CN115058735A - Porous catalyst with high hydrogen evolution performance by external magnetic field and preparation and use methods thereof - Google Patents

Porous catalyst with high hydrogen evolution performance by external magnetic field and preparation and use methods thereof Download PDF

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CN115058735A
CN115058735A CN202210797615.6A CN202210797615A CN115058735A CN 115058735 A CN115058735 A CN 115058735A CN 202210797615 A CN202210797615 A CN 202210797615A CN 115058735 A CN115058735 A CN 115058735A
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magnetic field
nickel
hydrogen evolution
porous catalyst
high hydrogen
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CN115058735B (en
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袁双
王钟
李成林
郝一帆
齐聪
王强
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Northeastern University China
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Abstract

A porous catalyst with high hydrogen evolution performance by an external magnetic field and a preparation and use method thereof are disclosed, wherein the catalyst is Co-P/Ni/NF with a porous structure. The preparation method comprises the following steps: (1) pretreating foamed nickel; (2) dissolving nickel chloride and ammonium chloride in water to prepare an electrodeposition solution; (3) carrying out constant current electrodeposition treatment on the pretreated foamed nickel to prepare deposited foamed nickel (Ni/NF); (4) dissolving cobalt sulfate, sodium hypophosphite and sodium acetate in water to prepare a reaction solution; (5) and carrying out second constant current electrodeposition treatment on the deposited foamed nickel to deposit cobalt and phosphorus on the surface. The using method comprises the following steps: (1) taking out the porous catalyst with high hydrogen evolution performance of the external magnetic field as a working electrode; (2) placing the electrolyte in an electrolytic cell; applying uniform magnetic field, and electrifying to electrolyze water and hydrogen. The Co-P/Ni/NF catalyst prepared by the invention has excellent performance of hydrogen evolution by water electrolysis; the overpotential is greatly reduced.

Description

Porous catalyst with high hydrogen evolution performance by external magnetic field and preparation and use methods thereof
Technical Field
The invention belongs to the technical field of new energy for hydrogen production by water electrolysis, and particularly relates to a porous catalyst with high hydrogen evolution performance by an external magnetic field and a preparation and use method thereof.
Background
With the increasing demand of energy and the increasing severity of environmental pollution, the development of clean and efficient renewable energy is urgent. Hydrogen is an ideal fuel and is an optimal carrier for replacing fossil fuel clean energy. The method for preparing hydrogen by electrolyzing water is simplest, most efficient and cleaner. Three main modes for producing hydrogen at the present stage are hydrogen production by water electrolysis, hydrogen production by fossil energy and hydrogen production by biological energy. The hydrogen production by electrolyzing water has the advantages of high purity, low cost, environmental protection and the like, but the energy consumption problem in the hydrogen production process is not negligible.
At present, compared with other catalysts, the Pt-based catalyst has the highest catalytic efficiency. However, the high cost and scarcity have prevented their large-scale commercial use, and therefore, there is an urgent need to develop inexpensive and efficient electrocatalysts. In recent years, transition metal phosphides have received increasing attention because the phosphides are inexpensive and have good electrical conductivity; the theoretical research result shows that: nickel-based and cobalt-based catalysts have catalytic activity superior to most transition metals and also have relatively high earth storage.
The electrolytic water Hydrogen Evolution Reaction (HER) needs higher overpotential to be carried out, and the slow reaction kinetics process limits the whole water electrolysis reaction rate, so that a method for improving the reaction rate is urgently needed to be found. Methods for improving catalyst performance can be largely divided into three approaches: the method starts from the intrinsic nature of materials, and achieves the purposes of reducing overpotential and accelerating electron transfer by increasing the contact area of ions in electrolyte and a catalyst, the number of active sites and the conductivity of the materials. How to simply and efficiently realize the high efficiency and low cost of the catalyst for the electrolytic water hydrogen evolution reaction is a bottleneck problem which troubles researchers.
Disclosure of Invention
The invention aims to provide a porous catalyst with high hydrogen evolution performance by an external magnetic field and a preparation method and a use method thereof.
The porous catalyst with the high hydrogen evolution performance by the external magnetic field is Co-P/Ni/NF with a porous structure and consists of deposited foam nickel and Co-P deposited on the surface of the foam nickel, wherein the deposited foam nickel is formed by depositing nickel on the surface of a nickel substrate; the molar ratio of Ni, Co and P in the Co-P/Ni/NF is 1 (0.2-0.4) to 0.01-0.04; the surface roughness of the porous catalyst with the high hydrogen evolution performance of the external magnetic field is 5-10 mu m.
The specific surface area of the porous catalyst with the high hydrogen evolution performance of the external magnetic field is 10-15 m 2 /g。
The porosity of the porous catalyst with the high hydrogen evolution performance of the external magnetic field is 60-80%.
