CN111244487B - Proton exchange membrane fuel cell electrode catalyst, preparation method and proton exchange membrane fuel cell - Google Patents
Proton exchange membrane fuel cell electrode catalyst, preparation method and proton exchange membrane fuel cell Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- 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 relates to a proton exchange membrane fuel cell electrode catalyst, a preparation method and a proton exchange membrane fuel cell, and belongs to the technical field of proton exchange membrane fuel cells. The catalyst comprises a carrier and platinum loaded on the surface of the carrier, wherein the carrier is carbon nano particles loaded with graphite-like phase carbon nitride quantum dots. According to the electrode material provided by the invention, the surface of the carbon particles is subjected to carboxylation modification, the surface of the carbon particles is modified with graphite-like phase carbon nitride quantum dots with amino groups, amidation reaction between the amino groups and the carboxyl groups is realized, and after a metal platinum layer is obtained by in-situ growth on the surface, the conductivity of the electrode is improved by a nitrogen carbide material between platinum and carbon. The electrode material provided by the invention has higher output power when being applied to a proton exchange membrane fuel cell.
Description
Technical Field
The invention relates to a proton exchange membrane fuel cell electrode catalyst, a preparation method and a proton exchange membrane fuel cell, and belongs to the technical field of proton exchange membrane fuel cells.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the characteristics of high energy conversion efficiency and no pollution, and are very suitable for being used as power energy of green new energy automobiles. The fuel cell electric automobile can solve the environmental and energy problems caused by the development of the automobile industry, and brings a new opportunity for the future development of the automobile industry. However, the problem of high cost of fuel cells is a great challenge in the way of large-scale industrialization and commercialization of power fuel cells. Currently, the catalyst used in fuel cells is a Pt-based catalyst. According to the 2010 DOE annual report, if the fuel cell automobile is commercialized by the prior art, the demand of the automobile fuel cell on Pt resources is up to 1160 t every year, which far exceeds the annual production (about 200 t) of Pt worldwide. From the viewpoint of cost reduction and limited platinum resources, the development of highly active non-noble metal catalysts is imperative. In recent years, many studies have been focused on improving the stability and utilization rate of Pt-based cathode oxygen reduction (ORR) catalysts, improving the electrode structure to reduce Pt loading, and reducing the cost of fuel cells.
The cathode Pt/C catalyst widely used in PEMFCs is susceptible to aggregation under actual cell operating conditions, resulting in an increase in particle size and a decrease in oxygen reduction activity with an increase in operating time.
In the prior art, reference [1 ]]Provides a preparation method of the PtNi/C catalyst, which comprises the following steps: synthesizing PtNi alloy nanoparticles in a mixed solvent composed of diphenyl ether, oleylamine, oleic acid, dichlorobenzene and the like by using nickel acetate and platinum acetylacetonate as metal precursors, and then loading the PtNi alloy nanoparticles on a carbon carrier to obtain PtNi/C; in HClO4Acid treatment in solution, and finally treatment at 400 ℃ in an inert atmosphere. CN103280583A discloses a method for preparing a catalytic layer structure of a proton exchange membrane fuel cell: adding carbon powder and an electrolyte resin solution into isopropanol to obtain a mixed solution, performing ultrasonic treatment to uniformly mix the mixed solution, then dispersing the mixed solution onto a proton exchange membrane, and performing drying treatment to form a carbon powder layer on the membrane, thus obtaining the proton exchange membrane with the carbon powder layer; immersing the proton exchange membrane with the carbon powder layer into a solution containing a platinum precursor and a weak reducing agent, standing for 48-72 hours at room temperature, taking out the proton exchange membrane, repeatedly washing the proton exchange membrane with deionized water for several times, and then drying; and spraying a layer of electrolyte solution on the surface of the platinum nanowire catalyst, and then drying to obtain the catalyst layer structure of the proton exchange membrane fuel cell. However, this type of fuel cell electrode is produced by directly reducing a platinum precursor on the surface of activated carbon, and has a problem of poor conductivity.
