CN115863676A - Preparation method of carbon-supported platinum electrocatalyst, carbon-supported platinum electrocatalyst and application - Google Patents
Preparation method of carbon-supported platinum electrocatalyst, carbon-supported platinum electrocatalyst and application Download PDFInfo
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- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
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Images
Abstract
The application relates to a preparation method of a carbon-supported platinum electrocatalyst, the carbon-supported platinum electrocatalyst and application, and belongs to the technical field of fuel cells. The preparation method of the carbon-supported platinum electrocatalyst comprises the following steps: heating and pretreating carbon black in a pretreatment solution to improve the hydrophilicity of the carbon black, and washing and drying the carbon black to obtain pretreated carbon black; mixing the pretreated carbon black, a platinum source, an impregnating solution and a complexing agent, heating and evaporating liquid, and drying to obtain a solid mixture; and (3) carrying out heat treatment on the solid mixture in a protective atmosphere, and loading the generated simple substance platinum on carbon black to obtain the carbon-supported platinum electrocatalyst. The electrochemical active area of the carbon-supported platinum electrocatalyst prepared by the preparation method provided by the application can reach 104m 2 /g (Pt) Much higher than the electrochemical active area of the carbon-supported platinum electrocatalyst of the traditional technology.
Description
Technical Field
The application relates to the technical field of fuel cells, in particular to a preparation method of a carbon-supported platinum electrocatalyst, the carbon-supported platinum electrocatalyst and application.
Background
A proton exchange membrane fuel cell (PFMFC) is a chemical device capable of directly converting hydrogen energy into electric energy, and the PFMFC comprises two electrodes, namely a cathode and an anode, wherein oxygen introduced into the cathode reacts with hydrogen introduced into the anode to release electric energy, and only water is discharged, so that the PFMFC is a recognized green power generation device.
Inside PEMFCs, a catalyst is one of the most critical constructions in fuel cells, with the highest cost ratio and the most direct performance impact, but is limited by factors such as process, cost and performance, and a carbon-supported platinum (Pt/C) nanoparticle catalyst is most widely used in engineering applications. Therefore, the utilization rate of the noble metal Pt is improved, and the use amount of the noble metal Pt is reduced, so that the method has great significance for promoting large-scale commercial application of the fuel cell.
The conventional technology discloses a preparation method of a platinum-carbon catalyst, which comprises the following steps: dissolving a platinum salt solution in an ethylene glycol solution to form a first mixed solution; dispersing the first mixed solution into a suspension prepared from carbon and ethylene glycol to form a second mixed solution; and heating and refluxing the second mixed solution in an alkaline environment to perform a first reaction, then cooling and performing a second reaction in an acidic environment, recovering the neutral environment of the second mixed solution, and drying to obtain the platinum-carbon catalyst. Although the preparation method can improve the preparation efficiency of the platinum-carbon catalyst, the prepared platinum metal nano particles are large, the average particle size is 2-4 nm, and the measured electrochemical activity area (ECSA) is 75m at most 2 /g (Pt) 。
The traditional technology also discloses a preparation method of the fuel cell catalyst, and the preparation method completes the reduction of the Pt precursor and the drying of the catalyst by combining microwave-assisted reduction, acid sedimentation and spray drying technologies without adopting a surfactant and a stabilizer, thereby greatly shortening the preparation time of the catalyst and reducing the agglomeration phenomenon of the catalyst. However, the ECSA of the catalyst prepared by the method is only 73.05m at most 2 /g (Pt) Corresponding to a commercial 40% platinum content catalyst from Johnson Matthey.
The traditional technology also discloses a preparation method of the carbon-supported platinum anode catalyst, which mainly comprises the steps of adsorption anchoring of Pt ions, in-situ reduction of Pt particles, removal and loading of a template agent and the like. Although the carbon-supported platinum anode catalyst prepared by the method has controllable particle size of Pt particles which are uniformly distributed on the surface of the carbon carrier, the reaction efficiency of the fuel cell and the utilization rate of the noble metal can be improved, the maximum ECSA of the carbon-supported platinum anode catalyst is only 67m 2 /g (Pt) 。
Therefore, how to prepare the Pt/C electrocatalyst with high electrochemical activity area by using a simple process is a problem to be solved in the current PEMFC engineering application.
