CN114430047A

CN114430047A - Carbon material, platinum-carbon catalyst, and preparation method and application thereof

Info

Publication number: CN114430047A
Application number: CN202011014105.4A
Authority: CN
Inventors: 顾贤睿; 荣峻峰; 王厚朋; 张家康; 赵红; 彭茜; 谢南宏
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2020-09-24
Filing date: 2020-09-24
Publication date: 2022-05-03
Anticipated expiration: 2040-09-24
Also published as: CN114430047B

Abstract

The invention relates to a carbon material, a platinum-carbon catalyst, a preparation method and application thereof, wherein the carbon material is sulfur-boron doped conductive carbon black, and the comprehensive performance of the platinum-carbon catalyst prepared by using the carbon material is superior to that of a commercial catalyst.

Description

Carbon material, platinum-carbon catalyst, and preparation method and application thereof

Technical Field

The invention relates to a carbon material, a platinum-carbon catalyst, and a preparation method and application thereof.

Background

In the field of chemistry, carbon materials are both important supports and commonly used catalysts. The carbon element has rich bonding modes, and the carbon material can be modified in various modes so as to obtain better performance.

The Oxygen Reduction Reaction (ORR) is a key reaction in the electrochemical field, for example in fuel cells and metal air cells, and is a major factor affecting cell performance. The carbon material doped with atoms can be directly used as a catalyst for oxygen reduction reaction. When used as an oxygen reduction catalyst, it has been reported in the literature that a carbon material is doped with elements such as nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine, iodine, etc., wherein nitrogen has a radius close to that of carbon atoms and easily enters into a carbon lattice, and thus is the most commonly used doping element. Although there are many reports of doped carbon materials as fuel cell catalysts and some research results show better activity, there is a large gap compared to platinum carbon catalysts and is far from commercial application. On one hand, the combination mode of the heteroatom and the carbon material and the catalytic mechanism thereof are not fully known in the field; on the other hand, each heteroatom has multiple bonding modes with the carbon material, and the situation is more complicated when multiple heteroatoms are doped, so that how to control the bonding mode of the heteroatoms and the carbon material is the difficulty of doping atoms. In addition, such catalysts are generally not suitable for acidic environments, especially for important Proton Exchange Membrane Fuel Cells (PEMFCs).

The most effective oxygen reduction catalyst to date is the platinum carbon catalyst, and the currently used commercial platinum carbon catalyst has an undesirable dispersion of platinum metal and is subject to agglomeration deactivation, and on the other hand, platinum dissolution and agglomeration at the cathode of a hydrogen fuel cell causes a significant decrease in platinum surface area over time, affecting fuel cell life. It is highly desirable in the art to substantially increase its catalytic activity and stability in an attempt to facilitate its large-scale commercial use. Factors influencing the activity and stability of the platinum-carbon catalyst are many and complex, and some literatures believe that the activity and stability of the platinum-carbon catalyst are related to the particle size, morphology and structure of platinum, and the type, property and platinum loading of a carrier. In the prior art, the performance of the platinum-carbon catalyst is improved mainly by controlling the particle size, morphology and structure of platinum, the specific surface area and pore structure of a carrier; there is also a literature report that modifying groups are attached to the carbon surface to improve the performance of platinum-carbon catalysts by modifying the carbon support.

The platinum loading of the platinum-carbon catalyst of the hydrogen fuel cell in practical application is at least more than 20 wt%, which is much more difficult than the manufacturing difficulty of the chemical platinum-carbon catalyst (the platinum loading is less than 5 wt%). The platinum-carrying quantity is improved, so that a thinner membrane electrode with better performance can be manufactured, but the platinum-carrying quantity is greatly improved, so that the accumulation among platinum metal particles is easily caused, and the utilization rate of an active site is sharply reduced. How to more effectively utilize the catalytic active sites of the platinum metal particles and increase the contactable three-phase catalytic reaction interface, thereby improving the platinum utilization rate and the comprehensive performance of the fuel cell and the metal-air battery, is a key problem to be solved in the field.

The carbon carrier has more defect sites which are beneficial to improving the platinum carrying amount, but simultaneously aggravates carbon corrosion and reduces the stability of the catalyst. The carbon corrosion can be effectively relieved by improving the graphitization degree, but the surface of the carbon carrier is chemically inert due to high graphitization degree, so that platinum is difficult to be uniformly dispersed on the carbon carrier, and the problem is particularly difficult when the platinum carrying amount is high.

The chemical reduction method is a commonly used method for preparing the platinum-carbon catalyst, and has the advantages of simple process and low utilization rate and catalytic activity of platinum. The reason for this may be that the platinum nanoparticles are not uniformly dispersed due to irregularities in the pore structure of the carbon support.

The information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and may include information that is not already known to those of ordinary skill in the art.

Disclosure of Invention

It is a first object of the present invention to provide a carbon material with unique properties. The second purpose of the invention is to improve the comprehensive performance of the platinum-carbon catalyst. It is a third object of the present invention to provide a platinum-carbon catalyst with a higher platinum loading in addition to the aforementioned objects. A fourth object of the present invention is to improve the aqueous phase reduction process for making platinum carbon catalysts.

In order to achieve the above object, the present invention provides the following technical solutions.

1. A carbon material, characterized in that it is a sulfur and boron doped conductive carbon black.

2. Push buttonThe carbon material as described in claim 1, characterized by S analyzed in XPS thereof_2PAmong the peaks, only the thiophene-type sulfur peaks were observed at 162 to 166eV, and the peak at 168. + -.1 eV was observed.

3. The carbon material according to 2, characterized in that S is analyzed by XPS_2PIn the spectrum peaks, the peak area ratio of the characteristic peak of the thiophene type sulfur to the characteristic peak at 168 +/-1 eV is more than 10.

4. A carbon material according to any one of the preceding claims, characterized in that said thiophenic sulfur has characteristic peaks of two peaks, at 163.6. + -. 0.5eV and 164.8. + -. 0.5eV, respectively.

5. A carbon material according to any one of the preceding claims, characterized in that it is analyzed by XPS B_1sAmong the spectral peaks, there is a characteristic peak between 190eV and 195eV, and there is no other characteristic peak between 185eV and 200 eV.

6. A carbon material according to any one of the preceding claims, characterized in that it is analyzed by XPS B_1sAmong the spectral peaks, there are two characteristic peaks between 191ev and 193ev, and there are no other characteristic peaks between 185ev and 200 ev.

7. A carbon material according to any one of the above, characterized in that it has a resistivity of <10. omega. m, preferably <5. omega. m, more preferably <3. omega. m.