Reference documents:
[1]Journal of the American Chemical Society，2011 ,133 ,14396-14403 .
disclosure of Invention
The purpose of the invention is: solves the problems of the prior art that the electrode platinum consumption of the proton exchange membrane fuel cell is too high and the conductivity of the supported catalyst is not good. According to the electrode material provided by the invention, the surface of the carbon particles is subjected to carboxylation modification, the surface of the carbon particles is modified with graphite-like phase carbon nitride quantum dots with amino groups, amidation reaction between the amino groups and the carboxyl groups is realized, and after a metal platinum layer is obtained by in-situ growth on the surface, the conductivity of the electrode is improved by a nitrogen carbide material between platinum and carbon. The electrode material provided by the invention has higher output power when being applied to a proton exchange membrane fuel cell.
A proton exchange membrane fuel cell electrode catalyst comprises a carrier and platinum loaded on the surface of the carrier, wherein the carrier is carbon nano particles loaded with graphite-like phase carbon nitride quantum dots.
The preparation method of the proton exchange membrane fuel cell electrode catalyst comprises the following preparation steps:
step a, preparing carboxyl modified nano activated carbon: adding 10-20 parts by weight of nano activated carbon into 50-80 parts by weight of concentrated nitric acid, heating to perform modification reaction, filtering the nano activated carbon after the reaction is finished, washing with deionized water, and drying to obtain carboxyl modified nano activated carbon;
step b, preparing the graphite-like phase carbon nitride quantum dots: uniformly mixing 5-8 parts of dicyandiamide, 200 parts of acetonitrile 180-one and 40-45 parts of diethylene glycol according to parts by weight, then carrying out reaction in a reaction kettle, separating a product after the reaction is finished, and drying to obtain the graphite-like phase carbon nitride quantum dots;
c, spraying a carbon film: uniformly mixing 10-15 parts by weight of carboxyl modified nano activated carbon, 25-30 parts by weight of Nafion solution and 4000 parts by weight of isopropanol 2000-containing agent to obtain dispersion liquid, uniformly spraying the dispersion liquid on the surface of a proton exchange membrane, and drying to obtain a supporting layer loading a carbon membrane;
d, loading the carbon nitride quantum dots on a carrier: the weight ratio of the graphite-like carbon nitride quantum dots to the deionized water is 1: 100-140 as a suspension; soaking the supporting layer loaded with the carbon membrane in the suspension, heating to react, and after the reaction is finished, cleaning and drying by using deionized water to obtain the supporting layer containing the carrier;
step e, in-situ deposition of platinum: preparing an aqueous solution containing a platinum precursor and a reducing agent, soaking a support layer containing a carrier in the aqueous solution to perform a reduction reaction, and after the reaction is finished, washing with deionized water and drying to obtain the catalyst loaded with platinum.
In one embodiment, the nano-activated carbon has an average particle size of 50 to 200 nm.
In one embodiment, the temperature of the modification reaction in step a is 55 to 65 ℃ and the time of the modification reaction is 1 to 3 hours.
In one embodiment, the temperature of the reaction in step b is 210 ℃ and 230 ℃, and the time of the reactive reaction is 20-60 h.
In one embodiment, the concentration of the resin in the Nafion solution in step c is 5-10 w%.
In one embodiment, the concentrations of the platinum precursor and the reducing agent in step e are 0.1-0.2wt% and 3-5wt%, respectively; the reaction temperature is 20-35 ℃, and the reaction time is 20-60 h; the platinum precursor is selected from chloroplatinic acid, and the reducing agent is selected from one of ascorbic acid, formic acid or acetic acid.
The proton exchange membrane fuel cell adopts the proton exchange membrane fuel cell electrode catalyst.
The application of the catalyst in a proton exchange membrane fuel cell.
The invention also provides application of the carboxyl modified nano activated carbon in a fuel cell electrode catalyst.
Advantageous effects
According to the electrode material provided by the invention, the surface of the carbon particles is subjected to carboxylation modification, the surface of the carbon particles is modified with graphite-like phase carbon nitride quantum dots with amino groups, amidation reaction between the amino groups and the carboxyl groups is realized, and after a metal platinum layer is obtained by in-situ growth on the surface, the conductivity of the electrode is improved by a nitrogen carbide material between platinum and carbon. The electrode material provided by the invention has higher output power when being applied to a proton exchange membrane fuel cell.
Drawings
FIG. 1 is a TEM photograph of the catalyst prepared by the present invention.
Figure 2 is an XRD pattern of the catalyst prepared according to the present invention.
Fig. 3 is a graph of the output power of a cell prepared according to the present invention.
Fig. 4 is a graph of the output voltage of a cell prepared according to the present invention.
