Nanocomposite materials based on porous carriers and their preparation methods and applications

Abstract

The present invention discloses a nanocomposite material based on a porous carrier, its preparation method, and application. The nanocomposite material comprises a porous carrier and nanoparticles supported thereon. The porous carrier has mesopores and other pores beyond the mesopores, and the nanoparticles are primarily supported within the mesopores. The nanoparticles comprise metals and metal compounds, and the nanocomposite material further comprises doping elements, some of which are used to form the metal compounds. When used as a catalyst, the nanocomposite material of the present invention exhibits advantages such as high catalytic activity and good high-temperature operating stability. The preparation method enables directional and controllable regulation of the loading sites of the nanoparticles on the porous carrier.

Description

Technical Field

[0001] The present invention relates to a nanocomposite material, in particular to a nanocomposite material based on a porous carrier and a preparation method and application thereof, belonging to the field of material science. Background Art

[0002] Nanocomposites based on porous carriers have shown broad application potential in many fields such as clean energy production, environmental and energy conversion, chemical energy storage, wearable and implantable bioelectronic devices due to their unique structural advantages such as high specific surface area, controllable pore size, excellent conductivity and mechanical adaptability. In particular, in the field of high-temperature fuel cells, the development of catalyst materials with high activity and high stability is of great significance.

[0003] For nanocomposites based on porous supports, the loading sites of active nanoparticles are crucial. For platinum-based catalysts, for example, the proportion of platinum particles within the mesopores of a porous support significantly influences its catalytic activity and anti-poisoning properties. However, existing technologies are unable to controllably adjust the proportion of platinum particles within the mesopores of a porous support. Specifically, currently common synthesis processes for platinum-based catalysts include the polyol method, ion exchange method, and colloid method. However, the reaction solvents used in these synthesis processes have excessively high surface tension, preventing the metal precursor from effectively infiltrating the mesopores. Consequently, the platinum nanoparticles are primarily distributed in the pores outside the mesopores, resulting in direct contact between the nanoparticles and poisoning substances, deactivating the active sites and affecting their catalytic performance. Researchers have successfully loaded nanoparticles in varying proportions onto the inner and outer surfaces of Ketjen Black supports using various synthesis methods, such as the incipient wetness method and the polyol reduction method. Catalytic nanoparticles prepared using the polyol method primarily deposit on the outer surface of the Ketjen Black support. Currently, no process has been reported that can achieve a controlled distribution of mesoporous nanoparticles on a single carbon support.

[0004] Furthermore, existing platinum-based catalysts are generally only suitable for low-temperature proton exchange membrane fuel cell devices operating at temperatures below 100°C. To further improve energy conversion efficiency, reduce hydrogen purity, and minimize water management requirements, the use of high-temperature proton exchange membrane fuel cell devices is becoming a promising future development direction. However, existing platinum-based catalysts are susceptible to metal dissolution and shedding during operation at temperatures above 100°C, causing rapid performance degradation. Summary of the Invention

[0005] The main purpose of the present invention is to provide a nanocomposite material based on a porous carrier and a preparation method and application thereof, so as to solve the above-mentioned problems in the prior art.

[0006] To achieve the aforementioned object of the invention, the technical solutions adopted by the present invention include:

[0007] A first aspect of the present invention provides a nanocomposite material based on a porous carrier, comprising a porous carrier and nanoparticles supported by the porous carrier, wherein the nanocomposite material further satisfies the following conditions:

[0008] (1.1) The porous carrier has mesopores and other pores other than mesopores, wherein the volume proportion of the mesopores is 50% to 90%;

[0009] (1.2) The nanoparticles are loaded in the mesopores and other pores outside the mesopores. The mass of the nanoparticles in the mesopores is defined as M, and the mass of the nanoparticles in other pores outside the mesopores is defined as N. Then, Fx≥0.3, Fx=M / (M+N);

[0010] (1.3) The nanoparticles comprise a metal and a metal compound, the mass ratio of the metal compound to the metal is 0.02 to 0.2, and the metal element in the metal compound is the same as at least part of the metal element in the metal;

[0011] (1.4) The nanocomposite material further comprises a doping element, wherein a portion of the doping element is used to form the metal compound, and a mass ratio of the doping element to the metal element contained in the nanoparticles is 0.1 to 0.3.

[0012] A second aspect of the present invention provides a method for preparing a nanocomposite material based on a porous carrier, comprising:

[0013] allowing a liquid mixed reaction system comprising a metal source, an organic auxiliary agent, and a solvent to fully react at room temperature to form a precursor liquid, wherein the molar ratio of the organic auxiliary agent to the metal source is 1:3 to 1:1, and the organic auxiliary agent comprises a doping element;

[0014] The porous carrier is dispersed in the precursor liquid and fully mixed and reacted at room temperature. The obtained reaction product is then dried and reduced in sequence, and directly etched after the reduction treatment, thereby obtaining the nanocomposite material based on the porous carrier.

[0015] The third aspect of the present invention provides use of the porous support-based nanocomposite material in preparing a fuel cell catalyst or a fuel cell.

[0016] A fourth aspect of the present invention provides a fuel cell catalyst comprising the aforementioned porous support-based nanocomposite material.

[0017] A fifth aspect of the present invention provides a fuel cell comprising the aforementioned fuel cell catalyst.

[0018] Compared with the prior art, the present invention has at least the following beneficial effects:

[0019] First, in the nanocomposite material based on a porous carrier provided by the present invention, the nanoparticles as the active material can be controllably enriched in the mesopores of the porous carrier, that is, the controllable loading of the nanoparticles on the porous carrier is achieved, so that when the nanocomposite material is used as a catalyst, it has the advantages of controllable catalytic performance, high mass activity, not easy to be poisoned, and high cycle stability; at the same time, doping elements are also introduced into the nanocomposite material, and the metal compounds formed by the combination of these doping elements and some metal elements in the nanoparticles can cooperate with the metal in the nanoparticles to form a synergistic catalytic system, improve the metal electron cloud structure, and further significantly enhance the activity of the nanocomposite material as a catalyst and the stability under high-temperature operating conditions. Exemplarily, a nanocomposite material based on a porous carrier provided by the present invention is a platinum-based catalyst, and its mass activity can be as high as 720 mA / mg Pt (0.9 V vs. RHE), the performance degradation rate after 30,000 cycles is less than 10%. During high-temperature operation above 105°C, the peak power of the membrane electrode can reach 1.55W / cm 2 It meets the high-temperature application requirements of low-temperature proton exchange membrane fuel cells, caters to the development of new proton exchange membrane fuel cells in the future, and can provide strong support for the commercial application of proton exchange membrane fuel cells.

