CN114430047B - Carbon material, platinum-carbon catalyst, and preparation method and application thereof - Google Patents

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

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CN114430047B
CN114430047B CN202011014105.4A CN202011014105A CN114430047B CN 114430047 B CN114430047 B CN 114430047B CN 202011014105 A CN202011014105 A CN 202011014105A CN 114430047 B CN114430047 B CN 114430047B
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platinum
sulfur
carbon
boron
carbon black
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CN114430047A (en
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顾贤睿
荣峻峰
王厚朋
张家康
赵红
彭茜
谢南宏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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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 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 chemical field, carbon materials are both important supports and commonly used catalysts. The bonding mode of the carbon element is rich, and the carbon material can be modified in various modes so as to obtain better performance.
Oxygen Reduction Reactions (ORR) are key reactions in the electrochemical field, such as in fuel cells and metal-air cells, and are a major factor affecting cell performance. The atomic doped carbon material can be used directly as a catalyst for the oxygen reduction reaction. When used as an oxygen reduction catalyst, it has been reported that carbon materials incorporate elements such as nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine, iodine, etc., wherein nitrogen has a radius close to that of carbon atoms and is easily incorporated into carbon lattices, and thus is the most commonly used doping element. Although there are many reports of carbon doped materials as fuel cell catalysts and some research results show better activity, there are large gaps compared to platinum carbon catalysts and far from commercial applications. On one hand, the combination mode of hetero atoms and carbon materials and the catalysis mechanism thereof are not fully known in the field; on the other hand, each heteroatom has multiple bonding modes with the carbon material, and when doping multiple heteroatoms, the situation is more complex, so how to control the bonding modes of the heteroatoms and the carbon material is a difficulty of doping atoms. In addition, such catalysts are generally not suitable for use in acidic environments, particularly Proton Exchange Membrane Fuel Cells (PEMFCs), which are important.
The most effective oxygen reduction catalysts to date have been platinum carbon catalysts in which the degree of dispersion of platinum metal has been undesirable and subject to agglomeration and deactivation, and on the other hand, dissolution and agglomeration of platinum at the cathode of a hydrogen fuel cell has resulted in significant reduction in platinum surface area over time, affecting fuel cell life. There is a great desire in the art to greatly increase the catalytic activity and stability thereof in an effort to promote its large-scale commercial use. Many factors and complications affect the activity and stability of the platinum carbon catalyst, and some documents believe that the activity and stability of the platinum carbon catalyst are related to the particle size, morphology, structure of the platinum, as well as the type, nature and platinum loading of the support. The prior art mainly improves the performance of the platinum-carbon catalyst by controlling the particle size, morphology, structure and specific surface area of the carrier and pore structure of the platinum; there are also reports of modification groups attached to the carbon surface to improve the performance of platinum carbon catalysts by modifying the carbon support.
The platinum loading of the practically applied hydrogen fuel cell platinum carbon catalyst is at least more than 20wt%, which is much more difficult to manufacture than chemical platinum carbon catalysts (platinum loading is less than 5 wt%). The increase of the platinum carrying amount is beneficial to manufacturing a thinner membrane electrode with better performance, but the increase of the platinum carrying amount greatly is easier to cause accumulation among platinum metal particles, so that the utilization rate of active sites is drastically reduced. How to more effectively utilize the catalytic active sites of platinum metal particles and increase the accessible three-phase catalytic reaction interface, thereby improving the utilization rate of platinum and the comprehensive performance of fuel cells and metal-air cells is a key problem to be solved in the art.
The defect sites of the carbon carrier are more favorable for improving the platinum carrying amount, but at the same time, the carbon corrosion is aggravated, and the stability of the catalyst is reduced. The improvement of the graphitization degree can effectively relieve carbon corrosion, but the high graphitization degree also makes the surface of the carbon carrier chemically inert, so that platinum is difficult to uniformly disperse on the carbon carrier, and the platinum carrying is particularly difficult when the platinum carrying amount is high.
The chemical reduction method is a common method for manufacturing platinum-carbon catalyst, and has the advantages of simple process, low utilization rate of platinum and low catalytic activity. The reason for this may be that the irregular pore structure of the carbon support causes uneven dispersion of the platinum nanoparticles.
The information disclosed in the foregoing background section is only for enhancement of understanding of the background 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 that is unique in nature. A second object of the present invention is to improve the overall performance of platinum carbon catalysts. A third object of the present invention is to provide a platinum carbon catalyst with a higher platinum-carrying amount in addition to the foregoing object. A fourth object of the present invention is to improve the aqueous phase reduction process for the manufacture of 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 the carbon material is a sulfur and boron doped conductive carbon black.
