CN111129510A - Preparation method and application of carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electro-catalyst - Google Patents
Preparation method and application of carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electro-catalyst Download PDFInfo
- Publication number
- CN111129510A CN111129510A CN201911300012.5A CN201911300012A CN111129510A CN 111129510 A CN111129510 A CN 111129510A CN 201911300012 A CN201911300012 A CN 201911300012A CN 111129510 A CN111129510 A CN 111129510A
- Authority
- CN
- China
- Prior art keywords
- mixed solution
- carbon nitride
- nitride nanosheet
- phase carbon
- carbon material
- 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.)
- Granted
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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- 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
- H01M4/88—Processes of manufacture
-
- 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 belongs to the field of fuel cell catalysts, and particularly relates to a preparation method and application of a carbon material modified graphite phase carbon nitride nanosheet supported platinum nano electrocatalyst; the method comprises the following steps: firstly, preparing a graphite phase carbon nitride nanosheet precursor and a graphite phase carbon nitride nanosheet, then, on the basis, obtaining the graphite phase carbon nitride nanosheet by taking melamine as a raw material under relatively low temperature and relatively simple process conditions, and modifying by taking the material as a carrier and using a carbon material to obtain a carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electrocatalyst; the electrochemical catalytic performance, electrochemical corrosion resistance and stability of the carbon material modified graphite-phase carbon nitride nanosheet-loaded platinum nano electro-catalyst prepared by the method are superior to those of commercial platinum-carbon catalysts.
Description
Technical Field
The invention belongs to the field of fuel cell catalysts, and particularly relates to a preparation method and application of a carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electrocatalyst.
Background
Polyelectrolyte membrane fuel cells (PEMFC), as a fifth generation fuel cell, are considered to be one of the most promising clean energy technologies in this century. The research on such fuel cells is a hot topic in the field, but in practical application, the fuel needs reforming and purification, the water heating management is difficult, the structure is complex, the cost is high, and the like. Increasing the operating temperature of fuel cells is considered to be an ideal way to solve the major problems facing current polymer electrolyte membrane fuel cells. Compared with the traditional low-temperature membrane fuel cell (LT-PEMFC), the high-temperature membrane fuel cell (HT-PEMFC) has the operation temperature of 120-200 ℃, and the catalyst has higher activity and CO poisoning resistance in the temperature range. Meanwhile, the waste heat generated by the high-temperature membrane fuel cell has higher recovery value, and the overall efficiency of the system is improved conveniently. In addition, due to a non-aqueous proton conduction mechanism, the high-temperature membrane fuel cell does not need to carry out any humidification treatment on reaction gas, so that a complex water management link in a low-temperature proton exchange membrane fuel cell system is eliminated, and the operation and management of the fuel cell system are fundamentally simplified. HT-PEMFCs have become an important development of PEMFCs.
Noble metal Pt is the most common catalytic material of PEMFCs, and the activity and stability of the catalyst play a crucial role for the commercial application of PEMFCs. Carbon materials are widely used for Pt-based catalyst supports due to their excellent electrical conductivity and high specific surface area. However, in the severe operating environment (acidic and high temperature) of HT-PEMFC, electrochemical corrosion phenomena occur for both Pt and carbon support materials. The electrochemical corrosion of the electrode catalyst directly causes the rapid performance attenuation of the fuel cell, and the requirements of practical application cannot be met.
Carbon nitride materials are widely considered as a potential new material due to simple preparation route, easy mass production, good chemical stability, thermal stability and mechanical stability and easy modification. However, carbon nitride itself is a semiconductor material and its performance is often limited in electrocatalytic reactions. To solve this problem, carbon nitride is modified, e.g., stripped to give a thinner material, which exposes more active sites; another method is to compound the materials, and improve the performance of the materials by means of special performance of other materials, so that the composite material hasHas more excellent electrocatalytic performance. Graphite phase carbon nitride (gC)3N4) The graphene oxide/carbon nitride. The graphite phase carbon nitride is used as the catalyst substrate, so that the purposes of improving the stability and the electrochemical corrosion resistance of the catalyst can be achieved.
Disclosure of Invention
The invention aims to overcome the technical defects in the prior art, and provides a method for preparing a graphite phase carbon nitride nanosheet-loaded platinum nano electrocatalyst by using melamine as a raw material, obtaining graphite phase carbon nitride nanosheets at a lower temperature under simpler process conditions, and modifying the graphite phase carbon nitride nanosheets with a carbon material as a carrier. The catalyst has excellent electrochemical catalytic performance and electrochemical corrosion resistance.
The present invention achieves the above-described object by the following technical means.
A preparation method of a carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electrocatalyst comprises the following steps:
s1, firstly, mixing isopropanol and ethylene glycol to obtain a mixed solution; adding the graphite phase carbon nitride nanosheets prepared in the step 2, and stirring for a period of time to obtain a dispersion liquid of the graphite phase carbon nitride nanosheets;
s2, mixing isopropanol and ethylene glycol to obtain a mixed solution; adding a carbon material, and stirring for a period of time to obtain a dispersion liquid of the carbon material;
s3, mixing chloroplatinic acid (H)2Pt6·6H2O) adding the mixed solution into the ethylene glycol solution A to obtain a mixed solution B; and then adding an ethylene glycol solution C to obtain a mixed solution D, adjusting the pH value of the mixed solution D, heating to a certain temperature by using an oil bath for reflux, cooling to room temperature, slowly dropping a graphite-phase carbon nitride nanosheet dispersion liquid, uniformly stirring, slowly dropping a carbon material dispersion liquid to obtain a mixed solution E, stirring for the second time, adjusting the pH value of the mixed solution E again after stirring, stirring for the third time, and performing suction filtration, washing and drying to obtain the carbon material modified graphite-phase carbon nitride nanosheet supported platinum nano electrocatalyst.
Preferably, in the step 1, the use amount ratio of the melamine to the phosphorous acid to the deionized water is 1g: 1-5 g: 100 mL.
