CN108963282A - A kind of fuel cell carbon carried platinum-based catalyst and the preparation method and application thereof of solvent-thermal method reduction - Google Patents

Abstract

The invention discloses a method for preparing a fuel cell carbon-supported platinum-based catalyst by a solvothermal method, which is applied to proton exchange membrane fuel cells, including hydrogen-oxygen fuel cells and direct alcohol fuel cell cathode reactions, and belongs to the field of electrochemical catalytic reactions . The present invention uses solvothermal reduction treatment, fully disperses the carrier carbon material in the solvent, adds the metal precursor solution under stirring, and the mass percentage content of the active component reaches 20wt% to 60wt% in the prepared catalyst, and uses The alkaline solution adjusts the pH value of the solution to above 9, and then reacts the mixed solution in a high-temperature and high-pressure sealed reaction vessel. After the reaction, an acidic solution is used to adjust the pH value to be lower than 5, and the reaction solution is filtered, washed, dried and ground to obtain a carbon-supported platinum-based electrocatalyst. The catalyst active component prepared by the invention has a small particle size, is highly uniformly dispersed on the carbon carrier, and has relatively high activity. The preparation process of the invention has the advantages of simple operation, fast reaction, less energy consumption, low cost, and easy realization of industrialized production in large quantities.

Description

A kind of solvothermal reduction fuel cell carbon-supported platinum-based catalyst and preparation method thereof and application

technical field

The invention belongs to the field of proton exchange membrane fuel cell catalysts, including hydrogen-oxygen fuel cell catalysts and direct alcohol fuel cell catalysts, and relates to a preparation method of a carbon-supported platinum-based material, in particular to a solvent using a sealed reaction vessel under high temperature and high pressure Thermal preparation methods and applications.

Background technique

A fuel cell is an energy conversion device that converts chemical energy into electrical energy. It has attracted people's attention due to its advantages of high energy conversion efficiency, low environmental pollution, and convenient fuel portability. Proton exchange membrane fuel cell (PEMFC) has attracted much attention due to its advantages of high energy density, low operating temperature and no pollution. There are generally two sources of fuel for PEMFC: one directly uses pure hydrogen or reformed hydrogen-rich gas as fuel, which is called hydrogen-oxygen fuel cell; the other directly uses small organic molecules as fuel, which is called direct fuel cell, such as direct use Methanol (ethanol) fuel cells are called direct alcohol fuel cells (DAFC). The hydrogen-oxygen fuel cell, which uses hydrogen as the raw material gas, is the most ideal chemical power source. The electrochemical reaction product that occurs when it works is clean water, without any pollution to the environment. Direct methanol fuel cells have been widely studied in the past 20 years because they use solid polymer proton exchange membranes as electrolytes, directly use liquid methanol as fuel, and do not require external reforming, and are considered to be developed into portable electronic devices and electric vehicles. The vehicle's power supply.

However, the cathode oxygen reduction reaction (ORR) is the bottleneck that limits the performance of PEMFCs, and due to its slow kinetic rate, efficient and stable ORR catalysts are necessary. The catalysts currently used have disadvantages such as high cost, short life, and easy deactivation. Therefore, the development of highly active cathode catalysts is of great significance for the commercial application of PEMFC.

Carbon-supported platinum-based (Pt/C) catalysts are currently widely used cathode catalysts in proton exchange membrane fuel cells. Although the precious metal Pt required for the catalyst is scarce and expensive, it is still considered as the best fuel cell cathode catalyst due to its good stability in the electrolyte and high ORR catalytic activity. At present, Pt/C catalysts are still a research hotspot in proton exchange membrane fuel cell catalysts, both in basic research and application development.

At present, the production methods of Pt/C include impregnation reduction method, pulse microwave-assisted polyol reduction method, protective agent method, reflux method, colloid method and microemulsion method, etc., among which different preparation methods are used. , particle size, stability and other physical and chemical properties play a decisive role, and these physical and chemical properties are closely related to the activity of the catalyst; hinder. For example, the protective agent method can prepare highly dispersed nano-noble metal particles by using surfactants or other organic macromolecules as protective agents, and load them on the carrier. With high metal dispersion, alloy catalysts of various elements can be prepared. However, this method has high requirements on solvents, surfactants or protective agents and operating conditions, and at the same time, the operation is complicated, the cost is high, and it is not easy to produce in large quantities.

