CN115094470B - Hierarchical pore carbon loaded cobalt-ruthenium nano alloy material and preparation method thereof - Google Patents
Hierarchical pore carbon loaded cobalt-ruthenium nano alloy material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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
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- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
Abstract
The invention provides a cobalt-ruthenium nano alloy supported composite catalytic material and a preparation method thereof, belonging to the field of composite material preparation methods. Firstly, organic monomers 2, 5-diaminobenzenesulfonic acid and 2,4, 6-tricarboxyl phloroglucinol undergo polymerization reaction under the catalysis of p-toluenesulfonic acid to form ionic coordination polymers which are wrapped on the surface of polystyrene nanospheres; and then obtaining the hierarchical pore carbon supported cobalt-ruthenium nano alloy catalytic material through ion exchange and high-temperature calcination. The electrocatalyst prepared by the invention has a multi-stage pore structure, and is beneficial to substance diffusion and hydrogen precipitation in the water electrolysis reaction. And has the advantages of low metal loading, high catalytic activity, good cycle stability and the like.
Description
Technical Field
The invention relates to the cross technical fields of material chemistry, catalytic chemistry, electrolyzed water hydrogen evolution and the like, in particular to a hierarchical pore carbon supported cobalt-ruthenium nano alloy electrocatalytic material and a preparation method thereof.
Background
Along with the industrialized development, fossil fuel is largely consumed, and carbon dioxide gas is released, so that a greenhouse effect is caused, and the ecological environment is destroyed. In the face of increasingly serious energy crisis and environmental problems, hydrogen has been attracting attention as a novel clean and environment-friendly energy source with high combustion value.
At present, the preparation method of hydrogen mainly comprises the following steps: fossil fuel hydrogen production, industrial side reaction hydrogen production, electrolysis of water to produce hydrogen, and the like. Compared with other methods, the method has no carbon dioxide emission in the hydrogen production process of the electrolysis water, and is a green and environment-friendly hydrogen production method. However, the current electrolysis of water to produce hydrogen has large power consumption and high cost, and the overpotential of the cathodic hydrogen evolution reaction must be reduced to realize large-scale application. Therefore, the use of the electrocatalyst is important in the hydrogen production reaction process of the electrolyzed water, and the use of the high-efficiency catalyst not only can realize large-current hydrogen production under low potential, but also can reduce the electric energy consumption and save the cost. The research shows that noble metal platinum (Pt) and related substances thereof have excellent electrolytic water hydrogen evolution catalytic performance, but the noble metal platinum (Pt) and related substances thereof have limited resources and high price, so that the practical industrial application of the electrocatalytic material is limited. Therefore, the development of novel high-efficiency electrocatalytic materials is particularly important for the expansion industrial application of the electrolytic water hydrogen production technology.
Disclosure of Invention
The invention aims to solve the problems that the prior electrolytic water hydrogen production reaction mostly adopts a Pt-based catalyst, has higher cost and is unfavorable for industrialization, and provides a hierarchical pore carbon supported cobalt ruthenium (CoRu) nano alloy electrocatalytic material and a preparation method thereof
The technical scheme adopted by the invention is that the invention provides a hierarchical pore carbon loaded CoRu nano alloy catalytic material, which is characterized in that a polystyrene nanosphere is used as a hard template, two organic monomers are polymerized on the surface of the polystyrene nanosphere, the obtained coordination polymer has an anion framework, and an adjustable cation is contained in a pore canal. Co incorporation by cation exchange 2+ Ion and Ru 3+ And (3) after the ions, sintering the composite material at a high temperature. In the calcining process, the coordination polymer forms graphitized carbon carrier, the polystyrene nanospheres form macroporous structure after high-temperature evaporation, co 2+ Ion and Ru 3+ The ion forming nano alloy is loaded on the hierarchical pore graphitized carbon carrier.