Detailed Description
EXAMPLE 1 preparation of proton exchange Membrane Fuel cell electrode catalyst
Step a, preparing carboxyl modified nano activated carbon: adding 15g of nano activated carbon with the average particle size of 100nm into 60g of concentrated nitric acid, heating to perform modification reaction, reacting for 2 hours at 60 ℃, filtering the nano activated carbon after the reaction is finished, washing with deionized water, and drying to obtain carboxyl modified nano activated carbon;
step b, preparing the graphite-like phase carbon nitride quantum dots: uniformly mixing 7g of dicyandiamide, 190g of acetonitrile and 42g of diethylene glycol, then carrying out reaction in a reaction kettle at 220 ℃ for 40h, separating a product after the reaction is finished, and drying to obtain graphite-like phase carbon nitride quantum dots;
c, spraying a carbon film: uniformly mixing 12g of carboxyl modified nano activated carbon, 28g of 5w% Nafion solution and 3500g of isopropanol to obtain dispersion liquid, uniformly spraying the dispersion liquid on the surface of a proton exchange membrane, and drying to obtain a supporting layer for loading a carbon membrane;
d, loading the carbon nitride quantum dots on a carrier: the weight ratio of the graphite-like carbon nitride quantum dots to the deionized water is 1: 120 as a suspension; soaking the supporting layer loaded with the carbon membrane in the suspension, heating to react, and after the reaction is finished, cleaning and drying by using deionized water to obtain the supporting layer containing the carrier;
step e, in-situ deposition of platinum: preparing an aqueous solution containing a platinum precursor chloroplatinic acid and a reducing agent ascorbic acid, wherein the concentrations of the platinum precursor and the reducing agent are 0.15wt% and 4wt%, respectively, soaking a support layer containing a carrier in the aqueous solution to perform a reduction reaction, and after the reaction is finished, washing with deionized water and drying to obtain the catalyst loaded with platinum.
EXAMPLE 2 preparation of proton exchange Membrane Fuel cell electrode catalyst
Step a, preparing carboxyl modified nano activated carbon: adding 10g of nano activated carbon with the average particle size of 100nm into 50g of concentrated nitric acid, heating to perform modification reaction, reacting for 1h at 70 ℃, filtering the nano activated carbon after the reaction is finished, washing with deionized water, and drying to obtain carboxyl modified nano activated carbon;
step b, preparing the graphite-like phase carbon nitride quantum dots: uniformly mixing 5g of dicyandiamide, 180g of acetonitrile and 40g of diethylene glycol, then carrying out reaction in a reaction kettle, reacting for 20 hours at 210 ℃, separating a product after the reaction is finished, and drying to obtain graphite-like phase carbon nitride quantum dots;
c, spraying a carbon film: uniformly mixing 10g of carboxyl modified nano activated carbon, 25g of 5w% Nafion solution and 2000g of isopropanol to obtain dispersion liquid, uniformly spraying the dispersion liquid on the surface of a proton exchange membrane, and drying to obtain a supporting layer loaded with a carbon membrane;
d, loading the carbon nitride quantum dots on a carrier: the weight ratio of the graphite-like carbon nitride quantum dots to the deionized water is 1: 100 as a suspension; soaking the supporting layer loaded with the carbon membrane in the suspension, heating to react, and after the reaction is finished, cleaning and drying by using deionized water to obtain the supporting layer containing the carrier;
step e, in-situ deposition of platinum: preparing an aqueous solution containing a platinum precursor chloroplatinic acid and a reducing agent ascorbic acid, wherein the concentrations of the platinum precursor and the reducing agent are 0.1wt% and 3wt%, respectively, soaking a support layer containing a carrier in the aqueous solution to perform a reduction reaction, and after the reaction is finished, washing with deionized water and drying to obtain the catalyst loaded with platinum.
