CN112301374A - Self-assembled vanadium modified NiSe/Ni3Se2Self-supporting electrode and synthesis method and application thereof - Google Patents

Self-assembled vanadium modified NiSe/Ni3Se2Self-supporting electrode and synthesis method and application thereof Download PDF

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CN112301374A
CN112301374A CN202011160489.0A CN202011160489A CN112301374A CN 112301374 A CN112301374 A CN 112301374A CN 202011160489 A CN202011160489 A CN 202011160489A CN 112301374 A CN112301374 A CN 112301374A
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nise
supporting electrode
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曹丽云
韩瑞雪
何丹阳
冯亮亮
黄剑锋
黄青青
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Shaanxi University of Science and Technology
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    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract

The invention discloses self-assembled vanadium modified NiSe/Ni3Se2In the synthesis method, foam nickel is used as a substrate, a selenium powder hydrazine hydrate solution is used as a selenium source, sodium metavanadate is used as a vanadium source, polyallylamine hydrochloride is used as a morphology regulator, and a hydrothermal method is adopted to synthesize and prepare the self-assembled vanadium modified NiSe/Ni3Se2The self-supporting electrode has mild process conditions, low cost, short preparation period and easy control of process, and the obtained self-assembled vanadium-modified NiSe/Ni3Se2The self-supporting electrode is beneficial to exposing more catalytic active sites and accelerating the intersection of substances on a multiphase heterogeneous interfaceThe transfer rate of the exchanged electrons is coordinated to enhance the catalytic activity and stability of the material, the current density is high, the long-term circulation stability and the high activity of the electrocatalytic reaction are realized, the electrocatalytic hydrogen production method is applied to the electrolytic water reaction under the alkaline condition, the high electrocatalytic activity is realized, and the electrocatalytic hydrogen production performance is improved.

Description

Self-assembled vanadium modified NiSe/Ni3Se2Self-supporting electrode and synthesis method and application thereof
Technical Field
The invention belongs to the field of new energy material preparation, relates to synthesis of a metallic nano array structure, and particularly relates to self-assembled vanadium-modified NiSe/Ni3Se2Self-supporting electrode, synthesis method and application.
Background
With the depletion of traditional fossil fuels and a series of environmental and social problems brought by the depletion of the traditional fossil fuels, the development of clean, safe, efficient and renewable new energy sources is particularly important for the sustainable development of society. At present, new energy sources such as solar energy, wind energy, tidal energy and biomass energy are widely applied in various fields, but the new energy sources are generally highly dependent on natural environments such as time and climate, have intermittent and discontinuous characteristics, and are difficult to meet the requirement of sustainable energy sources. Hydrogen (H)2) As one of the most ideal clean energy carriers in the 21 st century, the fuel has high combustion heat value (the energy density is 142MJ kg)-1) 3 times of gasoline, 3.9 times of alcohol and 4.5 times of coke; the product of hydrogen combustion is water, so that the environment is not polluted; and the method has rich resources and sustainable development, and arouses the wide attention of people, so how to efficiently and environmentally prepare the hydrogen is a key problem which needs to be solved urgently at present.
In recent years, researchers have made some breakthrough progress in the development of metal selenide hydrogen production electrocatalyst, and have confirmed that metal selenide really has excellent electrocatalytic hydrogen production performance. Wherein, metallic nickel-based selenide (NiSe )2And Ni3Se2) It has better electrocatalytic activity than the corresponding semiconductor/insulating catalyst, and is favored by researchers because electrons can realize faster electron transport in the metal electrocatalytic phase. At present, Sivanantham et al successfully synthesized Ni3Se2NF self-supporting electrodes, whose microstructure consists of aggregated particles, do not really achieve an exposure to the catalytic activity of the material, which is detrimental to the next stepStep lifting of Ni3Se2Electrocatalytic performance of the/NF material. NiSe/Ni with blocky appearance prepared by Zhang et al3Se2The self-supporting electrode has poor particle dispersibility and easy agglomeration, reduces the exposed area of reaction active sites, is not beneficial to the rapid transmission of electrons on an interface, and limits the activity of an electrocatalyst. Accordingly, further improvements are needed in the art.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides self-assembled vanadium modified NiSe/Ni3Se2Self-supporting electrode, synthesis method and application, mild synthesis and preparation conditions, low cost, short preparation period and easy control of technological process, and the obtained self-assembled vanadium-modified NiSe/Ni3Se2The self-supporting electrode is beneficial to exposing more catalytic active sites, and the exchange of substances at a multiphase heterogeneous interface and the transfer rate of electrons are accelerated, so that the catalytic activity and the stability of the material are synergistically enhanced.
