CN112038647B - Method for catalyzing ORR reaction based on COFs derived carbon nanotubes - Google Patents
Method for catalyzing ORR reaction based on COFs derived carbon nanotubes Download PDFInfo
- Publication number
- CN112038647B CN112038647B CN202010895107.2A CN202010895107A CN112038647B CN 112038647 B CN112038647 B CN 112038647B CN 202010895107 A CN202010895107 A CN 202010895107A CN 112038647 B CN112038647 B CN 112038647B
- Authority
- CN
- China
- Prior art keywords
- cofs
- derived
- solution
- reaction
- carbon nanotubes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- H01M4/9008—Organic or organo-metallic compounds
-
- 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
-
- 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
- Y02E60/50—Fuel cells
Abstract
The invention discloses a method for catalyzing ORR reaction based on COFs derived carbon nanotubes, belonging to the field of electrocatalytic oxygen reduction of a cathode part of a fuel cell. The application of the carbon nanotubes derived from covalent organic frameworks COFs in catalyzing the cathode oxygen reduction reaction comprises the following steps: the carbon nanotubes derived from Covalent Organic Frameworks (COFs) are used as a catalyst to be applied to cathode oxygen reduction reaction, wherein the adopted carbon nanotubes are derived from the COFs, and the regular and controllable metal/heteroatom doping or the diameter and the wall thickness of the carbon nanotubes are beneficial to the regulation and control of ORR activity, so that the catalyst has good application prospect, and the solvothermal preparation method is simple and safe.
Description
Technical Field
The invention relates to a method for catalyzing ORR reaction based on COFs derived carbon nanotubes, belonging to the field of electrocatalytic oxygen reduction of a cathode part of a fuel cell.
Background
The conventional fossil fuel has failed to satisfy the demand of economic development in the world due to its limited reserves and a series of environmental problems caused by its utilization. People urgently need to change the use mode and structure of energy and develop a new energy utilization technology with high efficiency, economy and environmental protection. The fuel cell is a chemical device which can directly convert chemical energy of fuel (such as hydrogen, methanol and the like) and oxidant (such as oxygen and the like) into electric energy through electrochemical reaction, is efficient and pollution-free, and has wide prospects. However, the electrochemically kinetically retarded cathode Oxygen Reduction Reaction (ORR) greatly reduces the efficiency of the fuel cell. Currently, the most common catalyst for catalytic oxygen reduction processes is a Pt-based noble metal catalyst, and most commercial fuel cells use a Pt/C catalyst. However, Pt has disadvantages of low reserves and high price, so it is a key to find a catalyst with low price and high ORR performance, and thus non-noble metal/metal-free doped atomic carbon materials have attracted much attention.
Disclosure of Invention
In order to solve at least one of the above problems, the present invention aims to provide a method for catalyzing ORR reaction based on COFs-derived carbon nanotubes, wherein the method for preparing covalent organic framework-derived carbon nanotubes comprises: selecting a metal nanowire as a template, carrying out solvothermal reaction in a vacuum environment to grow COFs on the surface of the metal nanowire in situ, calcining the obtained composite material at high temperature in an inert gas atmosphere, and etching metal by using a nitric acid solution to obtain a carbon nanotube; the method has simple and ingenious process, and the prepared carbon material is regular and controllable and has considerable ORR activity.
The first purpose of the present invention is to provide a method for catalyzing ORR reaction based on COFs derived carbon nanotubes, comprising the following steps: carbon nanotubes derived from Covalent Organic Frameworks (COFs) are used as a catalyst to be applied to a cathode oxygen reduction reaction; the preparation method of the COFs-derived carbon nanotube comprises the following steps:
(1) selecting metal nanowires as templates, and growing COFs on the surfaces of the metal nanowires in situ through solvothermal reaction in a vacuum environment to obtain a composite material;
(2) placing the composite material obtained in the step (1) in a reaction vessel, and heating to 800-1000 ℃; then cooling to obtain a carbonized material; wherein, the whole process is under the protection of inert gas;
(3) and (3) placing the carbonized material obtained in the step (2) into a container for acid washing, and then filtering, washing and drying to obtain the COFs-derived carbon nanotube.
Optionally, the preparation method of the carbon nanotubes derived from COFs comprises:
(1) selecting metal nanowires as templates, and growing COFs on the surfaces of the metal nanowires in situ through solvothermal reaction in a vacuum environment to obtain a composite material;
(2) placing the composite material obtained in the step (1) in a reaction vessel, heating to 800-; then cooling to room temperature to obtain a carbonized material; wherein, the whole carbonization process is under the protection of inert gas;
(3) placing the carbonized material obtained in the step (2) into a reaction container, adding the prepared acid solution, and uniformly stirring; then filtering and washing to obtain the carbon nanotubes derived from the COFs.
Optionally, the carbon nanotubes derived from Covalent Organic Frameworks (COFs) are used as a catalyst for a cathodic oxygen reduction reaction, and specifically: dissolving carbon nanotubes derived from Covalent Organic Frameworks (COFs) as a catalyst in a solvent to obtain a catalyst solution; then modifying a glassy carbon electrode by adopting a catalyst solution to serve as a working electrode; and finally, applying the working electrode to the oxygen precipitation reaction in the catalytic electrolysis water.
Optionally, the thickness of the COFs layer is in the range of 1-5 nm.
Optionally, the concentration of the catalyst solution is 0.001-0.01mg/μ L, and more preferably 0.0058mg/μ L.
Optionally, the dosage of the catalyst solution is 10 mu L/0.1-0.2cm2More preferably 10. mu.L/0.192 cm2(ii) a I.e. 10. mu.l of catalyst solution droplets at an area of 0.192cm2A glassy carbon electrode.
Optionally, the solvent is a mixed solution of isopropanol solution and Nafion solution; wherein the volume ratio of the isopropanol to the water in the isopropanol solution is 3-5: 1; the mass fraction of the Nafion solution is 4-6%; the volume ratio of the isopropanol solution to the Nafion solution is 75-85: 5.
optionally, the solvent is a mixed solution of isopropanol solution and Nafion solution; wherein the volume ratio of isopropanol to water in the isopropanol solution is 3: 1; the mass fraction of the Nafion solution is 5 percent; the volume ratio of the isopropanol solution to the Nafion solution is 80: 5.
optionally, the carbon nanotubes derived from Covalent Organic Frameworks (COFs) can be used as a catalyst to catalyze a cathode oxygen reduction reaction, and further can be used for a methanol direct fuel cell and a zinc air fuel cell.
