CN108754531B - Preparation method of Co-and Ru-containing bimetallic carbon nano composite electro-catalytic material - Google Patents
Preparation method of Co-and Ru-containing bimetallic carbon nano composite electro-catalytic material Download PDFInfo
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Abstract
The invention discloses a preparation method of a Co and Ru-containing bimetallic carbon nano composite electro-catalytic material, which comprises the following steps: 1) dissolving cobalt salt and polyvinylpyrrolidone in ethanolUniformly stirring the mixture and deionized water to obtain a solution A; 2) dissolving trimesic acid in a mixed solvent of ethanol and deionized water, and uniformly stirring to obtain a solution B; 3) adding the solution A into the solution B, stirring until a precipitate is formed, standing, centrifuging, collecting blue precipitate, washing with absolute ethyl alcohol, and drying to obtain Co3(BTC)2A precursor; 4) mixing Co3(BTC)2Dispersing in mixed solvent of deionized water and anhydrous ethanol, adding RuCl3·xH2Stirring, reacting and centrifuging O to obtain a precipitate, washing the precipitate with absolute ethyl alcohol, and drying to obtain a Co and Ru bimetal-containing MOFs material; 5) and (2) placing the MOFs material in an inert atmosphere, heating to 400-600 ℃, preserving the heat for 1-5h, and cooling to room temperature to obtain the Co-and Ru-containing bimetallic carbon nano composite electro-catalytic material CoRu/C. The preparation method is simple, low in cost and excellent in catalytic performance.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a preparation method of a Co and Ru bimetallic carbon nano composite electro-catalytic material.
Background
With the rapid development of social economy, energy and environment become increasingly concerned problems, and the consumption proportion of renewable energy sources such as solar energy, wind energy and the like in the total energy consumption of human society is gradually increased. However, since such renewable energy sources have a certain intermittency and fluctuation in the conversion and use processes of electric energy, technologies such as rechargeable batteries, electrochemical capacitors, electrolyzers, fuel cells and the like, such as electrochemical energy storage and conversion, will play a very important role in realizing efficient and sustainable energy utilization. Despite their different operating principles, these electrochemical devices are made up of similar key functional components, and the electrochemical properties (e.g., redox and catalytic activity) of the functional materials used in these components will determine the overall performance of the device. Therefore, the preparation of functional materials with excellent electrochemical properties has become an important research direction in the electrochemical field.
Hydrogen has the advantages of high energy density and environmental protection and is considered as an ideal energy carrier for sustainable energy economy. The water decomposition hydrogen production is a main component of the current clean energy technology, but the practical application of the water decomposition hydrogen production is very limited due to the overlarge potential in the water decomposition process. Therefore, the water decomposition technology with high efficiency and low cost plays an important role in the application of hydrogen energy sources. In the process of hydrogen production by water decomposition, the appropriate catalyst can effectively reduce the reaction activation energy, thereby accelerating the reaction process and the hydrogen production efficiency. At present, the most widely used catalyst is mainly based on Pt-based nano material, but the limited content in the earth crust has higher cost, so that the search for alternative catalytic material with low cost is one of the hot spots of current material research.
As a novel porous organic-inorganic hybrid material, a metal-organic framework (MOFs) material has the characteristics of various types, multiple functions, adjustable structure and the like. Similar to inorganic materials, MOFs containing redox active metal centers also have certain electrochemical activity. The MOFs have metal sites coordinated by organic molecules and easily-adjusted pore structures, and thus, a structural basis is provided for optimizing and improving the performance of the MOFs. At present, there are many reports in related literatures that MOFs is successfully used as electrode materials of rechargeable batteries and electrochemical capacitors, high-efficiency electrocatalysts for fuel cells, and even electrolytes for electrochemical devices by controlling metal and organic components to construct composite MOFs materials, but most MOFs still have the disadvantages of unstable chemical properties and poor conductivity. Recently, extensive attention has been paid to the research of converting MOFs materials into available metal compounds and carbide catalytic materials by heating, and the research shows that the MOF-derived functional materials not only retain the excellent characteristics of the original materials, but also have more stable chemical properties and better conductivity, generally have very excellent catalytic performance, and have very important development potential in the electrochemical field.
At present, the basic research of electrocatalytic hydrogen production (HER) is mainly carried out under acidic conditions, mainly because the reaction path is relatively simple, which also causes that the research and application of the direction have certain limitations. In recent years, there has been an increasing beginning of literature reports of Ru-doped materials for HER electrocatalytic test studies. Compared with Pt, the price of Ru has certain advantages, and the price is about one-fifteenth of that of Pt. Furthermore, Ru has similar binding strength to hydrogen, but there are still few reports of Ru as a HER catalyst. The catalytic activity of the material can also be optimized by doping the non-noble metal-based carbon composite material with foreign metal atoms. The doping of metal ions such as Cu can further reduce the content of Ru to reduce the cost and can further improve the material performance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a Co-and Ru-containing bimetallic carbon nano-composite electrocatalytic material with good HER electrocatalytic performance.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a Co and Ru-containing bimetallic carbon nano composite electro-catalytic material comprises the following steps:
1) dissolving cobalt salt and polyvinylpyrrolidone in a mixed solvent of ethanol and deionized water, and uniformly stirring to obtain a solution A;
2) dissolving trimesic acid in a mixed solvent of ethanol and deionized water, and uniformly stirring to obtain a solution B;
3) adding the solution A into the solution B, stirring until a precipitate is formed, standing for 20-30h, centrifuging to collect a blue precipitate, washing the precipitate with absolute ethanol, and drying in an oven at 40-80 ℃ for 1-3h to obtain Co3(BTC)2A precursor;
4) mixing the Co obtained in the step 3)3(BTC)2Dispersing in mixed solvent of deionized water and anhydrous ethanol, wherein the volume of the mixed solvent is 10-40ml, and adding RuCl3·xH2Stirring and reacting O for 4-24h, centrifuging to obtain a precipitate, washing the precipitate with absolute ethyl alcohol, and drying in a 50-70 ℃ oven for 1-3h to obtain a Co and Ru bimetal-containing MOFs material;
5) placing the MOFs material obtained in the step 4) into a tubular furnace, heating the reactant to 400-600 ℃ at the heating rate of 1-20 ℃/min in an inert atmosphere, preserving the heat for 1-5h, and cooling to room temperature to obtain the Co and Ru-containing bimetallic carbon nano composite electro-catalytic material CoRu/C.
Further, the cobalt salt in the step 1) is cobalt copper acetate, cobalt copper sulfate, or cobalt copper chloride, or a combination of any two or three of them.
Further, the volume ratio of the deionized water to the ethanol in the step 1) is 1: 1.
Further, the volume ratio of the deionized water to the ethanol in the step 2) is 1: 1-2.
Further, the mass ratio of the cobalt salt to the trimesic acid is 0.5-5: 1.
Further, Co in the step 4)3(BTC)2And RuCl3·xH2The mass ratio of O is 1-10: 1.
Further, the volume ratio of the deionized water to the ethanol in the step 4) is 1:1-2, and the volume of the mixed solvent is 20 ml.
Further, the inert atmosphere in the step 5) is nitrogen or argon.
Further, the temperature of the reactant in the step 5) is raised to 400-600 ℃ and maintained.
The preparation method aims at further searching the bimetallic carbon nano composite material with simple preparation method, low cost and excellent catalytic performance, and firstly synthesizes MOFs material Co3(BTC)2And the precursor is used for ion exchange with Ru to prepare the bimetallic MOFs material, and finally the bimetallic MOFs material is subjected to high-temperature pyrolysis at the temperature of 400-600 ℃ to obtain the carbon nano composite material derived from the bimetallic organic framework material with high graphitization degree.
The invention synthesizes cobalt-containing metal frame Materials (MOFs) Co by using cobalt salt (cobalt acetate/cobalt sulfate/cobalt chloride) as a cobalt source and trimesic acid as an organic ligand3(BTC)2Precursor, then reacted with RuCl3·xH2And performing O ion exchange to obtain a Co and Ru bimetallic MOFs material, and finally performing heat treatment carbonization in an inert environment to obtain the bimetallic carbon nano composite electro-catalytic material derived from the metal organic framework. The composite material has better HER performance, and the current density is 10mA/cm in 1mol/L KOH electrolyte2When the voltage is higher than the predetermined value, the overpotential is 133 mV.
The invention has the beneficial effects that: the MOFs material containing Co and Ru bimetal is synthesized by an ion exchange method, and then the MOFs material is calcined at high temperature to obtain the Co and Ru bimetal-containing carbon nano composite electro-catalytic material which has large specific surface area, regular structure and uniform doping, and is an electro-catalytic material with excellent performance.
Drawings
FIG. 1 is a scanning electron microscope picture of a sample CoRu/C bimetallic carbon nanocomposite electrocatalytic material prepared in example 1 of the invention.
Fig. 2 is an XRD chart of the bimetallic carbon nanocomposite electrocatalytic material containing Co and Ru prepared in example 1 of the present invention.
Fig. 3 is a LSV curve diagram of the Co and Ru-containing bimetallic carbon nanocomposite electrocatalytic material prepared in example 1 of the present invention.
Fig. 4 is a Tafel diagram of the bimetallic carbon nanocomposite electrocatalytic material containing Co and Ru prepared in example 1 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1)Co3(BTC)2The preparation of (1):
(a) 0.2g of Co (CH)3COO)2·4H2Dissolving O and 1.2g polyvinylpyrrolidone (PVP) in a mixed solution of 20mL of deionized water and 20mL of absolute ethyl alcohol, and uniformly stirring to obtain cobalt ions ([ Co ] ions2+]) Solution A with the concentration of 0.25 mmol/mL;
(b) 0.2g H3BTC is added into a mixed solution of 20mL deionized water and 20mL absolute ethyl alcohol and is stirred uniformly to obtain H3BTC solution with concentration of 0.25mmol/mLSolution B;
(c) adding the solution A into the solution B, stirring until a precipitate is formed, and then standing for 24 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 60 ℃ for 2 h;
(2) preparing a composite bimetal MOFs material:
(a) the obtained 100mg of Co3(BTC)2Dispersing in 10mL of deionized water and 10mL of absolute ethanol, adding 0.571mL of RuCl with the concentration of 10mg/mL3·xH2O, stirring for 24 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 60 ℃ for 2 h;
(3) preparation of CoRu/C-1 material:
and (3) placing the product obtained in the step (2) in a tube furnace, heating to 500 ℃ at the speed of 10 ℃/min in an inert gas atmosphere, preserving heat for 3h, and then cooling to room temperature to obtain the carbon nano composite material CoRu/C-1.
In FIG. 2, it can be seen that the XRD pattern and the main characteristic peak of CoRu/C-1 are both consistent with the simulated Co crystal pattern (15-0806), and the characteristic diffraction peak is also consistent with the characteristic diffraction peak of Cu crystal, which indicates that Co in the sample CoRu/C-1 has better crystallinity. There is no sharper C diffraction peak in the diffraction pattern, indicating that the carbon obtained is amorphous carbon.
Referring to FIGS. 3 and 4, it can be seen that the overpotential of the sample CoRu/C-1 is 133mV and the Tafel slope is 147mV dec at a current of 10mA-1The performance is superior to that of the best industrial electrolyzed water hydrogen production catalyst. The sample prepared by the invention has extremely excellent electro-catalytic performance, which is mainly dependent on the high dispersion of Co and Ru bimetal in the material in the whole body and the synergistic effect of the bimetal, and the characteristics of large specific surface area, high porosity and the like of the material provide a structural basis for the excellent electro-catalytic performance.
Example 2
(1)Co3(BTC)2The preparation of (1):
(a) 0.2g of Co (CH)3COO)2·4H2O and 1.2g PVP were dissolved in 20mL deionized water and 20mL absolute ethanolStirring the mixed solution evenly to obtain cobalt ions ([ Co ]2+]) Solution A with the concentration of 0.25 mmol/mL;
(b) 0.18g H3BTC is added into a mixed solution of 20mL deionized water and 40mL absolute ethyl alcohol and stirred evenly to obtain H3A solution B with the BTC concentration of 0.25 mmol/mL;
(c) adding the solution A into the solution B, stirring until a precipitate is formed, and then standing for 30 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 80 ℃ for 3 h;
(2) preparing a composite bimetal MOFs material:
(a) the obtained 100mg of Co3(BTC)2Dispersing in 10mL of deionized water and 10mL of absolute ethanol, adding 1.142mL of RuCl with the concentration of 10mg/mL3·xH2O, stirring for 20 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 60 ℃ for 3 h;
(3) preparation of CoRu/C-2 material:
and (3) placing the product obtained in the step (2) in a tube furnace, heating to 400 ℃ at the speed of 1 ℃/min in the inert gas atmosphere, preserving heat for 3h, and then cooling to room temperature carbon nano composite material CoRu/C-2.
Example 3
(1)Co3(BTC)2The preparation of (1):
(a) 0.2g of Co (CH)3COO)2·4H2Dissolving O and 1.2g PVP in a mixed solution of 20mL of deionized water and 20mL of absolute ethyl alcohol, and uniformly stirring to obtain cobalt ions ([ Co ] ions2+]) Solution A with the concentration of 0.25 mmol/mL;
(b) 0.18g H3BTC is added into a mixed solution of 20mL deionized water and 40mL absolute ethyl alcohol and stirred evenly to obtain H3A solution B with the BTC concentration of 0.25 mmol/mL;
(c) adding the solution A into the solution B, stirring until a precipitate is formed, and then standing for 20 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 40 ℃ for 3 h;
(2) preparing a composite bimetal MOFs material:
(a) the obtained 100mg of Co3(BTC)2Dispersing in 10mL deionized water and 10mL absolute ethyl alcohol, adding 0.285mL RuCl with concentration of 10mg/mL3·xH2O, stirring for 24 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 60 ℃ for 2 h;
(3) preparation of CoRu/C-3 material:
and (3) placing the product obtained in the step (2) in a tube furnace, heating to 600 ℃ at the speed of 15 ℃/min in an inert gas atmosphere, preserving heat for 4h, and then cooling to room temperature to obtain the carbon nano composite material CoRu/C-3.
Example 4
(1)Co3(BTC)2The preparation of (1):
(a) 0.1g of Co (CH)3COO)2·4H2Dissolving O and 1.2g polyvinylpyrrolidone (PVP) in a mixed solution of 20mL of deionized water and 20mL of absolute ethyl alcohol, and uniformly stirring to obtain cobalt ions ([ Co ] ions2+]) Solution A with the concentration of 0.125 mmol/mL;
(b) 0.2g H3BTC is added into a mixed solution of 20mL deionized water and 20mL absolute ethyl alcohol and is stirred uniformly to obtain H3A solution B with the BTC concentration of 0.25 mmol/mL;
(c) adding the solution A into the solution B, stirring until a precipitate is formed, and then standing for 28 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 70 ℃ for 2 h;
(2) preparing a composite bimetal MOFs material:
(a) the obtained 100mg of Co3(BTC)2Dispersing in 10mL of deionized water and 10mL of absolute ethanol, adding 0.571mL of RuCl with the concentration of 10mg/mL3·xH2O, stirring for 24 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 60 ℃ for 2 h;
(3) preparation of CoRu/C-4 material:
and (3) placing the product obtained in the step (2) in a tube furnace, heating to 600 ℃ at the speed of 10 ℃/min in an inert gas atmosphere, preserving heat for 4h, and then cooling to room temperature carbon nano composite material CoRu/C-4.
Example 5
(1)Co3(BTC)2The preparation of (1):
(a) 0.1g of Co (CH)3COO)2·4H2Dissolving O and 1.2g polyvinylpyrrolidone (PVP) in a mixed solution of 20mL of deionized water and 20mL of absolute ethyl alcohol, and uniformly stirring to obtain cobalt ions ([ Co ] ions2+]) Solution A with the concentration of 0.125 mmol/mL;
(b) 0.2g H3BTC is added into a mixed solution of 20mL deionized water and 20mL absolute ethyl alcohol and is stirred uniformly to obtain H3A solution B with the BTC concentration of 0.25 mmol/mL;
(c) adding the solution A into the solution B, stirring until a precipitate is formed, and then standing for 20 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 65 ℃ for 2.5 h;
(2) preparing a composite bimetal MOFs material:
(a) the obtained 100mg of Co3(BTC)2Dispersing in 5mL of deionized water and 5mL of absolute ethanol, adding 0.571mL of RuCl with the concentration of 10mg/mL3·xH2O, stirring for 4 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 55 ℃ for 3 h;
(3) preparation of CoRu/C-5 material:
and (3) placing the product obtained in the step (2) in a tube furnace, heating to 550 ℃ at the speed of 18 ℃/min in an inert gas atmosphere, preserving heat for 1h, and then cooling to room temperature to obtain the carbon nano composite material CoRu/C-5.
Example 6
(1)Co3(BTC)2The preparation of (1):
(a) 0.1g of Co (CH)3COO)2·4H2Dissolving O and 0.6g polyvinylpyrrolidone (PVP) in a mixed solution of 20mL of deionized water and 20mL of absolute ethyl alcohol, and uniformly stirring to obtain cobalt ions ([ Co ] ions2+]) Solution A with the concentration of 0.125 mmol/mL;
(b) 0.2g H3BTC was added to 20mL deionized waterAnd 10mL of absolute ethyl alcohol mixed solution, and uniformly stirring to obtain H3A solution B with the BTC concentration of 0.25 mmol/mL;
(c) adding the solution A into the solution B, stirring until a precipitate is formed, and then standing for 20 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 70 ℃ for 1.2 h;
(2) preparing a composite bimetal MOFs material:
(a) the obtained 100mg of Co3(BTC)2Dispersing in 5mL of deionized water and 5mL of absolute ethanol, adding 0.571mL of RuCl with the concentration of 10mg/mL3·xH2O, stirring for 24 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 60 ℃ for 2 h;
(3) preparation of CoRu/C-6 material:
and (3) placing the product obtained in the step (2) in a tube furnace, heating to 600 ℃ at the speed of 12 ℃/min in the inert gas atmosphere, preserving heat for 5h, and then cooling to room temperature carbon nano composite material CoRu/C-6.
Example 7
(1)Co3(BTC)2The preparation of (1):
(a) 0.1g of Co (CH)3COO)2·4H2Dissolving O and 0.6g polyvinylpyrrolidone (PVP) in a mixed solution of 20mL of deionized water and 20mL of absolute ethyl alcohol, and uniformly stirring to obtain cobalt ions ([ Co ] ions2+]) Solution A with the concentration of 0.125 mmol/mL;
(b) 0.2g H3BTC is added into a mixed solution of 20mL of deionized water and 10mL of absolute ethyl alcohol and stirred uniformly to obtain H3A solution B with the BTC concentration of 0.25 mmol/mL;
(c) adding the solution A into the solution B, stirring until a precipitate is formed, and then standing for 20 hours;
(d) the product was centrifuged and washed three times with ethanol and then dried at 60 ℃ for 2.8 h;
(2) preparing a composite bimetal MOFs material:
(a) the obtained 100mg of Co3(BTC)2Dispersing in 5mL deionized water and 5mL absolute ethyl alcohol, adding0.571mL of RuCl with a concentration of 10mg/mL3·xH2O, stirring for 14 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 58 ℃ for 2 h;
(3) preparation of CoRu/C-7 material:
and (3) placing the product obtained in the step (2) in a tube furnace, heating to 500 ℃ at the speed of 18 ℃/min in the inert gas atmosphere, preserving heat for 3h, and then cooling to room temperature to obtain the carbon nano composite material CoRu/C-7.
Example 8
(1)Co3(BTC)2The preparation of (1):
(a) 0.1g of Co (CH)3COO)2·4H2Dissolving O and 0.6g polyvinylpyrrolidone (PVP) in a mixed solution of 10mL of deionized water and 10mL of absolute ethyl alcohol, and uniformly stirring to obtain cobalt ions ([ Co ] ions2+]) Solution A with the concentration of 0.25 mmol/mL;
(b) 0.2g H3BTC is added into a mixed solution of 20mL of deionized water and 10mL of absolute ethyl alcohol and stirred uniformly to obtain H3A solution B with the BTC concentration of 0.25 mmol/mL;
(c) adding the solution A into the solution B, stirring until a precipitate is formed, and then standing for 20 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 60 ℃ for 2 h;
(2) preparing a composite bimetal MOFs material:
(a) the obtained 100mg of Co3(BTC)2Dispersing in 5mL of deionized water and 10mL of absolute ethanol, adding 0.571mL of RuCl with the concentration of 10mg/mL3·xH2O, stirring for 14 hours;
(d) the product was centrifuged and washed three times with ethanol and then dried at 68 ℃ for 2.2 h;
(3) preparation of CoRu/C-8 material:
and (3) placing the product obtained in the step (2) in a tube furnace, heating to 550 ℃ at the speed of 8 ℃/min in the inert gas atmosphere, preserving heat for 4h, and then cooling to room temperature to obtain the carbon nano composite material CoRu/C-8.