EXAMPLE 3 preparation of proton exchange Membrane Fuel cell electrode catalyst
Step a, preparing carboxyl modified nano activated carbon: adding 20g of nano activated carbon with the average particle size of 100nm into 80g of concentrated nitric acid, heating to perform modification reaction, reacting for 3 hours at 50 ℃, filtering the nano activated carbon after the reaction is finished, washing with deionized water, and drying to obtain carboxyl modified nano activated carbon;
step b, preparing the graphite-like phase carbon nitride quantum dots: uniformly mixing 8g of dicyandiamide, 200g of acetonitrile and 45g of diethylene glycol, then carrying out reaction in a reaction kettle, reacting for 60 hours at 230 ℃, separating a product after the reaction is finished, and drying to obtain graphite-like phase carbon nitride quantum dots;
c, spraying a carbon film: uniformly mixing 15g of carboxyl modified nano activated carbon, 30g of 10w% Nafion solution and 4000g of isopropanol to obtain dispersion liquid, uniformly spraying the dispersion liquid on the surface of a proton exchange membrane, and drying to obtain a supporting layer for loading a carbon membrane;
d, loading the carbon nitride quantum dots on a carrier: the weight ratio of the graphite-like carbon nitride quantum dots to the deionized water is 1: 140 as a suspension; soaking the supporting layer loaded with the carbon membrane in the suspension, heating to react, and after the reaction is finished, cleaning and drying by using deionized water to obtain the supporting layer containing the carrier;
step e, in-situ deposition of platinum: preparing an aqueous solution containing a platinum precursor chloroplatinic acid and a reducing agent ascorbic acid, wherein the concentrations of the platinum precursor and the reducing agent are 0.2wt% and 5wt%, respectively, soaking a support layer containing a carrier in the aqueous solution to perform a reduction reaction, and after the reaction is finished, washing with deionized water and drying to obtain the catalyst loaded with platinum.
Comparative example 1
The difference from example 1 is that the nano activated carbon is not modified by carboxyl group.
Step a, preparing carboxyl modified nano activated carbon: adding 15g of nano activated carbon with the average particle size of 100nm into 60g of concentrated nitric acid, heating to perform modification reaction, reacting for 2 hours at 60 ℃, filtering the nano activated carbon after the reaction is finished, washing with deionized water, and drying to obtain carboxyl modified nano activated carbon;
step b, preparing the graphite-like phase carbon nitride quantum dots: uniformly mixing 7g of dicyandiamide, 190g of acetonitrile and 42g of diethylene glycol, then carrying out reaction in a reaction kettle at 220 ℃ for 40h, separating a product after the reaction is finished, and drying to obtain graphite-like phase carbon nitride quantum dots;
c, spraying a carbon film: uniformly mixing 12g of carboxyl modified nano activated carbon, 28g of 5w% Nafion solution and 3500g of isopropanol to obtain dispersion liquid, uniformly spraying the dispersion liquid on the surface of a proton exchange membrane, and drying to obtain a supporting layer for loading a carbon membrane;
d, loading the carbon nitride quantum dots on a carrier: the weight ratio of the graphite-like carbon nitride quantum dots to the deionized water is 1: 120 as a suspension; soaking the supporting layer loaded with the carbon membrane in the suspension, heating to react, and after the reaction is finished, cleaning and drying by using deionized water to obtain the supporting layer containing the carrier;
step e, in-situ deposition of platinum: preparing an aqueous solution containing a platinum precursor chloroplatinic acid and a reducing agent ascorbic acid, wherein the concentrations of the platinum precursor and the reducing agent are 0.15wt% and 4wt%, respectively, soaking a support layer containing a carrier in the aqueous solution to perform a reduction reaction, and after the reaction is finished, washing with deionized water and drying to obtain the catalyst loaded with platinum.
EXAMPLE 2 preparation of proton exchange Membrane Fuel cell electrode catalyst
Step a, preparing carboxyl modified nano activated carbon: adding 10g of nano activated carbon with the average particle size of 100nm into 50g of concentrated nitric acid, heating to perform modification reaction, reacting for 1h at 70 ℃, filtering the nano activated carbon after the reaction is finished, washing with deionized water, and drying to obtain carboxyl modified nano activated carbon;
step b, preparing the graphite-like phase carbon nitride quantum dots: uniformly mixing 5g of dicyandiamide, 180g of acetonitrile and 40g of diethylene glycol, then carrying out reaction in a reaction kettle, reacting for 20 hours at 210 ℃, separating a product after the reaction is finished, and drying to obtain graphite-like phase carbon nitride quantum dots;
c, spraying a carbon film: uniformly mixing 10g of carboxyl modified nano activated carbon, 25g of 5w% Nafion solution and 2000g of isopropanol to obtain dispersion liquid, uniformly spraying the dispersion liquid on the surface of a proton exchange membrane, and drying to obtain a supporting layer loaded with a carbon membrane;
d, loading the carbon nitride quantum dots on a carrier: the weight ratio of the graphite-like carbon nitride quantum dots to the deionized water is 1: 100 as a suspension; soaking the supporting layer loaded with the carbon membrane in the suspension, heating to react, and after the reaction is finished, cleaning and drying by using deionized water to obtain the supporting layer containing the carrier;
step e, in-situ deposition of platinum: preparing an aqueous solution containing a platinum precursor chloroplatinic acid and a reducing agent ascorbic acid, wherein the concentrations of the platinum precursor and the reducing agent are 0.1wt% and 3wt%, respectively, soaking a support layer containing a carrier in the aqueous solution to perform a reduction reaction, and after the reaction is finished, washing with deionized water and drying to obtain the catalyst loaded with platinum.