In order to achieve the aim, the invention provides self-assembled vanadium modified NiSe/Ni3Se2The synthesis method of the self-supporting electrode comprises the following steps:
1) taking foamed nickel, cleaning and drying for later use;
2) weighing 77.96-79.96 mg of selenium powder, adding 1.8-2.2 ml of hydrazine hydrate, and uniformly stirring to obtain a solution A;
3) weighing 34.817-34.837 mg of sodium metavanadate and 25-30 mg of polyallylamine hydrochloride;
4) adding 18-22 mL of ultrapure water into a high-temperature high-pressure reaction kettle, adding the solution A obtained in the step 2) and the sodium metavanadate and polyallylamine hydrochloride obtained in the step 3) into the high-temperature high-pressure reaction kettle, and uniformly stirring to obtain a solution B;
5) putting 220-225 mg of foamed nickel obtained in the step 1) into a high-temperature high-pressure reaction kettle filled with the solution B, reacting for 10-15 h at 175-185 ℃, naturally cooling to room temperature after the reaction is finished, taking out the foamed nickel, cleaning and drying to obtain the NiSe/Ni modified by the self-assembled vanadium3Se2A self-supporting electrode.
Further, in the step 1), the foamed nickel is ultrasonically cleaned by acetone, hydrochloric acid, deionized water and absolute ethyl alcohol in sequence, impurities and an oxidation layer on the surface of the foamed nickel are removed, the foamed nickel is washed to be neutral, and the foamed nickel is dried at normal temperature.
Further, the concentration of the hydrochloric acid is 2.8-3.2 mol L-1The ultrasonic treatment time of acetone is 10-15 min, and the ultrasonic treatment time of hydrochloric acid, deionized water and absolute ethyl alcohol is 5-10 min respectively.
Further, the stirring in the step 2) is magnetic stirring at 45-55 ℃ for 1-1.2 h.
Further, the stirring in the step 4) is magnetic stirring at normal temperature.
Further, the high-temperature high-pressure reaction kettle comprises a p-polyphenyl lining, and the filling ratio of the high-temperature high-pressure reaction kettle in the step 5) is controlled to be 40-48%.
Further, repeatedly washing the foamed nickel reacted in the step 5) with ultrapure water and absolute ethyl alcohol for multiple times respectively, and then carrying out vacuum drying at the drying temperature of 50-60 ℃ for 4-5 h.
The invention also provides self-assembled vanadium modified NiSe/Ni3Se2The self-supporting electrode is prepared by adopting the synthesis method.
Further, self-assembling vanadium modified NiSe/Ni3Se2Electrolyzing water with a self-supporting electrode in 1M KOH solution at 100mA cm-2The overpotential for hydrogen production is 280-290 mV and the overpotential for oxygen production is 0.3-0.4 mV under the current density.
The invention also provides self-assembled vanadium modified NiSe/Ni3Se2The self-supporting electrode is applied to electrolytic water reaction under alkaline conditions.
Compared with the prior art, the invention has the following advantages:
1) the hydrothermal method adopted by the synthesis method has the characteristics of simple process, short preparation period and easily controlled reaction conditions, the reaction process and the morphology size are controlled by adjusting the temperature, various special structural morphologies can be obtained, and different morphological characteristics have great influence on the performance of the material.
2) The hydrothermal method has the advantages of high reaction rate, full reaction and the like, and overcomes the defects of difficult occurrence and control, low yield, complex process and the like of the traditional preparation process.
3) Preparation of self-assembled vanadium modified NiSe/Ni by using foamed nickel as substrate3Se2The structure of the self-supporting electrode is beneficial to exposing more catalytic active sites, and the exchange rate of substances at a multiphase heterogeneous interface and the transfer rate of electrons are accelerated, so that the catalytic activity and the stability of the material are synergistically enhanced.
