CN115522211A - Preparation method of Ni/Mo/Ru composite material and application of Ni/Mo/Ru composite material in hydrogen production by water electrolysis - Google Patents
Preparation method of Ni/Mo/Ru composite material and application of Ni/Mo/Ru composite material in hydrogen production by water electrolysis Download PDFInfo
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 6
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- 239000003054 catalyst Substances 0.000 abstract description 44
- 230000003197 catalytic effect Effects 0.000 abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
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- 238000004502 linear sweep voltammetry Methods 0.000 description 14
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- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 description 3
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to the field of functional material technology and hydrogen production by water electrolysis, in particular to a preparation method of a Ni/Mo/Ru composite material and application thereof in hydrogen production by water electrolysis. According to the invention, a nickel-molybdenum precursor is synthesized by a hydrothermal method, and then the precursor is used for adsorbing ruthenium ions and is reduced in an argon-hydrogen atmosphere, so that the Ni/Mo/Ru composite material catalyst uniformly loaded on foamed nickel is synthesized, the catalytic efficiency of the material is improved, and the cost of the use amount of ruthenium is reduced. The catalyst synthesized by the invention has good catalytic performance when being applied to electrolysis of water for hydrogen evolution, and the current density is 10mA/cm under 1M KOH 2 The overpotential in the working condition of the catalyst is only 25mV, the electron transmission rate of the catalyst is high, and the catalyst has good catalytic performance when being applied to water electrolysis oxygen evolution and full water electrolysis, and can promote the development and application of electrochemical hydrogen production technology.
Description
Technical Field
The invention relates to the field of functional material technology and hydrogen production by water electrolysis, in particular to a preparation method of a Ni/Mo/Ru composite material and application thereof in hydrogen production by water electrolysis.
Background
Hydrogen has the characteristics of high energy density and zero carbon dioxide emission, is considered to be a good green energy source, and can be used as a substitute of the traditional fossil fuel. Recently, the hydrogen production reaction (HER) by electrolysis of water has attracted increasing attention as an effective method for producing high-purity hydrogen. Noble metal platinum (Pt) plays a leading role in the current electrolytic water hydrogen evolution production process as a common benchmark HER electrocatalyst, but the scarcity and high cost of Pt seriously hinder the large-scale application of the Pt in the electrocatalytic HER. Therefore, there is a need to develop a non/low content noble metal electrocatalyst that is efficient and relatively abundant in global resources to replace the platinum-based material.
Compared with platinum, the price and the storage amount of the noble metal ruthenium are both advantageous, and the noble metal ruthenium is an ideal benign substitute. In 2019, research reports that a NiFeRu-LDH material is prepared by respectively adding Ni, fe and Ru metal salts into an aqueous solution and preparing a trimetal layered hydroxide catalyst through a hydrothermal synthesis method, wherein the catalyst shows good activity in the subsequent HER (HER) test process, and the current density is 10mV/cm 2 The overpotential is only 29mV, and the addition of ruthenium promotes the dissociation of water and accelerates the reaction kinetics. In addition, in the course of the previous research on the hydrogen evolution reaction by electrolysis of water, oxides, hydroxides and layered double hydroxides composed of various nickel or molybdenum groups are reported as HER catalysts, but the simple molybdenum-nickel group catalytic effect is not ideal, and the addition of ruthenium metal is required to enhance the catalytic performance. However, most of the catalysts require a large amount of added ruthenium and are costly, so that a method for improving the catalytic efficiency of ruthenium needs to be developed to reduce the amount of ruthenium in the catalyst and reduce the cost.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a Ni/Mo/Ru composite material and application thereof in hydrogen production by water electrolysis.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a Ni/Mo/Ru composite material, which consists of Ni, mo and Ru.
Preferably, the Ni/Mo/Ru composite material is a composite material formed by combining a Ni-Mo base material and ruthenium, and the Ni/Mo/Ru composite material is uniformly loaded on foamed nickel. The Ru particles of the Ni/Mo/Ru composite material are combined with the Ni-Mo base material through adsorption and are closely related with Ni/Mo oxide.