8. The carbon material according to any one of the preceding claims, characterized in that, in XPS analysis thereof, the sulfur mass fraction is 0.1% to 5%, and the boron mass fraction is 0.1% to 5%; preferably, the mass fraction of sulfur is 0.2-3%, and the mass fraction of boron is 0.2-3%; more preferably, the sulfur mass fraction is 0.4% to 1.5%. More preferably, the boron mass fraction is 0.4% to 2%.

9. A carbon material according to any one of the preceding claims, characterized in that it has a specific surface area of 10m²/g～2000m²A/g, preferably of 200m²/g～2000m²(ii)/g; the pore volume is 0.02mL/g to 6.0mL/g, preferably 0.2mL/g to 3.0 mL/g.

10. A carbon material according to any one of the preceding claims, characterized in that the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXAXK 40B 2.

11. A method of producing a carbon material, comprising:

(1) b doping: contacting the conductive carbon black with a boron source, and treating (preferably treating at constant temperature) for 0.5-10 h at 300-800 ℃ in inert gas to obtain boron-doped conductive carbon black; and

(2) a step of doping sulfur: contacting the boron-doped conductive carbon black in the step (1) with a sulfur source, and treating (preferably treating at constant temperature) for 0.5-10 h at 400-1500 ℃ in inert gas to obtain the sulfur-boron-doped conductive carbon black.

12. The preparation method according to any one of the preceding claims, characterized in that the boron source is one or more of boric acid, borate, boron oxide, sodium borohydride and potassium borohydride.

13. The production method according to any one of the preceding claims, characterized in that the mass of the boron source is based on the mass of boron contained therein, and the mass ratio of the conductive carbon black to the boron source is 100: 1-5: 1; preferably 60: 1-15: 1.

14. the process according to any one of the preceding claims, characterized in that the source of sulphur is elemental sulphur.

15. The preparation method according to any one of the preceding claims, characterized in that the mass ratio of the conductive carbon black to the sulfur source is 20: 1-2: 1; preferably 10: 1-4: 1, more preferably 8: 1-4: 1.

16. the process according to any one of the preceding claims, wherein the temperature in (1) is from 400 ℃ to 600 ℃.

17. The production method according to any of the above, wherein the temperature in (2) is 1000 to 1500 ℃, preferably 1100 to 1300 ℃.

18. The process according to any of the preceding claims, characterized in that the treatment time in (1) and/or (2) is from 1h to 5h, preferably from 2h to 4 h.

19. A process according to any one of the preceding claims, characterized in that the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXAXK 40B 2.

20. The production method according to any one of the preceding claims, wherein the conductive carbon black of (1) has an oxygen mass fraction of more than 4%, preferably 4% to 15% in XPS analysis.

21. The production process according to any of the preceding claims, characterized in that the conductive carbon black described in (1) has a resistivity of <10 Ω · m, preferably <5 Ω · m, more preferably <2 Ω · m.

22. The production process according to any of the preceding claims, characterized in that the specific surface area of the conductive carbon black in (1) is 10m²/g～2000m²A/g, preferably of 200m²/g～2000m²(ii)/g; the pore volume is 0.02mL/g to 6mL/g, preferably 0.2mL/g to 3 mL/g.

23. The production method according to any one of the preceding claims, characterized in that in (1), the conductive carbon black is brought into contact with the boron source by means of dipping in an aqueous solution of the boron source and drying.

24. A carbon material, characterized by being produced by any one of the aforementioned methods.

25. Use of a carbon material according to any of the preceding claims as an electrode material in electrochemistry.

26. The platinum-carbon catalyst is characterized by comprising a carbon carrier and platinum metal loaded on the carbon carrier, wherein the carbon carrier is conductive carbon black doped with sulfur and boron.

27. A platinum-carbon catalyst according to any one of the preceding claims, characterized in that S is analyzed in its XPS_2PAmong the peaks, only the thiophene-type sulfur peaks were observed at 162 to 166eV, and the peak at 168. + -.1 eV was observed.

28. A platinum-carbon catalyst according to any one of the preceding claims, characterized in that S is analyzed in its XPS_2PAmong the peaks, the peak area ratio of the characteristic peak of the thiophene-type sulfur to the characteristic peak at 168 +/-1 eV is more than 10.

29. A platinum-carbon catalyst according to any one of the preceding claims, characterized in that it has been XPS analyzed for B_1sAmong the spectral peaks, there was no characteristic peak between 185 to 200 eV.

30. The platinum-carbon catalyst according to any of the preceding claims, characterized in that the platinum-carbon catalyst has a resistivity of <10 Ω · m, preferably <2 Ω · m.

31. A platinum-carbon catalyst according to any one of the preceding claims, characterised in that the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXAXK 40B 2.

32. A method of preparing a platinum carbon catalyst comprising:

(1) the steps of manufacturing the boron-doped conductive carbon black: contacting the conductive carbon black with a boron source, and treating (preferably treating at constant temperature) for 0.5-10 h at 300-800 ℃ in inert gas to obtain boron-doped conductive carbon black; and;

(2) the method comprises the following steps of: contacting the boron-doped conductive carbon black in the step (1) with a sulfur source, and treating (preferably, treating at constant temperature) for 0.5-10 h at 400-1500 ℃ in inert gas to obtain the sulfur-boron-doped conductive carbon black;

(3) and (3) loading platinum by taking the sulfur-boron doped conductive carbon black obtained in the step (2) as a carrier.

33. The method for producing a platinum-carbon catalyst according to any one of the preceding claims, characterized in that in (1), the mass of the boron source is calculated on the mass of boron contained therein, and the mass ratio of the conductive carbon black to the boron source is 100: 1-5: 1; preferably 60: 1-15: 1.

34. the method for preparing a platinum-carbon catalyst according to any one of the preceding claims, wherein in (2), the mass ratio of the conductive carbon black to the sulfur source is 20: 1-2: 1; preferably 10: 1-4: 1, more preferably 8: 1-4: 1.

35. the method for producing a platinum-carbon catalyst according to any of the above processes, wherein the temperature in the step (1) is 400 to 600 ℃.

36. The process for producing a platinum-carbon catalyst according to any of the above processes, wherein the temperature in the step (2) is 1000 to 1500 ℃, preferably 1100 to 1300 ℃.

37. The method for preparing a platinum-carbon catalyst according to any one of the preceding claims, wherein the treatment time in (1) and/or (2) is 1 to 5 hours, preferably 2 to 4 hours.

38. The preparation method of any one of the platinum-carbon catalysts is characterized in that the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXAXK 40B 2.

