CN108754532B - Molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material and preparation method and application thereof - Google Patents
Molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material and a preparation method and application thereof. The preparation method comprises the steps of directly growing a FeNi-LDHs nanosheet array on a foamed nickel substrate by a hydrothermal method, doping metal Mo on the surface of the FeNi-LDHs nanosheet array serving as the substrate by the hydrothermal method, and finally carbonizing and reducing at high temperature to obtain the electrode material with electrocatalytic performance. The composite material has stable performance under alkaline conditions, higher repeated utilization degree and larger electrochemical active area, and greatly improves the catalytic activity of the material; the preparation method has the advantages of simple preparation process, low sintering temperature, low energy consumption in the preparation process and convenience for industrial production.
Description
Technical Field
The invention relates to the technical field of electrolytic water catalytic hydrogen evolution, in particular to a molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material and a preparation method and application thereof.
Background
Energy is the fundamental driving force for the development of human productivity as a cornerstone for various production activities in the human society. From ancient times to the present, fossil energy, which is a main energy source utilized by human, is consumed at a rate that becomes faster and faster as human develops, and particularly, since the fossil energy enters an industrial society, the existing storage is about to be depleted over centuries. The consumption of fossil energy also brings environmental pollution problems, and therefore, the development of sustainable and clean alternative energy is urgent. Hydrogen is considered a sustainable clean energy source because the combustion process of hydrogen releases huge energy and the product is water. From the aspect of environmental friendliness, hydrogen production by electrochemically catalyzing and decomposing water is one of ideal ways for preparing hydrogen. However, in water splitting reactions, an efficient hydrogen evolution catalyst is often required to allow the reaction to produce a large current at a low overpotential. The hydrogen evolution catalysts used at present are mainly platinum group noble metal materials, which have very low overpotential and excellent reaction kinetic behavior during the hydrogen evolution reaction. However, the high cost limits the large-scale industrial application. Therefore, in order to meet the requirement of developing sustainable energy, it is important to develop and apply a hydrogen evolution catalyst with high efficiency and low price to replace an expensive noble metal catalyst.
In recent years, some non-noble metals have been used as hydrogen evolution catalysts, but the catalytic stability and catalytic performance cannot meet the requirements of industrial production. Therefore, the development of a non-noble metal catalyst which is low in cost, easy to prepare and high in performance has important significance for promoting the development of hydrogen evolution industrialization. Researches find that the hydrogen evolution reaction under the alkaline condition has the advantages of no pollution, convenient operation, mature technology, easy large-scale production and the like, and becomes one of the research hotspots. However, the catalyst for hydrogen evolution reaction under alkaline conditions has problems such as poor stability, and further studies have been required.
In view of the above, the invention provides a molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material, and a preparation method and application thereof.
Disclosure of Invention
Based on the defects of the prior art, the invention provides a molybdenum-doped iron/nickel Layered array @ foam nickel-based composite electrode material (Mo/FeNi-Layered @ foam nickel) and a preparation method and application thereof.
Preferably, the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material and the preparation method and application thereof provided by the invention further comprise part or all of the following technical characteristics:
the utility model provides a molybdenum doped iron/nickel lamination array @ foam nickel base composite electrode material, the material uses foam nickel as the base, foam nickel's surface growth has iron/nickel lamination bimetal hydroxide array (FeNi-LDHs), be doped with metal molybdenum in the array.
The technical scheme of the application can be realized in the following way, and the preparation method of the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material comprises the following steps:
1) removing oil stains and an oxide layer on the surface of the foamed nickel by using an organic solvent and acid soaking, and pretreating the foamed nickel;
2) preparing ferric salt, nickel salt and deionized water into ferric salt and nickel salt compound precursor solution according to a proportion, putting the ferric salt and nickel salt compound precursor and foamed nickel together into a high-pressure kettle for closed reaction, and after the reaction is finished, washing and drying to obtain foamed nickel (FeNi-LDHs @ foamed nickel) with a ferric/nickel layered double metal hydroxide array growing on the surface;
3) putting the foamed nickel obtained in the step (2) into a molybdenum salt solution, reacting and doping metal molybdenum through a hydrothermal method, washing with water and drying to obtain the molybdenum-doped iron/nickel layered array @ foamed nickel-based composite electrode material without carbonization;
4) carbonizing the product obtained in the step (3) at high temperature in H2Calcining at high temperature in the atmosphere, and naturally cooling to obtain the molybdenum-doped iron/nickel Layered array @ foam nickel-based composite electrode material (Mo/FeNi-Layered @ foam nickel).