Disclosure of Invention
Accordingly, there is a need for a method of preparing a platinum electrocatalyst on carbon, and applications thereof, wherein the method is simple and can increase the electrochemical active area.
In a first aspect of the present application, there is provided a method for preparing a platinum-on-carbon electrocatalyst, comprising the steps of:
heating and pretreating carbon black in a pretreatment solution, and washing and drying the carbon black to obtain pretreated carbon black;
mixing the pretreated carbon black, a platinum source, an impregnation solution and a complexing agent, heating to evaporate liquid, and drying to obtain a solid mixture;
carrying out heat treatment on the solid mixture in a protective atmosphere, and loading the generated simple substance platinum on the pretreated carbon black to obtain a carbon-loaded platinum electrocatalyst;
wherein the temperature of the heat treatment is 100-500 ℃, and the time of the heat treatment is 1-5 h.
In some embodiments, the mass ratio of the pretreated carbon black, the platinum source, the impregnation solution, and the complexing agent is 1: (0.1-5.0): (0.1-0.5): (0.1-3.0).
In some embodiments, the carbon black comprises one or more of XC-72, XC-72R, EC-300J, and EC-600 JD; preferably EC-300J.
In some embodiments, the pretreatment solution comprises one or more of an acid solution, a base solution, and an oxidizing solution;
optionally, the acid solution comprises one or more of nitric acid, sulfuric acid and hydrochloric acid;
optionally, the lye comprises one or more of a sodium hydroxide solution, a potassium hydroxide solution and a calcium hydroxide solution;
optionally, the oxidizing solution comprises one or more of a hydrogen peroxide solution and a peracetic acid solution.
In some embodiments, the temperature of the thermal pretreatment is 40 ℃ to 90 ℃, and the time of the thermal pretreatment is 1h to 10h.
In some embodiments, the platinum source comprises one or more of chloroplatinic acid, platinum acetylacetonate, potassium chloroplatinate, potassium chloroplatinite, platinum nitrate, and ammonium chloroplatinate.
In some embodiments, the complexing agent comprises one or more of sodium gluconate, sodium alginate, sodium edetate, sodium citrate, polyvinylpyrrolidone, cetyltrimethylammonium chloride, and cetyltrimethylammonium bromide.
In some embodiments, the impregnation solution comprises one or more of ethanol, isopropanol, and deionized water.
In some embodiments, the protective atmosphere comprises one or more of hydrogen, nitrogen, and argon.
In some embodiments, the particle size of elemental platinum in the carbon-supported platinum electrocatalyst is between 1nm and 2nm;
optionally, the mass percentage of the simple substance platinum in the carbon-supported platinum electrocatalyst is 5% to 70%.
A second aspect of the present application provides a platinum on carbon electrocatalyst prepared by the above preparation method.
In a third aspect of the present application, there is provided a carbon-supported platinum electrocatalyst prepared as described above or the use of the above-described carbon-supported platinum electrocatalyst for the preparation of a fuel cell.
Compared with the prior art, the preparation method of the carbon-supported platinum electrocatalyst, the carbon-supported platinum electrocatalyst and the application have at least the following advantages:
the preparation method has the advantages that the carbon black is pretreated, so that the hydrophilicity of the carbon black can be improved, the pretreated carbon black, the platinum source, the impregnation solution and the complexing agent are favorably and uniformly mixed, the agglomeration of simple substance platinum generated in the heat treatment process is avoided by controlling the heat treatment temperature and the heat treatment time, the simple substance platinum can be uniformly loaded on the pretreated carbon black carrier, the electrochemical active area of the carbon-supported platinum electrocatalyst can be further improved, the preparation method of the carbon-supported platinum electrocatalyst does not need complicated steps, and the operation is simple.
Drawings
FIG. 1 is a TEM image of a Pt/C electrocatalyst prepared in example 1 of the present application.
FIG. 2 is a TEM image of a Pt/C electrocatalyst prepared according to comparative example 5 in the present application.
FIG. 3 is a TEM image of a Pt/C electrocatalyst prepared according to comparative example 6 in the present application.