The preparation method of the porous catalyst with the external magnetic field and high hydrogen evolution performance comprises the following steps:
(1) sequentially placing the foamed nickel into hydrochloric acid, acetone, ethanol and deionized water for ultrasonic treatment, and then drying to remove surface liquid to prepare pretreated foamed nickel;
(2) dissolving nickel chloride and ammonium chloride in deionized water, and uniformly mixing to prepare an electrodeposition solution;
(3) adopting an electrochemical workstation, taking the pretreated foamed nickel as a working electrode, taking graphite as a reference electrode and a counter electrode, putting the electrodes into an electrodeposition solution, electrifying to carry out constant-current electrodeposition treatment, and depositing nickel on the surface of the pretreated foamed nickel to prepare deposited foamed nickel (Ni/NF);
(4) dissolving cobalt sulfate, sodium hypophosphite and sodium acetate in deionized water, and uniformly mixing to prepare a reaction solution;
(5) taking out the deposited nickel foam by using an electrochemical workstation, and washing and drying the nickel foam to be used as a working electrode; and (3) taking a Pt electrode as a counter electrode and an Hg/HgO electrode as a reference electrode, placing the electrodes in a reaction solution, electrifying to carry out second constant-current electrodeposition treatment, and depositing cobalt and phosphorus on the surface of the deposited foamed nickel to prepare the porous catalyst with the externally applied magnetic field and high hydrogen evolution performance.
In the step (1), when ultrasonic treatment is performed, the ultrasonic treatment time of each liquid is 5-15 min.
In the step (1), the concentration of the hydrochloric acid is 1-3 mol/L.
In the step (1), the size of the foamed nickel is 0.5-1 cm in width and 1-3 cm in length.
In the step (1), the drying temperature is 15-30 ℃ and the drying time is 6-10 h.
In the step (2), the raw material of the nickel chloride is nickel chloride hexahydrate.
In the step (2), the electrodeposition solution contains (20 to 100) nickel chloride and ammonium chloride in a molar ratio of 1.
In the step (2), the electrodeposition solution contains nickel chloride and deionized water (0.0025-0.0075) in a mass ratio of 50.
In the step (2), ultrasonic treatment and/or mechanical stirring are adopted during mixing; wherein the time for ultrasonic treatment is 5-15 min, and the time for stirring is 30-60 min.
In the step (3), when the constant current electrodeposition treatment is performed, the current is-0.5 to-1.5A, and the time is 100 to 500 s.
In the step (4), the molar ratio of cobalt sulfate, sodium hypophosphite and sodium acetate to 1 is (6-20): 1.
In the step (4), the raw material of the cobalt sulfate is cobalt sulfate heptahydrate.
In the step (4), the raw material of the sodium hypophosphite is sodium hypophosphite monohydrate.
In the step (4), the mass ratio of cobalt sulfate to deionized water is (0.0025-0.0075): 50.
In the step (4), ultrasonic treatment and/or mechanical stirring are adopted during mixing; wherein the time for ultrasonic treatment is 5-15 min, and the time for stirring is 30-60 min.
In the step (5), the current is-0.5 to-1.5A for 10 to 30min during the second constant current electrodeposition treatment.
In the step (5), the washing is to wash the taken-out deposited nickel foam for 3-6 times by using absolute ethyl alcohol and water alternately.
In the step (5), the drying temperature is 30-60 ℃ and the drying time is 30-60 min.
The application method of the porous catalyst with high hydrogen evolution performance by the external magnetic field comprises the following steps:
(1) taking out the porous catalyst with high hydrogen evolution performance of the external magnetic field, washing and drying the porous catalyst to be used as a working electrode; taking a Pt electrode as a counter electrode and taking an Hg/HgO electrode or an SCE electrode as a reference electrode;
(2) placing the electrolyte into an electrolytic cell by using an electrochemical workstation; and (3) placing each electrode in electrolyte, applying a uniform magnetic field outside the electrolytic cell, and electrifying to electrolyze water and evolve hydrogen.
In the step (1) of the using method, the washing is to wash the taken-out deposited nickel foam for 3-6 times by using absolute ethyl alcohol and water alternately.
In the step (1) of the using method, the drying temperature is 30-60 ℃ and the time is 30-60 min.
In the step (2) of the using method, before water electrolysis and hydrogen evolution, nitrogen is introduced into the electrolyte in advance, wherein the nitrogen introduction time is 30-60 min.
In the step (2) of the above method, the intensity of the uniform magnetic field is 100 to 500 mT.
In the step (2) of the above method, the electrolyte is an acidic electrolyte or an alkaline electrolyte; when the electrolyte is an acid electrolyte, the SCE electrode is used as a reference electrode; when the electrolyte is an acid electrolyte, the Hg/HgO electrode serves as a reference electrode.
In the step (2) of the above method, the electrolyte is an acidic electrolyte or an alkaline electrolyte; when the electrolyte is an acid electrolyte, the electrolyte is 0.5M H 2 SO 4 A solution having a pH of 0.3; when the electrolyte is acidic electrolysisIn the case of liquid, the electrolyte was a 1M KOH solution with a pH of 13.7.
In the step (2) of the using method, before hydrogen evolution through electrolyzed water, CV scanning is carried out for 30-50 circles, and then LSV is tested; when the electrolyte is an acid electrolyte, the voltage range is: -0.2 to-0.6V; when the electrolyte is an acid electrolyte, the voltage range is: -0.8 to-1.4V.