Contents of the invention

Aiming at the deficiencies of the existing preparation technology, the object of the present invention is to provide a method for preparing a carbon-supported platinum-based electrocatalyst for fuel cells by using a sealed reaction vessel at high temperature and high pressure. The present invention can prepare highly active carbon-supported platinum-based catalysts simply, effectively and at low cost. Since the reaction is a next step reaction under high temperature and high pressure conditions, the reaction is very easy to expand production; meanwhile, the prepared catalyst particles are small and The particle size distribution is uniform, and the catalytic activity is better than that of the current commercial carbon-supported platinum base.

The purpose of the present invention and the solution to its technical problems are achieved by adopting the following technical solutions. A method for preparing a carbon-supported platinum-based electrocatalyst using a fuel cell according to the present invention, the method comprises the following steps:

1) Uniformly disperse the carbon-based material in the alcohol solution by ultrasonic and stirring; specifically, at room temperature, mix and fully disperse the carbon carrier and the alcohol reducing agent according to the mass ratio of 1:200-900;

2) Add a solution containing a noble metal precursor dropwise to the solution in step 1), and stir to obtain a mixed solution after fully dispersing; the quality of the noble metal in the noble metal precursor accounts for 20wt% to 60wt of the total mass of the carbon-supported platinum-based electrocatalyst %, the noble metal precursor is H ₂ PtCl ₆ ·6H ₂ O;

3) Using KOH alcohol solution or NaOH alcohol solution, adjust the pH value of the solution obtained in step 2) to 9-12, and fully disperse to obtain a mixed solution;

4) Place the mixed solution obtained in step 3) in a high-pressure sealed reaction container, heat it to 110-180°C with an external source, and heat it for 2-5 hours to obtain a reaction solution. After the reaction solution is naturally cooled to room temperature, drop by drop Add acid solution to adjust the pH to 1-4, and stir well;

5) Suction filter the reaction solution treated in step 4), and wash the filter cake with deionized water above 60°C until no chlorine ions are detected in the washing waste liquid, vacuum-dry the obtained filter cake, cool and grind to obtain solid powder.

In the preparation method of the carbon-supported platinum-based catalyst of the present invention, in step 1), the carbon carrier can specifically be XC-72 carbon powder, conductive carbon black, activated carbon, carbon nanotubes or ordered mesoporous carbon, etc.; The alcohol reducing agent is ethylene glycol, glycerol or propylene glycol.

In the preparation method of the carbon-supported platinum-based catalyst of the present invention, in step 3), the concentration of the alcohol solution is 1.0-5.0 mol/L, and the alcohol in the alcohol solution is ethylene glycol, propylene glycol or glycerol.

In the preparation method of the carbon-supported platinum-based catalyst of the present invention, in step 4), the reaction vessel used may specifically be a sealable high-pressure resistant vessel, including a stainless steel high-pressure sealed reaction vessel, a polytetrafluoroethylene high-pressure sealed reaction vessel, etc.; the acid used Specifically, it can be HNO ₃ aqueous solution, H ₂ SO ₄ aqueous solution or HCl aqueous solution; the concentration of the acid solution used is 0.1-3.0 mol/L, and the stirring time is more than 3 hours.

The catalyst prepared by the carbon-supported platinum-based catalyst preparation method of the invention can be applied to proton exchange membrane fuel cells, including hydrogen-oxygen fuel cell catalysts and direct alcohol fuel cells.

By means of the above technical solution, the present invention has the following advantages and beneficial effects:

1) The present invention uses a sealed reaction vessel to carry out the reaction under high temperature and high pressure conditions, which simply and effectively ensures the stability and consistency of the reaction environment, is not easily affected by the outside world and is easy to control, so it can easily expand the production scale and reduce production costs.

2) Since the organic polyhydric alcohol is used as a dispersant and a reducing agent at the same time, the sealed reaction vessel provides stable temperature and pressure, and a large number of dispersion methods are alternately carried out by stirring and ultrasonic dispersion, etc., the active material particles of the carbon-supported platinum-based catalyst are prepared Uniform, fine, and evenly dispersed, not easy to agglomerate, which improves the utilization rate of precious metals and reduces costs while ensuring performance.