Example 9
(1)Co3(BTC)2The preparation of (1):
(a) 0.1g of Co (CH)3COO)2·4H2Dissolving O and 0.6g polyvinylpyrrolidone (PVP) in a mixed solution of 10mL of deionized water and 10mL of absolute ethyl alcohol, and uniformly stirring to obtain cobalt ions ([ Co ] ions2+]) Solution A with the concentration of 0.25 mmol/mL;
(b) 0.2g H3BTC is added into a mixed solution of 20mL of deionized water and 10mL of absolute ethyl alcohol and stirred uniformly to obtain H3A solution B with the BTC concentration of 0.25 mmol/mL;
(c) adding the solution A into the solution B, stirring until a precipitate is formed, and then standing for 20 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 60 ℃ for 2 h;
(2) preparing a composite bimetal MOFs material:
(a) the obtained 100mg of Co3(BTC)2Dispersing in 5mL of deionized water and 10mL of absolute ethanol, adding 0.571mL of RuCl with the concentration of 10mg/mL3·xH2O, stirring for 14 hours;
(d) the product was centrifuged and washed three times with ethanol and subsequently dried at 60 ℃ for 2 h;
(3) preparation of CoRu/C-9 material:
and (3) placing the product obtained in the step (2) in a tube furnace, heating to 500 ℃ at the speed of 20 ℃/min in an inert gas atmosphere, preserving heat for 5 hours, and then cooling to room temperature to obtain the carbon nano composite material CoRu/C-9.
The foregoing detailed description is intended to illustrate and not limit the invention, which is intended to be within the spirit and scope of the appended claims, and any changes and modifications that fall within the true spirit and scope of the invention are intended to be covered by the following claims.
Claims (8)
1. A preparation method of a Co and Ru-containing bimetallic carbon nano composite electro-catalytic material is characterized by comprising the following steps:
1) dissolving cobalt salt and polyvinylpyrrolidone in a mixed solvent of ethanol and deionized water, and uniformly stirring to obtain a solution A;
2) dissolving trimesic acid in a mixed solvent of ethanol and deionized water, and uniformly stirring to obtain a solution B;
3) adding the solution A into the solution B, stirring until a precipitate is formed, standing for 20-30h, centrifuging to collect a blue precipitate, washing the precipitate with absolute ethanol, and drying in an oven at 40-80 ℃ for 1-3h to obtain Co3(BTC)2A precursor;
4) mixing the Co obtained in the step 3)3(BTC)2Dispersing in mixed solvent of deionized water and anhydrous ethanol, wherein the volume of the mixed solvent is 10-40ml, and adding RuCl3·xH2Stirring and reacting O for 4-24h, centrifuging to obtain a precipitate, washing the precipitate with absolute ethyl alcohol, and drying in a 50-70 ℃ oven for 1-3h to obtain a Co and Ru bimetal-containing MOFs material;
5) placing the MOFs material obtained in the step 4) into a tubular furnace, heating the reactant to 400-600 ℃ at the heating rate of 1-20 ℃/min in an inert atmosphere, preserving the heat for 1-5h, and cooling to room temperature to obtain the Co and Ru-containing bimetallic carbon nano composite electro-catalytic material CoRu/C.
2. The method of claim 1, wherein: the cobalt salt in the step 1) is cobalt acetate, cobalt sulfate or cobalt chloride, or a combination of any two or three of the above.
3. The method of claim 1, wherein: the volume ratio of the deionized water to the ethanol in the step 1) is 1: 1.
4. The method of claim 1, wherein: the volume ratio of the deionized water to the ethanol in the step 2) is 1: 1-2.
5. The method of claim 1, wherein: the mass ratio of the cobalt salt to the trimesic acid is 0.5-5: 1.
6. The method according to claim 1, wherein the reaction mixture is heated to a temperature in the reaction mixtureThe method comprises the following steps: co in said step 4)3(BTC)2And RuCl3·xH2The mass ratio of O is 1-10: 1.
7. The method of claim 1, wherein: the volume ratio of the deionized water to the ethanol in the step 4) is 1:1-2, and the volume of the mixed solvent is 20 ml.
8. The method of claim 1, wherein: the inert atmosphere in the step 5) is nitrogen or argon.
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