CN109794264B - Micro-popcorn-shaped high-performance full-hydrolysis bifunctional electrocatalyst FeOOH/Ni3S2Preparation method of (1) - Google Patents
Micro-popcorn-shaped high-performance full-hydrolysis bifunctional electrocatalyst FeOOH/Ni3S2Preparation method of (1) Download PDFInfo
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Abstract
The invention relates to a micro-popcorn-shaped high-performance full-hydrolysis bifunctional electrocatalyst FeOOH/Ni3S2The preparation method of (1). The method comprises the steps of firstly, adopting thiourea and nickel nitrate as raw materials, ethanol as a solution, cetyl trimethyl ammonium bromide as a surfactant, and growing Ni on a foam nickel substrate in situ by utilizing a solvothermal method3S2Then deposited on Ni through one-step electrochemical deposition3S2FeOOH/Ni with micro popcorn balls formed thereon3S2An electrocatalyst. FeOOH/Ni obtained by the invention3S2The composite catalyst has lower overpotential and better stability, and has wide application prospect in the aspects of preparing hydrogen clean energy by electrocatalytic water decomposition and the like.
Description
Technical Field
The invention belongs to the technical field of novel functional materials, and particularly relates to a method for utilizing solvent heat and electricityTwo-step chemical deposition process to grow micron flower ball shaped high performance full water decomposing double-function electrocatalyst FeOOH/Ni on foamed nickel substrate in situ3S2The preparation method and the application thereof.
Background
Current electrocatalytic materials for oxygen and hydrogen evolution reactions are noble metal oxides such as iridium dioxide (IrO)2) Ruthenium dioxide (RuO)2) And platinum (Pt) are the main ones, and although they have high catalytic performance, they are expensive, scarce in resources, high in synthesis cost, and poor in stability in the catalytic process, and are easily dissolved under acidic or alkaline reaction conditions. Therefore, the development and application of non-noble metal compounds, especially transition metal compounds, as bifunctional electrocatalytic materials for oxygen evolution and hydrogen evolution reactions have attracted extensive attention and research of researchers. Ni3S2The (trinickel disulfide) is a bifunctional electrocatalytic material with great application potential, has the advantages of good catalytic performance, energy conservation, environmental protection, good conductivity, stable structure and the like, and has wide application prospect in the fields of electrode materials, bifunctional oxygen catalysts and the like. FeOOH, however, cannot exhibit excellent performance as a catalyst due to its own semiconductor characteristics. At present Ni3S2The synthetic method mainly utilizes sulfur powder sintering, high temperature is needed, toxic gases such as sulfur dioxide and the like are discharged in the reaction process, the synthesized sample is large particles, the reaction kinetics is high, and the application of the synthesized sample as a full-hydrolysis water-electricity catalyst is greatly limited due to the large tafel slope.
FeOOH cannot exhibit excellent electrocatalytic properties due to its low electrical conductivity. In order to increase the conductivity of FeOOH, it is generally supported on a noble metal material with good conductivity, such as gold foil or platinum sheet, and although this method can increase the conductivity of FeOOH and improve its catalytic performance, these substrate materials are expensive and have low reserves, and the noble metal substrate is easily corroded in the electrochemical process, thereby affecting the stability of the catalyst. Ni3S2(trinickel disulfide) is a nickel-based sulfide material with very good chemical stability and electrical conductivity, but the bulk material is prepared by adopting the methodThe material has few reactive active sites and the reaction kinetics of the material as a catalyst are poor. Therefore if Ni can be substituted3S2Growing on the foam nickel in situ and further compounding with FeOOH, not only can enhance the electron transmission capability of FeOOH in electrochemical reaction, but also can effectively improve Ni3S2The shape and the reaction kinetics of the catalyst are expected to become a bifunctional catalyst for electrolyzing water with excellent performance. Based on the research background, how to develop the method for growing Ni on the nickel foam3S2The nano material is effectively compounded with FeOOH, and the practical voltage of the electrolyzed water is further reduced by the simple and convenient catalyst synthesis method, so that the method has very important research significance and application value.