Preferably, in the step 1, the temperature of the water bath is 60-90 ℃, and the stirring is carried out for 0.5-2 hours; the temperature for reaction in the high-pressure reaction kettle is 120-200 ℃, and the time is 6-24 hours.
Preferably, in the step 2, the mass ratio of the glycerol to the ethanol is 1: 1-6; the dosage ratio of the precursor to the mixed solution is 0.6 g: 10 to 50 ml.
Preferably, in the step 2, the temperature of the oil bath is 60-120 ℃, and the reflux time is 1-6 h; the calcining temperature is 350-600 ℃, the heating rate is 2 ℃/min, and the time is 1-5 h.
Preferably, in the step 2, the thickness of the graphite-phase carbon nitride nanosheet is 0.5-100 nm.
Preferably, in step 3, in S1, the volume ratio of the isopropanol to the ethylene glycol is 1: 3; the dosage ratio of the graphite-phase carbon nitride nanosheet to the mixed solution is 10-50 mg:40 mL; the stirring is carried out for 3-5 h.
Preferably, in step 3, in S2, the volume ratio of the isopropanol to the ethylene glycol is 1: 3; the dosage ratio of the carbon material to the mixed solution is 10-50 mg:40 mL; the carbon material is one or more of carbon black, activated carbon, graphene, carbon nanofiber, carbon nanotube or carbon nanosphere.
Preferably, in S3 of step 3, the chloroplatinic acid (H)2Pt6·6H2O) concentration of chloroplatinic acid in the mixed solution of ethylene glycol solution was 1.5mgPtml-1。
Preferably, in step 3, in S3, the volume ratio of the mixed solution B to the glycol solution C is 1: 5-20.
Preferably, in step 3, in S3, the pH is adjusted to 9 to 14 by using a mixed solution of sodium hydroxide and ethylene glycol; the concentration of the sodium hydroxide in the mixed solution of the sodium hydroxide and the ethylene glycol is 2mol L-1。
Preferably, in step 3, in S3, the oil bath is heated to a certain temperature of 100-180 ℃ and the refluxing time is 1-5 h.
Preferably, in step 3, in S3, the time for the second stirring is 0.5 to 2 hours, and the time for the third stirring is 4 to 10 hours; and the pH value of the mixed solution E is adjusted to be less than 4 by using a mixed solution of nitric acid and glycol, wherein the concentration of the nitric acid in the mixed solution of nitric acid and glycol is 5 wt%.
Preferably, in step 3S 3, the platinum accounts for 1 to 60 wt% of the carbon material modified graphite phase carbon nitride nanosheet supported platinum nano electrocatalyst; the mass ratio of the graphite-phase carbon nitride nanosheets to the carbon material is 1: 0-5.
Preferably, in the step 1-3, the drying temperature is 60-150 ℃, and the drying time is 5-10 hours.
The invention has the advantages and technical effects that:
(1) different from the traditional top-down graphite-phase carbon nitride nanosheet preparation method (firstly preparing blocky carbon nitride and then peeling the blocky carbon nitride into flaky carbon nitride), the bottom-up graphite-phase carbon nitride nanosheet preparation method is simple to operate and can be used for directly synthesizing the graphite-phase carbon nitride nanosheets.
(2) The prepared graphite-phase carbon nitride nanosheet has a high dispersion effect on the platinum nanoparticles, and compared with the diameter of 4-8 nm of the platinum nanoparticles in a common catalyst, the diameter of the Pt nanoparticles of the catalyst prepared by the invention is only 1.8nm, obvious agglomeration does not exist, and the electrochemical specific surface area of platinum is greatly improved.
(3) The prepared graphite-phase carbon nitride nanosheet and the platinum nanoparticles have strong interaction, and have a certain anchoring effect on the platinum nanoparticles, so that the stability of the catalyst is improved.
(4) The electrochemical catalytic performance, electrochemical corrosion resistance and stability of the carbon material modified graphite-phase carbon nitride nanosheet-loaded platinum nano electro-catalyst prepared by the method are superior to those of commercial platinum-carbon catalysts.
In FIG. 1, a, b and c are Pt/gC prepared in example 13N4(TEM images at different magnifications; d and e are Pt/gC prepared in example 2, respectively3N4TEM images of/C at different magnifications.
gC prepared for comparative example 1 in FIG. 23N4Pt/gC prepared in example 13N4Pt/gC prepared in example 23N4Commercial Pt/C for the comparative example 2 at 2mol L saturated with Nitrogen-1H3PO4Cyclic Voltammetry (CV) profile measured in electrolyte with sweep rate of 10mV s-1。
FIG. 3 shows Pt/gC prepared in example 2 before and after Accelerated Durability Test (ADT)3N42mol L saturated with C under nitrogen-1H3PO4CV diagram in electrolyte, sweep rate is 10mV s-1。
FIG. 4 shows Pt/gC prepared in example 2 before and after ADT3N4C2 mol L saturated in oxygen-1H3PO4Linear Sweep Voltammetry (LSV) profile in electrolyte, with sweep rate of 10mV s-1。
FIG. 5 shows the commercial Pt/C used in comparative example 2 at 2mol L saturated with nitrogen before and after ADT-1H3PO4CV diagram in electrolyte, sweeping in the diagramAt a speed of 10mV s-1。
FIG. 6 shows the commercial Pt/C used in comparative example 2 at 2mol L saturated with oxygen before and after ADT-1H3PO4LSV pattern in electrolyte, sweep rate is 10mV s-1。
Detailed Description
The invention is further described below with reference to the drawings and examples. However, the following examples are only for explaining the present invention, and the scope of the present invention should include the full contents of the claims, not limited to the following examples.