The preparation method of the hierarchical pore carbon loaded CoRu nano alloy catalytic material comprises the following steps:
step one: dispersing 2, 5-diaminobenzenesulfonic acid and p-toluenesulfonic acid in polystyrene nanosphere emulsion, adding 2,4, 6-tricarboxyl phloroglucinol into the emulsion, pouring the mixture into a surface dish after the mixture is uniformly mixed, and evaporating the solvent at room temperature; then the solid matter is placed in an oven to react for 48 hours at the temperature of 80 ℃; cooling to room temperature, washing the solid product with deionized water and absolute ethyl alcohol for 3-5 times, and drying at 60-100 ℃ for 10-12 hours under the vacuum degree of 133Pa to obtain the composite material PS@COF-SO 3 H is formed; the molar ratio of the 2, 5-diaminobenzene sulfonic acid to the p-toluene sulfonic acid to the 2,4, 6-tricarboxyl phloroglucinol to the polystyrene nanosphere emulsion is 1: 5-10: 0.7 to 1.5: 20-30 parts;
step two: the composite material PS@COF-SO 3 Dispersing H in ammonia water, and stirring at room temperature for 12-24 hours; washing the filtered solid matter with deionized water and absolute ethyl alcohol for 3-5 times, and drying at 60-100 deg.c under 133Pa for 10-12 hr to obtain composite material PS@COF-SO 3 NH 4 The method comprises the steps of carrying out a first treatment on the surface of the PS@COF-SO 3 NH 4 Dispersed in Co 2+ Ion and Ru 3+ Ion-mixed water-solubleStirring the solution for 12 to 24 hours at room temperature; washing the filtered solid matter with deionized water and absolute ethyl alcohol for 3-5 times, and drying at 60-100 deg.c under 133Pa for 10-12 hr to obtain composite material PS@COF-SO 3 CoRu。
Step three: PS@COF-SO of the composite material 3 Placing the CoRu into a tubular furnace, heating to 300-350 ℃ in an inert gas atmosphere, and maintaining for 1-2 hours; and then heating to 500-550 ℃, maintaining for 4-5 hours, and cooling to obtain the hierarchical pore carbon loaded CoRu nano alloy electrocatalytic material m-CoRu@NC.
The ammonia concentration was 10% wt.
The Co is 2+ Ion and Ru 3+ The metal salt used in the ion-mixed aqueous solution is preferably cobalt acetate or ruthenium chloride, and the concentration is preferably 0.003mol/L.
The inert gas is preferably nitrogen.
The heating rate is preferably 5 ℃/min.
The invention has the beneficial effects that:
the electrocatalytic hydrogen production hierarchical pore carbon loaded CoRu nano alloy catalytic material prepared by the synthesis method provided by the invention has the following advantages:
(1) Co is introduced and immobilized by adopting an ionic coordination polymer as a substrate 2+ Ion and Ru 3+ Ions, effectively avoid Co 2+ Ion and Ru 3+ The ions are aggregated during calcination, so that the CoRu alloy nano particles with smaller size and uniform distribution are obtained and used as high-efficiency catalytic active sites for producing hydrogen by electrolysis water;
(2) The polystyrene nanospheres are used as a hard template and removed during calcination to obtain a macroporous structure, which is helpful for the diffusion of reactants and the precipitation of hydrogen bubbles in the catalytic process and is helpful for the reaction.
Drawings
FIG. 1 is a Raman spectrum diagram of m-CoRu@NC prepared in example 1;
FIG. 2 is a diagram of an m-CoRu@NC scanning electron microscope prepared in example 1;
FIG. 3 is a graph of an m-CoRu@NC transmission electron microscope prepared in example 1;
FIG. 4 is a graph of electrolytic aqueous hydrogen polarization of m-CoRu@NC and commercial Pt/C catalysts prepared in example 1 in 1.0mol/L KOH solution;
FIG. 5 Tafel slope plots for m-CoRu@NC and commercial Pt/C prepared in example 1.
Detailed Description
The invention will be described in further detail with reference to the drawings and examples, it being noted that the purpose is only to better understand the content of the invention and not to limit the protection scope of the invention.
Example 1
Step one: dispersing 0.23mmol of 2, 5-diaminobenzenesulfonic acid and 1.5mmol of p-toluenesulfonic acid in 2.5mL polystyrene nanosphere emulsion, and vibrating for 15 minutes; adding 0.15mmol of 2,4, 6-tricarboxyl phloroglucinol into the mixture, shaking the mixture for 15 minutes, pouring the mixture into a surface dish, and evaporating the solvent at room temperature; then the solid matter is placed in an oven to react for 48 hours at the temperature of 80 ℃; cooling to room temperature, washing the solid product with deionized water and absolute ethyl alcohol for 3 times, and drying at 60deg.C under 133Pa for 12 hr to obtain composite material PS@COF-SO 3 H；
Step two: the composite material PS@COF-SO 3 H was dispersed in 40mL of 10% wt aqueous ammonia and stirred at room temperature for 12 hours; washing the filtered solid substance with deionized water and absolute ethyl alcohol for 3 times, and drying at 60deg.C under 133Pa for 12 hr to obtain composite material PS@COF-SO 3 NH 4 The method comprises the steps of carrying out a first treatment on the surface of the PS@COF-SO 3 NH 4 Dispersing in 20mL of aqueous solution of cobalt acetate and ruthenium chloride with concentration of 0.003mol/L, and stirring at room temperature for 12 hours; washing the filtered solid substance with deionized water and absolute ethyl alcohol for 3 times, and drying at 60deg.C under 133Pa for 12 hr to obtain composite material PS@COF-SO 3 CoRu。
Step three: PS@COF-SO of the composite material 3 Placing the CoRu into a tube furnace, heating to 300 ℃ in a nitrogen atmosphere, and maintaining for 1 hour; and then heating to 550 ℃, maintaining for 4 hours, and cooling to obtain the hierarchical pore carbon-loaded CoRu nano alloy electrocatalytic material m-CoRu@NC.
The structure of the m-CoRu@NC synthesized in example 1 and the hydrogen production performance of electrolyzed water were characterized.
FIG. 1 is a Raman spectrum of m-CoRu@NC prepared in example 1; as can be seen from fig. 1, there are two raman characteristic peaks corresponding to the D and G bands, respectively. I between two peaks D /I G At 0.85, graphitized carbon layer structures were demonstrated to exist.
FIG. 2 is a graph of an m-CoRu@NC scanning electron microscope prepared in example 1; as can be seen from the figure, the m-CoRu@NC has a macroporous structure.
FIG. 3 is a graph of an m-CoRu@NC transmission electron microscope prepared in example 1; as can be seen from the figure, the m-coru@nc has a macroporous structure and there are evenly dispersed alloy nanoparticles.
FIG. 4 is a graph of electrolytic water hydrogen polarization in 1.0mol/L KOH solution for m-CoRu@NC and commercial Pt/C catalysts prepared in example 1; as can be seen from the figure, a current density of 10mA/cm is to be achieved 2 The m-CoRu@NC only needs 9mV, and the commercial Pt/C needs 42mV, so that the m-CoRu@NC has more excellent hydrogen production performance of electrolyzed water.
FIG. 5 is a Tafel slope plot of m-CoRu@NC and commercial Pt/C prepared in example 1; as can be seen from the graph, the Tafel slope of m-CoRu@NC was 47mV/dec, which is lower than commercial Pt/C.
Example 2
Step one: dispersing 0.25mmol of 2, 5-diaminobenzenesulfonic acid and 1.5mmol of p-toluenesulfonic acid in 2.5mL polystyrene nanosphere emulsion, and vibrating for 30 minutes; adding 0.15mmol of 2,4, 6-tricarboxyl phloroglucinol into the mixture, shaking the mixture for 30 minutes, pouring the mixture into a surface dish, and evaporating the solvent at room temperature; then the solid matter is placed in an oven to react for 48 hours at the temperature of 80 ℃; cooling to room temperature, washing the solid product with deionized water and absolute ethyl alcohol for 3 times, and drying at 80deg.C under 133Pa for 12 hr to obtain composite material PS@COF-SO 3 H；
Step two: the composite material PS@COF-SO 3 H was dispersed in 40mL of 10% wt aqueous ammonia and stirred at room temperature for 12 hours; washing the filtered solid substance with deionized water and absolute ethyl alcohol for 3 times, and drying at 60deg.C under 133Pa for 12 hr to obtain composite material PS@COF-SO 3 NH 4 The method comprises the steps of carrying out a first treatment on the surface of the PS@COF-SO 3 NH 4 Dispersing in 20mL of cobalt acetate and ruthenium chloride aqueous solution with the concentration of 0.0035mol/L, and stirring for 12 hours at room temperature; washing the filtered solid substance with deionized water and absolute ethanol for 3 times, and drying at 100deg.C under vacuum degree of 133Pa for 10 hr to obtain composite material PS@COF-SO 3 CoRu。
Step three: PS@COF-SO of the composite material 3 Placing the CoRu into a tube furnace, heating to 300 ℃ in a nitrogen atmosphere, and maintaining for 1 hour; and then heating to 550 ℃, maintaining for 4 hours, and cooling to obtain the hierarchical pore carbon-loaded CoRu nano alloy electrocatalytic material m-CoRu@NC.