The principle of the invention is as follows: the reaction area can be increased by the porous catalyst, and the flowing space of the electrolyte is increased; the magnetic field is applied in the process of hydrogen evolution of electrolyzed water, so that the critical dimension of hydrogen bubbles on the surface of the electrode can be effectively reduced, the bubble coverage rate on the surface of the electrode is reduced, the hydrogen evolution efficiency of the electrolyzed water is improved, the mass transfer in the electrolytic cell can be enhanced by applying the magnetic field, the ohmic voltage drop between the electrodes in the process of water electrolysis is reduced, and particularly under high current density, the voltage of the electrolytic cell is obviously reduced; this variation is actually caused by the action of the lorentz force-driven electrolyte on the flow, and the interaction of the current and the magnetic field generates a directional lorentz force, thereby pushing the vortex around the bubble, generating Magnetohydrodynamic (MHD) convection; the additional convection current existing on the electrolyte can effectively reduce the harmful effect of bubble accumulation on the surface of the electrode, thereby promoting the hydrogen evolution of the electrolyzed water.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with a noble metal platinum catalyst, the prepared Co-P/Ni/NF catalyst has the advantages of low price, wide raw material source and environmental friendliness;
(2) the foam nickel is treated by adopting a constant current electrodeposition mode, so that the surface area of the foam nickel is increased, the porosity of the foam nickel is improved, a high-roughness 3D porous structure is formed, and the electrochemical active area of the foam nickel is increased;
(3) in the test process, by regulating and controlling the magnetic field intensity, the critical dimension of hydrogen bubbles on the surface of the electrode is reduced, the bubble coverage rate on the surface of the electrode is reduced, the mass transfer in an electrolytic cell is enhanced, the ohmic voltage drop between the electrodes in the water electrolysis process is reduced, and the hydrogen evolution efficiency of the electrolyzed water is improved;
(4) the prepared Co-P/Ni/NF catalyst has excellent performance of hydrogen evolution by water electrolysis; during electrochemical testing, when no additional magnetic field is appliedUnder acidic condition, when the current density is 10mA cm -2 The overpotential is 91 mV; under alkaline or acidic conditions, when the current density is 10mA cm -2 The overpotential is greatly reduced.
Drawings
FIG. 1 is an SEM image of nickel foam of example 1 of the present invention; in the figure, (a) is hypo-magnification and (b) is hyper-magnification;
FIG. 2 is an SEM image of nickel foam (Ni/NF) after deposition in example 1 of the present invention, wherein (a) is deposition time 100s, low magnification; (b) the deposition time is 100s, high times; (c) the deposition time is 300s, which is lower; (d) the deposition time is 100s, high times; (e) the deposition time is 500s, which is lower; (f) the deposition time is 500s, high times;
FIG. 3 is a graph showing the N content of nickel foam and nickel foam after deposition (Ni/NF) in example 1 of the present invention 2 Adsorption-desorption isotherm plot;
FIG. 4 is an SEM image of a magnetic field-applied high hydrogen evolution performance porous catalyst (Co-P/Ni/NF foam nickel) prepared in example 1 of the present invention;
FIG. 5 is an XRD pattern of deposited nickel foam (Ni/NF) and a porous catalyst with high hydrogen evolution performance by an applied magnetic field (Co-P/Ni/NF nickel foam) in example 1 of the present invention;
FIG. 6 is a projection diagram of a porous catalyst with high hydrogen evolution performance (Co-P/Ni/NF foam nickel) with an applied magnetic field according to example 1 of the present invention; in the figure, the white circle part is cobalt element;
FIG. 7 is a polarization curve diagram of different magnetic field strengths when the porous catalyst with high hydrogen evolution performance by an external magnetic field (Co-P/Ni/NF foam nickel) in the embodiment 1 of the invention is subjected to an electrolytic water hydrogen evolution test; in the figure, (a) is alkaline electrolyte condition and (b) is acidic electrolyte condition;
FIG. 8 is a graph of overpotential-time curve of an electrolyzed water hydrogen evolution test of the porous catalyst with high hydrogen evolution performance (Co-P/Ni/NF nickel foam) with an applied magnetic field in example 1 of the present invention; in the figure, (a) is an alkaline electrolyte condition, and (b) is an acidic electrolyte condition.
Detailed Description
The following non-limiting examples will provide those of ordinary skill in the art with a more complete understanding of the present invention and are not intended to limit the invention.
The test methods described in the following examples are, unless otherwise specified, conventional; the reagents used, unless otherwise specified, are commercially available.
In the embodiment of the invention, the raw material of the nickel chloride is nickel chloride hexahydrate.
In the embodiment of the invention, the raw material of the cobalt sulfate is cobalt sulfate heptahydrate.
In the embodiment of the invention, the raw material of the sodium hypophosphite is sodium hypophosphite monohydrate.
In the embodiment of the invention, in the steps (2) and (4), ultrasonic treatment and/or mechanical stirring are adopted during mixing; wherein the time for ultrasonic treatment is 5-15 min, and the time for stirring is 30-60 min.
In an embodiment of the present invention, the electrodeposition process uses a conventional three-electrode configuration system (electrochemical workstation, VSP, Bio-Logic).
In the embodiment of the invention, N is 2 The gas-treated solution was subjected to HER testing in a magnetic field of 500mT, and the magnetic field strength was measured with a Tesla meter.
In the embodiment of the invention, before HER test, a porous catalyst Co-P/Ni/NF foam nickel) with high hydrogen evolution performance of an external magnetic field is cut into the length of 0.5cm and the width of 0.5 cm.