4) Polyallylamine hydrochloride as morphology control agent: compared with the traditional preparation method, the method has the advantages that the process operation is simple, the synthesis is easy, the impurity ions and the surplus morphology regulating agent in the solution can be removed by using deionized water, the surplus morphology regulating agent is a recyclable green chemical reagent, and the method is environment-friendly and pollution-free.
In the synthetic method, foam nickel is used as a substrate, a selenium powder hydrazine hydrate solution is used as a selenium source, sodium metavanadate is used as a vanadium source, polyallylamine hydrochloride is used as a morphology regulator, and a two-step method is used for synthesizing the self-assembly vanadium modified NiSe/Ni with the interface effect3Se2The self-supporting electrode has mild process conditions, low cost, short preparation period, easy control of process, simple method and easy operation, and the self-assembly vanadium modified NiSe/Ni3Se2The self-supporting electrode is used as an electrode to carry out electrolytic water reaction in a 1M KOH solution at 100mAcm-2The hydrogen generation overpotential is 280-290 mV at 100mA cm under the current density-2The overpotential of oxygen generation is 0.3-0.4 mV under the current density, and the current density is high, and the long-term circulation stability and the high activity of electrocatalysis reaction are realized. The self-assembled vanadium-modified NiSe/Ni prepared by the invention3Se2The self-supporting electrode is used for water electrolysis reaction under an alkaline condition, has higher electro-catalytic activity and improves the electro-catalytic hydrogen production performance.
Drawings
FIG. 1 is a self-assembled vanadium modified prepared in example 2 of the present inventionNiSe/Ni3Se2An X-ray diffraction pattern of the self-supporting electrode material;
FIG. 2 is a self-assembled vanadium modified NiSe/Ni prepared in example 3 of the present invention3Se2Scanning electron micrographs of the self-supporting electrode material;
FIG. 3 is the self-assembled vanadium modified NiSe/Ni prepared in example 3 of the present invention3Se2A linear sweep voltammetry performance graph of hydrogen production from a self-supporting electrode;
FIG. 4 is the self-assembled vanadium modified NiSe/Ni prepared in example 3 of the present invention3Se2Linear sweep voltammogram performance plots of oxygen production from a free-standing electrode.
Detailed Description
The present invention will be further explained with reference to the drawings and specific examples in the specification, and it should be understood that the examples described are only a part of the examples of the present application, and not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention provides self-assembled vanadium modified NiSe/Ni3Se2The synthesis method of the self-supporting electrode comprises the following steps:
1) taking foamed nickel, cleaning and drying for later use; preferably, the foamed nickel is ultrasonically cleaned by acetone, hydrochloric acid, deionized water and absolute ethyl alcohol in sequence, impurities and an oxidation layer on the surface of the foamed nickel are removed, the foamed nickel is washed to be neutral, and the foamed nickel is dried at normal temperature; more preferably, the concentration of the hydrochloric acid is 2.8-3.2 mol L-1The ultrasonic treatment time of acetone is 10-15 min, and the ultrasonic treatment time of hydrochloric acid, deionized water and absolute ethyl alcohol is 5-10 min respectively. The normal temperature is room temperature, and is defined as 25 ℃.
2) Weighing 77.96-79.96 mg of selenium powder, adding 1.8-2.2 ml of hydrazine hydrate, and uniformly stirring to obtain a solution A; preferably, the stirring is magnetic stirring at 45-55 ℃ for 1-1.2 h.
3) Weighing 34.817-34.837 mg of sodium metavanadate and 25-30 mg of polyallylamine hydrochloride;
4) adding 18-22 mL of ultrapure water into a high-temperature high-pressure reaction kettle, adding the solution A obtained in the step 2) and the sodium metavanadate and polyallylamine hydrochloride obtained in the step 3) into the high-temperature high-pressure reaction kettle, and uniformly stirring to obtain a solution B; preferably, the stirring is magnetic stirring at normal temperature. Preferably, the autoclave comprises a lining of polyparaphenylene.
