CN115911424A - Noble metal/carbon catalyst, preparation method thereof and fuel cell - Google Patents
Noble metal/carbon catalyst, preparation method thereof and fuel cell Download PDFInfo
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Abstract
The application belongs to the technical field of catalysts, and particularly relates to a noble metal/carbon catalyst, a preparation method thereof and a fuel cell. The method comprises the following steps: introducing a polymer containing amino active groups on the surface of the carbon nano tube to obtain a functionalized carbon nano tube; mixing the functionalized carbon nano tube, the alkaline substance and the organic solvent; and adding the noble metal source solution and the stabilizer solution into the carbon nano tube mixed solution in a mixed state, carrying out thermal reduction reaction, and then carbonizing the solid powder to obtain the noble metal/carbon catalyst. According to the preparation method of the noble metal/carbon catalyst, the polymer containing the amino active group is introduced to the surface of the carbon nano tube, so that the carbon nano tube is prevented from agglomerating, the noble metal loading capacity and the loading uniformity are improved, and the small particle size is maintained. The noble metal/carbon catalyst with uniform load, small particles and stable combination is obtained.
Description
Technical Field
The application belongs to the technical field of catalysts, and particularly relates to a noble metal/carbon catalyst, a preparation method thereof and a fuel cell.
Background
The platinum Pt nano particles in the hydrogen fuel cell catalyst are very small, the particle size is about 3 nanometers, and the catalyst has a high specific surface area and is beneficial to improving the catalytic activity. But the high specific surface area leads the catalyst particles to have higher surface energy, and the catalyst particles have strong agglomeration tendency in the using process to reduce the surface energy and improve the stability. The hydrogen fuel cell has a wide range of voltage variation during operation, particularly at start-up and shut-down. When the hydrogen fuel cell operates at a low potential, the oxide film on the platinum surface disappears, and the platinum metal is exposed. If the voltage is increased at this time, the metal platinum is dissolved. During the continuous dissolution and precipitation process, loss and redistribution of platinum occurs, which leads to degradation of the platinum catalyst. The agglomeration and growth of platinum nano particles, and the loss and redistribution of platinum are reaction phenomena which cannot be completely eliminated in the operation of a fuel cell and can only be reduced to a certain extent, and the improvement of the performance of a catalyst carrier is one of effective means.
The search for a new catalyst carrier with high conductivity, high porosity and corrosion resistance to replace the traditional carbon black carrier is one of the important directions in recent research, and most of the research is the carbon nanotube carrier. The carbon nano tube has the characteristics of high specific surface area, high conductivity, good mass transfer performance and excellent corrosion resistance, and is expected to replace the traditional carbon material to become an excellent carrier of the fuel catalyst. However, in the reaction of loading Pt particles on carbon nanotubes, the size of the Pt particles is not easy to control, and the problems of large size, non-uniformity, agglomeration and the like are easy to occur.
Disclosure of Invention
The application aims to provide a noble metal/carbon catalyst, a preparation method thereof and a fuel cell, and aims to solve the problems that the particle size of noble metal particles such as platinum loaded in the existing noble metal/carbon catalyst is not easy to control, and the particle size of platinum is easy to be larger, uneven and agglomerated.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a noble metal/carbon catalyst, comprising the steps of:
introducing a polymer containing amino active groups on the surface of the carbon nano tube to obtain a functionalized carbon nano tube;
mixing the functionalized carbon nano tube, the alkaline substance and the organic solvent to obtain a carbon nano tube mixed solution;
adding a noble metal source solution and a stabilizer solution into the carbon nano tube mixed solution in a mixed state, carrying out thermal reduction reaction, and separating to obtain solid powder;
and carrying out carbonization treatment on the solid powder to obtain the noble metal/carbon catalyst.
In a second aspect, the present application provides a noble metal/carbon catalyst prepared by the above method, comprising a carbon nanotube substrate and noble metal nanoparticles supported on the surface of the carbon nanotube substrate.
In a third aspect, the present application provides a fuel cell comprising the noble metal/carbon catalyst prepared by the above method or the above noble metal/carbon catalyst.