Example 1
The porous catalyst with high hydrogen evolution performance by an external magnetic field is Co-P/Ni/NF with a porous structure and consists of a foam nickel matrix and Co-P deposited on the surface of the foam nickel matrix; the molar ratio of Ni, Co and P in the Co-P/Ni/NF is 1:0.3: 0.02; the surface roughness of the porous catalyst with high hydrogen evolution performance of the external magnetic field is 7 mu m; the specific surface area is 13m 2 (ii)/g; the porosity is 75%;
the preparation method comprises the following steps:
(1) sequentially placing the foamed nickel into hydrochloric acid, acetone, ethanol and deionized water for ultrasonic treatment, and then drying to remove surface liquid to prepare pretreated foamed nickel; when ultrasonic treatment is carried out, the ultrasonic treatment time of each liquid is 15 min; the concentration of hydrochloric acid is 3 mol/L; the size of the foamed nickel is 0.5cm in width and 2cm in length; the drying treatment temperature is 25 ℃, and the drying treatment time is 10 hours; the SEM image of the foamed nickel is shown in FIG. 1;
(2) dissolving nickel chloride and ammonium chloride in deionized water, and uniformly mixing to prepare an electrodeposition solution; in the electrodeposition solution, nickel chloride and ammonium chloride in a molar ratio of 1:20(5mmol:0.1 mol); in the electrodeposition solution, the mass ratio of nickel salt to deionized water is 0.0025: 50;
(3) adopting an electrochemical workstation, taking the pretreated foamed nickel as a working electrode, taking graphite as a reference electrode and a counter electrode, putting the electrodes into an electrodeposition solution, electrifying to carry out constant-current electrodeposition treatment, and depositing nickel on the surface of the pretreated foamed nickel to prepare deposited foamed nickel (Ni/NF); when constant current electrodeposition treatment is carried out, the current is-0.5A, and the time is 500 s;
SEM images of the nickel foam (Ni/NF) after deposition for different deposition times are shown in FIG. 2;
n of foamed nickel and deposited foamed nickel (Ni/NF) 2 The adsorption-desorption isotherm curves are shown in fig. 3; as can be seen, the deposited nickel foam (Ni/NF) has larger specific surface area, which is beneficial to providing sufficient deposition space for cobalt and phosphorus.
(4) Dissolving cobalt sulfate, sodium hypophosphite and sodium acetate in deionized water, and uniformly mixing to prepare a reaction solution; in the reaction solution, cobalt sulfate, sodium hypophosphite and sodium acetate are mixed according to a molar ratio of 1:6: 1; according to the mass ratio of cobalt sulfate to deionized water being 0.0025: 50;
(5) taking out the deposited nickel foam by using an electrochemical workstation, and washing and drying the nickel foam to be used as a working electrode; putting the Pt electrode as a counter electrode and the Hg/HgO electrode as a reference electrode into a reaction solution, electrifying to perform second constant-current electrodeposition treatment so that cobalt and phosphorus are deposited on the surface of the deposited foamed nickel, and preparing the porous catalyst with the high hydrogen evolution performance by an external magnetic field; when the second constant current electrodeposition treatment is carried out, the current is-0.5A, and the time is 10 min; washing, namely alternately washing the taken out deposited foamed nickel by using absolute ethyl alcohol and water for 3 times respectively; drying at 30 deg.C for 60 min;
the SEM image of the porous catalyst with high hydrogen evolution performance by the external magnetic field is shown in figure 4;
XRD patterns of the deposited nickel foam (Ni/NF) and the porous catalyst with high hydrogen evolution performance by the external magnetic field (Co-P/Ni/NF nickel foam) are shown in figure 5;
the projection diagram of the porous catalyst (Co-P/Ni/NF foam nickel) with high hydrogen evolution performance by an external magnetic field is shown in FIG. 6;
the using method comprises the following steps:
(1) taking out the porous catalyst with high hydrogen evolution performance of the external magnetic field, washing and drying the porous catalyst to be used as a working electrode; taking a Pt electrode as a counter electrode and taking an Hg/HgO electrode or an SCE electrode as a reference electrode; washing, namely alternately washing the taken out deposited foamed nickel by using absolute ethyl alcohol and water for 3 times respectively; drying at 30 deg.C for 60 min;
(2) placing the electrolyte into an electrolytic cell by using an electrochemical workstation; before water electrolysis and hydrogen evolution, nitrogen is introduced into the electrolyte in advance, and the nitrogen introduction time is 30 min; placing each electrode in an electrolyte, and applying a uniform magnetic field outside an electrolytic cell, wherein the strength of the uniform magnetic field is 100-500 mT; electrifying to electrolyze water to generate hydrogen; the electrolyte is acidic electrolyte or alkaline electrolyte; when the electrolyte is an acid electrolyte, the SCE electrode is used as a reference electrode; when the electrolyte is an acid electrolyte, the Hg/HgO electrode is used as a reference electrode; the electrolyte is acidic electrolyte or alkaline electrolyte; when the electrolyte is an acid electrolyte, the electrolyte is 0.5M H 2 SO 4 A solution having a pH of 0.3; when the electrolyte is an acid electrolyte, the electrolyte is a 1M KOH solution, and the pH value of the electrolyte is 13.7; before electrolytic water hydrogen evolution, CV scanning is carried out for 30-50 circles, and then LSV is tested; when the electrolyte is an acid electrolyte, the voltage range is: -0.2V to-0.6V; when the electrolyte is an acid electrolyte, the voltage range is: -0.8V to-1.4V;
the current density was 10mA cm without applying an additional magnetic field -2 The overpotential is 91 mV; under the condition of alkaline electrolyte, when the current density is 10mA cm -2 The overpotential is 128 mV;
when a 500mT magnetic field is applied, the current density is 10mA cm under the condition of acid electrolyte -2 The overpotential is 29 mV; under alkaline condition, the current density is 10mA cm -2 The overpotential is 35 mV;
the polarization curves of different magnetic field strengths in the electrolyzed water hydrogen evolution test are shown in FIG. 7;
FIG. 8 shows overpotential-time curves obtained when the test for hydrogen evolution from electrolyzed water was carried out.