39. The method for producing a platinum-carbon catalyst according to any one of the preceding claims, wherein in (1), the conductive carbon black has an oxygen mass fraction of more than 4%, preferably 4% to 15%, in XPS analysis.

40. The method for producing a platinum-carbon catalyst according to any one of the preceding claims, wherein (1) the conductive carbon black has a resistivity of <10 Ω · m, preferably <5 Ω · m, more preferably <2 Ω · m.

41. The process for producing a platinum-carbon catalyst according to any of the above processes, wherein in the step (1), the conductive carbon black has a specific surface area of 10m²/g～2000m²A/g, preferably of 200m²/g～2000m²(ii)/g; the pore volume is 0.02mL/g to 6mL/g, preferably 0.2mL/g to 3 mL/g.

42. The method for preparing a platinum-carbon catalyst according to any one of the preceding claims, wherein the step of supporting platinum comprises:

(a) dispersing the sulfur-boron doped conductive carbon black obtained in the step (2) and a platinum precursor in a water phase, and adjusting the pH to 8-12 (preferably, adjusting the pH value to 10 +/-0.5);

(b) adding a reducing agent for reduction;

(c) separating out solid, and post-treating to obtain the platinum-carbon catalyst.

43. The preparation method of any one of the platinum-carbon catalysts is characterized in that in (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5-5 mol/L.

44. The preparation method of any one of the platinum-carbon catalysts is characterized in that in the 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 the platinum is 2-100; the reduction temperature is 60-90 ℃; the reduction time is 4-15 h.

45. A platinum-carbon catalyst is characterized by being prepared by any one of the preparation methods of the platinum-carbon catalyst.

46. A hydrogen fuel cell, characterized in that any of the foregoing platinum-carbon catalysts is used in the anode and/or cathode of the hydrogen fuel cell.

The heteroatom and the carbon material have various combination modes, and the combination mode of the heteroatom and the carbon material is influenced by different doping methods and raw materials and different operation steps and conditions in the doping process, so that the property difference of the heteroatom and the carbon material is caused, and the functions of the heteroatom and the carbon material are changed. The situation is more complicated when multiple heteroatoms are doped simultaneously. In the art, how to control the bonding mode of the heteroatom to the carbon material is a difficulty in doping atoms. Controlling the manner in which the heteroatoms are bonded to the carbon material makes it possible to produce carbon materials with unique properties that make them suitable for particular applications. The invention discovers that a carbon material with unique properties can be obtained by doping the conductive carbon black with boron and then sulfur, and in the XPS analysis of the carbon material, B of boron_1sThe spectrum has double peaks between 190ev and 195ev, and S of sulfur_2pIn the spectrum, there are two kinds of sulfur peaks between 160eV and 170 eV. Further research shows that the sulfur-boron doped carbon material is a carbon carrier with excellent performance, and can improve the comprehensive performance of the platinum-carbon catalyst of the hydrogen fuel cell.

Compared with the prior art, the invention can realize the following beneficial technical effects.

Firstly, the invention can produce a carbon material with unique properties by doping the conductive carbon black with boron and then sulfur, and in the XPS analysis of the carbon material, B of boron_1sTwo characteristic peaks of boron and S of sulfur are present between 190ev and 195ev in the spectrum_2pIn the spectrogram, two kinds of sulfur have characteristic peaks between 160eV and 170eV, the ratio of the two kinds of sulfur can be adjusted greatly, wherein the peak area ratio of the characteristic peak of the thiophene type sulfur to the characteristic peak at 168 +/-1 eV can be more than 10.

Secondly, the method for preparing the sulfur-boron doped carbon material is simple, and the proportion of the doped elements is adjustable in a large range.

Thirdly, the carbon material of the invention is particularly suitable for being used as a carrier of a platinum-carbon catalyst, in particular a platinum-carbon catalyst with high platinum loading. On one hand, the catalytic activity of the platinum-carbon catalyst can be improved, and on the other hand, the stability of the platinum-carbon catalyst can be improved.

Fourthly, the platinum carrying amount of the platinum-carbon catalyst of the hydrogen fuel cell in practical application is generally more than 20 wt%, and the difficulty in manufacturing the high platinum carrying amount catalyst with excellent performance is great. The chemical reduction method has simple process, but the utilization rate of platinum is low and the catalytic activity is lower. However, the carbon material produced by the present invention is used as a carrier, and a chemical reduction method using an aqueous phase is used, so that a high-platinum-supported catalyst having good specific activity, ECSA and stability can be easily produced.

Fifthly, sulfur is generally considered to generate irreversible toxic action on the platinum catalyst, however, the invention discovers that the catalytic activity and the stability of the platinum-carbon catalyst are remarkably improved by carrying out sulfur-doping modification on a carbon material.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

FIG. 1 is an XPS spectrum of boron from sulfur boron doped conductive carbon black of example 1.

FIG. 2 is an XPS spectrum of the sulfur boron doped conductive carbon black of example 1.

FIG. 3 is an XPS spectrum of boron from sulfur boron doped conductive carbon black of example 2.

FIG. 4 is an XPS spectrum of sulfur from sulfur boron doped conductive carbon black of example 2.

FIG. 5 is an XPS spectrum of boron from sulfur boron doped conductive carbon black of example 3.

FIG. 6 is an XPS spectrum of sulfur from sulfur boron doped conductive carbon black of example 3.

FIG. 7 is an XPS spectrum of boron from the boron doped conductive carbon black of example 4.

FIG. 8 is an XPS spectrum of boron from sulfur boron doped conductive carbon black of example 4.

Fig. 9 is an XPS spectrum of sulfur of the sulfur boron doped conductive carbon black of example 4.

Fig. 10 is an XPS spectrum of sulfur for the platinum carbon catalyst of example 5.

Fig. 11 is a polarization curve (LSV) before and after 5000 cycles of the platinum-carbon catalyst of example 5.

Fig. 12 shows CV curves before and after 5000 cycles of the platinum-carbon catalyst in example 5.

Fig. 13 is an XPS spectrum of sulfur for the platinum carbon catalyst of example 6.

Fig. 14 is an XPS spectrum of sulfur for the platinum carbon catalyst of example 7.

Fig. 15 is an XPS spectrum of sulfur for the platinum carbon catalyst of example 8.

Fig. 16 is a polarization curve (LSV) before and after 5000 cycles of the commercial platinum-carbon catalyst of comparative example 3.

Detailed Description

The present invention will be described in detail with reference to the following embodiments, but it should be understood that the scope of the present invention is not limited by these embodiments and the principle of the present invention, but is defined by the claims.