As an improvement of the above technical solution, the specific method of step 2) is as follows: adding iron salt, nickel salt, ammonium fluoride, polyethylene glycol and urea into deionized water, fully dissolving to obtain an iron and nickel salt compound precursor solution, adding the treated foamed nickel, heating to 100 ℃ and 150 ℃, and reacting for 4-6 h to obtain the FeNi-LDHs @ foamed nickel.
As an improvement of the above technical scheme, the molar ratio of the dosage of the iron salt, the nickel salt, the ammonium fluoride, the polyethylene glycol and the urea is 1: 2-2.2: 1.9-17.2: 0.008-0.08: 7.5 to 8.6.
As an improvement of the above technical solution, the molar ratio of the iron salt, the nickel salt, the ammonium fluoride, the polyethylene glycol, and the urea is preferably 1: 2: 16: 0.008-0.08: 8.
as an improvement of the technical scheme, the concentration range of iron salt and nickel salt in the precursor solution of the iron salt and nickel salt compound is 1-2 mmol/L.
As an improvement of the technical scheme, the iron salt comprises ferric nitrate, ferric chloride and ferric sulfate, and the nickel salt comprises nickel nitrate, nickel chloride and nickel sulfate.
As an improvement of the technical scheme, the molecular weight of the polyethylene glycol is 1000-10000.
As an improvement of the above technical solution, the specific method of step 3) is as follows: firstly, dissolving molybdenum salt in water, adding foamed nickel with an iron/nickel layered double metal hydroxide array growing on the surface obtained in the step 2) into the molybdenum salt, placing the mixture into a high-pressure kettle for closed reaction, heating to 180-200 ℃, reacting for 10-12 hours, and separating, washing and drying after the reaction is finished; then placing the mixture into a tube furnace, introducing nitrogen for 15-30 min, heating to 300 ℃ at the heating rate of 5 ℃/min, preserving heat for 1-2 h, and cooling to room temperature at the same rate; then 5% H is introduced2And after 15-30 min of/95% Ar mixed gas, heating to 450 ℃ at the heating rate of 5 ℃/min, preserving heat for 1-2 h, cooling to room temperature at the same rate, and taking out to obtain the Mo/FeNi-Layered @ foamed nickel.
As an improvement of the above technical scheme, the molybdenum salt in the step 3) is ammonium heptamolybdate, the concentration of the molybdenum salt solution is 1-2 mmol/L, and the mass ratio of the molybdenum salt to the nickel foam with the iron/nickel layered double metal hydroxide array growing on the surface is 0.9-1.8: 100.
the technical scheme of the application can also be realized in the following way, and the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material is applied to hydrogen evolution through water electrolysis and is used as an electrode or a catalyst for hydrogen evolution through water electrolysis.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the electrolytic water hydrogen evolution electrode material adopts a novel inorganic functional material FeNi-LDHs with a bimetallic hydroxide Layer Structure (LDHs), and has the characteristics of acidity-basicity, interlaminar anion exchangeability and the like, so that the stability of the catalyst can be effectively improved, the catalytic hydrogen evolution performance of the catalyst under the alkaline condition can be obviously improved after the catalyst is further doped with metal Mo, and the defects of the existing non-noble metal catalyst are overcome;
(2) the catalytic components of the electrolytic water hydrogen evolution electrode material grow on the surface of a foam nickel skeleton structure, and the electrolytic water hydrogen evolution electrode material can be directly used as an electrode as a self-supported catalyst;
(3) the FeNi-LDHs array prepared by the invention has the advantage of large surface area, provides more active sites, and has better catalytic hydrogen evolution performance;
(4) the composite electrode material has good stability and high repeated utilization degree, can be widely used as an alkaline electrolysis water hydrogen evolution electrode material, and has wide application prospect.