Example 2
The porous catalyst with high hydrogen evolution performance under the external magnetic field is different from the porous catalyst in the embodiment 1 in that:
the porous catalyst with high hydrogen evolution performance by an external magnetic field is Co-P/Ni/NF with a porous structure and consists of a foam nickel matrix and Co-P deposited on the surface of the foam nickel matrix; the molar ratio of Ni, Co and P in the Co-P/Ni/NF is 1:0.25: 0.022; the surface roughness of the porous catalyst with high hydrogen evolution performance of the external magnetic field is 7 mu m; the specific surface area is 12m 2 (ii)/g; the porosity was 62%;
the preparation method is the same as example 1, and is different from the following steps:
(1) the ultrasonic treatment time of each liquid is 10 min; the concentration of hydrochloric acid is 2.5 mol/L; the size of the foamed nickel is 1cm in width and 3cm in length; the drying treatment temperature is 15 ℃, and the drying treatment time is 10 hours;
(2) in the electrodeposition solution, nickel chloride and ammonium chloride are mixed according to a molar ratio of 1: 30; according to the mass ratio of nickel salt to deionized water being 0.003 to 50;
(3) when constant current electrodeposition treatment is carried out, the current is-0.6A, and the time is 500 s;
(4) in the reaction solution, cobalt sulfate, sodium hypophosphite and sodium acetate are mixed according to a molar ratio of 1:8: 1; according to the mass ratio of cobalt sulfate to deionized water being 0.003 to 50;
(5) when the second constant current electrodeposition treatment is carried out, the current is-0.6A, and the time is 15 min; washing, namely alternately washing the taken out deposited foamed nickel with absolute ethyl alcohol and water for 4 times respectively; drying at 40 deg.C for 50 min;
the using method is different from that of the embodiment 1 in that:
(1) washing, namely alternately washing the taken out deposited foamed nickel with absolute ethyl alcohol and water for 4 times respectively; drying at 40 deg.C for 50 min;
(2) before water electrolysis and hydrogen evolution, nitrogen is introduced into the electrolyte in advance, and the nitrogen introduction time is 35 min;
the current density was 10mA cm without applying an additional magnetic field -2 The overpotential is 97 mV; under the condition of alkaline electrolyte, when the current density is 10mA cm -2 The overpotential is 121 mV;
when a 500mT magnetic field is applied, the current density is 10mA cm under the condition of acid electrolyte -2 The overpotential is 35 mV; under alkaline condition, when the current density is 10mA cm -2 The overpotential is 42 mV.
Example 3
The porous catalyst with high hydrogen evolution performance under the external magnetic field is the same as that in the example 1, and the difference is that:
the porous catalyst with high hydrogen evolution performance by an external magnetic field is Co-P/Ni/NF with a porous structure and consists of a foam nickel matrix and Co-P deposited on the surface of the foam nickel matrix; the molar ratio of Ni, Co and P in the Co-P/Ni/NF is 1:0.28: 0.025; the surface roughness of the porous catalyst with high hydrogen evolution performance of the external magnetic field is 6.5 mu m; the specific surface area is 12.5m 2 (ii)/g; the porosity is 65%;
the preparation method is the same as example 1, and is different from the following steps:
(1) the ultrasonic treatment time of each liquid is 5 min; the concentration of hydrochloric acid is 2 mol/L; the size of the foamed nickel is 0.5cm in width and 1cm in length; the drying treatment temperature is 30 ℃, and the drying treatment time is 6 hours;
(2) in the electrodeposition solution, nickel chloride and ammonium chloride are mixed according to a molar ratio of 1: 40; according to the mass ratio of nickel salt to deionized water, 0.004 to 50;
(3) when constant current electrodeposition treatment is carried out, the current is-0.7A, and the time is 300 s;
(4) in the reaction solution, cobalt sulfate, sodium hypophosphite and sodium acetate are mixed according to a molar ratio of 1:10: 1; according to the mass ratio of cobalt sulfate to deionized water being 0.004 to 50;
(5) when the second constant current electrodeposition treatment is carried out, the current is-0.7A, and the time is 20 min; washing is to wash the foam nickel after deposition taken out by using absolute ethyl alcohol and water alternately for 4 times respectively; drying at 50 deg.C for 40 min;
the using method is different from that of the embodiment 1 in that:
(1) washing is to wash the foam nickel after deposition taken out by using absolute ethyl alcohol and water alternately for 4 times respectively; drying at 50 deg.C for 40 min;
(2) before water electrolysis and hydrogen evolution, nitrogen is introduced into the electrolyte in advance, and the time for introducing the nitrogen is 40 min;
the current density was 10mA cm without applying an additional magnetic field -2 The overpotential is 94 mV; under the condition of alkaline electrolyte, when the current density is 10mA cm -2 The overpotential thereof is 115 mV;
when a 500mT magnetic field is applied, the current density is 10mA cm under the condition of acid electrolyte -2 The overpotential is 32 mV; under alkaline condition, when the current density is 10mA cm -2 The overpotential thereof was 43 mV.