In the present invention, anything or matters not mentioned is directly applicable to those known in the art without any change except those explicitly described. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas formed thereby are considered part of the original disclosure or description of the present invention and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.

All of the features disclosed in this application can be combined in any combination which is understood to be disclosed or described in this application and which, unless clearly considered to be too irrational by a person skilled in the art, is to be considered as being specifically disclosed and described in this application. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the examples but also the endpoints of each numerical range in the specification, and ranges in which any combination of the numerical points is disclosed or recited should be considered as ranges of the present invention.

Technical and scientific terms used herein are to be defined only in accordance with their definitions, and are to be understood as having ordinary meanings in the art without any definitions.

The "doping element" in the present invention means nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine.

In the present invention, unless the term "carbon material containing a doping element" is uniquely defined depending on the context or the self-definition, the term "carbon material" refers to a carbon material containing no doping element. So does the underlying concept of carbon material.

In the present invention, "carbon black" and "carbon black" are terms of art that can be substituted for each other.

The "inert gas" in the present invention means a gas that does not have any appreciable influence on the properties of the sulfur-boron-doped carbon material in the production method of the present invention. So does the underlying concept of carbon material.

In the present invention, all references to "pore volume" are to P/P, except where the context or self-definition may be clear₀The maximum single point adsorption total pore volume.

The invention provides a carbon material, which is characterized in that the carbon material is sulfur and boron doped conductive carbon black.

The carbon material according to the invention is free of doping elements other than sulphur and boron.

The carbon material according to the present invention contains no metal element.

Carbon material according to the invention, S analyzed in its XPS_2PAmong the peaks, only the thiophene-type sulfur peaks were observed at 162 to 166eV, and the peak at 168. + -.1 eV was observed.

According to the carbon material of the present invention, the characteristic peaks of the thiophenic sulfur are two peaks, which are 163.6. + -. 0.5eV and 164.8. + -. 0.5eV, respectively.

The carbon material according to the present invention has B between 190eV and 195eV in XPS analysis thereof_1sThe characteristic peak of (1) is not other between 185 to 200 eV.

Carbon material according to the invention, B in XPS analysis thereof_1sAmong the spectral peaks, there are two characteristic peaks between 191ev and 193ev, and there are no other characteristic peaks between 185ev and 200 ev.

The carbon material according to the invention has a resistivity of <10.0 Ω · m, preferably <5.0 Ω · m, more preferably <3.0 Ω · m.

According to the carbon material, in XPS analysis, the mass fraction of sulfur is 0.1-5%, and the mass fraction of boron is 0.1-5%; preferably, the mass fraction of sulfur is 0.2-3%, and the mass fraction of boron is 0.2-3%; more preferably, the sulfur mass fraction is 0.4% to 1.5%. The mass fraction of boron is 0.4-2%.

The specific surface area and pore volume of the carbon material according to the invention may vary within a relatively large range, for example the specific surface area may be 10m²/g～2000m²The pore volume may be from 0.02mL/g to 6.0 mL/g. In one embodiment, the specific surface area is 200m²/g～2000m²The pore volume is 0.2mL/g to 3.0 mL/g.

According to the carbon material of the present invention, the Conductive carbon black may be common Conductive carbon black (Conductive Blacks), Super Conductive carbon black (Super Conductive Blacks) or Extra Conductive carbon black (Extra Conductive Blacks), for example, the Conductive carbon black may be one or more of Ketjen black series superconducting carbon black, Cabot series Conductive carbon black and series Conductive carbon black produced by winning and developing solid race company; preferably Ketjen Black EC-300J, Ketjen Black EC-600JD, Ketjen Black ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B 2.

The carbon material according to the present invention is not limited in the production method and source of the conductive carbon black. The conductive carbon black may be acetylene black, furnace black, or the like.

According to the carbon material of the present invention, sulfur and boron are chemically bonded to the conductive carbon black.

Carbon material according to the invention, S analyzed in its XPS_2PAmong the peaks, the peak area ratio of the characteristic peak of the thiophenic sulfur to the characteristic peak at 168. + -.1 eV is more than 5, preferably more than 10.

The invention also provides a preparation method of the carbon material, which comprises the following steps:

(1) b doping: contacting the conductive carbon black with a boron source, and treating for 0.5 h-10 h (preferably constant temperature treatment) in inert gas at 300-800 ℃ to obtain boron-doped conductive carbon black; and

According to the method for preparing the carbon material of the present invention, if (1) and/or (2) require temperature rise, the temperature rise rate is 1 ℃/min to 20 ℃/min, preferably 3 ℃/min to 15 ℃/min, and more preferably 8 ℃/min to 15 ℃/min.

According to the method for producing a carbon material of the present invention, there is no particular limitation on the boron source, and any boron source known for use in a doped carbon material can be used in the present invention. The boron source can be one or more of boric acid, borate, boron oxide, sodium borohydride and potassium borohydride.

According to the method for producing a carbon material of the present invention, the mass of the boron source is calculated based on the mass of boron contained therein, and the mass ratio of the conductive carbon black to the boron source is 100: 1-5: 1; preferably 60: 1-15: 1.

according to the preparation method of the carbon material, the sulfur source is elemental sulfur.

According to the method for producing a carbon material of the present invention, the mass ratio of the conductive carbon black to the sulfur source is 20: 1-2: 1; preferably 10: 1-4: 1, more preferably 8: 1-4: 1.

according to the preparation method of the carbon material, the temperature of the constant temperature treatment in (1) is 400-600 ℃.

According to the method for producing a carbon material of the present invention, the temperature of the constant temperature treatment in (2) is 1000 to 1500 ℃, more preferably 1100 to 1300 ℃.

According to the preparation method of the carbon material, in the step (1) and/or the step (2), the constant temperature treatment time is 1-5 h, preferably 2-4 h.

According to the method for preparing the carbon material of the present invention, the conductive carbon black may be one or more of Ketjen black series superconducting carbon black, Cabot series conductive carbon black and series conductive carbon black produced by winning-developing-solid-match company; preferably EC-300J, EC-600JD, ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B 2. I of the conductive carbon black_D/I_GThe value is generally 0.8 to 5, preferably 1 to 4. In the Raman spectrum, it is located at 1320cm^-1The nearby peak is the D peak and is located at 1580cm^-1The nearby peak is the G peak, I_DRepresents the intensity of the D peak, I_GRepresenting the intensity of the G peak.

According to the method for producing a carbon material of the present invention, the inert gas is nitrogen or argon.