5) Putting 220-225 mg of the foamed nickel obtained in the step 1) into a high-temperature high-pressure reaction kettle filled with the solution B, reacting for 10-15 h at 175-185 ℃, naturally cooling to room temperature after the reaction is finished, taking out the foamed nickel, cleaning and drying to obtain the NiSe/Ni modified by the self-assembly vanadium3Se2A self-supporting electrode. Preferably, the filling ratio of the high-temperature high-pressure reaction kettle is controlled to be 40-48% during the reaction. Preferably, after the reacted foam nickel is repeatedly washed by ultrapure water and absolute ethyl alcohol for multiple times, vacuum drying is carried out, the drying temperature is 50-60 ℃, and the drying time is 4-5 hours.
The invention also provides the self-assembled vanadium modified NiSe/Ni prepared by the method3Se2Self-supporting electrode for electrolysis of water in 1M KOH solution at 100mA cm-2The overpotential for hydrogen production is 280-290 mV and the overpotential for oxygen production is 0.3-0.4 mV under the current density. The self-assembled vanadium modified NiSe/Ni3Se2The self-supporting electrode has the structure beneficial to exposing more catalytic active sites, accelerates the exchange of substances on a multiphase heterogeneous interface and the transfer rate of electrons, synergistically enhances the catalytic activity and stability of the material, has the advantages of high current density, long-term circulation stability and higher activity of electrocatalytic reaction, is applied to electrolytic water reaction under an alkaline condition, has higher electrocatalytic activity, and improves the electrocatalytic hydrogen production performance.
The invention is described in detail below with specific examples:
example 1:
1) using acetone with the concentration of 3mol L-1Ultrasonic cleaning the foamed nickel with dilute hydrochloric acid, deionized water and absolute ethyl alcohol in sequence to remove impurities and oxide layers on the surface, washing to neutrality, and drying at normal temperature to obtain the nickel-based composite materialTo the required foam nickel;
2) weighing selenium powder with the mass of 78.90mg, pouring the selenium powder into a beaker, adding 2ml of hydrazine hydrate, and magnetically stirring the mixture for 1.2 hours at the temperature of 45 ℃ to obtain a solution A;
3) weighing 34.825mg of sodium metavanadate as a vanadium source and 28mg of polyallylamine hydrochloride morphology regulator;
4) adding the mixed solution A in the step 2) and the vanadium source and the morphology regulating agent weighed in the step 3) into a high-temperature high-pressure reaction kettle with a para-polyphenyl lining filled with 20mL of pure water, and magnetically stirring at normal temperature to obtain a solution B;
5) putting 220-225 mg of foamed nickel treated in the step 1) into a high-temperature high-pressure reaction kettle with a p-polyphenyl lining filled with the solution B;
6) reacting the high-temperature high-pressure reaction kettle at 175 ℃ for 15h, naturally cooling to room temperature after the reaction is finished, taking out a sample, repeatedly washing the sample with ultrapure water and absolute ethyl alcohol for 5 times respectively, and finally drying the sample in vacuum at 50 ℃ for 5h, wherein the filling ratio of the high-temperature high-pressure reaction kettle is controlled to be 44%, so that the self-assembly vanadium modified NiSe/Ni3Se2A self-supporting electrode material.
Example 2:
1) using acetone with the concentration of 3mol L-1Ultrasonic cleaning the foamed nickel by dilute hydrochloric acid, deionized water and absolute ethyl alcohol in sequence, removing impurities and oxide layers on the surface, washing to be neutral, and drying at normal temperature to obtain the required foamed nickel;
2) weighing 78.58mg of selenium powder, pouring the selenium powder into a beaker, adding 2ml of hydrazine hydrate, and magnetically stirring the mixture for 1.2 hours at 47 ℃ to obtain solution A;
3) weighing 34.829mg of sodium metavanadate as a vanadium source and 25mg of polyallylamine hydrochloride morphology regulator;
4) adding the mixed solution A obtained in the step 2) and the vanadium source and the morphology regulating agent obtained in the step 3) into a high-temperature high-pressure reaction kettle filled with 19mL of pure water and lined with p-polyphenyl, and magnetically stirring at normal temperature to obtain a solution B;
5) putting 220-225 mg of foamed nickel treated in the step 1) into a high-temperature high-pressure reaction kettle with a p-polyphenyl lining filled with the solution B;
6) will be provided withStep 5) reacting the reaction kettle at 177 ℃ for 14h, naturally cooling to room temperature after the reaction is finished, taking out a sample, repeatedly washing the sample with ultrapure water and absolute ethyl alcohol for 5 times respectively, wherein the filling ratio of the reaction kettle is 42%, and performing vacuum drying at 50 ℃ for 5h to obtain the self-assembly vanadium modified NiSe/Ni3Se2A self-supporting electrode material.