2. The carbon material according to 1, wherein S is analyzed by XPS 2P Among the spectral peaks, between 162eV and 166eV, there is only a characteristic peak of thiophene-type sulfur, and there is a characteristic peak at 168±1 eV.
3. The carbon material according to 2, wherein,s in XPS analysis thereof 2P In the spectrum peak, 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. The carbon material according to any one of the preceding claims, wherein the characteristic peaks of the thiophene-type sulfur are bimodal and are located at 163.6±0.5ev and 164.8±0.5ev, respectively.
5. The carbon material according to any one of the preceding claims, characterized in that XPS analysis B thereof 1s The spectrum peak has a characteristic peak between 190ev and 195ev, and has no other characteristic peak between 185ev and 200 ev.
6. The carbon material according to any one of the preceding claims, characterized in that XPS analysis B thereof 1s Two characteristic peaks exist between 191ev and 193ev, and other characteristic peaks exist between 185ev and 200 ev.
7. The carbon material according to any one of the above, characterized in that the resistivity thereof is <10Ω·m, preferably <5Ω·m, more preferably <3Ω·m.
8. The carbon material according to any one of the above, characterized in that in XPS analysis thereof, the mass fraction of sulfur is 0.1% to 5%, and the mass fraction of boron is 0.1% to 5%; preferably, the mass fraction of sulfur is 0.2-3%, and preferably, the mass fraction of boron is 0.2-3%; more preferably, the mass fraction of sulfur is 0.4% to 1.5%. More preferably, the mass fraction of boron is 0.4% -2%.
9. The carbon material according to any one of the above, characterized in that the specific surface area thereof is 10m 2 /g～2000m 2 /g, preferably 200m 2 /g～2000m 2 /g; the pore volume is 0.02mL/g to 6.0mL/g, preferably 0.2mL/g to 3.0mL/g.
10. The carbon material according to any one of the preceding claims, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
11. A method of making a carbon material, comprising:
(1) Doping boron: the conductive carbon black is contacted with a boron source, and is treated (preferably, is treated at constant temperature) for 0.5 to 10 hours at 300 to 800 ℃ in inert gas, so as to obtain boron doped conductive carbon black; and
(2) A step of doping sulfur: and (3) contacting the boron doped conductive carbon black in the step (1) with a sulfur source, and treating (preferably carrying out constant temperature treatment) in an inert gas at 400-1500 ℃ for 0.5-10 h to obtain the sulfur-boron doped conductive carbon black.
12. The preparation method is characterized in that the boron source is one or more of boric acid, borate, boron oxide, sodium borohydride and potassium borohydride.
13. The preparation method according to any one of the preceding claims, characterized in that the mass ratio of the conductive carbon black to the boron source is 100:1 to 5:1, a step of; preferably 60:1 to 15:1.
14. The preparation method according to any one of the above, wherein the sulfur source is elemental sulfur.
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, a step of; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.
16. the process according to any one of the above, wherein the temperature in (1) is 400℃to 600 ℃.
17. The process according to any one of the preceding processes, wherein the temperature in (2) is 1000℃to 1500℃and preferably 1100℃to 1300 ℃.
18. The process according to any one of the above processes, wherein the treatment time in (1) and/or (2) is 1 to 5 hours, preferably 2 to 4 hours.
19. The preparation method according to any one of the above, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
20. The process according to any one of the above, wherein the XPS analysis of the conductive carbon black in (1) is performed with an oxygen mass fraction of more than 4%, preferably 4% to 15%.
21. The process according to any one of the above processes, wherein the conductive carbon black of (1) has a resistivity of <10Ω·m, preferably <5Ω·m, more preferably <2Ω·m.
22. The process according to any one of the preceding processes, characterized in that the conductive carbon black of (1) has a specific surface area of 10m 2 /g～2000m 2 /g, preferably 200m 2 /g～2000m 2 /g; the pore volume is 0.02mL/g to 6mL/g, preferably 0.2mL/g to 3mL/g.
23. The production method according to any one of the foregoing production methods, characterized in that (1) the conductive carbon black is contacted with the boron source by immersing in an aqueous solution of the boron source and then drying.
24. A carbon material, characterized by being produced by any of the aforementioned methods.
25. The use of any of the foregoing carbon materials as electrode materials 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 sulfur and boron doped conductive carbon black.