According to the method for producing a carbon material of the present invention, the conductive carbon black has a resistivity of <10 Ω · m, preferably <5 Ω · m, more preferably <2 Ω · m.

According to the preparation method of the carbon material, the conductive carbon black has an oxygen mass fraction of generally more than 4%, preferably 4% to 15% in XPS analysis.

According to the method for producing a carbon material of the present invention, the specific surface area of the conductive carbon black can be varied over a wide range. Generally, the specific surface area is 10m²/g～2000m²(ii)/g; the pore volume is 0.02 mL/g-6 mL/g.

According to the method for producing a carbon material of the present invention, a metal-containing catalyst is not used in the production of the carbon material.

According to the method for producing a carbon material of the present invention, (1) the conductive carbon black is brought into contact with the boron source by dipping in an aqueous solution of the boron source and then drying.

Use of a carbon material according to any of the preceding claims as an electrode material in electrochemistry.

A platinum-carbon catalyst comprises a carbon carrier and platinum metal loaded on the carbon carrier, wherein the carbon carrier is conductive carbon black doped with sulfur and boron.

The platinum-carbon catalyst according to the present invention does not contain other doping elements than sulfur and boron.

The platinum-carbon catalyst according to the present invention does not contain other metal elements than platinum.

According to the platinum-carbon catalyst of the present invention, sulfur and boron are chemically bonded to the conductive carbon black in the carbon support.

Platinum-carbon catalyst according to the invention, S analyzed in its XPS_2PAmong the peaks, only the thiophene-type sulfur peaks were observed at 162 to 166eV, and the peak at 168. + -.1 eV was observed.

According to the platinum-carbon catalyst, the characteristic peaks of the thiophene sulfur are double peaks and are respectively located at 163.6 +/-0.5 ev and 164.8 +/-0.5 ev.

Platinum-carbon catalyst according to the invention, S analyzed in its XPS_2PAmong the peaks, the peak area ratio of the characteristic peak of the thiophene-type sulfur to the characteristic peak at 168 +/-1 eV is more than 10.

Platinum-carbon catalyst according to the invention, B in XPS analysis thereof_1sAmong the spectral peaks, there was no characteristic peak between 185 to 200 eV.

According to the platinum-carbon catalyst of the present invention, a boron signal (B) was detected in a TG-MS (thermogravimetric-mass spectrometry) test₂O₃And B).

According to the platinum-carbon catalyst of 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.

The platinum-carbon catalyst according to the invention has a resistivity of <10.0 Ω · m, preferably <2.0 Ω · m.

According to the platinum-carbon catalyst of the present invention, the specific surface area of the platinum-carbon catalyst is 80m²/g～1500m²A/g, preferably of 100m²/g～200m²/g。

According to the platinum carbon catalyst of the invention, the conductive carbon black can be one or more of Ketjen black series superconducting carbon black, Cabot series conductive carbon black and series conductive carbon black produced by Wingda Gusai company; preferably Ketjen Black EC-300J, Ketjen Black EC-600JD, Ketjen Black ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B 2.

The preparation method and the source of the conductive carbon black are not limited by the platinum carbon catalyst. The conductive carbon black may be acetylene black, furnace black, or the like.

The invention provides a preparation method of a platinum-carbon catalyst, which comprises the following steps:

According to the preparation method of the platinum-carbon catalyst, if the temperature is required to be increased in the step (1) and/or the step (2), the temperature increase rate is 1-20 ℃/min, preferably 3-15 ℃/min, and more preferably 8-15 ℃/min.

According to the preparation method of the platinum-carbon catalyst, the boron source is one or more of boric acid, borate, boron oxide, sodium borohydride and potassium borohydride.

According to the preparation method of the platinum-carbon catalyst, in the step (1), the mass of the boron source is calculated by the mass of boron contained in the boron source, and the mass ratio of the conductive carbon black to the boron source is 100: 1-5: 1; preferably 60: 1-15: 1.

according to the preparation method of the platinum-carbon catalyst, the sulfur source is elemental sulfur.

According to the preparation method of the platinum-carbon catalyst, in the step (2), the mass of the sulfur source is calculated by the mass of sulfur contained in the sulfur source, and the mass ratio of the conductive carbon black to the sulfur source is 20: 1-2: 1; preferably 10: 1-4: 1, more preferably 8: 1-4: 1.

according to the preparation method of the platinum-carbon catalyst, in the step (1), the temperature is 400-600 ℃.

According to the preparation method of the platinum-carbon catalyst of the invention, in the step (2), the temperature is 1000 ℃ to 1500 ℃, and preferably 1100 ℃ to 1300 ℃.

According to the preparation method of the platinum-carbon catalyst, in (1) and/or (2), the treatment time is 1-5 h, preferably 2-4 h.

According to the preparation method of the platinum-carbon catalyst, the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXAXK 40B 2.

According to the preparation method of the platinum-carbon catalyst of the invention, (1), in the XPS analysis of the conductive carbon black, the oxygen mass fraction is more than 4%, and preferably 4-15%.

According to the method for preparing a platinum-carbon catalyst of the present invention, (1), the conductive carbon black has a resistivity of <10 Ω · m, preferably <5 Ω · m, more preferably <2 Ω · m.

According to the preparation method of the platinum-carbon catalyst of the present invention, in (1), the specific surface area of the conductive carbon black is 10m²/g～2000m²A/g, preferably of 200m²/g～2000m²(ii)/g; the pore volume is 0.02mL/g to 6mL/g, preferably 0.2mL/g to 3 mL/g.

According to the preparation method of the platinum-carbon catalyst of the present invention, (1), the conductive carbon black is contacted with the boron source by dipping in an aqueous solution of the boron source and then drying.

According to the preparation method of the platinum-carbon catalyst of the invention, in (2), the boron-doped conductive carbon black in (1) is contacted with a sulfur source by mixing.

According to the preparation method of the platinum-carbon catalyst of the present invention, the step of supporting platinum comprises:

(b) adding a reducing agent for reduction;

According to the preparation method of the platinum-carbon catalyst, in the step (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5-5 mol/L.

According to the preparation method of the platinum-carbon catalyst, in the 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 the platinum is 2-100; the reduction temperature is 60-90 ℃; the reduction time is 4-15 h.

A platinum-carbon catalyst is prepared by any one of the preparation methods of the platinum-carbon catalyst.

A hydrogen fuel cell comprising an anode and/or a cathode, wherein any one of the platinum-carbon catalysts described above is used.

When the platinum-carbon catalyst is used for oxygen reduction reaction, the specific mass activity reduction rate after 5000 turns is less than 10%, and the ECSA reduction rate after 5000 turns is less than 10%.