Self-assembled vanadium modified NiSe/Ni prepared in example 23Se2The self-supporting electrode material is subjected to an X-ray diffraction test, referring to figure 1, the X-ray diffraction spectrum of the product can be seen, and the diffraction peak of the product is shown by a phase Ni3Se2(PDF- #85-0754), NiSe (PDF- #65-3425) and NiSe (PDF- #89-2058) prove that the NiSe/Ni can be successfully synthesized on the foamed nickel substrate3Se2A substance.
Example 3:
1) using acetone with the concentration of 3mol L-1Ultrasonic cleaning the foamed nickel by dilute hydrochloric acid, deionized water and absolute ethyl alcohol in sequence, removing impurities and oxide layers on the surface, washing to be neutral, and drying at normal temperature to obtain the required foamed nickel;
2) weighing 78.32mg of selenium powder, pouring the selenium powder into a beaker, adding 2ml of hydrazine hydrate, and magnetically stirring the mixture for 1 hour at the temperature of 50 ℃ to obtain a solution A;
3) weighing 34.834mg of sodium metavanadate as a vanadium source and 27mg of polyallylamine hydrochloride morphology regulating agent;
4) adding the mixed solution A obtained in the step 2) and the vanadium source and the morphology regulating agent obtained in the step 3) into a high-temperature high-pressure reaction kettle filled with 21mL of pure water and lined with p-polyphenyl, and magnetically stirring at normal temperature to obtain a solution B;
5) putting 220-225 mg of foamed nickel treated in the step 1) into a high-temperature high-pressure reaction kettle with a p-polyphenyl lining filled with the solution B;
6) reacting the reaction kettle in the step 5) at 179 ℃ for 13h, naturally cooling to room temperature after the reaction is finished, taking out a sample, repeatedly washing the sample with ultrapure water and absolute ethyl alcohol for 5 times respectively, wherein the filling ratio of the reaction kettle is 46%, and finally performing vacuum drying at 55 ℃ for 4.5h to obtain the self-assembly vanadium modified NiSe/Ni3Se2A self-supporting electrode material.
Self-assembled vanadium modified NiSe/Ni prepared in example 33Se2The self-supporting electrode material is subjected to electron microscope scanning, see FIG. 2, and NiSe/Ni can be seen from FIG. 23Se2The micro-morphology structure of the nano flower cluster is presented, and the surface of the nano flower cluster fully exposes catalytic active sites, thereby being beneficial to the transmission of electrons and promoting the generation of full hydrodynamic. The research shows that NiSe/Ni is constructed on foamed nickel3Se2The nano-sheet cluster electrode provides experience and feasibility support. In addition, the self-assembled vanadium modified NiSe/Ni prepared in example 33Se2The self-supporting electrode material is subjected to an electrolytic water reaction test to obtain a linear sweep voltammetry curve for hydrogen production and oxygen production, see fig. 3 and 4, and NiSe/Ni can be seen from fig. 3 and 43Se2Self-supporting electrode for electrolysis of water in 1MKOH solution at 100mAcm-2The overpotential for hydrogen production is 280-290 mV and the overpotential for oxygen production is 0.3-0.4 mV under the current density.