FIG. 4 is a graph of electrochemical CV scans of Pt/C electrocatalysts prepared in example 1 of the present application.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present application more comprehensible, specific embodiments thereof are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. This application is capable of embodiment in many different forms than those described herein and those skilled in the art will be able to make similar modifications without departing from the spirit of the application and therefore the application is not limited to the specific embodiments disclosed below.
In the description of the present application, unless otherwise defined, terms of art and terminology not specifically described have the same meaning as commonly understood by those skilled in the art and are common general knowledge of those skilled in the art, and methods not specifically described are conventional methods well known to those skilled in the art. The term "plurality" in this application means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present application, the technical features described in the open manner include a closed technical solution including the listed features, and also include an open technical solution including the listed features.
One embodiment of the present application provides a method for preparing a platinum-on-carbon electrocatalyst, comprising the steps of:
heating and pretreating carbon black in a pretreatment solution, and washing and drying to obtain pretreated carbon black;
mixing the pretreated carbon black, a platinum source, an impregnating solution and a complexing agent, heating and evaporating liquid, and drying to obtain a solid mixture;
carrying out heat treatment on the solid mixture in protective atmosphere, and loading the generated simple substance platinum on the pretreated carbon black to obtain a carbon-loaded platinum electrocatalyst;
wherein the heat treatment temperature is 100-500 ℃, and the heat treatment time is 1-5 h.
The preparation method has the advantages that the carbon black is pretreated, so that the hydrophilicity of the carbon black can be improved, the pretreated carbon black, the platinum source, the impregnation solution and the complexing agent are favorably and uniformly mixed, and when the solid mixture is subjected to heat treatment in a protective atmosphere, platinum ions in the platinum source are reduced into simple substance platinum to be loaded on the pretreated carbon black carrier, so that the carbon-loaded platinum electrocatalyst is formed. By controlling the heat treatment temperature and the heat treatment time, the agglomeration of the elemental platinum generated in the heat treatment process is avoided, the elemental platinum can be uniformly loaded on the pretreated carbon black carrier, and the electrochemical active area of the carbon-supported platinum electrocatalyst can be further improved. It is understood that the temperature of the heat treatment may be, for example, 100 ℃, 150 ℃, 200 ℃, 250 ℃,300 ℃, 350 ℃, 400 ℃, 450 ℃ or 500 ℃ and the time of the heat treatment may be, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours.
In some embodiments, the mass ratio of the carbon black, the platinum source, the impregnating solution, and the complexing agent after pretreatment is 1: (0.1-5.0): (0.1-0.5): (0.1-3.0). It will be appreciated that the mass ratio of carbon black, platinum source, impregnating solution and complexing agent after pretreatment may be, for example, 1:0.1:0.1:0.1, 1:0.1:0.2:0.3, 1:0.5:0.5:0.5, 1:0.5:0.5:2.0, 1:1.5:0.1:3.0, 1:2.0:0.5:3.0, 1:4.0:0.4:2.5 or 1:5.0:0.5:3.0, etc.
In some embodiments, the carbon black comprises one or more of XC-72, XC-72R, EC-300J, and EC-600 JD.
In some more specific embodiments, the carbon black comprises EC-300J.
In some embodiments, the pretreatment solution comprises one or more of an acid solution, a base solution, and an oxidizing solution. It can be understood that the pretreatment solution does not contain any toxic chemical substances, so that the preparation method of the carbon-supported platinum electrocatalyst is green, environment-friendly and environment-friendly.
In some embodiments, the acid solution comprises one or more of nitric acid, sulfuric acid, and hydrochloric acid. Understandably, the acid solution does not contain any toxic chemical substance, so that the preparation method of the carbon-supported platinum electrocatalyst is green, environment-friendly and environment-friendly. Specifically, the concentration of the acid solution is 0.05M-5M. For example, the acid solution may be at a concentration of 0.05M, 0.1M, 0.5M, 1M, 2M, 3M, 4M, or 5M, etc.
In some embodiments, the lye comprises one or more of a sodium hydroxide solution, a potassium hydroxide solution and a calcium hydroxide solution. It can be understood that the alkali liquor does not contain any toxic chemical substance, so that the preparation method of the carbon-supported platinum electrocatalyst is green, environment-friendly and environment-friendly. Specifically, the concentration of the alkali liquor is 0.05M-5M. For example, the concentration of the alkali solution may be 0.05M, 0.1M, 0.5M, 1M, 2M, 3M, 4M or 5M, etc.
