sulfide in any proportion.
The hydrothermal reaction temperature in the step 4) is 150-170 ℃, and the reaction time is 18-26 h.
The vacuum drying temperature in the step 5) is 40-60 ℃, and the drying time is 4-12 h.
The method adopts a high-efficiency, simple and low-cost one-step hydrothermal method to prepare the vanadium disulfide nanosheet array electrocatalyst on the carbon cloth, and effectively improves the hydrogen evolution performance of electrolyzed water.
Compared with the prior art, the invention can obtain the following beneficial effects:
1) the invention adopts a one-step hydrothermal method by introducing dodecyl dimethyl amine oxide as a surfactant to prepare VS with uniform appearance and hierarchical structure2A nanosheet array electrode material.
2) The one-step hydrothermal process has the advantages of low cost, short reaction period, mild reaction conditions, simple preparation process, stable product quality, uniform appearance, environmental friendliness and suitability for large-scale production.
3) Hierarchical VS prepared by the invention2The nanosheet array greatly improves the catalytic activity of the catalyst, has a two-dimensional ultrathin nanosheet structure, exposes more catalytic active sites, can be used as an excellent electrocatalytic oxygen production electrocatalyst at 100mA/cm2The overpotential can be as low as 369mV at the current density of (1).
Drawings
FIG. 1 is VS grown on carbon cloth prepared in example 3 of the present invention2X-ray diffraction (XRD) pattern of (a);
FIG. 2 is VS grown on carbon cloth prepared in example 3 of the present invention2Scanning Electron Microscope (SEM) photograph of (a);
FIG. 3 is VS grown on carbon cloth prepared in example 3 of the present invention2Linear Sweep Voltammetry (LSV) performance test plots.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific embodiments:
example 1:
1) treating (1 × 5) cm carbon cloth by electrochemical anodic oxidation method, wherein the electrolyte is 3mol/L ammonium dihydrogen phosphate, the electrolytic current is 0.2A, and vacuum drying is carried out at 40 deg.C for 12 h;
2) according to the following steps: 3, taking vanadium acetylacetonate and thioacetamide according to the molar ratio, and adding a vanadium source and a sulfur source into 25ml of deionized water under stirring to ensure that the concentration of the vanadium source is 15mol/L to obtain a suspension A;
3) adding 0.002g of dodecyl dimethyl amine oxide into the suspension A, and uniformly stirring to obtain a solution B;
4) putting the solution B and the carbon cloth treated in the step 1) into a high-pressure reaction kettle, and then putting the high-pressure reaction kettle into a reaction oven to perform hydrothermal reaction for 18 hours at 150 ℃;
5) after the reaction is finished, cooling the reaction kettle to room temperature, alternately washing the product with deionized water and ethanol for 3 times, and drying the product in vacuum at 40 ℃ for 12 hours to obtain VS with a hierarchical structure2A nanosheet array electrode material.
Example 2:
1) treating (1 × 5) cm carbon cloth by electrochemical anodic oxidation method, wherein the selected electrolyte is ammonium dihydrogen phosphate with concentration of 4mol/L, the electrolysis current is 0.4A, and vacuum drying is carried out at 50 deg.C for 10 h;
2) according to the following steps: 5, taking sodium metavanadate and thiourea, adding a vanadium source and a sulfur source into 30ml of deionized water under stirring to enable the concentration of the vanadium source to be 25mol/L, and obtaining a suspension A;
3) adding 0.003g of dodecyl dimethyl amine oxide into the suspension A, and uniformly stirring to obtain a solution B;
4) putting the solution B and the carbon cloth treated in the step 1) into a high-pressure reaction kettle, and then putting the high-pressure reaction kettle into a reaction oven to perform hydrothermal reaction for 20 hours at 170 ℃;
5) after the reaction is finished, cooling the reaction kettle to room temperature, alternately washing the product with deionized water and ethanol for 3 times, and then drying the product in vacuum at 50 ℃ for 10 hours to obtain VS with a hierarchical structure2A nanosheet array electrode material.
Example 3:
1) treating (1 × 5) cm carbon cloth by electrochemical anodic oxidation method, wherein the electrolyte is ammonium dihydrogen phosphate with concentration of 5mol/L and the electrolytic current is 0.6A, and vacuum drying at 60 deg.C for 4 h;
2) according to the following steps: 6, taking sodium vanadate dodecahydrate and thioacetamide according to the molar ratio, and adding a vanadium source and a sulfur source into 35ml of deionized water under stirring to ensure that the concentration of the vanadium source is 30mol/L to obtain a suspension A;
3) adding 0.02g of dodecyl dimethyl amine oxide into the suspension A, and uniformly stirring to obtain a solution B;
4) putting the solution B and the carbon cloth treated in the step 1) into a high-pressure reaction kettle, and then putting the high-pressure reaction kettle into a reaction oven to perform hydrothermal reaction for 26 hours at 160 ℃;
5) after the reaction is finished, cooling the reaction kettle to room temperature, alternately washing the product with deionized water and ethanol for 3 times, and drying the product in vacuum at 60 ℃ for 4 hours to obtain VS with a hierarchical structure2A nanosheet array electrode material.
VS prepared in this example2The position where X-ray diffraction peak appears is shown as VS in FIG. 12Characteristic peaks of (A) indicating successful synthesis of VS2An electrode material.
From the SEM image of fig. 2, it can be seen that the sample is an array of nanosheets grown on carbon cloth, forming a VS with a hierarchical structure2A nanosheet array electrode material.
As can be seen from the linear scanning voltammogram of FIG. 3, the sample has a current density of 100mA/cm2When the material is used, the overpotential is low and is as low as 369mV, and the material has good electrocatalytic hydrogen evolution activity.