According to the preparation method of the noble metal/carbon catalyst provided by the first aspect of the application, the carbon nano tube is purified to remove impurity components in the carbon nano tube, then the polymer containing amino active groups is introduced to the surface of the carbon nano tube, the active groups contained in the introduced polymer are not only beneficial to preventing the carbon nano tube from agglomerating, but also beneficial to subsequently fixing the metal catalyst, the loading capacity is improved, metal ions are prevented from agglomerating into large particles, the loading uniformity of the metal catalyst is improved, the small particle size is maintained, and the functionalized carbon nano tube is obtained. And then preparing the functionalized carbon nano tube, the alkaline substance and the organic solvent into a carbon nano tube mixed solution, adding a noble metal source solution and a stabilizer solution in a mixed state, carrying out thermal reduction reaction to enable the noble metal source to be uniformly loaded on the surface of the functionalized carbon nano tube, and reducing the noble metal source into metal simple substance particles to obtain solid powder. And (3) carbonizing the solid powder to carbonize organic components in the solid powder into a carbon material, thus obtaining the noble metal/carbon catalyst with uniform load, small particles and stable combination. The preparation method of the noble metal/carbon catalyst provided by the application is simple in process and suitable for industrial large-scale production and application.
According to the noble metal/carbon catalyst provided by the second aspect of the application, the noble metal nanoparticles are stably and uniformly distributed in the carbon nanotubes, and the noble metal nanoparticles have small particle size and high uniformity. Therefore, the noble metal/carbon catalyst has large active specific surface area, excellent catalytic performance, good catalyst stability and long service life.
The fuel cell provided by the third aspect of the application has high catalytic activity and good stability due to the inclusion of the noble metal/carbon catalyst, which is beneficial to improving the electrochemical performance of the fuel cell; and the cycle stability of the fuel cell can be improved, so that the service life of the fuel cell is prolonged.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a method of making a noble metal/carbon catalyst as provided in an embodiment of the present application;
FIG. 2 is a transmission electron micrograph of a noble metal/carbon catalyst provided in example 1 of the present application;
FIG. 3 is a transmission electron micrograph of a noble metal/carbon catalyst provided in example 2 of the present application;
FIG. 4 is a transmission electron micrograph of a noble metal/carbon catalyst provided in example 3 of the present application;
fig. 5 is a transmission electron micrograph of the noble metal/carbon catalyst provided in comparative example 1 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a alone, A and B together, and B alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In this application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the examples of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components according to the examples of the present application is scaled up or down within the scope disclosed in the examples of the present application. Specifically, the mass in the examples of the present application may be in units of mass known in the chemical field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1, a first aspect of the embodiments of the present application provides a method for preparing a noble metal/carbon catalyst, comprising the steps of:
s10, introducing a polymer containing amino active groups on the surface of the carbon nano tube to obtain a functionalized carbon nano tube;
s20, mixing the functionalized carbon nano tube, the alkaline substance and the organic solvent to obtain a carbon nano tube mixed solution;
s30, adding a noble metal source solution and a stabilizer solution into the carbon nano tube mixed solution in a mixed state, carrying out thermal reduction reaction, and separating to obtain solid powder;
s40, carrying out carbonization treatment on the solid powder to obtain the noble metal/carbon catalyst.
In the preparation method of the noble metal/carbon catalyst provided in the first aspect of the embodiment of the present application, a polymer containing an amino active group is introduced to the surface of a carbon nanotube, and the active group contained in the introduced polymer is not only beneficial to preventing the carbon nanotube from agglomerating, but also beneficial to subsequently fixing the metal catalyst, so that the loading capacity is improved, the metal ions are prevented from agglomerating into large particles, the loading uniformity of the metal catalyst is improved, and the small particle size is maintained, thereby obtaining the functionalized carbon nanotube. And then preparing the functionalized carbon nano tube, the alkaline substance and the organic solvent into a carbon nano tube mixed solution, adding a noble metal source solution and a stabilizer solution in a mixed state, carrying out thermal reduction reaction to enable the noble metal source to be uniformly loaded on the surface of the functionalized carbon nano tube, and reducing the noble metal source into metal simple substance particles to obtain solid powder. And (3) carbonizing the solid powder to carbonize organic components in the solid powder into carbon materials, thus obtaining the noble metal/carbon catalyst with uniform load, small particles and stable combination. The preparation method of the noble metal/carbon catalyst provided by the embodiment of the application is simple in process and suitable for industrial large-scale production and application.