Optionally, the step (1) is:
adding metal nanowires and amino COFs monomers in a container according to a proportion, adding a mixed organic solvent, and uniformly mixing; then adding a catalyst, and continuously and uniformly mixing to obtain a mixed solution; dissolving aldehyde COFs monomers in a mixed solvent, and uniformly mixing to obtain an aldehyde COFs monomer solution; then dripping the aldehyde COFs monomer solution into the mixed solution, uniformly mixing, and then carrying out in-situ growth reaction; then washing, centrifuging and drying; thus obtaining the composite material.
Optionally, the step (1) specifically comprises:
adding metal nanowires and amino COFs monomers in a reaction container according to a ratio, adding a mixed organic solvent, and ultrasonically mixing uniformly; then adding a catalyst, and continuously and uniformly mixing by ultrasonic waves to obtain a mixed solution; dissolving aldehyde COFs monomers in a mixed solvent, and uniformly mixing by ultrasonic waves to obtain an aldehyde COFs monomer solution; then, dripping the aldehyde COFs monomer solution into the mixed solution, and continuing ultrasonic mixing to obtain a composite material mixed solution; then transferring the composite material mixed solution into a Pyrex bottle, and placing the Pyrex bottle for reaction after repeated freezing-vacuumizing-dissolving cycles; then washing, centrifuging and drying; thus obtaining the composite material.
Optionally, the freezing in the step (1) is to freeze liquid by using liquid nitrogen, and the vacuumizing is to vacuumize by using a double-row pipe; the dissolution is that the temperature is raised to the room temperature, and the frozen reaction mixture is dissolved again; the number of repeated freezing-vacuumizing-dissolving cycles in the step (1) is 3.
Optionally, the reaction conditions after the repeated freezing-vacuumizing-dissolving cycles in the step (1) are as follows: placing the mixture in an oven at 90-130 ℃ for reaction for 60-80 h.
Optionally, the washing in the step (1) is performed 3 to 5 times by using a cyclohexane/methanol mixed solution.
Optionally, the metal nanowire in step (1) is one or both of a copper nanowire and a silver nanowire, and the diameter of the metal nanowire is 15-200 nm.
Optionally, the diameter of the metal nanowire in the step (1) is in the range of 20-50 nm.
Optionally, the amino COFs monomer in step (1) is one or two of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin and 5,5 '-diamino-2, 2' -bipyridine.
Optionally, the aldehyde COFs monomer in step (1) is one or two of terephthalaldehyde and trialdehyde phloroglucinol.
Optionally, the mass ratio of the metal nanowire and the theoretically formed COFs in the step (1) is 15: 1-1: 2.
optionally, the proportion of the amino-aldehyde is different for different COFs, depending on the number of the amino-aldehyde functional groups on the monomer and the molecular weight, specifically, one molar equivalent of aldehyde group corresponds to one molar equivalent of amino group.
Optionally, the mixed organic solvent in the step (1) is ethanol/mesitylene, and the volume ratio of the ethanol to the mesitylene is 2:1-1: 2.
Optionally, the mass-to-volume ratio of the metal nanowires to the mixed organic solvent in the mixed solution in the step (1) is 2-15mg/mL, that is, 2-15mg of the metal nanowires are added into 1mL of the mixed organic solvent.
Optionally, the ultrasound parameters in step (1) are set as: the ultrasonic power is 200W, and the ultrasonic time is 30-70 min.
Optionally, the catalyst in the step (1) is a schiff base reaction acidic catalyst, specifically an acetic acid solution, and the concentration of the acetic acid solution is 3-6M.
Optionally, the adding amount of the catalyst in the step (1) is 5-20% of the volume of the mixed organic solvent.
Optionally, the mass-to-volume ratio of the amino COFs monomer in the step (1) to the mixed organic solvent is 0.5-20 mg/mL.
Optionally, the mass-to-volume ratio of the aldehyde COFs monomers to the mixed solvent in step (1) is 0.5-20mg/mL, that is, 0.5-20mg of the aldehyde COFs monomers are dissolved in 1mL of the mixed solvent.
Optionally, the mixing time of the mixed solution in the step (1) is 15-40min, the mixing time of the aldehyde COFs monomer solution is 10-20min, and the mixing time of the composite material solution is 20-40 min.
Optionally, the drying in step (1) is vacuum drying, and the specific parameters are as follows: the temperature is 60-80 ℃ and the time is 8-12 h.
Optionally, the temperature rise rate in the step (2) is 2-5 ℃/min.
Optionally, the inert gas in the step (2) is argon.
Optionally, the step (3) specifically includes: placing the carbonized material obtained in the step (2) into a reaction container, adding a prepared acid solution, uniformly stirring, filtering by using a microfiltration membrane, and repeatedly washing by using water until the filtrate is neutral; finally, vacuum drying is carried out overnight, and the carbon nanotubes derived from the COFs are obtained.
Optionally, the concentration of the acid solution in the step (3) is 8-15M.
Optionally, the strong acid solution in the step (3) is a nitric acid solution.
Optionally, the mass-to-volume ratio of the carbonized material to the acid solution in the step (3) is 0.2-1mg/mL, that is, 0.2-1mg of carbonized material is added to 1mL of acid solution.
Optionally, the stirring speed in the step (3) is 400-1000 rpm; stirring for 16-32 h; sonication can be performed prior to agitation.
Optionally, the microfiltration membrane in the step (3) is a water-based microfiltration membrane, and the specific parameters are as follows: the diameter of the hole is 50mm and the hole diameter is 0.22 μm.
Optionally, the vacuum drying parameters in step (3) are as follows: the temperature is 60-80 ℃.