In some embodiments, the oxidizing solution comprises one or more of a hydrogen peroxide solution and a peracetic acid solution. It can be understood that the oxidation solution does not contain any toxic chemical substances, so that the preparation method of the carbon-supported platinum electrocatalyst is green, environment-friendly and environment-friendly. Specifically, the concentration of the oxidizing solution is 0.05M to 5M. For example, the concentration of the oxidizing solution may be 0.05M, 0.1M, 0.5M, 1M, 2M, 3M, 4M, or 5M, etc.
In some embodiments, the temperature of the thermal pretreatment is 40 ℃ to 90 ℃ and the time of the thermal pretreatment is 1h to 10h. It will be appreciated that the temperature of the thermal pre-treatment may be any value between 40 ℃ and 90 ℃, for example: the heating pretreatment time may be, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours, etc., at 40 ℃, 45 ℃,50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, or 90 ℃.
In some embodiments, the source of platinum comprises one or more of chloroplatinic acid, platinum acetylacetonate, potassium chloroplatinate, platinum nitrate, and ammonium chloroplatinate. It can be understood that the platinum source does not contain any toxic chemical substances, so that the preparation method of the carbon-supported platinum electrocatalyst is green, environment-friendly and environment-friendly.
In some embodiments, the complexing agent comprises one or more of sodium gluconate, sodium alginate, sodium edetate, sodium citrate, polyvinylpyrrolidone, cetyltrimethylammonium chloride, and cetyltrimethylammonium bromide. It can be understood that the complexing agent does not contain any toxic chemical substance, so that the preparation method of the carbon-supported platinum electrocatalyst is green, environment-friendly and environment-friendly.
In some embodiments, the impregnation solution comprises one or more of ethanol, isopropanol, and deionized water. It can be understood that the impregnation solution does not contain any toxic chemical substances, so that the preparation method of the carbon-supported platinum electrocatalyst is green, environment-friendly and environment-friendly.
In some embodiments, the protective atmosphere comprises one or more of hydrogen, nitrogen, and argon.
In some embodiments, the particle size of the elemental platinum in the carbon-supported platinum electrocatalyst is between 1nm and 2nm. It is noted that when the particle size of the simple substance platinum in the carbon-supported platinum electrocatalyst is 1 nm-2 nm, the electrochemical active area of the prepared carbon-supported platinum electrocatalyst can reach 100m 2 /g (Pt) ～104m 2 /g (Pt) . It is understood that the particle size of the elemental platinum in the carbon-supported platinum electrocatalyst may be, for example, 1nm, 1.2nm, 1.4nm, 1.6nm, 1.8nm, 2nm, or the like.
In some embodiments, the elemental platinum is present in the carbon-supported platinum electrocatalyst in an amount in the range from 5% to 70% by weight. It is understood that the mass percentage of elemental platinum in the carbon-supported platinum electrocatalyst may be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%, and that the mass percentage of elemental platinum in the carbon-supported platinum electrocatalyst may also be other values between 5% and 70%.
Another embodiment of the present application provides a platinum-on-carbon electrocatalyst prepared by the above-described preparation method.
In still another embodiment, the present application provides a carbon-supported platinum electrocatalyst prepared by the above preparation method or an application of the above carbon-supported platinum electrocatalyst in preparing a fuel cell. For example, the carbon-supported platinum electrocatalyst prepared by the above preparation method or the above carbon-supported platinum electrocatalyst may be used in an oxygen reduction reaction of a cathode of a fuel cell.
In order to further illustrate the present application, the following detailed description of the technical solutions of the present application is provided in connection with specific examples and comparative examples.