[0020] Secondly, in the nanocomposite material synthesis process based on porous carriers provided by the present invention, by adding organic additives to the raw material system, on the one hand, the charge of the porous carrier surface can be regulated to achieve the enrichment and regulation of metal colloids as precursors of nanoparticles, so that the nanoparticles can be controllably loaded on the porous carrier; on the other hand, the doping elements introduced by the organic additives are combined with part of the metal elements used to constitute the nanoparticles to form metal compounds, so that the metal in the nanoparticles can form a synergistic catalytic system with the metal compounds.

[0021] Third, the present invention provides a porous support-based nanocomposite synthesis process. After drying and reducing the reaction product of the nanoparticle precursor and the porous support, the reaction product is directly etched in air, bypassing the 600-1000°C high-temperature treatment step. This simplifies the synthesis process and allows the doping elements to be well retained in the nanocomposite, thereby fully realizing the effectiveness of the aforementioned synergistic catalytic system. The synthesis process of the present invention overcomes the limitations of existing catalyst preparation technology and can provide a new technical solution and implementation paradigm for the design of high-performance catalysts in fields such as fuel cells and chemical catalysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following examples are

[0023] Or a brief introduction is given to the drawings required for the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0024] Figure 1 This is a SEM image of the nanocomposite material prepared in Example 3e of the present invention;

[0025] Figure 2 TEM image of the nanocomposite material prepared in Example 3e of the present invention;

[0026] Figure 3 Schematic diagram of the structure of the nanocomposite material prepared in Example 3e of the present invention;

[0027] Figure 4 TEM image of the nanocomposite material prepared in Example 5 of the present invention;

[0028] Figure 5 This is an elemental scanning diagram of the nanocomposite material prepared in Example 5 of the present invention;

[0029] Figure 6 TEM image of the nanocomposite material prepared in Comparative Example 3;

[0030] Figure 7 This is the SEM image of the nanocomposite material prepared in Comparative Example 4;

[0031] Figure 8 TEM image of the nanocomposite material prepared in Comparative Example 4;

[0032] Figure 9 Schematic diagram of the structure of the nanocomposite material prepared in Comparative Example 4;

[0033] Figure 10 This is a linear relationship diagram of the voltage power density-current density of the single cell membrane electrode of the catalysts prepared in Example 2, Example 4, Example 5, Comparative Example 1, and Comparative Example 5 of the present invention;

[0034] Figure 11 The XRD diffraction patterns of the nanocomposites prepared in Examples 1 to 4 and Comparative Example 3 of the present invention are shown. DETAILED DESCRIPTION

[0035] As mentioned above, existing synthetic platinum-based catalysts and other nanocomposites based on porous carriers generally have defects such as difficulty in adapting to high-temperature operating environments, and difficulty in controllably adjusting the distribution position of nanoparticles in the carrier during the synthesis process. In view of this, the inventors of the present invention have proposed the technical solution of the present invention after long-term research and extensive practice. In summary, the present invention mainly adds an excess of organic additives to the raw material system in the synthesis process of nanocomposites based on porous carriers. On the one hand, the organic additives are used to change the surface electronegativity of the porous carrier, drive the penetration of metal colloids as precursors of nanoparticles, dynamic confinement and fixation by solvent volatilization, and carrier-particle synergy, etc., to achieve precise control of the proportion of mesoporous nanoparticles. On the other hand, the organic additives are used to introduce doping elements, so that the metal compounds formed by the reaction of the doping elements with some of the metal elements constituting the nanoparticles form a synergistic catalytic system with the metal in the nanoparticles, thereby significantly improving the activity, stability and mass transfer efficiency of the nanocomposites.

[0036] The technical solution, implementation process and principle of the present invention will be further explained below.

[0037] Specifically, as one aspect of the technical solution of the present invention, a nanocomposite material based on a porous carrier includes a porous carrier and a plurality of nanoparticles supported by the porous carrier, wherein the nanoparticles contain a metal compound and a metal.

[0038] In some embodiments, the porous support comprises mesopores and other pores, wherein the volume fraction of the mesopores is 50-90%, preferably 60-90%, and more preferably 80-85%. If the volume fraction of the mesopores is too small, the internal space of the mesopores will not be able to accommodate a sufficient number of nanoparticles. If the volume fraction of the mesopores is too large, most of the nanoparticles will be inside the mesopores of the porous support, resulting in excessive resistance to oxygen permeation through the pores, which can also affect performance.

[0039] In some embodiments, the nanoparticles are loaded in the mesopores and other pores outside the mesopores. If the mass of the nanoparticles in the mesopores is defined as M, the mass of the nanoparticles in other pores outside the mesopores is defined as N, and the total mass of the nanoparticles in the porous carrier is M+N, then M and N satisfy Fx=M / (M+N), and Fx≥0.3.

[0040] Furthermore, the mass of the nanoparticles within the mesopores and the mass of the nanoparticles within pores other than the mesopores satisfy 0.3 ≤ Fx ≤ 0.9, preferably 0.5 to 0.6. If the proportion of nanoparticles within the mesopores is too high, the resistance of reactants to the metal active sites is too great, affecting performance. If the proportion of nanoparticles within the mesopores is too low, the metal active sites will directly contact the ionomer, poisoning the active sites and affecting performance.

[0041] In some embodiments, the average particle size of the nanoparticles is 1-5 nm. The nanoparticles in the porous carrier-based nanocomposite material synthesized in the present invention are characterized by small size.