The second purpose of the invention is to provide a method for catalyzing ORR reaction based on COFs derived metal-doped carbon nanotubes, which comprises the following steps: applying COFs-derived metal-doped carbon nanotubes as a catalyst in a cathode oxygen reduction reaction; the preparation method of the COFs-derived metal-doped carbon nanotube is that metal doping can be carried out before the step (2) of the preparation method of the carbon nanotube derived from the covalent organic framework, and specifically comprises the following steps:
(1) selecting metal nanowires as templates, and growing COFs on the surfaces of the metal nanowires in situ through solvothermal reaction in a vacuum environment to obtain a composite material;
(2) placing the composite material obtained in the step (1) in a reaction container, adding doped transition metal salt and an organic solvent, uniformly mixing, reacting at 75-90 ℃, and then cooling, washing and drying to obtain powder;
(3) putting the powder obtained in the step (2) into a reaction container, and heating to 800-1000 ℃; then cooling to obtain a carbonized material; wherein, the whole process is under the protection of inert gas;
(4) and (4) placing the carbonized material obtained in the step (3) into a reaction vessel, carrying out acid washing, and then filtering and washing to obtain the COFs-derived metal-doped carbon nanotube.
Optionally, the preparation method of the COFs derived metal-doped carbon nanotube comprises:
(1) selecting metal nanowires as templates, and growing COFs on the surfaces of the metal nanowires in situ through solvothermal reaction in a vacuum environment to obtain a composite material;
(2) placing the composite material obtained in the step (1) in a reaction vessel, adding doped transition metal salt and an organic solvent, uniformly mixing, heating to 75-90 ℃ in an oil bath, stirring, and keeping condensation and reflux for 6-10 h; cooling to room temperature, washing and drying to obtain powder;
(3) placing the powder obtained in the step (2) in a porcelain boat, heating to 800-; then cooling to room temperature to obtain a carbonized material; wherein, the whole carbonization process is under the protection of inert gas;
(4) placing the carbonized material obtained in the step (3) in a glass bottle, adding the prepared acid solution, and uniformly stirring; and then filtering and washing to obtain the COFs-derived metal-doped carbon nanotube.
Optionally, the doped transition metal salt in the step (2) is one or more of acetate, chloride, nitrate and acetylacetone.
Optionally, the organic solvent in step (2) is methanol.
Optionally, the mass ratio of the composite material, the doped metal and the organic solvent in the step (2) is 1: (0.5-5): (1-3.5).
Optionally, the organic solvent in step (2) is methanol.
Optionally, the washing in step (2) is 3-5 times with a cyclohexane/methanol mixed solution.
Optionally, the drying in step (2) is carried out in a vacuum oven at 60-80 ℃ overnight.
The invention has the beneficial effects that:
(1) the carbon nanotube material derived from COFs without metal doping can obtain higher limiting current density (5.8 mA/cm) in the oxidation-reduction reaction of the catalytic cathode2) And half-wave potential (0.81V vs. rhe).
(2) The carbon nanotube material derived from COFs doped with metal can obtain higher limiting current density (5.4 mA/cm) in the oxidation-reduction reaction of the catalytic cathode2) And half-wave potential (0.8V vs. rhe).
(3) The invention can flexibly regulate and control the inner diameter and the tube wall thickness of the carbon nano-tube by controlling the diameter of the silver nano-wire in the precursor COF @ Ag and the thickness of the COFs layer, thereby influencing the ORR activity expression of the carbon nano-tube.
Drawings
FIG. 1 is a graph showing oxygen reduction polarization curves of porphyrin-based COFs-CNT of example 1 and pyridine-based COFs-CNT of example 2 at 0.1M KOH.
FIG. 2 is a scanning electron micrograph of carbon nanotubes derived from porphyrin-based COFs in example 1.
FIG. 3 is a photograph showing the elemental analysis of carbon nanotubes derived from porphyrins COFs in example 1, wherein (a) is an original drawing; (b) is a photograph of element C; (c) is an N element photograph.
FIG. 4 is a scanning electron micrograph of carbon nanotubes derived from pyridine COFs in example 2.
FIG. 5 is an oxygen reduction polarization curve of porphyrin-based COFs-CoCNT of example 3 and pyridine-based COFs-FeCNT of example 4 at 0.1M KOH.
FIG. 6 is a microscopic morphology of porphyrin COF-Co derived cobalt-doped carbon nanotubes in example 3; (a) scanning an electron microscope picture; (b) and (5) transmission electron microscope photographs.
FIG. 7 is a microscopic morphology of the pyridine COFs-Fe-derived Fe-doped carbon nanotubes of example 4; (a) scanning an electron microscope picture; (b) and (5) transmission electron microscope photographs.
FIG. 8 shows the effect of COFs-derived carbon nanotubes solid powder with covalent organic frameworks on the electrocatalytic oxygen reduction activity.
Fig. 9 shows the effect of covalent organic framework COFs-derived carbon nanotube solid powders on electrocatalytic oxygen reduction activity at different calcination temperatures.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
Example 1
The application of carbon nanotubes derived from Covalent Organic Frameworks (COFs) in catalyzing cathode oxygen reduction reaction comprises the following steps: carbon nanotubes derived from Covalent Organic Frameworks (COFs) are used as a catalyst to be applied to a cathode oxygen reduction reaction; the method specifically comprises the following steps: weighing 0.5mg of carbon nanotube solid powder derived from Covalent Organic Frameworks (COFs) and adding the carbon nanotube solid powder into a mixed solution of 80 microliters of isopropanol aqueous solution (the volume ratio of isopropanol to water is 3:1) and 5 microliters of perfluorosulfonic acid Nafion solution (mass fraction is 5%), and carrying out ultrasonic homogenization; then, 10. mu.l was dropped and applied to an area of 0.192cm2Obtaining a working electrode on the glassy carbon electrode; and finally, applying the working electrode to the oxygen precipitation reaction in the catalytic electrolysis water.
The specific catalytic cathodic oxygen reduction reaction test is to place the working electrode in 0.1M potassium hydroxide solution to test the electrocatalytic oxygen reduction activity, and the obtained data are shown in figure 1.