Disclosure of Invention
The invention aims to provide a micro-popcorn-shaped high-performance full-hydrolysis dual-function electrocatalyst FeOOH/Ni against the defects in the prior art3S2The preparation method of (1). The method takes ethanol as a solvent and cetyl trimethyl ammonium bromide as a surfactant to grow Ni in situ on foam Nickel (NF) by a solvothermal method3S2And further carrying out electrodeposition in ferric nitrate electrolyte to successfully synthesize the micro popcorn ball-shaped FeOOH/Ni formed by stacking the defect-rich nanosheets3S2And (3) compounding a catalyst. FeOOH/Ni obtained by the invention3S2The composite catalyst has lower overpotential and better stability, and has wide application prospect in the aspects of preparing hydrogen clean energy by electrocatalytic water decomposition and the like.
The technical scheme of the invention is as follows:
micro-popcorn-shaped high-performance full-hydrolysis bifunctional electrocatalyst FeOOH/Ni3S2The preparation method comprises the following steps:
step 1: soaking the strip-shaped foamed nickel in an HCl solution with the concentration of 2-3M for 15-30min, taking out, cleaning and drying for later use;
step 2: adding nickel nitrate, thiourea and hexadecyl trimethyl ammonium bromide into absolute ethyl alcohol, stirring until the nickel nitrate, the thiourea and the hexadecyl trimethyl ammonium bromide are dissolved, and pouring the solution into a hydrothermal kettle;
wherein, the molar ratio is nickel nitrate: thiourea: hexadecyl trimethyl ammonium bromide, 1:1-3: 0.27-0.35; adding 0.001-0.0015mol of nickel nitrate into every 25mL of absolute ethyl alcohol;
and step 3: immersing the foamed Nickel (NF) obtained in the step (1) into the solution prepared in the step (2), keeping the temperature at 130-150 ℃ for 10-12 h, cleaning, and drying in a drying oven at 60-80 ℃ for 2-5 h to obtain Ni growing on the foamed nickel in situ3S2Materials, i.e. Ni3S2/NF；
And 4, step 4: mixing Ni3S2the/NF is used as a working electrode, the platinum wire electrode is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, the constant-pressure deposition is carried out for 100 to 400 seconds under the voltage of-1.1 to-1.2V, then the working electrode is taken out, washed and dried to obtain the micron flower-shaped FeOOH/Ni3S2An electrocatalyst material;
wherein the solvent of the electrolyte is a mixed solution of water and glycol, and the volume ratio of the water to the glycol is 3: 2; the solute is ferric nitrate, and 0.2-1.0 g of ferric nitrate is added into every 150ml of mixed solution.
The cleaning in the step 1 is ultrasonic cleaning by using ethanol, acetone and ultrapure water in sequence.
The invention has the substantive characteristics that:
the core of the invention is that the Ni grows in situ on the foam nickel by adopting two-step synthesis3S2The full-hydrolytic bifunctional electrocatalytic material compounded with FeOOH utilizes foamed nickel as a growth substrate, and nickel nitrate and thiourea are directly subjected to solvothermal synthesis to form Ni3S2/NF, then FeOOH is uniformly deposited on Ni by electrochemical deposition3S2on/NF, FeOOH/Ni with micrometer flower-shaped micro-morphology is synthesized3S2And (3) compounding a catalyst. The invention utilizes Ni3S2The interaction between the catalyst and FeOOH further improves the full-hydrolysis water electro-catalysis performance, and the product obtained by the method is used as the full-hydrolysis water electro-catalysis agent to be more RuO2And the Pt/C noble metal catalyst has better catalytic performance, and provides reference for improving the performance of the non-noble metal catalyst.
The invention has the beneficial effects that:
FeOOH/Ni provided by the invention3S2The preparation method of the micron flower-shaped composite catalyst is simple, convenient to operate and low in equipment requirement, and the safety in the experimental process is improved. FeOOH/Ni prepared by the method of the invention3S2the/NF has a micro flower-shaped micro appearance, good conductivity and good electrocatalytic full-hydrolytic performance.
FeOOH/Ni prepared by the technical scheme of the invention3S2The performance test of the/NF composite catalyst is carried out by utilizing an X-ray diffractometer (Rigaku Ultima IV) (the scanning range is 10-80 degrees, the scanning speed is 4 degrees/minute, the scanning step length is 0.02 degrees), an X-ray photoelectron spectrometer (PHI1600EXCA), a scanning electron microscope (Hitachi, S-4800), a transmission electron microscope (JEOL, 2100) and an electrochemical workstation (Shanghai Hua CHI750E) (the test range of Cyclic Voltammetry (CV) is 0-0.5V, the test range of Linear Scanning Voltammetry (LSV) is 0-0.7V, and the test voltage of alternating current impedance spectroscopy (EIS) is 0.45V), and the test results can be known as follows: the sample is FeOOH compounded in Ni3S2the/NF contains chemical elements such as Ni, Fe, O, H, S, etc. The prepared catalyst has the optimal performance of the full electrolysis water potential of 1.53V, has lower potential compared with the common noble metal catalyst of ruthenium dioxide and platinum-carbon combination, and has lower potential compared with pure Ni3S2The performance is greatly improved, the electrochemical alternating-current impedance is obviously reduced, the Tafel slope is also obviously lower than that of other catalysts, and the activity and the stability of the catalyst are obviously improved.