3) Compared with the existing commercial catalysts, the performance of the catalyst prepared by the present invention is significantly improved.

Description of drawings

Fig. 1 is a transmission electron micrograph of the 20wt% Pt/C catalyst prepared in Example 1 of the present invention.

Fig. 2 is the XRD spectrum of the 20wt% Pt/C catalyst prepared in Example 1 of the present invention.

Fig. 3 is a linear voltammetry scan diagram of 20wt% Pt/C catalyst prepared in Example 1 of the present invention and 20wt% Pt/C commercial catalyst in 0.5mol/L H ₂ SO ₄ solution.

Fig. 4 is the XRD spectrum of the 20wt% Pt/C catalyst prepared in Example 2 of the present invention.

Fig. 5 is a cyclic voltammetry scan diagram of 20wt% Pt/C catalyst prepared in Example 2 of the present invention and 20wt% Pt/C commercial catalyst in 0.5mol/L H ₂ SO ₄ solution.

Fig. 6 is a transmission electron micrograph of the 40wt% Pt/C catalyst prepared in Example 3 of the present invention.

Fig. 7 is the XRD spectrum of the 60wt% Pt/C catalyst prepared in Example 4 of the present invention.

Fig. 8 is a comparison chart of dynamic current density between the 60wt% Pt/C catalyst prepared in Example 4 of the present invention and the 60wt% Pt/C commercial catalyst.

Fig. 9 is the XRD spectrum of the 20wt% Pt/C catalyst prepared in Example 5 of the present invention.

Fig. 10 is a linear voltammetry scan diagram of 20wt% Pt/C catalyst prepared in Example 5 of the present invention and 20wt% Pt/C commercial catalyst in 0.5mol/L H ₂ SO ₄ solution.

Fig. 11 is a comparison chart of dynamic current density between the 20wt% Pt/C catalyst prepared in Example 5 of the present invention and the 20wt% Pt/C commercial catalyst.

Detailed ways

The method for preparing the electrocatalyst of the present invention will be described in further detail below through specific preferred embodiments in conjunction with the accompanying drawings, but the present invention is not limited to the following embodiments.

The invention discloses a method for preparing a carbon-supported platinum-based catalyst for a fuel cell by a solvothermal method, in particular to a carbon-supported platinum-based catalyst prepared by a polyol solvothermal reduction method, which is applied to a proton exchange membrane fuel cell, including hydrogen-oxygen In the cathode reaction of fuel cells and direct alcohol fuel cells, it belongs to the field of electrochemical catalytic reactions. The present invention uses solvothermal reduction treatment, fully disperses the carrier carbon material in the solvent, adds the metal precursor solution under stirring, and the mass percentage content of the active component reaches 20wt% to 60wt% in the prepared catalyst, and uses The alkaline solution adjusts the pH value of the solution to above 9, and then reacts the mixed solution in a high-temperature and high-pressure sealed reaction vessel. After the reaction, an acidic solution is used to adjust the pH value to be lower than 5, and the reaction solution is filtered, washed, dried and ground to obtain a carbon-supported platinum-based electrocatalyst.

The catalyst active component prepared by the invention has a small particle size, is highly uniformly dispersed on the carbon carrier, and has relatively high activity. The preparation process of the invention has the advantages of simple operation, fast reaction, less energy consumption, low cost, and easy realization of industrialized production in large quantities.

The direct preparation of carbon-supported platinum-based catalysts by using the solvothermal method is a simple and easy method for uniformly mixing raw materials such as carbon supports, solvents, reducing agents, and metal salt solutions, and then placing them in a sealed reaction vessel for one-step heating. The method has a simple device, is very easy to expand the production scale, and has the advantages of environmental protection, low energy consumption and the like. On the other hand, since the reaction vessel can provide a certain temperature and pressure, the prepared carbon-supported platinum-based catalyst active material is uniformly dispersed and has a small particle size, which has better catalytic activity for the cathode and anode of the fuel cell.