The preparation method of the carbon nanotube derived from the covalent organic framework comprises the following steps:
(1) putting 12mg of silver nanowires (the diameter is 20nm) and 3mg of 5,10,15, 20-tetra (4-aminophenyl) porphyrin into a glass bottle, adding a mixed solution of 2mL of ethanol/mesitylene (the volume ratio is 1:1), ultrasonically mixing for 30 minutes, adding 0.2mL of 3M acetic acid solution, and continuously ultrasonically mixing for 5 minutes to obtain a mixed solution; dissolving 1.2mg of terephthalaldehyde in 400 microliters of ethanol/mesitylene (volume ratio is 1:1) mixed solution, and uniformly performing ultrasonic treatment to obtain a terephthalaldehyde solution; slowly dripping the terephthalaldehyde solution into the mixed solution, and continuing to perform ultrasonic treatment for 20 minutes to obtain a composite material solution; then transferring the composite material solution into a Pyrex glass bottle, performing three freezing-vacuumizing-dissolving processes by using liquid nitrogen and a double-row pipe device, and finally placing the glass bottle in a 95 ℃ oven to react for 72 hours under the condition of keeping a vacuumizing state; after the reaction, washing the solution with cyclohexane/methanol mixed solution for 5 times, and drying the solution in a vacuum oven at 80 ℃ overnight to obtain COF @ Ag powder.
(2) Placing the COF @ Ag powder obtained in the step (1) in a porcelain boat, heating to 1000 ℃ at a speed of 5 ℃/min in an argon atmosphere by using a tube furnace, then preserving heat for 3h, and cooling to room temperature under the protection of inert gas to obtain a carbonized material;
(3) placing the carbonized material (14.5mg) obtained in the step (2) into a glass bottle, adding the prepared 30mL of 8M nitric acid solution, ultrasonically homogenizing, stirring (the stirring speed is 800rpm) for 24h, performing suction filtration by using a water-based microfiltration membrane (the parameter of the filtration membrane is that the diameter is 50mm, and the pore diameter is 0.22 mu M), and repeatedly washing by using water until the filtrate is neutral; finally, vacuum drying (temperature is 80 ℃) overnight to obtain the porphyrin COFs-CNT, wherein the surface appearance of the porphyrin COFs-CNT is shown in FIG. 2, and can be seen from FIG. 2: the porphyrin COFs-CNT has uniform tubular structure and the outer diameter of the tube is controlled to be about 40 nm; the surface element analysis is shown in fig. 3, and it can be seen from fig. 3 that: the porphyrin COFs-CNT is composed of C and N elements and is essentially different from a carbon nano tube composed of pure C.
Example 2
An application of carbon nanotubes derived from Covalent Organic Frameworks (COFs) in catalyzing cathode oxygen reduction reaction comprises the following steps: carbon nanotubes derived from Covalent Organic Frameworks (COFs) are used as a catalyst to be applied to a cathode oxygen reduction reaction; the method specifically comprises the following steps: weighing 0.5mg of carbon nanotube solid powder derived from Covalent Organic Frameworks (COFs) and adding the carbon nanotube solid powder into a mixed solution of 80 microliters of isopropanol aqueous solution (the volume ratio of isopropanol to water is 3:1) and 5 microliters of perfluorosulfonic acid Nafion solution (mass fraction is 5%), and carrying out ultrasonic homogenization; then, 10. mu.l was dropped and applied to an area of 0.192cm2Obtaining a working electrode on the glassy carbon electrode; and finally, applying the working electrode to the oxygen precipitation reaction in the catalytic electrolysis water. The specific catalytic cathodic oxygen reduction reaction test is to place the working electrode in 0.1M potassium hydroxide solution to test the electrocatalytic oxygen reduction activity, and the obtained data are shown in figure 1.
The preparation method of the carbon nanotube derived from the covalent organic framework comprises the following steps:
(1) putting 12mg of silver nanowires (the diameter is 30nm) and 2.4mg of 5,5 '-diamino-2, 2' -bipyridine into a glass bottle, adding a mixed solution of 2mL of ethanol/mesitylene (the volume ratio is 1:1), ultrasonically mixing for 30 minutes, adding 0.2mL of 3M acetic acid solution, and continuously ultrasonically mixing for 5 minutes to obtain a mixed solution; dissolving 1.8mg of trialdehyde phloroglucinol into 400 microliters of mixed solution of ethanol/mesitylene (volume ratio is 1:1) and performing ultrasonic homogenization to obtain trialdehyde phloroglucinol solution; slowly dripping the p-trialdehyde phloroglucinol solution into the mixed solution, and continuing to perform ultrasonic treatment for 20 minutes to obtain a composite material solution; then transferring the composite material solution into a Pyrex glass bottle, and performing three freezing-vacuumizing-dissolving processes by using liquid nitrogen and a double-row pipe device; finally, placing the mixture in a 95 ℃ oven to react for 72 hours under the condition of keeping the vacuumizing state; after the reaction, washing the solution with cyclohexane/methanol mixed solution for 5 times, and drying the solution in a vacuum oven at 80 ℃ overnight to obtain COF @ Ag powder.
(2) Placing the COF @ Ag powder obtained in the step (1) in a porcelain boat, heating to 1000 ℃ at a speed of 5 ℃/min in an argon atmosphere by using a tube furnace, then preserving heat for 3h, and cooling to room temperature under the protection of inert gas to obtain a carbonized material;
(3) placing the carbonized material (15mg) obtained in the step (2) into a glass bottle, adding the prepared 30mL of 8M nitric acid solution, ultrasonically homogenizing, stirring (the stirring speed is 800rpm) for 24h, performing suction filtration by using a water-based microfiltration membrane (the parameter of the filtration membrane is that the diameter is 50mm, and the aperture is 0.22 mu M), and repeatedly washing by using water until the filtrate is neutral; finally, vacuum drying (temperature 80 ℃) is carried out overnight, thus obtaining the pyridine COFs-CNT, the appearance of which is shown in FIG. 4, and can be seen from FIG. 4: the pyridine COFs-CNT is regular and uniform in tubular structure.