In some possible implementations, in step S10, the step of preparing the functionalized carbon nanotube includes:
s11, obtaining a carbon nano tube, and purifying the carbon nano tube to obtain a purified carbon nano tube;
s12, dispersing the purified carbon nano tube in a polymer solution, mixing, and separating to obtain the functionalized carbon nano tube.
According to the embodiment of the application, the carbon nano tube is purified firstly, after impurity components are removed, the polymer containing the amino active group is introduced to the surface of the carbon nano tube for functionalization treatment, and the improvement of the purity of the product is facilitated.
In some possible implementations, in step S11, the step of purifying includes: and (3) refluxing the carbon nano tube by using a strong acid solution, removing impurity components in the carbon nano tube by using the strong acid solution under a high-temperature refluxing condition, and separating to obtain the purified carbon nano tube. The carbon nanotubes used in the embodiments of the present application include, but are not limited to, single-walled carbon nanotubes, multi-walled carbon nanotubes, and the like.
In some possible implementations, the strong acid solution includes at least one of concentrated hydrochloric acid, concentrated sulfuric acid, concentrated nitric acid; the strong acid solutions have strong oxidizability, and particularly can effectively remove impurity components in the carbon nano tube under the condition of refluxing at high temperature.
In some possible implementations, the ratio of the volume of the strong acid solution to the mass of the carbon nanotubes is (1-5): 1; the strong acid solution with the proportion can fully ensure to remove impurity components in the carbon nano tube. In some embodiments, the ratio of the volume of the strong acid solution to the mass of the carbon nanotubes may be (1-2): 1. (2-3): 1. (3-4): 1. (4-5): 1, etc.
In some possible implementations, the temperature of the reflux treatment is 50 to 150 ℃ for a period of 3 to 15 hours. The refluxing condition ensures that the strong acid solution has better oxidation removal effect on impurity components in the carbon nano tube. In some embodiments, the temperature of the reflux treatment may be 50 to 80 ℃,80 to 100 ℃,100 to 120 ℃, 120 to 150 ℃ and the like for 3 to 5 hours, 5 to 8 hours, 8 to 10 hours, 10 to 12 hours, 12 to 15 hours and the like.
In some embodiments, 1 part by weight of the CNT powder is added to 1 to 5 parts by volume of concentrated hydrochloric acid, concentrated sulfuric acid, concentrated nitric acid, or the like, and refluxed at a temperature of 50 to 150 ℃ for 3 to 15 hours, and then washed with fatty alcohol and pure water until the pH of the supernatant is about 7. Wherein the aliphatic alcohol is one or more of methanol, ethanol, ethylene glycol, isopropanol, etc., and the pure water can be ultrapure water, deionized water or distilled water. Then, the filtered solid product is dried at a temperature of 50-100 ℃ for 8-24h to obtain purified CNT.
In some possible implementations, in step S12, the purified carbon nanotubes are dispersed in a polymer solution, mixed, and separated to obtain functionalized carbon nanotubes. Under the condition, the polymer is dissolved in the solvent in advance to fully ensure the uniform dissolution of the polymer, and then the purified carbon nano tube is dispersed in the solution of the polymer, so that the dispersing effect of the purified carbon nano tube is improved, the purified carbon nano tube and the polymer are uniformly and stably contacted, and then the polymer containing the amino active group is grafted to the surface of the carbon nano tube through mixing treatment, and the functionalized carbon nano tube is obtained.
In some possible implementations, the polymer solution has a concentration of 0.1 to 5wt%, which facilitates the formation of a uniformly and stably dispersed mixed solution with the purified carbon nanotubes. In some embodiments, the solution concentration of the polymer may be 0.1 to 1wt%, 1 to 2wt%, 2 to 3wt%, 3 to 4wt%, 4 to 5wt%, etc.