Example 1:
weighing 1g of melamine and 1.2g of phosphorous acid, dissolving the melamine and the phosphorous acid in 100mL of deionized water, stirring the solution for 1h under the condition of a water bath at the temperature of 80 ℃, then placing the solution in a sealed high-pressure reaction kettle, reacting the solution for 10h at the temperature of 180 ℃, and naturally cooling the solution to room temperature; carrying out suction filtration on the obtained product, washing the product for a plurality of times by using deionized water, and drying the product for 8 hours at the temperature of 60 ℃ to obtain a precursor;
mixing 5ml of glycerol and 15ml of ethanol to obtain a mixed solution, adding 0.6g of the precursor obtained in the step 1, and strongly stirring until the mixture is uniformly mixed; then refluxing for 3h under the condition of oil bath at 90 ℃, and naturally cooling to room temperature; then carrying out suction filtration, washing with absolute ethyl alcohol for a plurality of times, and drying at 60 ℃ for 8 h; putting the dried intermediate product into a covered ceramic crucible, heating to 500 ℃ at the heating rate of 2 ℃ per minute, keeping for 2 hours, and naturally cooling to room temperature to obtain faint yellow graphite-phase carbon nitride nanosheets, marked as gC3N4；
firstly, mixing isopropanol and ethylene glycol in a volume ratio of 1:3 to obtain a mixed solution; adding 30mg of the graphite phase carbon nitride nanosheet prepared in the step 2 into 40ml of the mixed solution, and stirring for 4 hours to obtain a dispersion liquid of the graphite phase carbon nitride nanosheet;
5ml of the solution is added to the solution with the concentration of 1.5mgPtml-1Firstly adding chloroplatinic acid into the ethylene glycol solution A to obtain a mixed solution B; then adding 50ml of ethylene glycol for uniform mixing, and adjusting the pH value of the mixed solution to 10 by using a mixed solution of sodium hydroxide and ethylene glycol, wherein the concentration of the sodium hydroxide in the mixed solution of the sodium hydroxide and the ethylene glycol is 2mol L-1(ii) a Then heating to 160 ℃ by using an oil bath, and refluxing for 3h at the temperature to obtain a brownish black Pt colloid solution; slowly dripping graphite phase carbon nitride nanosheet dispersion liquid, and strongly stirring for 0.5 h; adjusting the pH value of the mixed solution E to be less than 4 by using a mixed solution of nitric acid and ethylene glycol, wherein the concentration of the nitric acid in the mixed solution of nitric acid and ethylene glycol is 5 wt%; stirring for 6h, then carrying out suction filtration, washing with deionized water for several times, drying in vacuum at 80 ℃ for 6h, and grinding to obtain the graphite phase carbon nitride nanosheet supported Pt nano electrocatalyst, recorded as Pt/gC3N4The Pt content was 20 wt%.
Electrode modification and testing:
(1) modification of working electrodes
2mg of Pt/gC3N4Adding into 1ml mixed solution of water and isopropanol, then dripping 10 μ L5 wt% Nafion solution, and ultrasonically dispersing for 15min to obtain suspension; and (3) dripping 20 mu L of suspension liquid on a disc electrode, and airing at room temperature for later use.
(2) Electrochemical testing
Electrochemical test was performed using a three-electrode system using CHI 760E electrochemical workstation (shanghai chenhua instruments ltd), a rotating disk electrode device (Pine, usa); the modified electrode is a working electrode, the platinum wire is a counter electrode, and the Ag/AgCl electrode is a reference electrode (the Ag/AgCl electrode is 2mol L-1H3PO4The relative reversible hydrogen electrode RHE is 0.215V, all potentials of the electrode are relative to RHE), 2mol L-1H3PO4Is an electrolyte solution, the test temperature is room temperature, the test atmosphere is nitrogen or oxygen, and the scanning speed is 10mV s-1The potential range is 0.06-1.2V vs.
Example 2:
weighing 1g of melamine and 1.2g of phosphorous acid, dissolving the melamine and the phosphorous acid in 100mL of deionized water, stirring the solution for 1h under the condition of a water bath at the temperature of 80 ℃, then placing the solution in a sealed high-pressure reaction kettle, reacting the solution for 10h at the temperature of 180 ℃, and naturally cooling the solution to room temperature; carrying out suction filtration on the obtained product, washing the product for a plurality of times by using deionized water, and drying the product for 8 hours at the temperature of 60 ℃ to obtain a precursor;
mixing 5ml of glycerol and 15ml of ethanol to obtain a mixed solution, adding 0.6g of the precursor obtained in the step 1, and strongly stirring until the mixture is uniformly mixed; then refluxing for 3h under the condition of oil bath at 90 ℃, and naturally cooling to room temperature; then carrying out suction filtration, washing with absolute ethyl alcohol for a plurality of times, and drying at 60 ℃ for 8 h; putting the dried intermediate product into a covered ceramic crucible, heating to 500 ℃ at the heating rate of 2 ℃ per minute, keeping for 2 hours, and naturally cooling to room temperature to obtain faint yellow graphite-phase carbon nitride nanosheets, marked as gC3N4；
s1, firstly, mixing isopropanol and ethylene glycol in a volume ratio of 1:3 to obtain a mixed solution; adding 15mg of the graphite phase carbon nitride nanosheet prepared in the step 2 into 40ml of the mixed solution, and stirring for 4 hours to obtain a dispersion liquid of the graphite phase carbon nitride nanosheet;
s2, firstly, mixing isopropanol and ethylene glycol in a volume ratio of 1:3 to obtain a mixed solution; adding 15mg of carbon black into 40ml of mixed solution, and stirring for 4 hours to obtain a carbon black dispersion liquid;
s3, mixing 5ml of the mixture with the concentration of 1.5mgPtml-1Firstly adding chloroplatinic acid into the ethylene glycol solution A to obtain a mixed solution B; then adding 50ml of ethylene glycol for uniform mixing, and adjusting the pH value of the mixed solution to 10 by using a mixed solution of sodium hydroxide and ethylene glycol, wherein the concentration of the sodium hydroxide in the mixed solution of the sodium hydroxide and the ethylene glycol is 2mol L-1(ii) a Then heating to 160 ℃ by using an oil bath, and refluxing for 3h at the temperature to obtain a brownish black Pt colloid solution; slowly dropping stoneStrongly stirring the ink-phase carbon nitride nanosheet dispersion liquid for 0.5 h; slowly dropping carbon black dispersion liquid; adjusting the pH value of the mixed solution E to be less than 4 by using a mixed solution of nitric acid and ethylene glycol, wherein the concentration of the nitric acid in the mixed solution of nitric acid and ethylene glycol is 5 wt%; stirring for 6h, then carrying out suction filtration, washing with deionized water for several times, drying in vacuum at 80 ℃ for 6h, and grinding to obtain the graphite phase carbon nitride nanosheet supported Pt nano electrocatalyst, recorded as Pt/gC3N4The Pt content was 20 wt%.