The invention also provides a preparation method of the Ni/Mo/Ru composite material, which comprises the following steps:
s1, preparation of a Ni-Mo precursor: immersing the pretreated foamed nickel into a mixed solution of nickel nitrate hexahydrate and ammonium molybdate tetrahydrate, reacting by a hydrothermal method to synthesize a Ni-Mo precursor, and carrying out ultrasonic cleaning on the reacted foamed nickel to obtain foamed nickel loaded with the Ni-Mo precursor;
s2, adsorbing Ru: soaking the foam nickel loaded with the Ni-Mo precursor into a ruthenium chloride solution, standing at room temperature to enable the precursor to fully adsorb Ru, and taking out a sample for drying;
s3, preparing the Ni/Mo/Ru composite material: and calcining and reducing the dried sample of S2 in an argon-hydrogen mixed gas atmosphere, and cooling to room temperature to obtain the Ni/Mo/Ru composite material uniformly loaded on the foamed nickel.
Preferably, in step 1, the pretreatment is to cut the size of the foamed nickel into 2 × 3cm 2 And washed with 3M HCl and deionized water, respectively, for standby.
Preferably, in the step 1, the molar concentration of nickel nitrate hexahydrate in the mixed solution is 2-6 mu mol/ml, and the molar concentration of ammonium molybdate tetrahydrate in the mixed solution is 5-8 mu mol/ml. Further, the molar concentration of nickel nitrate hexahydrate is 2 mu mol/ml, and the molar concentration of ammonium molybdate tetrahydrate is 5 mu mol/ml
Preferably, in the step 1, the temperature of the hydrothermal reaction is 140-180 ℃, and the reaction time is 5-7 h. Further, the temperature of the hydrothermal reaction is 150 ℃, and the reaction time is 6h.
Preferably, in the step 2, the concentration of the ruthenium chloride solution is 1-2 mg/ml. Further, the concentration of the ruthenium chloride solution is 1mg/ml.
Preferably, in step 3, the gas flow rate during the calcination is 40-70 ml/min, and the calcination temperature is 450-550 ℃. Further, the gas flow in the calcination process is 50ml/min, and the calcination temperature is 500 ℃.
Preferably, in step 3, the volume of hydrogen in the argon-hydrogen gas is 5% of the total gas volume.
The invention also provides application of the Ni/Mo/Ru composite material prepared by the preparation method, and the Ni/Mo/Ru composite material is applied to catalytic electrolysis water hydrogen evolution, oxygen evolution and full water hydrolysis reaction.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a Ni/Mo/Ru composite material, which is a composite material formed by combining a Ni-Mo substrate material uniformly loaded on foamed nickel and ruthenium. The preparation method of the composite material comprises the steps of synthesizing a nickel-molybdenum oxide precursor by a hydrothermal method, adsorbing ruthenium by using the precursor to increase a large number of catalytic active sites, uniformly loading NMR on foamed nickel by gas reduction, further increasing the active area, enabling ruthenium particles to be closely connected with the nickel-molybdenum oxide by calcination, further improving the catalytic efficiency of metal ruthenium, and reducing the content of ruthenium. The composite material catalyst synthesized by the invention has good catalytic performance when being applied to electrolysis of water for hydrogen evolution, and the current density is 10mA/cm under 1M KOH 2 The overpotential in the working condition is only 25mV, the electron transmission rate of the catalyst is high, the catalyst has good catalytic performance when being applied to full water electrolysis and water electrolysis oxygen evolution, and the development and application of an electrochemical hydrogen production technology can be promoted.
Drawings
FIG. 1 is an X-ray diffraction analysis diagram of NF-co, NF-im, NMO, NMR catalysts;
FIG. 2 is an LSV curve of HER in 1M KOH for NF-co, NF-im, NMO, NMR catalysts;
FIG. 3 is a bar graph of the overpotential for the HER of NF-co, NF-im, NMO, NMR catalysts in 1M KOH;
FIG. 4 is an LSV curve of OER in 1M KOH for NF-co, NF-im, NMO, NMR catalysts;
FIG. 5 is a histogram of the overpotential of OERs for NF-co, NF-im, NMO, NMR catalysts in 1M KOH;
FIG. 6 is an LSV curve for the total hydrolysis of NF-co, NF-im, NMO, NMR catalysts in 1M KOH;
FIG. 7 is a bar graph of overpotential for total water splitting for NF-co, NF-im, NMO, NMR catalysts in 1M KOH;
FIG. 8 is an impedance plot of NF-co, NF-im, NMO, NMR catalysts in 1M KOH;
FIGS. 9a-d are CV diagrams for each catalyst in 1M KOH, where (a) NF-co; (b) NF-im; (c) NMO; (d) NMR;
FIG. 10 is a graph of the electric double layer capacitance of NF-co, NF-im, NMO, NMR catalysts in 1M KOH.