(5) The composite electrode material disclosed by the invention is simple in preparation process, low in sintering temperature, low in energy consumption in the preparation process and convenient for industrial production.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the contents of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is an SEM image of a non-carbonized Mo-doped FeNi-LDHs array composite grown on nickel foam prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a carbonized Mo/FeNi-Layered @ nickel foam composite material prepared in example 1 of the present invention;
FIG. 3 is a polarization curve diagram of a hydrogen evolution experiment under an alkaline condition, wherein Mo/FeNi-Layered @ nickel foam prepared in example 1 of the invention is used as a working electrode.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
Example 1
The molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material specifically comprises the following steps:
a. taking foamed nickel, cutting into a size of 1cm multiplied by 3cm, placing in a beaker, adding absolute ethyl alcohol until the foamed nickel is immersed, performing ultrasonic treatment for 15min, pouring the absolute ethyl alcohol, adding 1mol/L diluted hydrochloric acid until the foamed nickel is immersed, and performing ultrasonic treatment for 15min, and then washing with water for later use;
b. weighing 20mL of deionized water, placing the deionized water in a conical flask, adding 0.45g of ferric nitrate nonahydrate, 0.7g of nickel nitrate hexahydrate, 0.7g of ammonium fluoride, 0.05g of polyethylene glycol (with the molecular weight of 6000) and 0.5g of urea, stirring and ultrasonically treating for 15min until the ferric nitrate nonahydrate, the nickel nitrate hexahydrate, the ammonium fluoride, the polyethylene glycol (with the molecular weight of 6000) and the urea are completely dissolved, placing the mixture in a 25mL high-temperature autoclave, adding the foamed nickel treated in the step a, heating to 120 ℃ for reaction for 4h, and separating, washing and drying to obtain the foamed nickel (FeNi-LDHs @ foamed nickel) with the FeNi-LD.
c. Weighing 20mL of deionized water, placing the deionized water into a conical flask, adding 0.0247g of ammonium heptamolybdate, and carrying out ultrasonic treatment until the ammonium heptamolybdate is completely dissolved; and c, soaking the FeNi-LDHs @ foamed nickel obtained in the step b in an ammonium heptamolybdate water solution for 10 hours, then heating to 200 ℃ for reaction for 10 hours, and separating, washing and drying after the reaction to obtain the non-carbonized Mo-doped FeNi bimetal layered array foamed nickel composite material.
d. Putting the non-carbonized Mo-doped FeNi bimetal laminated array foamed nickel prepared in the step c into a tubular furnace, introducing nitrogen for 15min, heating to 300 ℃, preserving heat for 1H, naturally cooling to room temperature, and then introducing 5% H2And 95% Ar2Heating the mixed gas of hydrogen and argon to 450 ℃ after 15min, preserving the heat for 1h, and naturally cooling to room temperature to obtain the carbonized Mo/FeNi-layerred @ foamed nickel composite.
Fig. 1 is an SEM image of a composite material of a non-carbonized foamed nickel-based Mo-doped FeNi bimetallic Layered array prepared by the present invention, and fig. 2 is an SEM image of a carbonized Mo/FeNi-Layered @ foamed nickel composite material prepared by the present invention. The array of lamellar structures in the composite material is obvious from fig. 1 and has a 3D structure, and the composite material can be seen from fig. 2 to maintain a good array of lamellar structures after carbonization and reduction treatment, which indicates that the material has good thermal stability and porosity.
The Mo/FeNi-Layered @ foamed nickel composite material is used as a cathode hydrogen evolution reaction electrode (also called as a catalyst) in an electrolytic water device, and an electrochemical hydrogen evolution experiment is carried out on the cathode hydrogen evolution reaction electrode.
The specific test method comprises the following steps: controlling the test temperature to be 25 ℃; directly taking Mo/FeNi-Layered @ foamed nickel with the size of 0.5cm multiplied by 0.5cm as a working electrode, taking an Ag/AgCl electrode as a reference electrode, taking a graphite electrode as a counter electrode to assemble a three-electrode system, and respectively putting the three-electrode system into a three-way electrolytic cell; preparing 1mol/L potassium hydroxide solution, and adding the solution into a three-way electrolytic cell; activating the electrode by cyclic voltammetry, wherein the curve scanning speed is 50mV/s, and the number of scanning cycles is 30 cycles; the polarization curve was tested at a curve scan speed of 2mV/s with an IR compensation of 85% before testing. Commercial nickel foam was also used as a control experiment.