Example 1

A method for preparing a carbon-supported platinum-based catalyst applied to a fuel cell, comprising the following process steps:

1) Weigh 80 mg of the purchased XC-72 with an analytical balance, add 40.00 mL of ethylene glycol solution, and disperse alternately by ultrasonication and stirring for more than 1 hour until XC-72 is evenly dispersed in the ethylene glycol solution;

2) Add 5.25mL chloroplatinic acid ethylene glycol solution (3.81mg/mL) dropwise, and stir to disperse for more than 3h;

3) Add dropwise 1mol/L NaOH ethylene glycol solution, adjust the pH value of the solution obtained in step 2) to 11, and fully disperse to obtain a mixed solution;

4) Place the mixed solution obtained in step 3) in a high-pressure sealed reaction vessel, heat it to 140°C with an external source, and heat it for 3 hours to obtain a reaction solution; after the reaction solution is naturally cooled to room temperature, add 0.5mol/L drop by drop HNO ₃ aqueous solution is adjusted to pH 3, and fully stirred for 8 hours;

5) The reaction solution treated in step 4) is filtered under low pressure, and the filter cake is washed with deionized water above 60° C. until no chlorine ions are detected in the washing waste liquid. The resulting filter cake was vacuum-dried at 80° C., cooled and then ground to obtain carbon-supported platinum-based solid powder.

The carbon-supported platinum-based catalyst obtained in Example 1 was used for transmission electron microscope analysis. As shown in FIG. 1 , the platinum active components were uniformly and clearly distributed on the carbon support. The catalyst has better dispersibility and less agglomeration; and the particle size is finer. According to the analysis of Figure 1 by mathematical statistics method, it can be concluded that the particle size of the platinum active component of the catalyst is about 2.0nm, so its specific surface area is relatively high.

Carry out XRD spectrum analysis with the carbon-supported platinum-based catalyst obtained in this embodiment 1, as can be seen from Fig. 2, the active component platinum of the 20wt%Pt/C catalyst prepared in this embodiment is a face-centered cubic structure, according to Scherrer (Scherrer) formula calculation, its particle size is less than 2.1nm, basically consistent with the particle size results shown in Figure 1.

The carbon-supported platinum-based catalyst prepared by the present invention was used to test its oxygen reduction reaction activity, and the carbon-supported platinum-based catalyst with a commercial platinum loading of 20 wt% was jointly tested for activity comparison.

The catalyst-coated glassy carbon electrode obtained in Example 1 was used as the working electrode, the platinum sheet electrode was used as the counter electrode, and the saturated calomel electrode was used as the reference electrode, and _0.5mol /L _H SO was used as the electrolyte for linear voltammetry scanning test. It can be seen that the oxygen reduction activity of this example is much higher than that of the 20wt% Pt/C commercial catalyst, and the linear voltammetry scan diagram of the experimental process is shown in accompanying drawing 3. The oxygen reduction onset potential of the catalyst prepared in this example is 0.95V , the half-wave potential is 0.82V, and the limiting current density is as high as -4.65mA/cm ² , both of which are better than 20wt%Pt/C commercial catalysts. It can be seen that the oxygen reduction activity of the catalyst prepared by the method of the present invention is significantly improved.

Example 2

A method for preparing a carbon-supported platinum-based catalyst applied to a fuel cell, comprising the following process steps:

1) Weigh 80 mg of the purchased XC-72 with an analytical balance, add 40.00 mL of ethylene glycol solution, and disperse alternately by ultrasonication and stirring for more than 1 hour until XC-72 is evenly dispersed in the ethylene glycol solution;

2) Add 5.25mL chloroplatinic acid ethylene glycol solution (3.81mg/mL) dropwise, and stir to disperse for more than 3h;

3) Add dropwise 2mol/L KOH ethylene glycol solution, adjust the pH value of the solution obtained in step 2) to 13, and fully disperse to obtain a mixed solution;

4) Place the mixed solution obtained in step 3) in a high-pressure sealed reaction vessel, heat it to 140°C with an external source, and heat it for 2 hours to obtain a reaction solution. After the reaction solution is naturally cooled to room temperature, add 0.5mol/L dropwise HCl aqueous solution adjusts the pH to 3, and fully stirs for 8 hours;

5) filter the reaction solution treated in step 4) under low pressure, and wash the filter cake with deionized water above 60°C until no chlorine ions are detected in the washing waste liquid, and vacuum-dry the obtained filter cake at 80°C, Grinding after cooling to obtain carbon-supported platinum-based solid powder.

