Carbon-supported platinum group metal catalysts and their preparation methods, hydrogen fuel cells and carbon materials

Abstract

This invention relates to platinum-carbon catalysts, their preparation methods, and applications. In the S2P spectra of these catalysts analyzed by XPS, the area of ​​characteristic peaks (preferably characteristic peaks of thiophene-type sulfur) located between 162 and 166 eV, between 160 eV and 170 eV, is greater than 92%, or greater than 95%, or greater than 98%, or even only characteristic peaks (preferably characteristic peaks of thiophene-type sulfur) located between 162 and 166 eV are observed. The support for the platinum-carbon catalyst is sulfur-doped conductive carbon black. This invention modifies the conductive carbon black support for the platinum-carbon catalyst, significantly improving the specific activity and electrochemical active area of ​​the catalyst by controlling the doping form of the doping elements. Furthermore, it also improves the stability and carbon corrosion resistance of the platinum-carbon catalyst. In addition, this invention provides a simple method for preparing the above-mentioned platinum-carbon catalyst.

Description

[Technical Field]

[0001] This invention relates to carbon-supported platinum group metal catalysts, their preparation methods and applications, and particularly to carbon-supported platinum group metal catalysts for proton exchange membrane hydrogen fuel cells, their preparation methods and applications. [Previous Technology]

[0002] The oxygen reduction reaction (ORR) is a key reaction in the field of electrochemistry. For example, in fuel cells and metal-air batteries, the ORR is a major factor affecting battery performance. Doped carbon materials can be directly used as catalysts for the ORR. When used as ORR catalysts, literature reports the incorporation of elements such as nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine, and iodine into carbon materials. Among these, nitrogen, with an atomic radius close to that of carbon, easily enters the carbon lattice and is therefore the most commonly used doping element. Although there are many literature reports on the direct use of doped carbon materials as fuel cell catalysts, there is still a significant gap compared to platinum-carbon catalysts.

[0003] To date, the most effective oxygen reduction catalyst is the platinum-carbon catalyst, but it still has shortcomings. On the one hand, platinum resources are scarce and expensive. On the other hand, the dispersion of platinum metal in currently used commercial platinum-carbon catalysts is not ideal and it is prone to agglomeration and deactivation. The dissolution and agglomeration of platinum at the cathode of hydrogen fuel cells lead to a significant decrease in platinum surface area over time, affecting the lifespan of the fuel cell. Existing technologies mainly improve the performance of platinum-carbon catalysts by controlling the particle size, morphology, and structure of platinum, as well as the specific surface area and pore structure of the support; some literature also reports that the performance of platinum-carbon catalysts can be improved by modifying the carbon support.

[0004] Carbon supports can increase the specific surface area of ​​catalysts, reduce metal particle agglomeration, and improve metal utilization. Increasing the platinum loading on carbon supports is beneficial for manufacturing thinner, higher-performance membrane electrodes, but significantly increasing the platinum loading is more likely to cause accumulation between platinum metal particles, leading to a sharp decline in the utilization rate of active sites. In addition, the platinum loading of platinum-carbon catalysts for hydrogen fuel cells in practical applications is at least 20 wt%, which is much more difficult to manufacture than chemical platinum-carbon catalysts (platinum loading less than 5 wt%).

[0005] The deactivation of platinum-carbon catalysts caused by carbon corrosion in proton exchange membrane fuel cells has attracted considerable attention in this field. Furthermore, platinum accelerates the carbon corrosion rate; the higher the platinum loading, the faster the carbon corrosion. On the one hand, a higher number of defect sites on the carbon support is beneficial for increasing the platinum loading, but it also exacerbates carbon corrosion. On the other hand, increasing the degree of graphitization can alleviate carbon corrosion, but it also makes the carbon support surface chemically inert, making it difficult to uniformly disperse platinum on the carbon support.

[0006] The information disclosed in the foregoing background section is only used to enhance the understanding of the background of the present invention, and may include information that is not known to those skilled in the art. [Summary of the Invention]

[0007] The first objective of this invention is to provide a carbon-supported platinum group metal catalyst that significantly improves the specific activity and electrochemical active area, especially under high platinum loading conditions. The second objective of this invention, based on the foregoing objectives, is to improve the overall performance of the catalyst, particularly enhancing the stability of the specific activity and electrochemical active area. The third objective of this invention, based on the foregoing objectives, is to improve the carbon corrosion resistance of the carbon-supported platinum group metal catalyst. The fourth objective of this invention, based on the foregoing objectives, is to provide a simple method for preparing the carbon-supported platinum group metal catalyst. Other objectives of this invention are embodied through the detailed discussion and examples provided herein.

[0008] In order to achieve one or more of the aforementioned objectives, the present invention provides the following technical solutions.

[0009] 1. A carbon-supported platinum group metal catalyst, characterized in that, in the S2P spectrum of its XPS analysis, the area of ​​the characteristic peaks between 160 eV and 170 eV and between 162 eV and 166 eV is greater than 92%, or greater than 95%, or greater than 98%; the support of the carbon-supported platinum group metal catalyst is conductive carbon black doped with sulfur; the mass fraction of platinum group metal in the carbon-supported platinum group metal catalyst is 20% to 70%, preferably 40% to 70%, more preferably 45% to 65%.

[0010] 2. The carbon-supported platinum group metal catalyst according to aspect 1, characterized in that, in the range of 160 eV to 170 eV, the peak area of ​​any characteristic peak located outside the range of 162 eV to 166 eV is less than 5%, preferably less than 1%; or preferably, in the range of 160 eV to 170 eV, there is only a characteristic peak located between 162 eV and 166 eV.

[0011] 3. The carbon-supported platinum group metal catalyst according to aspect 1, characterized in that there are bimodal peaks between 162 eV and 166 eV.

[0012] 4. The carbon-supported platinum group metal catalyst according to aspect 1, characterized in that the conductive carbon black is ordinary conductive carbon black, superconducting carbon black or extra-conducting carbon black.

[0013] 5. The carbon-supported platinum group metal catalyst according to aspect 1, characterized in that the support for the carbon-supported platinum group metal catalyst is sulfur-boron-doped conductive carbon black.

[0014] 6. The carbon-supported platinum group metal catalyst according to aspect 5, characterized in that: no characteristic peaks are found in the B1s spectrum of its XPS analysis between 185 eV and 200 eV; and preferably, signals of B2O3 and B are detected in TG-MS testing.

[0015] 7. The carbon-supported platinum group metal catalyst according to aspect 1, characterized in that the support for the carbon-supported platinum group metal catalyst is sulfur-phosphorus-doped conductive carbon black.

[0016] 8. The carbon-supported platinum group metal catalyst according to aspect 7, characterized in that there are no characteristic peaks between 125 eV and 145 eV in the P2p spectrum of its XPS analysis; and preferably, signals of P, P2O3 and P2O5 are detected in TG-MS testing.

[0017] 9. The carbon-supported platinum group metal catalyst according to aspect 1, characterized in that the support for the carbon-supported platinum group metal catalyst is sulfur-phosphorus-boron-doped conductive carbon black.

[0018] 10. The carbon-supported platinum group metal catalyst according to aspect 9, characterized in that, in its XPS analysis, there is no characteristic peak of B1s between 185 eV and 200 eV, and no characteristic peak of P2p between 125 eV and 145 eV; and preferably, signals of B2O3 and B are detected in TG-MS testing, and signals of P, P2O3 and P2O5 are detected in TG-MS testing.

[0019] 11. The carbon-supported platinum group metal catalyst according to aspect 1, characterized in that the platinum group metal is selected from platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), osmium (Os), and ruthenium (Ru), preferably selected from platinum, palladium, rhodium, and iridium, and even more preferably selected from platinum and palladium, for example, platinum.

[0020] 12. The carbon-supported platinum group metal catalyst according to aspect 1, characterized in that the resistivity of the carbon-supported platinum group metal catalyst is <10 Ω·m, preferably <5 Ω·m, or preferably <2 Ω·m.

[0021] 13. A hydrogen fuel cell, characterized in that the anode and / or cathode of the hydrogen fuel cell use a carbon-supported platinum group metal catalyst as described in any one of aspects 1 to 12.

[0022] 14. A carbon material, characterized in that the carbon material is a sulfur-doped conductive carbon black; in its XPS analysis S2P spectrum peaks, there are only characteristic peaks between 162 eV and 166 eV between 160 eV and 170 eV; and preferably, in the XPS analysis of the carbon material, the oxygen mass fraction is greater than or equal to 4%, preferably 4% to 15%.

[0023] Not limited to any known theory, preferably, based on the analysis of experimental data on characteristic peaks located between 162 eV and 166 eV, for example, as illustrated and discussed in the present invention, the characteristic peaks located between 162 eV and 166 eV are believed to be characteristic peaks of thiophene-type sulfur. In one embodiment, preferably, the characteristic peaks of thiophene-type sulfur are believed to be bimodal.

[0024] Heteroatoms can bond with carbon materials in various ways, and there are various interactions between heteroatoms. Different preparation methods, raw materials, and different operation steps and conditions in the doping process will affect the bonding mode between heteroatoms and carbon materials and the interactions between heteroatoms, resulting in significant differences in the properties of heteroatoms and carbon materials, and causing significant changes in their functions. In this field, how to control the bonding mode between heteroatoms and carbon materials and the interactions between heteroatoms is a challenge when doping atoms. The research of this invention has found that when doping conductive carbon black, by controlling the bonding mode between heteroatoms and conductive carbon black and the interactions between heteroatoms, carbon materials with unique properties can be produced, thereby significantly improving the specific activity and electrochemical active area, improving the overall performance of the catalyst, improving the stability of the specific activity and electrochemical active area, and improving the carbon corrosion resistance of carbon-supported platinum group metal catalysts, etc.

[0025] Compared with the prior art, the present invention can achieve the following beneficial technical effects.

[0026] I. This invention uses a simple method to manufacture a type of conductive carbon black with unique surface-doped atoms. Compared with existing doped carbon materials, the sulfur doped on the surface of this conductive carbon black exists only in the form of thiophene-type sulfur, and the nitrogen doped on the surface can exist only in the form of pyrrole-type nitrogen. These characteristics can significantly improve the specific activity and electrochemical active area of ​​carbon-supported platinum group metal catalysts. Furthermore, the surface of this conductive carbon black can be doped with phosphorus and / or boron. The surface-doped phosphorus can have characteristic peaks only between 132.5 eV and 134.5 eV, and the surface-doped boron can have characteristic peaks only between 189 eV and 191 eV. These characteristics can improve the overall performance of carbon-supported platinum group metal catalysts, especially improving the stability of specific activity and electrochemical active area. Furthermore, the surface of this conductive carbon black can be multi-doped with multiple (e.g., three or four) heteroelements. This feature is beneficial to improving the carbon corrosion resistance of carbon-supported platinum group metal catalysts.

[0027] Second, the doped conductive carbon black of the present invention is suitable for manufacturing carbon-supported platinum group metal catalysts with high platinum group metal loading, and still has excellent comprehensive catalytic performance and carbon corrosion resistance when the platinum group metal loading is as high as 70 wt%.

[0028] III. The platinum group metal (PGM) loading content of carbon-supported platinum fuel cell catalysts in practical applications is generally above 20 wt%, and it is very difficult to manufacture high-performance catalysts with high PGM loading. Chemical reduction is a simple process, but the utilization rate of PGM is low, resulting in low catalytic activity. However, using the doped conductive carbon black manufactured in this invention as a support, a high PGM catalyst with excellent specific activity and stability can be easily manufactured using an aqueous phase chemical reduction method.

[0029] As examples, the present invention provides the following exemplary embodiments, or combinations thereof:

[0030] The first series of exemplary embodiments of the present invention include:

[0031] 1. A platinum-carbon catalyst, characterized in that, in the S2P spectrum of its XPS analysis, there is only a characteristic peak between 162 eV and 166 eV (preferably a characteristic peak of thiophene sulfur) between 160 eV and 170 eV.

[0032] 2. The platinum-carbon catalyst according to Example 1 is characterized in that, based on the mass of the catalyst, the mass fraction of platinum is 20% to 70%, preferably 40% to 70%.

[0033] 3. The platinum-carbon catalyst according to Example 1, characterized in that the characteristic peaks of the thiophene-type sulfur are located at 163.9 ± 0.5 eV and 165.1 ± 0.5 eV.

[0034] 4. The platinum-carbon catalyst according to Example 1, characterized in that the resistivity of the platinum-carbon catalyst is <10.0 Ωom.

[0035] 5. The platinum-carbon catalyst according to Example 1, characterized in that the support of the platinum-carbon catalyst is sulfur-doped conductive carbon black, sulfur-doped graphene or sulfur-doped carbon nanotubes.

[0036] 6. The platinum-carbon catalyst according to Example 5, characterized in that the conductive carbon black is EC-300J, EC-600JD, ECP600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.

[0037] 7. A method for preparing a platinum-carbon catalyst, comprising:

[0038] (1) Steps for manufacturing sulfur-doped carbon material: Place the carbon material in an inert gas containing thiophene, heat it to 1000℃~1500℃ at a rate of 8℃ / min~15℃ / min, and then keep it at a constant temperature for 0.5 h~10 h to obtain sulfur-doped carbon material;

[0039] (2)The step of loading platinum onto the sulfur-doped carbon material obtained in(1).

[0040] 8. The preparation method according to Example 7 is characterized in that the mass of thiophene is based on the mass of sulfur it contains, and the mass ratio of the carbon material to thiophene is 20:1 to 2:1.

[0041] 9. The preparation method according to Example 7, characterized in that the temperature of the isothermal treatment is 1150℃~1450℃.

[0042] 10. The preparation method according to Example 7, wherein the carbon material is conductive carbon black, graphene or carbon nanotube.

[0043] 11. The preparation method according to Example 10, wherein the conductive carbon black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.

[0044] 12. The preparation method according to Example 7 is characterized in that the oxygen mass fraction in the XPS analysis of the carbon material is greater than 4%.

[0045] 13. The preparation method according to Example 7 is characterized in that the resistivity of the carbon material is <10 Ωom.

[0046] 14. The preparation method according to Example 7 is characterized in that the specific surface area of ​​the carbon material is 10 m2 / g to 2000 m2 / g.

[0047] 15. The preparation method according to Example 7, characterized in that the step of loading platinum includes:

[0048] (a) Disperse the sulfur-doped carbon material obtained in (1) with the platinum precursor in an aqueous phase and adjust the pH to 8-12;

[0049] (b) Reduce by adding a reducing agent;

[0050] (c) The solid is separated and post-processed to obtain the platinum-carbon catalyst.

[0051] 16. The preparation method according to Example 15, characterized in that the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5 mol / L to 5 mol / L.

[0052] 17. The preparation method according to Example 15 is characterized in that, in (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the molar ratio of the reducing agent to platinum is 2 to 100; the reduction temperature is 60°C to 90°C; and the reduction time is 4 h to 15 h.

[0053] 18. A platinum-carbon catalyst, characterized in that the catalyst is prepared by any of the methods in Examples 7 to 17.

[0054] 19. A hydrogen fuel cell, characterized in that the anode and / or cathode of the hydrogen fuel cell use any of the platinum-carbon catalysts in Examples 1 to 6 and 18.

[0055] The second series of exemplary embodiments of the present invention includes:

[0056] 1. A sulfur-boron-doped carbon material, characterized in that, in the S2P spectrum of its XPS analysis, there are only characteristic peaks between 162 eV and 166 eV (preferably characteristic peaks of thiophene-type sulfur) between 160 eV and 170 eV.

[0057] 2. The sulfur-boron-doped carbon material according to Example 1 is characterized in that, in its XPS analysis B1s spectrum, there are two characteristic peaks between 191 eV and 193 eV, and no other characteristic peaks between 185 eV and 200 eV.

[0058] 3. The sulfur-boron-doped carbon material according to Example 1 is characterized in that, in its XPS analysis, the mass fraction of sulfur is 0.1% to 5% and the mass fraction of boron is 0.1% to 5%.

[0059] 4. The sulfur-boron-doped carbon material according to Example 1, characterized in that the sulfur-boron-doped carbon material is sulfur-boron-doped graphene, sulfur-boron-doped carbon nanotubes, or sulfur-boron-doped conductive carbon black.

[0060] 5. The sulfur-boron-doped carbon material according to Example 4, characterized in that the conductive carbon black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.

[0061] 6. A method for preparing a sulfur-boron-doped carbon material, comprising: contacting the sulfur-doped carbon material with a boron source, and treating it in an inert gas at 300°C to 800°C for 0.5 h to 10 h to obtain the sulfur-boron-doped carbon material.

[0062] 7. The method for preparing sulfur-boron-doped carbon material according to Example 6, characterized in that the sulfur-doped carbon material is prepared by the following method: contacting carbon material with a sulfur source and treating it in an inert gas at 400°C to 1500°C for 0.5 h to 10 h to obtain the sulfur-doped carbon material.

[0063] 8. The method for preparing sulfur-boron-doped carbon material according to Example 7, characterized in that, in the method for preparing sulfur-doped carbon material, the mass of sulfur source is based on the mass of sulfur it contains, and the mass ratio of carbon material to sulfur source is 20:1 to 2:1.

[0064] 9. The method for preparing sulfur-boron-doped carbon material according to Example 7, characterized in that the mass of the boron source is based on the mass of the boron it contains, and the mass ratio of the carbon material to the boron source is 100:1 to 5:1.

[0065] 10. The method for preparing sulfur-boron-doped carbon material according to Example 6, characterized in that the boron source is one or more of boric acid and borate.

[0066] 11. The method for preparing sulfur-boron-doped carbon material according to Example 7, characterized in that the sulfur source is one or more of elemental sulfur, hydrogen sulfide, carbon disulfide, sodium thiosulfate, thiophene, sulfate and sulfonate.

[0067] 12. The method for preparing sulfur-boron-doped carbon material according to Example 7, characterized in that the resistivity of the carbon material is <10 Ω•m, the specific surface area is 10 m2 / g to 2000 m2 / g, and the oxygen mass fraction is greater than 4%.

[0068] 13. A sulfur-boron-doped carbon material, characterized in that it is prepared by any one of the methods in Examples 6 to 12.

[0069] 14. Examples of the application of sulfur-boron-doped carbon materials described in any of embodiments 1 to 5 and 13 as electrode materials in electrochemistry.

[0070] 15. A platinum-carbon catalyst, characterized in that it comprises a carbon support and platinum metal supported thereon, wherein the carbon support is a sulfur-boron-doped carbon material; in the S2P spectrum of the XPS analysis of the platinum-carbon catalyst, there are only characteristic peaks between 162 eV and 166 eV (preferably characteristic peaks of thiophene sulfur) between 160 eV and 170 eV.

[0071] 16. The platinum-carbon catalyst according to Example 15 is characterized in that there are no characteristic peaks in the B1s spectrum of its XPS analysis between 185 eV and 200 eV.

[0072] 17. A method for preparing a platinum-carbon catalyst, comprising:

[0073] (1) Steps for manufacturing sulfur-boron-doped carbon material: The sulfur-doped carbon material is brought into contact with a boron source and treated in an inert gas at 300°C to 800°C for 0.5 h to 10 h to obtain the sulfur-boron-doped carbon material.

[0074] (2) Step of loading platinum on the sulfur-boron-doped carbon material obtained in (1).

[0075] 18. The method for preparing the platinum-carbon catalyst according to Example 17, characterized in that the sulfur-doped carbon material is prepared by contacting the carbon material with a sulfur source and treating it in an inert gas at 400°C to 1500°C for 0.5 h to 10 h to obtain the sulfur-doped carbon material.

[0076] 19. The method for preparing the platinum-carbon catalyst according to Example 17, characterized in that the step of supporting platinum includes:

[0077] (a) Disperse the sulfur-boron-doped carbon material obtained in (1) with the platinum precursor in an aqueous phase and adjust the pH to 8-12;

[0078] (b) Reduce by adding a reducing agent;

[0079] (c) The solid is separated and post-processed to obtain the platinum-carbon catalyst.

[0080] 20. The method for preparing the platinum-carbon catalyst according to Example 19, characterized in that, in (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; and the concentration of the platinum precursor is 0.5 mol / L to 5 mol / L.

[0081] 21. The method for preparing the platinum-carbon catalyst according to Example 19, characterized in that, in (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the molar ratio of the reducing agent to platinum is 2 to 100; the reduction temperature is 60°C to 90°C; and the reduction time is 4 h to 15 h.

[0082] 22. A platinum-carbon catalyst, characterized in that it is prepared by any of the methods in Examples 17 to 21.

[0083] 23. A hydrogen fuel cell, characterized in that the anode and / or cathode of the hydrogen fuel cell use a platinum-carbon catalyst as exemplified by embodiment 15 or 22.

[0084] The exemplary embodiments of the third series of the present invention include:

[0085] 1. A sulfur-phosphorus-doped carbon material, characterized in that, in the S2P spectrum of its XPS analysis, there is only a characteristic peak between 162 eV and 166 eV (preferably a characteristic peak of thiophene-type sulfur) between 160 eV and 170 eV.

[0086] 2. The sulfur-phosphorus-doped carbon material according to Example 1 is characterized in that there is a characteristic peak in the P2p spectrum of its XPS analysis between 125 eV and 145 eV.

[0087] 3. The sulfur-phosphorus-doped carbon material according to Example 1 is characterized in that, in its XPS analysis, the mass fraction of sulfur is 0.1% to 5% and the mass fraction of phosphorus is 0.01% to 5%.

[0088] 4. The sulfur-phosphorus-doped carbon material according to Example 1, characterized in that the sulfur-phosphorus-doped carbon material is sulfur-phosphorus-doped graphene, sulfur-phosphorus-doped carbon nanotubes, or sulfur-phosphorus-doped conductive carbon black.

[0089] 5. The sulfur-phosphorus doped carbon material according to Example 4, characterized in that the conductive carbon black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.

[0090] 6. A method for preparing a sulfur-phosphorus-doped carbon material, comprising:

[0091] (1) Phosphorus doping steps: Carbon material is contacted with a phosphorus source and treated in an inert gas at 300℃~800℃ for 0.5 h~10 h to obtain phosphorus-doped carbon material; and

[0092] (2) Step of doping with sulfur: The phosphorus-doped carbon material in (1) is brought into contact with a sulfur source and treated in an inert gas at 400℃~1500℃ for 0.5 h~10 h to obtain the sulfur-phosphorus-doped carbon material.

[0093] 7. The preparation method according to Example 6, wherein the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.

[0094] 8. The preparation method according to Example 6, characterized in that the mass of the phosphorus source is based on the mass of phosphorus contained therein, and the mass ratio of the carbon material to the phosphorus source is 10000:1 to 20:1.