Electrode modification and testing:
(1) modification of working electrodes
2mg of Pt/gC3N4Adding 1ml of mixed solution of water and isopropanol into the mixed solution, then dripping 10 mu L of 5 wt% Nafion solution, and performing ultrasonic dispersion for 15min to obtain suspension; and (3) dripping 20 mu L of suspension liquid on a disc electrode, and airing at room temperature for later use.
(2) Electrochemical testing
Electrochemical test was performed using a three-electrode system using CHI 760E electrochemical workstation (shanghai chenhua instruments ltd), a rotating disk electrode device (Pine, usa); the modified electrode is a working electrode, the platinum wire is a counter electrode, and the Ag/AgCl electrode is a reference electrode (the Ag/AgCl electrode is 2mol L-1H3PO4The relative reversible hydrogen electrode RHE is 0.215V, all potentials of the electrode are relative to RHE), 2mol L-1H3PO4The test temperature is room temperature, the test atmosphere is nitrogen or oxygen, the ADT potential scanning range is 0.6-1.0V vs. RHE, the number of cycle scanning circles is 5000 circles, and the scanning speed is 100mV s-1。
Example 3:
weighing 1g of melamine and 1.2g of phosphorous acid, dissolving the melamine and the phosphorous acid in 100mL of deionized water, stirring the solution for 1h under the condition of a water bath at the temperature of 80 ℃, then placing the solution in a sealed high-pressure reaction kettle, reacting the solution for 10h at the temperature of 180 ℃, and naturally cooling the solution to room temperature; carrying out suction filtration on the obtained product, washing the product for a plurality of times by using deionized water, and drying the product for 8 hours at the temperature of 60 ℃ to obtain a precursor;
mixing 5ml of glycerol and 15ml of ethanol to obtain a mixed solution, adding 0.6g of the precursor obtained in the step 1, and strongly stirring until the mixture is uniformly mixed; then refluxing for 3h under the condition of oil bath at 90 ℃, and naturally cooling to room temperature; then carrying out suction filtration, washing with absolute ethyl alcohol for a plurality of times, and drying at 60 ℃ for 8 h; putting the dried intermediate product into a covered ceramic crucible, heating to 500 ℃ at the heating rate of 2 ℃ per minute, keeping for 2 hours, and naturally cooling to room temperature to obtain faint yellow graphite-phase carbon nitride nanosheets, marked as gC3N4；
s1, firstly, mixing isopropanol and ethylene glycol in a volume ratio of 1:3 to obtain a mixed solution; adding 15mg of the graphite phase carbon nitride nanosheet prepared in the step 2 into 40ml of the mixed solution, and stirring for 4 hours to obtain a dispersion liquid of the graphite phase carbon nitride nanosheet;
s2, firstly, mixing isopropanol and ethylene glycol in a volume ratio of 1:3 to obtain a mixed solution; adding 15mg of carbon nanofiber into 40ml of mixed solution, and stirring for 4 hours to obtain dispersion liquid of the carbon nanofiber;
s3, mixing 5ml of the mixture with the concentration of 1.5mgPtml-1Firstly adding chloroplatinic acid into the ethylene glycol solution A to obtain a mixed solution B; then adding 50ml of ethylene glycol for uniform mixing, and adjusting the pH value of the mixed solution to 10 by using a mixed solution of sodium hydroxide and ethylene glycol, wherein the concentration of the sodium hydroxide in the mixed solution of the sodium hydroxide and the ethylene glycol is 2mol L-1(ii) a Then heating to 160 ℃ by using an oil bath, and refluxing for 3h at the temperature to obtain a brownish black Pt colloid solution; slowly dripping graphite phase carbon nitride nanosheet dispersion liquid, and strongly stirring for 0.5 h; slowly dropping the dispersion liquid of the carbon nano fiber; adjusting the pH value of the mixed solution E to be less than 4 by using a mixed solution of nitric acid and ethylene glycol, wherein the concentration of the nitric acid in the mixed solution of nitric acid and ethylene glycol is 5 wt%; stirring for 6h, vacuum filtering, washing with deionized water for several times, vacuum drying at 80 deg.C for 6h, and grinding to obtain graphite phase sodium carbonitrideThe rice flake supported Pt nano electro-catalyst is marked as Pt/gC3N4The Pt content was 20 wt%.
And (3) performance testing:
(1) modification of working electrodes
Catalyst was changed to Pt/gC3N4The rest of the same as example 2.
(2) Electrochemical testing
Same as in example 2.