The platinum-carbon catalyst of the present invention, when used in an oxygen reduction reaction, in some embodiments, ECSA>42m²g^-1Pt, e.g. at 42m² g^-1-Pt～74m² g^-1-Pt。

When the platinum-carbon catalyst of the present invention is used in an oxygen reduction reaction, in some examples, the specific mass activity>0.14A mg^-1-Pt, such as 0.14A mg^-1-Pt～0.22A mg^-1-Pt。

The platinum carbon catalyst of the present invention, when used in an oxygen reduction reaction, in some embodiments has a half-wave potential >0.88V, such as 0.88V to 0.91V.

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way.

Reagents, instruments and tests

Unless otherwise specified, all reagents used in the invention are analytically pure, and all reagents are commercially available.

The invention detects elements on the surface of the material by an X-ray photoelectron spectrum analyzer (XPS). The adopted X-ray photoelectron spectrum analyzer is an ESCALB 220i-XL type ray photoelectron spectrum analyzer which is manufactured by VG scientific company and is provided with Avantage V5.926 software, and the X-ray photoelectron spectrum analysis test conditions are as follows: the excitation source is monochromatized A1K alpha X-ray, the power is 330W, and the basic vacuum is 3X 10 during analysis and test^-9mbar. In addition, the electron binding energy was corrected with the C1s peak (284.3eV) of elemental carbon, and the late peak processing software was XPSPEAK. The characteristic peaks of the thiophene sulfur and the boron in the spectrogram are the characteristic peaks after peak separation.

Apparatus and method of elemental analysis, conditions: an element analyzer (Vario EL Cube), the reaction temperature is 1150 ℃, 5mg of the sample is weighed, the reduction temperature is 850 ℃, the flow rate of carrier gas helium is 200mL/min, the flow rate of oxygen is 30mL/min, and the oxygen introducing time is 70 s.

The instrument, the method and the conditions for testing the mass fraction of platinum in the platinum-carbon catalyst are as follows: and (3) adding 30mL of aqua regia into 30mg of the prepared Pt/C catalyst, condensing and refluxing for 12h at 120 ℃, cooling to room temperature, taking supernatant liquid for dilution, and testing the Pt content in the supernatant liquid by using ICP-AES (inductively coupled plasma-atomic emission Spectrometry).

The high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100(HRTEM) (Nippon electronics Co., Ltd.), and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200 kV. The particle size of the nanoparticles in the sample is measured by an electron microscope picture.

BET test method: in the invention, the pore structure property of a sample is measured by a Quantachrome AS-6B type analyzer, the specific surface area and the pore volume of the catalyst are obtained by a Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.

The Raman detection adopts a LabRAM HR UV-NIR laser confocal Raman spectrometer produced by HORIBA company of Japan, and the laser wavelength is 532 nm.

Electrochemical performance test, instrument Model Solartron analytical energy lab and Princeton Applied Research (Model 636A), methods and test conditions: polarization curve LSV of catalyst at 1600rpm₂Saturated 0.1M HClO₄Test in (1), CV Curve under Ar atmosphere 0.1M HClO₄To calculate the electrochemically active area ECSA. At O in the stability test₂Saturated 0.1M HClO₄After 5000 cycles of scanning in the range of 0.6V to 0.95V, LSV and ECSA were tested as described above. During the test, the catalyst is prepared into evenly dispersed slurry and coated on a glassy carbon electrode with the diameter of 5mm, and the platinum content of the catalyst on the electrode is 3-4 mu g.

Resistivity test four-probe resistivity tester, instrument model KDY-1, method and test conditions: the applied pressure is 3.9 plus or minus 0.03MPa, and the current is 500 plus or minus 0.1 mA.

TG-MS test: the test is carried out by adopting a German Chiz-resistant STA449F5-QMS403D type thermogravimetric-mass spectrometer, an ion source is an EI source, a quadrupole mass spectrometer adopts an MID mode, a transmission pipeline is a capillary tube with the length of 3 meters, and the temperature is 260 ℃; the temperature range is 55-1000 ℃, and the heating rate is 10 ℃/min.

VXC72(Vulcan XC72, produced by Kabot, USA) was purchased from Suzhou wingong sandisk energy science and technology, Inc. The results of the tests by the instrument method show that: specific surface area 258m²Per g, pore volume 0.388mL/g, oxygen mass fraction 8.72%, I_D/I_G1.02, and a resistivity of 1.22. omega. m.

Ketjenblack ECP600JD (manufactured by Lion corporation, japan) was purchased from tsuzhou wingong sandisk energy science and technology limited. The results of the tests by the instrument method show that: specific surface area 1362m²G, pore volume 2.29mL/g, oxygen mass fraction 6.9%, I_D/I_G1.25, and resistivity of 1.31. omega. m.

Commercial platinum carbon catalyst (trade name HISPEC4000, manufactured by Johnson Matthey corporation) was purchased from Alfa Aesar. The test result shows that: the mass fraction of platinum was 40.2%.

Example 1

This example illustrates sulfur boron doped conductive carbon black of the present invention.

1g of Vulcan XC72 was immersed in 15mL of 4.0 wt% aqueous sodium borate solution for 16 h; drying in an oven at 100 ℃; and then placing the mixture into a tube furnace, heating the tube furnace to 400 ℃ at the speed of 10 ℃/min, carrying out constant temperature treatment for 3h, and naturally cooling to obtain the boron-doped conductive carbon black.

Uniformly mixing the boron-doped conductive carbon black with 0.167g of elemental sulfur, putting the mixture into a tubular furnace, heating the tubular furnace to 1100 ℃ at the speed of 8 ℃/min, and carrying out constant-temperature treatment for 3 h; and naturally cooling to obtain the sulfur-boron doped conductive carbon black numbered as a carbon carrier A.

Sample characterization and testing

The sulfur boron doped conductive carbon black of the embodiment has a sulfur mass fraction of 0.93% by XPS analysis; the boron mass fraction of XPS analysis is 0.95%; specific surface area of 245m²(ii)/g; the resistivity was 1.28. omega. m.

In FIG. 2, the peak area ratio of the characteristic peak of thiophenic sulfur to the characteristic peak at 168. + -.1 eV was 11.16.

Example 2

1g of Vulcan XC72 was immersed in 15mL of 4.8 wt% aqueous sodium borate solution for 24 h; drying in an oven at 100 ℃; and then putting the mixture into a tube furnace, heating the tube furnace to 400 ℃ at the speed of 8 ℃/min, carrying out constant temperature treatment for 3h, and naturally cooling to obtain the boron-doped conductive carbon black.