In some possible implementations, the polymer includes: at least one of polyethyleneimine, polyacrylamide and maleimide; the amino active groups contained in the polymers are not only beneficial to preventing the carbon nano tube from agglomerating, but also beneficial to subsequently fixing the metal catalyst, improving the loading capacity of the metal catalyst, preventing metal ions from agglomerating into large particles, improving the loading uniformity of the metal catalyst, and maintaining the small particle size to obtain the functionalized carbon nano tube. Particularly, the amino group can better fix the metal, prevent the metal particles from agglomerating and further control the particle size.
In some possible implementations, the mass ratio of the purified carbon nanotubes to the polymer is 1: (0.001-0.5). Under the condition of the proportioning, the polymer molecules can be stably and uniformly combined on the surface of the carbon nano tube, thereby being beneficial to uniform and stable loading of a subsequent noble metal source. If the polymer proportion is too high or too low, the load uniformity is affected. In some embodiments, the mass ratio of purified carbon nanotubes to polymer can be 1: (0.001-0.005), 1: (0.005-0.01), 1: (0.01 to 0.1), 1: (0.1-0.2), 1: (0.2 to 0.3), 1: (0.3 to 0.4), 1: (0.4-0.5), and the like.
In some embodiments, 1 part of the purified carbon nanotube CNT is dispersed in 1-10 parts of 0.1wt% -5wt% polymer solution of polyethyleneimine, polyacrylamide, maleimide, etc., and magnetically stirred at room temperature for 5-24h to obtain a uniformly dispersed mixed solution. And washing the mixed solution with water, centrifuging, and drying at 50-100 ℃ for 8-24h to obtain the functionalized carbon nanotube.
In some possible implementations, in step S30, the preparing step of the carbon nanotube mixed solution includes: dispersing the functionalized carbon nano tube into an organic solvent, adding an alkaline substance, and stirring for 2-4 hours at the rotation speed of 200-600rpm to obtain a carbon nano tube mixed solution. Under the condition, the functionalized carbon nanotubes are fully and uniformly dispersed in the organic solvent, and the alkaline substance is uniformly dissolved in the solvent, so that the subsequent thermal reduction reaction can be uniformly and stably carried out.
In some possible implementation modes, the mass ratio of the functionalized carbon nanotubes to the alkaline substances is (80-100): (0.01-10); the alkaline substance with the proportion is beneficial to fully reducing the noble metal source into the noble metal simple substance particles in the thermal reduction reaction. In some embodiments, the mass ratio of the functionalized carbon nanotubes to the alkaline substance may be (80-100): (0.01-1), (80-100): (1 to 3), (80 to 100): (3-5), (80-100): (5-8), (80-100): (8 to 10) and the like.
In some possible implementations, the basic substance includes at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate; the alkaline substances have good reduction performance on the noble metal source, and can efficiently reduce the noble metal source into the noble metal simple substance.
In some possible implementations, the organic solvent includes at least one fatty alcohol solvent of methanol, ethanol, ethylene glycol, isopropanol; the fatty alcohol solvent has a good dispersing effect on the functionalized carbon nano tubes and a good dissolving effect on alkaline substances, so that the components are uniformly and stably dispersed in the solvent, and a solvent environment is provided for the thermal reduction reaction.
In some embodiments, 80-100 parts by weight of the functionalized carbon nanotube is sonicated in 40-200 parts by volume of fatty alcohol for 10-30min (weight and volume units are mg for mL, g for L), then 10-100 parts of 0.1-10wt% NaOH fatty alcohol solution is added, and then magnetic stirring is carried out for 2-4h at the rotating speed of 200-600rpm/min, so as to obtain the carbon nanotube mixed solution. Wherein the fatty alcohol comprises one or more of methanol, ethanol, ethylene glycol, isopropanol, etc.
In the step S40, in a mixed state, the noble metal source solution and the stabilizer solution are added to the carbon nanotube mixed solution, so that the noble metal source is uniformly adsorbed on the surface of the functionalized carbon nanotube, and then a thermal reduction reaction is performed, so that the noble metal source is reduced in situ to form a noble metal simple substance which is uniformly adsorbed on the surface of the carbon nanotube, and the noble metal simple substance is separated to obtain the solid powder. Wherein, the stabilizer plays the purpose of delaying the growth of the noble metal simple substance particles, prevents the agglomeration of metal particles and further controls the particle size.