Drawings
FIG. 1 shows the results obtained in example 5 with Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2/NF composite catalyst, FeOOH nanosheet and Ni3S2X-ray diffraction pattern of/NF.
FIG. 2 shows the ratio of Ni: s1: 2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2Scanning electron microscope images of the/NF composite catalyst.
FIG. 3 shows the results of example 5 in which Ni: S ═ 1:2, in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2Transmission electron microscopy of nanoplatelets.
FIG. 4 shows examples 1-3 wherein Ni-S-1: 1, 1:2, 1:3 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The polarization curve of oxygen evolution reaction of the/NF composite catalyst is compared with a graph.
FIG. 5 shows examples 1-3 wherein Ni-S-1: 1, 1:2, 1:3 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The polarization curve of hydrogen evolution reaction of the/NF composite catalyst is compared with a graph.
FIG. 6 shows the results of examples 4-7 with Ni-S-1: 2 in Fe (NO)3)3FeOOH/Ni prepared by depositing 100-400s in electrolyte3S2The polarization curve of oxygen evolution reaction of the/NF composite catalyst is compared with a graph.
FIG. 7 shows the results of examples 4-7 with Ni-S-1: 2 in Fe (NO)3)3FeOOH/Ni prepared by depositing 100-400s in electrolyte3S2The polarization curve of hydrogen evolution reaction of the/NF composite catalyst is compared with a graph.
FIG. 8 shows the results of example 5 in which Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The polarization curves of oxygen evolution reaction of the/NF composite catalyst and other catalysts are compared.
FIG. 9 shows the results of example 5 in which Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2Comparison graph of oxygen evolution reaction tower Phil slope of/NF composite catalyst and other catalysts.
FIG. 10 shows the results of example 5 in which Ni, S, is 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2Comparison graph of electrochemical alternating-current impedance of oxygen evolution reaction of/NF composite catalyst and other catalysts.
FIG. 11 shows the results of example 5 with Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The polarization curves of hydrogen evolution reaction of the/NF composite catalyst and other catalysts are compared.
FIG. 12 shows a schematic view of the preferred embodiment 5Ni S1: 2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2Comparison graph of the Phillips slopes of hydrogen evolution reaction towers of the/NF composite catalyst and other catalysts.
FIG. 13 shows the results of example 5 with Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2Comparison graph of electrochemical alternating-current impedance of hydrogen evolution reaction of/NF composite catalyst and other catalysts.
FIG. 14 shows the results of example 5 with Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2A polarization curve comparison graph of electrocatalytic full-hydrolysis of the combination of the/NF composite catalyst and the noble metal electrocatalyst.
FIG. 15 shows the results of example 5 in which Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The electrochemical stability test result of the electrocatalytic full-hydrolytic water of the combination of the/NF composite catalyst and the noble metal electrocatalyst is shown in the figure.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
The invention aims at the problems of poor electrocatalytic reaction performance caused by poor conductivity of pure-phase FeOOH, high composite price with a noble metal substrate and Ni3S2The problem of generating a large amount of toxic gas in the synthesis process of the nickel foam is solved, and the method provides a simple, convenient and feasible two-step method for in-situ growth of Ni on the nickel foam3S2The preparation method of the FeOOH composite full-hydrolysis bifunctional electrocatalyst improves the performance of the electrocatalyst. The method comprises the steps of firstly, adopting thiourea and nickel nitrate as raw materials, ethanol as a solution, cetyl trimethyl ammonium bromide as a surfactant, and growing Ni on a foam nickel substrate in situ by using a hydrothermal method3S2Then deposited on Ni through one-step electrochemical deposition3S2FeOOH/Ni with micro popcorn balls formed thereon3S2An electrocatalyst. The appearance of the special 3D structure and a large number of defects on the nano-chip are beneficial to the hydrogen evolution and oxygen evolution electrocatalytic reaction.