[0095] 9. The preparation method according to Example 6, wherein the sulfur source is elemental sulfur.

[0096] 10. The preparation method according to Example 6, characterized in that the mass of the sulfur source is based on the mass of sulfur it contains, and the mass ratio of the carbon material to the sulfur source is 20:1 to 2:1.

[0097] 11. The preparation method according to Example 6, characterized in that the temperature in (2) is 1000℃~1500℃.

[0098] 12. The preparation method according to Example 6 is characterized in that the resistivity of the carbon material in (1) is <10 Ω•m, the specific surface area is 10 m2 / g to 2000 m2 / g, and the oxygen mass fraction analyzed by XPS is greater than 4%.

[0099] 13. The preparation method according to Example 6 is characterized in that, in (1), the carbon material is contacted with the phosphorus source by immersing the carbon material in an aqueous solution of the phosphorus source and then drying it.

[0100] 14. A sulfur-phosphorus-doped carbon material, characterized in that it is prepared by any one of the methods in Examples 6 to 13.

[0101] 15. Examples of the application of any of the sulfur-phosphorus-doped carbon materials in embodiments 1 to 5 and 14 as electrode materials in electrochemistry.

[0102] 16. A platinum-carbon catalyst, characterized in that it comprises a carbon support and platinum metal supported thereon, wherein the carbon support is a sulfur-phosphorus-doped carbon material; in the S2P spectrum of the platinum-carbon catalyst analyzed by XPS, there are only characteristic peaks between 162 eV and 166 eV (preferably characteristic peaks of thiophene sulfur) between 160 eV and 170 eV.

[0103] 17. The platinum-carbon catalyst according to Example 16 is characterized in that there are no characteristic peaks in the P2p spectrum of its XPS analysis between 125 eV and 145 eV.

[0104] 18. A method for preparing a platinum-carbon catalyst, comprising:

[0105] (1) Steps for manufacturing phosphorus-doped carbon materials: Carbon materials are contacted with a phosphorus source and treated in an inert gas at 300℃~800℃ for 0.5 h~10 h to obtain phosphorus-doped carbon materials; and

[0106] (2) Steps for manufacturing sulfur-phosphorus doped carbon material: The phosphorus doped carbon material in (1) is brought into contact with a sulfur source and treated in an inert gas at 400℃~1500℃ for 0.5 h~10 h to obtain the sulfur-phosphorus doped carbon material.

[0107] (3) Step of loading platinum onto the sulfur-phosphorus-doped carbon material obtained in (2).

[0108] 19. The method for preparing the platinum-carbon catalyst according to Example 18, characterized in that the step of supporting platinum includes:

[0109] (a) Disperse the sulfur-phosphorus-doped carbon material obtained in (2) with the platinum precursor in an aqueous phase and adjust the pH to 8-12;

[0110] (b) Reduce by adding a reducing agent;

[0111] (c) The solid is separated and post-processed to obtain the platinum-carbon catalyst.

[0112] 20. The method for preparing the platinum-carbon catalyst according to Example 19, characterized in that, in (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; and the concentration of the platinum precursor is 0.5 mol / L to 5 mol / L.

[0113] 21. The method for preparing the platinum-carbon catalyst according to Example 19, characterized in that, in (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the molar ratio of the reducing agent to platinum is 2 to 100; the reduction temperature is 60°C to 90°C; and the reduction time is 4 h to 15 h.

[0114] 22. A platinum-carbon catalyst, characterized in that it is prepared by any one of the methods in Examples 18 to 21.

[0115] 23. A hydrogen fuel cell, characterized in that the anode and / or cathode of the hydrogen fuel cell use a platinum-carbon catalyst as exemplified by Embodiment 16 or 22.

[0116] 24. The exemplary embodiments of the fourth series of the present invention include:

[0117] 1. A sulfur-phosphorus-boron-doped carbon material, characterized in that, in the S2P spectrum of its XPS analysis, there is only a characteristic peak between 162 eV and 166 eV (preferably a characteristic peak of thiophene-type sulfur) between 160 eV and 170 eV.

[0118] 2. The sulfur-phosphorus-boron-doped carbon material according to Example 1 is characterized in that, in its XPS analysis of the B1s spectrum, there is a characteristic peak between 190.2 eV and 191.2 eV.

[0119] 3. The sulfur-phosphorus-boron-doped carbon material according to Example 1, characterized in that the sulfur-phosphorus-boron-doped carbon material is sulfur-phosphorus-boron-doped graphene, sulfur-phosphorus-boron-doped carbon nanotubes, or sulfur-phosphorus-boron-doped conductive carbon black.

[0120] 4. The sulfur-phosphorus-boron-doped carbon material according to Example 3, characterized in that the conductive carbon black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.

[0121] 5. The sulfur-phosphorus-boron-doped carbon material according to Example 1 is characterized in that, in its XPS analysis, the mass fraction of sulfur is 0.01% to 4%, the mass fraction of phosphorus is 0.01% to 4%, and the mass fraction of boron is 0.01% to 4%.

[0122] 6. A method for doping carbon material, comprising: (1) contacting the carbon material with a phosphorus source and a boron source and treating it in an inert gas at 300℃~800℃ for 0.5 h~10 h; (2) then contacting it with a sulfur source and treating it in an inert gas at 1000℃~1500℃ for 0.5 h~10 h.

[0123] 7. The method for doping carbon materials according to Example 7, wherein the sulfur source is elemental sulfur.

[0124] 8. The method for doping carbon material according to Example 7, characterized in that the mass of the sulfur source is based on the mass of sulfur it contains, and the mass ratio of the carbon material to the sulfur source is 20:1 to 2:1.

[0125] 9. The method for doping carbon materials according to Example 7, wherein the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.

[0126] 10. The method for doping carbon material according to Example 7, characterized in that the mass of the phosphorus source is based on the mass of phosphorus it contains, and the mass ratio of the carbon material to the phosphorus source is 10000:1 to 10:1.

[0127] 11. The method for doping carbon materials according to Example 7, characterized in that the boron source is one or more of boric acid and borate.

[0128] 12. The method for doping carbon material according to Example 7, characterized in that the mass of the boron source is based on the mass of boron it contains, and the mass ratio of the carbon material to the boron source is 10000:1 to 10:1.

[0129] 13. A sulfur-phosphorus-boron-doped carbon material, characterized in that it is prepared by any one of the methods in Examples 6 to 12.

[0130] 14. Examples of the application of sulfur-phosphorus-boron-doped carbon materials as electrode materials in electrochemistry according to any one of embodiments 1 to 5 and 13.

[0131] 15. A platinum-carbon catalyst, comprising a carbon support and platinum metal supported thereon, characterized in that the carbon support is a sulfur-phosphorus-boron-doped carbon material, and the S2P spectrum of the platinum-carbon catalyst in XPS analysis has only a characteristic peak between 162 eV and 166 eV (preferably a characteristic peak of thiophene sulfur) between 160 eV and 170 eV.

[0132] 16. The platinum-carbon catalyst according to Example 15 is characterized in that, in its XPS analysis, there is no characteristic peak of B1s between 185 eV and 200 eV, and no characteristic peak of P2p between 125 eV and 145 eV.

[0133] 17. The platinum-carbon catalyst according to Example 15, characterized in that its carbon support is a sulfur-phosphorus-boron-doped carbon material as described in any one of Examples 1 to 6 and 16.

[0134] 18. A method for preparing a platinum-carbon catalyst, comprising:

[0135] (1) Steps for manufacturing carbon support: first contact the carbon material with a phosphorus source and a boron source, and treat it in an inert gas at 300℃~800℃ for 0.5 h~10 h; then contact it with a sulfur source, and treat it in an inert gas at 1000℃~1500℃ for 0.5 h~10 h to obtain the carbon support;

[0136] (2)The step of loading platinum onto the carbon support obtained in (1).

[0137] 19. The method for preparing a platinum-carbon catalyst according to Example 18, characterized in that the step (2) of supporting platinum includes:

[0138] (a) Disperse the carbon support obtained in (1) with the platinum precursor in an aqueous phase and adjust the pH to 8-12;

[0139] (b) Reduce by adding a reducing agent;

[0140] (c) The solid is separated and post-processed to obtain the platinum-carbon catalyst.

[0141] 20. The method for preparing the platinum-carbon catalyst according to Example 22, characterized in that, in (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; and the concentration of the platinum precursor is 0.5 mol / L to 5 mol / L.

[0142] 21. The method for preparing the platinum-carbon catalyst according to Example 22 is characterized in that, in (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the molar ratio of the reducing agent to platinum is 2 to 100; the reduction temperature is 60°C to 90°C; and the reduction time is 4 h to 15 h.

[0143] 22. A platinum-carbon catalyst, characterized in that it is prepared by any one of the methods in Examples 18 to 21.

[0144] 23. A hydrogen fuel cell, characterized in that the anode and / or cathode of the hydrogen fuel cell use a platinum-carbon catalyst as described in any of the exemplary embodiments 15 to 17 and 22.

[0145] The exemplary embodiments of the fifth series of the present invention include:

[0146] 1. A sulfur-doped carbon material, characterized in that, in the S2P spectrum of its XPS analysis, there is only a characteristic peak between 162 eV and 166 eV (preferably a characteristic peak of thiophene sulfur) between 160 eV and 170 eV.

[0147] 2. The sulfur-doped carbon material according to Example 1, characterized in that the resistivity of the sulfur-doped carbon material is <10.0 Ωom.

[0148] 3. The sulfur-doped carbon material according to Example 1, characterized in that the sulfur mass fraction in the XPS analysis of the sulfur-doped carbon material is 0.1% to 10%.

[0149] 4. The sulfur-doped carbon material according to Example 1, characterized in that the oxygen mass fraction is greater than 4% in the XPS analysis of the sulfur-doped carbon material.

[0150] 5. The sulfur-doped carbon material according to Example 1, characterized in that the specific surface area of ​​the sulfur-doped carbon material is 10 m2 / g to 2000 m2 / g.

[0151] 6. The sulfur-doped carbon material according to Example 1, characterized in that the sulfur-doped carbon material is sulfur-doped conductive carbon black, sulfur-doped graphene, or sulfur-doped carbon nanotube.

[0152] 7. A carbon support for a platinum-carbon catalyst, characterized in that the carbon support is sulfur-doped conductive carbon black, and in its XPS analysis S2P spectrum, there is only a characteristic peak between 162 eV and 166 eV (preferably a characteristic peak of thiophene-type sulfur) between 160 eV and 170 eV; in its XPS analysis, the oxygen mass fraction is 4% to 15%, the sulfur mass fraction is 0.2% to 3%; and its specific surface area is 200 m2 / g to 2000 m2 / g.

[0153] 8. The carbon carrier according to Example 7, wherein the conductive carbon black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.

[0154] 9. A method for preparing a sulfur-doped carbon material, comprising: placing the carbon material in an inert gas containing thiophene, heating it to 1000℃~1500℃ at a rate of 8℃ / min~15℃ / min, and then holding it at a constant temperature for 0.5 h~10 h to obtain the sulfur-doped carbon material.

[0155] 10. The preparation method according to Example 9, characterized in that the mass of thiophene is based on the mass of sulfur it contains, and the mass ratio of the carbon material to thiophene is 20:1 to 2:1.

[0156] 11. The preparation method according to Example 9, characterized in that the temperature of the isothermal treatment is 1150°C to 1450°C.

[0157] 12. Examples of the application of sulfur-doped carbon materials or carbon supports as electrode materials in electrochemistry according to any one of embodiments 1 to 8.

[0158] 13. A fuel cell, characterized in that the fuel cell uses sulfur-doped carbon material or carbon support as described in any one of the exemplary embodiments 1 to 8.

[0159] 14. The fuel cell according to Example Embodiment 13, wherein the fuel cell is a hydrogen fuel cell.

[0160] 15. A metal-air battery, characterized in that the metal-air battery uses sulfur-doped carbon material or carbon carrier as described in any one of the exemplary embodiments 1 to 8.

[0161] 16. The metal-air battery according to Example Embodiment 15, wherein the metal-air battery is a lithium-air battery.

[0162] The sixth series of exemplary embodiments of the present invention includes:

[0163] 1. A carbon-doped material, characterized in that, in the S2P spectrum of its XPS analysis, there is only a characteristic peak between 162 eV and 166 eV (preferably a characteristic peak of thiophene sulfur) between 160 eV and 170 eV.

[0164] 2. The doped carbon material according to Example 1 is characterized in that there are three characteristic peaks between 189 eV and 194 eV in the B1s spectrum peak of its XPS analysis.

[0165] 3. The doped carbon material according to Example 1, characterized in that the carbon material is sulfur-nitrogen-boron doped conductive carbon black.

[0166] 4. The doped carbon material according to Example 5, characterized in that the conductive carbon black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.

[0167] 5. The carbon-doped material according to Example 1 is characterized in that, in its XPS analysis, the mass fraction of sulfur is 0.1% to 6%, the mass fraction of nitrogen is 0.01% to 6%, and the mass fraction of boron is 0.01% to 6%.

[0168] 6. A method for doping carbon material, comprising: contacting carbon material with a sulfur source, a nitrogen source and a boron source, and treating it in an inert gas at 1000℃~1500℃ for 0.5 h~10 h to obtain the doped carbon material.

[0169] 7. The method for doping carbon material according to Example 7, characterized in that the mass of the sulfur source is based on the mass of sulfur it contains, and the mass ratio of the carbon material to the sulfur source is 20:1 to 2:1.

[0170] 8. The method for doping carbon material according to Example 7, characterized in that the mass of the nitrogen source is based on the mass of nitrogen it contains, and the mass ratio of the carbon material to the nitrogen source is 500:1 to 5:1.

[0171] 9. The method for doping carbon material according to Example 7, characterized in that the mass of the boron source is based on the mass of boron it contains, and the mass ratio of the carbon material to the boron source is 10000:1 to 10:1.

[0172] 10. The method for doping carbon materials according to Example 7, wherein the sulfur source is elemental sulfur.

[0173] 11. The method for doping carbon materials according to Example 7, wherein the nitrogen source is ammonia / or urea.

[0174] 12. The method for doping carbon materials according to Example 7, characterized in that the boron source is one or more of boric acid and borate.

[0175] 13. A carbon-doped material, characterized in that it is prepared by any one of the methods in Examples 7 to 13.

[0176] 14. Examples of the application of the doped carbon material described in any of embodiments 1 to 6 and 14 as an electrode material in electrochemistry.

[0177] 15. A platinum-carbon catalyst, characterized in that, in the N1s spectrum peaks of its XPS analysis, the area of ​​the characteristic peaks between 397.5 eV and 398.5 eV accounts for more than 60% of the total area of ​​the characteristic peaks between 395 eV and 405 eV.

[0178] 16. The platinum-carbon catalyst according to Example 16 is characterized in that, in the S2P spectrum of its XPS analysis, there is only a characteristic peak between 162 eV and 166 eV (preferably a characteristic peak of thiophene sulfur) between 160 eV and 170 eV.

[0179] 17. The platinum-carbon catalyst according to Example 16, characterized in that its carbon support is a sulfur-nitrogen-boron-doped carbon material.

[0180] 18. The platinum-carbon catalyst according to Example 16, characterized in that its carbon support is a doped carbon material as described in any one of Examples 1 to 6 and 14.

[0181] 19. A method for preparing a platinum-carbon catalyst, comprising:

[0182] (1)Doping steps of carbon materials: The carbon material is contacted with sulfur source, nitrogen source and boron source, and treated in an inert gas at 1000℃~1500℃ (preferably isothermal treatment) for 0.5 h~10 h to obtain doped carbon material;

[0183] (2)The step of loading platinum on the doped carbon material obtained in(1).

[0184] 20. The method for preparing the platinum-carbon catalyst according to Example 19, characterized in that the step of supporting platinum includes:

[0185] (a) Disperse the doped carbon material obtained in (1) with the platinum precursor in an aqueous phase and adjust the pH to 8-12;

[0186] (b) Reduce by adding a reducing agent;

[0187] (c) The solid is separated and post-processed to obtain the platinum-carbon catalyst.

[0188] 21. The method for preparing the platinum-carbon catalyst according to Example 20, characterized in that, in (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; and the concentration of the platinum precursor is 0.5 mol / L to 5 mol / L.

[0189] 22. The method for preparing the platinum-carbon catalyst according to Example 20, characterized in that, in (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the molar ratio of the reducing agent to platinum is 2 to 100; the reduction temperature is 60°C to 90°C; and the reduction time is 4 h to 15 h.

[0190] 23. A platinum-carbon catalyst, characterized in that it is prepared by any one of the methods in Examples 19 to 22.

[0191] 24. A hydrogen fuel cell, characterized in that the anode and / or cathode of the hydrogen fuel cell use a platinum-carbon catalyst as described in any of the exemplary embodiments 16 to 18 and 23.

[0192] Other features and advantages of the present invention will be described in detail in the Detailed Description section.

Implementation Method

[0193] The present invention will be described in detail below with reference to specific embodiments. However, it should be noted that the scope of protection of the present invention is not limited by these specific embodiments and principle explanations, but is determined by the scope of the claims.

[0194] In this invention, except for the contents explicitly stated, any matters or matters not mentioned are directly applicable to those known in the art without any changes. Moreover, any implementation described herein can be freely combined with one or more other implementations described herein, and the resulting technical solutions or technical ideas are considered as part of the original disclosure or record of this invention, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination to be obviously unreasonable.

[0195] All features disclosed in this invention can be combined arbitrarily, and such combinations should be understood as the content disclosed or recorded in this invention. Unless those skilled in the art consider such combinations to be obviously unreasonable, they should all be regarded as specifically disclosed and recorded in this invention. The numerical points disclosed in this specification include not only the numerical points specifically disclosed in the embodiments, but also the endpoints of each numerical range in the specification. Any range of combinations of these numerical points should be regarded as the range disclosed or recorded in this invention.

[0196] The technical and scientific terms in this invention, where defined, shall be used as defined, and where not defined, shall be understood according to their common meaning in the art.

[0197] The “doping element” in this invention includes nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine, or is selected from these elements.

[0198] In this invention, the term "doped with" a certain element means that the one or more elements specifically mentioned are doped into the material. However, the material may also be doped with other elements besides the one or more elements specifically mentioned, especially those commonly used in the art.

[0199] In this invention, a material "doped" with a certain element means that one or more of the specifically mentioned elements are doped into the material; wherein, in one embodiment, the material may also be doped with other elements besides the specifically mentioned one or more elements; and preferably, the material does not contain any doping elements other than the specifically mentioned one or more elements.

[0200] In this invention, except for "carbon materials containing doped elements" which can be uniquely identified based on context or its own limitations, all other references to "carbon materials" refer to carbon materials without doped elements. The same applies to subordinate concepts of carbon materials.

[0201] In this invention, "carbon black" and "carbon black" are interchangeable technical terms. In this invention, the graphene, carbon nanotubes, and conductive carbon black used in the carbon materials described herein have concepts well-known in the art and belong to different concepts. However, according to this invention, a carbon material may contain a low content of one or more other carbon materials, as long as it still belongs to the kind of carbon material recognized by those skilled in the art. For example, "graphene" may contain trace amounts (e.g., less than 1%, or less than 0.1% by weight) of conductive carbon black and / or carbon nanotubes for various reasons. Preferably, for example, for the purposes of this invention, the conductive carbon black contains less than 5% by weight, preferably less than 2% by weight of graphene and / or carbon nanotubes.

[0202] In this invention, "inert gas" refers to a gas that, in the preparation method of this invention, does not cause any perceptible effect on the performance of the doped carbon material. The same applies to the sub-concept of carbon material.

[0203] The numerical range defined in this invention includes the endpoints of the numerical range. The "range" disclosed herein is given in the form of a lower limit and an upper limit, for example, one or more lower limits and one or more upper limits. A given range can be defined by selecting a lower limit and an upper limit, the selected lower and upper limits defining the boundaries of the given range. All ranges defined in this way are inclusive and composable, meaning that any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-110 and 80-120 are listed for a specific parameter, it is understood that ranges of 60-120 and 80-110 are also predictable. Furthermore, if the listed lower limits are 1 and 2 and the listed upper limits are 3, 4 and 5, then the following ranges are all predictable: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5.

[0204] In this invention, unless otherwise stated, the terms "comprising," "including," "containing," "having," and similar terms indicate an open-ended meaning, but should also be understood to explicitly disclose a closed-ended meaning. For example, "comprising" means that other elements not listed may also be included, but also explicitly discloses the inclusion of only the listed elements. Furthermore, as used herein, "comprising / including" is interpreted as explicitly stating the presence of the mentioned feature, integer, step, or component, but does not exclude the presence or addition of one or more other features, integers, steps, components, or groups thereof. Additionally, the term "comprising" is intended to include embodiments covered by the terms "substantially consisting of" and "consisting of." Similarly, the term "substantially consisting of" is intended to include embodiments covered by the term "consisting of."

[0205] In this invention, unless otherwise stated, all embodiments and preferred embodiments mentioned herein can be combined with each other to form new technical solutions. In particular, for example, with embodiments I, VI, VII, and VIII covered by this invention, the technical features and solutions mentioned therein can be combined internally and with each other, unless such combination is contrary to the purpose of this invention; as well as with the exemplary embodiments of the first to sixth series covered by this invention, the technical features and solutions mentioned therein can be combined internally and with each other, and can also be combined with embodiments I, VI, VII, and VIII, unless such combination is contrary to the purpose of this invention.

[0206] In this invention, unless otherwise stated, all technical features and preferred features mentioned herein can be combined to form new technical solutions.

[0207] In this invention, unless otherwise specified by context or self-definition, the term "pore volume" refers to the total pore volume of single-point adsorption when P / P0 is at its maximum.

[0208] Implementation Method I

[0209] Embodiment I of the present invention provides a carbon-supported platinum group metal catalyst, in which the S2P spectrum of its XPS analysis has only a characteristic peak between 162 eV and 166 eV (preferably the characteristic peak of thiophene sulfur) between 160 eV and 170 eV; the support of the carbon-supported platinum group metal catalyst is sulfur-doped conductive carbon black.

[0210] In one embodiment of Embodiment I, the carbon-supported platinum group metal catalyst according to the present invention is a sulfur-doped catalyst, preferably free of other doping elements besides sulfur.

[0211] In one embodiment of Embodiment I, the platinum group metal is platinum.

[0212] In one embodiment of Embodiment I, the carbon-supported platinum group metal catalyst according to the present invention does not contain any metal elements other than platinum group metals.