Example 4
The porous catalyst with high hydrogen evolution performance under the external magnetic field is different from the porous catalyst in the embodiment 1 in that:
the porous catalyst with high hydrogen evolution performance by an external magnetic field is Co-P/Ni/NF with a porous structure and consists of a foam nickel matrix and Co-P deposited on the surface of the foam nickel matrix; the molar ratio of Ni, Co and P in the Co-P/Ni/NF is 1:0.25: 0.022; the surface roughness of the porous catalyst with the high hydrogen evolution performance of the external magnetic field is 7 mu m; the specific surface area is 12m 2 (ii)/g; the porosity was 68%;
the preparation method is the same as example 1, and is different from the following steps:
(1) the ultrasonic treatment time of each liquid is 8 min; the concentration of hydrochloric acid is 1.5 mol/L; the size of the foamed nickel is 1cm in width and 2cm in length; the drying treatment temperature is 20 ℃, and the drying treatment time is 8 hours;
(2) in the electrodeposition solution, nickel chloride and ammonium chloride are mixed according to a molar ratio of 1: 50; nickel salt and deionized water in a mass ratio of 0.005: 50;
(3) when constant current electrodeposition treatment is carried out, the current is-0.8A, and the time is 400 s;
(4) in the reaction solution, the molar ratio of cobalt sulfate, sodium hypophosphite and sodium acetate is 1:12: 1; according to the mass ratio of cobalt sulfate to deionized water being 0.005: 50;
(5) when the second constant current electrodeposition treatment is carried out, the current is-0.8A, and the time is 10 min; washing is to wash the foam nickel after deposition taken out by using absolute ethyl alcohol and water alternately for 4 times respectively; drying at 60 deg.C for 30 min;
the SEM image of the porous catalyst with high hydrogen evolution performance under the external magnetic field is shown in FIG. 6;
the using method is different from that of the embodiment 1 in that:
(1) washing, namely alternately washing the taken out deposited foamed nickel with absolute ethyl alcohol and water for 4 times respectively; drying at 60 deg.C for 30 min;
(2) introducing nitrogen into the electrolyte in advance for 45min before water electrolysis and hydrogen evolution;
the current density was 10mA cm without applying an additional magnetic field -2 The overpotential is 95 mV; under the condition of alkaline electrolyte, when the current density is 10mA cm -2 The overpotential is 113 mV;
when a 500mT magnetic field is applied, the current density is 10mA cm under the condition of acid electrolyte -2 The overpotential is 34 mV; under alkaline condition, when the current density is 10mA cm -2 The overpotential is 42 mV.
Example 5
The porous catalyst with high hydrogen evolution performance under the external magnetic field is different from the porous catalyst in the embodiment 1 in that:
the porous catalyst with high hydrogen evolution performance by an external magnetic field is Co-P/Ni/NF with a porous structure and consists of a foam nickel matrix and Co-P deposited on the surface of the foam nickel matrix; the molar ratio of Ni, Co and P in the Co-P/Ni/NF is 1:0.32: 0.028; the surface roughness of the porous catalyst with high hydrogen evolution performance of the external magnetic field is 6.2 mu m; the specific surface area is 10.1m 2 (ii)/g; the porosity is 58%;
the preparation method is the same as example 1, and is different from the following steps:
(1) the ultrasonic treatment time of each liquid is 12 min; the concentration of hydrochloric acid is 1 mol/L; the size of the foamed nickel is 1cm in width and 1cm in length; the drying treatment temperature is 20 ℃, and the drying treatment time is 8 hours;
(2) in the electrodeposition solution, nickel chloride and ammonium chloride are mixed according to a molar ratio of 1: 60; according to the mass ratio of nickel salt to deionized water, the mass ratio is 0.006: 50;
(3) when constant current electrodeposition treatment is carried out, the current is-0.9A, and the time is 100 s;
(4) in the reaction solution, cobalt sulfate, sodium hypophosphite and sodium acetate are mixed according to a molar ratio of 1:14: 1; cobalt sulfate and deionized water in a mass ratio of 0.006 to 50;
(5) performing second constant current electrodeposition with current of-0.9A for 20 min; washing, namely alternately washing the taken out deposited foamed nickel with absolute ethyl alcohol and water for 5 times respectively; drying at 60 deg.C for 30 min;
the method of use is the same as in example 1, except that:
(1) washing, namely alternately washing the taken out deposited foamed nickel with absolute ethyl alcohol and water for 5 times respectively; drying at 60 deg.C for 30 min;
(2) before water electrolysis and hydrogen evolution, nitrogen is introduced into the electrolyte in advance, and the nitrogen introduction time is 50 min;
the current density was 10mA cm without applying an additional magnetic field -2 The overpotential is 96 mV; under the condition of alkaline electrolyte, when the current density is 10mA cm -2 The overpotential is 108 mV;
when a 500mT magnetic field is applied, the current density is 10mA cm under the condition of acid electrolyte -2 The overpotential is 36 mV; under alkaline condition, when the current density is 10mA cm -2 The overpotential is 45 mV.