Example 1
The preparation method of the Pt/C electrocatalyst comprises the following steps:
s1, weighing 80mg of commercial carbon black EC-300J, mixing with 30mL of 0.1M sulfuric acid solution, then treating for 1h under a water bath heating condition at 70 ℃, fully washing after the treatment, and drying for later use;
s2, mixing the commercial carbon black pretreated in the step S1, potassium chloroplatinate, ethanol and sodium citrate according to a mass ratio of 1:0.1:0.2:0.3, uniformly mixing, heating to evaporate liquid, and drying to obtain a solid mixture;
and S3, carrying out heat treatment on the solid mixture obtained in the step S2 for 2h at 300 ℃ in a mixed protective atmosphere formed by hydrogen and argon to obtain the Pt/C electrocatalyst, wherein the mass percentage of Pt in the Pt/C electrocatalyst is 5%.
Example 2
The preparation method of the Pt/C electrocatalyst comprises the following steps:
s1, weighing 80mg of commercial carbon black EC-600JD and 30mL of 0.1M hydrochloric acid solution, mixing, treating for 1h under the water-bath heating condition of 70 ℃, fully washing after the treatment, and drying for later use;
s2, mixing the commercial carbon black pretreated in the step S1, potassium chloroplatinite, ethanol and sodium alginate according to a mass ratio of 1:5.0:0.5:3.0, uniformly mixing, heating to evaporate liquid, and drying to obtain a solid mixture;
and S3, carrying out heat treatment on the solid mixture obtained in the step S2 for 2h at 300 ℃ in a mixed protective atmosphere formed by hydrogen and argon to obtain the Pt/C electrocatalyst, wherein the mass percentage of Pt in the Pt/C electrocatalyst is 70%.
Example 3
The preparation method of the Pt/C electrocatalyst comprises the following steps:
s1, weighing 80mg of commercial carbon black XC-72R, mixing with 30mL of 0.1M sodium hydroxide solution, then treating for 1h under a water bath heating condition at 70 ℃, fully washing after the treatment, and drying for later use;
s2, mixing the commercial carbon black pretreated in the step S1, platinum acetylacetonate, isopropanol and hexadecyl trimethyl ammonium chloride according to a mass ratio of 1:3.0:0.4:2.0, uniformly mixing, heating to evaporate liquid, and drying to obtain a solid mixture;
s3, carrying out heat treatment on the solid mixture obtained in the step S2 for 1h at 500 ℃ in a mixed protective atmosphere formed by hydrogen and nitrogen to obtain the Pt/C electrocatalyst, wherein the mass percentage of Pt in the Pt/C electrocatalyst is 60%.
Example 4
The preparation method of the Pt/C electrocatalyst comprises the following steps:
s1, weighing 80mg of commercial carbon black XC-72, mixing the carbon black XC-72 with 30mL of 0.1M hydrogen peroxide solution, then treating for 1h under the water bath heating condition of 70 ℃, fully washing after the treatment, and drying for later use;
s2, mixing the commercial carbon black pretreated in the step S1, chloroplatinic acid, deionized water and sodium ethylene diamine tetracetate according to a mass ratio of 1:0.5:0.1:0.1, uniformly mixing, heating to evaporate liquid, and drying to obtain a solid mixture;
s3, carrying out heat treatment on the solid mixture obtained in the step S2 for 5 hours at 100 ℃ in a mixed protective atmosphere formed by hydrogen and nitrogen to obtain the Pt/C electrocatalyst, wherein the mass percentage of Pt in the Pt/C electrocatalyst is 20%.
Comparative example 1
The preparation method of the Pt/C electrocatalyst comprises the following steps:
s1, mixing commercial carbon black EC-300J, potassium chloroplatinate, ethanol and sodium citrate according to a mass ratio of 1:0.1:0.2:0.3, uniformly mixing, heating to evaporate liquid, and drying to obtain a solid mixture;
s3, carrying out heat treatment on the solid mixture obtained in the step S1 for 2h at 300 ℃ in a mixed protective atmosphere formed by hydrogen and nitrogen to obtain the Pt/C electrocatalyst, wherein the mass percentage of Pt in the Pt/C electrocatalyst is 5%.
Comparative example 2
The preparation method of the Pt/C electrocatalyst comprises the following steps:
s1, mixing commercial carbon black EC-600JD, potassium platinochloride, ethanol and sodium alginate according to a mass ratio of 1:5.0:0.5:3.0, uniformly mixing, heating to evaporate liquid, and drying to obtain a solid mixture;
s2, carrying out heat treatment on the solid mixture obtained in the step S1 for 2h at 300 ℃ in a mixed protective atmosphere formed by hydrogen and argon to obtain the Pt/C electrocatalyst, wherein the mass percentage of Pt in the Pt/C electrocatalyst is 70%.
