CN113293406A - 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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CN113293406A
CN113293406A CN202110621829.3A CN202110621829A CN113293406A CN 113293406 A CN113293406 A CN 113293406A CN 202110621829 A CN202110621829 A CN 202110621829A CN 113293406 A CN113293406 A CN 113293406A
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carbon material
carbon
salt
nano
metal
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CN113293406B (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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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9016Oxides, hydroxides or oxygenated metallic salts
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9041Metals or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9075Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel 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 electro-catalyst, 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 techniques2) 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 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 immersion 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 object of the present invention is to provide a nano-electrocatalyst and a synthesis method, a test electrode and a preparation method, which are intended 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 temperature reduction process, the size of metal or metal oxide in the nano electro-catalyst is favorably reduced, and the utilization rate of the active site 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 for 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 present 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, mastering and developing the technology to prepare the nano electro-catalyst 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, including: 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" herein 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 CO2The 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 shaped 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: connecting the carbon material to a second DC power source, and performing 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 0.1-10 s. 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 0.1-10 s.
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 0.10 mol/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 molded carbon material, the method of subjecting the dried molded 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 0.1-10 s.
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-10 mg/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 solution 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 for preparing an Ag/XC 72 powder nano electrocatalyst, 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;
step 2: 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 step 3: preparing 4mL of 0.05mol/L silver nitrate aqueous solution, weighing 20mg of activated carbon powder, placing the powder in the silver nitrate aqueous solution, carrying out ultrasonic treatment for 1h, then placing the solution in a vacuum environment for 1h, and carrying out freeze drying to obtain precursor powder;
and 4, step 4: the AvCarb MGL190 type carbon paper is cut into 15 x 55mm, the copper foil is cut into 40 x 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 carbon paper respectively, so that the exposed size of the carbon paper between the two copper foils is 15 x 35 mm. The copper foil was sandwiched by two ceramic plates each, and fixed by a binder clip to obtain a heating stage, 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.
From FIG. 2a, it can be seen that metallic silver exists in a simple substance state, and from FIG. 2b, it can be seen that the particle size of the electrocatalyst powder of the present embodiment 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 slurry is dripped on a 10 x 10mm area of a 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 KHCO3The water solution is taken as electrolyte, the Nafion 117 cation exchange membrane is taken as a diaphragm, and CO is introduced2And setting the mass flow of the gas to be 20sccm, and assembling the gas into the carbon dioxide electrocatalytic H-shaped electrolytic cell.
Introducing CO into the assembled carbon dioxide electro-catalysis device2The gas was saturated for 30min and 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/cm2The 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 RuCl3And NiCl2The solution (wherein the molar ratio of Ru to Ni is 1: 1), the thermal shock condition is 30V, 30A and 1s, 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, which shows that RuNi nano alloy particles are loaded on activated carbon spheres, and the size of the alloy particles is about 5 nm.
Mixing a nano RuNi/XC 72 alloy powder nano electro-catalyst, a Nafion 117 solution with the concentration of 5% 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 rotating disc electrode, and assembling the 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 H2The 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 NiFeCoOxThe 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 dimension of the carbon paper between the two copper foils was 10 × 20 mm. 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 operating to obtain the NiCoFeOx @ ACF catalyst.
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 seenxThe particles are distributed in the nano holes of the activated carbon felt, and the particle size is 50-150 nm.
Self-supporting nano NiFeCoOxThe @ 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 a graph of OER test performance showing that the prepared self-supporting nanotubes are preparedRice NiFeCoOxThe @ ACF electrocatalyst has a low initial overpotential, which can reach 10mA/cm at 1.5V vs2Noble metal RuO with overpotential lower than that of common carbon felt2A 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 (10)

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;
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.
2. The method of claim 1, wherein prior to soaking the carbon material in the metal salt solution, the method further comprises: activating the carbon material;
preferably, the carbon material is a carbon powder material or a molded carbon material;
preferably, when the carbon material is a carbon powder material, the method of the activation treatment is: putting the carbon material into concentrated nitric acid, and heating and refluxing;
preferably, when the carbon material is a molded carbon material, the method of the activation treatment is: connecting the carbon material to a second direct current power supply to perform second thermal shock;
preferably, 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;
preferably, the time of the second thermal shock is 0.1 to 10 s.
3. The method of claim 1, wherein the soaking time is greater than or equal to 1 hour;
preferably, the time of the first thermal shock is 0.1 to 10 s;
preferably, the metal salt solution is a metal chloride solution or a metal nitrate solution;
preferably, 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;
preferably, the concentration of the metal salt solution is 0.001-0.10 mol/L;
preferably, the drying mode is freeze drying;
preferably, after the carbon material is soaked in the metal salt solution, the method further comprises performing ultrasonic treatment on the metal salt solution soaked with the carbon material;
preferably, after the metal salt solution soaked with the carbon material is subjected to ultrasound and before the carbon material adsorbed with the metal salt is dried, the method further comprises placing the metal salt solution soaked with the carbon material in a vacuum oven;
preferably, the carbon powder material is graphene, graphite, carbon quantum dots, activated carbon, carbon nanofibers or carbon nanotubes;
preferably, the molded carbon material is a carbon felt, a carbon cloth or a carbon paper;
preferably, when the carbon material is a shaped carbon material, the shaped carbon material is trimmed.
4. The method according to claim 2, wherein, when the carbon material is a carbon powder material, the method of performing the first thermal shock on the dried carbon powder material comprises:
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 the heating platform for heating to obtain the powder nano electro-catalyst.
5. The method of claim 2, wherein, 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.
6. The method according to claim 4 or 5, wherein the voltage of the first direct current power supply is 0-30V and the current produced by the first direct current power supply is 0-40A.
7. A nanoelectrocatalyst prepared using the method of any one of claims 1 to 6, 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.
8. A method of making a test electrode comprising:
preparing a nanoelectrocatalyst using the method of any one of claims 1-6;
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 shaped carbon material, the nanoelectrocatalyst is used directly as the test electrode.
9. The method of making a test electrode of claim 8, wherein the binder is perfluorosulfonic acid 117;
preferably, the concentration of the binder ranges from 5% to 10%;
preferably, the solvent is isopropanol or ethanol;
preferably, the mass ratio of the binder to the nano electrocatalyst in the slurry is in the range of 1: 1 to 1: 5;
preferably, the mass concentration of the nano electro-catalyst in the slurry is 2mg/mL-10 mg/mL;
preferably, 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.
10. A test electrode prepared by the preparation method according to claim 8 or 9.
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