Different Ni3S2FeOOH/Ni in supported amount3S2a/NF composite catalyst.
Example 1:
step 1: cutting commercially available foam nickel into strips with the size of 2cm x 1cm, cleaning in 3M HCl solution for 15min, respectively ultrasonically cleaning with ethanol and acetone for 20min, finally ultrasonically cleaning with ultrapure water for 10min, and drying for later use;
step 2: a weighed amount of 0.8724g (3mmol) of nickel nitrate, 0.2283g (3mmol) of thiourea, and 0.1g (0.3mmol) of cetyltrimethyl-ammonium bromide were added to 25mL of ethanol, stirred until completely dissolved, and the solution was poured into a 30mL hydrothermal kettle.
And step 3: immersing the cleaned foam Nickel (NF) in the solution prepared in the step 2, keeping the solution in an oven for 10 hours at 150 ℃, naturally cooling to room temperature, taking out, washing with deionized water and ethanol, and drying in the oven for 3 hours at 80 ℃ to obtain Ni growing in situ on the foam nickel3S2A material;
and 4, step 4: dissolving weighed 0.606g of ferric nitrate into 150mL of mixed solution of water and glycol (the volume ratio is 3: 2), stirring until the ferric nitrate is completely dissolved, and pouring the solution into a 200mL electrolytic cell;
and 5: prepared Ni3S2the/NF is used as a working electrode, a platinum wire electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, constant-pressure deposition is carried out for 400s under the voltage of-1.1V, then the working electrode is taken out, washed and dried to obtain micrometer flower-shaped FeOOH/Ni3S2An electrocatalyst material.
Example 2:
the other steps are the same as example 1, except that the amount of nickel nitrate in step 2 is changed from 0.8724g to 0.4362 g.
Example 3:
the other steps are the same as example 1, except that 0.8724g of nickel nitrate in step 2 is changed to 0.2908 g.
And (3) testing results: different Ni is prepared by changing the dosage of nickel nitrate3S2FeOOH/Ni in supported amount3S2the/NF composite catalyst is subjected to X-ray diffraction, a scanning electron microscope, a transmission electron microscope, a linear volt-ampere scanning test, an electrochemical alternating current impedance test and a stability test, and the test results are shown in figures 1-15.
FIG. 1 shows the results obtained in example 5 with Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2/NF composite catalyst, FeOOH nanosheet and Ni3S2In an X-ray diffraction pattern of/NF, FeOOH nanosheets have a plurality of strong diffraction peaks at 34.1 degrees, 42.2 degrees, 53.6 degrees and 63.5 degrees, and correspond to standard PDF card PDF # 77-0247. Ni3S2the/NF sample has several stronger diffraction peaks at 21.7 degrees, 31.1 degrees, 44.3 degrees, 49.7 degrees and 50.1 degrees, and is shown to be Ni by comparing with a standard PDF card (PDF #44-1418)3S2The diffraction peak of (1). FeOOH/Ni3S2the/NF presents a main phase of Ni3S2. FIG. 2 shows the results obtained in example 5 with Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The scanning electron microscope image of the/NF composite catalyst shows that the appearance of the sample is a micro popcorn ball structure formed by stacking sheets. FIG. 3 shows the results of example 5 in which Ni: S ═ 1:2, in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The nano sheet surface has a large number of defects formed after the second step deposition in a transmission electron microscope image of the nano sheet. By analyzing the above results, it can be concluded that the prepared sample is FeOOH/Ni3S2the/NF nanometer slice compound catalyst. FIG. 4 shows examples 1-3 wherein Ni-S-1: 1, 1:2, 1:3 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The polarization curve of oxygen evolution reaction of the/NF composite catalyst is compared with a graph. The result shows that the oxygen evolution reaction performance is optimal when the Ni: S is 1:2 in the sample, and the concentration is 10mA/cm2The overpotential at (a) was 199 mV. FIG. 5 shows examples 1-3 wherein Ni-S-1: 1, 1:2, 1:3 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The results show that the Ni and S in the sample are analyzed when the ratio of Ni to S is 1:2Optimum hydrogen reaction performance, 10mA/cm2The overpotential at (a) was 129 mV.
FeOOH/Ni prepared in different electrodeposition time3S2a/NF composite catalyst.