Detailed Description
The following further describes embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
EXAMPLE 1 preparation of Ni/Mo/Ru composite (NMR)
(1) Preparation of Ni-Mo precursor:
1. cutting the foamed nickel into 2 × 3cm 2 Respectively cleaning the mixture by using 3M HCl and deionized water, and drying the mixture for later use; adding 0.06mmol of nickel nitrate hexahydrate and 0.15mmol of ammonium molybdate tetrahydrate into 30mL of deionized water, stirring at room temperature for 30min at the stirring speed of 400-600rpm, and dissolving and mixing to obtain a mixed solution;
2. soaking the foamed nickel into the mixed solution, transferring the foamed nickel into an inner container of a polytetrafluoroethylene reaction kettle, putting the inner container into a high-pressure reaction kettle, reacting for 6 hours at 150 ℃ in an oven to form a Ni-Mo precursor on the foamed nickel, and cooling to room temperature;
3. ultrasonically treating the reacted foam nickel with water and absolute ethyl alcohol respectively (power is 360W), and washing away floating objects to obtain a Ni-Mo precursor loaded on the foam nickel;
(2) Adsorption of Ni-Mo precursor to Ru: 4mg of ruthenium chloride was dissolved in 4ml of a 50% ethanol solution, and 1X 3cm 2 The foam nickel loaded with the Ni-Mo precursor is immersed into the solution, placed at room temperature for 18 hours to enable the Ni-Mo precursor to fully adsorb Ru, taken out and dried in an oven;
(3) Preparation of NMR: putting the sample into a tubular furnace, heating to 500 ℃ under the atmosphere of argon-hydrogen mixed gas (hydrogen volume ratio is 5%), calcining for 2 hours at 500 ℃ to uniformly distribute NMR on the foamed nickel, wherein the gas flow is about 50ml/min in the calcining process, and the heating speed is 5 ℃/min; after cooling to room temperature, the Ni/Mo/Ru composite material (NMR) uniformly loaded on the foamed nickel was taken out.
Comparative example 1 preparation of Ni-Mo composite (NMO)
(1) The preparation steps of the Ni-Mo precursor are the same as those of the embodiment 1;
(2) Preparation of Ni-Mo mixture (NMO): mixing 1X 3cm 2 Putting the Ni-Mo precursor into a tube furnace, heating to 500 ℃ in the atmosphere of argon-hydrogen mixed gas (hydrogen volume ratio is 5%), calcining for 2 hours at 500 ℃ to uniformly distribute the NMO on the foamed nickel, wherein the gas flow is about 50ml/min in the calcining process, and the heating speed is 5 ℃/min; and cooling to room temperature, and taking out to obtain the Ni-Mo composite material (NMO) loaded on the foamed nickel.
Comparative example 2 preparation of ruthenium adsorbing-foam nickel Material (NF-im)
4mg of ruthenium chloride were dissolved in 4ml of 50% ethanol solution to a size of 1X 3cm 2 The nickel foam of (2) was immersed in the mixed solution, left at room temperature for 18 hours, and then taken out and dried in an oven. Putting the sample into a tube furnace, heating to 500 ℃ in the atmosphere of argon-hydrogen mixed gas (hydrogen volume ratio is 5%), calcining for 2 hours at 500 ℃, wherein the gas flow is about 50ml/min in the calcining process, and the heating speed is 5 ℃/min; and cooling to room temperature, and taking out to obtain the ruthenium adsorption-foam nickel material (NF-im).