Carry out XRD spectrum analysis with the carbon-supported platinum-based catalyst that this embodiment 2 obtains, as can be seen from Fig. 4, the active component platinum of the 20wt%Pt/C catalyst that this embodiment prepares is face-centered cubic structure, according to Scherrer (Scherrer) formula calculation, its particle size is about 3.2nm.

The carbon-supported platinum-based catalyst prepared by the present invention was used to test its oxygen reduction reaction activity, and the carbon-supported platinum-based catalyst with a commercial platinum loading of 20 wt% was jointly tested for activity comparison.

The catalyst-coated glassy carbon electrode obtained in this embodiment ₂ was used as the working electrode, the platinum sheet electrode was used as the counter electrode, and the saturated calomel electrode was used as the reference electrode, and _0.5mol /LH SO was used as the electrolyte for cyclic voltammetry The test, the cyclic voltammetry scan diagram of the test result is in accompanying drawing 5. It can be seen that the oxygen reduction onset potential of the catalyst prepared in this example is better than that of the 20wt% Pt/C commercial catalyst, and the oxygen reduction activity is higher than that of the 20wt% Pt/C commercial catalyst.

Example 3

A method for preparing a carbon-supported platinum-based catalyst applied to a fuel cell, comprising the following process steps:

1) Weigh 80 mg of purchased XC-72 with an analytical balance, add 35 mL of ethylene glycol solution, and disperse alternately by ultrasonication and stirring for more than 1 hour until XC-72 is uniformly dispersed in the ethylene glycol solution;

2) Add 10.5mL chloroplatinic acid ethylene glycol solution (3.81mg/mL) dropwise, and stir to disperse for more than 3h;

3) Add 1mol/L NaOH ethylene glycol solution dropwise, adjust the pH value of the solution obtained in step 2) to 13, and fully disperse to obtain a mixed solution;

4) Place the mixed solution obtained in step 3) in a high-pressure sealed reaction vessel, heat it to 140°C with an external source, and heat it for 5 hours to obtain a reaction solution. After the reaction solution is naturally cooled to room temperature, add 0.5mol/L dropwise HNO ₃ aqueous solution is adjusted to pH 3, and fully stirred for 8 hours;

5) Filter the reaction solution treated in step 4), and wash the filter cake with deionized water above 60°C until no chlorine ions are detected in the washing waste liquid, vacuum-dry the obtained filter cake at 80°C, and after cooling Grinding to obtain carbon-supported platinum-based solid powder.

The carbon-supported platinum-based catalyst obtained in Example 3 was analyzed by transmission electron microscopy. As shown in Figure 6, the platinum active component was evenly and clearly distributed on the carbon carrier. According to the analysis of Figure 6 by mathematical statistical methods, it can be drawn that the catalyst The particle size of the platinum active component is about 3.6nm. The particle size of the catalyst is finer, and it still maintains good dispersion and less agglomeration under the condition of higher platinum loading.

Example 4

A method for preparing a carbon-supported platinum-based catalyst applied to a fuel cell, comprising the following process steps:

1) Weigh 80 mg of purchased XC-72 with an analytical balance, add 40.00 mL of glycerol solution, and disperse by ultrasonication and stirring for more than 1 hour alternately, until XC-72 is evenly dispersed in the glycerol solution;

2) Add 15.75mL of chloroplatinic acid glycerol solution (3.81mg/mL) dropwise, and stir to disperse for more than 3h;

3) Add dropwise 1mol/L NaOH glycerin solution, adjust the pH value of the solution obtained in step 2) to 11, and fully disperse to obtain a mixed solution;

4) Place the mixed solution obtained in step 3) in a high-pressure sealed reaction vessel, heat it to 150°C with an external source, and heat it for 4 hours to obtain a reaction solution. After the reaction solution is naturally cooled to room temperature, add 0.5mol/L dropwise HNO ₃ aqueous solution is adjusted to pH 3, and fully stirred for 8 hours;

5) filter the reaction solution treated in step 4) under low pressure, and wash the filter cake with deionized water above 60°C until no chlorine ions are detected in the washing waste liquid, and vacuum-dry the obtained filter cake at 80°C, Grinding after cooling to obtain carbon-supported platinum-based solid powder.