[0213] In one embodiment of Embodiment I, in the S2P spectrum of the carbon-supported platinum group metal catalyst according to the present invention, the area of ​​the characteristic peak (preferably the characteristic peak of thiophene sulfur) located between 162 eV and 166 eV is greater than 92%, or greater than 95%, or greater than 98%, or even only the characteristic peak (preferably the characteristic peak of thiophene sulfur) located between 162 eV and 166 eV.

[0214] In one embodiment of Embodiment I, the XPS analysis of the carbon-supported platinum group metal catalyst according to the present invention showed no characteristic peaks between 166 eV and 170 eV.

[0215] In one embodiment of Embodiment I, the carbon-supported platinum group metal catalyst according to the present invention has a platinum mass fraction of 0.1% to 80%, preferably 20% to 70%, and more preferably 40% to 70%, based on the mass of the catalyst.

[0216] In one embodiment of Embodiment I, the resistivity of the carbon-supported platinum group metal catalyst according to the present invention is <10.0 Ω·m, preferably <2.0 Ω·m.

[0217] In one embodiment of Embodiment I, the specific surface area of ​​the carbon-supported platinum group metal catalyst according to the present invention is 80 m2 / g to 1500 m2 / g, preferably 100 m2 / g to 200 m2 / g.

[0218] In one embodiment of Embodiment I, the conductive carbon black of the carbon-supported platinum group metal catalyst according to the present invention may be one or more of the following: Ketjen black series superconducting carbon black, Cabot series conductive carbon black, and series of conductive carbon blacks produced by Evonik Degussa; preferably EC-300J, EC-600JD, ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2.

[0219] In one embodiment of Embodiment I, the characteristic peak (preferably a characteristic peak of thiophene-type sulfur) located between 162 eV and 166 eV of the carbon-supported platinum group metal catalyst according to the present invention is a double peak, located at 163.9 ± 0.5 eV and 165.1 ± 0.5 eV, respectively. In some embodiments of the present invention, the characteristic peak (preferably a characteristic peak of thiophene-type sulfur) located between 162 eV and 166 eV is a double peak, located at 163.5 ± 0.1 eV and 164.7 ± 0.1 eV, respectively.

[0220] Embodiment I of the present invention also provides a method for preparing a carbon-supported platinum group metal catalyst, comprising:

[0221] (1) Steps for manufacturing sulfur-doped carbon materials: Place the carbon material in an inert gas containing thiophene, heat it to 1000℃~1500℃ at a rate of 8℃ / min~15℃ / min, and then keep it at a constant temperature for 0.5 h~10 h to obtain sulfur-doped carbon materials.

[0222] (2) The step of loading platinum group metals (e.g., platinum) onto the sulfur-doped carbon material obtained in (1).

[0223] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment I of the present invention, the mass of thiophene is based on the mass of sulfur it contains, and the mass ratio of the carbon material to thiophene is 20:1 to 2:1; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.

[0224] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment I of the present invention, for the sulfur-doped carbon material in step (1), in its XPS analysis S2P spectrum peak, the area of ​​the characteristic peak (preferably the characteristic peak of thiophene sulfur) between 160 eV and 170 eV is greater than 92%, or greater than 95%, or greater than 98%, or even only the characteristic peak (preferably the characteristic peak of thiophene sulfur) between 162 eV and 166 eV.

[0225] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment I of the present invention, the characteristic peak (preferably the characteristic peak of thiophene sulfur) located between 162 eV and 166 eV is a double peak, located at 163.9 ± 0.5 eV and 165.1 ± 0.5 eV respectively. In some embodiments of the present invention, the characteristic peak (preferably the characteristic peak of thiophene sulfur) located between 162 eV and 166 eV is a double peak, located at 163.5 ± 0.1 eV and 164.7 ± 0.1 eV respectively.

[0226] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment I of the present invention, the temperature of the isothermal treatment is 1150℃~1450℃, preferably 1200℃~1400℃; the time of the isothermal treatment is 1 h~5 h, preferably 2 h~4 h.

[0227] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment I of the present invention, the carbon material is conductive carbon black. The conductive carbon black can be ordinary conductive black, super conductive black, or extra conductive black. For example, the conductive carbon black can be one or more of the Ketjen black series superconducting carbon black, Cabot series conductive carbon black, and the series of conductive carbon blacks produced by Evonik Degussa; preferably, Ketjen black EC-300J, Ketjen black EC-600JD, Ketjen black ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2.

[0228] The preparation method of the carbon-supported platinum group metal catalyst according to Embodiment I of the present invention does not limit the method or source of the conductive carbon black. The conductive carbon black may be acetylene black, furnace black, etc.

[0229] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment I of the present invention, the resistivity of the carbon material can be <10.0 Ω•m, preferably <5.0 Ω•m, and more preferably <2.0 Ω•m.

[0230] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment I of the present invention, when the carbon material in (1) is conductive carbon black, in the Raman spectrum, the ID / IG value of the sulfur-doped conductive carbon black obtained in (1) is smaller than the ID / IG value of the conductive carbon black before doping. In the Raman spectrum, the peak located near 1320 cm-1 is the D peak, and the peak located near 1580 cm-1 is the G peak. ID represents the intensity of the D peak, and IG represents the intensity of the G peak.

[0231] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment I of the present invention, the ID / IG value of the conductive carbon black is generally 0.8 to 5, preferably 1 to 4.

[0232] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment I of the present invention, the specific surface area and pore volume of the carbon material can vary within a large range. Generally, the specific surface area is 10 m2 / g to 2000 m2 / g, and the pore volume is 0.02 mL / g to 6 mL / g.

[0233] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment I of the present invention, the specific surface area of ​​conductive carbon black is 200 m2 / g to 2000 m2 / g.

[0234] In the preparation method of the carbon-supported platinum group metal catalyst according to Embodiment I of the present invention, the inert gas can be nitrogen or argon.

[0235] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment I of the present invention, in one embodiment, carbon material is placed in a tube furnace, a carrier gas containing thiophene is introduced, and the tube furnace is heated to 1000°C to 1500°C at a rate of 8°C / min to 15°C / min, and then kept at a constant temperature for 0.5 h to 10 h to obtain the sulfur-doped carbon material.

[0236] The carrier gas can be nitrogen or argon.

[0237] The volume fraction of thiophene in the carrier gas can be 0.1% to 5.0%.

[0238] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment I of the present invention, in the XPS analysis of the carbon material, the oxygen mass fraction is greater than 4%, preferably 4% to 15%.

[0239] According to the method for preparing a carbon-supported platinum group metal catalyst of Embodiment I of the present invention, the step of supporting the platinum group metal (e.g., platinum) includes:

[0240] (a) Disperse the sulfur-doped carbon material obtained in step (1) with a platinum group metal precursor (e.g., a platinum precursor) in an aqueous phase and adjust the pH to 8 to 12 (preferably adjust the pH to 10 ± 0.5).

[0241] (b)Reduction is carried out by adding a reducing agent;

[0242] (c) The solid is separated and post-processed to obtain the carbon-supported platinum group metal (e.g., carbon-supported platinum) catalyst.

[0243] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment I of the present invention, the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5 mol / L to 5 mol / L.

[0244] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment I of the present invention, in step (a), the pH value of the aqueous phase is adjusted by sodium carbonate aqueous solution, potassium carbonate aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution or ammonia.

[0245] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment I of the present invention, in step (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol.

[0246] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment I of the present invention, in step (b), the molar ratio of the reducing agent to platinum is 2 to 100.

[0247] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment I of the present invention, in step (b), the reduction temperature is 50℃~150℃, preferably 60℃~90℃; the reduction time is 4 h~15 h, preferably 8 h~12 h.

[0248] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment I of the present invention, the sulfur-doped carbon material obtained in step (1) can be easily dispersed in the aqueous phase. However, for some carbon materials, such as Ketjen Black, it is difficult to directly disperse them in the aqueous phase.

[0249] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment I of the present invention, the post-treatment includes: washing, filtering and drying.

[0250] Embodiment I of the present invention also provides a carbon-supported platinum group metal catalyst (e.g., a platinum-carbon catalyst), which is prepared by any of the methods described in Embodiment I of the present invention above.

[0251] Embodiment I of the present invention also provides a hydrogen fuel cell, wherein the anode and / or cathode of the hydrogen fuel cell use any of the carbon-supported platinum group metal catalysts described in Embodiment I of the present invention.

[0252] In one embodiment of Embodiment I, when the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention is used for oxygen reduction reaction, in some embodiments, ECSA > 95 m2g-1-Pt, for example, in the range of 95 m2g-1-Pt to 260 m2g-1-Pt.

[0253] In one embodiment of Embodiment I, when the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention is used for oxygen reduction reaction, in some embodiments, the rate of decrease in mass specific activity after 5000 cycles is <10%.

[0254] In one embodiment of Embodiment I, when the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention is used for oxygen reduction reaction, in some embodiments, the half-wave potential is >0.89V, for example 0.89V to 0.93V.

[0255] In one embodiment of Embodiment I, when the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention is used for oxygen reduction reaction, in some embodiments, the mass specific activity is > 0.18 A mg-1-Pt, for example 0.18 A mg-1-Pt to 0.39 A mg-1-Pt.

[0256] Existing platinum-carbon catalysts for hydrogen fuel cells have the disadvantages of low specific activity and poor stability. This invention significantly improves the specific activity and stability of platinum-carbon catalysts by doping sulfur in the form of thiophene-type sulfur on the surface of conductive carbon black.

[0257] In one embodiment of Embodiment I, the carbon-supported platinum group metal catalyst of the present invention is a platinum-carbon catalyst.

[0258] Implementation Method VI

[0259] Embodiment VI of the present invention provides a sulfur-boron-doped carbon material in which the area of ​​the characteristic peaks (preferably the characteristic peaks of thiophene sulfur) located between 162 eV and 166 eV in the S2P spectrum of XPS analysis is greater than 92%, or greater than 95%, or greater than 98%, or even only the characteristic peaks (preferably the characteristic peaks of thiophene sulfur) located between 162 eV and 166 eV are present.

[0260] In one embodiment of embodiment VI, the sulfur-boron doped carbon material according to the present invention does not contain any doping elements other than sulfur and boron.

[0261] In one embodiment of embodiment VI, the sulfur-boron-doped carbon material according to the present invention does not contain any metal elements.

[0262] In one embodiment of embodiment VI, in the S2P spectrum of the sulfur-boron-doped carbon material according to the present invention, the area of ​​the characteristic peak (preferably the characteristic peak of thiophene sulfur) located between 162 eV and 166 eV is greater than 92%, or greater than 95%, or greater than 98%, or even only the characteristic peak (preferably the characteristic peak of thiophene sulfur) located between 162 eV and 166 eV.

[0263] In one embodiment of embodiment VI, the XPS analysis of the sulfur-boron-doped carbon material according to the present invention shows no characteristic peaks between 166 eV and 170 eV.

[0264] In one embodiment of embodiment VI, for the sulfur-boron-doped carbon material according to the present invention, the characteristic peak (preferably the characteristic peak of thiophene sulfur) located between 162 eV and 166 eV is a double peak located at 163.6 ± 0.5 eV and 164.8 ± 0.5 eV, respectively.

[0265] In one embodiment of embodiment VI, the XPS analysis of the sulfur-boron-doped carbon material according to the present invention shows a characteristic peak of B1s between 190 eV and 195 eV, and no other characteristic peaks between 185 eV and 200 eV.

[0266] In one embodiment of embodiment VI, the XPS analysis of the sulfur-boron-doped carbon material according to the present invention shows two characteristic peaks between 191 eV and 193 eV, and no other characteristic peaks between 185 eV and 200 eV.

[0267] In one embodiment of embodiment VI, the resistivity of the sulfur-boron-doped carbon material according to the present invention is <10.0 Ω•m, preferably <5.0 Ω•m, and more preferably <3.0 Ω•m.

[0268] In one embodiment of Embodiment VI, in the XPS analysis of the sulfur-boron-doped carbon material according to the present invention, the sulfur mass fraction is 0.1% to 5%, and the boron mass fraction is 0.1% to 5%; preferably, the sulfur mass fraction is 0.2% to 3%, and the boron mass fraction is 0.2% to 3%; more preferably, the sulfur mass fraction is 0.4% to 2%, and the boron mass fraction is 0.4% to 2%.

[0269] In one embodiment of embodiment VI, the oxygen content of the sulfur-boron-doped carbon material according to the present invention is not particularly limited. In one embodiment, the oxygen mass fraction analyzed by XPS is >4%, and can be 4% to 15%.

[0270] In one embodiment of Embodiment VI, the specific surface area and pore volume of the sulfur-boron-doped carbon material according to the present invention can vary within a wide range, for example, its specific surface area can be 10 m² / g to 2000 m² / g, and its pore volume can be 0.02 mL / g to 6.0 mL / g. In one embodiment, its specific surface area is 200 m² / g to 2000 m² / g, and its pore volume is 0.2 mL / g to 3.0 mL / g. In this case, the sulfur-boron-doped carbon material is suitable as a support for a platinum-carbon catalyst with high platinum loading.

[0271] In one embodiment of embodiment VI, the sulfur-boron-doped carbon material according to the present invention can be sulfur-boron-doped graphene, sulfur-boron-doped carbon nanotubes, or sulfur-boron-doped conductive carbon black. The conductive carbon black can be ordinary conductive blacks, superconducting blacks, or extraconducting blacks, such as one or more of the Ketjen black series of superconducting carbon blacks, the Cabot series of conductive carbon blacks, and the series of conductive carbon blacks produced by Evonik Degussa; preferably, Ketjen black EC-300J, Ketjen black EC-600JD, Ketjen black ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2. The graphene or carbon nanotubes can be either oxidized graphene or carbon nanotubes, or unoxidized graphene or carbon nanotubes.

[0272] In one embodiment of Embodiment VI, there are no restrictions on the method of preparation or source of the conductive carbon black for the sulfur-boron doped carbon material according to the present invention. The conductive carbon black may be acetylene black, furnace black, etc.

[0273] In one embodiment of embodiment VI, in the sulfur-boron-doped carbon material according to the present invention, sulfur and boron are chemically bonded to the carbon material.

[0274] Embodiment VI of the present invention also provides a method for preparing sulfur-boron-doped carbon material, comprising: contacting sulfur-doped carbon material with a boron source, and treating it in an inert gas at 300°C to 800°C for 0.5 h to 10 h to obtain the sulfur-boron-doped carbon material.

[0275] In one embodiment of Embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, there are no restrictions on the contact method between the sulfur-doped carbon material and the boron source. Preferably, the method is to "mix the sulfur-doped carbon material with a boron source solution (e.g., an aqueous solution of a boron source), impregnate it, and then dry it".

[0276] In one embodiment of Embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, the sulfur-doped carbon material is prepared by the following method: contacting the carbon material with a sulfur source and treating it in an inert gas at 400°C to 1500°C for 0.5 h to 10 h to obtain the sulfur-doped carbon material.

[0277] In one embodiment of Embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, there are no particular limitations on the contact method between the carbon material and the sulfur source. Different sulfur sources can be used, and different contact methods can be adopted. For example, the carbon material can be pre-mixed with the sulfur source (solid sulfur source or liquid containing sulfur source), or the carbon material can be contacted with an inert gas containing sulfur source.

[0278] In one embodiment of Embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, the carbon material may be graphene, carbon nanotubes, or conductive carbon black. The conductive carbon black may be one or more of the following: Ketjen black series superconducting carbon black, Cabot series conductive carbon black, and a series of conductive carbon blacks produced by Evonik Degussa; preferably EC-300J, EC-600JD, ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2. The ID / IG value of the carbon material is generally 0.8 to 5, preferably 1 to 4. In Raman spectroscopy, the peak near 1320 cm⁻¹ is the D peak, and the peak near 1580 cm⁻¹ is the G peak; ID represents the intensity of the D peak, and IG represents the intensity of the G peak.

[0279] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, the sulfur source is one or more of elemental sulfur, hydrogen sulfide, carbon disulfide, sodium thiosulfate, thiophene, sulfate and sulfonate.

[0280] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, the mass of the sulfur source is based on the mass of sulfur it contains, and the mass ratio of the carbon material to the sulfur source is 20:1 to 2:1; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.

[0281] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, the boron source is one or more of boric acid and borate.

[0282] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, the mass of the boron source is based on the mass of the boron it contains, and the mass ratio of the carbon material to the boron source is 100:1 to 5:1; preferably 60:1 to 15:1.

[0283] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, the inert gas is nitrogen or argon.

[0284] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, if heating is required, the heating rate in the sulfur doping and boron doping operations is independently 1°C / min to 20°C / min, preferably 3°C / min to 15°C / min, and more preferably 8°C / min to 15°C / min.

[0285] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material according to the present invention, the temperature during the sulfur doping operation can be 400℃~1500℃, preferably 1000℃~1500℃, and more preferably 1100℃~1300℃.

[0286] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, the temperature during the boron doping operation can be 300°C to 800°C, preferably 400°C to 600°C.

[0287] In one embodiment of Embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, the treatment time for the sulfur doping operation and the boron doping operation is independently 1 h to 5 h, preferably 2 h to 4 h.

[0288] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material according to the present invention, the resistivity of the carbon material is <10 Ω•m, preferably <5 Ω•m, more preferably <2 Ω•m.

[0289] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, the oxygen mass fraction in the XPS analysis of the carbon material is generally greater than 4%, preferably 4% to 15%.

[0290] In one embodiment of Embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, the specific surface area of ​​the carbon material can vary within a wide range. Generally, the specific surface area is 10 m² / g to 2000 m² / g; the pore volume is 0.02 mL / g to 6 mL / g.

[0291] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, no metal-containing catalyst is used in the process of manufacturing the sulfur-boron-doped carbon material.

[0292] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, no metal-containing catalyst is used in the process of manufacturing the sulfur-doped carbon material.

[0293] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, in the sulfur-doped carbon material, sulfur is chemically bonded to the carbon material.

[0294] In one embodiment of embodiment VI, according to the method for preparing sulfur-boron-doped carbon material of the present invention, in the sulfur-doped carbon material, sulfur is combined with carbon material in the form of oxidized sulfur and thiophene sulfur.

[0295] In one embodiment of embodiment VI, for the method of preparing sulfur-doped carbon material according to the present invention, one embodiment is to mix carbon material with sulfur source, place it in a tube furnace, and treat it in an inert gas at 400°C to 1500°C for 0.5 h to 10 h to obtain the sulfur-doped carbon material.

[0296] In one embodiment of embodiment VI, the sulfur-boron-doped carbon material described in this embodiment is prepared by the method for preparing the sulfur-boron-doped carbon material.

[0297] Embodiment VI of the present invention also provides the application of any of the sulfur-boron-doped carbon materials described in Embodiment VI of the present invention as electrode materials in electrochemistry.

[0298] Embodiment VI of the present invention also provides a carbon-supported platinum group metal catalyst (e.g., a platinum-carbon catalyst), comprising a carbon support and a platinum group metal (e.g., platinum metal) supported thereon, wherein the carbon support is a sulfur-boron-doped carbon material; in the S2P spectrum of the XPS analysis of the carbon-supported platinum group metal catalyst (e.g., a platinum-carbon catalyst), the area of ​​the characteristic peaks (preferably the characteristic peaks of thiophene sulfur) located between 162 eV and 166 eV between 160 eV and 170 eV is greater than 92%, or greater than 95%, or greater than 98%, or even only the characteristic peaks (preferably the characteristic peaks of thiophene sulfur) located between 162 eV and 166 eV are present.

[0299] In one embodiment of embodiment VI, the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention does not contain any doping elements other than sulfur and boron.

[0300] In one embodiment of Embodiment VI, the platinum group metal is platinum. In one embodiment of Embodiment VI, the platinum-carbon catalyst according to the present invention does not contain any metal elements other than platinum.

[0301] In one embodiment of embodiment VI, in the carbon support of the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention, the sulfur and boron are chemically bonded to the carbon material.

[0302] In one embodiment of embodiment VI, for the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention, the characteristic peak (preferably the characteristic peak of thiophene sulfur) located between 162 eV and 166 eV is a double peak located at 163.6 ± 0.5 eV and 164.8 ± 0.5 eV, respectively.

[0303] In one embodiment of embodiment VI, the XPS analysis of the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention shows no characteristic peaks in the B1s spectrum between 185 eV and 200 eV.

[0304] In one embodiment of embodiment VI, boron signals (B2O3 and B) were detected in TG-MS (thermogravimetric-mass spectrometry) tests for the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the invention.

[0305] In one embodiment of embodiment VI, for the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention, the mass fraction of platinum is 0.1% to 80%, preferably 20% to 70%, and more preferably 40% to 70%, based on the mass of the catalyst.

[0306] In one embodiment of embodiment VI, the resistivity of the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the invention is <10.0 Ω·m, preferably <2.0 Ω·m.

[0307] In one embodiment of embodiment VI, the specific surface area of ​​the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention is 80 m2 / g to 1500 m2 / g, preferably 100 m2 / g to 200 m2 / g.

[0308] In one embodiment of embodiment VI, for the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention, the carbon material may be one or more of the following: Ketjen black series superconducting carbon black, Cabot series conductive carbon black, and a series of conductive carbon blacks produced by Evonik Degussa; preferably Ketjen black EC-300J, Ketjen black EC-600JD, Ketjen black ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2.

[0309] Embodiment VI of the present invention also provides a method for preparing a carbon-supported platinum group metal catalyst (e.g., a platinum-carbon catalyst).

[0310] (1) Steps for manufacturing sulfur-boron-doped carbon material: The sulfur-doped carbon material is contacted with a boron source (preferably mixed with a boron source solution, impregnated and then dried; more preferably mixed with an aqueous boron source solution, impregnated and then dried), and treated in an inert gas at 300°C to 800°C (preferably 400°C to 600°C) (preferably isothermal treatment) for 0.5 h to 10 h to obtain the sulfur-boron-doped carbon material;

[0311] (2) Step of loading platinum group metals (e.g., platinum) onto the sulfur boron doped carbon material obtained in (1).

[0312] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment VI of the present invention, the sulfur-doped carbon material is prepared by the following method: the carbon material is contacted with a sulfur source and treated in an inert gas at 400°C to 1500°C (preferably 1000°C to 1500°C) (preferably isothermal treatment) for 0.5 h to 10 h to obtain the sulfur-doped carbon material.

[0313] According to the method for preparing a carbon-supported platinum group metal catalyst according to Embodiment VI of the present invention, in the method for preparing the sulfur-doped carbon material, the mass of the sulfur source is based on the mass of the sulfur it contains, and the mass ratio of the carbon material to the sulfur source is 20:1 to 2:1; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.

