CN114054097B - Preparation method and application of ultrathin lamellar material - Google Patents

Preparation method and application of ultrathin lamellar material Download PDF

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CN114054097B
CN114054097B CN202111205249.2A CN202111205249A CN114054097B CN 114054097 B CN114054097 B CN 114054097B CN 202111205249 A CN202111205249 A CN 202111205249A CN 114054097 B CN114054097 B CN 114054097B
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cellulose
ultrathin
heat treatment
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hydrogen evolution
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CN114054097A (en
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曾黎明
吴岱丰
朱用洋
李睿
王英
唐仁衡
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Institute of Resource Utilization and Rare Earth Development of Guangdong Academy of Sciences
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—
    • B01J35/33—
    • 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
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon
    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
    • 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 discloses a preparation method and application of an ultrathin slice material, wherein the ultrathin slice material is obtained by rapid self-assembly reaction of metal ruthenium salt and cellulose modified with different types of functional groups, the prepared ultrathin slice material has uniform thickness, dark brown color, laver-like shape, slice thickness of 1-3 nm and amorphous structure of crystal characteristics. The preparation method is simple and convenient to operate, can realize rapid batch preparation, has lower cost, does not need to use organic solvents and surfactants, and is environment-friendly; the obtained ultrathin sheet material can be used as an acidic hydrogen evolution catalyst after further composite heat treatment with a carbon carrier, and has excellent catalytic activity in hydrogen evolution reaction under an acidic medium.

Description

Preparation method and application of ultrathin lamellar material
Technical Field
The invention relates to the technical field of a preparation method and electrocatalysis of a nano material, in particular to a preparation method and application of an ultrathin sheet material.
Background
Compared with the bulk material, the two-dimensional sheet thin-layer material has wide application potential in the fields of catalysis, energy storage and conversion, environmental management, biological medicine and the like due to the large specific surface area. Particularly in catalytic application, the larger specific surface area is favorable for exposing active sites, and the lamellar structure is also favorable for transferring charges and transmitting substances in the reaction, so that the catalytic reaction can be remarkably accelerated.
In the water electrolysis reaction, the kinetic rate of the anode oxygen evolution reaction is far slower than that of the cathode hydrogen evolution reaction, so that the method becomes one of the main reasons that the cost of water electrolysis hydrogen production is high and is difficult to match the cost of traditional chemical reforming hydrogen production at present, and the large-scale popularization and application of the water electrolysis technology are greatly promoted. Thus, it is important to develop efficient, low cost hydrogen evolution catalysts to increase the hydrogen evolution efficiency of electrolyzed water.
Disclosure of Invention
The invention aims to provide a preparation method and application of a super-thin sheet layer material, the preparation method is simple to operate, can realize rapid batch preparation, has lower preparation cost, does not need to use an organic solvent and a surfactant, is environment-friendly, and can be used as a hydrogen evolution catalyst after further heat treatment, and the super-thin sheet layer material shows better activity in catalyzing acidic hydrogen evolution reaction.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
a preparation method of an ultrathin sheet material comprises the following steps: firstly, stirring and dissolving cellulose modified with alkyl functional groups in deionized water at normal temperature to form colorless transparent viscous cellulose colloidal solution with the concentration of 5-100 mg/ml, then preparing metal ruthenium salt into solution with the concentration of 0.01-2 mmol/L, dripping the metal ruthenium salt solution into the colorless transparent viscous cellulose colloidal solution while stirring at the speed of 100-800 rpm/min, and then carrying out displacement cleaning with deionized water to remove residual cellulose molecules, thus obtaining the purified ultrathin slice layer material.
As a further improvement of the above-mentioned scheme, the cellulose modified with an alkyl functional group is at least one of methyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and hydroxyethyl cellulose; the metal ruthenium salt is at least one of ruthenium trichloride, ruthenium acetate, potassium pentachlororuthenate hydrate, ammonium hexachlororuthenate and ruthenium hexachloride.
As a further improvement of the above scheme, the concentration of the colorless transparent viscous cellulose gum-like solution is 10mg/mL, and the concentration of the metallic ruthenium salt solution is 0.1mmol/L.
As a further improvement of the above-mentioned scheme, the stirring rate at the time of dropping the metallic ruthenium salt solution into the colorless transparent viscous cellulose gum-like solution was 500rpm/min.
As a further improvement of the scheme, the thickness of the ultrathin sheet layer material is 1-3 nm.
The second aspect of the invention is to provide an ultrathin sheet material prepared by the preparation method.