The polarization curves of the electrochemical hydrogen evolution experiment of the catalyst prepared by the invention and the electrochemical hydrogen evolution experiment of commercial foam nickel are shown in figure 3. Comparing the two curves, it can be seen that the catalyst prepared by the invention reaches 10mA/cm in the hydrogen evolution experiment3The overpotential required by the current density is 69mV, which is far lower than the overpotential of 132mV of commercial foam nickel, and the good hydrogen evolution catalytic performance is shown, which indicates that the catalyst has strong application potential in industry.
Example 2
a. Taking foamed nickel, cutting into a size of 1cm multiplied by 3cm, placing in a beaker, adding absolute ethyl alcohol until the foamed nickel is immersed, performing ultrasonic treatment for 15min, pouring the absolute ethyl alcohol, adding 1mol/L diluted hydrochloric acid until the foamed nickel is immersed, and performing ultrasonic treatment for 15min, and then washing with water for later use;
b. weighing 20mL of deionized water, placing the deionized water in a conical flask, adding 0.5g of ferric nitrate nonahydrate, 0.73g of nickel nitrate hexahydrate, 0.72g of ammonium fluoride, 0.1g of polyethylene glycol (molecular weight is 6000) and 0.6g of urea, stirring and ultrasonically treating for 20min until the ferric nitrate nonahydrate, the nickel nitrate hexahydrate, the ammonium fluoride, the polyethylene glycol (molecular weight is 6000) and the urea are completely dissolved, placing the mixture in a 25mL high-temperature autoclave, adding the foamed nickel treated in the step a, heating to 150 ℃ for reaction for 5h, and separating, washing and drying to obtain the FeNi-LDHs @ foamed nickel.
c. Weighing 20mL of deionized water, placing the deionized water into a conical flask, adding 0.0247g of ammonium heptamolybdate, and carrying out ultrasonic treatment until the ammonium heptamolybdate is completely dissolved; and c, soaking the FeNi-LDHs @ foamed nickel obtained in the step b in an ammonium heptamolybdate water solution for 10 hours, then heating to 200 ℃ for reaction for 12 hours, and separating, washing and drying after the reaction to obtain the non-carbonized Mo-doped FeNi bimetal layered array foamed nickel composite material.
d. Putting the non-carbonized Mo-doped FeNi bimetal laminated array foamed nickel prepared in the step c into a tubular furnace, introducing nitrogen for 30min, heating to 300 ℃, preserving heat for 2H, naturally cooling to room temperature, and then introducing 5% H2And 95% Ar2And heating the mixed gas of hydrogen and argon to 450 ℃ after 30min, preserving the heat for 2h, and naturally cooling to room temperature to obtain the carbonized Mo/FeNi-Layered @ foamed nickel composite material.
Example 3
a. Taking foamed nickel, cutting into a size of 1cm multiplied by 3cm, placing in a beaker, adding absolute ethyl alcohol until the foamed nickel is immersed, performing ultrasonic treatment for 15min, pouring the absolute ethyl alcohol, adding 1mol/L diluted hydrochloric acid until the foamed nickel is immersed, and performing ultrasonic treatment for 15min, and then washing with water for later use;
b. weighing 20mL of deionized water, placing the deionized water in a conical flask, adding 0.55g of ferric nitrate nonahydrate, 0.75g of nickel nitrate hexahydrate, 0.75g of ammonium fluoride, 0.15g of polyethylene glycol (molecular weight is 6000) and 0.7g of urea, stirring and ultrasonically treating for 20min until the ferric nitrate nonahydrate, the nickel nitrate hexahydrate, the ammonium fluoride, the polyethylene glycol (molecular weight is 6000) and the urea are completely dissolved, placing the mixture in a 25mL high-temperature autoclave, adding the foamed nickel treated in the step a, heating to 100 ℃ for reaction for 6h, and separating, washing and drying to obtain the FeNi-LDHs @ foamed nickel.
