Preparation method of nickel-ruthenium alloy nanoparticle catalyst and catalyst

Abstract

In order to solve the technical problem that a fcc single-phase alloy catalyst with higher energy cannot be prepared by an existing preparation method, the preparation method of the nickel-ruthenium alloy nanoparticle catalyst and the catalyst are provided, and the preparation method comprises the following steps: sequentially dissolving a nickel compound and a ruthenium compound in a polyol solvent to obtain a nickel-ruthenium precursor solution; a protective agent and a reducing agent are mixed and heated to 210-270 DEG C, and a mixed solution is obtained; and dropwise adding the nickel-ruthenium precursor solution into the mixed solution to react, and then centrifuging, washing and drying to obtain the nickel-ruthenium alloy nanoparticle catalyst. The fcc-phase nickel-ruthenium alloy nanoparticle catalyst with different proportions can be prepared by adjusting the dosage ratio of ruthenium atoms to nickel atoms and controlling the reaction temperature and the reaction atmosphere.

Description

Technical Field

[0001] The present invention relates to a catalyst synthesis method, and in particular to a preparation method of a nickel-ruthenium alloy nanoparticle catalyst and a catalyst. Background Art

[0002] Metal nanomaterials have broad applications in catalysis, biomedicine, aerospace and other fields. Single-phase alloys obtained by uniformly adding one element to another often have more ideal properties than multiphase alloys and single metals. However, according to the binary alloy phase diagram, more than half of the metal elements in the periodic table cannot be mixed with each other, and the traditional binary single-phase alloy synthesis method is not applicable to many metal elements.

[0003] Currently, nickel-based immiscible alloys have attracted extensive attention due to their excellent performance in hydrogen evolution reaction (HER), oxygen evolution reaction (OER), etc. Metallic Ru (ruthenium) has been used in many fields, such as carbon monoxide oxidation, carbon dioxide methanation and HER reaction; at the same time, Ru also has good OER catalytic performance.

[0004] A Chinese invention patent with publication number CN107570172 A discloses a method for preparing a ruthenium / nickel alloy nanocatalyst and its application, but the catalyst prepared by this method is a mixed-phase alloy, and it is impossible to prepare an fcc single-phase alloy catalyst with higher energy. Therefore, it is urgent to develop a new method for preparing nickel-ruthenium nanoparticle catalysts. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing a nickel-ruthenium alloy nanoparticle catalyst and a catalyst, which are used to solve the technical problem that the existing preparation method cannot prepare a higher energy FCC single-phase alloy catalyst.

[0006] In order to solve the above technical problems, the technical solution of the present invention is as follows:

[0007] A method for preparing a nickel-ruthenium alloy nanoparticle catalyst is characterized in that it comprises the following steps:

[0008] Step 1, weighing a nickel compound and a ruthenium compound respectively, and dissolving them in a polyol solvent at room temperature in turn to obtain a nickel-ruthenium precursor solution; wherein the nickel compound, the ruthenium compound and the polyol solvent are respectively calculated in parts by weight: 1 part of the ruthenium compound, 0.1 to 10 parts of the nickel compound, and 70 to 230 parts of the polyol solvent;

[0009] Step 2, weighing a protective agent and a reducing agent respectively, mixing the protective agent and the reducing agent and heating them to 210° C. to 270° C. to obtain a mixed solution; based on 1 part by weight of the ruthenium compound, the protective agent and the reducing agent are calculated in parts by weight as follows: 0.5 to 10 parts by weight of the protective agent and 500 to 2300 parts by weight of the reducing agent;

[0010] Step 3, adding the nickel-ruthenium precursor solution obtained in step 1 dropwise into the mixed solution of step 2, stirring at a temperature of 210° C. to 270° C. for more than 10 minutes, obtaining an intermediate product after centrifugation, and then washing the intermediate product with an organic solvent for multiple times, and obtaining a nickel-ruthenium alloy nanoparticle catalyst after drying.

[0011] Further, in step 1, the nickel compound is any one of nickel formate dihydrate, nickel acetylacetonate, nickel acetate, nickel chloride, nickel sulfate, nickel nitrate, nickel hydroxide or nickel hydroxide;

[0012] The ruthenium compound is any one of ruthenium formate dihydrate, ruthenium acetylacetonate, ruthenium acetate, ruthenium chloride, ruthenium sulfate, ruthenium nitrate, ruthenium hydroxide, bis(cyclopentadienyl)ruthenium, dichlorophenylruthenium or ruthenium hydroxide;

[0013] The polyol solvent is selected from any one of diethylene glycol, methanol, ethanol, n-propanol, isopropanol, n-butanol, pentanol, hexanol, ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, dibutylene glycol, tributylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, glycerol, diglycerol, polyglycerol, trimethylolpropane, pentaerythritol or oleylamine with a volume concentration of more than 95%.