[0314] In the preparation method of the carbon-supported platinum group metal catalyst according to Embodiment VI of the present invention, in the boron doping step, the mass of the boron source is based on the mass of the boron it contains, and the mass ratio of the carbon material to the boron source is 100:1 to 5:1; preferably 60:1 to 15:1.

[0315] According to the method for preparing a carbon-supported platinum group metal catalyst according to Embodiment VI of the present invention, the sulfur source is one or more of elemental sulfur, hydrogen sulfide, carbon disulfide, sodium thiosulfate, thiophene, sulfate and sulfonate.

[0316] According to the method for preparing a carbon-supported platinum group metal catalyst according to Embodiment VI of the present invention, the boron source is one or more of boric acid and borate.

[0317] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment VI of the present invention, if heating is required, the heating rate can be the same or different in sulfur doping and boron doping, each independently ranging from 1°C / min to 20°C / min, preferably from 3°C / min to 15°C / min, and more preferably from 8°C / min to 15°C / min.

[0318] In the preparation method of the carbon-supported platinum group metal catalyst according to Embodiment VI of the present invention, the temperature during sulfur doping is 400℃~1500℃, and can be 1000℃~1500℃.

[0319] In the preparation method of the carbon-supported platinum group metal catalyst according to Embodiment VI of the present invention, the temperature during boron doping is 300℃~800℃, preferably 400℃~600℃.

[0320] In the preparation method of the carbon-supported platinum group metal catalyst according to Embodiment VI of the present invention, the treatment time in sulfur doping and boron doping can be the same or different, and each can be 1 h to 5 h, preferably 2 h to 4 h.

[0321] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment VI of the present invention, the carbon material can be graphene, carbon nanotubes, or conductive carbon black. The conductive carbon black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2.

[0322] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VI of the present invention, the oxygen mass fraction in the XPS analysis of the carbon material is greater than 4%, preferably 4% to 15%.

[0323] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment VI of the present invention, the resistivity of the carbon material is <10 Ω•m, preferably <5 Ω•m, more preferably <2 Ω•m.

[0324] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment VI of the present invention, the specific surface area of ​​the carbon material is 10 m2 / g to 2000 m2 / g, preferably 200 m2 / g to 2000 m2 / g; the pore volume is 0.02 mL / g to 6 mL / g, preferably 0.2 mL / g to 3 mL / g.

[0325] According to the method for preparing a carbon-supported platinum group metal catalyst (e.g., a platinum-carbon catalyst) according to Embodiment VI of the present invention, the step of supporting the platinum group metal (e.g., platinum) includes:

[0326] (a) Disperse the sulfur-boron-doped carbon material obtained in step (1) with a platinum group metal precursor (e.g., a platinum precursor) in an aqueous phase and adjust the pH to 8 to 12 (preferably adjust the pH to 10 ± 0.5).

[0327] (b)Reduction is carried out by adding a reducing agent;

[0328] (c) The solid is separated and post-processed to obtain the carbon-supported platinum group metal (e.g., carbon-supported platinum) catalyst.

[0329] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment VI of the present invention, in step (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5 mol / L to 5 mol / L.

[0330] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment VI of the present invention, in step (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol.

[0331] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment VI of the present invention, in step (b), the molar ratio of the reducing agent to platinum is 2 to 100.

[0332] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment VI of the present invention, in step (b), the reduction temperature is 60℃~90℃; the reduction time is 4 h~15 h.

[0333] In one embodiment of Embodiment VI, the carbon-supported platinum group metal catalyst (e.g., platinum carbon catalyst) described in this embodiment is prepared by the preparation method of the carbon-supported platinum group metal catalyst (e.g., platinum carbon catalyst).

[0334] Embodiment VI of the present invention also provides a hydrogen fuel cell in which the anode and / or cathode of the hydrogen fuel cell use any of the carbon-supported platinum group metal catalysts described in Embodiment VI of the present invention.

[0335] In one embodiment of embodiment VI, the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention, when used for oxygen reduction reaction, exhibits an ECSA decrease rate of <10% after 5000 cycles and a mass specific activity decrease rate of <10% after 5000 cycles.

[0336] In one embodiment of embodiment VI, when the carbon-supported platinum group metal catalyst of the present invention is used for oxygen reduction reaction, in some embodiments VI-, ECSA > 36m2g-1-Pt, for example, in the range of 36m2g-1-Pt to 82m2g-1-Pt.

[0337] In one embodiment of embodiment VI, the carbon-supported platinum group metal catalyst of the present invention, when used for oxygen reduction reaction, has a mass-to-activity ratio > 0.146 A mg-1-Pt, for example, 0.146 A mg-1-Pt to 0.233 A mg-1-Pt.

[0338] In one embodiment of embodiment VI, when the carbon-supported platinum group metal catalyst of the present invention is used for oxygen reduction reaction, in some embodiments VI-, the half-wave potential is >0.89V, for example 0.89 to 0.91V.

[0339] In one embodiment of Embodiment VI, the carbon-supported platinum group metal catalyst of the present invention is a platinum-carbon catalyst.

[0340] Implementation Method VII

[0341] Embodiment VII of the present invention provides a sulfur-phosphorus-doped carbon material in which the area of ​​the characteristic peak (preferably the characteristic peak of thiophene sulfur) between 162 eV and 166 eV in the S2P spectrum of XPS analysis is greater than 92%, or greater than 95%, or greater than 98%, or even only the characteristic peak (preferably the characteristic peak of thiophene sulfur) between 162 eV and 166 eV.

[0342] In one embodiment of embodiment VII, the sulfur-phosphorus doped carbon material according to the present invention does not contain any doping elements other than sulfur and phosphorus.

[0343] In one embodiment of embodiment VII, the sulfur-phosphorus doped carbon material according to the present invention does not contain any metal elements.

[0344] In one embodiment of embodiment VII, for the sulfur-phosphorus doped carbon material according to the present invention, the characteristic peak (preferably the characteristic peak of thiophene sulfur) located between 162 eV and 166 eV is a double peak located at 163.5 ± 0.5 eV and 164.7 ± 0.5 eV, respectively.

[0345] In one embodiment of Embodiment VII, the XPS analysis of the sulfur-phosphorus-doped carbon material according to the present invention has a characteristic peak between 125 eV and 145 eV, located at 133.5 eV ± 0.5 eV.

[0346] In one embodiment of embodiment VII, the resistivity of the sulfur-phosphorus-doped carbon material according to the present invention is <10.0 Ω•m, preferably <5.0 Ω•m, more preferably <3.0 Ω•m.

[0347] In one embodiment of Embodiment VII, in the XPS analysis of the sulfur-phosphorus-doped carbon material according to the present invention, the sulfur mass fraction is 0.1% to 5%, and the phosphorus mass fraction is 0.01% to 5%; preferably, the sulfur mass fraction is 0.2% to 3%, and the phosphorus mass fraction is 0.02% to 3%; more preferably, the sulfur mass fraction is 0.3% to 2%, and the phosphorus mass fraction is 0.05% to 2%.

[0348] In one embodiment of Embodiment VII, the specific surface area and pore volume of the sulfur-phosphorus-doped carbon material according to the present invention can vary within a wide range, for example, its specific surface area can be 10 m² / g to 2000 m² / g, and its pore volume can be 0.02 mL / g to 6.0 mL / g. In one embodiment, the specific surface area is 200 m² / g to 2000 m² / g, and the pore volume is 0.2 mL / g to 3.0 mL / g.

[0349] In one embodiment of embodiment VII, the sulfur-phosphorus doped carbon material according to the present invention is sulfur-phosphorus doped graphene, sulfur-phosphorus doped carbon nanotubes or sulfur-phosphorus doped conductive carbon black, preferably sulfur-phosphorus doped conductive carbon black.

[0350] In one embodiment of Embodiment VII, for the sulfur-phosphorus doped carbon material according to the present invention, the conductive carbon black may be ordinary conductive black, super conductive black, or extra conductive black. For example, the conductive carbon black may be one or more of the Ketjen black series superconducting carbon black, the Cabot series conductive carbon black, and the series of conductive carbon blacks produced by Evonik Degussa; preferably, Ketjen black EC-300J, Ketjen black EC-600JD, Ketjen black ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2.

[0351] In one embodiment of Embodiment VII, there are no restrictions on the method of preparation or source of the conductive carbon black for the sulfur-phosphorus doped carbon material according to the present invention. The conductive carbon black may be acetylene black, furnace black, etc.

[0352] In one embodiment of embodiment VII, for the sulfur-phosphorus doped carbon material according to the present invention, sulfur and phosphorus are bonded to the carbon material in the form of chemical bonds.

[0353] In one embodiment of embodiment VII, the sulfur-phosphorus-doped carbon material according to the present invention has a symmetrical spike in the O1s spectrum of its XPS analysis between 530 eV and 535 eV.

[0354] Embodiment VII of the present invention also provides a method for preparing a sulfur-phosphorus-doped carbon material, comprising:

[0355] (1) Phosphorus doping steps: Carbon material is contacted with a phosphorus source and treated in an inert gas at 300℃~800℃ for 0.5 h~10 h to obtain phosphorus-doped carbon material; and

[0356] (2) Step of doping with sulfur: The phosphorus-doped carbon material in (1) is brought into contact with a sulfur source and treated in an inert gas at 400℃~1500℃ for 0.5 h~10 h to obtain the sulfur-phosphorus-doped carbon material.

[0357] In one embodiment of Embodiment VII, the sulfur-phosphorus-doped carbon material described in this embodiment is obtained by the preparation method of the sulfur-phosphorus-doped carbon material.

[0358] In one embodiment of Embodiment VII, according to the method for preparing sulfur-phosphorus-doped carbon material according to the present invention, in steps (1) and (2), if heating is required, the heating rate is independently 1℃ / min to 20℃ / min, preferably 3℃ / min to 15℃ / min, and more preferably 8℃ / min to 15℃ / min.

[0359] In one embodiment of Embodiment VII, in the method for preparing sulfur-phosphorus-doped carbon materials according to the present invention, there are no particular limitations on the phosphorus source; any phosphorus source that can be used in the art for doping carbon materials can be used in the present invention. The phosphorus source can be one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite, and hypophosphite.

[0360] In one embodiment of Embodiment VII, for the preparation method of sulfur-phosphorus doped carbon material according to the present invention, the mass of the phosphorus source is based on the mass of phosphorus it contains, and the mass ratio of the carbon material to the phosphorus source is 10000:1 to 20:1; preferably 2500:1 to 30:1.

[0361] In one embodiment of Embodiment VII, the sulfur source for the preparation method of the sulfur-phosphorus-doped carbon material according to the present invention is elemental sulfur.

[0362] In one embodiment of Embodiment VII, for the preparation method of sulfur-phosphorus doped carbon material according to the present invention, the mass of the sulfur source is based on the mass of sulfur it contains, and the mass ratio of the carbon material to the sulfur source is 20:1 to 2:1; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.

[0363] In one embodiment of embodiment VII, according to the method for preparing sulfur-phosphorus doped carbon material according to the present invention, in step (1), the temperature is 400°C to 600°C.

[0364] In one embodiment of Embodiment VII, according to the method for preparing sulfur-phosphorus doped carbon material according to the present invention, in step (2), the temperature can be 400℃~600℃, 600℃~1000℃ or 1000℃~1500℃.

[0365] In one embodiment of Embodiment VII, according to the method for preparing sulfur-phosphorus-doped carbon material according to the present invention, in steps (1) and (2), the processing time is independently 1 h to 5 h, preferably 2 h to 4 h.

[0366] In one embodiment of Embodiment VII, according to the method for preparing sulfur-phosphorus doped carbon material of the present invention, the carbon material may be carbon nanotubes, conductive carbon black, or graphene. The conductive carbon black is one or more of the following: Ketjen black series superconducting carbon black, Cabot series conductive carbon black, and a series of conductive carbon blacks produced by Evonik Degussa; preferably EC-300J, EC-600JD, ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2.

[0367] In one embodiment of Embodiment VII, according to the method for preparing sulfur-phosphorus doped carbon material of the present invention, the ID / IG value of the carbon material in step (1) is generally 0.8 to 5, preferably 1 to 4. In Raman spectroscopy, the peak located near 1320 cm⁻¹ is the D peak, and the peak located near 1580 cm⁻¹ is the G peak. ID represents the intensity of the D peak, and IG represents the intensity of the G peak.

[0368] In one embodiment of Embodiment VII, according to the method for preparing sulfur-phosphorus doped carbon material of the present invention, the inert gas is nitrogen or argon.

[0369] In one embodiment of embodiment VII, according to the method for preparing sulfur-phosphorus doped carbon material according to the present invention, the resistivity of the carbon material in step (1) is <10 Ω•m, preferably <5 Ω•m, more preferably <2 Ω•m.

[0370] In one embodiment of embodiment VII, according to the method for preparing sulfur and phosphorus doped carbon materials according to the present invention, in the XPS analysis of the carbon material in step (1), the oxygen mass fraction is generally greater than 4%, preferably 4% to 15%.

[0371] In one embodiment of Embodiment VII, according to the method for preparing sulfur-phosphorus doped carbon material of the present invention, the specific surface area of ​​the carbon material in step (1) can vary within a wide range. Generally, the specific surface area is 10 m² / g to 2000 m² / g; the pore volume is 0.02 mL / g to 6 mL / g.

[0372] In one embodiment of embodiment VII, according to the method for preparing sulfur-phosphorus doped carbon material according to the present invention, in step (1), the carbon material is contacted with the phosphorus source by immersing the carbon material in an aqueous solution of the phosphorus source and then drying it.

[0373] In one embodiment of embodiment VII, according to the method for preparing sulfur-phosphorus doped carbon material according to the present invention, in step (2), the contact mode between the phosphorus doped carbon material and the sulfur source is: mixing the phosphorus doped carbon material with elemental sulfur.

[0374] In one embodiment of Embodiment VII, according to the method for preparing sulfur-phosphorus-doped carbon material of the present invention, no metal-containing catalyst is used in the process of manufacturing sulfur-phosphorus-doped carbon material.

[0375] In one embodiment of Embodiment VII, the sulfur-phosphorus-doped carbon material described in this embodiment is prepared by the method for preparing the sulfur-phosphorus-doped carbon material.

[0376] Embodiment VII of the present invention also provides the application of any of the sulfur-phosphorus-doped carbon materials described in Embodiment VII of the present invention as electrode materials in electrochemistry.

[0377] Embodiment VII of the present invention also provides a carbon-supported platinum group metal catalyst (e.g., a platinum-carbon catalyst), comprising a carbon support and a platinum group metal (e.g., platinum metal) supported thereon, wherein the carbon support is a sulfur-phosphorus-doped carbon material; in the S2P spectrum peaks of the carbon-supported platinum group metal catalyst analyzed by XPS, the area of ​​the characteristic peaks (preferably the characteristic peaks of thiophene sulfur) located between 162 eV and 166 eV between 160 eV and 170 eV is greater than 92%, or greater than 95%, or greater than 98%, or even only the characteristic peaks (preferably the characteristic peaks of thiophene sulfur) located between 162 eV and 166 eV are present.

[0378] In one embodiment of Embodiment VII, the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the invention does not contain any doping elements other than sulfur and phosphorus.

[0379] In one embodiment of Embodiment VII, the platinum group metal is platinum. In one embodiment of Embodiment VII, the carbon-supported platinum group metal catalyst (e.g., a platinum-carbon catalyst) according to the present invention does not contain any metal elements other than platinum.

[0380] In one embodiment of Embodiment VII, in the carbon support of the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention, sulfur and phosphorus are chemically bonded to the carbon material.

[0381] In one embodiment of Embodiment VII, the XPS analysis of the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention shows no characteristic peaks in the P2p spectrum between 125 eV and 145 eV.

[0382] In one embodiment of Embodiment VII, for the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention, the sulfur-phosphorus doped carbon material is sulfur-phosphorus doped graphene, sulfur-phosphorus doped carbon nanotubes, or sulfur-phosphorus doped conductive carbon black.

[0383] In one embodiment of Embodiment VII, for the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention, the conductive carbon black may be one or more of the following: Ketjen black series superconducting carbon black, Cabot series conductive carbon black, and a series of conductive carbon blacks produced by Evonik Degussa; preferably Ketjen black EC-300J, Ketjen black EC-600JD, Ketjen black ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2.

[0384] In one embodiment of Embodiment VII, the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention does not limit the method of preparation or source of the conductive carbon black. The conductive carbon black may be acetylene black, furnace black, etc.

[0385] In one embodiment of Embodiment VII, for the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention, the mass fraction of platinum is 0.1% to 80%, preferably 20% to 70%, and more preferably 40% to 70%, based on the mass of the catalyst.

[0386] In one embodiment of embodiment VII, the resistivity of the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the invention is <10.0 Ω·m, preferably <2.0 Ω·m.

[0387] In one embodiment of Embodiment VII, the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention has a specific surface area of ​​80 m2 / g to 1500 m2 / g, preferably 100 m2 / g to 200 m2 / g.

[0388] In one embodiment of Embodiment VII, the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the invention was found to have phosphorus signals (P, P2O3 and P2O5) in TG-MS (thermogravimetric-mass spectrometry) tests.

[0389] Embodiment VII of the present invention also provides a method for preparing a carbon-supported platinum group metal catalyst (e.g., a platinum-carbon catalyst), comprising:

[0390] (1) Steps for manufacturing phosphorus-doped carbon materials: Contact carbon materials with a phosphorus source and treat them in an inert gas at 300℃~800℃ for 0.5 h~10 h to obtain phosphorus-doped carbon materials;

[0391] (2)Steps for manufacturing sulfur-phosphorus doped carbon material: The phosphorus doped carbon material in (1) is brought into contact with a sulfur source and treated in an inert gas at 400℃~1500℃ for 0.5 h~10 h to obtain the sulfur-phosphorus doped carbon material.

[0392] (3) The step of loading platinum group metals (e.g., platinum) onto the sulfur-phosphorus-doped carbon material obtained in (2).

[0393] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VII of the present invention, if heating is required in steps (1) and (2), the heating rate is 1℃ / min to 20℃ / min, preferably 3℃ / min to 15℃ / min, and more preferably 8℃ / min to 15℃ / min.

[0394] According to the method for preparing the carbon-supported platinum group metal catalyst of Embodiment VII of the present invention, the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.

[0395] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment VII of the present invention, in step (1), the mass of phosphorus source is based on the mass of phosphorus contained therein, and the mass ratio of carbon material to phosphorus source is 10000:1 to 20:1; preferably 2500:1 to 30:1.

[0396] In the preparation method of the carbon-supported platinum group metal catalyst according to Embodiment VII of the present invention, the sulfur source is elemental sulfur.

[0397] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment VII of the present invention, in step (2), the mass of the sulfur source is based on the mass of sulfur it contains, and the mass ratio of the carbon material to the sulfur source is 20:1 to 2:1; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.

[0398] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment VII of the present invention, in step (1), the temperature is 400℃~600℃.

[0399] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment VII of the present invention, in step (2), the temperature can be 400℃~600℃, 600℃~1000℃ or 1000℃~1500℃.

[0400] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VII of the present invention, in steps (1) and (2), the treatment time is 1 h to 5 h, preferably 2 h to 4 h.

[0401] According to the method for preparing the carbon-supported platinum group metal catalyst of Embodiment VII of the present invention, the carbon material is graphene, conductive carbon black, or carbon nanotubes. The conductive carbon black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2.

[0402] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VII of the present invention, in step (1), the oxygen mass fraction in the XPS analysis of the carbon material is greater than 4%, preferably 4% to 15%.

[0403] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment VII of the present invention, in step (1), the resistivity of the carbon material is <10 Ω•m, preferably <5 Ω•m, more preferably <2 Ω•m.

[0404] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment VII of the present invention, in step (1), the specific surface area of ​​the carbon material is 10 m2 / g to 2000 m2 / g, preferably 200 m2 / g to 2000 m2 / g; the pore volume is 0.02 mL / g to 6 mL / g, preferably 0.2 mL / g to 3 mL / g.

[0405] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VII of the present invention, in step (1), the contact method between the carbon material and the phosphorus source is: the carbon material is impregnated in the phosphorus source aqueous solution and then dried.

[0406] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VII of the present invention, in step (2), the contact mode between the phosphorus-doped carbon material and the sulfur source is: mixing the phosphorus-doped carbon material with elemental sulfur.

[0407] According to the method for preparing a carbon-supported platinum group metal catalyst according to Embodiment VII of the present invention, the step of supporting the platinum group metal (e.g., platinum) includes:

[0408] (a) Disperse the sulfur-phosphorus-doped carbon material obtained in step (2) with a platinum group metal precursor (e.g., a platinum precursor) in an aqueous phase and adjust the pH to 8 to 12 (preferably adjust the pH to 10 ± 0.5).

[0409] (b) Reduce by adding a reducing agent;

[0410] (c) The solid is separated and post-processed to obtain the carbon-supported platinum group metal (e.g., carbon-supported platinum) catalyst.

[0411] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment VII of the present invention, in step (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5 mol / L to 5 mol / L.

[0412] According to the preparation method of carbon-supported platinum group metal catalyst of Embodiment VII of the present invention, in step (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the molar ratio of the reducing agent to platinum is 2 to 100; the reduction temperature is 60°C to 90°C; and the reduction time is 4 h to 15 h.

[0413] In one embodiment of Embodiment VII, the carbon-supported platinum group metal catalyst (e.g., platinum carbon catalyst) described in this embodiment is prepared by the preparation method of the carbon-supported platinum group metal catalyst (e.g., platinum carbon catalyst).

[0414] Embodiment VII of the present invention also provides a hydrogen fuel cell in which the anode and / or cathode of the hydrogen fuel cell use any of the aforementioned sulfur-phosphorus doped carbon materials or any of the aforementioned carbon-supported platinum group metal catalysts.

[0415] In one embodiment of Embodiment VII, the carbon-supported platinum group metal catalyst of the present invention is a platinum-carbon catalyst.

[0416] Implementation Method VIII

[0417] Embodiment VIII of the present invention provides a sulfur-phosphorus-boron-doped carbon material, in which the S2P spectrum of its XPS analysis has only a characteristic peak between 162 eV and 166 eV (preferably the characteristic peak of thiophene sulfur) between 160 eV and 170 eV.

[0418] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material according to the present invention is in which sulfur, phosphorus and boron are chemically bonded to the carbon material.

[0419] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material according to the present invention does not contain any doping elements other than sulfur, phosphorus and boron.