Comparative example 2
The difference from example 1 is that interlayer supporting was not performed using graphite-like phase carbon nitride.
Step a, preparing the graphite-like phase carbon nitride quantum dots: uniformly mixing 7g of dicyandiamide, 190g of acetonitrile and 42g of diethylene glycol, then carrying out reaction in a reaction kettle at 220 ℃ for 40h, separating a product after the reaction is finished, and drying to obtain graphite-like phase carbon nitride quantum dots;
step b, spraying a carbon film: uniformly mixing 12g of nano activated carbon with the average particle size of 100nm, 28g of 5w% Nafion solution and 3500g of isopropanol to obtain dispersion liquid, uniformly spraying the dispersion liquid on the surface of a proton exchange membrane, and drying to obtain a supporting layer for loading a carbon membrane;
step c, loading of the carbon nitride quantum dots on the carrier: the weight ratio of the graphite-like carbon nitride quantum dots to the deionized water is 1: 120 as a suspension; soaking the supporting layer loaded with the carbon membrane in the suspension, heating to react, and after the reaction is finished, cleaning and drying by using deionized water to obtain the supporting layer containing the carrier;
step d, in-situ deposition of platinum: preparing an aqueous solution containing a platinum precursor chloroplatinic acid and a reducing agent ascorbic acid, wherein the concentrations of the platinum precursor and the reducing agent are 0.15wt% and 4wt%, respectively, soaking a support layer containing a carrier in the aqueous solution to perform a reduction reaction, and after the reaction is finished, washing with deionized water and drying to obtain the catalyst loaded with platinum.
EXAMPLE 2 preparation of proton exchange Membrane Fuel cell electrode catalyst
Step a, preparing carboxyl modified nano activated carbon: adding 10g of nano activated carbon with the average particle size of 100nm into 50g of concentrated nitric acid, heating to perform modification reaction, reacting for 1h at 70 ℃, filtering the nano activated carbon after the reaction is finished, washing with deionized water, and drying to obtain carboxyl modified nano activated carbon;
step b, spraying a carbon film: uniformly mixing 10g of carboxyl modified nano activated carbon, 25g of 5w% Nafion solution and 2000g of isopropanol to obtain dispersion liquid, uniformly spraying the dispersion liquid on the surface of a proton exchange membrane, and drying to obtain a supporting layer loaded with a carbon membrane;
step c, in-situ deposition of platinum: preparing an aqueous solution containing a platinum precursor chloroplatinic acid and a reducing agent ascorbic acid, wherein the concentrations of the platinum precursor and the reducing agent are 0.1wt% and 3wt%, respectively, soaking a support layer containing a carrier in the aqueous solution to perform a reduction reaction, and after the reaction is finished, washing with deionized water and drying to obtain the catalyst loaded with platinum.
The catalyst is used as a cathode catalyst layer of a proton exchange membrane fuel cell, meanwhile, 10g of a commercial carbon platinum catalyst, 25g of 5w% Nafion solution and 2000g of isopropanol are uniformly mixed to obtain dispersion liquid, the dispersion liquid is uniformly sprayed on the back surface of a cathode membrane, and then drying is carried out to obtain an anode catalyst layer; and then respectively coating a layer of carbon paper on the surfaces of the cathode catalyst layer and the anode catalyst layer, and obtaining the single cell after hot pressing treatment.
Fig. 1 is a TEM image of the catalyst prepared by the present invention, and it can be seen that the graphite-like phase nitrogen carbide material is uniformly dispersed on the surface of the nano-carbon.