Comparative example 3
The preparation method of the Pt/C electrocatalyst comprises the following steps:
s1, mixing commercial carbon black XC-72R, platinum acetylacetonate, isopropanol and hexadecyl trimethyl ammonium chloride according to a mass ratio of 1:3.0:0.4:2.0, uniformly mixing, heating to evaporate liquid, and drying to obtain a solid mixture;
s2, carrying out heat treatment on the solid mixture obtained in the step S1 for 1h at 500 ℃ in a mixed protective atmosphere formed by hydrogen and nitrogen to obtain the Pt/C electrocatalyst, wherein the mass percentage of Pt in the Pt/C electrocatalyst is 60%.
Comparative example 4
The preparation method of the Pt/C electrocatalyst comprises the following steps:
s1, mixing commercial carbon black XC-72, chloroplatinic acid, deionized water and sodium ethylene diamine tetracetate according to a mass ratio of 1:0.5:0.1:0.1, uniformly mixing, heating to evaporate liquid, and drying to obtain a solid mixture;
s2, carrying out heat treatment on the solid mixture obtained in the step S1 for 5 hours at 100 ℃ in a mixed protective atmosphere formed by hydrogen and nitrogen to obtain the Pt/C electrocatalyst, wherein the mass percentage of Pt in the Pt/C electrocatalyst is 20%.
Comparative example 5
Substantially the same as example 1, except that no sodium citrate was added as a complexing agent in step S2, and the mass ratio of the commercial carbon black, potassium chloroplatinate and ethanol after pretreatment in step S2 was 1:0.5:0.2.
comparative example 6
Substantially the same as in example 1, except that the temperature of the heat treatment of the solid mixture in step S3 was 600 ℃ and the time of the heat treatment was 5 hours.
Comparative example 7
Substantially the same as in example 1, except that the temperature of the heat treatment of the solid mixture in step S3 was 50 ℃ and the time of the heat treatment was 5 hours.
Comparative example 8
Substantially the same as in example 1, except that the temperature of the heat treatment of the solid mixture in step S3 was 300 ℃ and the time of the heat treatment was 6 hours.
Comparative example 9
Substantially the same as in example 1, except that the temperature of the heat treatment of the solid mixture in step S3 was 300 ℃ and the time of the heat treatment was 0.5 hour.
TEM test
TEM tests were performed on the Pt/C electrocatalysts prepared in example 1, comparative example 5 and comparative example 6, as shown in fig. 1 to 3. As can be seen from FIG. 1, the Pt nanoparticles of example 1 are uniformly distributed on the carbon black carrier, and have small particle size dispersion, the particle size is 1 nm-2 nm; as can be seen from FIG. 2, the Pt particles of comparative example 5 are large (average particle diameter of 8 nm), unevenly distributed on the carbon black support and are highly agglomerated; as can be seen from fig. 3, the Pt particles of comparative example 6 have large dispersion in particle size, serious agglomeration and uneven distribution on the carbon black support, and the particle size of the Pt particles can reach up to 10nm. The Pt/C electrocatalysts prepared in examples 2-4 were also subjected to TEM tests, and the results were similar to those of example 1. The Pt/C electrocatalyst prepared by the preparation method provided by the application has the advantages of small Pt nano-particles, small particle size dispersion and uniform distribution on a carbon black carrier.