[0042] In some embodiments, the nanocomposite material further comprises a doping element, wherein a portion of the doping element is used to combine with a portion of the metal element in the nanoparticles to form the metal compound. In some cases, a portion of the doping element may also be distributed in locations such as pore walls within the porous support.

[0043] In some preferred embodiments, the metal elements contained in the nanoparticles include one or a combination of two or more of Pt, Al, Ti, V, Cr, Mn, Co, Ni, etc., but are not limited thereto.

[0044] In some more preferred embodiments, the metal element is Pt, or the metal element includes a combination of one or more of Al, Ti, V, Cr, Mn, Co, Ni, etc. and Pt.

[0045] In some preferred embodiments, the mass ratio of the doping element to the metal element contained in the nanoparticles is 0.1 to 0.3, preferably 0.2 to 0.3. If the doping element is too much, it will cause pore blocking, while if the doping element is too little, the synthesized nanocomposite material will be larger in size, thereby reducing the catalyst activity.

[0046] Furthermore, the doping element may include one or more combinations of N, P, S, etc., but is not limited thereto.

[0047] Taking Pt as an example, when nitrogen is used as the doping element, the lone pair of electrons from nitrogen forms a Pt-N coordination bond with the Pt nanoparticles, stabilizing the Pt nanoparticles and regulating the electronic structure. The specific mechanism is that nitrogen's electron-donating effect raises the Pt d-band center, enhancing the adsorption of reactants (such as H2 and O2), and improving hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) activity. N-containing sites can form localized positive charge sites, promoting the adsorption and activation of O2.

[0048] When P is selected as the doping element, the lone pair of electrons of P forms a Pt-P bond with Pt, inhibiting sintering and lowering the d-band center. The electronegativity of P is lower than that of C, and it feeds electrons back to Pt, weakening intermediate poisoning (such as CO) and enhancing corrosion resistance. P doping improves the oxidation resistance of the carrier and prolongs the life of the catalyst.

[0049] When S is used as the doping element, S forms a PtS2 compound with Pt, changing the electron cloud distribution and improving stability. Furthermore, defect sites can be introduced, and S doping produces carbon lattice distortion, increasing the density of active sites. It also has a dual-functional catalytic effect, and the S site can adsorb H+ or O2, synergistically with Pt to promote reactions (such as ORR).

[0050] In some more preferred embodiments, the metal compound includes one or more combinations of metal sulfides, metal nitrides, metal phosphides, etc., but is not limited thereto.

[0051] Taking the metal element Pt as an example, the metal in the nanoparticles may be metallic platinum, and the metal compound may be a combination of one or more of platinum sulfide, platinum phosphide, platinum nitride, etc., but is not limited thereto.

[0052] In some embodiments, the mass ratio of the metal compound to the metal is 0.02 to 0.2, preferably 0.05 to 0.15, and the metal element in the metal compound is the same as at least some of the metal elements in the metal. For example, the metal can be platinum or an alloy of platinum with a metal such as Al, Ti, V, Cr, Mn, Co, or Ni, while the metal compound can be platinum sulfide. Excessive amounts of metal compound can result in a loss of metal active sites, affecting performance; insufficient amounts of metal compound can weaken the force that induces changes in the metal's electronic structure.

[0053] In some embodiments, the porous support is made of one or more of carbon, metal oxides, silicon, silicon carbide, and silicon nitride, but is not limited thereto. For example, the porous support may include one or more of porous graphite, porous graphene, SiC, SnO2, and ZrO2, but is not limited thereto.

[0054] In some preferred embodiments, the porous carrier is made of carbon. Carbon-based materials have excellent electron transport properties and good compatibility with nanoparticles whose main component is metal.

[0055] In some embodiments, the ratio of the mass of the metal element contained in the nanocomposite material to the mass of the porous support is 1:4 to 3:2.

[0056] As another aspect of the technical solution of the present invention, it also relates to a method for preparing the aforementioned nanocomposite material based on a porous carrier, comprising:

[0057] allowing a liquid mixed reaction system comprising a metal source, an organic auxiliary agent and a solvent to fully react at room temperature to form a precursor liquid, wherein the organic auxiliary agent comprises a doping element;

[0058] The porous carrier is dispersed in the precursor liquid and fully mixed and reacted at room temperature. The obtained reaction product is then dried and reduced in sequence, and directly etched after the reduction treatment to obtain the nanocomposite material based on the porous carrier.

[0059] The organic auxiliary agent contains at least one active group, wherein at least one active group has a coordination function and is used to coordinate with metal ions derived from a metal source to form metal colloids. This active group can be defined as a first group.

[0060] Furthermore, the doping element may be distributed in the first group, and may be selected from but not limited to one or more combinations of N, P, S, etc.

[0061] By ensuring that the organic auxiliary agent is present in excess and its molar ratio to the metal source is maintained within an appropriate range, it can not only promote the reduction of at least part of the metal ions provided by the metal source to form metal colloids as nanoparticle precursors, but also provide doping elements to combine with part of the metal elements in the nanoparticles to form metal compounds, thereby changing the electronic structure of the metal in the nanoparticles and further improving their catalytic activity and durability.

[0062] Furthermore, the molar ratio of the organic additive to the metal source is 1:3 to 1:1. If the molar ratio of the organic additive to the metal source is greater than 1:1, the organic additive may partially clog the pores within the porous support, affecting the contact between the active sites within the pores and the reactants. If the molar ratio of the organic additive to the metal source is less than 1:3, the organic additive is too little, resulting in incomplete reduction of the metal ions and excessively large nanoparticles.

[0063] Meanwhile, one or more active groups in the organic auxiliary agent are hydrophilic groups, which can be defined as the second group.

[0064] The first group and the second group may include one or more combinations of groups such as thiocarboxyl, sulfhydryl, sulfonic acid, hydroxyl, amine, nitro, phosphate, carboxyl, and aldehyde. Furthermore, the first group and the second group may be groups of the same type or groups of different types. For example, both the first group and the second group may be sulfhydryl.

[0065] When the porous carrier is porous carbon particles, etc., the amphiphilic hydrophobic groups of the organic auxiliary agent, such as its alkyl main chain, can be combined with the hydrophobic surface of the carrier, while its hydrophilic groups can interact outward with solvents such as water to form a hydrophilic layer, making the carrier easier to be wetted by the solvent.