c. Weighing 20mL of deionized water, placing the deionized water into a conical flask, adding 0.0247g of ammonium heptamolybdate, and carrying out ultrasonic treatment until the ammonium heptamolybdate is completely dissolved; and c, soaking the FeNi-LDHs @ foamed nickel obtained in the step b in an ammonium heptamolybdate water solution for 12 hours, then heating to 200 ℃ for reaction for 12 hours, and separating, washing and drying after the reaction to obtain the non-carbonized Mo-doped FeNi bimetal layered array foamed nickel composite material.
d. Putting the non-carbonized Mo-doped FeNi bimetal laminated array foamed nickel prepared in the step c into a tubular furnace, introducing nitrogen for 30min, heating to 300 ℃, preserving heat for 1H, naturally cooling to room temperature, and then introducing 5% H2And 95% Ar2And heating the mixed gas of hydrogen and argon to 450 ℃ after 30min, preserving the heat for 2h, and naturally cooling to room temperature to obtain the carbonized Mo/FeNi-Layered @ foamed nickel composite material.
Example 4
a. Taking foamed nickel, cutting into a size of 1cm multiplied by 3cm, placing in a beaker, adding absolute ethyl alcohol until the foamed nickel is immersed, carrying out ultrasonic treatment for 30min, pouring out the absolute ethyl alcohol, adding 1mol/L diluted hydrochloric acid until the foamed nickel is immersed, and carrying out ultrasonic treatment for 30min, and then washing with water for later use;
b. weighing 20mL of deionized water, placing the deionized water in a conical flask, adding 0.5g of ferric nitrate nonahydrate, 0.72g of nickel nitrate hexahydrate, 0.75g of ammonium fluoride, 0.1g of polyethylene glycol (molecular weight is 6000) and 0.6g of urea, stirring and ultrasonically treating for 30min until the ferric nitrate nonahydrate, the nickel nitrate hexahydrate, the ammonium fluoride, the polyethylene glycol (molecular weight is 6000) and the urea are completely dissolved, placing the mixture in a 25mL high-temperature autoclave, adding the foamed nickel treated in the step a, heating to 120 ℃ for reaction for 5h, and separating, washing and drying to obtain the FeNi-LDHs @ foamed nickel.
c. Measuring 20mL of deionized water, placing the deionized water into a conical flask, adding 0.0494g of ammonium heptamolybdate, and carrying out ultrasonic treatment until the ammonium heptamolybdate is completely dissolved; and c, soaking the FeNi-LDHs @ foamed nickel obtained in the step b in an ammonium heptamolybdate water solution for 12 hours, then heating to 200 ℃ for reaction for 10 hours, and separating, washing and drying after the reaction to obtain the non-carbonized Mo-doped FeNi bimetal layered array foamed nickel composite material.
d. Putting the non-carbonized Mo-doped FeNi bimetal laminated array foamed nickel prepared in the step c into a tubular furnace, introducing nitrogen for 30min, heating to 300 ℃, preserving heat for 1H, naturally cooling to room temperature, and then introducing 5% H2And 95% Ar2Heating the mixed gas of hydrogen and argon to 450 ℃ after 30min, preserving the heat for 2h, and naturally cooling to room temperature to obtain carbonized MoThe composite material is/FeNi-Layered @ foamed nickel.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (9)
1. The molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material is characterized in that foam nickel is used as a substrate, an iron/nickel layered double metal hydroxide array grows on the surface of the foam nickel, and metal molybdenum is doped in the array; the preparation raw materials comprise ferric salt and nickel salt, and the molar ratio of the dosage of the ferric salt to the dosage of the nickel salt is 1: 1.5-2.5; in the preparation process, ammonium fluoride and polyethylene glycol are added, wherein the molecular weight of the polyethylene glycol is 1000-10000; the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material reaches 10mA/cm in a hydrogen evolution experiment3The overpotential required for the current density of the capacitor is 69 mV;
the preparation method of the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material comprises the following steps of:
1) removing oil stains and an oxide layer on the surface of the foamed nickel by using an organic solvent and acid soaking, and pretreating the foamed nickel;
2) preparing ferric salt, nickel salt and deionized water into ferric salt and nickel salt compound precursor solution according to a proportion, putting the ferric salt and nickel salt compound precursor and foamed nickel together into a high-pressure kettle for closed reaction, and after the reaction is finished, washing and drying to obtain the foamed nickel with a ferric/nickel layered double metal hydroxide array growing on the surface;
3) putting the foamed nickel obtained in the step 2) into a molybdenum salt solution, reacting and doping metal molybdenum through a hydrothermal method, washing with water and drying;
4) and 3) carbonizing the product obtained in the step 3) at high temperature, calcining the product at high temperature in a hydrogen-argon mixed gas atmosphere, and naturally cooling the product to obtain the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrolytic hydrogen evolution catalyst.