[0420] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material according to the present invention does not contain any metal elements.

[0421] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material according to the present invention has a characteristic peak of thiophene sulfur located between 162 eV and 166 eV.

[0422] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material according to the present invention has a double peak (preferably the characteristic peak of thiophene sulfur) located between 162 eV and 166 eV, located at 163.4 ± 0.5 eV and 164.6 ± 0.5 eV respectively.

[0423] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material according to the present invention has two characteristic peaks in the P2P spectrum of its XPS analysis between 132.5 eV and 134.5 eV, and no other characteristic peaks between 125 eV and 145 eV.

[0424] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material according to the present invention has a characteristic peak in the B1s spectrum of its XPS analysis between 190.2 eV and 191.2 eV.

[0425] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material according to the present invention has a characteristic peak in the B1s spectrum of its XPS analysis between 190.2 eV and 191.2 eV, a characteristic peak between 191.3 eV and 192.3 eV, and no other characteristic peaks between 185 eV and 200 eV.

[0426] In one embodiment of embodiment VIII, in the XPS analysis of the sulfur-phosphorus-boron-doped carbon material according to the present invention, the mass fraction of sulfur is 0.01% to 4%, the mass fraction of phosphorus is 0.01% to 4%, and the mass fraction of boron is 0.01% to 4%; preferably, the mass fraction of sulfur is 0.1% to 3%, preferably, the mass fraction of phosphorus is 0.02% to 2%, and preferably, the mass fraction of boron is 0.05% to 3%.

[0427] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material according to the present invention, in some embodiments of XPS analysis, has a sulfur mass fraction of 0.1% to 0.6%, preferably a phosphorus mass fraction of 0.01% to 0.1%, and preferably a boron mass fraction of 0.1% to 1%.

[0428] In one embodiment of embodiment VIII, the resistivity of the sulfur-phosphorus-boron-doped carbon material according to the present invention is <10 Ω·m, preferably <5 Ω·m, more preferably <3 Ω·m.

[0429] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material according to the present invention has no particular limitation on its oxygen content. Generally, its oxygen mass fraction as determined by XPS analysis is 2% to 15%.

[0430] In one embodiment of Embodiment VIII, the specific surface area and pore volume of the sulfur-phosphorus-boron-doped carbon material according to the present invention can vary within a wide range, for example, its specific surface area can be 10 m² / g to 2000 m² / g, and its pore volume can be 0.02 mL / g to 6.0 mL / g. In one embodiment, the specific surface area is 200 m² / g to 2000 m² / g, and the pore volume is 0.2 mL / g to 3.0 mL / g.

[0431] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material according to the present invention can be sulfur-phosphorus-boron-doped graphene, sulfur-phosphorus-boron-doped carbon nanotubes, or sulfur-phosphorus-boron-doped conductive carbon black. The conductive carbon black can be ordinary conductive black, super conductive black, or extra conductive black, for example, the conductive carbon black can be one or more of the Ketjen black series superconducting carbon black, the Cabot series conductive carbon black, and the series of conductive carbon blacks produced by Evonik Degussa; preferably, Ketjen black EC-300J, Ketjen black EC-600JD, Ketjen black ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2.

[0432] In one embodiment of Embodiment VIII, the sulfur-phosphorus-boron-doped carbon material according to the present invention does not limit the method of preparation or source of the conductive carbon black. The conductive carbon black may be acetylene black, furnace black, etc.

[0433] In one embodiment of embodiment VIII, the carbon nanotube or graphene doped with sulfur, phosphorus and boron according to the present invention can be either carbon nanotube or graphene that has undergone oxidation treatment or carbon nanotube or graphene that has not undergone oxidation treatment.

[0434] Embodiment VIII of the present invention also provides a method for doping carbon materials, comprising: (1) contacting the carbon material with a phosphorus source and a boron source, and treating it in an inert gas at 300°C to 800°C (preferably isothermal treatment) for 0.5 h to 10 h to obtain a phosphorus-boron doped carbon material (intermediate product); (2) then contacting it with a sulfur source, and treating it in an inert gas at 1000°C to 1500°C for 0.5 h to 10 h to obtain a sulfur-phosphorus-boron doped carbon material.

[0435] In one embodiment of embodiment VIII, according to the carbon material doping method of the present invention, the carbon material may be graphene, carbon nanotubes, or conductive carbon black. The conductive carbon black may be one or more of the following: Ketjen black series superconducting carbon black, Cabot series conductive carbon black, and a series of conductive carbon blacks produced by Evonik Degussa; preferably EC-300J, EC-600JD, ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2.

[0436] In one embodiment of embodiment VIII, according to the carbon material doping method of the present invention, the carbon nanotube or graphene may be either an oxidized carbon nanotube or graphene or an unoxidized carbon nanotube or graphene.

[0437] In one embodiment of Embodiment VIII, the method for doping carbon materials according to the present invention does not limit the method of preparation or source of the conductive carbon black. The conductive carbon black may be acetylene black, furnace black, etc.

[0438] In one embodiment of Embodiment VIII, according to the carbon material doping method of the present invention, the ID / IG value of the carbon material is generally 0.8 to 5, preferably 1 to 4. In the Raman spectrum, the peak located near 1320 cm⁻¹ is the D peak, and the peak located near 1580 cm⁻¹ is the G peak. ID represents the intensity of the D peak, and IG represents the intensity of the G peak.

[0439] Embodiment VIII of the present invention does not limit the contact method between the carbon material and the phosphorus and boron sources. Those skilled in the art can select a suitable method based on the teachings and / or existing knowledge of the present invention. The present invention preferably contacts the carbon material with the phosphorus and boron sources in a mixed manner. The present invention also does not limit the mixing order and method of the carbon material with the phosphorus and boron sources. Those skilled in the art can easily select a method based on the teachings and / or existing knowledge of the present invention. The present invention provides a preferred mixing method: mixing the carbon material with a solution of phosphorus and boron sources (preferably an aqueous solution), impregnating, and then drying.

[0440] Embodiment VIII of the present invention does not limit the contact method between the phosphorus-boron doped carbon material (intermediate product) and the sulfur source. Those skilled in the art can select a suitable method according to the teachings and / or existing knowledge of the present invention. In the carbon material doping method of the present invention, it is preferable to contact the intermediate product with the sulfur source (e.g., elemental sulfur) in a mixed manner.

[0441] In one embodiment of embodiment VIII, according to the carbon material doping method of the present invention, if heating is required, the heating rate is 3°C / min to 7°C / min when doping with phosphorus and boron, and the heating rate is 8°C / min to 10°C / min when doping with sulfur.

[0442] In one embodiment of embodiment VIII, in the carbon material doping method according to the present invention, in steps (1) and (2), the processing time is independently 1 h to 5 h, preferably 2 h to 4 h.

[0443] In one embodiment of embodiment VIII, in the carbon material doping method according to the present invention, the temperature in step (1) is 450°C to 700°C.

[0444] In one embodiment of embodiment VIII, according to the carbon material doping method of the present invention, in step (2), the temperature is 1150°C to 1450°C.

[0445] In one embodiment of embodiment VIII, the sulfur source is elemental sulfur in the carbon material doping method according to the present invention.

[0446] In one embodiment of embodiment VIII, according to the carbon material doping method of the present invention, the mass of the sulfur source is based on the mass of sulfur it contains, and the mass ratio of the carbon material to the sulfur source is 20:1 to 2:1; preferably 10:1 to 4:1; more preferably 8:1 to 4:1.

[0447] In one embodiment of embodiment VIII, according to the method for doping carbon materials according to the present invention, the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.

[0448] In one embodiment of embodiment VIII, according to the carbon material doping method of the present invention, the mass of the phosphorus source is based on the mass of phosphorus it contains, and the mass ratio of the carbon material to the phosphorus source is 10000:1 to 10:1; preferably 2000:1 to 20:1.

[0449] In one embodiment of embodiment VIII, the boron source in the carbon material doping method according to the present invention is one or more of boric acid and borate.

[0450] In one embodiment of embodiment VIII, according to the carbon material doping method of the present invention, the mass of the boron source is based on the mass of boron it contains, and the mass ratio of the carbon material to the boron source is 10000:1 to 10:1; preferably 2000:1 to 20:1.

[0451] In one embodiment of embodiment VIII, the inert gas in the carbon material doping method according to the present invention is nitrogen or argon.

[0452] In one embodiment of embodiment VIII, according to the carbon material doping method of the present invention, the oxygen mass fraction in the XPS analysis of the carbon material is generally greater than 4%, preferably 4% to 15%.

[0453] In one embodiment of embodiment VIII, according to the carbon material doping method of the present invention, the resistivity of the carbon material is <10 Ω•m, preferably <5 Ω•m, more preferably <2 Ω•m.

[0454] In one embodiment of embodiment VIII, according to the carbon material doping method of the present invention, the specific surface area of ​​the carbon material can vary within a large range. Generally, the specific surface area is 10 m² / g to 2000 m² / g; the pore volume is 0.02 mL / g to 6 mL / g.

[0455] In one embodiment of embodiment VIII, according to the method of doping carbon material according to the present invention, in one embodiment, (1) the carbon material impregnated with phosphorus source and boron source in aqueous solution is dried, placed in a tube furnace, and heated to 300°C to 800°C (preferably 450°C to 700°C) in an inert gas at a rate of 3°C / min to 7°C / min, and then kept at a constant temperature for 0.5 h to 10 h to obtain phosphorus-boron doped carbon material (intermediate product); (2) the intermediate product is mixed with sulfur powder, and placed in a tube furnace, and heated to 1000°C to 1500°C (preferably 1150°C to 1450°C) in an inert gas at a rate of 8°C / min to 10°C / min, and then kept at a constant temperature for 0.5 h to 10 h to obtain sulfur-phosphorus-boron doped carbon material of the present invention.

[0456] The inert gas is nitrogen or argon.

[0457] In one embodiment of embodiment VIII, the carbon material doping method according to the present invention does not use a metal-containing catalyst during the doping process of the carbon material.

[0458] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material described in this embodiment is prepared by the method for preparing the sulfur-phosphorus-boron-doped carbon material.

[0459] Embodiment VIII of the present invention also provides the application of the sulfur-phosphorus-boron-doped carbon material of the present invention as an electrode material in electrochemistry in any of the foregoing embodiments VIII of the present invention.

[0460] Embodiment VII of the present invention also provides a carbon-supported platinum group metal catalyst (e.g., a platinum-carbon catalyst), comprising a carbon support and a platinum group metal (e.g., platinum metal) supported thereon, wherein the carbon support is a sulfur-phosphorus-boron-doped carbon material, and the S2P spectrum of the carbon-supported platinum group metal catalyst in XPS analysis has only a characteristic peak between 162 eV and 166 eV (preferably a characteristic peak of thiophene-type sulfur) between 160 eV and 170 eV.

[0461] In one embodiment of embodiment VIII, the characteristic peak of the thiophene sulfur in the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention is located between 162 eV and 166 eV.

[0462] In one embodiment of embodiment VIII, the characteristic peak (preferably the characteristic peak of thiophene sulfur) located between 162 eV and 166 eV of the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention is a double peak located at 163.3 ± 0.5 eV and 164.6 ± 0.5 eV respectively.

[0463] In one embodiment of embodiment VIII, the XPS analysis of the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention shows no characteristic peak of B1s between 185 eV and 200 eV, and no characteristic peak of P2p between 125 eV and 145 eV.

[0464] In one embodiment of embodiment VIII, the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the invention was found to have signals of P, P2O3 and P2O5 in TG-MS (thermogravimetric-mass spectrometry) test.

[0465] In one embodiment of embodiment VIII, a boron signal (B and B2O3) was detected in a TG-MS (thermogravimetric-mass spectrometry) test of a carbon-supported platinum group metal catalyst (e.g., a platinum-carbon catalyst) according to the invention.

[0466] In one embodiment of embodiment VIII, the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the invention does not contain any doping elements other than sulfur, phosphorus and boron.

[0467] In one embodiment of Embodiment VIII, the platinum group metal is platinum. In one embodiment of Embodiment VIII, the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention does not contain any metal elements other than platinum.

[0468] In one embodiment of embodiment VIII, in the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the invention, sulfur, phosphorus and boron are chemically bonded to the carbon material.

[0469] In one embodiment of embodiment VIII, the carbon support of the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention is any of the sulfur-phosphorus-boron-doped carbon materials of the present invention.

[0470] In one embodiment of embodiment VIII, the sulfur-phosphorus-boron-doped carbon material of the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention can be sulfur-phosphorus-boron-doped graphene, sulfur-phosphorus-boron-doped carbon nanotubes, or sulfur-phosphorus-boron-doped conductive carbon black. The conductive carbon black can be one or more of the Ketjen black series of superconducting carbon black, the Cabot series of conductive carbon black, and the series of conductive carbon blacks produced by Evonik Degussa; preferably, Ketjen black EC-300J, Ketjen black EC-600JD, Ketjen black ECP-600JD, VXC72, Black Pearls 2000, PRINTEX XE2-B, PRINTEX L6, or HIBLAXK 40B2.

[0471] In one embodiment of embodiment VIII, the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention has a platinum mass fraction of 0.1% to 80%, preferably 20% to 70%, and more preferably 40% to 70%, based on the mass of the catalyst.

[0472] In one embodiment of embodiment VIII, the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the invention has a resistivity of <10.0 Ω·m, preferably <2.0 Ω·m.

[0473] In one embodiment of embodiment VIII, the carbon-supported platinum group metal catalyst (e.g., platinum-carbon catalyst) according to the present invention has a specific surface area of ​​80 m2 / g to 1500 m2 / g, preferably 100 m2 / g to 200 m2 / g.

[0474] Embodiment VIII of the present invention also provides a method for preparing a carbon-supported platinum group metal catalyst (e.g., a platinum-carbon catalyst), comprising:

[0475] (1) Steps for manufacturing carbon support: First, contact the carbon material with a phosphorus source and a boron source, and treat it in an inert gas at 300℃~800℃ for 0.5 h~10 h; then contact it with a sulfur source and a nitrogen source, and treat it in an inert gas at 1000℃~1500℃ for 0.5 h~10 h to obtain the carbon support;

[0476] (2)The step of loading platinum group metals (e.g., platinum) onto the carbon support obtained in (1).

[0477] In the preparation method of the carbon-supported platinum group metal catalyst according to Embodiment VIII of the present invention, in step (1), the "contact mode of carbon material with sulfur source, phosphorus source and boron source" is the same as the corresponding part in the previous text, and the present invention will not repeat it again.

[0478] In the preparation method of the carbon-supported platinum group metal catalyst according to Embodiment VIII of the present invention, the sulfur source is elemental sulfur.

[0479] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VIII of the present invention, in step (1), the mass of the sulfur source is based on the mass of sulfur it contains, and the mass ratio of the carbon material to the sulfur source is 20:1 to 2:1; preferably 10:1 to 4:1; preferably 8:1 to 4:1.

[0480] According to the method for preparing the carbon-supported platinum group metal catalyst of Embodiment VIII of the present invention, the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.

[0481] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VIII of the present invention, in step (1), the mass of phosphorus source is based on the mass of phosphorus contained therein, and the mass ratio of carbon material to phosphorus source is 10000:1 to 10:1; preferably 2000:1 to 20:1.

[0482] In the preparation method of the carbon-supported platinum group metal catalyst according to Embodiment VIII of the present invention, the boron source is one or more of boric acid and borate.

[0483] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VIII of the present invention, in step (1), the mass of the boron source is based on the mass of the boron it contains, and the mass ratio of the carbon material to the boron source is 10000:1 to 10:1; preferably 2000:1 to 20:1.

[0484] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VIII of the present invention, if heating is required in step (1), the heating rate is 3℃ / min to 7℃ / min when doped with phosphorus and boron, and the heating rate is 8℃ / min to 10℃ / min when doped with sulfur.

[0485] In the preparation method of the carbon-supported platinum group metal catalyst according to Embodiment VIII of the present invention, in the phosphorus-boron doping operation in step (1), the temperature is 450℃~700℃.

[0486] According to the preparation method of the carbon-supported platinum group metal catalyst of Embodiment VIII of the present invention, in the sulfur and nitrogen doping operation in step (1), the temperature is 1150℃~1450℃.

[0487] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VIII of the present invention, in the phosphorus and boron doping operation in step (1), the treatment time is 1 h to 5 h, preferably 2 h to 4 h.

[0488] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VIII of the present invention, in the sulfur and nitrogen doping operation in step (2), the treatment time is 1 h to 5 h, preferably 2 h to 4 h.

[0489] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VIII of the present invention, in step (1), the carbon material can be graphene, carbon nanotubes or conductive carbon black; the conductive carbon black is preferably EC-300J, EC-600JD, ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.

[0490] According to the method for preparing the carbon-supported platinum group metal catalyst of Embodiment VIII of the present invention, the sulfur-phosphorus-boron-doped carbon material obtained in step (1) can be easily dispersed in the aqueous phase. However, for some carbon materials, such as Ketjen Black, it is difficult to directly disperse in the aqueous phase.

[0491] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VIII of the present invention, in step (1), the oxygen mass fraction in the XPS analysis of the carbon material is greater than 4%, preferably 4% to 15%.

[0492] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VIII of the present invention, in step (1), the resistivity of the carbon material is <10 Ω•m, preferably <5 Ω•m, more preferably <2 Ω•m.

[0493] According to the preparation method of carbon-supported platinum group metal catalyst of embodiment VIII of the present invention, in step (1), the specific surface area of ​​the carbon material is 10 m2 / g to 2000 m2 / g, preferably 200 m2 / g to 2000 m2 / g; the pore volume is 0.02 mL / g to 6 mL / g, preferably 0.2 mL / g to 3 mL / g.

[0494] In one embodiment of embodiment VIII, the carbon-supported platinum group metal catalyst (e.g., platinum carbon catalyst) described in this embodiment is prepared by the preparation method of the carbon-supported platinum group metal catalyst (e.g., platinum carbon catalyst).

[0495] Embodiment VIII of the present invention also provides a hydrogen fuel cell in which the anode and / or cathode of the hydrogen fuel cell use any of the carbon-supported platinum group metal catalysts described in Embodiment VIII of the present invention.

[0496] In one embodiment of embodiment VIII, the carbon-supported platinum group metal catalyst of the present invention is a platinum-carbon catalyst.

[0497] Example Section

[0498] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way.

[0499] Unless otherwise specified, all reagents used in this invention are of analytical purity and are commercially available.

[0500] Implementation Method I

[0501] Reagents, Instruments and Tests

[0502] This invention uses X-ray photoelectron spectroscopy (XPS) to detect elements on the surface of materials. The X-ray photoelectron spectroscopy instrument used is the VG Scientific ESCALab220i-XL model equipped with Avantage V5.926 software. The X-ray photoelectron spectroscopy analysis test conditions are: the excitation source is monochromatic AlKα X-rays, the power is 330W, and the basic vacuum during analysis is 3×10-9 mbar. In addition, the electron binding energy is corrected using the C1s peak (284.3 eV) of elemental carbon, and the post-peaking processing software is XPSPEAK.

[0503] Elemental analysis instruments, methods and conditions: Elemental analyzer (Vario EL Cube), reaction temperature 1150℃, 5 mg sample weighed, reduction temperature 850℃, carrier gas helium flow rate 200 mL / min, oxygen flow rate 30 mL / min, oxygen passage time 70s.

[0504] The instrument, method and conditions for testing the platinum mass fraction in the platinum-carbon catalyst: Take 30 mg of the prepared Pt / C catalyst, add 30 mL of aqua regia, reflux at 120℃ for 12 h, cool to room temperature, take the supernatant, dilute it and test the Pt content by ICP-AES.

[0505] The high-resolution transmission electron microscope (HRTEM) used in this invention is model JEM-2100 (HRTEM) (Nippon Electron Ltd.). The high-resolution transmission electron microscope test conditions are: accelerating voltage of 200 kV. The particle size of the nanoparticles in the sample was measured by electron microscope image I.

[0506] BET test method: In this invention, the pore structure properties of the sample were determined by a Quantacam AS-6B analyzer, the specific surface area and pore volume of the catalyst were obtained by the Brunauer-Emmett-Taller (BET) method, and the pore distribution curve was calculated from the desorption curve using the Barrett-Joyner-Halenda (BJH) method.

[0507] The Raman detection of the present invention uses a LabRAM HR UV-NIR laser confocal Raman spectrometer manufactured by HORIBA Corporation of Japan, with a laser wavelength of 532nm.

[0508] Electrochemical performance testing: Instruments used were Solartron Analytical EnergyLab and Princeton Applied Research (Model 636A). Methods and testing conditions: The catalyst polarization curve (LSV) was measured at 1600 rpm in O2-saturated 0.1 M HClO4. The CV curve was measured in Ar atmosphere in 0.1 M HClO4. The electrochemical active area (ECSA) was calculated based on these results. For stability testing, 5000 cycles were performed in O2-saturated 0.1 M HClO4 within the range of 0.6 V to 0.95 V. The LSV and ECSA were then tested using the same method. For all tests, the catalyst was prepared as a uniformly dispersed slurry and coated onto a 5 mm diameter glassy carbon electrode. The platinum content of the catalyst on the electrode was 3 μg to 4 μg.

[0509] Resistivity tester with four probes, instrument model KDY-1, method and test conditions: applied pressure 3.9±0.03 MPa, current 500±0.1mA.

[0510] VXC72 (Vulcan XC72, manufactured by Cabot Corporation, USA, production batch number) was purchased from Suzhou Yilongsheng Energy Technology Co., Ltd. Tested using the aforementioned instrumental methods, the results showed: specific surface area 258 m² / g, pore volume 0.388 mL / g, oxygen mass fraction 8.72%, ID / IG ratio 1.02, and resistivity 1.22 Ω•m.

[0511] Ketjenblack ECP600JD (manufactured by Lion Corporation, Japan, production batch number) was purchased from Suzhou Yilongsheng Energy Technology Co., Ltd. Tested using the aforementioned instrumental methods, the results showed: specific surface area 1362 m² / g, pore volume 2.29 mL / g, oxygen mass fraction 6.9%, ID / IG ratio 1.25, and resistivity 1.31 Ω•m.

[0512] The commercial platinum-carbon catalyst (code name HISPEC4000, manufactured by Johnson & Johnson) was purchased from Alfa Aesar. Test results showed that the mass fraction of platinum was 40.2%.

[0513] Example I-1

[0514] This embodiment is used to illustrate the preparation of the sulfur-doped carbon support of the present invention.