Example 4:
step 1: cutting commercially available foam nickel into strips with the size of 2cm x 1cm, cleaning in 3M HCl solution for 30min, respectively ultrasonically cleaning with ethanol and acetone for 15min, finally ultrasonically cleaning with ultrapure water for 10min, and drying for later use;
step 2: adding 0.4362g (1.5mmol) of nickel nitrate, 0.2283g (3mmol) of thiourea and 0.1g (0.3mmol) of hexadecyl trimethyl ammonium bromide into 25mL of ethanol, stirring until the materials are completely dissolved, and pouring the solution into a 30mL hydrothermal kettle;
and step 3: immersing the cleaned foam Nickel (NF) in the solution prepared in the step 2, keeping the solution in an oven at 140 ℃ for 12 hours, naturally cooling to room temperature, taking out, washing with deionized water and ethanol, and drying in an oven at 80 ℃ for 4 hours to obtain Ni growing in situ on the foam nickel3S2A material;
and 4, step 4: dissolving weighed 0.606g of ferric nitrate into 150mL of mixed solution of water and glycol (the volume ratio is 3: 2), stirring until the ferric nitrate is completely dissolved, and pouring the solution into a 200mL electrolytic cell;
and 5: prepared Ni3S2the/NF is used as a working electrode, a platinum wire electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, constant-pressure deposition is carried out for 100s under the voltage of-1.2V, then the working electrode is taken out, washed and dried to obtain micrometer flower-shaped FeOOH/Ni3S2An electrocatalyst material.
Example 5:
the other steps were the same as example 4 except that the constant-pressure deposition time in step 5 was changed to 200 s.
Example 6:
the other steps were the same as example 4 except that the constant-pressure deposition time in step 5 was changed to 300 s.
Example 7:
the other steps were the same as example 4 except that the constant-pressure deposition time in step 5 was changed to 400 seconds.
And (3) testing results: FeOOH/Ni was prepared by varying the different deposition times in ferric nitrate electrolyte3S2the/NF three-dimensional electro-catalyst material is used for carrying out X-ray diffraction, a scanning electron microscope, a transmission electron microscope, a linear volt-ampere scanning test, an electrochemical alternating-current impedance test and a stability test on a sample. FIG. 6 shows the results of examples 4-7 with Ni-S-1: 2 in Fe (NO)3)3FeOOH/Ni prepared by depositing 100-400s in electrolyte3S2The oxygen evolution reaction polarization curve contrast diagram of the/NF composite catalyst shows that the performance is optimal when the deposition time is 200 and 10mA/cm2The overpotential at (a) was 199 mV. FIG. 7 shows the results of examples 4-7 with Ni-S-1: 2 in Fe (NO)3)3FeOOH/Ni prepared by depositing 100-400s in electrolyte3S2The hydrogen evolution reaction polarization curve contrast diagram of the/NF composite catalyst has the same optimal performance when the deposition time is 200 and 10mA/cm2The overpotential at (a) was 129 mV. FIG. 8 shows the results of example 5 in which Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The contrast graph of the oxygen evolution reaction polarization curve of the/NF composite catalyst and other catalysts can show that compared with single-phase FeOOH/NF and Ni3S2/NF, pure nickel foam, and RuO2Catalyst of/C/NF, FeOOH/Ni3S2the/NF composite catalyst is at the same current density (10 mA/cm)2) And a lower overpotential for oxygen evolution reaction (199 mV). FIG. 9 shows the results of example 5 in which Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The Phillips slope of the oxygen evolution reaction tower of the/NF composite catalyst and other catalysts is compared, and the graph shows that the single-phase FeOOH/NF and Ni are compared with the single-phase FeOOH/Ni3S2/NF, pure nickel foam, and RuO2Catalyst of/C/NF, FeOOH/Ni3S2the/NF composite catalyst has lower reaction tower Phillips rate and higher reaction kinetics. FIG. 10 shows the results of example 5 in which Ni, S, is 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The comparison graph of the electrochemical alternating-current impedance of the oxygen evolution reaction of the/NF composite catalyst and other catalysts shows that the single-phase FeOOH/NF and Ni are compared with the single-phase FeOOH/NF and Ni3S2/NF, pure nickel foam, and RuO2The catalyst such as/C/NF has lower electrochemical alternating current impedance and better conductivity. FIG. 11 shows the results of example 5 with Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The contrast graph of the hydrogen evolution reaction polarization curve of the/NF composite catalyst and other catalysts can show that compared with single-phase FeOOH/NF and Ni3S2Catalyst of/NF, pure foam nickel, etc., FeOOH/Ni3S2the/NF composite catalyst is at