2. The preparation method of the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material is characterized by comprising the following steps of:
1) removing oil stains and an oxide layer on the surface of the foamed nickel by using an organic solvent and acid soaking, and pretreating the foamed nickel;
2) preparing ferric salt, nickel salt and deionized water into ferric salt and nickel salt compound precursor solution according to a proportion, putting the ferric salt and nickel salt compound precursor and foamed nickel together into a high-pressure kettle for closed reaction, and after the reaction is finished, washing and drying to obtain the foamed nickel with a ferric/nickel layered double metal hydroxide array growing on the surface;
3) putting the foamed nickel obtained in the step 2) into a molybdenum salt solution, reacting and doping metal molybdenum through a hydrothermal method, washing with water and drying;
4) and 3) carbonizing the product obtained in the step 3) at high temperature, calcining the product at high temperature in a hydrogen-argon mixed gas atmosphere, and naturally cooling the product to obtain the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrolytic hydrogen evolution catalyst.
3. The preparation method of the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material as claimed in claim 2, wherein the specific method of the step 2) is as follows: adding iron salt, nickel salt, ammonium fluoride, polyethylene glycol and urea into deionized water, fully dissolving to obtain an iron and nickel salt compound precursor solution, adding the treated foamed nickel, heating to 100 ℃ and 150 ℃, and reacting for 4-6 h to obtain the foamed nickel with the iron/nickel layered double metal hydroxide array growing on the surface.
4. The preparation method of the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material as claimed in claim 3, wherein the molar ratio of the usage amounts of the iron salt, the nickel salt, the ammonium fluoride, the polyethylene glycol and the urea is 1: 1.5-2.5: 1.5-20: 0.01-0.1: 5 to 10.
5. The method for preparing the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material as claimed in claim 3, wherein the iron salt comprises ferric nitrate, ferric chloride and ferric sulfate, and the nickel salt comprises nickel nitrate, nickel chloride and nickel sulfate.
6. The preparation method of the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material as claimed in claim 3, wherein the molecular weight of the polyethylene glycol is 1000-10000.
7. The preparation method of the molybdenum-doped iron/nickel layered array @ foam nickel-based composite electrode material as claimed in claim 2, wherein the specific method of the step 3) is as follows: firstly, dissolving molybdenum salt in water, adding foamed nickel with an iron/nickel layered double metal hydroxide array growing on the surface obtained in the step 2) into the molybdenum salt, placing the mixture into a high-pressure kettle for closed reaction, heating to 180-200 ℃, reacting for 10-12 hours, and separating, washing and drying after the reaction is finished; then placing the mixture into a tube furnace, introducing nitrogen for 15-30 min, heating to 300 ℃ at the heating rate of 5 ℃/min, preserving heat for 1-2 h, and cooling to room temperature at the same rate; then 5% H is introduced2And after 15-30 min of the/95% Ar mixed gas, heating to 450 ℃ at the heating rate of 5 ℃/min, preserving heat for 1-2 h, cooling to room temperature at the same rate, and taking out to obtain the target product.
8. The preparation method of the molybdenum-doped iron/nickel layered array @ foamed nickel-based composite electrode material as claimed in claim 7, wherein the molybdenum salt in the step 3) is ammonium heptamolybdate, the concentration of the molybdenum salt solution is 1-2 mmol/L, and the mass ratio of the molybdenum salt to the foamed nickel with the iron/nickel layered double metal hydroxide array growing on the surface is 0.9-1.8: 100.
9. the use of the molybdenum-doped iron/nickel layered array @ nickel foam composite electrode material as defined in claim 1, wherein the molybdenum-doped iron/nickel layered array @ nickel foam composite electrode material is used for hydrogen evolution by electrolysis.
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