[0515] Ketjenblack ECP600JD was placed in a tube furnace. Carrier gas (nitrogen) entered the tube furnace after passing through a bubbling flask containing thiophene. The furnace was heated to 1200℃ at a rate of 10℃ / min, then held at that temperature for 3 hours. After natural cooling, sulfur-doped carbon material was obtained, designated as carbon support A. The mass of thiophene was based on the mass of sulfur it contained, with a mass ratio of Ketjenblack ECP600JD to thiophene of 20:1. The amount of thiophene used was controlled by the carrier gas flow rate. The corresponding carrier gas flow rate for different thiophene dosages was pre-calibrated based on the flow time.

[0516] Sample Characterization and Testing

[0517] The sulfur mass fraction determined by XPS analysis was 0.76%; the oxygen mass fraction determined by XPS analysis was 12.8%; the specific surface area was 1161 m2 / g; the pore volume was 2.15 mL / g; the ID / IG ratio was 1.19; and the resistivity was 1.37 Ω•m.

[0518] Figure I-1 shows the Raman spectra of the sulfur-doped carbon material (Ketjen-S) and Ketjen in Example 1.

[0519] Figure I-2 is the XPS spectrum of the sulfur-doped carbon material of Example 1.

[0520] Example I-2

[0521] This embodiment is used to illustrate the preparation of the sulfur-doped carbon support of the present invention.

[0522] Vulcan XC72 was placed in a tube furnace. Carrier gas (nitrogen) was introduced into the tube furnace after passing through a bubbling flask containing thiophene. The furnace was heated to 1200°C at a rate of 10°C / min, then held at that temperature for 3 hours. After natural cooling, sulfur-doped carbon material was obtained, designated as carbon support B. The mass of thiophene was based on the mass of sulfur it contained, with a Vulcan XC72 to thiophene mass ratio of 10:1. The amount of thiophene used was controlled by the carrier gas flow rate. The corresponding carrier gas flow rate for different thiophene dosages was pre-calibrated based on the flow time.

[0523] Sample Characterization and Testing

[0524] The sulfur mass fraction determined by XPS analysis was 0.89%; the oxygen mass fraction determined by XPS analysis was 8.39%; the specific surface area was 210 m2 / g; the pore volume was 0.430 mL / g; the ID / IG ratio was 0.37; and the resistivity was 1.25 Ω•m.

[0525] Figure I-3 shows the Raman spectra of sulfur-doped carbon material (Vulcan XC72-S) and Vulcan XC72 in Example I-2.

[0526] Figure I-4 is the XPS spectrum of the sulfur-doped carbon material of Example I-2.

[0527] Figure I-5 shows the nitrogen adsorption-desorption curves of the sulfur-doped carbon material in Example I-2.

[0528] Figure I-6 shows the pore distribution curve of the sulfur-doped carbon material in Example I-2.

[0529] Example I-3

[0530] This embodiment is used to illustrate the preparation of the sulfur-doped carbon support of the present invention.

[0531] Sulfur-doped carbon materials were prepared according to the method of Examples I-2, except that the isothermal treatment temperature was 1400°C and the sulfur-doped carbon support was numbered as carbon support C.

[0532] Sample Characterization and Testing

[0533] Figure I-7 is the XPS spectrum of the sulfur-doped carbon material of Example I-3.

[0534] Example I-4

[0535] This embodiment is used to illustrate the preparation of the platinum-carbon catalyst of the present invention.

[0536] Carbon support A was dispersed in deionized water at a ratio of 250 mL of water per gram of carbon support. 12 mmol of chloroplatinic acid was added per gram of carbon support, and the mixture was ultrasonically dispersed to form a suspension. 1 mol / L potassium hydroxide aqueous solution was added to adjust the pH of the system to 10. The suspension was heated to 80 °C, and sodium borohydride was added under stirring to carry out a reduction reaction. The molar ratio of the reducing agent to the platinum precursor was 5:1, and the reaction was maintained for 12 h. The mixture after the reaction was filtered, washed until the pH of the solution was neutral, and dried at 100 °C to obtain the carbon-supported platinum catalyst.

[0537] Sample Characterization and Testing

[0538] The platinum mass fraction of the platinum-carbon catalyst is 70.2%.

[0539] Figure I-8 is the XPS spectrum of the platinum-carbon catalyst of Example I-4.

[0540] The performance test results of the platinum-carbon catalyst are shown in Table I-1.

[0541] Example I-5

[0542] This embodiment is used to illustrate the preparation of the platinum-carbon catalyst of the present invention.

[0543] Carbon support B was dispersed in deionized water at a ratio of 250 mL of water per gram of carbon support. 3.4 mmol of chloroplatinic acid was added per gram of carbon support, and the mixture was ultrasonically dispersed to form a suspension. 1 mol / L sodium carbonate aqueous solution was added to adjust the pH of the system to 10. The suspension was heated to 80°C, and formic acid was added with stirring to carry out a reduction reaction. The molar ratio of formic acid to chloroplatinic acid was 50:1. The reaction was maintained for 10 h. The mixture after the reaction was filtered, washed with deionized water until the pH of the filtrate was neutral, filtered again, and then dried at 100°C to obtain the platinum-carbon catalyst.

[0544] Sample Characterization and Testing

[0545] The platinum mass fraction of the platinum-carbon catalyst is 40.1%.

[0546] Figure I-9 is a TEM image of the platinum-carbon catalyst of Example I-5.

[0547] Figure I-10 shows the polarization curves of the platinum-carbon catalyst in Example I-5.

[0548] Figure I-11 is the XPS spectrum of the platinum-carbon catalyst of Example I-5.

[0549] The performance test results of the platinum-carbon catalyst are shown in Table I-1.

[0550] Example I-6

[0551] This example illustrates the preparation of a platinum-carbon catalyst.

[0552] The platinum-carbon catalyst was prepared according to the method of Examples I-5, except that the carbon support C prepared in Example 3 was used.

[0553] Sample Characterization and Testing

[0554] The platinum mass fraction of the platinum-carbon catalyst is 39.8%.

[0555] The performance test results of the platinum-carbon catalyst are shown in Table I-1.

[0556] Example I-7

[0557] This example illustrates the preparation of a platinum-carbon catalyst.

[0558] The platinum-carbon catalyst was prepared according to the method of Examples I-5, except that 1.3 mmol of chloroplatinic acid was added per gram of carbon support.

[0559] Sample Characterization and Testing

[0560] The platinum mass fraction of the platinum-carbon catalyst is 20.2%.

[0561] The performance test results of the platinum-carbon catalyst are shown in Table I-1.

[0562] Comparative Example I-1

[0563] The platinum-carbon catalyst was manufactured and tested in the same manner as in Examples I-5, except that when the carbon support B was manufactured in Example I-2, the tubular furnace was heated to 1200°C at a rate of 5°C / min.

[0564] Sample Characterization and Testing

[0565] I. Sulfur-doped carbon materials

[0566] The sulfur mass fraction determined by XPS analysis was 0.84%; the oxygen mass fraction determined by XPS analysis was 9.4%; the specific surface area was 214 m² / g; the pore volume was 0.436 mL / g; the ID / IG ratio was 0.96; and the resistivity was 1.28 Ω•m.

[0567] Figure 12 shows the Raman spectra of sulfur-doped carbon material of Comparative Example I-1 and Vulcan XC72.

[0568] Figure 13 is the XPS spectrum of the sulfur-doped carbon material of Comparative Example I-1.

[0569] Figure 14 shows the nitrogen adsorption-desorption curve of the sulfur-doped carbon material of Comparative Example I-1.

[0570] Figure 15 shows the pore distribution curve of the sulfur-doped carbon material of Comparative Example I-1.

[0571] II. Platinum-carbon catalysts

[0572] The platinum mass fraction of the platinum-carbon catalyst is 40.2%.

[0573] Figure I-16 is a TEM image of the platinum-carbon catalyst of Comparative Example I-1.

[0574] Figure I-17 shows the polarization curve of the platinum-carbon catalyst of Comparative Example I-1.

[0575] The performance test results of the platinum-carbon catalyst are shown in Table I-1.

[0576] Compare with Example 2

[0577] Platinum-carbon catalysts were manufactured and tested in the same manner as in Examples I-5, except that the isothermal treatment temperature was 400°C when sulfur-doped carbon materials were manufactured in Example I-2.

[0578] Sample Characterization and Testing

[0579] Sulfur-doped carbon material: The sulfur mass fraction was 1.17% according to XPS analysis; the oxygen mass fraction was 8.46% according to XPS analysis.

[0580] Figure I-18 is the XPS spectrum of the sulfur-doped carbon material of Comparative Example I-2.

[0581] The performance test results of the platinum-carbon catalyst are shown in Table I-1.

[0582] Compare with Example 3

[0583] Platinum-carbon catalysts were prepared and tested in the same manner as in Examples I-4, except that the carbon support was Ketjenblack ECP600JD and each gram of carbon support was dispersed with 200 mL of water and 50 mL of ethanol when loaded with Pt.

[0584] Sample Characterization and Testing

[0585] The platinum mass fraction of the platinum-carbon catalyst is 69.7%.

[0586] The performance test results of the platinum-carbon catalyst are shown in Table I-1.

[0587] Compare with Example 4

[0588] The platinum-carbon catalyst was prepared and tested in the same manner as in Examples I-5, except that the carbon support was Vulcan XC72.

[0589] Sample Characterization and Testing

[0590] The platinum mass fraction of the platinum-carbon catalyst is 40.1%.

[0591] The performance test results of the platinum-carbon catalyst are shown in Table I-1.

[0592] Compare with Example 5

[0593] The platinum-carbon catalyst is a commercially available catalyst, code HISPEC4000.

[0594] Sample Characterization and Testing

[0595] The platinum mass fraction of the platinum-carbon catalyst is 40.2%.

[0596] Figure I-19 shows the polarization curve of the platinum-carbon catalyst of Comparative Example I-5.

[0597] The performance test results of the platinum-carbon catalyst are shown in Table I-1.

[0598] Table I-1 sample Half-wave potential / V ECSA / m 2 g -1 -Pt Mass-to-activity ratio / A mg -1 -Pt Intrinsic activity / mA cm -2 The percentage decrease in activity after 5000 cycles / Example I-4 0.89 95.59 0.181 0.189 3 Example I-5 0.93 198.5 0.337 0.170 6 Example I-6 0.90 131.79 0.210 0.159 8 Example I-7 0.93 259.97 0.386 0.149 5 Comparative Example I-1 0.88 70.83 0.127 0.179 9 Comparative Example I-2 0.90 60.94 0.205 0.336 16 Comparative Example I-3 0.83 62.26 0.086 0.138 34 Comparative Example I-4 0.89 33.63 0.135 0.401 28 Comparative Example I-5 0.88 57.32 0.124 0.216 twenty three

[0599] As shown in Figures I-13 and I-18, if sulfur-doped carbon materials are not manufactured according to the method of the present invention, the doping form of sulfur includes not only thiophene sulfur, but also oxidized sulfur.

[0600] As shown in Table I-1, compared with "Comparative Examples 3, 4 and 5", the sulfur-doped conductive carbon black significantly improved the ECSA and mass ratio activity and stability of the platinum-carbon catalyst.

[0601] As shown in Table I-1, compared with Comparative Examples 1 and 2, it can be seen that conductive carbon black doped with single thiophene sulfur significantly improves the ECSA and mass ratio activity and stability of platinum-carbon catalyst.

[0602] Implementation Method VI

[0603] This invention uses X-ray photoelectron spectroscopy (XPS) to detect elements on the surface of materials. The X-ray photoelectron spectroscopy instrument used is the VG Scientific ESCALab220i-XL model equipped with Avantage V5.926 software. The X-ray photoelectron spectroscopy analysis test conditions are: the excitation source is monochromatic AlKα X-rays, the power is 330W, and the basic vacuum during analysis is 3×10-9 mbar. In addition, the electron binding energy is corrected using the C1s peak (284.3 eV) of elemental carbon, and the post-peak segmentation software is XPSPEAK. The characteristic peaks of thiophene-type sulfur and boron in the spectrum are the characteristic peaks after peak segmentation.

[0604] Elemental analysis instruments, methods and conditions: Elemental analyzer (Vario EL Cube), reaction temperature 1150℃, 5 mg sample weighed, reduction temperature 850℃, carrier gas helium flow rate 200 mL / min, oxygen flow rate 30 mL / min, oxygen passage time 70s.

[0605] The instrument, method and conditions for testing the mass fraction of platinum in platinum-carbon catalyst: Take 30 mg of the prepared Pt / C catalyst, add 30 mL of aqua regia, reflux at 120℃ for 12 h, cool to room temperature, take the supernatant, dilute it and test the Pt content by ICP-AES.

[0606] The high-resolution transmission electron microscope (HRTEM) used in this invention is model JEM-2100 (HRTEM) (Nippon Electron Ltd.). The high-resolution transmission electron microscope test conditions are: accelerating voltage of 200 kV. The particle size of the nanoparticles in the sample was measured by electron microscope image VI-1.

[0607] BET test method: In this invention, the pore structure properties of the sample were determined by a Quantacam AS-6B analyzer, the specific surface area and pore volume of the catalyst were obtained by the Brunauer-Emmett-Taller (BET) method, and the pore distribution curve was calculated from the desorption curve using the Barrett-Joyner-Halenda (BJH) method.

[0608] The Raman detection of the present invention uses a LabRAM HR UV-NIR laser confocal Raman spectrometer manufactured by HORIBA Corporation of Japan, with a laser wavelength of 532nm.

[0609] Electrochemical performance testing was conducted using Solartron Analytical EnergyLab and Princeton Applied Research (Model 636A). The methods and testing conditions were as follows: The catalyst polarization curve (LSV) was measured at 1600 rpm in O2-saturated 0.1 M HClO4, and the CV curve was measured in Ar atmosphere in 0.1 M HClO4. The electrochemical active area (ECSA) was calculated based on these results. For stability testing, 5000 cycles were performed in O2-saturated 0.1 M HClO4 within the range of 0.6 V to 0.95 V, followed by testing the LSV and ECSA using the same method. During these tests, the catalyst was prepared as a uniformly dispersed slurry and coated onto a 5 mm diameter glassy carbon electrode. The platinum content of the catalyst on the electrode was 3 μg to 4 μg.

[0610] Resistivity tester with four probes, instrument model KDY-1, method and test conditions: applied pressure 3.9±0.03 MPa, current 500±0.1mA.

[0611] TG-MS test method: The test was performed using a German Netzsch STA449F5-QMS403D thermogravimetric-mass spectrometer. The ion source was an EI source, the quadrupole mass spectrometer was in MID mode, the transfer line was a 3-meter long capillary, the temperature was 260℃, the temperature range was 55℃~1000℃, and the heating rate was 10℃ / min.

[0612] VXC72 (Vulcan XC72, manufactured by Cabot Corporation, USA) was purchased from Suzhou Yilongsheng Energy Technology Co., Ltd. Tested using the aforementioned instrumental methods, the results shown in Table VI are as follows: specific surface area 258 m² / g, pore volume 0.388 mL / g, oxygen mass fraction 8.72%, ID / IG ratio 1.02, and resistivity 1.22 Ω•m.

[0613] Ketjenblack ECP600JD (manufactured by Lion Corporation, Japan) was purchased from Suzhou Yilongsheng Energy Technology Co., Ltd. Tested using the aforementioned instrumental methods, the results shown in Table VI are as follows: specific surface area 1362 m² / g, pore volume 2.29 mL / g, oxygen mass fraction 6.9%, ID / IG ratio 1.25, and resistivity 1.31 Ω•m.

[0614] The commercial platinum-carbon catalyst (code name HISPEC4000, manufactured by Johnson & Johnson) was purchased from Alfa Aesar. Test results in Table VI show that the mass fraction of platinum is 40.2%.

[0615] Example VI-1

[0616] This embodiment VI is used to illustrate the sulfur-boron-doped carbon material of the present invention.

[0617] Vulcan XC72 and elemental sulfur were mixed evenly at a mass ratio of 6:1. The mixture was placed in a tube furnace and heated to 800°C at a rate of 8°C / min. The mixture was then kept at a constant temperature for 3 h and allowed to cool naturally to obtain sulfur-doped carbon material.

[0618] 1 g of the aforementioned sulfur-doped carbon material was immersed in 15 mL of 3 wt% sodium borate aqueous solution for 24 h; dried in an oven at 100 °C; then placed in a tube furnace and heated to 600 °C at a rate of 8 °C / min, and kept at that temperature for 3 h; after natural cooling, sulfur-boron-doped carbon material was obtained, designated as carbon support A.

[0619] Sample Characterization and Testing

[0620] The sulfur-boron-doped carbon material in this embodiment VI- has a sulfur mass fraction of 1.23% and a boron mass fraction of 0.57% as analyzed by XPS; a specific surface area of ​​253 m2 / g; and a resistivity of 1.31 Ω•m.

[0621] Figure VI-1 is the XPS spectrum of sulfur in the sulfur-doped carbon material of Example VI-1.

[0622] Figure VI-2 is the XPS spectrum of sulfur in the sulfur-boron-doped carbon material of Example VI-1.

[0623] Figure VI-3 is the XPS spectrum of boron in the sulfur-boron-doped carbon material of Example VI-1.

[0624] Example VI-2

[0625] This embodiment VI is used to illustrate the sulfur-boron-doped carbon material of the present invention.

[0626] Ketjenblack ECP600JD and elemental sulfur were mixed evenly at a mass ratio of 4:1. The mixture was placed in a tube furnace and heated to 1200℃ at a rate of 5℃ / min. The mixture was then kept at a constant temperature for 2 h and allowed to cool naturally to obtain sulfur-doped carbon material.

[0627] 1g of the aforementioned sulfur-doped carbon material was added to 35 mL of 0.6 wt% sodium borate aqueous solution and impregnated for 24 h; dried in an oven at 100°C; then placed in a tube furnace and heated to 400°C at a rate of 5°C / min, and then kept at a constant temperature for 3 h. After natural cooling, sulfur-boron-doped carbon material was obtained, designated as carbon support B.

[0628] Sample Characterization and Testing

[0629] The sulfur-boron-doped carbon material of this embodiment VI- has a sulfur mass fraction of 0.49% and a boron mass fraction of 0.57% as determined by XPS analysis; a specific surface area of ​​241 m2 / g; and a resistivity of 1.29 Ω•m.

[0630] Figure VI-4 is the XPS spectrum of sulfur in the sulfur-doped carbon material of Example VI-2.

[0631] Figure VI-5 is the XPS spectrum of sulfur in the sulfur-boron-doped carbon material of Example VI-2.

[0632] Figure VI-6 is the XPS spectrum of boron in the sulfur-boron-doped carbon material of Example VI-2.

[0633] Example VI-3

[0634] This Example VI - is used to illustrate the platinum-carbon catalyst of the present invention.

[0635] Carbon support A was dispersed in deionized water at a ratio of 250 mL of water per gram of carbon support. 3.4 mmol of chloroplatinic acid was added per gram of carbon support, and the mixture was ultrasonically dispersed to form a suspension. 1 mol / L sodium carbonate aqueous solution was added to adjust the pH of the system to 10. The suspension was heated to 80°C, and formic acid was added with stirring to carry out a reduction reaction. The molar ratio of formic acid to chloroplatinic acid was 50:1. The reaction was continued for 10 h. The mixture after the reaction was filtered, washed with deionized water until the pH of the filtrate was neutral, filtered again, and then dried at 100°C to obtain the platinum-carbon catalyst.

[0636] Sample Characterization and Testing

[0637] The platinum mass fraction of the platinum-carbon catalyst is 40.3%.

[0638] In the XPS analysis of the platinum-carbon catalyst, there was no characteristic peak of B1s between 185 eV and 200 eV.

[0639] Signals of B2O3 and B were detected in the TG-MS test of the platinum-carbon catalyst.

[0640] Figure VI-7 is the XPS spectrum of sulfur in the platinum-carbon catalyst of Example VI-3.

[0641] The performance test results of the platinum-carbon catalyst are shown in Table VI-1.

[0642] Example VI-4

[0643] This embodiment is used to illustrate the platinum-carbon catalyst of the present invention.

[0644] The platinum-carbon catalyst was prepared according to the method of Example VI-3, except that 1.3 mmol of chloroplatinic acid was added per gram of carbon support.

[0645] Sample Characterization and Testing

[0646] The platinum mass fraction of the platinum-carbon catalyst is 20.1%.

[0647] In the XPS analysis of the platinum-carbon catalyst, there was no characteristic peak of B1s between 185 eV and 200 eV.

[0648] Signals of B2O3 and B were detected in the TG-MS test of the platinum-carbon catalyst.

[0649] The performance test results of the platinum-carbon catalyst are shown in Table VI-1.

[0650] Example VI-5

[0651] This Example VI - is used to illustrate the platinum-carbon catalyst of the present invention.

[0652] Carbon support B was dispersed in deionized water at a ratio of 250 mL of water per gram of carbon support. 12 mmol of chloroplatinic acid was added per gram of carbon support, and the mixture was ultrasonically dispersed to form a suspension. A 1 mol / L potassium hydroxide aqueous solution was added to adjust the pH of the system to 10. The suspension was heated to 80°C, and sodium borohydride was added under stirring to carry out a reduction reaction. The molar ratio of the reducing agent to the platinum precursor was 5:1, and the reaction was maintained for 12 h. The mixture after the reaction was filtered, washed until the pH of the solution was neutral, and dried at 100°C to obtain the carbon-supported platinum catalyst.

[0653] Sample Characterization and Testing

[0654] The platinum mass fraction of the platinum-carbon catalyst is 70.1%.

[0655] In the XPS analysis of the platinum-carbon catalyst, there was no characteristic peak of B1s between 185 eV and 200 eV.

[0656] Signals of B2O3 and B were detected in the TG-MS test of the platinum-carbon catalyst.

[0657] Figure VI-8 is the XPS spectrum of sulfur in the platinum-carbon catalyst of Example VI-6.

[0658] The performance test results of the platinum-carbon catalyst are shown in Table VI-1.

[0659] Comparative Example VI-1

[0660] Vulcan XC72 was dispersed in deionized water at a ratio of 250 mL of water per gram of carbon support. 3.4 mmol of chloroplatinic acid was added per gram of carbon support, and the mixture was ultrasonically dispersed to form a suspension. A 1 mol / L sodium carbonate aqueous solution was added to adjust the pH of the system to 10. The suspension was heated to 80°C, and formic acid was added with stirring to carry out a reduction reaction. The molar ratio of formic acid to chloroplatinic acid was 50:1. The reaction was continued for 10 h. The mixture after the reaction was filtered, washed with deionized water until the pH of the filtrate was neutral, filtered again, and then dried at 100°C to obtain the platinum-carbon catalyst.