In some possible implementations, the ratio of the mass of the functionalized carbon nanotubes, the molar amount of the noble metal source, and the molar amount of the stabilizer is (80-100) wt: (0.1 to 5) mol: (0.1-5) mol; under the condition of the proportioning, the noble metal source can be uniformly and stably grafted to the surface of the functionalized carbon nano tube, and the noble metal source can be better combined on the surface of the carbon nano tube through the polymer which is combined on the surface of the carbon nano tube and contains the active group, so that the load uniformity and stability of the noble metal source are improved, and the load capacity is improved. The dosage of the stabilizer can effectively delay the excessive growth of the noble metal elementary substance particles when the subsequent noble metal source is reduced into the noble metal elementary substance, prevent the noble metal ions from agglomerating and control the particle size.
In some possible implementations, the concentration of the noble metal source solution is 0.1 to 1mol/L, and the concentration of the stabilizer solution is 0.1 to 1mol/L; the noble metal source solution and the stabilizer solution are added into the carbon nano tube mixed solution under the stirring state under the concentration condition, can be rapidly and uniformly dispersed into a reaction system, ensures the dispersion uniformity of each raw material component, and is beneficial to the subsequent thermal reduction reaction. In some embodiments, the concentration of the noble metal source solution can be 0.1 to 0.3mol/L, 0.3 to 0.5mol/L, 0.5 to 0.8mol/L, 0.8 to 1mol/L, and the like; the concentration of the stabilizer solution may be 0.1 to 0.3mol/L, 0.3 to 0.5mol/L, 0.5 to 0.8mol/L, 0.8 to 1mol/L, or the like.
In some possible implementations, the noble metal source includes at least one of a platinum source, a palladium source, a gold source, a rhodium source, a ruthenium source, and an iridium source, and the noble metal source has a high catalytic activity after being replaced with corresponding noble metal nano elementary particles. In some possible implementations, the source of platinum includes at least one of chloroplatinic acid, platinum acetylacetonate, platinum chloride, tetraammineplatinum acetate, platinum nitrate. In some possible implementations, the palladium source includes palladium dichloride and/or sodium tetrachloropalladate. In some possible implementations, the gold source includes at least one of chloroauric acid, gold chloride, triphenylphosphine, gold chloride. In some possible implementations, the source of rhodium includes at least one of rhodium chloride, rhodium acetate, rhodium nitrate. In some possible implementations, the ruthenium source includes at least one of ruthenium chloride, ruthenium acetate, ruthenium nitrate. In some possible implementations, the source of iridium includes at least one of chloroiridate, ammonium chloroiridate, iridium nitrate. The noble metal sources such as the platinum source, the palladium source, the gold source, the rhodium source, the ruthenium source and the iridium source adopted in the embodiments of the present application have good solubility, and can be uniformly and stably loaded in the carbon nanotube.
In some possible implementations, the stabilizing agent includes at least one of citric acid, sodium citrate, potassium citrate, magnesium citrate, calcium citrate. The stabilizers can effectively delay the excessive growth of noble metal elementary substance particles when a subsequent noble metal source is reduced into the noble metal elementary substance, prevent noble metal ions from agglomerating and control the particle size.
In some possible implementations, the thermal reduction reaction is carried out at a temperature of 170 to 450 ℃ for a period of 10 to 24 hours. Under the condition, the alkaline substance can efficiently reduce the noble metal source, so that the noble metal source is reduced and converted into a noble metal simple substance; and the particle size of the loaded noble metal is controlled by controlling the thermal reduction temperature. The size of the noble metal particles is related to the thermal reduction temperature, under the thermal reduction temperature condition, the catalyst particles which are small in size, uniformly distributed and not easy to agglomerate can be obtained, the catalytic performance of the catalyst particles is optimal, and the circulation stability is good. In some embodiments, the temperature conditions for the thermal reduction reaction may be 170 to 200 ℃, 200 to 250 ℃, 250 to 300 ℃, 300 to 350 ℃, 350 to 400 ℃, 400 to 450 ℃ and the like, and the duration may be 10 to 13 hours, 13 to 15 hours, 15 to 18 hours, 18 to 20 hours, 20 to 22 hours, 22 to 24 hours and the like.
In some embodiments, 1-5 unit volumes of 0.1-1mol/l chloroplatinic acid solution and 1-5 unit volumes of 0.1-1mol/l sodium citrate solution are added dropwise into the solution under vigorous stirring, the temperature is raised to 170-450 ℃, and stirring is continued for 10-24 h. Then cooling to room temperature while stirring, filtering, washing with water, centrifuging, and drying at 50-100 deg.C for 8-24h to obtain solid powder.
In some possible implementations, in step S50, the step of carbonizing includes: and (3) preserving the heat of the solid powder for 6 to 24 hours in an inert atmosphere at the temperature of between 400 and 600 ℃ to carbonize organic components such as polymers in the solid powder into carbon materials. Wherein the inert atmosphere includes, but is not limited to, at least one of nitrogen, helium, argon, and the like.
In a second aspect, the present embodiment provides a noble metal/carbon catalyst prepared by the above method, including a carbon nanotube substrate and noble metal nanoparticles supported on the surface of the carbon nanotube substrate.
According to the noble metal/carbon catalyst provided by the second aspect of the embodiments of the present application, the noble metal nanoparticles are stably and uniformly distributed in the carbon nanotubes, and the noble metal nanoparticles have a small particle size and a high uniformity. Therefore, the noble metal/carbon catalyst has large active specific surface area, excellent catalytic performance, good catalyst stability and long service life.
In some possible implementations, the noble metal nanoparticles include at least one noble metal of platinum, palladium, gold, rhodium, ruthenium, iridium; the noble metals have high catalytic activity and excellent catalytic performance.
In some possible implementations, the noble metal nanoparticles have an average particle size of 8nm or less. According to the embodiment of the application, the noble metal ions loaded in the noble metal/carbon catalyst have small particle size and high uniformity, so that the specific surface area of catalytic activity is large, and the catalytic activity of the noble metal/carbon catalyst is favorably improved. In some embodiments, the noble metal nanoparticles have an average particle diameter of 6nm or less, further 4nm or less, and the like.
In some possible implementations, the noble metal nanoparticles are supported in the noble metal/carbon catalyst at a loading of 15 to 20wt%. The catalytic activity of the noble metal/carbon catalyst is fully ensured in the load range, and if the load is too low, the catalytic efficiency of the noble metal/carbon catalyst is reduced; if the loading is too high, the supported noble metal nanoparticles tend to agglomerate, which also affects the catalytic activity of the noble metal/carbon catalyst. In some embodiments, the noble metal nanoparticles may be supported in the noble metal/carbon catalyst in an amount of 15 to 16wt%, 16 to 17wt%, 17 to 18wt%, 18 to 19wt%, 19 to 20wt%, etc.
A third aspect of the embodiments of the present application provides a fuel cell including the noble metal/carbon catalyst prepared by the above method or the above noble metal/carbon catalyst.
The fuel cell provided by the third aspect of the embodiment of the present application includes the noble metal/carbon catalyst, which has high catalytic activity and good stability, and is beneficial to improving the electrochemical performance of the fuel cell; and the cycle stability of the fuel cell can be improved, so that the service life of the fuel cell is prolonged.
In order to make the details of the above-described implementation and operation of the present application clearly understandable to those skilled in the art and to make the advanced properties of the noble metal/carbon catalyst and the preparation method and application thereof obvious in the examples of the present application, the above-described technical solution is illustrated below by way of a plurality of examples.
Example 1
A platinum carbon catalyst, the preparation of which comprises the steps of:
1. the CNT is purified by concentrated sulfuric acid. CNT powder 1 part by weight was added to concentrated acid 3 parts by volume and treated with reflux acidity for 6h at 120 ℃. Then washed with ethylene glycol and deionized water until the pH of the wash supernatant was 7. Drying at 100 deg.C for 8h to obtain purified CNT.
2. The surface functionalization treatment is carried out on the CNT by Polyethyleneimine (PEI) solution. 1 part of the purified CNT was added to 3 parts of a 2wt% PEI solution and magnetically stirred at room temperature for 24 hours to obtain a uniformly dispersed CNT/PEI solution. And (3) washing, centrifuging and drying the CNT/PEI solution to obtain the PEI-CNT. The drying temperature is 100 ℃, and the drying time is 10h.
3. Pt/CNT preparation. First, 80 parts by weight of PEI-CNT were sonicated in 120 parts by volume of ethylene glycol for 30min, then 100 parts by volume of 5wt% NaOH in ethylene glycol was added, followed by magnetic stirring for 4h at 600rpm/min. Then, 1 unit volume of 0.1mol/l chloroplatinic acid solution and 3 parts unit volume of 0.1mol/l sodium citrate solution were added dropwise to the above solution under vigorous stirring, the temperature was raised to 170 ℃, and stirring was continued for 24 hours. And cooling to room temperature during stirring, filtering, washing with water, centrifuging, and drying at 100 ℃ for 8h to obtain the Pt/PEI-CNT solid powder.
4. And (3) heating the solid powder to 400 ℃ in the nitrogen atmosphere, and carbonizing the PEI to obtain the Pt/CNT catalyst which is small in size, uniformly distributed and not easy to agglomerate.
Example 2
A platinum carbon catalyst, which was prepared by the steps different from those of example 1: step 3 in the Pt/CNT preparation process, the temperature was raised to 200 ℃ for chloroplatinic acid reduction, and the remaining operations and conditions were the same as in example 1.
Example 3
A platinum carbon catalyst, prepared by steps different from those of example 1: step 3. The temperature was raised to a reaction temperature of 250 ℃ in the Pt/CNT preparation process to perform chloroplatinic acid reduction, and the remaining operations and conditions were the same as in example 1.
Comparative example 1
A platinum carbon catalyst, prepared by steps different from those of example 1: the surface functionalization treatment in step 2 was not performed, but the temperature in step 3 was raised to a reaction temperature of 170 ℃ to perform chloroplatinic acid reduction, and the remaining operations and conditions were the same as in example 1.
Further, in order to verify the advancement of the examples of the present application, the following performance tests were performed on the examples and comparative examples:
1. the shapes of the platinum carbon catalysts prepared in the embodiments 1 to 3 and the comparative example 1 are respectively observed by adopting a transmission electron microscope, and the test results are sequentially shown in the accompanying drawings of fig. 2 to 5, so that the platinum nanoparticles in the platinum carbon catalysts prepared in the embodiments 1 to 3 are small in particle size, uniformly loaded in the carbon nanotubes and densely loaded.
2. The particle size distribution of platinum nanoparticles in the platinum-carbon catalysts of examples 1 to 3 and comparative example 1 was measured, and the loading amount of platinum nanoparticles (measured by ICP after digestion) was measured, respectively, and the results of the measurements are shown in table 1 below:
TABLE 1
From the above test results, it can be seen that the platinum nanoparticles in the platinum-carbon catalysts prepared in examples 1 to 3 of the present application have small particle size and uniform particle size distribution, the particle size is substantially less than 8nm, the loading of the platinum nanoparticles is high, and the loading amount of the platinum nanoparticles reaches 19.46wt%, so that the catalytic effect of the platinum-carbon catalyst is fully ensured. The platinum-carbon catalyst prepared in the comparative example 1 is not modified by a polymer containing an active group, wherein the platinum nanoparticle loading is significantly reduced and is only 6.41wt%, and the platinum nanoparticles are agglomerated, the particle distribution is not uniform, the particle size is different, and the catalytic effect of the platinum-carbon catalyst is reduced.
The above description is only a preferred embodiment of the present application and should not be taken as limiting the present application, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A method for preparing a noble metal/carbon catalyst, comprising the steps of:
introducing a polymer containing amino active groups on the surface of the carbon nano tube to obtain a functionalized carbon nano tube;
mixing the functionalized carbon nano tube, the alkaline substance and the organic solvent to obtain a carbon nano tube mixed solution;
adding a noble metal source solution and a stabilizer solution into the carbon nano tube mixed solution in a mixed state, carrying out thermal reduction reaction, and separating to obtain solid powder;
and carrying out carbonization treatment on the solid powder to obtain the noble metal/carbon catalyst.