Comparative example 3 preparation of ruthenium coated-foamed Nickel Material (NF-co)
4mg of ruthenium chloride are dissolved in 300ulAdding 50% ethanol solution, and uniformly dripping into 1 × 3cm 2 Drying the nickel foam in an oven. Putting the sample into a tube furnace, heating to 500 ℃ in the atmosphere of argon-hydrogen mixed gas (hydrogen volume ratio is 5%), calcining for 2 hours at 500 ℃, wherein the gas flow is about 50ml/min in the calcining process, and the heating speed is 5 ℃/min; after cooling to room temperature, the ruthenium coated-foamed nickel material (NF-co) was taken out.
Experimental example 1X-ray diffraction analysis and catalytic Performance test
(1) X-ray diffraction analysis
The catalysts of example 1, comparative example 2 and comparative example 3 were subjected to X-ray diffraction analysis, and the analysis spectra are shown in fig. 1, in which no extra diffraction peak is present, and the diffraction peak positions of the four groups of materials are the same as those of pure nickel foam, and no impurity is generated.
(2) Test for catalytic Performance
The catalysts of example 1, comparative example 2 and comparative example 3 were subjected to an electrolytic water catalytic performance test. Electrocatalysis test in 1M KOH solution, a three-electrode system is used for testing a linear sweep voltammetry LSV curve, an electrochemical resistance curve and a cyclic voltammetry CV curve, and the three electrodes are divided into a working electrode, a reference electrode and a counter electrode. Wherein the reference electrode is an Ag/AgCl electrode, the counter electrode is a platinum electrode, the working electrode is the catalyst of example 1 and the three comparative examples, and the scanning rate of the linear scanning cyclic voltammetry curve is 5mV/s; the potential in the polarization curve chart is converted from an Ag/AgCl electrode to a standard hydrogen electrode E RHE The conversion relationship is as follows: e RHE ＝(E Ag/AgCl +0.197+0.059 pH) V, ph =14 at 1M KOH.
The catalysts of example 1, comparative example 2 and comparative example 3 were subjected to HER performance test of hydrogen evolution by electrolysis in water, and the LSV curve of linear sweep voltammetry was as shown in fig. 2, and each catalyst was prepared at a current density of 10mA/cm based on the LSV curve 2 And 50mA/cm 2 The overpotential of the lower catalytic hydrogen evolution is shown in FIG. 3, and the histogram of the overpotential is shown in FIG. 3, from which NMR at a current density of 10mA/cm is obtained 2 And 100mA/cm 2 Under operating conditions of (a) and at a lower overpotential than the rest of the catalyst, indicates NMR electrolytic water catalytic precipitationThe hydrogen performance is excellent.
The catalysts of example 1, comparative example 2 and comparative example 3 were subjected to the performance test of electrolytic water catalytic oxygen evolution OER, the LSV curve of the linear sweep voltammetry is shown in FIG. 4, and the current density of each catalyst is 50mA/cm according to the LSV curve 2 And 100mA/cm 2 Overpotential of lower catalytic oxygen evolution, overpotential histogram is shown in FIG. 5, and NMR at a current density of 50mA/cm is obtained from FIG. 5 2 And 100mA/cm 2 The overpotential of the catalyst is lower than that of the rest catalysts, and the NMR electrolyzed water catalytic oxygen evolution performance is excellent.
The catalysts of example 1, comparative example 2 and comparative example 3 were subjected to full hydrolytic catalysis OWS performance tests, and the linear sweep voltammetry LSV curves are shown in FIG. 6, and the current density of each catalyst at 50mA/cm was determined according to the LSV curves 2 And 100mA/cm 2 Overpotential of the lower catalytic total hydrolysis, the overpotential histogram is shown in FIG. 7, and NMR at a current density of 50mA/cm is obtained from FIG. 7 2 And 100mA/cm 2 The overpotential was lower than that of the remaining catalyst, indicating that the NMR full water decomposability was excellent.
Electrochemical impedance spectroscopy tests were performed on each of the catalysts of example 1, comparative example 2 and comparative example 3 to evaluate the interfacial properties of the synthesized catalyst and the speed of charge transfer between the catalyst and the electrolyte, the impedance spectroscopy is shown in fig. 8, the semi-circular arc reflects the magnitude of the charge transfer resistance, the smaller the semi-circular arc, the better the electrode activity, and the smallest the semi-circular arc of NMR, indicating that NMR has less resistance and stronger catalytic power.
The cyclic voltammetry CV curves of the catalysts of example 1, comparative example 2 and comparative example 3 were measured over a non-faradaic potential range (0.773-0.823V) at different scan rates (20-100 mV/s) and are shown in FIGS. 9 a-d; and linearly fitting the difference between the cathode current density and the anode current density (Δ J = Janodic-Jcathodic) in fig. 9 with the scanning rate under 0.823V (vs. rhe), wherein the slope of the fitted line is equal to twice the double-layer capacitance (Cdl), and then the electrochemical active surface area (ECSA) value is estimated, and the electric double-layer capacitance graph of each catalyst is shown in fig. 10, wherein the slope of NMR is the maximum, which indicates that the Cdl of NMR is the maximum, the active area is the maximum, the catalytic active sites are more than that of Ni-co, and the effect is better than that of direct coating.
In conclusion, the Ni/Mo/Ru composite material catalyst (NMR) uniformly loaded on the foamed nickel is synthesized by synthesizing the nickel-molybdenum oxide precursor by a hydrothermal method, adsorbing ruthenium ions by the precursor and reducing in an argon-hydrogen atmosphere. The electrochemical catalytic performance test of NF-co, NF-im, NMO and NMR catalysts is carried out by utilizing a three-electrode system, and the results show that the overpotential of the NMR catalysts during hydrogen evolution, oxygen evolution and full water decomposition is minimum, the electrochemical active surface area value is maximum, and the activity is best.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. An Ni/Mo/Ru composite material, which is characterized by consisting of Ni, mo and Ru.
2. The Ni/Mo/Ru composite material of claim 1, wherein the Ni/Mo/Ru composite material is a composite material formed by combining a Ni-Mo base material and ruthenium, and the Ni/Mo/Ru composite material is uniformly loaded on foamed nickel.
3. The Ni/Mo/Ru composite material according to claim 1 or 2, wherein the Ni/Mo/Ru composite material is produced by a method comprising the steps of:
s1, preparation of a Ni-Mo precursor: immersing the pretreated foamed nickel into a mixed solution of nickel nitrate hexahydrate and ammonium molybdate tetrahydrate, reacting by a hydrothermal method to synthesize a Ni-Mo precursor, and carrying out ultrasonic cleaning on the reacted foamed nickel to obtain foamed nickel loaded with the Ni-Mo precursor;
s2, adsorbing Ru: soaking foam nickel loaded with a Ni-Mo precursor into a ruthenium chloride solution, standing at room temperature to enable the precursor to fully adsorb Ru, and taking out a sample for drying;
s3, preparing a Ni/Mo/Ru composite material: and calcining and reducing the dried sample of S2 in an argon-hydrogen mixed gas atmosphere, and cooling to room temperature to obtain the Ni/Mo/Ru composite material uniformly loaded on the foamed nickel.
4. A Ni/Mo/Ru composite material according to claim 3, wherein in step 1, the pretreatment is to cut the foamed nickel to a size of 2 x 3cm 2 And washed with 3M HCl and deionized water, respectively, for standby.
5. The Ni/Mo/Ru composite material according to claim 3, wherein in the step 1, the molar concentration of nickel nitrate hexahydrate in the mixed solution is 2-6 μmol/ml, and the molar concentration of ammonium molybdate tetrahydrate in the mixed solution is 5-8 μmol/ml.
6. The Ni/Mo/Ru composite material of claim 3, wherein the hydrothermal reaction temperature in step 1 is 140-180 ℃ and the reaction time is 5-7 h.
7. A Ni/Mo/Ru composite material according to claim 3, wherein in step 2, the concentration of the ruthenium chloride solution is 1 to 2mg/ml.
8. The Ni/Mo/Ru composite material as claimed in claim 3, wherein in step 3, the gas flow during the calcination is 40-70 ml/min, and the calcination temperature is 450-550 ℃.
9. A Ni/Mo/Ru composite material according to claim 3, wherein in the argon-hydrogen gas in the step 3, the volume of hydrogen gas is 5% of the total gas volume.
10. The Ni/Mo/Ru composite material according to claim 1 or 2, wherein the Ni/Mo/Ru composite material is used for catalyzing electrolysis hydrogen evolution reaction.
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