The m-CoRu@NC catalyst is subjected to electrolytic water hydrogen production test in a KOH solution with the concentration of 1.0mol/L, and the current density is required to be 11mV to be 10mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The Tafel slope was 52mV/dec.
Example 3
Step one: dispersing 0.25mmol of 2, 5-diaminobenzenesulfonic acid and 1.5mmol of p-toluenesulfonic acid in 2.5mL polystyrene nanosphere emulsion, and vibrating for 30 minutes; adding 0.15mmol of 2,4, 6-tricarboxyl phloroglucinol into the mixture, shaking the mixture for 30 minutes, pouring the mixture into a surface dish, and evaporating the solvent at room temperature; then the solid matter is placed in an oven to react for 48 hours at the temperature of 80 ℃; cooling to room temperature, washing the solid product with deionized water and absolute ethyl alcohol for 5 times, and drying at 80deg.C under 133Pa for 12 hr to obtain composite material PS@COF-SO 3 H；
Step two: the composite material PS@COF-SO 3 H was dispersed in 40mL of 10% wt aqueous ammonia and stirred at room temperature for 12 hours; washing the filtered solid substances with deionized water and absolute ethyl alcohol for 5 times respectively, and drying at 60 ℃ for 12 hours under the condition of 133Pa vacuum degree to obtain the composite material PS@COF-SO 3 NH 4 The method comprises the steps of carrying out a first treatment on the surface of the PS@COF-SO 3 NH 4 Dispersing in 20mL of cobalt acetate and ruthenium chloride aqueous solution with the concentration of 0.0035mol/L, and stirring for 12 hours at room temperature; washing the filtered solid substance with deionized water and absolute ethyl alcohol for 3 times, and drying at 70deg.C under vacuum degree of 133Pa for 10 hr to obtain composite material PS@COF-SO 3 CoRu。
Step three: will be compoundedMaterial PS@COF-SO 3 Placing the CoRu into a tube furnace, heating to 300 ℃ in a nitrogen atmosphere, and maintaining for 2 hours; and then heating to 550 ℃, maintaining for 5 hours, and cooling to obtain the hierarchical pore carbon-loaded CoRu nano alloy electrocatalytic material m-CoRu@NC.
The m-CoRu@NC catalyst is subjected to electrolytic water hydrogen production test in a KOH solution with the concentration of 1.0mol/L, and 15mV is needed to realize the current density of 10mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The Tafel slope was 51mV/dec.
Example 4
Step one: dispersing 0.25mmol of 2, 5-diaminobenzenesulfonic acid and 1.75mmol of p-toluenesulfonic acid in 3.5mL polystyrene nanosphere emulsion, and shaking for 30 minutes; adding 0.15mmol of 2,4, 6-tricarboxyl phloroglucinol into the mixture, shaking the mixture for 30 minutes, pouring the mixture into a surface dish, and evaporating the solvent at room temperature; then the solid matter is placed in an oven to react for 48 hours at the temperature of 80 ℃; cooling to room temperature, washing the solid product with deionized water and absolute ethyl alcohol for 3 times, and drying at 80deg.C under 133Pa for 12 hr to obtain composite material PS@COF-SO 3 H；
Step two: the composite material PS@COF-SO 3 H was dispersed in 60mL of 10% wt aqueous ammonia and stirred at room temperature for 12 hours; washing the filtered solid substance with deionized water and absolute ethyl alcohol for 3 times, and drying at 60deg.C under 133Pa for 12 hr to obtain composite material PS@COF-SO 3 NH 4 The method comprises the steps of carrying out a first treatment on the surface of the PS@COF-SO 3 NH 4 Dispersing in 20mL of aqueous solution of cobalt acetate and ruthenium chloride with concentration of 0.0045mol/L, and stirring at room temperature for 12 hours; washing the filtered solid substance with deionized water and absolute ethyl alcohol for 3 times, and drying at 60deg.C under 133Pa for 10 hr to obtain composite material PS@COF-SO 3 CoRu。
Step three: PS@COF-SO of the composite material 3 Placing the CoRu into a tube furnace, heating to 300 ℃ in a nitrogen atmosphere, and maintaining for 1 hour; and then heating to 550 ℃, maintaining for 4 hours, and cooling to obtain the hierarchical pore carbon-loaded CoRu nano alloy electrocatalytic material m-CoRu@NC.