Example 4:
weighing 1g of melamine and 1g of phosphorous acid, dissolving in 100mL of deionized water, stirring for 2h under the condition of a water bath at 60 ℃, then placing in a sealed high-pressure reaction kettle, reacting for 24h at 120 ℃, and naturally cooling to room temperature; carrying out suction filtration on the obtained product, washing the product for a plurality of times by using deionized water, and drying the product for 10 hours at 100 ℃ to obtain a precursor;
mixing 5ml of glycerol and 5ml of ethanol to obtain a mixed solution, adding 0.6g of the precursor obtained in the step 1, and strongly stirring until the mixture is uniformly mixed; then refluxing for 6h under the condition of oil bath at 60 ℃, and naturally cooling to room temperature; then carrying out suction filtration, washing with absolute ethyl alcohol for a plurality of times, and drying at 60 ℃ for 8 h; putting the dried intermediate product into a covered ceramic crucible, heating to 350 ℃ at the heating rate of 2 ℃ per minute, keeping for 5 hours, and naturally cooling to room temperature to obtain faint yellow graphite-phase carbon nitride nanosheets, marked as gC3N4；
s1, firstly, mixing isopropanol and ethylene glycol in a volume ratio of 1:3 to obtain a mixed solution; adding 10mg of the graphite phase carbon nitride nanosheet prepared in the step 2 into 40ml of the mixed solution, and stirring for 4 hours to obtain a dispersion liquid of the graphite phase carbon nitride nanosheet;
s2, mixing isopropanol and ethylene glycol in a volume ratio of 1:3 to obtain a mixed solution; adding 50mg of graphene into 40ml of mixed solution, and stirring for 4 hours to obtain graphene dispersion liquid;
s3, mixing 10ml of the mixture with the concentration of 1.5mgPtml-1Firstly adding chloroplatinic acid into the ethylene glycol solution A to obtain a mixed solution B; then 100ml of ethylene glycol is added for even mixing, and the pH value of the mixed solution is adjusted to 10 by using the mixed solution of sodium hydroxide and ethylene glycol, wherein the concentration of the sodium hydroxide in the mixed solution of the sodium hydroxide and the ethylene glycol is 2mol L-1(ii) a Then heating to 160 ℃ by using an oil bath, and refluxing for 3h at the temperature to obtain a brownish black Pt colloid solution; slowly dripping graphite phase carbon nitride nanosheet dispersion liquid, and strongly stirring for 0.5 h; then dropwise adding a graphene dispersion liquid; adjusting the pH value of the mixed solution E to be less than 4 by using a mixed solution of nitric acid and ethylene glycol, wherein the concentration of the nitric acid in the mixed solution of nitric acid and ethylene glycol is 5 wt%; stirring for 6h, then carrying out suction filtration, washing with deionized water for several times, drying in vacuum at 80 ℃ for 6h, and grinding to obtain the graphite phase carbon nitride nanosheet supported Pt nano electrocatalyst, recorded as Pt/gC3N4. The Pt content was 20 wt%.
Electrode modification and testing:
(1) modification of working electrodes
2mg of Pt/gC3N4Adding 1ml of mixed solution of water and isopropanol into the mixed solution, then dripping 10 mu L of 5 wt% Nafion solution, and performing ultrasonic dispersion for 15min to obtain suspension; and (3) dripping 20 mu L of suspension liquid on a disc electrode, and airing at room temperature for later use.
(2) Electrochemical testing
Electrochemical test was performed using a three-electrode system using CHI 760E electrochemical workstation (shanghai chenhua instruments ltd), a rotating disk electrode device (Pine, usa); the modified electrode is a working electrode, the platinum wire is a counter electrode, and the Ag/AgCl electrode is a reference electrode (the Ag/AgCl electrode is 2mol L-1H3PO4The relative reversible hydrogen electrode RHE is 0.215V, all potentials of the electrode are relative to RHE), 2mol L-1H3PO4The test temperature is room temperature, the test atmosphere is nitrogen or oxygen, the ADT potential scanning range is 0.6-1.0V vs. RHE, and the steps are circulatedThe number of scanning turns is 5000 turns, and the scanning speed is 100mV s-1。
Example 5:
weighing 1g of melamine and 5g of phosphorous acid, dissolving in 100mL of deionized water, stirring for 0.5h under the condition of a water bath at 90 ℃, then placing in a sealed high-pressure reaction kettle, reacting for 6h at 200 ℃, and naturally cooling to room temperature; carrying out suction filtration on the obtained product, washing the product for a plurality of times by using deionized water, and drying the product for 5 hours at the temperature of 150 ℃ to obtain a precursor;
mixing 5ml of glycerol and 30ml of ethanol to obtain a mixed solution, adding 0.6g of the precursor obtained in the step 1, and strongly stirring until the mixture is uniformly mixed; then refluxing for 1h under the condition of oil bath at 120 ℃, and naturally cooling to room temperature; then carrying out suction filtration, washing with absolute ethyl alcohol for a plurality of times, and drying at 60 ℃ for 8 h; putting the dried intermediate product into a covered ceramic crucible, heating to 600 ℃ at the heating rate of 2 ℃ per minute, keeping for 1h, and naturally cooling to room temperature to obtain faint yellow graphite-phase carbon nitride nanosheets, marked as gC3N4；
s1, firstly, mixing isopropanol and ethylene glycol in a volume ratio of 1:3 to obtain a mixed solution; adding 15mg of the graphite phase carbon nitride nanosheet prepared in the step 2 into 40ml of the mixed solution, and stirring for 4 hours to obtain a dispersion liquid of the graphite phase carbon nitride nanosheet;
s2, mixing isopropanol and ethylene glycol in a volume ratio of 1:3 to obtain a mixed solution; adding 45mg of graphene into 40ml of mixed solution, and stirring for 4 hours to obtain graphene dispersion liquid;
s3, adding 10ml of chloroplatinic acid into the ethylene glycol solution A to obtain a mixed solution B, wherein the concentration of the chloroplatinic acid is 1.5mgPtml-1(ii) a Then 100ml of ethylene glycol is added for even mixing, and the mixed solution pH is adjusted by using the mixed solution of sodium hydroxide and ethylene glycolThe value is 10, wherein the concentration of the sodium hydroxide in the mixed solution of the sodium hydroxide and the ethylene glycol is 2mol L-1(ii) a Then heating to 180 ℃ by using an oil bath, and refluxing for 1h at the temperature to obtain a brownish black Pt colloid solution; slowly dripping graphite phase carbon nitride nanosheet dispersion liquid, and strongly stirring for 0.5 h; then dropwise adding a graphene dispersion liquid; adjusting the pH value of the mixed solution E to be less than 4 by using a mixed solution of nitric acid and ethylene glycol, wherein the concentration of the nitric acid in the mixed solution of nitric acid and ethylene glycol is 5 wt%; stirring for 6h, then carrying out suction filtration, washing with deionized water for several times, drying in vacuum at 80 ℃ for 6h, and grinding to obtain the graphite phase carbon nitride nanosheet supported Pt nano electrocatalyst, recorded as Pt/gC3N4. The Pt content was 20 wt%.