2. The method of preparing a noble metal/carbon catalyst according to claim 1, wherein the step of preparing the functionalized carbon nanotube comprises:
obtaining a carbon nano tube, and purifying the carbon nano tube to obtain a purified carbon nano tube;
dispersing the purified carbon nano tube in the solution of the polymer, mixing, and separating to obtain the functionalized carbon nano tube;
and/or, the polymer comprises: at least one of polyethyleneimine, polyacrylamide and maleimide.
3. The method for preparing a noble metal/carbon catalyst according to claim 2, wherein the preparing of the carbon nanotube mixed solution comprises: dispersing the functionalized carbon nano tube into the organic solvent, adding the alkaline substance, and stirring for 2-4 hours at the rotating speed of 200-600rpm to obtain the carbon nano tube mixed solution;
and/or the mass ratio of the functionalized carbon nano tube to the alkaline substance is (80-100): (0.01 to 10);
and/or the mass ratio of the purified carbon nano tube to the polymer is 1: (0.001-0.5);
and/or the alkaline substance comprises at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate;
and/or the organic solvent comprises at least one fatty alcohol solvent of methanol, ethanol, glycol and isopropanol;
and/or the solution concentration of the polymer is 0.1-5 wt%.
4. The method for producing a noble metal/carbon catalyst according to any one of claims 2 to 3, wherein the concentration of the noble metal source solution is 0.1 to 1mol/L, and the concentration of the stabilizer solution is 0.1 to 1mol/L;
and/or the ratio of the mass of the functionalized carbon nanotubes, the molar amount of the noble metal source and the molar amount of the stabilizer is (80-100) wt: (0.1 to 5) mol: (0.1-5) mol;
and/or the noble metal source comprises at least one of a platinum source, a palladium source, a gold source, a rhodium source, a ruthenium source, an iridium source;
and/or the stabilizing agent comprises at least one of citric acid, sodium citrate, potassium citrate, magnesium citrate and calcium citrate.
5. The method for preparing a noble metal/carbon catalyst according to claim 4, wherein the carbonizing step comprises: keeping the temperature of the solid powder for 6 to 24 hours in an inert atmosphere at the temperature of 400 to 600 ℃;
and/or the temperature condition of the thermal reduction reaction is 170-450 ℃, and the duration is 10-24 hours;
and/or the platinum source comprises at least one of chloroplatinic acid, platinum acetylacetonate, platinum chloride, tetraammineplatinum acetate and platinum nitrate;
and/or, the palladium source comprises palladium dichloride and/or sodium tetrachloropalladate;
and/or the gold source comprises at least one of chloroauric acid, gold chloride and triphenylphosphine gold chloride;
and/or the rhodium source comprises at least one of rhodium chloride, rhodium acetate and rhodium nitrate;
and/or the ruthenium source comprises at least one of ruthenium chloride, ruthenium acetate and ruthenium nitrate;
and/or the iridium source comprises at least one of chloroiridate, ammonium chloroiridate and iridium nitrate.
6. The method for preparing a noble metal/carbon catalyst according to claim 2, 3 or 5, wherein the purification treatment comprises: and carrying out reflux treatment on the carbon nano tube by adopting a strong acid solution, and separating to obtain the purified carbon nano tube.
7. The method of preparing a noble metal/carbon catalyst according to claim 6, wherein the strong acid solution comprises at least one of concentrated hydrochloric acid, concentrated sulfuric acid, and concentrated nitric acid;
and/or the mass ratio of the volume of the strong acid solution to the carbon nano tube is (1-5): 1;
and/or the temperature of the reflux treatment is 50-150 ℃, and the time duration is 3-15 hours.
8. A noble metal/carbon catalyst prepared by the method according to any one of claims 1 to 7, comprising a carbon nanotube substrate and noble metal nanoparticles supported on the surface of the carbon nanotube substrate.
9. The noble metal/carbon catalyst of claim 8, wherein the noble metal nanoparticles comprise at least one noble metal of platinum, palladium, gold, rhodium, ruthenium, iridium;
and/or the average particle diameter of the noble metal nano-particles is less than or equal to 8nm;
and/or the loading amount of the noble metal nanoparticles in the noble metal/carbon catalyst is 15-20 wt%.
10. A fuel cell comprising the noble metal/carbon catalyst prepared by the method according to any one of claims 1 to 7 or the noble metal/carbon catalyst according to any one of claims 8 to 9.
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