Example 3
An application of carbon nanotubes derived from Covalent Organic Frameworks (COFs) in catalyzing cathode oxygen reduction reaction comprises the following steps: carbon nanotubes derived from Covalent Organic Frameworks (COFs) are used as a catalyst to be applied to a cathode oxygen reduction reaction; the method specifically comprises the following steps: weighing 0.5mg of carbon nanotube solid powder derived from Covalent Organic Frameworks (COFs) and adding the carbon nanotube solid powder into a mixed solution of 80 microliters of isopropanol aqueous solution (the volume ratio of isopropanol to water is 3:1) and 5 microliters of perfluorosulfonic acid Nafion solution (mass fraction is 5%), and carrying out ultrasonic homogenization; then, 10. mu.l was dropped and applied to an area of 0.192cm2Obtaining a working electrode on the glassy carbon electrode; finally, the working electrode is applied to the catalystAnd (4) carrying out oxygen precipitation reaction in the electrolyzed water. The specific catalytic cathodic oxygen reduction reaction test is to place the working electrode in 0.1M potassium hydroxide solution to test the electrocatalytic oxygen reduction activity, and the obtained data are shown in figure 5.
The preparation method of the carbon nanotube derived from the covalent organic framework comprises the following steps:
(1) putting 12mg of silver nanowires (the diameter is 40nm) and 3mg of 5,10,15, 20-tetra (4-aminophenyl) porphyrin into a glass bottle, adding a mixed solution of 2mL of ethanol/mesitylene (the volume ratio is 1:1), ultrasonically mixing for 30 minutes (the ultrasonic power is 200W), adding 0.2mL of 3M acetic acid solution, and continuously ultrasonically treating for 5 minutes to obtain a mixed solution; dissolving 1.2mg of terephthalaldehyde in 400 microliters of ethanol/mesitylene (volume ratio is 1:1) mixed solution, and uniformly performing ultrasonic treatment to obtain a terephthalaldehyde solution; slowly dripping the terephthalaldehyde solution into the mixed solution, and continuing to perform ultrasonic treatment for 20 minutes to obtain a composite material solution; then transferring the composite material solution into a Pyrex glass bottle, and performing three freezing-vacuumizing-dissolving processes by using liquid nitrogen and a double-row pipe device; finally, the mixture is placed in an oven at 95 ℃ for reaction for 72 hours under the condition of keeping the vacuumizing state. After the reaction, washing the solution with cyclohexane/methanol mixed solution for 5 times, and drying the solution in a vacuum oven at 80 ℃ overnight to obtain COF @ Ag powder.
(2) Placing the COF @ Ag powder (15.6mg) obtained in the step (1) into a 50mL round-bottom flask, adding 5mg of cobalt acetate and 20mL of methanol, uniformly mixing, heating to 80 ℃ in an oil bath, stirring, and keeping condensation reflux for 8 hours; cooling to room temperature, washing with cyclohexane/methanol mixed solution for 3 times, and drying in a vacuum oven at 80 deg.C overnight to obtain powder;
(3) placing the powder obtained in the step (2) in a porcelain boat, heating to 900 ℃ at the speed of 5 ℃/min in an argon atmosphere by using a tube furnace, then preserving heat for 3h, and cooling to room temperature under the protection of inert gas to obtain a carbonized material;
(4) placing the carbonized material (15.2mg) obtained in the step (3) into a glass bottle, adding the prepared 30mL of 8M nitric acid solution, ultrasonically homogenizing, stirring (the stirring speed is 700rpm) for 24h, performing suction filtration by using a water-based microfiltration membrane (the parameter of the filtration membrane is that the diameter is 50mm, and the pore diameter is 0.22 mu M), and repeatedly washing by using water until the filtrate is neutral; finally, vacuum drying (temperature is 80 ℃) overnight to obtain the porphyrin COFs-CoCNT, wherein the appearance of the porphyrin COFs-CoCNT is shown in FIG. 6, and can be seen from FIG. 6: porphyrin class COFs-CoCNT combines cobalt ions by utilizing the N coordination of porphyrin and is reduced at high temperature to form a metal-doped carbon nanotube; no metal particles are observed in the transmission electron microscope, visible metal silver or cobalt particles are completely removed, and the tubular structure of the carbon nanotube is regular and uniform.
Example 4
An application of carbon nanotubes derived from Covalent Organic Frameworks (COFs) in catalyzing cathode oxygen reduction reaction comprises the following steps: the method specifically comprises the following steps: carbon nanotubes derived from Covalent Organic Frameworks (COFs) are used as a catalyst to be applied to a cathode oxygen reduction reaction; the method specifically comprises the following steps: weighing 0.5mg of carbon nanotube solid powder derived from Covalent Organic Frameworks (COFs) and adding the carbon nanotube solid powder into a mixed solution of 80 microliters of isopropanol aqueous solution (the volume ratio of isopropanol to water is 3:1) and 5 microliters of perfluorosulfonic acid Nafion solution (mass fraction is 5%), and carrying out ultrasonic homogenization; then, 10. mu.l was dropped and applied to an area of 0.192cm2Obtaining a working electrode on the glassy carbon electrode; and finally, applying the working electrode to the oxygen precipitation reaction in the catalytic electrolysis water. The specific catalytic cathodic oxygen reduction reaction test is to place the working electrode in 0.1M potassium hydroxide solution to test the electrocatalytic oxygen reduction activity, and the obtained data are shown in figure 5.