[0066] In some embodiments, the organic auxiliary agent may include any one or more combinations of thioglycolic acid or its salts, L-cysteine ​​or its salts, ethylenediamine, glutathione, penicillamine, dithiothreitol, adenosine triphosphate, and the like, but is not limited thereto. For example, the organic auxiliary agent may preferably be a thioglycolate salt such as STG (sodium thioglycolate). The thiol groups contained in STG have strong coordination ability and can combine with metal ions provided by the metal source to form a complex. At the same time, STG has a mild reducing ability that allows metal atoms to slowly nucleate, inhibiting excessive reduction and aggregation of metal ions, thereby effectively controlling the size of metal-based nanoparticles. In addition, STG can modify the surface of porous carriers through chemical bonding, increasing the active sites on the porous carrier surface and promoting the uniform distribution of nanoparticles.

[0067] In some embodiments, the metal source may be a soluble metal salt. Further, the metal element contained in the metal salt may include any one or a combination of two or more of Pt, Al, Ti, V, Cr, Mn, Co, and Ni. For example, it may be Pt, or a combination of one or more of Al, Ti, V, Cr, Mn, Co, Ni, etc. and Pt, but is not limited thereto.

[0068] Exemplarily, the metal source can be an acid (such as chloroplatinic acid) or a salt containing the aforementioned metal element. Furthermore, the metal source can be a nitrate, a hydrochloride, a sulfate or other forms of salt, such as potassium chloroplatinate, sodium chloroplatinate, platinum nitrate, platinum acetylacetonate, platinum sulfate, ammonium chloroplatinate, etc.

[0069] In some embodiments, the solvent includes water or a combination of water and an organic solvent. For example, the organic solvent may include acetone, methanol, ethanol, isopropanol, or acetonitrile, and is not limited thereto.

[0070] In some embodiments, the preparation method may specifically include: allowing the liquid-phase mixed reaction system to react at room temperature for more than 1 hour, for example, 1 hour to 2 hours, to form the precursor liquid.

[0071] In some embodiments, the preparation method may specifically include: uniformly dispersing the porous carrier in the precursor liquid and fully reacting at room temperature, wherein the residual organic additive in the precursor liquid can change the electronegativity of the porous carrier surface, thereby prompting the metal colloid particles in a specified mass proportion in the precursor liquid to enter the mesopores in the porous carrier, and further convert them into nanoparticles in the mesopores, thereby achieving controllable loading of nanoparticles in the porous carrier.

[0072] If the nanoparticles loaded in the mesopores are defined as mesoporous nanoparticles, then generally speaking, the proportion of the mesoporous nanoparticles is positively correlated with the immersion time of the porous carrier in the precursor liquid.

[0073] Furthermore, the porous support can be dispersed in the precursor solution and allowed to react at room temperature for at least 6 hours, preferably 6 to 36 hours, after which the reaction product can be isolated from the reaction mixture. During this reaction, as the reaction time increases, the porous support continuously attracts the metal colloids into its interior, resulting in a gradual increase in the number of mesoporous nanoparticles. When the reaction time exceeds 36 hours, the internal enrichment force reaches saturation, and the mesoporous nanoparticles no longer accumulate over time. At this point, the proportion of mesoporous nanoparticles is 0.7 to 0.9.

[0074] In some embodiments, during the drying process of the present invention, only the solvent in the reaction mixture is volatilized and removed, and the remaining components are retained in the final reaction product.

[0075] In some embodiments, the reduction treatment is carried out in an atmosphere containing a reducing gas, the temperature of the reduction treatment is 200-500°C, and the time is 1-5 hours. Through this reduction treatment, the platinum precursor can be completely converted into metal , ensuring that the catalytic active sites are fully exposed. If the reduction temperature is too high, irreversible sintering will occur, and if the reduction temperature is too low, the reduction will be insufficient.

[0076] In some embodiments, the etching process is performed in an air atmosphere at a temperature of 200-500°C for 1-6 hours. This air etching process can remove amorphous carbon, unclog pores, and improve mass transfer efficiency. If the etching temperature is too high or the etching time is too long, the support structure may collapse. If the etching temperature is too low or the etching time is too short, the removal of amorphous carbon and unclogging of pores may not be achieved.

[0077] In the preparation method of the present invention, air etching is directly performed on the reaction product after reduction treatment without high-temperature annealing and other processes, so that the metal compound can be stably retained in the nanoparticles and form a synergistic catalytic system with the metal components in the nanoparticles. At the same time, damage to the porous carrier structure and migration of nanoparticles caused by high-temperature treatment can be avoided, making the distribution position of the nanoparticles in the porous carrier more controllable.

[0078] The preparation process of the present invention has process compatibility and can be adapted to a variety of porous supports and metal precursors. The activity, stability and mass transfer efficiency of the catalyst are optimized. This strategy provides a new paradigm for the design of high-performance catalysts in fuel cells, chemical catalysis and other fields.

[0079] Furthermore, the preparation method of the present invention can synthesize small-sized, highly dispersible nanoparticles with metal as the main component, thereby improving catalytic activity and stability. It also has the advantages of simple process (few steps, low equipment requirements), economic efficiency (low raw material and energy consumption costs, suitable for large-scale application), and environmental friendliness (low solvent and by-product pollution, in line with the principles of green chemistry).

[0080] As another aspect of the technical solution of the present invention, it also relates to the use of the porous carrier-based nanocomposite material in the fields of preparing fuel cell catalysts or fuel cells.

[0081] Correspondingly, another aspect of the technical solution of the present invention further provides a fuel cell catalyst comprising the aforementioned nanocomposite material based on a porous carrier.

[0082] Another aspect of the technical solution of the present invention further provides a fuel cell, which includes the aforementioned fuel cell catalyst.