Carry out XRD pattern analysis with the carbon-supported platinum-based catalyst obtained in this embodiment 4, as can be seen from Figure 7, the active component platinum of the 60wt%Pt/C catalyst prepared in this embodiment is a face-centered cubic structure, according to Scherrer (Scherrer) formula calculation, its platinum active component particle size is about 5.6nm.

The oxygen reduction reaction activity of the carbon-supported platinum-based catalyst prepared by the present invention was tested together with the commercialized carbon-supported platinum-based catalyst with a platinum loading of 60 wt%, and their kinetic current densities were compared.

The catalyst-coated glassy carbon electrode obtained in this embodiment ₄ is used as the working electrode, the platinum sheet electrode is used as the counter electrode, and the saturated calomel electrode is used as the reference electrode, and 0.5mol/ _LH SO is used as the electrolyte for linear voltammetry scanning The kinetic current density of the carbon-supported platinum-based catalyst with a commercial platinum loading of 60 wt% was tested and compared. It can be seen from Fig. 8 that the kinetic current density of the catalyst prepared in this example is as high as 0.718mA/cm ² , much higher than that of the 60wt% Pt/C commercial catalyst (0.234mA/cm ² ). This shows that the carbon-supported platinum-based catalyst prepared by the present invention is less controlled by the diffusion step in the oxygen reduction reaction process, and the mass transfer process can be carried out rapidly in the electrode reaction. Compared with the commercial carbon-supported platinum-based catalyst, this The carbon-supported platinum-based catalyst prepared by the invention has better kinetic reaction rate.

Example 5

A method for preparing a carbon-supported platinum-based catalyst applied to a fuel cell, comprising the following process steps:

1) Weigh 160 mg of the purchased XC-72 with an analytical balance, add 60.00 mL of ethylene glycol solution, and disperse alternately by ultrasonication and stirring for more than 1 hour until XC-72 is uniformly dispersed in the ethylene glycol solution;

2) Add 10.50mL chloroplatinic acid ethylene glycol solution (3.81mg/mL) dropwise, and stir to disperse for more than 3h;

3) Add dropwise 3mol/L NaOH ethylene glycol solution, adjust the pH value of the solution obtained in step 2) to 11, and fully disperse to obtain a mixed solution;

4) Place the mixed solution obtained in step 3) in a high-pressure sealed reaction vessel, heat it to 150°C with an external source, and heat it for 3 hours to obtain a reaction solution. After the reaction solution is naturally cooled to room temperature, add 0.5mol/LH ₂ SO ₄ aqueous solution to adjust the pH to 2, and fully stirred for 8 hours;

5) Filter the reaction solution treated in step 4), and wash the filter cake with deionized water above 60°C until no chlorine ions are detected in the washing waste liquid, vacuum-dry the obtained filter cake at 80°C, and after cooling Grinding to obtain carbon-supported platinum-based solid powder.

Carry out XRD pattern analysis with the carbon-supported platinum-based catalyst obtained in this embodiment 5, as can be seen from Figure 9, the active component platinum of the 20wt%Pt/C catalyst prepared in this embodiment is a face-centered cubic structure, according to Scherrer (Scherrer) formula calculation, the particle size of the platinum active component is about 4.2nm.

The carbon-supported platinum-based catalyst prepared by the present invention was used to test its oxygen reduction reaction activity, and the carbon-supported platinum-based catalyst with a commercial platinum loading of 20 wt% was jointly tested for activity comparison.

The glassy carbon electrode coated with the catalyst obtained in this embodiment 5 is used as the working electrode, the platinum sheet electrode is used as the counter electrode, and the saturated calomel electrode is used as the reference electrode, and _0.5mol / _LH SO is used as the electrolyte for linear voltammetry scanning test. It can be seen that the oxygen reduction activity of this example is much higher than that of the 20wt% Pt/C commercial catalyst. The linear voltammetry scan diagram of the experimental process is shown in Figure 10. The oxygen reduction onset potential of the catalyst prepared in this example is 0.95V. The half-wave potential of 0.82V is better than that of 20wt%Pt/C commercial catalyst. It can be seen that the oxygen reduction activity of the catalyst prepared by the method of the present invention is significantly improved.