The preparation method of the carbon nanotube derived from the covalent organic framework comprises the following steps:
(1) putting 12mg of silver nanowires (the diameter is 20nm) and 2.4mg of 5,5 '-diamino-2, 2' -bipyridine into a glass bottle, adding a mixed solution of 2mL of ethanol/mesitylene (the volume ratio is 1:1), ultrasonically mixing for 30 minutes (the ultrasonic power is 200W), adding 0.2mL of 3M acetic acid solution, and continuously ultrasonically treating for 5 minutes to obtain a mixed solution; dissolving 1.8mg of trialdehyde phloroglucinol into 400 microliters of mixed solution of ethanol/mesitylene (volume ratio is 1:1) and performing ultrasonic homogenization to obtain trialdehyde phloroglucinol solution; slowly dripping the trialdehyde phloroglucinol solution into the mixed solution, and continuing to perform ultrasonic treatment for 20 minutes to obtain a composite material solution; then transferring the composite material solution into a Pyrex glass bottle, performing three freezing-vacuumizing-dissolving processes by using liquid nitrogen and a double-row pipe device, and finally placing the glass bottle in a 95 ℃ oven to react for 72 hours under the condition of keeping a vacuumizing state; after the reaction is finished, washing the reaction product for 5 times by using a cyclohexane/methanol mixed solution, and drying the reaction product in a vacuum oven at 80 ℃ overnight to obtain COF @ Ag powder;
(2) placing the COF @ Ag powder (15.8mg) obtained in the step (1) into a 50mL round-bottom flask, adding 5mg of ferric chloride and 20mL of methanol, uniformly mixing, heating to 80 ℃ in an oil bath, stirring, and keeping the mixture under condensation reflux for 8 hours; cooling to room temperature, washing with cyclohexane/methanol mixed solution for 3 times, and drying in a vacuum oven at 80 deg.C overnight to obtain powder;
(3) placing the powder obtained in the step (2) in a porcelain boat, heating to 900 ℃ at the speed of 5 ℃/min in an argon atmosphere by using a tube furnace, then preserving heat for 3h, and cooling to room temperature under the protection of inert gas to obtain a carbonized material;
(4) and (3) placing the carbonized material (15.4mg) obtained in the step (3) into a glass bottle, adding the prepared 30mL of 8M nitric acid solution, performing ultrasonic homogenization, stirring at the stirring speed of 700rpm for 24 hours, performing suction filtration by using a water-based microfiltration membrane (the parameter of the filtration membrane is that the diameter is 50mm, and the pore diameter is 0.22 mu M), and repeatedly washing by using water until the filtrate is neutral. Finally, vacuum drying (the temperature is 80 ℃) overnight to obtain the pyridine COFs-FeCNT, wherein the appearance of the pyridine COFs-FeCNT is shown in FIG. 7, and can be seen from FIG. 7: pyridine COFs-FeCNT combines iron ions by utilizing the N coordination of pyridine and is reduced at high temperature to form a metal-doped carbon nanotube; clear tubular structures can be observed, the inner diameter of the tube is 30nm, and the wall thickness is 1-5 nm. .
Fig. 1 and 5 are graphs of oxygen reduction performance of porphyrin-based COFs and pyridine-based COFs derived carbon nanotubes without metal-doped N series and with metal-doped N series, respectively. The data in the figure are polarization curves tested in 0.1M KOH solution by a rotating disk electrode device at a rotation rate of 1600rpm/min, and the ORR activity of the catalyst can be preliminarily judged by the limiting current and the half-wave potential (generally, the larger the limiting current or the larger the half-wave potential, the better the performance). As can be seen from fig. 1: the limiting current density of the porphyrin COFs-CNT as the catalyst in the catalytic cathodic oxygen reduction of example 1 reaches 5.1mA/cm2) The half-wave potential reaches 0.77V vs. RHE; the pyridine COFs-CNT of example 2 is used as a catalyst to achieve the limiting current density in the catalytic cathodic oxygen reduction5.4mA/cm2) The half-wave potential reaches 0.81V vs. RHE; as can be seen from fig. 5: the limiting current density of the porphyrin COFs-CoCNT serving as the catalyst in the catalytic cathodic oxygen reduction of example 3 reaches 5mA/cm2The half-wave potential reaches 0.79V vs. RHE; the limiting current density of the pyridine COFs-FeCNT serving as a catalyst in catalytic cathodic oxygen reduction of example 4 reaches 5.4mA/cm2The half-wave potential reaches 0.8V vs. rhe. As can be seen from fig. 1 and 5: even without metal, the metal-free conductive coating still has large limiting current and considerable half-wave potential.
Example 5
The mass ratio of silver nanowires to COFs monomer charge (5,10,15, 20-tetrakis (4-aminophenyl) porphyrin) in example 1 was adjusted to be shown in Table 1, wherein the number is the mass ratio of silver nanowires to COFs monomer charge (5,10,15, 20-tetrakis (4-aminophenyl) porphyrin), and other parameters and example 1 were kept unchanged, and the electrocatalytic oxygen reduction activity was detected. The results are shown in table 1 and fig. 8:
TABLE 1 influence of composite-derived carbon nanotube solid powder on electrocatalytic oxygen reduction activity, obtained from different mass ratios of silver nanowires to COFs monomer charge
From the polarization curve of fig. 8, the obtained half-wave potential and limiting current density are summarized in table 1. As can be seen from table 1: the catalytic performance of the carbon nanotube derived from the composite material can be optimized by changing the mass ratio of the silver nanowire to the COFs monomer, wherein when the mass ratio of the silver nanowire to the COFs monomer is 3, the maximum half-wave potential of 0.78V can be obtained, and when the mass ratio of the silver nanowire to the COFs monomer is 2 or 4, the maximum limiting current of 5.1mA/cm can be obtained2。
Example 6
The electrocatalytic oxygen reduction activity was measured by adjusting the calcination temperature in example 1 to the value shown in Table 2, while keeping the other parameters and example 1. The results are shown in table 2 and fig. 9:
TABLE 2 influence of covalent organic frameworks COFs derived carbon nanotubes solid powders of different calcination temperatures on the electrocatalytic oxygen reduction activity
From the polarization curve of fig. 9, the obtained half-wave potential and limiting current density are summarized in table 2. As can be seen from table 2: the catalytic performance of the carbon nanotube derived from the composite material can be optimized by changing the calcination temperature, wherein when the calcination temperature is 900 ℃, the obtained carbon nanotube can obtain the maximum half-wave potential and the maximum limiting current which are respectively 0.81V and 5.8mA/cm2。
Example 7 diameter optimization of nanowires
The diameter of the nano silver of example 2 was adjusted to be as shown in table 3, and the electrocatalytic oxygen reduction activity was measured while keeping other parameters and example 2. The results are shown in table 3:
TABLE 3 influence of carbon nanotube solid powder derived from different nanosilver diameter composites on electrocatalytic oxygen reduction activity
As can be seen from table 3: the diameter of the silver nanowire can optimize the catalytic performance of the carbon nanotube derived from the composite material, wherein when the diameter of the silver nanowire is 30nm, the obtained carbon nanotube can obtain the maximum half-wave potential and the maximum limiting current which are respectively 0.81V and 5.4mA/cm2。
Comparative example 1
The carbon nanotubes derived from covalent organic frameworks COFs of example 1 were modified to commercial Pt/C catalysts (20%, Alfa Aesar), otherwise in agreement with example 1, and the catalytic performance was tested as shown in Table 4:
table 4 effect of the catalysts of example 1 and comparative example 1 on the electrocatalytic oxygen reduction activity
As can be seen from table 4: the catalytic performance of the obtained carbon nano-tube is close to that of a commercial Pt/C catalyst, and the limiting current density can even exceed that of the commercial Pt/C catalyst.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for catalyzing ORR reaction based on COFs derived carbon nanotubes is characterized by comprising the following steps: the carbon nanotubes derived from Covalent Organic Frameworks (COFs) are used as a catalyst to be applied to a cathode oxygen reduction (ORR) reaction; the preparation method of the COFs derived carbon nanotube comprises the following steps:
(1) selecting metal nanowires as templates, and growing COFs on the surfaces of the metal nanowires in situ through solvothermal reaction in a vacuum environment to obtain a composite material;
(2) placing the composite material obtained in the step (1) in a reaction vessel, and heating to 800-1000 ℃; then cooling to obtain a carbonized material; wherein, the whole process is under the protection of inert gas;
(3) and (3) placing the carbonized material obtained in the step (2) into a container for acid washing, and then filtering, washing and drying to obtain the COFs-derived carbon nanotube.