[0083] To more clearly understand the objectives, technical solutions, and advantages of the present invention, the following examples will further explain the technical solutions, their implementation processes, and principles. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0084] The mesopore ratio of the carrier used in the following examples is ≥50%, and the specific types can be porous carbon carrier (CMK1-C12-FA), tin oxide (Tiannai Technology-688116), silicon carbide (Beijing Dekedaojin Technology Co., Ltd.-DK-SiC-001), etc.

[0085] Example 1

[0086] The preparation method of a platinum-carbon catalyst in this embodiment includes:

[0087] S1. Sodium thioglycolate and chloroplatinic acid in a molar ratio of about 1:1 were added to deionized water at room temperature, and stirred at room temperature for about 2 hours to form a precursor solution.

[0088] S2. Add a porous carbon support (CMK1-C12-FA-2400) with a mesopore ratio of about 50% to the precursor liquid obtained in step S1, and control the mass ratio of the metal element in the metal source to the carbon support to be approximately 1:4. Stir at room temperature for about 6 hours, and then dry the obtained reaction mixture at a temperature of about 70°C to obtain a powder.

[0089] S3. The powder obtained in step S2 is placed in a tube furnace for heating and reduction. The reduction conditions are: temperature of about 200° C., time of about 1 h, and reaction atmosphere of 5% H 2 / Ar mixed gas to obtain a reduced product.

[0090] S4. Wash the reduction product obtained in step S3 with clean water and suction filtration until the conductivity of the filtrate is about 5 μs / cm, thereby obtaining a washed powder.

[0091] S5. The cleaned powder obtained in step S4 is subjected to air etching under the following conditions: temperature of about 200° C. and time of about 1 hour to obtain the target product.

[0092] Example 1a

[0093] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 1, with the only difference being that a porous carbon support (CMK1-C12-FA-2000) with a mesopore ratio of approximately 60% is used in S2.

[0094] Example 1b

[0095] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 1, with the only difference being that a porous carbon support (CMK1-C12-FA-1600) with a mesopore ratio of approximately 70% is used in S2.

[0096] Example 1c

[0097] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 1, with the only difference being that S2 uses a porous carbon support (CMK1-C12-FA-1200) with a mesopore ratio of approximately 80%.

[0098] Example 1d

[0099] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 1, with the only difference being that a porous carbon support (CMK1-C12-FA-900) with a mesopore ratio of approximately 85% is used in S2.

[0100] Example 1e

[0101] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 1, with the only difference being that S2 uses a porous carbon support (CMK1-C12-FA) with a mesopore ratio of approximately 90%.

[0102] Example 2

[0103] The preparation method of a platinum-carbon catalyst in this embodiment includes:

[0104] S1. Sodium thioglycolate and chloroplatinic acid in a molar ratio of about 1:2 were added to deionized water at room temperature, and stirred at room temperature for about 2 hours to form a precursor solution.

[0105] S2. Add a porous carbon support (CMK1-C12-FA-1200) with a mesopore ratio of about 80% to the precursor liquid obtained in step S1, and control the mass ratio of the metal element in the metal source to the carbon support to be approximately 1:4. Stir at room temperature for about 12 hours, and then dry the obtained reaction mixture at a temperature of about 70°C to obtain a powder.

[0106] S3. The powder obtained in step S2 is placed in a tube furnace for heating and reduction. The reduction conditions are: temperature of about 300° C., time of about 3 h, and reaction atmosphere of 5% H 2 / Ar mixed gas to obtain a reduced product.

[0107] S4. Wash the reduction product obtained in step S3 with clean water and suction filtration until the conductivity of the filtrate is about 5 μs / cm, thereby obtaining a washed powder.

[0108] S5. The cleaned powder obtained in step S4 is subjected to air etching under the following conditions: temperature of about 300° C. and time of about 3 hours to obtain the target product.

[0109] Example 2a

[0110] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 2, except that in S1, the molar ratio of sodium thioglycolate to chloroplatinic acid is 1:3.

[0111] Example 2b

[0112] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 2, except that: in S1, the molar ratio of sodium thioglycolate to chloroplatinic acid is 1:1.

[0113] Example 3

[0114] The preparation method of a platinum-carbon catalyst in this embodiment includes:

[0115] S1. Sodium thioglycolate and chloroplatinic acid in a molar ratio of about 1:3 were added to deionized water at room temperature and stirred at room temperature for about 2 hours to form a precursor solution.

[0116] S2. Add a porous carbon support (CMK1-C12-FA-1200) with a mesopore ratio of about 80% to the precursor liquid obtained in step S1, and control the mass ratio of the metal element in the metal source to the carbon support to be approximately 1:4. Stir at room temperature for about 20 hours, and then dry the obtained reaction mixture at a temperature of about 70°C to obtain a powder.

[0117] S3. The powder obtained in step S2 is placed in a tube furnace for heating and reduction. The reduction conditions are: temperature of about 400° C., time of about 5 h, and reaction atmosphere of 5% H 2 / Ar mixed gas to obtain a reduced product.

[0118] S4. Wash the reduction product obtained in step S3 with clean water and suction filtration until the conductivity of the filtrate is about 5 μs / cm, thereby obtaining a washed powder.

[0119] S5. The cleaned powder obtained in step S4 is subjected to air etching under the following conditions: temperature of about 500° C. and time of about 5 h to obtain the target product.

[0120] Example 3a

[0121] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 3, except that: S2, a porous carbon support (CMK1-C12-FA-1200) with a mesopore ratio of about 80% is added to the precursor liquid, and then stirred at room temperature for about 6 hours.

[0122] Example 3b

[0123] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 3, except that: S2, a porous carbon support (CMK1-C12-FA-1200) with a mesopore ratio of about 80% is added to the precursor liquid, and then stirred at room temperature for about 12 hours.

[0124] Example 3c

[0125] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 3, except that: S2, a porous carbon support (CMK1-C12-FA-1200) with a mesopore ratio of about 80% is added to the precursor liquid, and then stirred at room temperature for about 18 hours.

[0126] Example 3d

[0127] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 3, except that: S2, a porous carbon support (CMK1-C12-FA-1200) with a mesopore ratio of about 80% is added to the precursor liquid, and then stirred at room temperature for about 30 hours.