[0661] Sample Characterization and Testing

[0662] The platinum mass fraction of the platinum-carbon catalyst is 40.1%.

[0663] The performance test results of the platinum-carbon catalyst are shown in Table VI-1.

[0664] Comparative Example VI-2

[0665] Ketjenblack ECP600JD was dispersed at a ratio of 200 mL of water and 50 mL of ethanol per gram of carbon support. 12 mmol of chloroplatinic acid was added per gram of carbon support, and the mixture was ultrasonically dispersed to form a suspension. A 1 mol / L potassium hydroxide aqueous solution was added to adjust the pH of the system to 10. The suspension was heated to 80°C, and sodium borohydride was added under stirring to carry out a reduction reaction. The molar ratio of the reducing agent to the platinum precursor was 5:1, and the reaction was maintained for 12 h. The mixture after the reaction was filtered, washed until the pH of the solution was neutral, and dried at 100°C to obtain the carbon-supported platinum catalyst.

[0666] Sample Characterization and Testing

[0667] The platinum mass fraction of the platinum-carbon catalyst is 69.7%.

[0668] The performance test results of the platinum-carbon catalyst are shown in Table VI-1.

[0669] Comparative Example VI-3

[0670] The platinum-carbon catalyst is a commercially available catalyst, code HISPEC4000.

[0671] Sample Characterization and Testing

[0672] The platinum mass fraction of the platinum-carbon catalyst is 40.2%.

[0673] The performance test results of the platinum-carbon catalyst are shown in Table VI-1.

[0674] Table VI-1 sample Half-wave potential / V ECSA / m 2 g -1 -Pt Mass ratio activity / A mg -1 -Pt The percentage decrease in activity after 5000 cycles / ECSA decline rate after 5000 laps / % Example VI-3 0.90 36.67 0.146 4 9 Example VI-4 0.91 59.43 0.233 5 9 Example VI-5 0.89 81.60 0.157 8 10 Comparative Example VI-1 0.89 33.63 0.135 28 16 Comparative Example VI-2 0.83 62.26 0.086 34 twenty three Comparative Example VI-3 0.88 57.32 0.124 twenty three 15

[0675] Implementation Method VII

[0676] This invention uses X-ray photoelectron spectroscopy (XPS) to detect the elements on the surface of material VII. The X-ray photoelectron spectroscopy instrument used is an ESCALab220i-XL model manufactured by VG Scientific and equipped with Avantage V5.926 software. The X-ray photoelectron spectroscopy analysis test conditions are: the excitation source is monochromatic AlKα X-rays, the power is 330W, and the basic vacuum during analysis is 3×10-9 mbar. In addition, the electron binding energy is corrected using the C1s peak (284.3 eV) of elemental carbon, and the post-peak-splitting software is XPSPEAK. The characteristic peak of thiophene-type sulfur in the spectrum is the characteristic peak after peak splitting.

[0677] Elemental analysis instruments, methods and conditions: Elemental analyzer (Vario EL Cube), reaction temperature 1150℃, 5 mg sample weighed, reduction temperature 850℃, carrier gas helium flow rate 200 mL / min, oxygen flow rate 30 mL / min, oxygen passage time 70s.

[0678] The instrument, method and conditions for testing the platinum mass fraction in the platinum-carbon catalyst: Take 30 mg of the prepared Pt / C catalyst, add 30 mL of aqua regia, reflux at 120℃ for 12 h, cool to room temperature, take the supernatant, dilute it and test the Pt content by ICP-AES.

[0679] The high-resolution transmission electron microscope (HRTEM) used in this invention is model JEM-2100 (HRTEM) (Nippon Electron Ltd.). The high-resolution transmission electron microscope test conditions are: accelerating voltage of 200 kV. The particle size of the nanoparticles in the sample was measured by electron microscope image VII-.

[0680] BET test method: In this invention, the pore structure properties of the sample are determined by a Quantacam AS-6B analyzer, the specific surface area and pore volume of the catalyst are obtained by the Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is calculated from the desorption curve according to the Barrett-Joyner-Halenda (BJH) method.

[0681] The Raman detection of the present invention uses a LabRAM HR UV-NIR laser confocal Raman spectrometer manufactured by HORIBA Corporation of Japan, with a laser wavelength of 532nm.

[0682] Electrochemical performance testing: Instruments used were Solartron Analytical EnergyLab and Princeton Applied Research (Model 636A). Methods and testing conditions: The catalyst polarization curve (LSV) was measured at 1600 rpm in O2-saturated 0.1 M HClO4, and the CV curve was measured in Ar atmosphere in 0.1 M HClO4. The electrochemical active area (ECSA) was calculated based on these results. For stability testing, 5000 cycles were performed in O2-saturated 0.1 M HClO4 within the range of 0.6 V to 0.95 V, followed by testing LSV and ECSA using the same method. During the above tests, the catalyst was prepared as a uniformly dispersed slurry and coated onto a 5 mm diameter glassy carbon electrode. The platinum content of the catalyst on the electrode was 3 μg to 4 μg.

[0683] Resistivity tester with four probes, instrument model KDY-1, method and test conditions: applied pressure 3.9±0.03 MPa, current 500±0.1mA.

[0684] TG-MS test: The test was performed using a German Netzsch STA449F5-QMS403D thermogravimetric-mass spectrometer. The ion source was an EI source, the quadrupole mass spectrometer was in MID mode, the transfer line was a 3-meter long capillary, the temperature was 260℃, the temperature range was 55℃~1000℃, and the heating rate was 10℃ / min.

[0685] VXC72 (Vulcan XC72, manufactured by Cabot Corporation, USA) was purchased from Suzhou Yilongsheng Energy Technology Co., Ltd. Tested using the aforementioned instrumental methods, result VII shows: specific surface area 258 m² / g, pore volume 0.388 mL / g, oxygen mass fraction 8.72%, ID / IG ratio 1.02, and resistivity 1.22 Ω•m.

[0686] Ketjenblack ECP600JD (manufactured by Lion Corporation, Japan) was purchased from Suzhou Yilongsheng Energy Technology Co., Ltd. Tested using the aforementioned instrumental methods, result VII shows: specific surface area 1362 m² / g, pore volume 2.29 mL / g, oxygen mass fraction 6.9%, ID / IG ratio 1.25, and resistivity 1.31 Ω•m.

[0687] The commercial platinum-carbon catalyst (code name HISPEC4000, manufactured by Johnson & Johnson) was purchased from Alfa Aesar. Test result VII indicates that the mass fraction of platinum is 40.2%.

[0688] Example VII-1

[0689] This embodiment is used to illustrate the sulfur-phosphorus-doped carbon material of the present invention.

[0690] 1g of Vulcan XC72 was impregnated in 15 mL of 4.0 wt% phosphoric acid aqueous solution for 16 h; dried in an oven at 100℃; then placed in a tube furnace and heated to 400℃ at a rate of 10℃ / min, kept at a constant temperature for 3 h, and then cooled naturally to obtain phosphorus-doped carbon material.

[0691] The aforementioned phosphorus-doped carbon material was mixed evenly with 0.167 g of elemental sulfur and placed in a tube furnace. The tube furnace was heated to 400 °C at a rate of 8 °C / min and kept at a constant temperature for 3 h. After natural cooling, the sulfur-phosphorus-doped carbon material was obtained.

[0692] Sample Characterization and Testing

[0693] The sulfur-phosphorus doped carbon material of this embodiment VII- has a sulfur mass fraction of 1.44% and a phosphorus mass fraction of 1.57% as determined by XPS analysis; a specific surface area of ​​239 m2 / g; and a resistivity of 1.31 Ω•m.

[0694] Figure VII-1 is the XPS spectrum of phosphorus in the sulfur-phosphorus doped carbon material of Example VII-1.

[0695] Figure VII-2 is the XPS spectrum of sulfur in the sulfur-phosphorus-doped carbon material of Example VII-1.

[0696] Figure VII-3 is the XPS spectrum of oxygen in the sulfur-phosphorus-doped carbon material of Example VII-1.

[0697] Example VII-2

[0698] This embodiment is used to illustrate the sulfur-phosphorus-doped carbon material of the present invention.

[0699] 1g of Vulcan XC72 was immersed in 15 mL of 4.8 wt% sodium phosphate aqueous solution for 24 h; dried in an oven at 100℃; then placed in a tube furnace and heated to 400℃ at a rate of 8℃ / min, and kept at a constant temperature for 3 h. After natural cooling, phosphorus-doped carbon material was obtained.

[0700] The aforementioned phosphorus-doped carbon material was mixed evenly with 0.2g of elemental sulfur and placed in a tube furnace. The tube furnace was heated to 1400℃ at a rate of 8℃ / min and kept at a constant temperature for 3 h. After natural cooling, the sulfur-phosphorus-doped carbon material was obtained and designated as carbon carrier A.

[0701] Sample Characterization and Testing

[0702] The sulfur-phosphorus doped carbon material in this embodiment VII- has a sulfur mass fraction of 0.97% and a phosphorus mass fraction of 0.55% as determined by XPS analysis; a specific surface area of ​​231 m2 / g; and a resistivity of 1.27 Ω•m.

[0703] Figure VII-4 is the XPS spectrum of phosphorus in the sulfur-phosphorus doped carbon material of Example VII-2.

[0704] Figure VII-5 is the XPS spectrum of sulfur in the sulfur-phosphorus-doped carbon material of Example VII-2.

[0705] Example VII-3

[0706] This embodiment is used to illustrate the sulfur-phosphorus-doped carbon material of the present invention.

[0707] Add 10 mL of anhydrous ethanol to 1 g of Ketjenblack ECP600JD, then add 25 mL of 1.8 wt% phosphoric acid aqueous solution and impregnate for 24 h; dry in an oven at 100 °C; then place in a tube furnace and heat the tube furnace to 600 °C at a rate of 10 °C / min, keep at a constant temperature for 3 h, and then cool naturally to obtain phosphorus-doped carbon material.

[0708] The aforementioned phosphorus-doped carbon material was mixed evenly with 0.15g of elemental sulfur and placed in a tube furnace. The tube furnace was heated to 700℃ at a rate of 10℃ / min and kept at a constant temperature for 3 hours. After natural cooling, the sulfur-phosphorus-doped carbon material was obtained.

[0709] Sample Characterization and Testing

[0710] The sulfur-phosphorus-doped carbon material of the present invention has a sulfur mass fraction of 1.41% and a phosphorus mass fraction of 0.18% as determined by XPS analysis; a specific surface area of ​​1325 m² / g; and a resistivity of 1.37 Ω•m.

[0711] Figure VII-6 is the XPS spectrum of phosphorus in the sulfur-phosphorus doped carbon material of Example VII-3.

[0712] Figure VII-7 is the XPS spectrum of sulfur in the sulfur-phosphorus-doped carbon material of Example VII-3.

[0713] Example VII-4

[0714] This embodiment is used to illustrate the sulfur-phosphorus-doped carbon material of the present invention.

[0715] Add 10 mL of anhydrous ethanol to 1 g of Ketjenblack ECP600JD, then add 25 mL of 1 wt% sodium phosphate aqueous solution and soak for 16 h; dry in an oven at 100 °C; then place in a tube furnace and heat the tube furnace to 600 °C at a rate of 10 °C / min, keep at a constant temperature for 3 h, and then cool naturally to obtain phosphorus-doped carbon material.

[0716] The aforementioned phosphorus-doped carbon material was mixed evenly with 0.25g of elemental sulfur and placed in a tube furnace. The tube furnace was heated to 1200℃ at a rate of 10℃ / min and kept at a constant temperature for 3 h. After natural cooling, the sulfur-phosphorus-doped carbon material was obtained and designated as carbon carrier B.

[0717] Sample Characterization and Testing

[0718] The sulfur-phosphorus-doped carbon material of the present invention has a sulfur mass fraction of 1.06% and a phosphorus mass fraction of 0.11% as determined by XPS analysis; a specific surface area of ​​1306 m² / g; and a resistivity of 1.35 Ω•m.

[0719] Figure VII-8 is the XPS spectrum of phosphorus in the sulfur-phosphorus doped carbon material of Example VII-4.

[0720] Figure VII-9 shows the XPS spectrum of sulfur in the sulfur-phosphorus-doped carbon material of Example VII-4.

[0721] Figure VII-10 is the XPS spectrum of oxygen in the sulfur-phosphorus-doped carbon material of Example VII-4.

[0722] Example VII-5

[0723] This embodiment is used to illustrate the platinum-carbon catalyst of the present invention.

[0724] Carbon support A was dispersed in deionized water at a ratio of 250 mL of water per gram of carbon support. 3.4 mmol of chloroplatinic acid was added per gram of carbon support, and the mixture was ultrasonically dispersed to form a suspension. 1 mol / L sodium carbonate aqueous solution was added to adjust the pH of the system to 10. The suspension was heated to 80°C, and formic acid was added with stirring to carry out a reduction reaction. The molar ratio of formic acid to chloroplatinic acid was 50:1. The reaction was continued for 10 h. The mixture after the reaction was filtered, washed with deionized water until the pH of the filtrate was neutral, filtered again, and then dried at 100°C to obtain the platinum-carbon catalyst.

[0725] Sample Characterization and Testing

[0726] The platinum mass fraction of the platinum-carbon catalyst is 40.2%.

[0727] In the XPS analysis of the platinum-carbon catalyst, there was no characteristic peak of P2p between 125 eV and 145 eV.

[0728] Figure VII-11 is the XPS spectrum of sulfur in the platinum-carbon catalyst of Example VII-5.

[0729] Signals of P, P2O3 and P2O5 were detected in TG-MS test.

[0730] The performance test results of the platinum-carbon catalyst are shown in Table VII-1.

[0731] Example VII-6

[0732] This embodiment is used to illustrate the platinum-carbon catalyst of the present invention.

[0733] ​​Carbon support B was dispersed in deionized water at a ratio of 250 mL of water per gram of carbon support. 12 mmol of chloroplatinic acid was added per gram of carbon support, and the suspension was formed by ultrasonic dispersion. The pH of the system was adjusted to 10 by adding 1 mol / L potassium hydroxide aqueous solution. The suspension was heated to 80°C, and sodium phosphide was added under stirring to carry out a reduction reaction. The molar ratio of reducing agent to platinum precursor was 5:1, and the reaction was maintained for 12 h. The mixture after the reaction was filtered, washed until the pH of the solution was neutral, and dried at 100°C to obtain the carbon-supported platinum catalyst.

[0734] Sample Characterization and Testing

[0735] The platinum mass fraction of the platinum-carbon catalyst is 69.8%.

[0736] In the XPS analysis of the platinum-carbon catalyst, there was no characteristic peak of P2p between 125 eV and 145 eV.

[0737] Figure VII-12 is the XPS spectrum of sulfur in the platinum-carbon catalyst of Example VII-6.

[0738] Signals of P, P2O3 and P2O5 were detected in TG-MS test.

[0739] The performance test results of the platinum-carbon catalyst are shown in Table VII-1.

[0740] Comparison with Example VII-1

[0741] Vulcan XC72 was dispersed in deionized water at a ratio of 250 mL of water per gram of carbon support. 3.4 mmol of chloroplatinic acid was added per gram of carbon support, and the mixture was ultrasonically dispersed to form a suspension. 1 mol / L sodium carbonate aqueous solution was added to adjust the pH of the system to 10. The suspension was heated to 80°C, and formic acid was added with stirring to carry out a reduction reaction. The molar ratio of formic acid to chloroplatinic acid was 50:1. The reaction was continued for 10 h. The mixture after the reaction was filtered, washed with deionized water until the pH of the filtrate was neutral, filtered again, and then dried at 100°C to obtain the platinum-carbon catalyst.

[0742] Sample Characterization and Testing

[0743] The platinum mass fraction of the platinum-carbon catalyst is 40.1%.

[0744] The performance test results of the platinum-carbon catalyst are shown in Table VII-1.

[0745] Comparative Example VII-2

[0746] Ketjenblack ECP600JD was dispersed at a ratio of 200 mL of water and 50 mL of ethanol per gram of carbon support. 12 mmol of chloroplatinic acid was added per gram of carbon support, and the mixture was ultrasonically dispersed to form a suspension. A 1 mol / L potassium hydroxide aqueous solution was added to adjust the pH of the system to 10. The suspension was heated to 80°C, and sodium phosphide was added under stirring to carry out a reduction reaction. The molar ratio of the reducing agent to the platinum precursor was 5:1, and the reaction was maintained for 12 h. The mixture after the reaction was filtered, washed until the pH of the solution was neutral, and dried at 100°C to obtain the carbon-supported platinum catalyst.

[0747] Sample Characterization and Testing

[0748] The platinum mass fraction of the platinum-carbon catalyst is 69.7%.

[0749] The performance test results of the platinum-carbon catalyst are shown in Table VII-1.

[0750] Comparative Example VII-3

[0751] The platinum-carbon catalyst is a commercially available catalyst, code HISPEC4000.

[0752] Sample Characterization and Testing

[0753] The platinum mass fraction of the platinum-carbon catalyst is 40.2%.

[0754] The performance test results of the platinum-carbon catalyst are shown in Table VII-1.

[0755] Comparative Example VII-4

[0756] Vulcan XC72 and elemental sulfur were mixed evenly at a mass ratio of 6:1. The mixture was placed in a tube furnace and heated to 400°C at a rate of 8°C / min. The mixture was then kept at a constant temperature for 3 hours and allowed to cool naturally to obtain sulfur-doped carbon material.

[0757] Sample Characterization and Testing

[0758] Figure VII-13 is the XPS spectrum of sulfur in the sulfur-doped carbon material of Comparative Example VII-4.

[0759] Table VII-1 sample Half-wave potential / V ECSA / m 2 g -1 -Pt Mass ratio activity / A mg -1 -Pt The percentage decrease in activity after 5000 cycles / ECSA decline rate after 5000 laps / % Examples VII-5 0.90 44.05 0.168 5 8 Examples VII-6 0.89 62.12 0.149 8 11 Compare with Example VII-1 0.89 33.63 0.135 28 16 Compare with Example VII-2 0.83 62.26 0.086 34 twenty three Compare with Example VII-3 0.88 57.32 0.124 twenty three 15

[0760] Implementation Method VIII

[0761] This invention uses X-ray photoelectron spectroscopy (XPS) to detect elements on the surface of materials. The X-ray photoelectron spectroscopy instrument used is an ESCALab220i-XL model manufactured by VG Scientific and equipped with Avantage V5.926 software. The X-ray photoelectron spectroscopy analysis test conditions are: the excitation source is monochromatic AlKα X-rays, the power is 330W, and the basic vacuum during analysis is 3×10-9 mbar. In addition, the electron binding energy is corrected using the C1s peak (284.3 eV) of elemental carbon, and the post-peak-splitting software is XPSPEAK. The characteristic peaks of thiophene-type sulfur, phosphorus, and boron in the spectrum are the characteristic peaks after peak splitting.

[0762] Elemental analysis instruments, methods and conditions: Elemental analyzer (Vario EL Cube), reaction temperature 1150℃, 5 mg sample weighed, reduction temperature 850℃, carrier gas helium flow rate 200 mL / min, oxygen flow rate 30 mL / min, oxygen passage time 70s.

[0763] The instrument, method and conditions for testing the mass fraction of platinum in platinum-carbon catalyst: Take 30 mg of the prepared Pt / C catalyst, add 30 mL of aqua regia, reflux at 120℃ for 12 h, cool to room temperature, take the supernatant, dilute it and test the Pt content by ICP-AES.

[0764] The high-resolution transmission electron microscope (HRTEM) used in this invention is model JEM-2100 (HRTEM) (Nippon Electron Ltd.). The high-resolution transmission electron microscope test conditions are: accelerating voltage of 200 kV. The particle size of the nanoparticles in the sample was measured using electron microscope image VIII-1.

[0765] BET test method: In this invention, the pore structure properties of the sample are determined by a Quantacam AS-6B analyzer, the specific surface area and pore volume of the catalyst are obtained by the Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is calculated from the desorption curve using the Barrett-Joyner-Halenda (BJH) method.

[0766] The Raman detection of the present invention uses a LabRAM HR UV-NIR laser confocal Raman spectrometer manufactured by HORIBA Corporation of Japan, with a laser wavelength of 532nm.

[0767] Electrochemical performance testing was conducted using Solartron Analytical EnergyLab and Princeton Applied Research (Model 636A). The methods and testing conditions were as follows: The catalyst polarization curve (LSV) was measured at 1600 rpm in O2-saturated 0.1 M HClO4, and the CV curve was measured in Ar atmosphere in 0.1 M HClO4. The electrochemical active area (ECSA) was calculated based on these results. For stability testing, 5000 cycles were performed in O2-saturated 0.1 M HClO4 within the range of 1.0 V to 1.5 V, followed by testing LSV and ECSA using the same method. During these tests, the catalyst was prepared as a uniformly dispersed slurry and coated onto a 5 mm diameter glassy carbon electrode. The platinum content of the catalyst on the electrode was 3 μg to 4 μg.

[0768] Resistivity tester with four probes, instrument model KDY-1, method and test conditions: applied pressure 3.9±0.03 MPa, current 500±0.1mA.

[0769] TG-MS test method: The test was performed using a German Netzsch STA449F5-QMS403D thermogravimetric-mass spectrometer. The ion source was an EI source, the quadrupole mass spectrometer was in MID mode, the transfer line was a 3-meter long capillary, the temperature was 260℃, the temperature range was 55℃~1000℃, and the heating rate was 10℃ / min.

[0770] VXC72 (Vulcan XC72, manufactured by Cabot Corporation, USA) was purchased from Suzhou Yilongsheng Energy Technology Co., Ltd. Tested using the aforementioned instrumental methods, the results showed: specific surface area 258 m² / g, pore volume 0.388 mL / g, oxygen mass fraction (XPS analysis) 8.72%, ID / IG ratio 1.02, and resistivity 1.22 Ω•m.

[0771] Ketjenblack ECP600JD (manufactured by Lion Corporation, Japan) was purchased from Suzhou Yilongsheng Energy Technology Co., Ltd. Tested using the aforementioned instrumental methods, the results showed: specific surface area 1362 m² / g, pore volume 2.29 mL / g, oxygen mass fraction (XPS analysis) 6.9%, ID / IG ratio 1.25, and resistivity 1.31 Ω•m.

[0772] Black Pearls 2000 (manufactured by Cabot Corporation, USA) was purchased from Suzhou Yilongsheng Energy Technology Co., Ltd. Tested using the aforementioned instrumental methods, the results showed: specific surface area 1479 m² / g, oxygen mass fraction 9.13% according to XPS analysis, ID / IG ratio 1.14, and resistivity 1.19 Ω•m.