2. The method according to claim 1, characterized in that said carbon nanotubes derived from Covalent Organic Frameworks (COFs) are used as catalysts in cathodic oxygen reduction (ORR) reactions, in particular: dissolving carbon nanotubes derived from Covalent Organic Frameworks (COFs) as a catalyst in a solvent to obtain a catalyst solution; then modifying a glassy carbon electrode by adopting a catalyst solution to serve as a working electrode; and finally, applying the working electrode to the oxygen precipitation reaction in the catalytic electrolysis water.
3. The method of claim 2, wherein the concentration of the catalyst solution is 0.001 to 0.01mg/μ L.
4. The method of claim 2, wherein the catalyst solution is used in an amount of 10 μ L/0.1-0.2cm2。
5. The method according to claim 2, wherein the solvent is a mixed solution of an isopropanol solution and a Nafion solution; wherein the volume ratio of the isopropanol to the water in the isopropanol solution is 3-5: 1; the mass fraction of the Nafion solution is 4-6%; the volume ratio of the isopropanol solution to the Nafion solution is 75-85: 5.
6. the method according to claim 1, wherein the step (1) is specifically:
adding metal nanowires and amino COFs monomers into a container, adding a mixed organic solvent, and uniformly mixing; then adding a catalyst, and continuously and uniformly mixing to obtain a mixed solution; dissolving aldehyde COFs monomers in a mixed solvent, and uniformly mixing to obtain an aldehyde COFs monomer solution; then dripping the aldehyde COFs monomer solution into the mixed solution, uniformly mixing, and then carrying out in-situ growth reaction; then washing, centrifuging and drying; thus obtaining the composite material.
7. The method of claim 6, wherein the metal nanowires of step (1) are one of copper nanowires and silver nanowires; the diameter of the metal nanowire is 15-200 nm; and (2) the mass-volume ratio of the metal nanowires to the mixed organic solvent in the mixed solution in the step (1) is 2-15 mg/mL.
8. A method for catalyzing ORR reaction based on COFs derived metal-doped carbon nanotubes is characterized by comprising the following steps: applying COFs-derived metal-doped carbon nanotubes as a catalyst in a cathode oxygen reduction reaction; the preparation method of the COFs-derived metal-doped carbon nanotube is a method for doping metal in the step (2) of the preparation method of the carbon nanotube derived from the covalent organic framework, and specifically comprises the following steps:
(1) selecting metal nanowires as templates, and growing COFs on the surfaces of the metal nanowires in situ through solvothermal reaction in a vacuum environment to obtain a composite material;
(2) placing the composite material obtained in the step (1) in a reaction container, adding doped transition metal salt and an organic solvent, uniformly mixing, reacting at 75-90 ℃, and then cooling, washing and drying to obtain powder;
(3) putting the powder obtained in the step (2) into a porcelain boat, and heating to 800-1000 ℃; then cooling to obtain a carbonized material; wherein, the whole process is under the protection of inert gas;
(4) and (4) placing the carbonized material obtained in the step (3) into a reaction vessel, carrying out acid washing, and then filtering and washing to obtain the COFs-derived metal-doped carbon nanotube.
9. The method according to claim 8, wherein the doped transition metal salt in step (2) is one or more of acetate, chloride, nitrate and acetylacetonate.