The catalyst obtained in Example 5 was tested together with the commercial platinum-supported platinum-based catalyst with a platinum loading of 20 wt%, and their kinetic current densities were compared. It can be seen from Fig. 11 that the kinetic current density of the catalyst prepared in this example is as high as 0.545 mA/cm ² , which is much higher than that of the 20 wt% Pt/C commercial catalyst (0.094 mA/cm ² ). This shows that the carbon-supported platinum-based catalyst prepared by the present invention is less controlled by the diffusion step in the oxygen reduction reaction process, and the mass transfer process can be carried out rapidly in the electrode reaction. Compared with the commercial carbon-supported platinum-based catalyst, this The carbon-supported platinum-based catalyst prepared by the invention has better kinetic reaction rate.

The above is only a preferred embodiment of the present invention, and does not limit the present invention in any form, so any simple modification made to the above embodiments according to the technical essence of the present invention does not depart from the content of the technical solution of the present invention. , equivalent changes and modifications all still belong to the scope of the technical solution of the present invention.

Claims (10)

1. a preparation method of fuel cell carbon-supported platinum-based catalyst of solvothermal reduction, is characterized in that, the method may further comprise the steps: 1) At room temperature, mix and fully disperse the carbon carrier and the alcohol reducing agent according to the mass ratio of 1:200-900; 2) Add dropwise a solution containing a noble metal precursor to the mixed solution in step 1), and fully stir to obtain a mixed solution; 3) Add KOH alcohol solution or NaOH alcohol solution to the mixed solution obtained in step 2), adjust the pH value to 8-14, and stir fully to obtain the processed pre-reaction mixed solution; 4) Put the mixed solution obtained in step 3) in a sealed reaction container, control the reaction temperature at 120°C to 200°C, and heat for 1 to 6 hours to obtain the reaction solution. After the reaction solution is cooled to room temperature, add dropwise under stirring Adjust the pH of the acidic solution to 1-4, and stir for 2-12 hours; 5) Filter the reaction liquid obtained in step 4), and wash the filter cake with deionized water until no chlorine ions are detected in the washing waste liquid, dry the obtained filter cake and grind to obtain a solid powder. 2. method according to claim 1, is characterized in that: step 1) in, described carbon carrier is XC-72 carbon powder, conductive carbon black, gac, carbon nanotube or ordered mesoporous carbon etc.; The alcohol reducing agent is ethylene glycol, glycerol or propylene glycol. 3. The method according to claim 1, characterized in that: in step 2), the noble metal precursor is chloroplatinic acid (H ₂ PtCl ₆ 6H ₂ O) etc.; the carbon carrier is added dropwise with the noble metal precursor After solidification, it needs to be fully stirred to disperse, and the stirring time is 1 to 5 hours. 4. The method according to claim 3, characterized in that: in step 2), the mass of the noble metal in the noble metal precursor accounts for 20wt% to 60wt% of the total mass of the carbon-supported platinum-based electrocatalyst. 5. method according to claim 1, is characterized in that: step 3) in, the mass concentration in described NaOH alcoholic solution or KOH alcoholic solution is 3%～10%; Described alcoholic solvent comprises ethylene glycol, Glycerin or Propylene Glycol. 6. The method according to claim 1, characterized in that: in step ₄ ), the heating mode of the sealed reaction vessel is external heat or internal heat; the acidic solution comprises HNO aqueous solution, H ₂ SO aqueous solution or HCl aqueous solution _; using The concentration of the acidic solution is 0.1-3.0mol/L. 7. The method according to claim 6, characterized in that: in step 4), the reaction vessel used is a sealable high-pressure resistant vessel, including a stainless steel high-pressure sealed reaction vessel, a polytetrafluoroethylene high-pressure sealed reaction vessel, and the like. 8. The method according to claim 1, characterized in that: in step 5), the filtration methods include normal pressure filtration, low pressure filtration, pressure filtration, etc.; the temperature of the deionized water for washing the filter cake should be 20°C to 100°C ; Drying methods include vacuum drying, blast drying, freeze drying, etc. 9. The carbon-supported platinum-based electrocatalyst prepared by the method for preparing the carbon-supported platinum-based electrocatalyst according to any one of claims 1-8. 10. the prepared carbon-supported platinum-based catalyst prepared by the preparation method described in any one of claims 1-8, the application in the proton exchange membrane fuel cell, comprises hydrogen-oxygen fuel cell catalyst and direct alcohol fuel cell application.