Example 4:
1) using acetone with the concentration of 3mol L-1Ultrasonic cleaning the foamed nickel by dilute hydrochloric acid, deionized water and absolute ethyl alcohol in sequence, removing impurities and oxide layers on the surface, washing to be neutral, and drying at normal temperature to obtain the required foamed nickel;
2) weighing 78.45mg selenium powder, pouring into a beaker, adding 2ml hydrazine hydrate, and magnetically stirring for 1h at 52 ℃ to obtain a solution A;
3) weighing 34.836mg of sodium metavanadate as a vanadium source and 29mg of polyallylamine hydrochloride morphology regulator;
4) adding the mixed solution A obtained in the step 2) and the vanadium source and the morphology regulating agent obtained in the step 3) into a high-temperature high-pressure reaction kettle filled with 22mL of water and lined with p-polyphenyl, and magnetically stirring at normal temperature to obtain a solution B;
5) putting 220-225 mg of foamed nickel treated in the step 1) into a high-temperature high-pressure reaction kettle with a p-polyphenyl lining filled with the solution B;
6) reacting the reaction kettle in the step 5) at 181 ℃ for 12h, naturally cooling to room temperature after the reaction is finished, taking out the sample, repeatedly washing with ultrapure water and absolute ethyl alcohol for 5 times respectively, and carrying out reverse reactionThe pot filling ratio is 48 percent, and finally the NiSe/Ni modified by the self-assembly vanadium is obtained after vacuum drying for 4.5h at 57 DEG C3Se2A self-supporting electrode material.
Example 5:
1) using acetone with the concentration of 3mol L-1Ultrasonic cleaning the foamed nickel by dilute hydrochloric acid, deionized water and absolute ethyl alcohol in sequence, removing impurities and oxide layers on the surface, washing to be neutral, and drying at normal temperature to obtain the required foamed nickel;
2) weighing 79.26mg of selenium powder, pouring the selenium powder into a beaker, adding 2ml of hydrazine hydrate, and magnetically stirring the mixture for 1 hour at the temperature of 55 ℃ to obtain a solution A;
3) weighing 34.836mg of sodium metavanadate as a vanadium source and 28mg of polyallylamine hydrochloride morphology regulator;
4) adding the mixed solution A obtained in the step 2) and the vanadium source and the morphology regulating agent obtained in the step 3) into a high-temperature high-pressure reaction kettle with a p-polyphenyl lining filled with 19mL of water, and magnetically stirring at normal temperature to obtain a solution B;
5) putting 220-225 mg of foamed nickel treated in the step 1) into a high-temperature high-pressure reaction kettle with a p-polyphenyl lining filled with the solution B;
6) reacting the reaction kettle in the step 5) at 183 ℃ for 11h, naturally cooling to room temperature after the reaction is finished, taking out a sample, repeatedly washing the sample for 5 times respectively with ultrapure water and absolute ethyl alcohol, wherein the filling ratio of the reaction kettle is 42%, and finally performing vacuum drying at 60 ℃ for 4h to obtain the self-assembly vanadium modified NiSe/Ni3Se2A self-supporting electrode material.
Example 6:
1) using acetone with the concentration of 3.2mol L-1Ultrasonic cleaning the foamed nickel by dilute hydrochloric acid, deionized water and absolute ethyl alcohol in sequence, removing impurities and oxide layers on the surface, washing to be neutral, and drying at normal temperature to obtain the required foamed nickel;
2) weighing 79.96mg of selenium powder, pouring the selenium powder into a beaker, adding 2.2ml of hydrazine hydrate, and magnetically stirring the mixture for 1.2h at the temperature of 55 ℃ to obtain a solution A;
3) weighing 34.837mg of sodium metavanadate and 30mg of polyallylamine hydrochloride;
4) adding the mixed solution A obtained in the step 2) and the vanadium source and the morphology regulating agent obtained in the step 3) into a high-temperature high-pressure reaction kettle filled with 22mL of water and lined with p-polyphenyl, and magnetically stirring at normal temperature to obtain a solution B;
5) putting 225mg of the foamed nickel treated in the step 1) into a high-temperature high-pressure reaction kettle with a p-polyphenyl lining filled with the solution B;
6) reacting the reaction kettle in the step 5) at 185 ℃ for 15h, naturally cooling to room temperature after the reaction is finished, taking out a sample, repeatedly washing the sample for 5 times respectively with ultrapure water and absolute ethyl alcohol, wherein the filling ratio of the reaction kettle is 48%, and finally performing vacuum drying at 60 ℃ for 4h to obtain the self-assembly vanadium modified NiSe/Ni3Se2A self-supporting electrode material.
Example 7:
1) using acetone with the concentration of 2.8mol L-1Ultrasonic cleaning the foamed nickel by dilute hydrochloric acid, deionized water and absolute ethyl alcohol in sequence, removing impurities and oxide layers on the surface, washing to be neutral, and drying at normal temperature to obtain the required foamed nickel;
2) weighing 77.96mg selenium powder, pouring into a beaker, adding 1.8ml hydrazine hydrate, and magnetically stirring for 1h at 45 ℃ to obtain a solution A;
3) weighing 34.817mg of sodium metavanadate and 25mg of polyallylamine hydrochloride;
4) adding the mixed solution A obtained in the step 2) and the vanadium source and the morphology regulating agent obtained in the step 3) into a high-temperature high-pressure reaction kettle filled with 18mL of water and lined with p-polyphenyl, and magnetically stirring at normal temperature to obtain a solution B;
5) putting 220mg of foamed nickel treated in the step 1) into a high-temperature high-pressure reaction kettle with a p-polyphenyl lining filled with the solution B;
6) reacting the reaction kettle in the step 5) at 175 ℃ for 10h, naturally cooling to room temperature after the reaction is finished, taking out a sample, repeatedly washing the sample for 5 times respectively with ultrapure water and absolute ethyl alcohol, wherein the filling ratio of the reaction kettle is 40%, and finally performing vacuum drying at 50 ℃ for 4h to obtain the self-assembly vanadium modified NiSe/Ni3Se2A self-supporting electrode material.
Example 8:
1) using acetone with the concentration of 2.9mol L-1Dilute hydrochloric acid, deionizationUltrasonically cleaning the foamed nickel by water and absolute ethyl alcohol in sequence, removing impurities and an oxidation layer on the surface, washing to be neutral, and drying at normal temperature to obtain the required foamed nickel;
2) weighing 78.96mg selenium powder, pouring into a beaker, adding 1.9ml hydrazine hydrate, and magnetically stirring at 50 ℃ for 1.1h to obtain a solution A;
3) weighing 34.827mg of sodium metavanadate and 28mg of polyallylamine hydrochloride;
4) adding the mixed solution A obtained in the step 2) and the vanadium source and the morphology regulating agent obtained in the step 3) into a high-temperature high-pressure reaction kettle filled with 21mL of water and lined with p-polyphenyl, and magnetically stirring at normal temperature to obtain a solution B;
5) putting 223mg of foamed nickel treated in the step 1) into a high-temperature high-pressure reaction kettle with a p-polyphenyl lining filled with the solution B;
6) reacting the reaction kettle in the step 5) at 181 ℃ for 12h, naturally cooling to room temperature after the reaction is finished, taking out the sample, repeatedly washing the sample with ultrapure water and absolute ethyl alcohol for 5 times respectively, wherein the filling ratio of the reaction kettle is 45%, and finally performing vacuum drying at 55 ℃ for 5h to obtain the self-assembly vanadium modified NiSe/Ni3Se2A self-supporting electrode material.
In the synthesis method, foam nickel is used as a substrate, a selenium powder hydrazine hydrate solution is used as a selenium source, sodium metavanadate is used as a vanadium source, polyallylamine hydrochloride is used as a morphology regulator, and a hydrothermal method is adopted to synthesize and prepare the self-assembled vanadium-modified NiSe/Ni3Se2The obtained self-assembly vanadium modified NiSe/Ni3Se2 self-supporting electrode is beneficial to exposing more catalytic active sites, accelerates the exchange of substances on a multiphase heterogeneous interface and the transfer rate of electrons so as to synergistically enhance the catalytic activity and stability of the material, has high current density, long-term circulation stability and high activity of electrocatalytic reaction, is applied to electrolytic water reaction under an alkaline condition, has high electrocatalytic activity, and improves the electrocatalytic hydrogen production performance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. Self-assembled vanadium modified NiSe/Ni3Se2The synthesis method of the self-supporting electrode is characterized by comprising the following steps:
1) taking foamed nickel, cleaning and drying for later use;
2) weighing 77.96-79.96 mg of selenium powder, adding 1.8-2.2 ml of hydrazine hydrate, and uniformly stirring to obtain a solution A;
3) weighing 34.817-34.837 mg of sodium metavanadate and 25-30 mg of polyallylamine hydrochloride;
4) adding 18-22 mL of ultrapure water into a high-temperature high-pressure reaction kettle, adding the solution A obtained in the step 2) and the sodium metavanadate and polyallylamine hydrochloride obtained in the step 3) into the high-temperature high-pressure reaction kettle, and uniformly stirring to obtain a solution B;
5) putting 220-225 mg of foamed nickel obtained in the step 1) into a high-temperature high-pressure reaction kettle filled with the solution B, reacting for 10-15 h at 175-185 ℃, naturally cooling to room temperature after the reaction is finished, taking out the foamed nickel, cleaning and drying to obtain the NiSe/Ni modified by the self-assembled vanadium3Se2A self-supporting electrode.