10. The method according to claim 8, wherein the mass ratio of the composite material, the doping metal and the organic solvent in the step (2) is 1: (0.5-5): (1-3.5).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010895107.2A CN112038647B (en) | 2020-08-31 | 2020-08-31 | Method for catalyzing ORR reaction based on COFs derived carbon nanotubes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010895107.2A CN112038647B (en) | 2020-08-31 | 2020-08-31 | Method for catalyzing ORR reaction based on COFs derived carbon nanotubes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112038647A CN112038647A (en) | 2020-12-04 |
| CN112038647B true CN112038647B (en) | 2021-07-27 |
Family
ID=73586840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010895107.2A Active CN112038647B (en) | 2020-08-31 | 2020-08-31 | Method for catalyzing ORR reaction based on COFs derived carbon nanotubes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112038647B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114725418B (en) * | 2022-03-23 | 2024-03-15 | 大连理工大学 | Ion screening flow battery diaphragm with function polymer/covalent organic framework penetrating shrinkage cavity structure |
| CN114864971A (en) * | 2022-04-14 | 2022-08-05 | 深圳市氢瑞燃料电池科技有限公司 | Anti-reversal catalysis layer of fuel cell and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2011326825A1 (en) * | 2010-11-12 | 2013-07-04 | Appem Ltd. | Fuel cell electrode having porous carbon core with macrocyclic metal chelates thereon |
| CN104538596A (en) * | 2014-12-22 | 2015-04-22 | 哈尔滨工业大学 | Carbon material/covalent organic two-dimensional gird composite electrode material as well as preparation method and application thereof |
| WO2018111777A1 (en) * | 2016-12-12 | 2018-06-21 | The Regents Of The University Of California | Pore size engineering of porous carbonaceous materials using covalent organic frameworks |
| CN109148165A (en) * | 2018-08-01 | 2019-01-04 | 曲阜师范大学 | A kind of preparation and application of covalent organic frame/graphene composite material |
| CN109354137A (en) * | 2018-11-27 | 2019-02-19 | 浙江工业大学 | The preparation and application of the derivative porous carbon composite electrode material of carbon nanotube/MOF |
| CN110227357A (en) * | 2019-06-29 | 2019-09-13 | 华南理工大学 | A kind of flexibility can cut nano-cellulose/covalent organic framework composite membrane and preparation method thereof |
| CN110368931A (en) * | 2019-07-31 | 2019-10-25 | 合肥工业大学 | A kind of preparation method of the monatomic composite material of covalent organic frame material derived carbon skeleton adulteration metal |
| CN111171369A (en) * | 2020-01-05 | 2020-05-19 | 复旦大学 | Covalent organic framework nanotube and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108671962B (en) * | 2018-05-29 | 2021-12-21 | 北京化工大学 | Method for modifying catalytic performance of COFs-based electrocatalyst based on graphene load |
-
2020
- 2020-08-31 CN CN202010895107.2A patent/CN112038647B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2011326825A1 (en) * | 2010-11-12 | 2013-07-04 | Appem Ltd. | Fuel cell electrode having porous carbon core with macrocyclic metal chelates thereon |
| CN104538596A (en) * | 2014-12-22 | 2015-04-22 | 哈尔滨工业大学 | Carbon material/covalent organic two-dimensional gird composite electrode material as well as preparation method and application thereof |
| WO2018111777A1 (en) * | 2016-12-12 | 2018-06-21 | The Regents Of The University Of California | Pore size engineering of porous carbonaceous materials using covalent organic frameworks |
| CN109148165A (en) * | 2018-08-01 | 2019-01-04 | 曲阜师范大学 | A kind of preparation and application of covalent organic frame/graphene composite material |
| CN109354137A (en) * | 2018-11-27 | 2019-02-19 | 浙江工业大学 | The preparation and application of the derivative porous carbon composite electrode material of carbon nanotube/MOF |
| CN110227357A (en) * | 2019-06-29 | 2019-09-13 | 华南理工大学 | A kind of flexibility can cut nano-cellulose/covalent organic framework composite membrane and preparation method thereof |
| CN110368931A (en) * | 2019-07-31 | 2019-10-25 | 合肥工业大学 | A kind of preparation method of the monatomic composite material of covalent organic frame material derived carbon skeleton adulteration metal |
| CN111171369A (en) * | 2020-01-05 | 2020-05-19 | 复旦大学 | Covalent organic framework nanotube and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Copper-assisted thermal conversion of microporous covalent melamin-boroxine frameworks to hollow B,N-codoped carbon capsules as bifunctional metal-free electrode materials";Ziqian Zhou等;《Electrochimica Acta》;20181217;第298卷;第210-218页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112038647A (en) | 2020-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109841854B (en) | Nitrogen-doped carbon-supported monatomic oxygen reduction catalyst and preparation method thereof | |
| CN111509236A (en) | One-dimensional porous platinum-containing alloy nanowire catalyst and preparation method thereof | |
| CN103495432A (en) | Method for preparing efficient stable fuel cell catalyst | |
| CN112133932A (en) | Three-metal-based Ni-Co-Zn-N Co-doped porous carbon catalyst and preparation method and application thereof | |
| CN111933960B (en) | PtCo @ N-GNS catalyst and preparation method and application thereof | |
| CN112103520B (en) | Anode catalyst of alcohol fuel cell | |
| CN108722453B (en) | Molybdenum phosphide/carbon composite nano material for alkaline electro-catalysis hydrogen evolution | |
| CN111437864B (en) | High-dispersion Cu/NC nano-cluster catalyst and preparation method thereof | |
| CN113363514A (en) | Carbon aerogel supported cobalt monoatomic catalyst for metal air battery, preparation method and application thereof | |
| CN111215056B (en) | Preparation method and application of low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst | |
| CN112038647B (en) | Method for catalyzing ORR reaction based on COFs derived carbon nanotubes | |
| CN111653792A (en) | Method for synchronously preparing hierarchical pore cobalt and nitrogen co-doped nanorod supported platinum-cobalt alloy nano oxygen reduction electrocatalyst | |
| CN113862693A (en) | Preparation method and application of nitrogen-doped mesoporous carbon-loaded high-dispersion Ru nanoparticle catalyst | |
| CN113437314A (en) | Nitrogen-doped carbon-supported low-content ruthenium and Co2Three-function electrocatalyst of P nano particle and preparation method and application thereof | |
| CN112993278A (en) | Flower-shaped titanium dioxide/reduced graphene composite carrier supported platinum and alloy catalyst thereof, and preparation and application thereof | |
| CN109261154B (en) | Graphene-like framework loaded monoatomic structural material and preparation method and application thereof | |
| CN112968181A (en) | Preparation method of carbon-coated titanium dioxide nanoflower carrier and application of carbon-coated titanium dioxide nanoflower carrier to carrying platinum or platinum alloy nanocatalyst | |
| CN109499602B (en) | Synthesis method for systematically regulating and controlling number of atoms of load type iron atom cluster | |
| CN115570143B (en) | Low-platinum high-entropy alloy nano-particle and preparation method and application thereof | |
| CN114797900A (en) | Carbon-supported cobalt sulfide electrocatalyst derived from metal organic framework and preparation method and application thereof | |
| CN108091890B (en) | Preparation method of silver-cobalt-guanine-based nano flaky material | |
| CN113809344A (en) | High-stability nano platinum-based intermetallic compound direct methanol fuel cell electrocatalyst and preparation method thereof | |
| CN107376973B (en) | SiO (silicon dioxide)2Preparation method of-nitrogen-doped graphene-supported palladium ruthenium bismuth nano catalyst | |
| CN111977638B (en) | Carbon nanotube material derived from covalent organic framework and preparation method thereof | |
| CN112371119B (en) | Preparation method and application of multi-metal pairing alkaline catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |