CN113293406B - Nano electro-catalyst, synthesis method, test electrode and preparation method - Google Patents

Nano electro-catalyst, synthesis method, test electrode and preparation method Download PDF

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CN113293406B
CN113293406B CN202110621829.3A CN202110621829A CN113293406B CN 113293406 B CN113293406 B CN 113293406B CN 202110621829 A CN202110621829 A CN 202110621829A CN 113293406 B CN113293406 B CN 113293406B
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carbon material
salt
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metal
carbon
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CN113293406A (en
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陈维
刘双
蒋涛立
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University of Science and Technology of China USTC
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • 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
    • Y02E60/50—Fuel cells

Abstract

A nanometer electric catalyst and a synthesis method, a test electrode and a preparation method thereof are provided, the method for synthesizing the nanometer electric catalyst comprises the following steps: activating a carbon material, namely soaking the activated carbon material in a metal salt solution to enable the metal salt to be adsorbed on the carbon material; drying the carbon material having the metal salt adsorbed thereon; and carrying out thermal shock on the dried carbon material to form nano metal or nano metal oxide loaded on the carbon material, namely forming the nano electrocatalyst.

Description

Nano electro-catalyst, synthesis method, test electrode and preparation method
Technical Field
The invention relates to the technical field of electrochemical energy, in particular to a nano electrocatalyst, a synthesis method, a test electrode and a preparation method.
Background
The acceleration of the human industrialization process not only leads to energy crisis, but also causes a series of environmental and climate problems. Exhaust gas (e.g. CO) using electrocatalytic techniques 2 ) The method has wide application prospect under the urgent requirement of realizing 'carbon neutralization' society, such as recycling and converting, realizing the preparation and utilization of clean energy (such as H2), using of green pollution-free fuel cells and the like.
The electric catalyst is the key of the large-scale application of the electric catalysis technology. However, there are still a series of problems in the industrial process: for example, the conventional electrocatalyst is unstable and easy to deactivate, and has higher reaction overpotential and the like. Therefore, the development of efficient, stable, low cost electrocatalysts is the key to solving these problems.
At present, methods for improving the performance of electrocatalysts mainly include the improvement of specific surface area by preparing a nano structure or the adjustment of the adsorption strength of a reaction intermediate on a catalytic site by alloying and the like. The preparation method generally comprises a hydrothermal method, an electrolytic method, an impregnation method, a coprecipitation method, an ion exchange method, an electrochemical reduction/deposition method and the like. However, most of the synthesis methods are complex in regulation and control, complex in process and difficult to realize scale production. For example, the roasting process of the precursor by the liquid-phase chemical reduction method is not only long in time consumption, but also consumes a large amount of electric energy, brings a series of problems of sewage treatment and the like, and cannot show advantages in the aspects of energy efficiency and overall benefits. In order to promote the recycling of electro-catalytic exhaust gas and the energy storage and conversion technology to industrialization, a new catalyst preparation method is urgently needed to be developed.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a nano electrocatalyst and a synthesis method, a test electrode and a preparation method, so as to at least partially solve at least one of the above-mentioned technical problems.
In order to achieve the above object, as a first aspect of the present invention, there is provided a method of synthesizing a nanoelectrocatalyst, comprising: soaking a carbon material in a metal salt solution to adsorb metal salt on the carbon material; drying the carbon material having the metal salt adsorbed thereon; and carrying out first thermal shock on the dried carbon material to form nano metal or nano metal oxide loaded on the carbon material, namely forming the nano electrocatalyst.
As a second aspect of the present invention, there is also provided a nanoelectrocatalyst prepared by the above method, comprising: nano metal or nano metal oxide particles and a carbon material, wherein the nano metal or nano metal oxide particles are uniformly supported on the carbon material.