2. The self-assembled vanadium modified NiSe/Ni of claim 13Se2The synthesis method of the self-supporting electrode is characterized in that acetone, hydrochloric acid, deionized water and absolute ethyl alcohol are adopted in the step 1) to sequentially and ultrasonically clean the foamed nickel, impurities and an oxidation layer on the surface of the foamed nickel are removed, the foamed nickel is washed to be neutral, and the foamed nickel is dried at normal temperature.
3. The self-assembled vanadium modified NiSe/Ni of claim 23Se2The synthesis method of the self-supporting electrode is characterized in that the concentration of the hydrochloric acid is 2.8-3.2 mol L-1The ultrasonic treatment time of acetone is 10-15 min, and the ultrasonic treatment time of hydrochloric acid, deionized water and absolute ethyl alcohol is 5-10 min respectively.
4. The self-assembled vanadium modified NiSe/Ni of claim 13Se2The synthesis method of the self-supporting electrode is characterized in that the stirring in the step 2) is magnetic stirring at 45-55 ℃ for 1-1.2 h.
5. The self-assembled vanadium modified NiSe/Ni of claim 13Se2The synthesis method of the self-supporting electrode is characterized in that the stirring in the step 4) is magnetic stirring at normal temperature.
6. The self-assembled vanadium modified NiSe/Ni of claim 13Se2The synthesis method of the self-supporting electrode is characterized in that the high-temperature high-pressure reaction kettle comprises a p-polyphenyl lining, and the filling ratio of the high-temperature high-pressure reaction kettle in the step 5) is controlled to be 40-48%.
7. The self-assembled vanadium modified NiSe/Ni of claim 13Se2The synthesis method of the self-supporting electrode is characterized in that the foamed nickel reacted in the step 5) is repeatedly washed with ultrapure water and absolute ethyl alcohol for multiple times, and then is dried in vacuum at the drying temperature of 50-60 ℃ for 4-5 hours.
8. Self-assembled vanadium modified NiSe/Ni3Se2Self-supporting electrode, characterized in that it uses a self-assembled vanadium modified NiSe/Ni according to any one of claims 1 to 73Se2The self-supporting electrode is prepared by a synthesis method.
9. The self-assembled vanadium modified NiSe/Ni of claim 83Se2Self-supporting electrode, characterised in that the electrolysis of water is carried out in a 1M KOH solution at 100mA cm-2The overpotential for hydrogen production is 280-290 mV and the overpotential for oxygen production is 0.3-0.4 mV under the current density.
10. A self-assembled vanadium modified NiSe/Ni as claimed in claim 8 or 93Se2The self-supporting electrode is applied to electrolytic water reaction under alkaline conditions.
CN202011160489.0A 2020-10-27 2020-10-27 Self-assembled vanadium modified NiSe/Ni3Se2Self-supporting electrode and synthesis method and application thereof Pending CN112301374A (en)

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CN106098397A (en) * 2016-08-11 2016-11-09 浙江大学 NiSe Ni for ultracapacitor3se2three-dimensional Folium Pini shape nano material and preparation method thereof
CN106158420A (en) * 2016-08-11 2016-11-23 浙江大学 A kind of NiSe Ni for ultracapacitor3se2porous nano ball material and preparation method thereof
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