Example 6
The porous catalyst with high hydrogen evolution performance under the external magnetic field is different from the porous catalyst in the embodiment 1 in that:
the porous catalyst with high hydrogen evolution performance by an external magnetic field is Co-P/Ni/NF with a porous structure and consists of a foam nickel matrix and Co-P deposited on the surface of the foam nickel matrix; the molar ratio of Ni, Co and P in the Co-P/Ni/NF is 1:0.35: 0.032; the surface roughness of the porous catalyst with high hydrogen evolution performance of the external magnetic field is 6.8 mu m; the specific surface area is 10.5m 2 (ii)/g; the porosity is 75%;
the preparation method is the same as example 1, and is different from the following steps:
(1) the ultrasonic treatment time of each liquid is 6 min; the concentration of hydrochloric acid is 1.5 mol/L; the size of the foamed nickel is 0.5cm in width and 1cm in length; the drying treatment temperature is 20 ℃, and the drying treatment time is 9 hours;
(2) in the electrodeposition solution, nickel chloride and ammonium chloride are mixed according to a molar ratio of 1: 70; according to the mass ratio of nickel salt to deionized water, the ratio is 0.007 to 50;
(3) when constant current electrodeposition treatment is carried out, the current is-1A, and the time is 100 s;
(4) in the reaction solution, the molar ratio of cobalt sulfate, sodium hypophosphite and sodium acetate is 1:16: 1; cobalt sulfate and deionized water in a mass ratio of 0.007 to 50;
(5) performing second constant current electrodeposition with current of-1A for 20 min; washing, namely alternately washing the taken out deposited foamed nickel with absolute ethyl alcohol and water for 5 times respectively; drying at 60 deg.C for 30 min;
the using method is different from that of the embodiment 1 in that:
(1) washing, namely alternately washing the taken out deposited foamed nickel with absolute ethyl alcohol and water for 5 times respectively; drying at 60 deg.C for 30 min;
(2) before water electrolysis and hydrogen evolution, nitrogen is introduced into the electrolyte in advance, and the nitrogen introduction time is 55 min;
the current density was 10mA cm without applying an additional magnetic field -2 The overpotential is 98 mV; under the condition of alkaline electrolyte, when the current density is 10mA cm -2 The overpotential is 112 mV;
when a 500mT magnetic field is applied, the current density is 10mA cm under the condition of acid electrolyte -2 The overpotential is 34 mV; under alkaline condition, when the current density is 10mA cm -2 The overpotential thereof was 43 mV.
Example 7
The porous catalyst with high hydrogen evolution performance under the external magnetic field is different from the porous catalyst in the embodiment 1 in that:
the porous catalyst with high hydrogen evolution performance by an external magnetic field is Co-P/Ni/NF with a porous structure and consists of a foam nickel matrix and Co-P deposited on the surface of the foam nickel matrix; the molar ratio of Ni, Co and P in the Co-P/Ni/NF is 1:0.36: 0.032; the surface roughness of the porous catalyst with high hydrogen evolution performance of the external magnetic field is 6.8 mu m; the specific surface area is 12.6m 2 (ii)/g; the porosity is 82%;
the preparation method is the same as example 1, and is different from the following steps:
(1) the ultrasonic treatment time of each liquid is 9 min; the concentration of hydrochloric acid is 2 mol/L; the size of the foamed nickel is 0.5cm in width and 3cm in length; the drying treatment temperature is 20 ℃, and the drying treatment time is 10 hours;
(2) in the electrodeposition solution, nickel chloride and ammonium chloride are mixed according to a molar ratio of 1: 80; according to the mass ratio of nickel salt to deionized water, 0.0075: 50;
(3) when constant current electrodeposition treatment is carried out, the current is-1.2A, and the time is 500 s;
(4) in the reaction solution, cobalt sulfate, sodium hypophosphite and sodium acetate are mixed according to a molar ratio of 1:18: 1; according to the mass ratio of the cobalt sulfate to the deionized water being 0.0075: 50;
(5) when the second constant current electrodeposition treatment is carried out, the current is-1.2A, and the time is 10 min; washing is to wash the foam nickel taken out after deposition for 6 times by alternately using absolute ethyl alcohol and water; drying at 50 deg.C for 40 min;
the using method is different from that of the embodiment 1 in that:
(1) washing, namely alternately washing the taken out deposited foamed nickel for 6 times by using absolute ethyl alcohol and water respectively; drying at 50 deg.C for 40 min;
(2) before water electrolysis and hydrogen evolution, nitrogen is introduced into the electrolyte in advance, and the nitrogen introduction time is 60 min;
the current density was 10mA cm without applying an additional magnetic field -2 The overpotential is 97 mV; under the condition of alkaline electrolyte, when the current density is 10mA cm -2 The overpotential is 115 mV;
when a 500mT magnetic field is applied, the current density is 10mA cm under the condition of acid electrolyte -2 The overpotential is 30 mV; under alkaline condition, when the current density is 10mA cm -2 The overpotential was 39 mV.