As a third aspect of the present invention, there is also provided a method of manufacturing a test electrode, comprising: preparing a nano electrocatalyst by using the method; when the carbon material is a carbon powder material, the prepared nano electro-catalyst, a binder and a solvent are mixed into slurry to be coated on the working electrode in a dripping mode, and the test electrode is formed after the slurry is dried; or when the carbon material is a molded carbon material, the nanoelectrocatalyst may be used directly as the test electrode.
As a fourth aspect of the present invention, there is also provided a test electrode prepared by the above-described preparation method.
According to the technical scheme, the nano electro-catalyst, the synthesis method, the test electrode and the preparation method have one or part of the following beneficial effects:
(1) The nano electro-catalyst adopts a thermal shock method, the method has a highly controllable temperature rise and drop process, the size of metal or metal oxide in the nano electro-catalyst is favorably reduced, and the utilization rate of the active sites of the nano electro-catalyst can be improved by the smaller size of the metal or metal oxide; the multi-component catalyst prepared by the method is in a solid solution phase, and all components are extremely uniformly distributed, so that the method can be used for designing a low-cost and high-efficiency catalytic material; all energy of the thermal impact method almost acts on the catalytic material, and compared with other thermal synthesis methods, the method greatly saves electric energy loss; the method has the advantages of short synthesis period within several seconds, shortened catalyst preparation period, convenient supply and demand balance, and reduced waste.
(2) The nano electro-catalyst can synthesize different types of electro-catalysts by regulating and controlling the composition of raw materials, can be applied to various catalysis types, and has good universality.
(3) The nano electro-catalyst has low requirements on devices and is easy to scale.
Drawings
FIG. 1 is a schematic view of the heating platform for the synthesis of nanoelectrocatalysts in examples 1-3 of the present invention;
FIG. 2a is an X-ray diffraction pattern of Ag/XC 72 catalyst powder prepared in example 1 of the present invention;
FIG. 2b is a scanning electron micrograph of Ag/XC 72 catalyst powder prepared in example 1 of the present invention;
FIG. 3a is a graph of the selectivity of the Ag/XC 72 catalyst prepared in example 1 of the present invention to carbon dioxide electrocatalysis at different potentials;
FIG. 3b is a graph of the current density of carbon dioxide electrocatalysis of the Ag/XC 72 catalyst prepared in example 1 of the present invention;
FIG. 4 is a transmission electron micrograph of RuNi/XC 72 catalyst prepared in example 2 of the present invention;
FIG. 5 is a graph of the performance of RuNi/XC 72 catalyst powder material prepared in example 2 of the invention in a hydrogen oxidation and reduction (HER/HOR) catalytic reaction;
FIG. 6 is a scanning electron micrograph of an activated carbon felt prepared according to example 3 of the present invention;
FIG. 7 is a scanning electron micrograph of a NiFeCoOx @ ACF electrode prepared in example 3 of the present invention;
FIG. 8 is a graph of the performance of a NiFeCoOx @ ACF electrode prepared in example 3 of the present invention as an OER reaction catalyst.
Detailed Description
In the process of implementing the invention, the rapid high-temperature thermal impact method has the characteristics of simple and easily obtained raw materials and equipment, simple and convenient operation, energy conservation, environmental protection, short period, low energy consumption and high efficiency, and provides a potential technical choice for the design and synthesis of various high-quality nano materials. Therefore, the method for preparing the nano electro-catalyst by mastering and developing the technology has extremely high research value and application prospect.
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
According to an embodiment of the present invention, there is provided a method of synthesizing a nanoelectrocatalyst, comprising: soaking a carbon material in a metal salt solution to make the metal salt adsorbed on the carbon material; drying the carbon material adsorbing the metal salt; and carrying out first thermal shock on the dried carbon material to form nano metal or nano metal oxide loaded on the carbon material, namely forming the nano electrocatalyst. The "metal salt" here may be a single metal salt or a mixture of a plurality of metal salts, and accordingly, the formed "nano metal" or "nano metal oxide" may be a single nano metal, or a single nano metal oxide, or a nano alloy oxide.