Comparative example 1:
preparing a graphite phase carbon nitride nanosheet precursor;
weighing 1g of melamine and 1.2g of phosphorous acid, dissolving the melamine and the phosphorous acid in 100mL of deionized water, stirring the solution for 1h under the condition of a water bath at the temperature of 80 ℃, then placing the solution in a sealed high-pressure reaction kettle, reacting the solution for 10h at the temperature of 180 ℃, and naturally cooling the solution to room temperature; carrying out suction filtration on the obtained product, washing the product for a plurality of times by using deionized water, and drying the product for 8 hours at the temperature of 60 ℃ to obtain a precursor;
mixing 5ml of glycerol and 15ml of ethanol to obtain a mixed solution, adding 0.6g of the precursor obtained in the step 1, and strongly stirring until the mixture is uniformly mixed; then refluxing for 3h under the condition of oil bath at 90 ℃, and naturally cooling to room temperature; then carrying out suction filtration, washing with absolute ethyl alcohol for a plurality of times, and drying at 60 ℃ for 8 h; putting the dried intermediate product into a covered ceramic crucible, heating to 500 ℃ at the heating rate of 2 ℃ per minute, keeping for 2 hours, and naturally cooling to room temperature to obtain faint yellow graphite-phase carbon nitride nanosheets, marked as gC3N4。
Electrode modification and testing:
(1) modification of working electrodes
2mg of gC3N4Adding into 1ml mixed solution of water and isopropanol, dropping 10 μ L5 wt% Nafion solution, and ultrasonic dispersing for 15minObtaining a suspension; and (3) dripping 20 mu L of suspension liquid on a disc electrode, and airing at room temperature for later use.
(2) Electrochemical testing
Electrochemical test was performed using a three-electrode system using CHI 760E electrochemical workstation (shanghai chenhua instruments ltd), a rotating disk electrode device (Pine, usa); the modified electrode is a working electrode, the platinum wire is a counter electrode, and the Ag/AgCl electrode is a reference electrode (the Ag/AgCl electrode is 2mol L-1H3PO4The relative reversible hydrogen electrode RHE is 0.215V, all potentials of the electrode are relative to RHE), 2mol L-1H3PO4Is an electrolyte solution, the test temperature is room temperature, the test atmosphere is nitrogen or oxygen, and the scanning speed is 10mV s-1The potential range is 0.06-1.2V vs.
Comparative example 2:
adding 2mg of commercial Pt/C (Pt content 20 wt%) catalyst into 1ml of a mixed solution of water and isopropanol, then dropping 10. mu.L of 5 wt% Nafion solution, and performing ultrasonic dispersion for 15min to obtain a suspension; 20 mu L of suspension liquid is dripped on a disk electrode and is aired at room temperature for standby, and the electrochemical test method is the same as that of the embodiment 2.
In FIG. 1, FIGS. a, b and c show Pt/gC prepared in example 13N4TEM images at different magnifications, a diagram shows the prepared gC3N4For the nano-platelet structure, b diagram illustrates Pt particles at gC3N4The distribution is very uniform, and the graph c can calculate that the particle size of the Pt particles is about 1.9 nm; FIG. d, e is the Pt/gC prepared in example 23N4TEM image of/C at different magnifications, d-diagram shows Pt particles mainly along carbon spheres and gC3N4The carbon spheres can enhance the conductivity of the catalyst carrier and can play a role in space confinement to Pt particles to a certain extent so as to be more stable, and the particle size of the Pt particles is about 2.1nm according to the e diagram.
FIG. 2 is gC3N4，Pt/gC3N4,Pt/gC3N42mol L of Pt/C saturated with nitrogen-1H3PO4CV diagram (1). gC3N4And Pt/gC3N4CV diagrams of the compounds are almost overlapped, and obvious H adsorption and desorption peaks can be seen at 0.05-0.35V after C is added, which indicates that gC3N4The conductivity is poor, but the performance of the catalyst is obviously improved after C is added.
FIG. 3 shows Pt/gC before and after ADT3N4C2 mol L saturated with nitrogen-1H3PO4CV diagram in (1); the desorption peak of H after ADT was slightly decreased, and the electrochemical specific surface area of Pt was found to be 87.6% of that before ADT by calculation.
FIG. 4 shows Pt/gC before and after ADT3N4At 2mol L saturated with oxygen-1H3PO4LSV map of (1). The latter half-slope potential of ADT was reduced by 17 mV.
FIG. 5 shows Pt/C at 2mol L after nitrogen saturation before and after ADT-1H3PO4CV diagram (1). The desorption peak of H after ADT is obviously reduced, and the calculation shows that the electrochemical specific surface area of Pt is 54.2 percent of that before ADT, compared with Pt/gC3N487.6% of/C, indicating Pt/gC3N4The stability of the/C is better than that of the commercial Pt/C.
FIG. 6 shows Pt/C at 2mol L after oxygen saturation before and after ADT-1H3PO4LSV map of (1). The post-half-slope potential of ADT is reduced by 32mV compared to Pt/gC3N417mV of/C, indicating Pt/gC3N4The stability of the/C is better than that of the commercial Pt/C.
As can be seen from the above examples and comparative examples, the carbon material-modified graphite-phase carbon nitride-supported platinum nano electrocatalyst disclosed by the present invention has excellent electrochemical catalytic performance and electrochemical corrosion resistance, compared to commercial Pt/C catalysts.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (10)
1. A preparation method of a carbon material modified graphite phase carbon nitride nanosheet loaded platinum nanometer electrocatalyst is characterized by comprising the following specific steps:
step 1, adding melamine and phosphorous acid into deionized water for dissolving, then stirring for a period of time under the condition of water bath, placing the stirred mixture into a sealed high-pressure reaction kettle for reaction, and performing suction filtration, washing and drying after the reaction to obtain a precursor;
step 2, mixing glycerol and ethanol to obtain a mixed solution; adding the precursor obtained in the step 1, refluxing under the condition of oil bath, cooling, washing by absolute ethyl alcohol, and drying to obtain an intermediate product; calcining the intermediate product to obtain a graphite-phase carbon nitride nanosheet;
step 3, preparing a carbon material modified graphite phase carbon nitride nanosheet supported platinum nano electro-catalyst:
s1, firstly, mixing isopropanol and ethylene glycol to obtain a mixed solution; adding the graphite phase carbon nitride nanosheets prepared in the step 2, and stirring for a period of time to obtain a dispersion liquid of the graphite phase carbon nitride nanosheets;
s2, mixing isopropanol and ethylene glycol to obtain a mixed solution; adding a carbon material, and stirring for a period of time to obtain a dispersion liquid of the carbon material;
s3, adding chloroplatinic acid into the ethylene glycol solution A to obtain a mixed solution B; and then adding an ethylene glycol solution C to obtain a mixed solution D, adjusting the pH value of the mixed solution D, heating to a certain temperature by using an oil bath for reflux, cooling to room temperature, slowly dropping a graphite-phase carbon nitride nanosheet dispersion liquid, uniformly stirring, slowly dropping a carbon material dispersion liquid to obtain a mixed solution E, stirring for the second time, adjusting the pH value of the mixed solution E again after stirring, stirring for the third time, and performing suction filtration, washing and drying to obtain the carbon material modified graphite-phase carbon nitride nanosheet supported platinum nano electrocatalyst.
2. The method for preparing the carbon material modified graphite-phase carbon nitride nanosheet supported platinum nano electrocatalyst according to claim 1, wherein in step 1, the ratio of the melamine, the phosphorous acid and the deionized water is 1g: 1-5 g: 100 mL; the temperature of the water bath is 60-90 ℃, and the stirring is carried out for a period of time of 0.5-2 hours; the temperature for reaction in the high-pressure reaction kettle is 120-200 ℃, and the time is 6-24 hours.
3. The method for preparing the carbon material modified graphite phase carbon nitride nanosheet supported platinum nano electrocatalyst according to claim 1, wherein in step 2, the mass ratio of glycerol to ethanol is 1: 1-6; the dosage ratio of the precursor to the mixed solution is 0.6 g: 10 to 50 ml.
4. The preparation method of the carbon material modified graphite phase carbon nitride nanosheet supported platinum nano electrocatalyst according to claim 1, wherein in the step 2, the temperature of the oil bath is 60-120 ℃, and the refluxing time is 1-6 h; the calcining temperature is 350-600 ℃, the heating rate is 2 ℃/min, and the time is 1-5 h; the thickness of the graphite phase carbon nitride nanosheet is 0.5-100 nm.
5. The method for preparing the carbon material modified graphite phase carbon nitride nanosheet supported platinum nano electrocatalyst according to claim 1, wherein in step 3, in S1, the volume ratio of the isopropanol to the ethylene glycol is 1: 3; the dosage ratio of the graphite-phase carbon nitride nanosheet to the mixed solution is 10-50 mg:40 mL; the stirring is carried out for 3-5 h.
6. The method for preparing the carbon material modified graphite phase carbon nitride nanosheet supported platinum nano electrocatalyst according to claim 1, wherein in step 3, in S2, the volume ratio of the isopropanol to the ethylene glycol is 1: 3; the dosage ratio of the carbon material to the mixed solution is 10-50 mg:40 mL; the carbon material is one or more of carbon black, activated carbon, graphene, carbon nanofiber, carbon nanotube or carbon nanosphere.
7. The method for preparing the carbon material modified graphite phase carbon nitride nanosheet supported platinum nano electrocatalyst according to claim 1, wherein in step 3, in S3, the chloroplatinic acid (H) is used2Pt6·6H2O) concentration of chloroplatinic acid in the mixed solution of ethylene glycol solution was 1.5mgPtml-1(ii) a The volume ratio of the mixed solution B to the glycol solution C is 1: 5-20; the pH value is adjusted to 9-14 by using a mixed solution of sodium hydroxide and ethylene glycol; the concentration of the sodium hydroxide in the mixed solution of the sodium hydroxide and the ethylene glycol is 2mol L-1。
8. The method for preparing the carbon material modified graphite phase carbon nitride nanosheet supported platinum nano electrocatalyst according to claim 1, wherein in step 3, in S3, the oil bath is heated to a certain temperature of 100-180 ℃ and the refluxing time is 1-5 h; the time for the second stirring is 0.5-2 hours, and the time for the third stirring is 4-10 hours; the pH value of the mixed solution E is adjusted to be less than 4 by using a mixed solution of nitric acid and glycol, wherein the concentration of the nitric acid in the mixed solution of nitric acid and glycol is 5 wt%; the mass ratio of the platinum in the carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electro-catalyst is 1-60 wt%; the mass ratio of the graphite-phase carbon nitride nanosheets to the carbon material is 1: 0-5.
9. The method for preparing the carbon material modified graphite phase carbon nitride nanosheet supported platinum nano electrocatalyst according to claim 1, wherein in the steps 1 to 3, the drying temperature is 60 to 150 ℃ and the drying time is 5 to 10 hours.
10. The catalyst prepared by the method according to any one of claims 1 to 9 is applied to a high-temperature membrane fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911300012.5A CN111129510B (en) | 2019-12-16 | 2019-12-16 | Preparation method and application of carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electro-catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911300012.5A CN111129510B (en) | 2019-12-16 | 2019-12-16 | Preparation method and application of carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electro-catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111129510A true CN111129510A (en) | 2020-05-08 |
| CN111129510B CN111129510B (en) | 2022-07-22 |
Family
ID=70499221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911300012.5A Active CN111129510B (en) | 2019-12-16 | 2019-12-16 | Preparation method and application of carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electro-catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111129510B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113943949A (en) * | 2021-10-21 | 2022-01-18 | 南京林业大学 | Platinum edge-modified nickel-based nano material and preparation method and application thereof |
| CN115845893A (en) * | 2022-10-14 | 2023-03-28 | 景德镇陶瓷大学 | Method for in-situ construction of metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure and product thereof |
| CN116053487A (en) * | 2023-01-31 | 2023-05-02 | 广东工业大学 | Platinum-rare earth alloy catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100041544A1 (en) * | 2007-05-10 | 2010-02-18 | Nanjing University | Electrode Catalyst of Carbon Nitride Nanotubes Supported by Platinum and Ruthenium Nanoparticles and Preparation Method Thereof |
| CN103928691A (en) * | 2014-04-10 | 2014-07-16 | 哈尔滨工业大学 | Platinum-based catalyst carrier of direct methanol fuel cell and preparation method thereof |
| CN105244513A (en) * | 2015-09-28 | 2016-01-13 | 南京理工大学 | Graphite-phase carbon nitride-modified carbon black-loaded platinum-palladium alloy nano electrocatalyst and preparation method |
| CN109772418A (en) * | 2019-03-05 | 2019-05-21 | 苏州大学 | P-doped tubulose carbonitride micro Nano material and its application in exhaust fume catalytic processing |
| CN110064429A (en) * | 2019-05-31 | 2019-07-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of sulfur doping azotized carbon nano piece and products thereof and application |
-
2019
- 2019-12-16 CN CN201911300012.5A patent/CN111129510B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100041544A1 (en) * | 2007-05-10 | 2010-02-18 | Nanjing University | Electrode Catalyst of Carbon Nitride Nanotubes Supported by Platinum and Ruthenium Nanoparticles and Preparation Method Thereof |
| CN103928691A (en) * | 2014-04-10 | 2014-07-16 | 哈尔滨工业大学 | Platinum-based catalyst carrier of direct methanol fuel cell and preparation method thereof |
| CN105244513A (en) * | 2015-09-28 | 2016-01-13 | 南京理工大学 | Graphite-phase carbon nitride-modified carbon black-loaded platinum-palladium alloy nano electrocatalyst and preparation method |
| CN109772418A (en) * | 2019-03-05 | 2019-05-21 | 苏州大学 | P-doped tubulose carbonitride micro Nano material and its application in exhaust fume catalytic processing |
| CN110064429A (en) * | 2019-05-31 | 2019-07-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of sulfur doping azotized carbon nano piece and products thereof and application |
Non-Patent Citations (1)
| Title |
|---|
| ZHAO LU ET AL.: "Enhanced visible-light photocatalytic performance of highly-dispersed Pt/g-C3N4 nanocomposites by one-step solvothermal treatment", 《RSC. ADV.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113943949A (en) * | 2021-10-21 | 2022-01-18 | 南京林业大学 | Platinum edge-modified nickel-based nano material and preparation method and application thereof |
| CN115845893A (en) * | 2022-10-14 | 2023-03-28 | 景德镇陶瓷大学 | Method for in-situ construction of metal-doped two-dimensional carbon nitride nanosheet/carbon nanotube multilevel structure and product thereof |
| CN115845893B (en) * | 2022-10-14 | 2024-03-05 | 景德镇陶瓷大学 | Method for in-situ construction of metal-doped two-dimensional carbon nitride nano sheet/carbon nano tube multi-stage structure and product thereof |
| CN116053487A (en) * | 2023-01-31 | 2023-05-02 | 广东工业大学 | Platinum-rare earth alloy catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111129510B (en) | 2022-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101733094B (en) | Pt-CeO2/graphene electro-catalyst and preparation method thereof | |
| CN111129510B (en) | Preparation method and application of carbon material modified graphite phase carbon nitride nanosheet loaded platinum nano electro-catalyst | |
| CN104923204A (en) | Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst | |
| CN102513139B (en) | Pt-WC (Wolfram Carbide)/ graphene composite electric catalyst and preparation method thereof | |
| CN103227334A (en) | Carbon-containing metal catalyst, preparation method and application thereof | |
| CN110201715B (en) | Non-noble metal CO derived from iron-doped polymers2Reductive composite catalyst, preparation method and application thereof | |
| CN111569928B (en) | MOFs-derived carbon-based material anchored high-dispersion metal Pt nanocluster and preparation method and application thereof | |
| CN103537299A (en) | Carbon-loaded Co core-Pt shell nanoparticle catalyst as well as preparation method thereof | |
| CN112838225A (en) | Fuel cell catalyst and preparation method and application thereof | |
| Li et al. | PdNi nanoparticles decorated on defective mesoporous carbon: An efficient bifunctional electrocatalysts in alkaline direct methanol fuel cells | |
| CN109731599B (en) | 2D oxygen reduction catalyst Fe3O4Preparation method of @ FeNC nanosheet | |
| CN110534754A (en) | A kind of package Fe3The carbon nanotube and its preparation method and application of C nano crystalline substance | |
| WO2022099793A1 (en) | Orr catalyst material, preparation method therefor, and use thereof | |
| Yan et al. | Electrochemically corroded thick microporous NC layer encapsulated Pt/C as highly active and ultra-highly stable electrocatalyst for methanol oxidation and oxygen reduction reaction in acidic media | |
| Taei et al. | Electrocatalytic oxidation of ethanol on a glassy carbon electrode modified with a gold nanoparticle-coated hydrolyzed CaFe–Cl layered double hydroxide in alkaline medium | |
| CN104037427B (en) | A kind of preparation method of high active core shell structure catalyst and application thereof | |
| CN113707895B (en) | Preparation method and application of heterostructure catalyst with rich interface active sites | |
| CN112510217B (en) | Carbon-supported platinum yttrium catalyst and preparation method and application thereof | |
| CN114497583A (en) | Preparation method of PtRu/CN catalyst for fuel cell | |
| CN108325546A (en) | A kind of difunctional electrochemical catalyst | |
| CN103887530A (en) | Pt/(C-Pb) catalyst and preparation thereof | |
| CN113258085A (en) | Oxygen-containing silicon nanosheet supported noble metal catalyst and preparation method and application thereof | |
| TW201223634A (en) | Catalysts and methods for manufacturing the same | |
| CN112717980A (en) | Composite catalyst and preparation method and application thereof | |
| CN115092911B (en) | Has rich Fe-N x Preparation method and application of site bamboo-shaped N, F double-doped carbon nano tube |
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 |