[0014] Furthermore, in step 2, the protective agent and the reducing agent are mixed, the dissolved oxygen is removed by a vacuum deoxygenation method, and the mixture is heated to 210° C. to 270° C. under an inert atmosphere to obtain a mixed solution.

[0015] Furthermore, in step 2, the protective agent is any one of poly (N-vinyl-2-pyrrolidone), polyethylene glycol, polyvinyl alcohol, polyvinyl ether, polymethacrylic acid, polymethacrylate, tri-n-octylphosphine oxide, sodium alginate or cellulose derivatives;

[0016] The reducing agent is any one of diethylene glycol, methanol, ethanol, n-propanol, isopropanol, n-butanol, amyl alcohol, hexanol, ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, dibutylene glycol, tributylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, glycerol, diglycerol, polyglycerol, trimethylolpropane or pentaerythritol and oleylamine;

[0017] The gas in the inert atmosphere is selected to be nitrogen with a concentration of more than 95%.

[0018] Furthermore, in step 3, the stirring speed is 350-450 rpm, and the stirring time is 10-15 min;

[0019] The centrifugation refers to centrifugation in a centrifugal device with a rotation speed of 8500 to 9500 rpm;

[0020] The washing times are more than 3 times, and the organic solvent used for washing is selected from acetone, methanol, ethanol, isopropanol, petroleum ether, ether, dichloromethane, n-butanol, glycerol, ethylene glycol, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, methyl acetate, ethyl acetate, propyl acetate, pentane, hexane, octane, benzene, toluene, xylene, methyl butyl ketone, methyl isobutyl ketone, cyclohexane, cyclohexanone or toluene cyclohexanone;

[0021] The drying is carried out under vacuum conditions at room temperature, and the drying time is 15-25 minutes.

[0022] At the same time, the present invention also provides a nickel-ruthenium alloy nanoparticle catalyst, which is prepared by the above-mentioned preparation method of the nickel-ruthenium alloy nanoparticle catalyst, and its special features are:

[0023] The chemical formula is Ni x Ru 1-x , 0.1<x<0.9; it is an atomically miscible fcc single-phase nickel-ruthenium alloy nanoparticle.

[0024] Furthermore, the chemical expression is Ni 0.8 Ru 0.2 or Ni 0.7 Ru 0.3 .

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The present invention adopts a synthesis method of ruthenium-nickel co-reduction, which can adjust the dosage ratio of nickel compounds and ruthenium compounds, and then adjust the dosage ratio of nickel atoms and ruthenium atoms. At the same time, by controlling the reaction temperature, fcc phase nickel-ruthenium alloy nanoparticle catalysts with different proportions can be prepared, providing a theoretical basis for the controllable synthesis of nickel-ruthenium metal nanomaterials with different proportions.

[0027] 2. The present invention can select different types of nickel compounds and ruthenium compounds to prepare different nickel-ruthenium precursor solutions, and obtain nickel-ruthenium alloy nanoparticle catalysts by controlling the reaction temperature. The method is simple and easy to operate, and the obtained catalyst has better stability.

[0028] 3. The catalyst prepared by the method of the present invention is an atomic-level uniformly miscible fcc single-phase nickel-ruthenium alloy nanoparticle catalyst, which has good stability and fills the gap in the crystal phase structure of this type of catalyst.

[0029] 4. Ni prepared by the present invention 0.8 Ru 0.2 with Ni 0.7 Ru 0.3 Compared with iridium catalysts and ruthenium catalysts, it has stronger catalytic activity in OER reactions and broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 The XRPD spectra of the catalysts prepared in Examples 1 to 5 and Comparative Examples 1 and 2 of the present invention;

[0031] Figure 2 This is the STEM-EDX spectrum of the catalyst prepared in Example 5 of the present invention, wherein: Figure 2 a is a scanning transmission electron image of the catalyst, Figure 2 b is the distribution diagram of nickel atoms in the catalyst, Figure 2 c is the distribution diagram of ruthenium atoms in the catalyst, Figure 2 d is the relative distribution diagram of nickel atoms and ruthenium atoms in the catalyst;

[0032] Figure 3 The electrochemical measurement results of the catalysts prepared in Examples 1 to 5 and Comparative Examples 1 and 2 of the present invention are shown in FIG. Figure 3 a is the LSV polarization curve of various catalysts measured by linear voltammetry. Figure 3 b is the Tafel slope curve of each catalyst;

[0033] Figure 4 This is a comparison chart of the OER reaction overpotentials of the catalysts prepared in Examples 1 to 5 of the present invention and Comparative Examples 1 and 2. DETAILED DESCRIPTION

[0034] The present invention provides a nickel-ruthenium alloy nanoparticle catalyst, which is an atomic-level miscible fcc single-phase nickel-ruthenium alloy nanoparticle catalyst, and the chemical expression is Ni x Ru 1-x , wherein 0.1<x<0.9. The Ni of the present invention 0.8 Ru 0.2 with Ni 0.7 Ru 0.3 Compared with iridium catalysts and ruthenium catalysts, it has stronger catalytic activity in OER reactions and broad application prospects.

[0035] In order to better illustrate the purpose, technical scheme and advantages of the present invention, the present invention will be further described below in conjunction with specific examples. In the examples, the test methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified. The protective agent, reducing agent, organic solvent, and polyol solvent used in each example are analytically pure unless otherwise specified.

[0036] Example 1

[0037] Step 1, weigh 0.2 mmol (51.4 mg) of nickel acetylacetonate and 0.9 mmol (358.5 mg) of ruthenium acetylacetonate, and dissolve them in 10 mL of diethylene glycol solvent at room temperature to prepare 10 mL of nickel ruthenium precursor solution.

[0038] Step 2, weigh 275 mg of poly (N-vinyl-2-pyrrolidone) and 100 mL of diethylene glycol, mix the two evenly to obtain a solution, remove the dissolved oxygen in the solution by vacuum deoxygenation, heat to 240° C. in a nitrogen atmosphere with a purity of 95%, and obtain 110 mL of a mixed solution.

[0039] Step 3, adding the nickel-ruthenium precursor solution obtained in step 1 to the mixed solution of step 2 while stirring, maintaining the temperature at 240°C, stirring at a speed of 400 rpm, and stirring for 10 minutes to obtain a black mixed reaction solution. The mixed reaction solution was separated into a black precipitate by a high-speed centrifuge at 9000 rpm, and then the black precipitate was washed 3 times with 30 mL of petroleum ether to remove the by-products in the black precipitate. After drying under vacuum conditions at room temperature for 20 minutes, 97.1 mg of nickel-ruthenium alloy nanoparticle catalyst Ni 0.1 Ru 0.9 , Figure 1 Curve ① in FIG. 1 is the XRPD spectrum of the catalyst obtained by X-ray powder diffraction. From the figure, it can be seen that the nickel-ruthenium alloy nanoparticle catalyst prepared in this embodiment is a fcc single phase.

[0040] Example 2

[0041] Step 1, weigh 0.3 mmol (74.7 mg) of nickel acetate and 0.7 mmol (278.87 mg) of ruthenium acetylacetonate, and dissolve them in 10 mL of diethylene glycol solvent at room temperature to prepare 10 mL of nickel-ruthenium precursor solution.

[0042] Step 2, weigh 275 mg of poly (N-vinyl-2-pyrrolidone) and 100 mL of diethylene glycol, mix the two evenly to obtain a solution, remove the dissolved oxygen in the solution by vacuum deoxygenation, heat to 240° C. in a nitrogen atmosphere with a purity of 95%, and obtain 110 mL of a mixed solution.

[0043] Step 3, adding the nickel-ruthenium precursor solution obtained in step 1 to the mixed solution of step 2 while stirring, maintaining the temperature at 240°C, stirring at a speed of 400 rpm, and stirring for 10 minutes to obtain a black mixed reaction solution. The mixed reaction solution was separated into a black precipitate by a high-speed centrifuge at 9000 rpm, and then the black precipitate was washed 3 times with 30 mL of petroleum ether to remove the by-products in the black precipitate. After drying under vacuum conditions at room temperature for 20 minutes, 83.5 mg of nickel-ruthenium alloy nanoparticle catalyst Ni 0.3 Ru 0.7 , Figure 1 Curve ② in FIG. 1 is the XRPD spectrum of the catalyst obtained using X-ray powder diffraction.

[0044] Example 3

[0045] Step 1, weigh 0.5 mmol (124.4 mg) of nickel acetate and 0.5 mmol (199.92 mg) of ruthenium acetylacetonate, and dissolve them in 10 mL of diethylene glycol solvent at room temperature to prepare 10 mL of nickel-ruthenium precursor solution.

[0046] Step 2, weigh 275 mg of poly (N-vinyl-2-pyrrolidone) and 100 mL of diethylene glycol, mix the two evenly to obtain a solution, remove the dissolved oxygen in the solution by vacuum deoxygenation, and heat to 240° C. in a nitrogen atmosphere with a purity of 98% to obtain 110 mL of a mixed solution.

[0047] Step 3, adding the nickel-ruthenium precursor solution obtained in step 1 to the mixed solution of step 2 while stirring, maintaining the temperature at 240°C, stirring at a speed of 400 rpm, and stirring for 10 minutes to obtain a black mixed reaction solution. The mixed reaction solution was separated into a black precipitate by a high-speed centrifuge at 9000 rpm, and then the black precipitate was washed 3 times with 30 mL of petroleum ether to remove the by-products in the black precipitate. After vacuum drying at room temperature for 20 minutes, 76.8 mg of nickel-ruthenium alloy nanoparticle catalyst Ni 0.5 Ru 0.5 , Figure 1 Curve ③ in FIG. 3 is the XRPD spectrum of the catalyst obtained by X-ray powder diffraction.

[0048] Example 4

[0049] Step 1: Weigh 1.55 mmol (398 mg) of nickel acetylacetonate and 0.6 mmol (239 mg) of ruthenium acetylacetonate, and dissolve them in 30 mL of diethylene glycol solvent at room temperature to prepare 30 mL of nickel ruthenium precursor solution.

[0050] Step 2, weigh 440 mg of poly (N-vinyl-2-pyrrolidone) and 200 mL of diethylene glycol, mix the two evenly to obtain a solution, remove the dissolved oxygen in the solution by vacuum deoxygenation, heat to 220° C. in a nitrogen atmosphere with a purity of 97%, and obtain 230 mL of a mixed solution.

[0051] Step 3, adding the nickel-ruthenium precursor solution obtained in step 1 to the mixed solution of step 2 while stirring, maintaining the temperature at 220°C, stirring at a speed of 400 rpm, and stirring for 10 minutes to obtain a black mixed reaction solution. The mixed reaction solution was separated into a black precipitate by a high-speed centrifuge at 9000 rpm, and then the black precipitate was washed 3 times with 100 mL of petroleum ether to remove the by-products in the black precipitate. After drying under vacuum conditions at room temperature for 20 minutes, 141.6 mg of nickel-ruthenium alloy nanoparticle catalyst Ni 0.7 Ru 0.3 , Figure 1 Curve ④ in FIG. 4 is the XRPD spectrum of the catalyst obtained using X-ray powder diffraction.

[0052] Example 5

[0053] Step 1: Weigh 1.6 mmol (411 mg) of nickel acetylacetonate and 0.4 mmol (160 mg) of ruthenium acetylacetonate, and dissolve them in 30 mL of diethylene glycol solvent at room temperature to prepare 30 mL of nickel ruthenium precursor solution.

[0054] Step 2, weigh 440 mg of poly (N-vinyl-2-pyrrolidone) and 200 mL of diethylene glycol, mix the two evenly to obtain a solution, remove the dissolved oxygen in the solution by vacuum deoxygenation, heat to 220° C. in a nitrogen atmosphere with a purity of 99%, and obtain 230 mL of a mixed solution.

[0055] Step 3, adding the nickel-ruthenium precursor solution obtained in step 1 to the mixed solution of step 2 while stirring, maintaining the temperature at 220°C, stirring at a speed of 400 rpm, and stirring for 10 minutes to obtain a black mixed reaction solution. After the mixed reaction solution is separated from the black precipitate by a high-speed centrifugal device at 9000 rpm, the black precipitate is washed 3 times with 100 mL of petroleum ether to remove the by-products in the black precipitate, and dried under vacuum conditions at room temperature for 20 minutes to obtain 123.6 mg of nickel-ruthenium alloy nanoparticle catalyst Ni 0.8 Ru 0.2 , Figure 1 Curve ⑤ in the figure is the XRPD spectrum of the catalyst obtained by X-ray powder diffraction; Figure 2 This is the electron microscope scanning result of the catalyst.

[0056] Comparative Example 1

[0057] Step 1, weigh 0.5 mmol (199.2 mg) of ruthenium acetylacetonate and dissolve it in 10 mL of diethylene glycol solvent to prepare 10 mL of ruthenium precursor solution.

[0058] Step 2: Mix 275 mg of poly (N-vinyl-2-pyrrolidone) protective agent and 100 mL of diethylene glycol evenly, and heat to 270° C. to obtain 110 mL of a mixed solution.

[0059] Step 3, add the ruthenium precursor solution prepared in step 1 dropwise to the mixed solution of step 2 while stirring, keep the temperature at 240°C, stir at 400 rpm, and stir for 10 minutes to obtain a black mixed reaction solution. After the mixed reaction solution is separated from the solid by a high-speed centrifuge at 9000 rpm, it is washed three times with 30 ml of petroleum ether, and after removing the by-products, it is dried under vacuum conditions at room temperature to obtain 45.3 mg of ruthenium nanoparticle catalyst. Figure 1 The bottom curve is the XRPD spectrum of the catalyst obtained using X-ray powder diffraction.

[0060] Comparative Example 2

[0061] Step 1, weigh 0.5 mmol (124 mg) of nickel acetate and dissolve it in 10 mL of diethylene glycol solvent to prepare 10 mL of nickel precursor solution.

[0062] Step 2: Mix 275 mg of poly (N-vinyl-2-pyrrolidone) protective agent and 100 mL of diethylene glycol evenly, and heat to 210° C. to obtain 110 mL of a mixed solution.

[0063] Step 3, adding the nickel precursor solution obtained in step 1 dropwise to the mixed solution of step 2 while stirring, the stirring speed is 400 rpm, and after stirring for 10 minutes, a black mixed reaction solution is obtained. After the mixed reaction solution is separated from the solid by a high-speed centrifugal device at 9000 rpm, it is washed three times with 30 mL of petroleum ether to remove the by-products, and dried under vacuum conditions at room temperature for 20 minutes to obtain 29.3 mg of nickel nanoparticle catalyst. Figure 1 The top curve is the XRPD spectrum of the catalyst obtained using X-ray powder diffraction.

[0064] In summary, Figure 1 The X-ray powder diffraction (XRPD) technique was used to explore the crystalline structures of various catalysts prepared under different reaction conditions. The results showed that the catalysts prepared in Examples 1 to 5 were all fcc single phase.

[0065] Figure 2 The catalyst Ni prepared in Example 5 was observed under an electron microscope. 0.8 Ru 0.2The distribution of elements in , where Figure 2 a shows a scanning transmission electron image of the catalyst. Figure 2 b shows the distribution of nickel atoms in the catalyst. Figure 2 c shows the distribution of ruthenium atoms in the catalyst. Figure 2 d shows the relative distribution of nickel atoms and ruthenium atoms in the catalyst. The results show that the nickel-ruthenium catalyst Ni prepared in Example 5 0.8 Ru 0.2 Miscible and homogeneous at the atomic level.

[0066] like Figure 3 As shown, under alkaline conditions, the OER reaction catalytic performance of the catalysts prepared under different reaction conditions of Examples 1 to 5 and Comparative Examples 1 to 2 was tested using a three-electrode system. Figure 3 a is the LSV polarization curve of various catalysts measured by linear voltammetry. It can be seen that the nickel-ruthenium alloy nanoparticle catalyst Ni prepared by the preparation method of the present invention 0.7 Ru 0.3 And Ni 0.8 Ru 0.2 , the overpotential is lower than that of nickel catalyst and ruthenium catalyst. Figure 3 b is the Tafel slope curve of each catalyst. It can be seen that Ni 0.8 Ru 0.2 The Tafel slope of was the lowest among all samples, indicating that its reaction rate was the fastest.

[0067] Figure 4 The OER reaction overpotential measurement results of various catalysts prepared are compared. It can be seen from this figure that the nickel-ruthenium alloy nanoparticle catalyst Ni prepared by the preparation method of the present invention 0.7 Ru 0.3 And Ni 0.8 Ru 0.2 , compared with nickel catalysts and ruthenium catalysts, it has higher catalytic activity in OER reactions.

[0068] The above are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention. All equivalent transformations made using the contents of the present invention's specification and drawings under the inventive concept of the present invention, or direct / indirect application of the technical solution of the present invention in other related technical fields, should be within the patent protection scope of the present invention.

Claims

1. A method for preparing a nickel-ruthenium alloy nanoparticle catalyst, characterized in that: The following steps are involved: Step 1, weighing a nickel compound and a ruthenium compound respectively, and dissolving them in a polyol solvent at room temperature in turn to obtain a nickel-ruthenium precursor solution; wherein the nickel compound, the ruthenium compound and the polyol solvent are respectively calculated in parts by weight: 1 part of the ruthenium compound, 0.1 to 10 parts of the nickel compound, and 70 to 230 parts of the polyol solvent; Step 2, weighing a protective agent and a reducing agent respectively, mixing the protective agent and the reducing agent and heating them to 210° C. to 270° C. to obtain a mixed solution; based on 1 part by weight of the ruthenium compound, the protective agent and the reducing agent are respectively in parts by weight: 0.5 to 10 parts by weight of the protective agent and 500 to 2300 parts by weight of the reducing agent; Step 3, adding the nickel-ruthenium precursor solution obtained in step 1 dropwise into the mixed solution of step 2, stirring at a temperature of 210° C. to 270° C. for more than 10 minutes, obtaining an intermediate product after centrifugation, and then washing the intermediate product with an organic solvent for multiple times, and obtaining a nickel-ruthenium alloy nanoparticle catalyst after drying.

2. The method for preparing the nickel-ruthenium alloy nanoparticle catalyst according to claim 1, characterized in that: In step 1, the nickel compound is any one of nickel formate dihydrate, nickel acetylacetonate, nickel acetate, nickel chloride, nickel sulfate, nickel nitrate, nickel hydroxide or nickel hydroxide; The ruthenium compound is any one of ruthenium formate dihydrate, ruthenium acetylacetonate, ruthenium acetate, ruthenium chloride, ruthenium sulfate, ruthenium nitrate, ruthenium hydroxide, bis(cyclopentadienyl)ruthenium, dichlorophenylruthenium or ruthenium hydroxide; The polyol solvent is selected from any one of diethylene glycol, methanol, ethanol, n-propanol, isopropanol, n-butanol, pentanol, hexanol, ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, dibutylene glycol, tributylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, glycerol, diglycerol, polyglycerol, trimethylolpropane, pentaerythritol or oleylamine with a volume concentration of more than 95%.

3. The method for preparing the nickel-ruthenium alloy nanoparticle catalyst according to claim 2, characterized in that: In step 2, the protective agent and the reducing agent are mixed, the dissolved oxygen is removed by a vacuum deoxygenation method, and the mixture is heated to 210° C. to 270° C. in an inert atmosphere to obtain a mixed solution.

4. The method for preparing the nickel-ruthenium alloy nanoparticle catalyst according to claim 3, characterized in that: In step 2, the protective agent is any one of poly (N-vinyl-2-pyrrolidone), polyethylene glycol, polyvinyl alcohol, polyvinyl ether, polymethacrylic acid, polymethacrylate, tri-n-octylphosphine oxide, sodium alginate or cellulose derivatives; The reducing agent is any one of diethylene glycol, methanol, ethanol, n-propanol, isopropanol, n-butanol, amyl alcohol, hexanol, ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, dibutylene glycol, tributylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, glycerol, diglycerol, polyglycerol, trimethylolpropane or pentaerythritol and oleylamine; The gas in the inert atmosphere is selected to be nitrogen with a concentration of more than 95%.

5. The method for preparing the nickel-ruthenium alloy nanoparticle catalyst according to claim 1, characterized in that: In step 3, the stirring speed is 350-450 rpm, and the stirring time is 10-15 min; The centrifugation refers to centrifugation in a centrifugal device with a rotation speed of 8500 to 9500 rpm; The washing times are more than 3 times, and the organic solvent used for washing is selected from one of acetone, methanol, ethanol, isopropanol, petroleum ether, ether, dichloromethane, n-butanol, glycerol, ethylene glycol, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, methyl acetate, ethyl acetate, propyl acetate, pentane, hexane, octane, benzene, toluene, xylene, methyl butyl ketone, methyl isobutyl ketone, cyclohexane, cyclohexanone or toluene cyclohexanone; The drying is carried out under vacuum conditions at room temperature, and the drying time is 15-25 minutes.

6. A nickel-ruthenium alloy nanoparticle catalyst prepared by the method for preparing the nickel-ruthenium alloy nanoparticle catalyst according to any one of claims 1 to 5, characterized in that: The chemical formula is Ni x Ru 1-x , 0.1<x<0.9; It is an atomically miscible fcc single-phase nickel-ruthenium alloy nanoparticle.

7. The nickel-ruthenium alloy nanoparticle catalyst according to claim 6, characterized in that: The chemical formula is Ni 0.8 Ru 0.2 or Ni 0.7 Ru 0.3 .

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