The method for synthesizing the nano electrocatalyst is a high-efficiency, stable and controllable rapid synthesis method of the electrocatalyst. The synthesis process is simple and convenient, energy-saving and environment-friendly, and has low cost. Applying it to CO 2 The preparation of electrocatalysts such as electrocatalysts, CO electrocatalysts, water electrolysis, methane electrooxidation and the like can obtain higher overall benefits.
According to an embodiment of the present invention, the method of synthesizing a nanoelectrocatalyst prior to immersing the carbon material in the metal salt solution further comprises: and (3) activating the carbon material.
According to an embodiment of the invention, the carbon material is a carbon powder material or a shaped carbon material. Optionally, the carbon powder material is graphene, graphite, carbon quantum dots, activated carbon, carbon nanofibers, or carbon nanotubes. Optionally, the formed carbon material is a carbon felt, a carbon cloth, or a carbon paper.
According to an embodiment of the present invention, when the carbon material is a carbon powder material, the method of the activation treatment is: placing the carbon material in concentrated nitric acid, and heating and refluxing.
According to an embodiment of the present invention, when the carbon material is a shaped carbon material, the method of the activation treatment is: the carbon material is connected to a second dc power source and subjected to a second thermal shock.
Optionally, the voltage of the second dc power supply is 0-30V, the current of the second dc power supply is 0-40A, and the time of the second thermal shock is 0.1-10s. According to an embodiment of the present invention, the soaking time is 1 hour or more.
According to an embodiment of the invention, the time of the second thermal shock is 0.1-10s.
According to an embodiment of the invention, the metal salt solution is a metal chloride solution or a metal nitrate solution.
According to an embodiment of the present invention, the metal salt is selected from one or more of silver salt, ruthenium salt, gold salt, platinum salt, iridium salt, rhodium salt, palladium salt, tin salt, nickel salt, iron salt, cobalt salt, molybdenum salt, tungsten salt, copper salt, zinc salt, chromium salt.
According to an embodiment of the present invention, the metal salt solution has a concentration of 0.001 to 0.10mol/L.
According to the embodiment of the invention, after the carbon material is soaked in the metal salt solution, the method for synthesizing the nano catalyst further comprises the step of carrying out ultrasonic treatment on the metal salt solution soaked with the carbon material, so that the metal salt solution can be fully soaked in the carbon material.
According to an embodiment of the present invention, the method of synthesizing a nano electrocatalyst after the ultrasonic treatment of the metal salt solution impregnated with the carbon material further includes placing the metal salt solution impregnated with the carbon material in a vacuum oven.
According to the embodiment of the invention, the metal salt solution soaked with the carbon material is placed in the vacuum oven for 1 hour, so that the metal salt can be adsorbed on the carbon material fully. According to the embodiment of the invention, the drying mode is freeze drying, so that the metal or metal oxide in the prepared nano electrocatalyst can be more uniformly loaded on the carbon material.
According to an embodiment of the invention, the time of freeze-drying is 24 to 48 hours. According to the embodiment of the invention, when the carbon material is the formed carbon material, the formed carbon material is cut, so that the formed carbon material is heated more uniformly and the heating temperature is controllable.
According to an embodiment of the present invention, when the carbon material is a carbon powder material, a method of performing a first thermal shock on the dried carbon powder material includes: connecting a heating platform to a first direct current power supply, wherein the heating platform is a molded carbon material; and placing the dried carbon powder material on a heating platform for heating to obtain the powder nano electro-catalyst.
According to an embodiment of the present invention, when the carbon material is a shaped carbon material, the method of subjecting the dried shaped carbon material to a first thermal shock comprises: and connecting the dried molded carbon material to a first direct current power supply, and heating to obtain the self-supporting nano electrocatalyst.
Optionally, the voltage of the first dc power supply is 0-30V, the current generated by the first dc power supply is 0-40A, and the time of the first thermal shock is 0.1-10s.