The m-CoRu@NC catalyst is subjected to electrolytic water hydrogen production test in a KOH solution with the concentration of 1.0mol/L, and 16mV is needed to realize the current density of10mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The Tafel slope was 58mV/dec.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. Corresponding changes and substitutions can be made by those skilled in the art according to the technical scheme and the inventive concept, and the same performance or use should be regarded as the protection scope of the present invention.
Claims (4)
1. The preparation method of the hierarchical pore carbon supported cobalt-ruthenium nano alloy electrocatalytic material is characterized by comprising the following steps of:
step one: dispersing 2, 5-diaminobenzenesulfonic acid and p-toluenesulfonic acid in polystyrene nanosphere emulsion, adding 2,4, 6-tricarboxyl phloroglucinol into the emulsion, pouring the mixture into a surface dish after the mixture is uniformly mixed, and evaporating the solvent at room temperature; then placing the solid matters in an oven to react for 48 hours at the temperature of 80 ℃; cooling to room temperature, washing the solid product with deionized water and absolute ethyl alcohol for 3-5 times, and drying at 60-100 ℃ for 10-12 hours under the vacuum degree of 133Pa to obtain the composite material PS@COF-SO 3 H is formed; the molar ratio of the 2, 5-diaminobenzene sulfonic acid to the p-toluene sulfonic acid to the 2,4, 6-tricarboxyl phloroglucinol to the polystyrene nanosphere emulsion is 1: 5-10: 0.7 to 1.5: 20-30 parts;
step two: the composite material PS@COF-SO 3 Dispersing H in ammonia water, and stirring at room temperature for 12-24 hours; washing the filtered solid matter with deionized water and absolute ethyl alcohol for 3-5 times, and drying at 60-100 deg.c under 133Pa for 10-12 hr to obtain composite material PS@COF-SO 3 NH 4 The method comprises the steps of carrying out a first treatment on the surface of the PS@COF-SO 3 NH 4 Dispersing in a mixed aqueous solution of cobalt ions and ruthenium ions, and stirring for 12-24 hours at room temperature; washing the filtered solid matter with deionized water and absolute ethyl alcohol for 3-5 times, and drying at 60-100 deg.c under 133Pa for 10-12 hr to obtain composite material PS@COF-SO 3 CoRu；
Step three: PS@COF-SO of the composite material 3 Placing CoRu in a tube furnace, and inertHeating to 300-350 ℃ in a gas atmosphere, and maintaining for 1-2 hours; and then heating to 500-550 ℃, maintaining for 4-5 hours, and cooling to obtain the hierarchical pore carbon loaded CoRu nano alloy electrocatalytic material m-CoRu@NC.
2. The method for preparing the hierarchical porous carbon supported cobalt-ruthenium nano alloy electrocatalytic material according to claim 1, wherein the concentration of the ammonia water in the step II is 10% wt.
3. The method for preparing the hierarchical porous carbon supported cobalt-ruthenium nano alloy electrocatalytic material according to claim 1, wherein the inert gas in the third step is nitrogen.
4. The method for preparing the hierarchical porous carbon supported cobalt-ruthenium nano alloy electrocatalytic material according to claim 1, wherein the temperature rising speed in the step three is 5-10 ℃/min.
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| CN108262019A (en) * | 2018-02-11 | 2018-07-10 | 中国烟草总公司郑州烟草研究院 | A kind of magnetism sulfonic functional COFs materials and its preparation method and application |
| AU2020101584A4 (en) * | 2019-07-31 | 2020-09-10 | Hefei University Of Technology | Preparation method of metal monatomic composite loaded with covalent organic framework (COF)-derived carbon skeleton |
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| CN108262019A (en) * | 2018-02-11 | 2018-07-10 | 中国烟草总公司郑州烟草研究院 | A kind of magnetism sulfonic functional COFs materials and its preparation method and application |
| AU2020101584A4 (en) * | 2019-07-31 | 2020-09-10 | Hefei University Of Technology | Preparation method of metal monatomic composite loaded with covalent organic framework (COF)-derived carbon skeleton |
| CN113930803A (en) * | 2021-11-04 | 2022-01-14 | 陕西科技大学 | Nitrogen-carbon-loaded cobalt-ruthenium nanoparticle full-electrolysis water electro-catalytic material and preparation method thereof |
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