the same current density (10 mA/cm)2) And has a lower overpotential for hydrogen evolution reaction (129 mV). FIG. 12 shows the results of example 5 with Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2Comparison graph of Phillir slopes of hydrogen evolution reaction towers of/NF composite catalyst and other catalysts, and the same FeOOH/Ni3S2the/NF composite catalyst has lower reaction tower Phillips rate and higher reaction kinetics. FIG. 13 shows the results of example 5 with Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The comparison graph of the electrochemical alternating-current impedance of the hydrogen evolution reaction of the/NF composite catalyst and other catalysts has better conductivity in the hydrogen evolution reaction. FIG. 14 shows the results of example 5 with Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2A comparison graph of the polarization curves of the electrocatalytic full-hydrolytic water of the combination of the/NF composite catalyst and the noble metal electrocatalyst is formed by FeOOH/Ni3S2The water electrolysis device with the NF respectively forming the cathode and the anode has full electrolysis water electro-catalytic performance in 1.0M KOH and has lower reaction potential compared with the combination of noble metals. FIG. 15 shows the results of example 5 in which Ni: S ═ 1:2 in Fe (NO)3)3FeOOH/Ni prepared by deposition in electrolyte for 200s3S2The electrochemical stability test result chart of the electrocatalytic total hydrolysis of the combination of the/NF composite catalyst and the noble metal electrocatalyst is formed by FeOOH/Ni3S2/NF scoreThe water electrolysis device respectively comprising the cathode and the anode has better full hydrolysis stability in 1.0M KOH compared with the noble metal combination, and the current density has no obvious attenuation under the reaction of 20 h.
From the above results, it can be seen that the method proposed by the present invention successfully produces microsporoidal FeOOH/Ni with stacked nanosheets3S2the/NF composite catalyst effectively enhances the electron transmission capability of FeOOH in electrochemical reaction and can effectively improve Ni3S2The shape and the reaction kinetics of the catalyst are further changed into the electrolytic water bifunctional catalyst material with excellent performance. The preparation method is simple and easy, and FeOOH/Ni3S2the/NF composite catalyst further reduces the actual voltage of the electrolyzed water, and has very important research significance and application value.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
The invention is not the best known technology.
Claims (2)
1. Micro-popcorn-shaped high-performance full-hydrolysis bifunctional electrocatalyst FeOOH/Ni3S2The preparation method is characterized by comprising the following steps:
step 1: soaking the strip-shaped foamed nickel in an HCl solution with the concentration of 2-3M for 15-30min, taking out, cleaning and drying for later use;
step 2: adding nickel nitrate, thiourea and hexadecyl trimethyl ammonium bromide into absolute ethyl alcohol, stirring until the nickel nitrate, the thiourea and the hexadecyl trimethyl ammonium bromide are dissolved, and pouring the solution into a hydrothermal kettle;
wherein, the molar ratio is nickel nitrate: thiourea: hexadecyl trimethyl amine bromide =1:1-3: 0.27-0.35; adding 0.001-0.0015mol of nickel nitrate into every 25mL of absolute ethyl alcohol;
and step 3: immersing the foam nickel NF obtained in the step 1 into the solution prepared in the step 2, keeping the temperature at 130-150 ℃ for 10-12 h, cleaning, and putting into a 60-80 ℃ drying ovenDrying for 2-5 h to obtain Ni growing on the foam nickel in situ3S2Materials, i.e. Ni3S2/NF；
And 4, step 4: dissolving ferric nitrate in a mixed solution of water and glycol, stirring until the ferric nitrate is completely dissolved, and pouring the mixed solution into a 200mL electrolytic cell; wherein the volume ratio of water to ethylene glycol =3:2 in the mixed solution; adding 0.2-1.0 g of ferric nitrate into every 150ml of mixed solution;
and 5: mixing Ni3S2the/NF is used as a working electrode, the platinum wire electrode is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, the constant-pressure deposition is carried out for 100 to 400 seconds under the voltage of-1.1 to-1.2V, then the working electrode is taken out, washed and dried to obtain the micro-popcorn spherical FeOOH/Ni3S2An electrocatalyst material.
2. The popcorn sphere-shaped high-performance full-hydrolysis bifunctional electrocatalyst of claim 1, FeOOH/Ni3S2The preparation method is characterized in that the cleaning in the step 1 is ultrasonic cleaning by using ethanol, acetone and ultrapure water in sequence.
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