According to an embodiment of the present invention, there is provided a nano electrocatalyst prepared using the method as described above, comprising: nano metal, nano alloy or nano metal oxide particles and a carbon material, wherein the nano metal or nano metal oxide particles are uniformly supported on the carbon material.
According to an embodiment of the present invention, there is provided a method of manufacturing a test electrode, including: preparing a nano electrocatalyst by using the method; when the carbon material is a carbon powder material, the prepared nano electro-catalyst, a binder and a solvent are mixed into slurry to be coated on the working electrode in a dripping mode, and the slurry is dried to form a test electrode; or when the carbon material is a molded carbon material, the nano-electrocatalyst is directly used as a test electrode.
According to an embodiment of the invention, the binder is perfluorosulfonic acid 117.
According to an embodiment of the invention, the concentration of the binder ranges from 5% to 10%.
According to an embodiment of the invention, the solvent is isopropanol or ethanol.
According to the embodiment of the invention, the mass ratio of the binder to the nano electrocatalyst in the slurry is in the range of 1: 1 to 1: 5.
According to the embodiment of the invention, the mass concentration of the nano electrocatalyst in the slurry is 2mg/mL-10mg/mL.
According to an embodiment of the present invention, the working electrode is a glassy carbon electrode, a carbon cloth, a nickel foam, a copper foam, an iron foam, a carbon paper, or a gas diffusion layer.
There is also provided, in accordance with an embodiment of the present invention, a test electrode prepared using the preparation method as described above.
The technical means of the present invention will be described in detail below with reference to specific examples. It should be noted that the following specific examples are only for illustration and are not intended to limit the invention.
Example 1
A method of making a Ag/XC 72 powder nanoelectrocatalyst, comprising the steps of:
step 1: 1g of Vulcan XC 72 conductive carbon black is put into 100mL of concentrated nitric acid and heated and refluxed for 5 hours at 80 ℃ in an oil bath pan;
and 2, step: after cooling, centrifuging the liquid at 9000rpm for 5min to separate conductive carbon black powder, repeatedly washing the carbon black powder with ultrapure water having a resistivity of 18.2M Ω to pH =7, and freeze-drying to obtain dried activated carbon powder;
and 3, step 3: preparing 4mL of 0.05mol/L silver nitrate aqueous solution, weighing 20mg of active carbon powder, placing the active carbon powder in the silver nitrate aqueous solution, carrying out ultrasonic treatment for 1h, then placing the active carbon powder in a vacuum environment, and carrying out freeze drying to obtain precursor powder;
and 4, step 4: the AvCarb MGL190 type carbon paper is cut into 15 × 55mm, the copper foil is cut into 40 × 60mm two pieces, the short sides of the two copper foils are folded in half respectively, and the two ends of the carbon paper are wrapped by the two pieces of the carbon paper respectively, so that the exposed size of the carbon paper between the two copper foils is 15 × 35mm. The copper foils were sandwiched by two ceramic plates and fixed with a binder clip to obtain a heating platform, as shown in FIG. 1.
And 5: and respectively connecting the outer ends of the two copper foils of the heating platform with two ends of a direct current power supply, then placing the heating platform into a quartz tube filled with Ar, spreading 5mg of precursor powder on the surface of the bare carbon paper, setting the voltage of the direct current power supply to be 30V and the current to be 30A, lasting for 0.5s, and collecting the powder after operation to obtain the Ag/XC 72 catalyst.
It can be seen from FIG. 2a that metallic silver exists in a simple substance state, and from FIG. 2b that the particle diameter of the electrocatalyst powder according to this example is between 30 and 80 nm.