FIG. 2 is an XRD pattern of the catalyst prepared by the present invention, wherein peaks at 39.2 °, 45.8 ° and 67.2 ° are characteristic peaks of platinum, which correspond to the (111), (200) and (311) planes, respectively, and peaks at 9.7 ° and 15.7 ° and 30.2 ° are diffraction peaks of the produced graphite-like carbon nitride.
FIG. 3 is a graph showing the output of a single cell prepared, and it can be seen from the graph that the maximum output of a single cell prepared by the catalyst of example 1 is about 0.56W/cm2In comparative example 1, the maximum output of the single cell prepared from the catalyst was about 0.47W/cm2The carboxyl modification of the activated carbon can be carried out with amidation reaction with amino on the surface of the graphite-like phase nitrogen carbide material, so that the conductive transmission performance of the material is improved, and the output power is improved; the maximum output of the single cell obtained by the preparation of the catalyst of comparative example 2 was about 0.39W/cm2The result shows that the graphite-like phase nitrogen carbide material as the intermediate layer can effectively improve the conductivity of the catalytic material, so that the output power of the battery is obviously improved.
Fig. 4 is a voltage-current curve of the prepared single cell, and it can be seen that the single cell prepared by the catalyst of example 1 has a higher output voltage, and the conductivity is improved by the amidation reaction between the carboxyl group of the activated carbon and the amino group on the surface of the graphite-like phase nitrogen carbide material, thereby improving the output voltage of the battery.
Claims (6)
1. A proton exchange membrane fuel cell electrode catalyst comprises a carrier and platinum loaded on the surface of the carrier, and is characterized in that the carrier is carbon nano-particles loaded with graphite-like phase carbon nitride quantum dots;
the preparation method of the proton exchange membrane fuel cell electrode catalyst comprises the following preparation steps:
step a, preparing carboxyl modified nano activated carbon: adding 10-20 parts by weight of nano activated carbon into 50-80 parts by weight of concentrated nitric acid, heating to perform modification reaction, filtering the nano activated carbon after the reaction is finished, washing with deionized water, and drying to obtain carboxyl modified nano activated carbon;
step b, preparing the graphite-like phase carbon nitride quantum dots: uniformly mixing 5-8 parts of dicyandiamide, 200 parts of acetonitrile 180-one and 40-45 parts of diethylene glycol according to parts by weight, then carrying out reaction in a reaction kettle, separating a product after the reaction is finished, and drying to obtain the graphite-like phase carbon nitride quantum dots;
c, spraying a carbon film: uniformly mixing 10-15 parts by weight of carboxyl modified nano activated carbon, 25-30 parts by weight of Nafion solution and 4000 parts by weight of isopropanol 2000-containing agent to obtain dispersion liquid, uniformly spraying the dispersion liquid on the surface of a proton exchange membrane, and drying to obtain a supporting layer loading a carbon membrane;
d, loading the carbon nitride quantum dots on a carrier: the weight ratio of the graphite-like carbon nitride quantum dots to the deionized water is 1: 100-140 as a suspension; soaking the supporting layer loaded with the carbon membrane in the suspension, heating to react, and after the reaction is finished, cleaning and drying by using deionized water to obtain the supporting layer containing the carrier;
step e, in-situ deposition of platinum: preparing an aqueous solution containing a platinum precursor and a reducing agent, soaking a support layer containing a carrier in the aqueous solution to perform a reduction reaction, and after the reaction is finished, washing with deionized water and drying to obtain the catalyst loaded with platinum.
2. The pem fuel cell electrode catalyst of claim 1 wherein said nano-activated carbon has an average particle size of 50-200 nm.
3. The proton exchange membrane fuel cell electrode catalyst as claimed in claim 1, wherein the temperature of the modification reaction in step a is 55-65 ℃ and the time of the modification reaction is 1-3 h.
4. The PEM fuel cell electrode catalyst according to claim 1 wherein the reaction temperature in step b is 210-230 ℃ and the reaction time is 20-60 h.
5. The pem fuel cell electrode catalyst of claim 1 wherein the concentration of resin in the Nafion solution in step c is 5-10 w%.
6. The proton exchange membrane fuel cell electrode catalyst according to claim 1, wherein the concentrations of the platinum precursor and the reducing agent in step e are 0.1-0.2wt% and 3-5wt%, respectively; the reaction temperature is 20-35 ℃, and the reaction time is 20-60 h; the platinum precursor is selected from chloroplatinic acid, and the reducing agent is selected from one of ascorbic acid, formic acid or acetic acid.
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