The ultrathin slice layer material prepared by the invention has uniform thickness, dark brown color, similar laver shape, slice thickness of 1-3 nm and amorphous structure of crystallographic characteristics.
In a third aspect, the present invention provides the use of a ultrathin sheet material as described above for the preparation of a hydrogen evolution reaction catalyst.
Specifically, the application is that the ultra-thin sheet material is subjected to ultrasonic recombination and pyrolysis with a carbon carrier in absolute ethyl alcohol and then is applied to catalysis of electrolytic water hydrogen evolution reaction in an acidic medium.
As a further improvement of the scheme, the ultrathin slice layer material and the carbon carrier are subjected to ultrasonic compositing in absolute ethyl alcohol for 10-60 minutes, the mass ratio of the metal ruthenium in the ultrathin slice layer material to the carbon carrier is 1:10-1:40, then drying and heat treatment are carried out, the heat treatment atmosphere is nitrogen or hydrogen-argon mixed gas with the volume fraction of 5-20%, the heat treatment temperature is 200, 300, 400, 500, 600 or 700 ℃, and the heat treatment time is 0.5-2 hours.
As a further improvement of the scheme, the ultrasonic time is 30 minutes, and the mass ratio of the metal ruthenium to the carbon carrier in the ultrathin sheet material is 1:10; the carbon carrier is at least one of carbon black (carbon XC-72R), acetylene black, active carbon, graphene and carbon nano tube; the heat treatment atmosphere is nitrogen, the heat treatment temperature is 300 ℃, and the heat treatment time is 1 hour.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method disclosed by the invention is simple to operate, mild in condition, easy to prepare in batches, environment-friendly, and capable of obtaining the ultrathin sheet layer material with large specific surface area, and is favorable for uniformly dispersing and exposing metal active sites after being subjected to pyrolysis compounding with a carbon carrier, and has better activity in catalyzing acid electrolysis water hydrogen-evolution reaction when being used as an electrolysis water hydrogen-evolution catalyst.
Drawings
FIG. 1a is a digital photograph of the ultrathin sheet material Ru-NS prepared in example 1;
FIG. 1b is a Scanning Electron Micrograph (SEM) of an ultra-thin sheet of Ru-NS material prepared in example 1;
FIG. 2 is an X-ray diffraction pattern (XRD) of the ultrathin sheet material Ru-NS prepared in example 1;
FIG. 3 is an X-ray diffraction pattern (XRD) of the corresponding electrocatalyst (Ru-NS/C-1, ru-NS/C-2, ru-NS/C-3, ru-NS/C-4, ru-NS/C-5, ru-NS/C-6, ru-NS/C-7) prepared by compositing the ultrathin layer material prepared in examples 1-4 with a carbon support;
FIG. 4 is a Linear Sweep Voltammogram (LSV) of the corresponding electrocatalyst (Ru-NS/C-1, ru-NS/C-2, ru-NS/C-3, ru-NS/C-4, ru-NS/C-5, ru-NS/C-6, ru-NS/C-7) prepared by compositing the ultrathin layer material prepared in examples 1-4 with a carbon support.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1:
30mg of methyl cellulose is dissolved in 3mL of deionized water, after a transparent solution is formed, 1mL of ruthenium trichloride aqueous solution with the concentration of 0.02g/mL is dropwise added under stirring, the stirring speed is 500rpm/min, after the dark brown ruthenium trichloride solution is converted into a lamellar sheet form, a proper amount of deionized water is used for replacement cleaning to remove residual cellulose molecules, and a purified ultrathin layer material (Ru-NS) is obtained. After the ultrathin sheet material is dried, adding 3mL of ethanol for ultrasonic treatment for 30 minutes, then weighing 100mg of carbon black (carbon XC-72R), adding into the dispersion system, continuing ultrasonic treatment for 30 minutes, then drying at 80 ℃ for 12 hours, cooling, transferring into a tubular furnace, carrying out heat treatment at 300 ℃ for 1 hour under nitrogen atmosphere, cooling and collecting to obtain the hydrogen evolution catalytic material Ru-NS/C-1.
The digital picture and scanning electron microscope image of the ultra-thin sheet layer material (Ru-NS) of this embodiment are shown in FIGS. 1a and 1b, respectively, and the X-ray diffraction pattern is shown in FIG. 2; the X-ray diffraction pattern of the prepared catalyst RuNS/C-1 is shown in FIG. 3, and the catalyst is prepared in an acidic electrolyte solution (0.5M H 2 SO 4 ) The hydrogen evolution linear sweep voltammogram of the medium test linear sweep voltammogram is shown in figure 4, which shows that Ru-NS/C-1 shows better hydrogen evolution catalytic activity.
Example 2:
30mg of methyl cellulose is dissolved in 3mL of deionized water, after a transparent colloidal solution is formed, 1mL of ruthenium trichloride aqueous solution with the concentration of 0.02g/mL is dropwise added under stirring, the stirring speed is 500rpm/min, after the dark brown ruthenium trichloride solution is converted into a lamellar sheet form, a proper amount of deionized water is used for displacement cleaning to remove residual cellulose molecules, and a purified ultrathin sheet material is obtained. After the ultrathin sheet material is dried, 3mL of ethanol is added for ultrasonic treatment for 30 minutes, then 100mg of carbon black (carbon XC-72R) is weighed and added into the dispersion system, ultrasonic treatment is continued for 30 minutes, then drying is carried out at 80 ℃ for 12 hours, cooling is carried out, the obtained product is transferred into a tubular furnace for heat treatment at 500 ℃ for 1 hour under nitrogen atmosphere, cooling is carried out, and collection is carried out, thus obtaining the hydrogen evolution catalytic material Ru-NS/C-2, the X-ray diffraction diagram of which is shown in figure 3, and the hydrogen evolution catalytic material Ru-NS/C-2 is obtained after the reaction is carried out in an acidic electrolyte solution (0.5M H) 2 SO 4 ) The hydrogen evolution linear sweep voltammogram of the medium test linear sweep voltammogram is shown in figure 4, which shows that Ru-NS/C-2 shows better hydrogen evolution catalytic activity.
Example 3:
dissolving 30mg of methylcellulose in 3mL of deionized water, dropwise adding 1mL of 0.02g/mL ruthenium trichloride aqueous solution under stirring after forming transparent colloidal solution, stirring at 500rpm/min, and replacing the clear solution with appropriate amount of deionized water after the dark brown ruthenium trichloride solution is converted into lamellar formWashing to remove the remaining cellulose molecules to obtain a purified ultrathin layer material. After the ultrathin sheet material is dried, 3mL of ethanol is added for ultrasonic treatment for 30 minutes, then 100mg of carbon black (carbon XC-72R) is weighed and added into the dispersion system, ultrasonic treatment is continued for 30 minutes, then drying is carried out at 80 ℃ for 12 hours, cooling is carried out, the obtained product is transferred into a tubular furnace for heat treatment at 700 ℃ for 1 hour under nitrogen atmosphere, cooling is carried out, and collection is carried out, thus obtaining the hydrogen evolution catalytic material Ru-NS/C-3, the X-ray diffraction diagram of which is shown in figure 3, and the hydrogen evolution catalytic material Ru-NS/C-3 is obtained after the reaction is carried out in an acidic electrolyte solution (0.5M H) 2 SO 4 ) The hydrogen evolution linear sweep voltammogram of the medium test linear sweep voltammogram is shown in figure 4, which shows that Ru-NS/C-3 shows better hydrogen evolution catalytic activity.
Example 4:
30mg of methyl cellulose is dissolved in 3mL of deionized water, after a transparent colloidal solution is formed, 1mL of ruthenium trichloride aqueous solution with the concentration of 0.02g/mL is dropwise added under stirring, the stirring speed is 500rpm/min, after the dark brown ruthenium trichloride solution is converted into a lamellar sheet form, a proper amount of deionized water is used for displacement cleaning to remove residual cellulose molecules, and a purified ultrathin sheet material is obtained. After the ultrathin sheet material is dried, 3mL of ethanol is added for ultrasonic treatment for 30 minutes, then 100mg of carbon black (carbon XC-72R) is weighed and added into the dispersion system, ultrasonic treatment is continued for 30 minutes, then drying is carried out at 80 ℃ for 12 hours, cooling is carried out, then the mixture is transferred into a tubular furnace for heat treatment at 500 ℃ for 1 hour under a hydrogen-argon mixed atmosphere (volume fraction 5 percent), cooling is carried out, and collection is carried out, thus obtaining the hydrogen evolution catalytic material Ru-NS/C-4, the X-ray diffraction diagram of which is shown in figure 3, and the catalyst material Ru-NS/C-4 is obtained after heat treatment in an acidic electrolyte solution (0.5M H) 2 SO 4 ) The hydrogen evolution linear sweep voltammogram of the medium test linear sweep voltammogram is shown as figure 4, which shows that Ru-NS/C-4 shows better hydrogen evolution catalytic activity.
Example 5:
dissolving 30mg of carboxymethyl cellulose in 3mL of deionized water, dropwise adding 1mL of ruthenium acetate aqueous solution with the concentration of 0.02g/mL under stirring after forming a transparent colloidal solution, stirring at the stirring speed of 100rpm/min, and carrying out displacement cleaning with a proper amount of deionized water after the ruthenium acetate solution is converted into a lamellar sheet form so as to removeThe remaining cellulose molecules, a purified ultrathin layer material is obtained. After the ultrathin sheet material is dried, 3mL of ethanol is added for ultrasonic treatment for 10 minutes, then 100mg of carbon black (carbon XC-72R) is weighed and added into the dispersion system, ultrasonic treatment is continued for 10 minutes, then drying is carried out for 12 hours at 80 ℃, cooling is carried out, the obtained product is transferred into a tubular furnace for heat treatment for 0.5 hour at 200 ℃ under nitrogen atmosphere, cooling is carried out, and collection is carried out, thus obtaining the hydrogen evolution catalytic material Ru-NS/C-5, the X-ray diffraction diagram of which is shown in figure 3, and the catalyst material Ru-NS/C-5 is obtained after heat treatment in an acidic electrolyte solution (0.5M H) 2 SO 4 ) The hydrogen evolution linear sweep voltammogram of the medium test linear sweep voltammogram is shown in figure 4, which shows that Ru-NS/C-5 shows better hydrogen evolution catalytic activity.
Example 6:
dissolving 30mg of hydroxypropyl cellulose in 3mL of deionized water, dropwise adding 1mL of hydrated potassium pentachlororuthenate aqueous solution with the concentration of 0.02g/mL under stirring after a transparent colloidal solution is formed, stirring at the speed of 300rpm/min, and after the hydrated potassium pentachlororuthenate solution is converted into a lamellar sheet form, carrying out displacement cleaning with a proper amount of deionized water to remove residual cellulose molecules, thereby obtaining the purified ultrathin sheet material. After the ultrathin sheet material is dried, 3mL of ethanol is added for ultrasonic treatment for 10 minutes, then 100mg of carbon black (carbon XC-72R) is weighed and added into the dispersion system, ultrasonic treatment is continued for 20 minutes, then drying is carried out for 12 hours at 80 ℃, cooling is carried out, the obtained product is transferred into a tubular furnace for heat treatment for 1.5 hours at 400 ℃ under nitrogen atmosphere, cooling is carried out, and collection is carried out, thus obtaining the hydrogen evolution catalytic material Ru-NS/C-6, the X-ray diffraction diagram of which is shown in figure 3, and the catalyst material Ru-NS/C-6 is obtained after heat treatment in an acidic electrolyte solution (0.5M H) 2 SO 4 ) The hydrogen evolution linear sweep voltammogram of the medium test linear sweep voltammogram is shown in figure 4, which shows that Ru-NS/C-6 shows better hydrogen evolution catalytic activity.
Example 7:
dissolving 30mg of hydroxyethyl cellulose in 3mL of deionized water, dropwise adding 1mL of ammonium hexachlororuthenate aqueous solution with the concentration of 0.02g/mL under stirring after a transparent colloidal solution is formed, stirring at the speed of 600rpm/min, and carrying out displacement cleaning with a proper amount of deionized water after the ammonium hexachlororuthenate solution is converted into a lamellar form to remove the restTo obtain a purified ultrathin layer material. After the ultrathin sheet material is dried, adding 3mL of ethanol for ultrasonic treatment for 10 minutes, then weighing 100mg of carbon black (carbon XC-72R) and adding the carbon black into the dispersion system, continuing ultrasonic treatment for 40 minutes, then drying at 80 ℃ for 12 hours, cooling, transferring the cooled material into a tubular furnace, carrying out heat treatment at 500 ℃ for 2 hours in a nitrogen atmosphere, cooling and collecting the cooled material to obtain a hydrogen evolution catalytic material Ru-NS/C-7, wherein an X-ray diffraction pattern of the hydrogen evolution catalytic material Ru-NS/C-7 is shown as shown in figure 3, and the hydrogen evolution catalytic material Ru-NS/C-7 is prepared by using an acidic electrolyte solution (0.5M H 2 SO 4 ) The hydrogen evolution linear sweep voltammogram of the medium test linear sweep voltammogram is shown in figure 4, which shows that Ru-NS/C-7 shows better hydrogen evolution catalytic activity.