Uniformly mixing the boron-doped conductive carbon black with 0.2g of elemental sulfur, putting the mixture into a tubular furnace, heating the tubular furnace to 400 ℃ at the speed of 8 ℃/min, and carrying out constant-temperature treatment for 3 hours; and naturally cooling to obtain the sulfur-boron doped conductive carbon black numbered as a carbon carrier B.

Sample characterization and testing

In the sulfur-boron doped conductive carbon black in the example, the sulfur mass fraction analyzed by XPS is 1.09%; the boron mass fraction by XPS analysis is 1.56%; specific surface area of 259m²(ii)/g; the resistivity was 1.31. omega. m.

Example 3

Adding 10mL of absolute ethanol into 1g of Ketjenblack ECP600JD, and then adding 25mL of 3.8 wt% sodium borate aqueous solution for soaking for 24 h; drying in an oven at 100 ℃; then placing the mixture into a tube furnace, heating the tube furnace to 600 ℃ at the speed of 10 ℃/min, carrying out constant temperature treatment for 3h, and naturally cooling to obtain the boron-doped conductive carbon black.

Uniformly mixing the boron-doped conductive carbon black with 0.25g of elemental sulfur, putting the mixture into a tubular furnace, heating the tubular furnace to 1300 ℃ at the speed of 10 ℃/min, and carrying out constant-temperature treatment for 3 hours; and naturally cooling to obtain the sulfur-boron doped conductive carbon black numbered as a carbon carrier C.

Sample characterization and testing

The sulfur and boron doped conductive carbon black disclosed by the invention has the sulfur mass fraction of 0.96% by XPS analysis; the boron mass fraction by XPS analysis is 1.43%; the specific surface area is 1311m²(ii)/g; the resistivity was 1.36. omega. m.

In FIG. 6, the peak area ratio of the characteristic peak of thiophenic sulfur to the characteristic peak at 168. + -.1 eV was 11.45.

Example 4

Adding 10mL of absolute ethanol into 1g of Ketjenblack ECP600JD, and then adding 25mL of 1 wt% sodium borate aqueous solution for soaking for 16 h; drying in an oven at 100 ℃; then placing the mixture into a tube furnace, heating the tube furnace to 600 ℃ at the speed of 10 ℃/min, carrying out constant temperature treatment for 3h, and naturally cooling to obtain the boron-doped conductive carbon black.

Uniformly mixing the boron-doped conductive carbon black with 0.15g of elemental sulfur, putting the mixture into a tubular furnace, heating the tubular furnace to 700 ℃ at the speed of 10 ℃/min, and carrying out constant-temperature treatment for 3 hours; and naturally cooling to obtain the sulfur-boron doped conductive carbon black numbered as a carbon carrier D.

Sample characterization and testing

The sulfur-boron doped conductive carbon black disclosed by the invention has the sulfur mass fraction of 0.72% by XPS analysis; the boron mass fraction of XPS analysis is 0.58%; specific surface area of 1344m²(ii)/g; the resistivity was 1.35. omega. m.

FIG. 7 is an XPS spectrum of boron doped conductive carbon black of example 4.

Example 5

This example serves to illustrate the platinum carbon catalyst of the present invention.

Dispersing a carbon carrier A into deionized water according to the proportion that 250mL of water is used for each gram of carbon carrier, adding 3.4mmol of chloroplatinic acid into each gram of carbon carrier, performing ultrasonic dispersion to form a suspension, and adding 1mol/L of sodium carbonate aqueous solution to enable the pH value of the system to be 10; heating the suspension to 80 ℃, adding formic acid to carry out reduction reaction while stirring, wherein the molar ratio of the formic acid to the chloroplatinic acid is 50:1, and continuously maintaining the reaction for 10 hours; and filtering the reacted mixture, washing the mixture by deionized water until the pH value of the filtrate is neutral, filtering the mixture, and drying the filtrate at 100 ℃ to obtain the platinum-carbon catalyst.

Sample characterization and testing

The platinum mass fraction of the platinum-carbon catalyst was 40.0%.

No B was found in XPS analysis of the platinum-carbon catalyst at 185 to 200eV_1sCharacteristic peak of (2).

Detection of B in TG-MS test₂O₃And B.

In FIG. 10, the peak area ratio of the characteristic peak of thiophenic sulfur to the characteristic peak at 168. + -.1 eV was 10.8.

Fig. 11 is a plot of polarization (LSV) before and after 5000 cycles of the platinum-carbon catalyst of example 5.

The results of the platinum carbon catalyst performance tests are shown in table 1.

Example 6

A platinum carbon catalyst was prepared according to the method of example 5, except that: the carbon support B prepared in example 2 was used.

Sample characterization and testing

The platinum mass fraction of the platinum-carbon catalyst was 40.2%.

Detection of B in TG-MS test₂O₃And B.

In FIG. 13, the peak area ratio of the characteristic peak of thiophenic sulfur to the characteristic peak at 168. + -.1 eV was 5.8.

Example 7

Dispersing a carbon carrier C in deionized water according to the proportion that 250mL of water is used for each gram of carbon carrier, adding 12mmol of chloroplatinic acid into each gram of carbon carrier, performing ultrasonic dispersion to form a suspension, and adding 1mol/L of potassium hydroxide aqueous solution to adjust the pH value of the system to 10; heating the suspension to 80 ℃, adding sodium borohydride while stirring for reduction reaction, wherein the molar ratio of the reducing agent to the platinum precursor is 5:1, and maintaining the reaction for 12 hours; and filtering the reacted mixture, washing until the pH value of the solution is neutral, and drying at 100 ℃ to obtain the carbon-supported platinum catalyst.

Sample characterization and testing

The platinum mass fraction of the platinum-carbon catalyst was 70.3%.

Detection of B in TG-MS test₂O₃And B.

In FIG. 14, the peak area ratio of the characteristic peak of thiophenic sulfur to the characteristic peak at 168. + -.1 eV was 11.4.

Example 8

A platinum carbon catalyst was prepared according to the method of example 7, except that: using the carbon support D prepared in example 4, 1.3mmol of chloroplatinic acid per gram of carbon support was added.

Sample characterization and testing

The platinum mass fraction of the platinum-carbon catalyst was 20.6%.

Detection of B in TG-MS test₂O₃And B.

In FIG. 15, the peak area ratio of the characteristic peak of thiophenic sulfur to the characteristic peak at 168. + -.1 eV was 3.6.

Comparative example 1

Dispersing Vulcan XC72 in deionized water according to the proportion that each gram of carbon carrier uses 250mL of water, adding 3.4mmol of chloroplatinic acid into each gram of carbon carrier, performing ultrasonic dispersion to form suspension, and adding 1mol/L of sodium carbonate aqueous solution to ensure that the pH value of the system is 10; heating the suspension to 80 ℃, adding formic acid to carry out reduction reaction while stirring, wherein the molar ratio of the formic acid to the chloroplatinic acid is 50:1, and continuously maintaining the reaction for 10 hours; and filtering the reacted mixture, washing the mixture by deionized water until the pH value of the filtrate is neutral, filtering the mixture, and drying the filtrate at 100 ℃ to obtain the platinum-carbon catalyst.

Sample characterization and testing

The platinum mass fraction of the platinum-carbon catalyst was 40.1%.

Comparative example 2

Dispersing Ketjenblack ECP600JD according to the proportion of 200mL of water to 50mL of ethanol used for each gram of carbon carrier, adding 12mmol of chloroplatinic acid into each gram of carbon carrier, performing ultrasonic dispersion to form a suspension, and adding 1mol/L of potassium hydroxide aqueous solution to adjust the pH value of the system to 10; heating the suspension to 80 ℃, adding sodium borohydride while stirring for reduction reaction, wherein the molar ratio of the reducing agent to the platinum precursor is 5:1, and maintaining the reaction for 12 hours; and filtering the reacted mixture, washing until the pH value of the solution is neutral, and drying at 100 ℃ to obtain the carbon-supported platinum catalyst.

Sample characterization and testing

The platinum mass fraction of the platinum-carbon catalyst was 69.7%.

Comparative example 3

The platinum carbon catalyst was a commercial catalyst purchased under the designation HISPEC 4000.

Sample characterization and testing

The platinum mass fraction of the platinum-carbon catalyst was 40.2%.

Fig. 16 is a polarization curve before and after 5000 cycles of the commercial platinum-carbon catalyst of comparative example 3.

TABLE 1

Claims

2. The carbon material according to claim 1, wherein S is analyzed by XPS_2PAmong the peaks, only the thiophene-type sulfur peaks were observed at 162 to 166eV, and the peak at 168. + -.1 eV was observed.

3. Carbon material according to claim 1, characterized in that B is analyzed in its XPS_1sAmong the spectral peaks, there are two characteristic peaks between 191ev and 193ev, and there are no other characteristic peaks between 185ev and 200 ev.

4. The carbon material according to claim 1, wherein the XPS analysis shows that the sulfur content is 0.1 to 5% by mass and the boron content is 0.1 to 5% by mass.

5. The carbon material as claimed in claim 1, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXAXK 40B 2.

6. A method of producing a carbon material, comprising:

(1) b doping: contacting conductive carbon black with a boron source, and treating for 0.5-10 h at 300-800 ℃ in inert gas to obtain boron-doped conductive carbon black; and

(2) a step of doping sulfur: contacting the boron-doped conductive carbon black in the step (1) with a sulfur source, and treating for 0.5-10 h at 400-1500 ℃ in inert gas to obtain the sulfur-boron-doped conductive carbon black.

7. The method according to claim 6, wherein the boron source is one or more of boric acid, borate, boron oxide, sodium borohydride and potassium borohydride.

8. The production method according to claim 6, wherein the mass ratio of the conductive carbon black to the boron source is 100: 1-5: 1.

9. the method according to claim 6, wherein the sulfur source is elemental sulfur.

10. The production method according to claim 6, wherein the mass ratio of the conductive carbon black to the sulfur source is 20: 1-2: 1.

11. the process according to claim 6, wherein the temperature in (2) is 1000 ℃ to 1500 ℃.

12. The method according to claim 6, wherein the conductive carbon black of (1) has a specific resistance<10 omega. m, specific surface area of 10m²/g～2000m²(iv)/g, XPS analysis oxygen mass fraction greater than 4%.

13. The production method according to claim 6, wherein in (1), the conductive carbon black is brought into contact with the boron source by means of dipping in an aqueous solution of the boron source followed by drying.

14. A carbon material produced by the method according to any one of claims 6 to 13.

15. Use of the carbon material as claimed in any one of claims 1 to 5 and 14 as an electrode material in electrochemistry.

16. The platinum-carbon catalyst is characterized by comprising a carbon carrier and platinum metal loaded on the carbon carrier, wherein the carbon carrier is conductive carbon black doped with sulfur and boron.

17. Platinum-carbon catalyst according to claim 16, characterized in that S is analyzed in its XPS_2PAmong the peaks, only the thiophene-type sulfur peaks were observed at 162 to 166eV, and the peak at 168. + -.1 eV was observed.

18. Platinum-carbon catalyst according to claim 17, characterized in that S is analyzed in its XPS_2PIn the spectrum peaks, the peak area ratio of the characteristic peak of the thiophene type sulfur to the characteristic peak at 168 +/-1 eV is more than 10.

19. Platinum-carbon catalyst according to claim 16, characterised in that B is analyzed in its XPS_1sAmong the spectral peaks, there was no characteristic peak between 185 to 200 eV.

20. A method of preparing a platinum carbon catalyst comprising:

(1) the steps of manufacturing the boron-doped conductive carbon black: contacting conductive carbon black with a boron source, and treating for 0.5-10 h at 300-800 ℃ in inert gas to obtain boron-doped conductive carbon black; and;

(2) the method comprises the following steps of: contacting the boron-doped conductive carbon black in the step (1) with a sulfur source, and treating for 0.5-10 h at 400-1500 ℃ in inert gas to obtain the sulfur-boron-doped conductive carbon black;

21. The method for preparing a platinum-carbon catalyst according to claim 20, wherein the step of supporting platinum comprises:

(a) dispersing the sulfur-boron doped conductive carbon black obtained in the step (2) and a platinum precursor in a water phase, and adjusting the pH to 8-12;

(b) adding a reducing agent for reduction;

22. The method for preparing a platinum-carbon catalyst according to claim 20, wherein in (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate, or sodium chloroplatinate; the concentration of the platinum precursor is 0.5-5 mol/L.

23. The method for preparing a platinum-carbon catalyst according to claim 20, wherein 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 the platinum is 2-100; the reduction temperature is 60-90 ℃; the reduction time is 4-15 h.

24. A platinum carbon catalyst, characterized in that it is obtainable by a process according to any one of claims 20 to 23.

25. A hydrogen fuel cell characterized in that the platinum-carbon catalyst of claim 16 or 24 is used in the anode and/or the cathode of the hydrogen fuel cell.