27. The platinum carbon catalyst according to any one of the preceding claims, characterized by S in XPS analysis thereof 2P Among the spectral peaks, between 162eV and 166eV, there is only a characteristic peak of thiophene-type sulfur, and there is a characteristic peak at 168±1 eV.
28. The platinum carbon catalyst according to any one of the preceding claims, characterized by S in XPS analysis thereof 2P In the spectrum peak, the peak area ratio of the characteristic peak of thiophene-type sulfur to the characteristic peak at 168+/-1 eV is more than 10.
29. The platinum carbon catalyst according to any one of the preceding claims, characterized in that B is analyzed by XPS 1s There are no characteristic peaks between 185ev and 200ev in the spectrum peaks.
30. The platinum carbon catalyst according to any one of the preceding claims, characterized in that the platinum carbon catalyst has a resistivity of <10 Ω -m, preferably <2 Ω -m.
31. The platinum carbon catalyst according to any one of the preceding claims, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
32. A method for preparing a platinum carbon catalyst, comprising:
(1) The method comprises the following steps of: the conductive carbon black is contacted with a boron source, and is treated (preferably, is treated at constant temperature) for 0.5 to 10 hours at 300 to 800 ℃ in inert gas, so as 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 carrying out constant temperature treatment) in an inert gas at 400-1500 ℃ for 0.5-10 h to obtain the sulfur-boron doped conductive carbon black;
(3) And (3) taking the sulfur-boron doped conductive carbon black obtained in the step (2) as a carrier to load platinum.
33. The method for preparing a platinum carbon catalyst according to any one of the preceding methods, wherein in (1), the mass ratio of the conductive carbon black to the boron source is 100:1 to 5:1, a step of; preferably 60:1 to 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, a step of; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.
35. the process for producing a platinum carbon catalyst according to any one of the above (1), wherein the temperature is 400℃to 600 ℃.
36. The process for producing a platinum carbon catalyst according to any one of the preceding (2), wherein the temperature is 1000 to 1500 ℃, preferably 1100 to 1300 ℃.
37. The process for producing a platinum carbon catalyst according to any one of the above (1) and/or (2), wherein the treatment time 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 pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLASK 40B2.
39. The method for producing a platinum carbon catalyst according to any one of the above (1), wherein in the XPS analysis of the conductive carbon black, the mass fraction of oxygen is more than 4%, preferably 4% to 15%.
40. The method for producing a platinum carbon catalyst according to any one of the above (1), wherein in (1), the specific resistance of the conductive carbon black is <10Ω·m, preferably <5Ω·m, and more preferably <2Ω·m.
41. The process for producing a platinum carbon catalyst according to any one of the preceding steps, wherein (1) the specific surface area of the conductive carbon black is 10m 2 /g～2000m 2 /g, preferably 200m 2 /g～2000m 2 /g; the pore volume is 0.02mL/g to 6mL/g, preferably 0.2mL/g to 3mL/g.
42. The method for preparing the platinum-carbon catalyst according to any one of the preceding claims, wherein the step of supporting platinum comprises the steps of:
(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 to 10+/-0.5);
(b) Reducing agent is added for reduction;
(c) Separating out solid, and post-treating to obtain the platinum carbon catalyst.
43. The method for preparing the platinum carbon catalyst according to any one of the preceding methods, wherein in (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5 mol/L-5 mol/L.
44. The preparation method of any platinum-carbon catalyst 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 mol 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, characterized by being prepared by any one of the aforementioned platinum carbon catalyst preparation methods.
46. A hydrogen fuel cell characterized in that any one of the platinum carbon catalysts described above is used for an anode and/or a cathode of the hydrogen fuel cell.
The combination of the hetero atoms and the carbon materials is affected by different doping methods and raw materials and different operation steps and conditions of the doping process, so that the properties of the hetero atoms and the carbon materials are causedThe difference in quality changes the functions of the two. The situation is more complicated when doping multiple heteroatoms simultaneously. How to control the way heteroatoms are bound to carbon materials is a difficulty in the art when doping atoms. Controlling the manner in which heteroatoms are bonded to the carbon material makes it possible to produce carbon materials that are unique in nature, thereby making them suitable for a particular use. The invention discovers that a carbon material with unique properties can be obtained by doping boron and then sulfur into the conductive carbon black, and in XPS analysis of the carbon material, B of boron 1s The spectrum has double peaks between 190ev and 195ev, S of sulfur 2p In the spectrogram, there are two characteristic peaks of sulfur 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.