Comparative example 1:
30mg of cellulose acetate is taken and dissolved in 3mL of deionized water, after a transparent solution is formed, 1mL of ruthenium trichloride aqueous solution with the concentration of 0.02g/mL is dropwise added under the stirring state, the stirring speed is 500rpm/min, and the ruthenium trichloride solution is found not to perform self-assembly reaction with the cellulose acetate, namely cannot be converted into a lamellar sheet form.
By comparing comparative example 1 with examples 1 to 7, it was found that comparative example 1 using cellulose acetate (cellulose modified with only carboxyl groups) could not be formed into a sheet form, whereas examples 1 to 7 using cellulose modified with alkyl groups could be formed into a sheet form, and it was found that modification of alkyl groups in cellulose has a large effect on the formation of a sheet form of a material, and that the specific surface area of the material was increased due to the formation of the sheet form, and finally, examples 1 to 7 all exhibited a good hydrogen evolution catalytic activity, wherein example 1 was the most active; in contrast, comparative example 1 did not exhibit hydrogen evolution catalytic activity because it could not be converted into a lamellar morphology.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and substitutions can be made by those skilled in the art without departing from the technical principles of the present invention, and these modifications and substitutions should also be considered as being within the scope of the present invention.

Claims (7)

1. The use of an ultrathin slice material for preparing a hydrogen evolution reaction catalyst is characterized in that the ultrathin slice material is subjected to ultrasonic recombination and pyrolysis with a carbon carrier in absolute ethyl alcohol and then is applied to catalysis of an electrolytic water hydrogen evolution reaction under an acidic medium, and the preparation method of the ultrathin slice material comprises the following steps: firstly, stirring and dissolving cellulose modified with alkyl functional groups in deionized water at normal temperature to form colorless transparent viscous cellulose colloidal solution with the concentration of 5-100 mg/ml, then preparing metal ruthenium salt into solution with the concentration of 0.01-2 mmol/L, dripping the metal ruthenium salt solution into the colorless transparent viscous cellulose colloidal solution while stirring at the speed of 100-800 rpm/min, and then carrying out displacement cleaning with deionized water to remove residual cellulose molecules, thus obtaining the purified ultrathin slice layer material.
2. The use according to claim 1, wherein the cellulose modified with alkyl functional groups is at least one of methyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and hydroxyethyl cellulose; the metal ruthenium salt is at least one of ruthenium trichloride, ruthenium acetate, potassium pentachlororuthenate hydrate, ammonium hexachlororuthenate and ruthenium hexaammine chloride.
3. Use according to claim 1, characterized in that the concentration of the colorless transparent viscous cellulose gum-like solution is 10mg/mL and the concentration of the metallic ruthenium salt solution is 0.1mmol/L.
4. Use according to claim 1, characterized in that the stirring rate of the metallic ruthenium salt solution when it is added dropwise to the colorless transparent viscous cellulose gum solution is 500rpm/min.
5. Use according to claim 1, characterized in that the thickness of the ultrathin layer material is 1-3 nm.
6. Use according to claim 1, characterized in that the ultra-thin layer material and the carbon carrier are subjected to ultrasonic compounding in absolute ethyl alcohol for 10-60 minutes, the mass ratio of the metal ruthenium in the ultra-thin layer material to the carbon carrier is 1:10-1:40, then the ultra-thin layer material and the carbon carrier are subjected to drying and heat treatment, the heat treatment atmosphere is nitrogen or hydrogen-argon mixture with the volume fraction of 5-20%, the heat treatment temperature is 200, 300, 400, 500, 600 or 700 ℃, and the heat treatment time is 0.5-2 hours.
7. The use according to claim 6, wherein the ultrasonic time is 30 minutes, and the mass ratio of the metal ruthenium to the carbon carrier ultrasonic composite in the ultrathin sheet material is 1:10; the carbon carrier is at least one of carbon black, acetylene black, active carbon, graphene and carbon nano tube; the heat treatment atmosphere is nitrogen, the heat treatment temperature is 300 ℃, and the heat treatment time is 1 hour.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109301270A (en) * 2018-11-06 2019-02-01 陕西瑞科新材料股份有限公司 A kind of preparation method of high-performance ruthenium catalyst
CN110211813A (en) * 2019-06-25 2019-09-06 中原工学院 Rodlike nickel hydroxide electrode material, preparation method and its supercapacitor of preparation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109301270A (en) * 2018-11-06 2019-02-01 陕西瑞科新材料股份有限公司 A kind of preparation method of high-performance ruthenium catalyst
CN110211813A (en) * 2019-06-25 2019-09-06 中原工学院 Rodlike nickel hydroxide electrode material, preparation method and its supercapacitor of preparation

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