[0128] Example 3e

[0129] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 3, except that: S2, a porous carbon support (CMK1-C12-FA-1200) with a mesopore ratio of about 80% is added to the precursor liquid, and then stirred at room temperature for about 36 hours.

[0130] Example 4

[0131] The preparation method of a platinum-carbon catalyst in this embodiment includes:

[0132] S1. Sodium thioglycolate and chloroplatinic acid in a molar ratio of about 1:2 were added to deionized water at room temperature, and stirred at room temperature for about 2 hours to form a precursor solution.

[0133] S2. Add a porous carbon support (CMK1-C12-FA-1200) with a mesopore ratio of about 80% to the precursor liquid obtained in step S1, and control the mass ratio of the metal element in the metal source to the carbon support to be approximately 1:3. Stir at room temperature for about 20 hours, and then dry the obtained reaction mixture at a temperature of about 70°C to obtain a powder.

[0134] S3. The powder obtained in step S2 is placed in a tube furnace for heating and reduction. The reduction conditions are: temperature of about 400° C., time of about 5 h, and reaction atmosphere of 5% H 2 / Ar mixed gas to obtain a reduced product.

[0135] S4. Wash the reduction product obtained in step S3 with clean water and suction filtration until the conductivity of the filtrate is about 5 μs / cm, thereby obtaining a washed powder.

[0136] S5. The cleaned powder obtained in step S4 is subjected to air etching under the following conditions: temperature of about 500° C. and time of about 5 h to obtain the target product.

[0137] Example 4a

[0138] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 3, except that in S2, the mass ratio of the metal element in the metal source to the mass of the carbon support is controlled to be approximately 1:2.

[0139] Example 4b

[0140] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 3, except that in S2, the mass ratio of the metal element in the metal source to the mass of the carbon support is controlled to be approximately 1:1.

[0141] Example 4c

[0142] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 3, except that in S2, the mass ratio of the metal element in the metal source to the mass of the carbon support is controlled to be approximately 2:1.

[0143] Example 4d

[0144] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 3, except that in S2, the mass ratio of the metal element in the metal source to the mass of the carbon support is controlled to be approximately 3:2.

[0145] Example 5

[0146] The preparation method of a platinum-carbon catalyst in this embodiment includes:

[0147] S1. Add sodium thioglycolate, chloroplatinic acid and CoCl2 into deionized water at room temperature, wherein the molar ratio of the sum of the moles of chloroplatinic acid and CoCl2 to sodium thioglycolate is about 2:1, and stir at room temperature for about 2 hours to form a precursor liquid.

[0148] S2. Add a porous carbon support (CMK1-C12-FA-1200) with a mesopore ratio of about 80% to the precursor liquid obtained in step S1, and control the mass ratio of the metal element in the metal source to the carbon support to be approximately 1:1. Stir at room temperature for about 20 hours, and then dry the obtained reaction mixture at a temperature of about 70°C to obtain a powder.

[0149] S3. The powder obtained in step S2 is placed in a tube furnace for heating and reduction. The reduction conditions are: temperature of about 500° C., time of about 2 h, and reaction atmosphere of 5% H 2 / Ar mixed gas to obtain a reduced product.

[0150] S4. Wash the reduction product obtained in step S3 with clean water and suction filtration until the conductivity of the filtrate is about 5 μs / cm, thereby obtaining a washed powder.

[0151] S5. The cleaned powder obtained in step S4 is subjected to air etching under the following conditions: temperature of about 200° C. and time of about 5 h to obtain the target product.

[0152] Example 6

[0153] The preparation method of a platinum-carbon catalyst in this embodiment includes:

[0154] S1. Sodium thioglycolate, chloroplatinic acid and MnSO4 are added to deionized water at room temperature, wherein the molar ratio of the sum of the moles of chloroplatinic acid and MnSO4 to sodium thioglycolate is about 2:1, and stirred at room temperature for about 2 hours to form a precursor liquid.

[0155] S2. Add silicon carbide with a mesoporous content of about 80% to the precursor liquid obtained in step S1, and control the mass ratio of the metal element in the metal source to the mass of the carbon carrier to be approximately 1:1. After stirring at room temperature for about 20 hours, dry the obtained reaction mixture at a temperature of about 70°C to obtain a powder.

[0156] S3. The powder obtained in step S2 is placed in a tube furnace for heating and reduction. The reduction conditions are: temperature of about 500° C., time of about 2 h, and reaction atmosphere of 5% H 2 / Ar mixed gas to obtain a reduced product.

[0157] S4. Wash the reduction product obtained in step S3 with clean water and suction filtration until the conductivity of the filtrate is about 5 μs / cm, thereby obtaining a washed powder.

[0158] S5. The cleaned powder obtained in step S4 is subjected to air etching under the following conditions: temperature of about 200° C. and time of about 3 hours to obtain the target product.

[0159] Example 7

[0160] The preparation method of a platinum-carbon catalyst in this embodiment includes:

[0161] S1. Sodium thioglycolate, chloroplatinic acid and TiCl4 are added to deionized water at room temperature, wherein the molar ratio of the sum of the moles of chloroplatinic acid and TiCl4 to sodium thioglycolate is about 2:1, and stirred at room temperature for about 2 hours to form a precursor liquid.

[0162] S2. Add tin oxide with a mesoporous content of about 85% to the precursor liquid obtained in step S1, and control the mass ratio of the metal element in the metal source to the mass of the carbon support to be approximately 1:1. Stir at room temperature for about 20 hours, and then dry the obtained reaction mixture at a temperature of about 70°C to obtain a powder.

[0163] S3. The powder obtained in step S2 is placed in a tube furnace for heating and reduction. The reduction conditions are: temperature of about 500° C., time of about 2 h, and reaction atmosphere of 5% H 2 / Ar mixed gas to obtain a reduced product.

[0164] S4. Wash the reduction product obtained in step S3 with clean water and suction filtration until the conductivity of the filtrate is about 5 μs / cm, thereby obtaining a washed powder.

[0165] S5. The cleaned powder obtained in step S4 is subjected to air etching under the following conditions: temperature of about 200° C. and time of about 6 hours to obtain the target product.