1. The invention can prepare a carbon material with unique property by doping boron and then sulfur into the conductive carbon black, and in XPS analysis of the carbon material, B of boron 1s The spectrum has two characteristic peaks of boron between 190ev and 195ev, S of sulfur 2p In the spectrogram, there are two kinds of characteristic peaks of sulfur between 160eV and 170eV, and the ratio of the characteristic peaks of thiophene sulfur to the characteristic peak at 168+/-1 eV can be regulated greatly, wherein the peak area ratio of the characteristic peak of thiophene sulfur to the characteristic peak at 168+/-1 eV can be more than 10.
2. The method for manufacturing the sulfur-boron doped carbon material is simple, and the proportion of doping elements is adjustable in a larger range.
3. The carbon material of the present invention is particularly suitable for use as a carrier for platinum carbon catalysts, especially high platinum loading platinum carbon catalysts. On the 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.
4. The platinum-carrying amount of the practically applied platinum-carbon catalyst of the hydrogen fuel cell is generally more than 20 weight percent, and the difficulty in manufacturing the high-platinum-carrying 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 low. However, the carbon material produced by the present invention is used as a carrier, and a high platinum-carrying catalyst having excellent mass specific activity, ECSA and stability thereof can be easily produced by a chemical reduction method using an aqueous phase.
5. Sulfur is generally believed to have an irreversible deleterious effect on platinum catalysts, however, the present inventors have discovered that by modifying carbon materials with sulfur doping, the catalytic activity of platinum carbon catalysts and their stability are significantly improved.
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 of the sulfur-boron doped conductive carbon black of example 1.
Fig. 2 is an XPS spectrum of sulfur of the sulfur-boron doped conductive carbon black of example 1.
Fig. 3 is an XPS spectrum of boron of the sulfur-boron doped conductive carbon black of example 2.
Fig. 4 is an XPS spectrum of sulfur of the sulfur-boron doped conductive carbon black of example 2.
Fig. 5 is an XPS spectrum of boron of the sulfur-boron doped conductive carbon black of example 3.
Fig. 6 is an XPS spectrum of sulfur of the sulfur-boron doped conductive carbon black of example 3.
Fig. 7 is an XPS spectrum of boron of the boron doped conductive carbon black of example 4.
Fig. 8 is an XPS spectrum of boron of the 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 of the platinum carbon catalyst of example 5.
Fig. 11 is a polarization curve (LSV) of the platinum carbon catalyst of example 5 before and after 5000 turns.
FIG. 12 is a CV curve before and after 5000 cycles of the Pt-C catalyst of example 5.
Fig. 13 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 6.
Fig. 14 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 7.
Fig. 15 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 8.
Fig. 16 is a polarization curve (LSV) of a commercial platinum carbon catalyst of comparative example 3 before and after 5000 turns.
Detailed Description
The invention is described in detail below in connection with the embodiments, but it should be noted that the scope of the invention is not limited by these embodiments and the principle explanation, but is defined by the claims.
In the present invention, any matters or matters not mentioned are directly applicable to those known in the art without modification except for those explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all considered as 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 such combination would obviously be unreasonable to one skilled in the art.
All of the features disclosed in this invention may be combined in any combination which is known or described in the present invention and should be interpreted as specifically disclosed and described in the present invention unless the combination is obviously unreasonable by those skilled in the art. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the embodiments but also the end points of each numerical range in the specification, and any combination of these numerical points should be considered as a disclosed or described range of the present invention.
Technical and scientific terms used in the present invention are defined to have their meanings, and are not defined to have their ordinary meanings in the art.
The "doping element" in the present invention means nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine.
In the present invention, reference to "carbon material" refers to carbon material that does not contain a doping element, except that it may be uniquely determined to be "carbon material containing a doping element" depending on the context or definition itself. The same is true of the underlying concept of carbon materials.
In the present invention, "carbon black" and "carbon black" are interchangeable terms of art.
The "inert gas" in the present invention refers to a gas that does not have any appreciable effect on the properties of the sulfur-boron doped carbon material in the preparation process of the present invention. The same is true of the underlying concept of carbon materials.
In the present invention, other references to "pore volume" refer to P/P unless otherwise clear from context or definition of the same 0 The single point adsorption total pore volume at maximum.
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 present invention does not contain other doping elements than sulfur and boron.
The carbon material according to the present invention is free of metal elements.