Mixing an Ag/XC 72 catalyst, a Nafion 117 solution with the concentration of 5 percent and isopropanol according to the proportion of 10mg to 40 mu L to 1mL, and performing ultrasonic treatment for 30min to obtain uniform slurry; 0.5mL of the slurry is dripped on a 10 x 10mm area of the glassy carbon electrode and is placed in a vacuum oven for vacuum drying; clamping the dried electrode with platinum sheet electrode clamp, using graphite rod electrode as counter electrode, silver/silver chloride electrode as reference electrode, 0.5mol/L KHCO 3 The water solution is taken as electrolyte, the Nafion 117 cation exchange membrane is taken as a diaphragm, and CO is introduced 2 And (4) setting the mass flow of the gas to be 20sccm, and assembling the carbon dioxide electrocatalytic H-shaped electrolytic cell.
Introducing CO into the assembled carbon dioxide electro-catalytic device 2 The gas was saturated for 30min and then tested, and the composition of the product was analyzed by gas chromatography.
As can be seen from FIG. 3a, the Faraday efficiencies of CO are both above 50%, and under the conditions of-1V vs RHE and-1.15V vs RHE, the Faraday efficiencies of CO are above 70%. From FIG. 3b it can be seen that the current density of CO can reach 10mA/cm 2 As described above.
Example 2:
a RuNi/XC 72 alloy type powder nano electro-catalyst preparation method is the same as example 1, and is different in that the metal salt solution is 0.05mol/L RuCl 3 And NiCl 2 The solution (in which the molar ratio of Ru to Ni is 1: 1), the thermal shock condition is 30V,30A and 1s, and the catalyst is an alloy phase and is used for HOR/HER catalytic process.
Fig. 4 is a transmission electron microscope image of the RuNi/XC 72 alloy type powder nano electro-catalyst prepared in this example, and it can be seen that RuNi nano alloy particles are supported on activated carbon spheres, and the size of the alloy particles is about 5 nm.
Mixing a nano RuNi/XC 72 alloy type powder nano electro-catalyst, a Nafion 117 solution with the concentration of 5 percent and ethanol according to the proportion of 5mg to 20 mu L to 1mL, and performing ultrasonic treatment for 30min to obtain uniform slurry; dripping 5uL of slurry on a glassy carbon electrode with the diameter of 5mm, and airing in the air; and fixing the dried electrode on a rotary disk electrode, and assembling a three-electrode testing device by taking a graphite rod electrode as a counter electrode, a mercury/mercury oxide electrode as a reference electrode and 0.1mol/L KOH aqueous solution as electrolyte.
Introducing Ar gas into the device for HER test, and introducing H 2 The HOR test was performed.
FIG. 5 is a graph of HER/HOR test performance, which shows that the performance of the nano RuNi/XC 72 alloy type powder nano electrocatalyst is superior to that of a commercial Pt/C catalyst.
Example 3:
self-supporting nano NiFeCoO x The preparation method of the @ ACF electrocatalyst is detailed as follows:
step 1: the carbon felt was cut to a size of 10 × 40 × 2mm, and both ends were wrapped with copper foils, respectively, so that the exposed size of the carbon paper between the two copper foils was 10 × 20mm. The copper foil is clamped by two ceramic plates and fixed by a binder clip to obtain the heating platform.
Step 2: and placing the heating platform in an air atmosphere, respectively connecting the outer ends of the two copper foils with the two ends of a direct current power supply, setting the voltage of the direct current power supply to be 30V, setting the current to be 25A, setting the duration to be 2s, and operating to obtain the activated carbon felt.
And step 3: preparing 10mL (the molar ratio is 1: 1) of 0.05mol/L mixed aqueous solution of ferric nitrate, cobalt nitrate and nickel nitrate, soaking an activated carbon felt in the solution, placing the activated carbon felt in a vacuum environment for 1h, and then freeze-drying to obtain a precursor.
And 4, step 4: fixing the precursor on a heating platform according to the step 1), setting the voltage of a direct current power supply to be 30V, the current to be 30A and the duration to be 0.2s, and obtaining the NiCoFeOx @ ACF catalyst after operation.