Example 8
The porous catalyst with high hydrogen evolution performance under the external magnetic field is different from the porous catalyst in the embodiment 1 in that:
the porous catalyst with high hydrogen evolution performance by an external magnetic field is Co-P/Ni/NF with a porous structure and consists of a foam nickel matrix and Co-P deposited on the surface of the foam nickel matrix;the molar ratio of Ni, Co and P in the Co-P/Ni/NF is 1:0.28: 0.025; the surface roughness of the porous catalyst with high hydrogen evolution performance of the external magnetic field is 7.5 mu m; the specific surface area is 11.8m 2 (ii)/g; the porosity is 72%;
the preparation method is the same as example 1, and is different from the following steps:
(1) the ultrasonic treatment time of each liquid is 13 min; the concentration of hydrochloric acid is 2.5 mol/L; the size of the foamed nickel is 0.5cm in width and 1.5cm in length; the drying treatment temperature is 20 ℃, and the drying treatment time is 7 hours;
(2) in the electrodeposition solution, nickel chloride and ammonium chloride are mixed according to a molar ratio of 1: 100; according to the mass ratio of nickel salt to deionized water, 0.0075: 50;
(3) when constant current electrodeposition treatment is carried out, the current is-1.5A, and the time is 500 s;
(4) in the reaction solution, cobalt sulfate, sodium hypophosphite and sodium acetate are mixed according to a molar ratio of 1:20: 1; according to the mass ratio of the cobalt sulfate to the deionized water being 0.0075: 50;
(5) when the second constant current electrodeposition treatment is carried out, the current is-1.5A, and the time is 15 min; washing, namely alternately washing the taken out deposited foamed nickel for 6 times by using absolute ethyl alcohol and water respectively; drying at 40 deg.C for 50 min;
the using method is different from that of the embodiment 1 in that:
(1) washing, namely alternately washing the taken out deposited foamed nickel for 6 times by using absolute ethyl alcohol and water respectively; drying at 40 deg.C for 50 min;
(2) before water electrolysis and hydrogen evolution, nitrogen is introduced into the electrolyte in advance, and the time for introducing the nitrogen is 60 min;
the current density was 10mA cm without applying an additional magnetic field -2 The overpotential is 102 mV; under the condition of alkaline electrolyte, when the current density is 10mA cm -2 The overpotential is 113 mV;
when a 500mT magnetic field is applied, the current density is 10mA cm under the condition of acid electrolyte -2 The overpotential is 36 mV; under alkaline condition, when the current density is 10mA cm -2 The overpotential thereof was 43 mV.

Claims (10)

1. A porous catalyst with high hydrogen evolution performance by an external magnetic field is characterized in that the catalyst is Co-P/Ni/NF with a porous structure and consists of deposited foam nickel and Co-P deposited on the surface of the foam nickel, wherein the deposited foam nickel is formed by depositing nickel on the surface of a nickel substrate; the molar ratio of Ni, Co and P in the Co-P/Ni/NF is 1 (0.2-0.4) to 0.01-0.04; the surface roughness of the porous catalyst with the high hydrogen evolution performance of the external magnetic field is 5-10 mu m.
2. The porous catalyst with high hydrogen evolution performance under the action of an external magnetic field according to claim 1, which is characterized in that the specific surface area of the porous catalyst is 10-15 m 2 /g。
3. The porous catalyst with high hydrogen evolution performance under an external magnetic field according to claim 1, wherein the porosity of the porous catalyst is 60-80%.
4. A preparation method of the porous catalyst with high hydrogen evolution performance by an external magnetic field according to claim 1 is characterized by comprising the following steps:
(1) sequentially placing the foamed nickel into hydrochloric acid, acetone, ethanol and deionized water for ultrasonic treatment, and then drying to remove surface liquid to prepare pretreated foamed nickel;
(2) dissolving nickel chloride and ammonium chloride in deionized water, and uniformly mixing to prepare an electrodeposition solution;
(3) adopting an electrochemical workstation, taking the pretreated foamed nickel as a working electrode, taking graphite as a reference electrode and a counter electrode, putting each electrode in an electrodeposition solution, electrifying to carry out constant current electrodeposition treatment, and depositing nickel on the surface of the pretreated foamed nickel to prepare deposited foamed nickel;
(4) dissolving cobalt sulfate, sodium hypophosphite and sodium acetate in deionized water, and uniformly mixing to prepare a reaction solution;
(5) taking out the deposited nickel foam by using an electrochemical workstation, and washing and drying the nickel foam to be used as a working electrode; and (3) taking a Pt electrode as a counter electrode and an Hg/HgO electrode as a reference electrode, placing the electrodes in a reaction solution, electrifying to carry out second constant-current electrodeposition treatment, and depositing cobalt and phosphorus on the surface of the deposited foamed nickel to prepare the porous catalyst with the externally applied magnetic field and high hydrogen evolution performance.
5. The preparation method of the porous catalyst with the high hydrogen evolution performance under the external magnetic field according to claim 1, wherein in the step (1), the size of the foamed nickel is 0.5-1 cm in width and 1-3 cm in length.
6. The method for preparing the porous catalyst with the high hydrogen evolution performance under the action of the applied magnetic field according to claim 1, wherein in the step (2), nickel chloride and ammonium chloride are added into the electrodeposition solution according to a molar ratio of (20-100).
7. The method for preparing the porous catalyst with the high hydrogen evolution performance by the external magnetic field according to claim 1, wherein in the step (2), the weight ratio of nickel chloride to deionized water is (0.0025-0.0075) to (50) in the electrodeposition solution.
8. The method for preparing a porous catalyst with high hydrogen evolution performance by an external magnetic field according to claim 1, wherein in the step (3), when the constant current electrodeposition treatment is carried out, the current is between-0.5 and-1.5A, and the time is between 100 and 500 s.
9. The method for preparing the porous catalyst with the high hydrogen evolution performance by the external magnetic field according to claim 1, wherein in the step (5), the current is between-0.5 and-1.5A for 10 to 30min when the second constant current electrodeposition treatment is carried out.
10. The use method of the porous catalyst with high hydrogen evolution performance under the external magnetic field as set forth in claim 1 is characterized by comprising the following steps:
(1) taking out the porous catalyst with high hydrogen evolution performance of the external magnetic field, washing and drying the porous catalyst to be used as a working electrode; taking a Pt electrode as a counter electrode and taking an Hg/HgO electrode or an SCE electrode as a reference electrode;
(2) placing the electrolyte into an electrolytic cell by using an electrochemical workstation; and (3) placing each electrode in electrolyte, applying a uniform magnetic field outside the electrolytic cell, and electrifying to electrolyze water and evolve hydrogen.
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