Electrochemical testing
The Pt/C electrocatalysts prepared in examples 1-4 and comparative examples 1-9 are respectively prepared into slurry for electrochemical test, and the specific method comprises the following steps: adding 50 mu L of 5% Nafion solution, 2mL of deionized water and 2mL of isopropanol into the weighed catalyst in sequence; performing ultrasonic treatment with ultrasonic wave with power of not less than 200W for 30min to mix the slurry uniformly, wherein the water bath temperature is not more than 20 deg.C during the ultrasonic treatment; according to the loading amount of the catalyst Pt on the surface of the electrode of 20 mu g/cm 2 Uniformly dripping a proper amount of dispersed slurry on the surface of a smooth and clean disc electrode twice to ensure that the disc electrode is naturally and completely dried to be used as a working electrode; placing the electrodes in an electrolytic cell to form a three-electrode system, wherein the reference electrode is a Reversible Hydrogen Electrode (RHE), the counter electrode is a Pt sheet, and the electrolyte is N 2 A saturated 0.1M perchloric acid solution; then testing cyclic voltammetry curve, firstly activating the catalyst at the scanning speed of 200mV/s until the hydrogen desorption peak area is not increased any more, and then scanning for 3 circles at the speed of 20mV/s, wherein the potential scanning range is 0.025V-1.2V (relative to a reversible hydrogen electrode). The electrochemical active area (ESCA) of Pt in the Pt/C electrocatalyst was tested according to cyclic voltammetry curve, and the calculation method of ESCA was: integrating the hydrogen desorption curve in the voltage range of 0.025V-0.4V, and substituting the integrated value into the following formula to obtain the ESCA. The test results are shown in fig. 4 and table 1.
In the above calculation formula of ESCA, A is the integral area of the hydrogen desorption curve, V is the scanning speed, and M is Pt The amount of Pt on the surface of the electrode is used as the loading amount.
TABLE 1
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the claims. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the patent is subject to the appended claims, and the description and the drawings can be used for explaining the contents of the claims.
Claims (11)
1. A preparation method of a carbon-supported platinum electrocatalyst is characterized by comprising the following steps:
heating and pretreating carbon black in a pretreatment solution, and washing and drying to obtain pretreated carbon black;
mixing the pretreated carbon black, a platinum source, an impregnating solution and a complexing agent, heating and evaporating liquid, and drying to obtain a solid mixture;
carrying out heat treatment on the solid mixture in a protective atmosphere, and loading the generated simple substance platinum on the pretreated carbon black to obtain a carbon-loaded platinum electrocatalyst;
wherein the temperature of the heat treatment is 100-500 ℃, and the time of the heat treatment is 1-5 h.
2. The production method according to claim 1, wherein the mass ratio of the pretreated carbon black, the platinum source, the impregnation solution, and the complexing agent is 1: (0.1-5.0): (0.1-0.5): (0.1-3.0).
3. The method of claim 1, wherein the carbon black comprises one or more of XC-72, XC-72R, EC-300J, and EC-600 JD.
4. The method of claim 1, wherein the pre-treatment solution comprises one or more of an acid solution, a base solution, and an oxidizing solution;
optionally, the acid solution comprises one or more of nitric acid, sulfuric acid and hydrochloric acid;
optionally, the lye comprises one or more of a sodium hydroxide solution, a potassium hydroxide solution and a calcium hydroxide solution;
optionally, the oxidizing solution comprises one or more of a hydrogen peroxide solution and a peracetic acid solution.
5. The method according to claim 1, wherein the temperature of the heat pretreatment is 40 ℃ to 90 ℃ and the time of the heat pretreatment is 1 hour to 10 hours.
6. The method of claim 1, wherein the source of platinum comprises one or more of chloroplatinic acid, platinum acetylacetonate, potassium chloroplatinate, platinum nitrate, and ammonium chloroplatinate.
7. The method of claim 1, wherein the complexing agent comprises one or more of sodium gluconate, sodium alginate, sodium edetate, sodium citrate, polyvinylpyrrolidone, cetyltrimethylammonium chloride, and cetyltrimethylammonium bromide.
8. The method of claim 1, wherein the impregnating solution comprises one or more of ethanol, isopropanol, and deionized water.
9. The method according to any one of claims 1 to 8, wherein the particle size of elemental platinum in the carbon-supported platinum electrocatalyst is from 1nm to 2nm;
optionally, the mass percentage of the simple substance platinum in the carbon-supported platinum electrocatalyst is 5% to 70%.
10. A platinum-on-carbon electrocatalyst characterized by being prepared by the process according to any one of claims 1 to 9.
11. Use of the carbon-supported platinum electrocatalyst prepared by the preparation method according to any one of claims 1 to 9 or the carbon-supported platinum electrocatalyst according to claim 10 for the preparation of a fuel cell.
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