From fig. 6, it can be seen that the activated carbon felt has dense nano-pores on the surface, which can provide sites for supporting metal oxides. From FIG. 7, niCoFeO can be seen x The particles are distributed in the nanometer holes of the activated carbon felt, and the particle size is 50-150 nm.
The self-supporting nano NiFeCoO x The @ ACF electrocatalyst is used as a working electrode, a graphite rod electrode is used as a counter electrode, a mercury/mercury oxide electrode is used as a reference electrode, 1mol/L KOH aqueous solution is used as electrolyte, and after Ar is introduced to reach saturation, an OER test is carried out. FIG. 8 is the OER test performance chart, and it can be seen that the prepared self-supporting nano NiFeCoO x The @ ACF electrocatalyst has lower initial overpotential, and can reach 10mA/cm under 1.5V vs 2 Noble metal RuO with overpotential lower than that of common carbon felt 2 A catalyst.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (15)

1. A method of synthesizing a nanoelectrocatalyst, comprising:
soaking a carbon material in a metal salt solution to adsorb metal salt on the carbon material;
drying the carbon material having the metal salt adsorbed thereon;
carrying out first thermal shock on the dried carbon material to form nano metal or nano metal oxide loaded on the carbon material, namely forming a nano electrocatalyst;
wherein the metal salt is selected from one or more of silver salt, ruthenium salt, gold salt, platinum salt, iridium salt, rhodium salt, palladium salt, tin salt, nickel salt, iron salt, cobalt salt, molybdenum salt, tungsten salt, copper salt, zinc salt and chromium salt;
wherein prior to soaking the carbon material in the metal salt solution, the method further comprises: activating the carbon material, wherein the carbon material is a molded carbon material, and the method for activating the carbon material comprises the following steps: connecting the carbon material to a second direct current power source to perform a second thermal shock.
2. The method of claim 1, wherein,
the voltage of the second direct current power supply is 0-30V, and the current of the second direct current power supply is 0-40A;
the time of the second thermal shock is 0.1-10s.
3. The method of claim 1, wherein the carbon material is soaked for a time of greater than or equal to 1 hour.
4. The method of claim 1, wherein,
the time of the first thermal shock is 0.1-10s.
5. The method of claim 1, wherein,
the metal salt solution is a metal chloride solution or a metal nitrate solution.
6. The method of claim 1, wherein,
the concentration of the metal salt solution is 0.001-0.10mol/L.
7. The method of claim 1, wherein,
the drying mode is freeze drying.
8. The method of claim 1, wherein,
after the carbon material is soaked in the metal salt solution, the method further comprises the step of carrying out ultrasonic treatment on the metal salt solution soaked with the carbon material;
after the metal salt solution impregnated with the carbon material is subjected to ultrasound, and before the carbon material adsorbed with the metal salt is dried, the method further includes placing the metal salt solution impregnated with the carbon material in a vacuum oven.
9. The method of claim 1, wherein,
the molded carbon material is carbon felt, carbon cloth or carbon paper.
10. The method of claim 1, further comprising:
and cutting the formed carbon material.
11. The method of claim 1, wherein the first thermal shock to the dried shaped carbon material comprises:
and connecting the dried molded carbon material to a first direct current power supply, and heating to obtain the self-supporting nano electrocatalyst.
12. The method of claim 11, wherein the voltage of the first dc power source is 0-30V and the current produced by the first dc power source is 0-40A.
13. A nanoelectrocatalyst prepared by the method of any one of claims 1 to 12, comprising: nano metal or nano metal oxide particles and a carbon material, wherein the nano metal or nano metal oxide particles are uniformly supported on the carbon material.
14. A method of making a test electrode comprising:
preparing a nanoelectrocatalyst using the method of any one of claims 1-12;
the nanoelectrocatalyst was directly used as the test electrode.
15. A test electrode prepared by the preparation method of claim 14.
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