Example 4:
1) treating (1 × 5) cm carbon cloth by electrochemical anodic oxidation method, wherein the electrolyte is 3.5mol/L ammonium dihydrogen phosphate, the electrolytic current is 0.3A, and vacuum drying is carried out at 55 deg.C for 6 h;
2) according to the following steps: 4, taking a mixture of vanadium acetylacetonate and sodium metavanadate and sodium sulfide according to the molar ratio, and adding a vanadium source and a sulfur source into 40ml of deionized water under stirring to enable the concentration of the vanadium source to be 20mol/L to obtain a suspension A;
3) adding 0.01g of dodecyl dimethyl amine oxide into the suspension A, and uniformly stirring to obtain a solution B;
4) putting the solution B and the carbon cloth treated in the step 1) into a high-pressure reaction kettle, and then putting the high-pressure reaction kettle into a reaction oven to perform hydrothermal reaction for 24 hours at 155 ℃;
5) after the reaction is finished, cooling the reaction kettle to room temperature, alternately washing the product with deionized water and ethanol for 4 times, and then drying the product in vacuum at 55 ℃ for 6 hours to obtain VS with a hierarchical structure2A nanosheet array electrode material.
Example 5:
1) treating (1 × 5) cm carbon cloth by electrochemical anodic oxidation method, wherein the electrolyte is ammonium dihydrogen phosphate with concentration of 4.5mol/L, the electrolysis current is 0.5A, and vacuum drying is carried out at 45 deg.C for 8 h;
2) according to the following steps: taking a mixture of vanadium acetylacetonate, sodium metavanadate and sodium dodecahydrate and a mixture of thioacetamide and thiourea according to a molar ratio of 6, and adding a vanadium source and a sulfur source into 30ml of deionized water under stirring to enable the concentration of the vanadium source to be 28mol/L so as to obtain a suspension A;
3) adding 0.015g of dodecyl dimethyl amine oxide into the suspension A, and uniformly stirring to obtain a solution B;
4) putting the solution B and the carbon cloth treated in the step 1) into a high-pressure reaction kettle, and then putting the high-pressure reaction kettle into a reaction oven to perform hydrothermal reaction for 20 hours at 165 ℃;
5) after the reaction is finished, cooling the reaction kettle to room temperature, alternately washing the product with deionized water and ethanol for 5 times, and drying the product in vacuum at 45 ℃ for 8 hours to obtain VS with a hierarchical structure2A nanosheet array electrode material.
Claims (6)
1. VS with hierarchical structure2The synthesis method of the nanosheet array electrode material is characterized by comprising the following steps:
1) treating the carbon cloth by adopting an electrochemical anodic oxidation method, wherein the selected electrolyte is 3-5 mol/L ammonium dihydrogen phosphate, the electrolytic current is 0.2-0.6A, and then, drying in vacuum;
2) according to the following steps: (3-6) taking a vanadium source and a sulfur source according to the molar ratio, adding the vanadium source and the sulfur source into 25ml-40ml of deionized water under stirring to enable the concentration of the vanadium source to be 15-30 mol/L, and obtaining a suspension A;
3) adding 0.002-0.02 g of dodecyl dimethyl amine oxide into the suspension A, and uniformly stirring to obtain a solution B;
4) putting the solution B and the carbon cloth treated in the step 1) into a high-pressure reaction kettle, and then putting the high-pressure reaction kettle into a reaction oven for hydrothermal reaction;
5) after the reaction is finished, cooling the reaction kettle to room temperature, alternately washing the product with deionized water and ethanol for a plurality of times, and then drying in vacuum to obtain VS with a hierarchical structure2A nanosheet array electrode material.
2. The hierarchically structured VS of claim 12The synthesis method of the nanosheet array electrode material is characterized by comprising the following steps: the vacuum drying temperature in the step 1) is 40-60 ℃, and the drying time is 4-12 h.
3. The hierarchically structured VS of claim 12The synthesis method of the nanosheet array electrode material is characterized by comprising the following steps: the vanadium source in the step 2) is one or a mixture of more than one of vanadium acetylacetonate, sodium metavanadate or sodium vanadate dodecahydrate in any proportion.
4. The hierarchically structured VS of claim 12The synthesis method of the nanosheet array electrode material is characterized by comprising the following steps: the sulfur source in the step 2) is one or a mixture of more than one of thiourea, thioacetamide and sodium sulfide in any proportion.
5. The hierarchically structured VS of claim 12The synthesis method of the nanosheet array electrode material is characterized by comprising the following steps: the hydrothermal reaction temperature in the step 4) is 150-170 ℃, and the reaction time is 18-26 h.
6. The hierarchically structured VS of claim 12The synthesis method of the nanosheet array electrode material is characterized by comprising the following steps: the vacuum drying temperature in the step 5) is 40-60 ℃, and the drying time is 4-12 h.
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| CN110064409B (en) * | 2019-05-10 | 2022-03-11 | 深圳大学 | Pt/VS2Catalytic material, preparation method and application thereof |
| CN110171828B (en) * | 2019-06-14 | 2021-02-09 | 陕西科技大学 | FeS nano material based on carbon cloth directional growth and preparation method and application thereof |
| CN113206235B (en) * | 2021-04-30 | 2022-11-18 | 陕西科技大学 | Multi-component (V, zn) metal sulfide and preparation method thereof |
| CN114142043B (en) * | 2021-11-30 | 2023-10-27 | 成都先进金属材料产业技术研究院股份有限公司 | Method for improving electrochemical performance of electrode for vanadium battery |
| CN114142048B (en) * | 2021-11-30 | 2023-10-27 | 成都先进金属材料产业技术研究院股份有限公司 | Electrode modification method for vanadium battery |
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