[0166] Example 8

[0167] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 4, except that sodium thioglycolate is replaced by dithiothreitol.

[0168] Example 9

[0169] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 4, except that sodium thioglycolate is replaced by L-cysteine.

[0170] Example 10

[0171] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 4, except that sodium thioglycolate is replaced by penicillamine.

[0172] Example 11

[0173] The preparation method of a platinum-carbon catalyst provided in this embodiment is basically the same as that in Example 4, except that sodium thioglycolate is replaced by adenosine triphosphate.

[0174] Comparative Example 1

[0175] The preparation method of a platinum-based catalyst provided in this comparative example is basically the same as that in Example 5, except that:

[0176] In step S1, an excess amount of chloroplatinic acid is added, with a molar ratio of sodium thioglycolate to chloroplatinic acid of about 1:5, and the mixture is stirred at room temperature for about 2 hours to form a precursor liquid.

[0177] Comparative Example 2

[0178] The preparation method of a platinum-based catalyst provided in this comparative example is basically the same as that in Example 5, except that:

[0179] In step S1, an excess amount of sodium thioglycolate is added, with a molar ratio of sodium thioglycolate to chloroplatinic acid of about 2:1, and the mixture is stirred at room temperature for about 2 hours to form a precursor liquid.

[0180] Comparative Example 3

[0181] The preparation method of a platinum-based catalyst provided in this comparative example is basically the same as that in Example 5, except that sodium thioglycolate is not added in step S1.

[0182] Comparative Example 4

[0183] The preparation method of a platinum-based catalyst provided in this comparative example is basically the same as that in Example 5, except that:

[0184] In step S2, the carbon support is added to the precursor solution obtained in step S1, and then stirred at room temperature for about 2 hours.

[0185] Comparative Example 5

[0186] The preparation method of a platinum-based catalyst provided in this comparative example is basically the same as that in Example 5, with the only difference being that the mesopore ratio of the porous carbon support used in step S2 is 30%.

[0187] Figure 1 、 Figure 2 and Figure 3The SEM image, TEM image and structural diagram of the nanocomposite material prepared in Example 3e are shown respectively. It can be seen that Example 3e achieves the enrichment of platinum nanoparticles inside the mesopores.

[0188] Figure 4 TEM image of the nanocomposite material obtained in Example 5, Figure 5 This is an element scan of the nanocomposite material. It can be seen that the overlap of sulfur and platinum elements has an anchoring effect.

[0189] Figure 6 TEM image of the nanocomposite material obtained in Comparative Example 3; Figure 4 and Figure 6 It can be seen from the transmission electron microscope diagram that in Example 5 and Comparative Example 3, the size of the nanoparticles gradually increases as the amount of organic additive added decreases. Therefore, the content of the organic additive significantly affects the size of the metal nanoparticles.

[0190] Figure 7 、 Figure 8 and Figure 9 The SEM image, TEM image and structural diagram of the nanocomposite material prepared in Comparative Example 4 respectively show that Comparative Example 4 cannot achieve the enrichment and loading of platinum nanoparticles inside the mesopores, and the proportion of platinum nanoparticles inside the mesopores is less than 0.3.

[0191] Figure 10 The linear relationship diagram of the single cell membrane electrode voltage power density-current density of the catalysts prepared in Example 2, Example 4, Example 5, Comparative Example 1, and Comparative Example 5 shows that the performance of the examples is much higher than that of the comparative examples, and the performance of Example 5 reaches a peak.

[0192] Figure 11 The XRD diffraction patterns of the nanocomposites prepared in Examples 1 to 4 and Comparative Example 3 indicate that the organic additive promotes the presence of the metal compound.

[0193] The catalyst performance data shown in Table 2 were tested using the following methods: a biologic-50e electrochemical workstation was used, and the RDE apparatus was a PINE electrode set sold by Hong Kong Physics and Chemical Industry Co., Ltd. A three-electrode system was employed: a catalyst-loaded glassy carbon electrode (PINE) as the working electrode, a saturated calomel electrode (SCE) as the reference electrode, and a platinum carbon rod as the counter electrode. The perchloric acid solution used in this test was 0.1 M. Cyclic voltammetry was performed over a scanning potential range of 0.05 V vs. RHE to 1.05 V vs. RHE, with a scan rate of 50 mV s. -1The electrochemical specific surface area (ECSA) of platinum can be calculated from the adsorption area of ​​potential deposited hydrogen. The LSV test was performed in the potential range of 0.05 V vs. RHE to 1.05 V vs. RHE with a scan rate of 10 mV s -1 The rotating disk electrode rotated at 1600 rpm, and ORR performance was evaluated using half-wave potential and mass activity (MA). Durability testing involved a 30-second constant potential test at 0.6 V vs. RHE in nitrogen-saturated 0.1 M HClO₄. Square wave cycling was then performed at 0.95 V vs. RHE–0.6 V vs. RHE, with each potential lasting 3 seconds, and a 6-second cycle consisting of 100,000 cycles. Membrane electrode activation and polarization curve tests were conducted in a hydrogen-air environment at 80°C, 90% RH, and a single-cell backpressure of 70 kPa. Prior to testing, the membrane electrode was activated at a constant voltage of 0.3 V until the current density reached a steady state. Once stable, subsequent testing was performed, and the fuel cell's current density-voltage curve was measured over a specific current range to determine the material's peak power density. High-temperature membrane electrode test activation and polarization curve tests were carried out in a hydrogen-air environment, and the test temperature was above 105°C. The raw materials and amounts used in Examples 1 to 11 and Comparative Examples 1 to 5 are shown in Table 1, and the catalyst structure data obtained are shown in Table 2.

[0194] Table 1 Raw materials and dosages of Examples 1 to 11 and Comparative Examples 1 to 5

[0195] ;

[0196]

[0197] Table 2 Catalyst structure data of Examples 1 to 11 and Comparative Examples 1 to 5

[0198]

[0199] Note: The proportion of mesoporous nanoparticles = the mass of nanoparticles in the mesopores / (the mass of nanoparticles in the mesopores + the mass of nanoparticles in other pores outside the mesopores); the proportion of doping elements = the mass of doping elements / the mass of metal; the proportion of metal compounds = the mass of metal compounds / the mass of metal.