[0773] The commercial platinum-carbon catalyst (code name HISPEC4000, manufactured by Johnson & Johnson) was purchased from Alfa Aesar. Test results showed that the mass fraction of platinum was 40.2%.

[0774] Example VIII-1

[0775] This embodiment VIII is used to illustrate the preparation of the sulfur-phosphorus-boron-doped carbon material of the present invention.

[0776] 1 g of Vulcan XC72 was immersed in 15 mL of an aqueous solution of sodium borate (1% wt%) and phosphoric acid (0.8 wt%) for 20 h; dried in an oven at 100 °C; then placed in a tube furnace and heated to 450 °C at a rate of 5 °C / min, and kept at that temperature for 2 h; after natural cooling, boron-phosphorus doped carbon material was obtained.

[0777] The aforementioned boron-phosphorus doped carbon material was mixed evenly with 0.167g of elemental sulfur and placed in a tube furnace. The tube furnace was heated to 1200℃ at a rate of 8℃ / min and kept at a constant temperature for 3 h. After natural cooling, sulfur-phosphorus-boron doped carbon material was obtained, which was designated as carbon carrier A.

[0778] Sample Characterization and Testing

[0779] The mass fraction of sulfur analyzed by XPS was 0.3%; the mass fraction of phosphorus analyzed by XPS was 0.04%; the mass fraction of boron analyzed by XPS was 0.5%; the specific surface area was 228 m2 / g; and the resistivity was 1.26 Ω•m.

[0780] Figure VIII-1 is the XPS spectrum of sulfur in the sulfur-phosphorus-boron-doped carbon material of Example VIII-1.

[0781] Figure VIII-2 is the XPS spectrum of phosphorus in the sulfur-phosphorus-boron-doped carbon material of Example VIII-1.

[0782] Figure VIII-3 is the XPS spectrum of boron in the sulfur-phosphorus-boron-doped carbon material of Example VIII-1.

[0783] Example VIII-2

[0784] This embodiment VIII is used to illustrate the preparation of the sulfur-phosphorus-boron-doped carbon material of the present invention.

[0785] Add 10 mL of anhydrous ethanol to 1 g of Ketjenblack ECP600JD, then add 25 mL of an aqueous solution of 0.3 wt% boric acid and 0.3 wt% sodium dihydrogen phosphate and impregnate for 24 h; dry in an oven at 100 °C; then place in a tube furnace and heat the tube furnace to 700 °C at a rate of 5 °C / min, and keep at that temperature for 2 h; after natural cooling, obtain boron-phosphorus doped carbon material.

[0786] The aforementioned boron-phosphorus doped carbon material was mixed evenly with 0.25g of elemental sulfur and placed in a tube furnace. The tube furnace was heated to 1400℃ at a rate of 10℃ / min and kept at a constant temperature for 3 h. After natural cooling, sulfur-phosphorus-boron doped carbon material was obtained, which was designated as carbon carrier B.

[0787] Sample Characterization and Testing

[0788] The mass fraction of sulfur analyzed by XPS was 0.4%; the mass fraction of phosphorus analyzed by XPS was 0.02%; the mass fraction of boron analyzed by XPS was 0.3%; the specific surface area was 1296 m2 / g; and the resistivity was 1.36 Ω•m.

[0789] Figure VIII-4 is the XPS spectrum of sulfur in the sulfur-phosphorus-boron-doped carbon material of Example VIII-2.

[0790] Figure VIII-5 is the XPS spectrum of phosphorus in the sulfur-phosphorus-boron-doped carbon material of Example VIII-2.

[0791] Figure VIII-6 is the XPS spectrum of boron in the sulfur-phosphorus-boron-doped carbon material of Example VIII-2.

[0792] Example VIII-3

[0793] This Example VIII is used to illustrate the preparation of the platinum-carbon catalyst of the present invention.

[0794] Carbon support A was dispersed in deionized water at a ratio of 250 mL of water per gram of carbon support. 3.4 mmol of chloroplatinic acid was added per gram of carbon support, and the mixture was ultrasonically dispersed to form a suspension. 1 mol / L sodium carbonate aqueous solution was added to adjust the pH of the system to 10. The suspension was heated to 80°C, and formic acid was added with stirring to carry out a reduction reaction. The molar ratio of formic acid to chloroplatinic acid was 50:1. The reaction was continued for 10 h. The mixture after the reaction was filtered, washed with deionized water until the pH of the filtrate was neutral, filtered again, and then dried at 100°C to obtain the platinum-carbon catalyst.

[0795] Sample Characterization and Testing

[0796] The platinum mass fraction of the platinum-carbon catalyst is 40.3%.

[0797] Figure VIII-7 is the XPS spectrum of sulfur in the platinum-carbon catalyst of Example VIII-3.

[0798] In the XPS analysis of the platinum-carbon catalyst, there was no characteristic peak of P2p between 125 eV and 145 eV.

[0799] Signals of P, P2O3 and P2O5 were detected in the TG-MS test of the platinum-carbon catalyst.

[0800] In the XPS analysis of the platinum-carbon catalyst, there was no characteristic peak of B1s between 185 eV and 200 eV.

[0801] Signals of B and B2O3 were detected in the TG-MS test of the platinum-carbon catalyst.

[0802] The performance test results of the platinum-carbon catalyst are shown in Table 1.

[0803] Example VIII-4

[0804] This Example VIII is used to illustrate the preparation of platinum-carbon catalyst.

[0805] The platinum-carbon catalyst was prepared according to the method of Example VIII-3, except that 1.3 mmol of chloroplatinic acid was added per gram of carbon support.

[0806] Sample Characterization and Testing

[0807] The platinum mass fraction of the platinum-carbon catalyst is 20.2%.

[0808] Signals of P, P2O3 and P2O5 were detected in the TG-MS test of the platinum-carbon catalyst.

[0809] Signals of B and B2O3 were detected in the TG-MS test of the platinum-carbon catalyst.

[0810] The performance test results of the platinum-carbon catalyst are shown in Table 1.

[0811] Example VIII-5

[0812] This Example VIII is used to illustrate the preparation of the platinum-carbon catalyst of the present invention.

[0813] Carbon support B was dispersed in a solution at a ratio of 600 mL of water and 600 mL of ethylene glycol per gram of carbon support. 12 mmol of chloroplatinic acid was added per gram of carbon support, and sodium acetate was added at a molar ratio of 2:1 to chloroplatinic acid. The mixture was ultrasonically dispersed to form a suspension. A 1 mol / L sodium carbonate aqueous solution was added to adjust the pH of the system to 10. The suspension was heated to 80°C, and sodium borohydride was added with stirring to carry out a reduction reaction at a molar ratio of 5:1 to chloroplatinic acid. The reaction was continued for 10 h. The mixture after the reaction was filtered, washed with deionized water until the pH of the filtrate was neutral, filtered again, and then dried at 100°C to obtain the platinum-carbon catalyst.

[0814] Sample Characterization and Testing

[0815] The platinum mass fraction of the platinum-carbon catalyst is 69.2%.

[0816] Figure VIII-8 is the XPS spectrum of sulfur in the platinum-carbon catalyst of Example VIII-5.

[0817] Figure VIII-9 is a TEM image of the platinum-carbon catalyst of Example VIII-5.

[0818] In the XPS analysis of the platinum-carbon catalyst, there was no characteristic peak of P2p between 125 eV and 145 eV.

[0819] Signals of P, P2O3 and P2O5 were detected in the TG-MS test of the platinum-carbon catalyst.

[0820] In the XPS analysis of the platinum-carbon catalyst, there was no characteristic peak of B1s between 185 eV and 200 eV.

[0821] Signals of B and B2O3 were detected in the TG-MS test of the platinum-carbon catalyst.

[0822] The performance test results of the platinum-carbon catalyst are shown in Table 1.

[0823] Comparative Example VIII-1

[0824] The platinum-carbon catalyst was prepared according to the method of Example VIII-3, except that the support was Vulcan XC72.

[0825] Sample Characterization and Testing

[0826] The platinum mass fraction of the platinum-carbon catalyst is 40.1%.

[0827] The performance test results of the platinum-carbon catalyst are shown in Table 1.

[0828] Comparative Example VIII-2

[0829] The platinum-carbon catalyst was prepared and tested in the same manner as in Examples VIII-5, except that the carbon support was Ketjenblack ECP600JD.

[0830] Sample Characterization and Testing

[0831] The platinum mass fraction of the platinum-carbon catalyst is 69.9%.

[0832] The performance test results of the platinum-carbon catalyst are shown in Table 1.

[0833] Comparative Example VIII-3

[0834] The platinum-carbon catalyst is a commercially available catalyst, code HISPEC4000.

[0835] Sample Characterization and Testing

[0836] The platinum mass fraction of the platinum-carbon catalyst is 40.2%.

[0837] The performance test results of the platinum-carbon catalyst are shown in Table 1.

[0838] Comparative Example VIII-4

[0839] This comparative example VIII is used to illustrate the preparation of phosphorus-doped carbon materials.

[0840] 1g of Vulcan XC72 was impregnated in 15 mL of 0.8 wt% phosphoric acid aqueous solution for 16 h; dried in an oven at 100℃; then placed in a tube furnace and heated to 400℃ at a rate of 8℃ / min, and kept at that temperature for 2 h; after natural cooling, phosphorus-doped carbon material was obtained.

[0841] Sample Characterization and Testing

[0842] Figure VIII-10 is the XPS spectrum of phosphorus in the phosphorus-doped carbon material of Comparative Example VIII-4.

[0843] Comparative Example VIII-5

[0844] This comparative example is used to illustrate the preparation of boron-doped carbon materials.

[0845] 1 g of Vulcan XC72 was immersed in 15 mL of 4.5 wt% sodium borate aqueous solution for 16 h; dried in an oven at 100 °C; then placed in a tube furnace and heated to 400 °C at a rate of 10 °C / min, and kept at the temperature for 3 h; after natural cooling, boron-doped carbon material was obtained.

[0846] Sample Characterization and Testing

[0847] Figure VIII-11 is the XPS spectrum of boron in the boron-doped carbon material of Comparative Example VIII-5.

[0848] Comparative Example VIII-6

[0849] This comparative example is used to illustrate the preparation of sulfur-doped carbon materials.

[0850] 1g of Ketjenblack ECP600JD was mixed with 0.25g of elemental sulfur and placed in a tube furnace. The tube furnace was heated to 500℃ at a rate of 5℃ / min and kept at a constant temperature for 3 h. After natural cooling, sulfur-doped carbon material was obtained.

[0851] Sample Characterization and Testing

[0852] Figure VIII-12 is the XPS spectrum of sulfur in the sulfur-doped carbon material of Comparative Example VIII-6.

[0853] Table 1 sample Half-wave potential / V Half-wave potential / V after 5000 cycles ECSA / m 2 g -1 -Pt Mass ratio activity / A mg -1 -Pt The percentage decrease in activity after 5000 cycles / ECSA decline rate after 5000 laps / % Example VIII-3 0.90 0.88 45.71 0.169 twenty one 13 Example VIII-4 0.91 0.90 55.26 0.197 15 8 Example VIII-5 0.88 0.86 87.95 0.148 18 10 Comparative Example VIII-1 0.89 0.87 35.65 0.141 42 31 Comparative Example VIII-2 0.85 0.82 62.26 0.112 38 25 Comparative Example VIII-3 0.88 0.86 59.43 0.128 31 20 [Simplified Explanation of the Diagram]

[0855] Embodiment I Figure I-1 shows the Raman spectra of the sulfur-doped carbon material (Ketjen-S) and Ketjen in Example I-1. Figure I-2 shows the XPS spectrum of the sulfur-doped carbon material in Example I-1. Figure I-3 shows the Raman spectra of the sulfur-doped carbon material (Vulcan XC72-S) and Vulcan XC72 in Example I-2. Figure I-4 shows the XPS spectrum of the sulfur-doped carbon material in Example I-2. Figure I-5 shows the nitrogen adsorption-desorption curve of the sulfur-doped carbon material in Example I-2. Figure I-6 shows the pore distribution curve of the sulfur-doped carbon material in Example I-2. Figure I-7 shows the XPS spectrum of the sulfur-doped carbon material in Example I-3. Figure I-8 shows the XPS spectrum of the platinum-carbon catalyst in Example I-4. Figure I-9 shows the TEM image of the platinum-carbon catalyst in Example I-5. Figure I-10 shows the polarization curve of the platinum-carbon catalyst in Example I-5. Figure 1-11 shows the XPS spectrum of the platinum-carbon catalyst in Example 1-5. Figure 1-12 shows the Raman spectra of the sulfur-doped carbon material (Vulcan XC72-s) and Vulcan XC72 in Comparative Example 1-1. Figure 1-13 shows the XPS spectrum of the sulfur-doped carbon material in Comparative Example 1-1. Figure 1-14 shows the nitrogen adsorption-desorption curve of the sulfur-doped carbon material in Comparative Example 1-1. Figure 1-15 shows the pore distribution curve of the sulfur-doped carbon material in Comparative Example 1-1. Figure 1-16 shows the TEM image of the platinum-carbon catalyst in Comparative Example 1-1. Figure 1-17 shows the polarization curve of the platinum-carbon catalyst in Comparative Example 1-1. Figure 1-18 shows the XPS spectrum of the sulfur-doped carbon material in Comparative Example 1-2. Figure 1-19 shows the polarization curve of the platinum-carbon catalyst in Comparative Example 1-5. Embodiment VI: Figure VI-1 shows the XPS spectrum of sulfur in the sulfur-doped carbon material of Example VI-1. Figure VI-2 is the XPS spectrum of sulfur in the sulfur-boron-doped carbon material of Example VI-1. Figure VI-3 is the XPS spectrum of boron in the sulfur-boron-doped carbon material of Example VI-1. Figure VI-4 is the XPS spectrum of sulfur in the sulfur-doped carbon material of Example VI-2. Figure VI-5 is the XPS spectrum of sulfur in the sulfur-boron-doped carbon material of Example VI-2. Figure VI-6 is the XPS spectrum of boron in the sulfur-boron-doped carbon material of Example VI-2. Figure VI-7 is the XPS spectrum of sulfur in the platinum-carbon catalyst of Example VI-4. Figure VI-8 is the XPS spectrum of sulfur in the platinum-carbon catalyst of Example VI-6. Embodiment VII: Figure VII-1 is the XPS spectrum of phosphorus in the sulfur-phosphorus-doped carbon material of Example VII-1. Figure VII-2 is the XPS spectrum of sulfur in the sulfur-phosphorus-doped carbon material of Example VII-1. Figure VII-3 is the XPS spectrum of oxygen in the sulfur-phosphorus-doped carbon material of Example VII-1. Figure VII-4 is the XPS spectrum of phosphorus in the sulfur-phosphorus-doped carbon material of Example VII-2. Figure VII-5 shows the XPS spectrum of sulfur in the sulfur-phosphorus-doped carbon material of Example VII-2.Figures VII-6 are XPS spectra of phosphorus in the sulfur-phosphorus-doped carbon material of Example VII-3. Figure VII-7 is an XPS spectra of sulfur in the sulfur-phosphorus-doped carbon material of Example VII-3. Figure VII-8 is an XPS spectra of phosphorus in the sulfur-phosphorus-doped carbon material of Example VII-4. Figure VII-9 is an XPS spectra of sulfur in the sulfur-phosphorus-doped carbon material of Example VII-4. Figure VII-10 is an XPS spectra of oxygen in the sulfur-phosphorus-doped carbon material of Example VII-4. Figure VII-11 is an XPS spectra of sulfur in the platinum-carbon catalyst of Example VII-5. Figure VII-12 is an XPS spectra of sulfur in the platinum-carbon catalyst of Example VII-6. Figure VII-13 is an XPS spectra of sulfur in the sulfur-doped carbon material of Comparative Example VII-4. Embodiment VIII: Figure VIII-1 is an XPS spectra of sulfur in the sulfur-phosphorus-boron-doped carbon material of Example VIII-1. Figure VIII-2 is an XPS spectra of phosphorus in the sulfur-phosphorus-boron-doped carbon material of Example VIII-1. Figure VIII-3 is the XPS spectrum of boron in the sulfur-phosphorus-boron-doped carbon material of Example VIII-1. Figure VIII-4 is the XPS spectrum of sulfur in the sulfur-phosphorus-boron-doped carbon material of Example VIII-2. Figure VIII-5 is the XPS spectrum of phosphorus in the sulfur-phosphorus-boron-doped carbon material of Example VIII-2. Figure VIII-6 is the XPS spectrum of boron in the sulfur-phosphorus-boron-doped carbon material of Example VIII-2. Figure VIII-7 is the XPS spectrum of sulfur in the platinum-carbon catalyst of Example VIII-3. Figure VIII-8 is the XPS spectrum of sulfur in the platinum-carbon catalyst of Example VIII-5. Figure VIII-9 is a TEM image of the platinum-carbon catalyst of Example VIII-5. Figure VIII-10 is the XPS spectrum of phosphorus in the phosphorus-doped carbon material of Comparative Example VIII-4. Figure VIII-11 is the XPS spectrum of boron in the boron-doped carbon material of Comparative Example VIII-5. Figure VIII-12 is the XPS spectrum of sulfur in the sulfur-doped carbon material of Comparative Example VIII-6.

Claims

1. A carbon-supported platinum group metal catalyst, characterized in that, in its XPS analysis S2P spectrum, the area of ​​the characteristic peaks between 162 eV and 166 eV, between 160 eV and 170 eV, is greater than 92%; the support of the carbon-supported platinum group metal catalyst is sulfur-doped conductive carbon black, wherein the sulfur-doped conductive carbon black is sulfur-doped conductive carbon black, sulfur-boron-doped conductive carbon black, sulfur-phosphorus-doped conductive carbon black, or sulfur-phosphorus-boron-doped conductive carbon black; the mass fraction of platinum group metals in the carbon-supported platinum group metal catalyst is 20% to 70%; in XPS analysis, the sulfur mass fraction in the sulfur-doped conductive carbon black is 0.1% to 10%, the sulfur mass fraction in the sulfur-boron-doped conductive carbon black is 0.1% to 5%, the sulfur mass fraction in the sulfur-phosphorus-doped conductive carbon black is 0.1% to 5%, and the sulfur mass fraction in the sulfur-phosphorus-boron-doped conductive carbon black is 0.01% to 4%.

2. The carbon-supported platinum group metal catalyst as claimed in claim 1, wherein the area of ​​the characteristic peaks between 160 eV and 170 eV and between 162 eV and 166 eV is greater than 98%; and the mass fraction of the platinum group metals in the carbon-supported platinum group metal catalyst is 45% to 65%.

3. The carbon-supported platinum group metal catalyst as claimed in claim 1, wherein the peak area of ​​any characteristic peak located between 160 eV and 170 eV, and outside of 162 eV and 166 eV, is less than 5%.

4. The carbon-supported platinum group metal catalyst as claimed in claim 3, wherein in the range of 160 eV to 170 eV, there is only a characteristic peak located between 162 eV and 166 eV.

5. The carbon-supported platinum group metal catalyst as claimed in claim 1, wherein there is a bimodal distribution between 162 eV and 166 eV.

6. The carbon-supported platinum group metal catalyst as claimed in claim 1, wherein the conductive carbon black is ordinary conductive carbon black, superconducting carbon black, or extra-conducting carbon black.

7. The carbon-supported platinum group metal catalyst as claimed in claim 1, wherein the support for the carbon-supported platinum group metal catalyst is sulfur-boron-doped conductive carbon black.

8. The carbon-supported platinum group metal catalyst as claimed in claim 7, wherein there are no characteristic peaks in the B1s spectrum of its XPS analysis between 185 eV and 200 eV.

9. The carbon-supported platinum group metal catalyst as claimed in claim 7, wherein signals of B2O3 and B are detected in TG-MS testing.

10. The carbon-supported platinum group metal catalyst as claimed in claim 1, wherein the support for the carbon-supported platinum group metal catalyst is sulfur-phosphorus-doped conductive carbon black.

11. The carbon-supported platinum group metal catalyst as claimed in claim 10, wherein there are no characteristic peaks in the P2p spectrum of its XPS analysis between 125 eV and 145 eV.

12. The carbon-supported platinum group metal catalyst as claimed in claim 10, wherein signals of P, P2O3 and P2O5 are detected in TG-MS testing.

13. The carbon-supported platinum group metal catalyst as claimed in claim 1, wherein the support for the carbon-supported platinum group metal catalyst is sulfur-phosphorus-boron-doped conductive carbon black.

14. The carbon-supported platinum group metal catalyst as claimed in claim 13, wherein in its XPS analysis, there are no characteristic peaks of B1s between 185 eV and 200 eV, and no characteristic peaks of P2p between 125 eV and 145 eV.

15. The carbon-supported platinum group metal catalyst as claimed in claim 13, wherein signals of B2O3 and B are detected in TG-MS testing, and signals of P, P2O3 and P2O5 are detected in TG-MS testing.

16. The carbon-supported platinum group metal catalyst as claimed in claim 1, wherein the platinum group metal is selected from platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), osmium (Os), and ruthenium (Ru).

17. The carbon-supported platinum group metal catalyst as claimed in claim 1, wherein the platinum group metal is platinum.

18. The carbon-supported platinum group metal catalyst as claimed in claim 1, wherein the resistivity of the carbon-supported platinum group metal catalyst is <10 Ω·m.

19. A hydrogen fuel cell, characterized in that the anode and / or cathode of the hydrogen fuel cell use a carbon-supported platinum group metal catalyst as described in any one of claims 1 to 18.

20. A carbon material, characterized in that the carbon material is a sulfur-doped conductive carbon black; in its XPS analysis S2P spectrum, there is only a characteristic peak between 162 eV and 166 eV between 160 eV and 170 eV; in the XPS analysis of the carbon material, the oxygen mass fraction is 4% to 15%; the sulfur-doped conductive carbon black is sulfur-doped conductive carbon black, sulfur-boron-doped conductive carbon black, sulfur-phosphorus-doped conductive carbon black, or sulfur-phosphorus-boron-doped conductive carbon black; in the XPS analysis, the sulfur mass fraction in the sulfur-doped conductive carbon black is 0.1% to 10%, the sulfur mass fraction in the sulfur-boron-doped conductive carbon black is 0.1% to 5%, the sulfur mass fraction in the sulfur-phosphorus-doped conductive carbon black is 0.1% to 5%, and the sulfur mass fraction in the sulfur-phosphorus-boron-doped conductive carbon black is 0.01% to 4%.

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