[0200] When the catalyst of the present invention is used in a fuel cell, the test performance data of the corresponding battery are shown in Table 3.

[0201] Table 3 Test performance of batteries

[0202]

[0203] The activity of the catalysts of Examples 1 to 11 of the present invention was tested. The results showed that the mass activity (MA) of these catalysts could be increased to 720 mA / mgPt (0.9 V vs. RHE), which is much higher than the 200 mA / mgPt of current commercial catalysts. This may be attributed to the high dispersion of the internal nanoparticles and the enhanced intrinsic activity due to the confinement effect.

[0204] The stability of the catalysts of Examples 1 to 11 of the present invention was tested. The results showed that in an accelerated aging test (ADT), the ECSA decay rate of these catalysts could be reduced to 6%, which is much lower than the 50% of current commercial catalysts. This is probably due to the significant confinement effect of the carrier, which effectively inhibits the dissolution and agglomeration of platinum.

[0205] Furthermore, the half-cell mass activity prepared based on the catalysts of Examples 1 to 11 of the present invention is 400 to 720.04 mA / mg. Pt (0.9 V vs. RHE), the peak power density of the single cell at 80°C is 1.06~2.0W / cm 2 , and the peak power density of the single cell at an operating temperature of 105°C is 0.93~1.55W / cm 2 .

[0206] In addition, the applicant also conducted experiments with reference to the preparation methods of Examples 1 to 11 above, using other raw materials and process conditions listed in this specification, and tested the composition, structure, and application performance of the products obtained from these experiments using the series of characterization methods described above, and found that they performed well in terms of catalytic activity and stability. For example, the applicant used graphene (NanoXplore-XG-Porous), graphitic carbon nitride (carbon nitride - Xi'an Ruixi Biological Company - RC-1220), and metal-organic framework material (BASF - CALF-20) to replace the porous carbon support in Example 4, and the mass activity of the obtained catalyst products was above 450 mA / mgPt (0.9 V vs. RHE), and the ECSA decay rate was below 15%.

[0207] Although the embodiments of the present invention have been described in detail above, professionals in the relevant fields may make deletions and modifications to the embodiments once they become aware of the creative content and concepts therein, and such deletions and modifications shall fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent of the present invention shall be based on the appended claims.

[0208] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

Claims

1. A nanocomposite material based on a porous carrier, comprising a porous carrier and nanoparticles supported by the porous carrier, characterized in that: The nanocomposite material also meets the following conditions: (1.1) The porous carrier has mesopores and other pores other than mesopores, wherein the volume of the mesopores accounts for 80% to 90%; (1.2) The nanoparticles are loaded in the mesopores and other pores outside the mesopores. The mass of the nanoparticles in the mesopores is defined as M, and the mass of the nanoparticles in other pores outside the mesopores is defined as N. Then Fx is greater than 0.5 and ≤ 0.9, and Fx = M / (M + N); (1.3) The nanoparticles comprise a metal and a metal compound, the mass ratio of the metal compound to the metal is 0.02 to 0.15, and the metal element in the metal compound is the same as at least part of the metal element in the metal; (1.4) The nanocomposite material further comprises a doping element, wherein a portion of the doping element is used to form the metal compound, and the mass ratio of the doping element to the metal element contained in the nanoparticles is 0.1 to 0.3, and the metal element is Pt, or the metal element is selected from a combination of one or more of Ti, Mn, and Co and Pt, and the doping element is selected from a combination of one or more of N, P, and S.

2. The porous carrier-based nanocomposite material according to claim 1, characterized in that: The average particle size of the nanoparticles is 1-5 nm.

3. The porous carrier-based nanocomposite material according to claim 1, characterized in that: The metal compound includes one or more combinations of metal sulfides, metal nitrides, and metal phosphides.

4. The porous carrier-based nanocomposite material according to claim 1, characterized in that: The material of the porous carrier is selected from one or more combinations of carbon, metal oxides, silicon, silicon carbide, and silicon nitride.

5. A method for preparing the nanocomposite material based on a porous carrier according to any one of claims 1 to 4, characterized in that: include: A liquid-phase mixed reaction system comprising a metal source, an organic auxiliary agent, and a solvent is allowed to react at room temperature for more than 2 hours to form a precursor liquid, wherein the molar ratio of the organic auxiliary agent to the metal source is 1:3 to 1:2, the metal source is a soluble metal salt, and the metal element contained in the metal salt is Pt, or the metal element is selected from any one or a combination of two or more of Ti, Mn, and Co and Pt, and the organic auxiliary agent contains a doping element, and the organic auxiliary agent is selected from a combination of one or more of thioglycolic acid or a salt thereof, L-cysteine ​​or a salt thereof, penicillamine, dithiothreitol, and adenosine triphosphate; The porous carrier is dispersed in the precursor liquid and fully mixed and reacted at room temperature for more than 20 hours, the mass ratio of the metal element to the porous carrier is 1:3~2:1, and the volume proportion of the mesopores in the porous carrier is 80%~90%; the obtained reaction product is then dried and reduced in sequence, and directly etched after the reduction treatment, so as to obtain the nanocomposite material based on the porous carrier.

6. The method according to claim 5, characterized in that: The solvent is selected from water or a combination of water and an organic solvent.

7. The method according to claim 5, characterized in that: The reduction treatment is carried out in an atmosphere containing a reducing gas, the temperature of the reduction treatment is 200-500° C., and the time is 1-5 hours.

8. The method according to claim 5, wherein: The etching process is performed in an air atmosphere at a temperature of 200-500° C. and for a time of 1-6 hours.

9. Use of the porous support-based nanocomposite material according to any one of claims 1 to 4 in the preparation of a fuel cell catalyst or a fuel cell.

10. A fuel cell catalyst, characterized in that: The invention comprises the nanocomposite material based on a porous carrier according to any one of claims 1 to 4.

11. A fuel cell, characterized in that: Comprising the fuel cell catalyst according to claim 10.

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