According to the carbon material of the present invention, S is analyzed in XPS thereof 2P Among the spectral peaks, between 162eV and 166eV, there is only a characteristic peak of thiophene-type sulfur, and there is a characteristic peak at 168±1 eV.
According to the carbon material of the present invention, the characteristic peaks of the thiophene-type sulfur are bimodal, and are located at 163.6.+ -. 0.5ev and 164.8.+ -. 0.5ev, respectively.
According to the carbon material of the present invention, in XPS analysis thereof, B is present between 190ev and 195ev 1s No other characteristic peak is present between 185ev and 200 ev.
B of the carbon Material according to the invention in its XPS analysis 1s Two characteristic peaks exist between 191ev and 193ev, and other characteristic peaks exist between 185ev and 200 ev.
The carbon material according to the present 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% -1.5%. The mass fraction of the boron is 0.4-2%.
The specific surface area and the pore volume of the carbon material according to the invention can vary within a wide range, such as the specific ratio thereof The surface area can be 10m 2 /g～2000m 2 The pore volume may be 0.02mL/g to 6.0mL/g. In one embodiment, the specific surface area is 200m 2 /g～2000m 2 Per gram, the pore volume is 0.2 mL/g-3.0 mL/g.
According to the carbon material of the present invention, the conductive carbon black may be a general conductive carbon black (Conductive Blacks), a super conductive carbon black (Super Conductive Blacks) or a special conductive carbon black (Extra Conductive Blacks), for example, the conductive carbon black may be one or more of Ketjen black series super conductive carbon black, cabot series conductive carbon black and series conductive carbon black produced by wining-chunking firm; preferably Ketjen Black EC-300J, ketjen Black EC-600JD, ketjen Black ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
According to the carbon material of the present invention, there is no limitation on the production method and source of the conductive carbon black. The conductive carbon black can be acetylene black, furnace black and the like.
According to the carbon material of the present invention, sulfur and boron are chemically bonded to conductive carbon black.
According to the carbon material of the present invention, S is analyzed in XPS thereof 2P Of the spectral peaks, the peak area ratio of the characteristic peak of thiophene-type 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) Doping boron: the conductive carbon black is contacted with a boron source, and is treated for 0.5h to 10h (preferably constant temperature treatment) at 300 ℃ to 800 ℃ in inert gas, so as to obtain boron doped conductive carbon black; and
(2) A step of doping sulfur: and (3) contacting the boron doped conductive carbon black in the step (1) with a sulfur source, and treating (preferably carrying out constant temperature treatment) in an inert gas at 400-1500 ℃ for 0.5-10 h to obtain the sulfur-boron doped conductive carbon black.
According to the preparation method of the carbon material, the temperature is required to be raised as in (1) and/or (2), and the temperature raising rate is respectively and independently 1-20 ℃/min, preferably 3-15 ℃/min, and more preferably 8-15 ℃/min.
According to the method for producing a carbon material of the present invention, there is no particular limitation on the boron source, and the existing boron sources for doping carbon materials may 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 preparation method of the carbon material, the mass ratio of the conductive carbon black to the boron source is 100, wherein the mass ratio of the boron source to the conductive carbon black is calculated according to the mass of boron contained in the boron source: 1 to 5:1, a step of; preferably 60:1 to 15:1.
According to the preparation method of the carbon material, the sulfur source is elemental sulfur.
According to the preparation method of the carbon material, the mass ratio of the conductive carbon black to the sulfur source is 20, wherein the mass ratio of the sulfur source to the sulfur contained in the conductive carbon black is calculated as the mass of sulfur: 1-2: 1, a step of; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.
according to the method for preparing the carbon material of the present invention, the temperature of the constant temperature treatment in (1) is 400 to 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 method for producing a carbon material of the present invention, in (1) and/or (2), the time of the constant temperature treatment is 1 to 5 hours, preferably 2 to 4 hours.
According to the preparation method of 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 wining-wound-decurser company; preferably EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2. I of the conductive carbon black D /I G The value is generally from 0.8 to 5, preferably from 1 to 4. In Raman spectrum, at 1320cm -1 The nearby peak is D peak, which is located at 1580cm -1 The nearby peak is G peak, I D Representing the intensity of the D peak, I G Representing the intensity of the G peak.
According to the preparation method of the carbon material, the inert gas is nitrogen or argon.
According to the method for producing a carbon material of the present invention, the resistivity of the conductive carbon black is <10Ω·m, preferably <5Ω·m, more preferably <2Ω·m.
According to the preparation method of the carbon material, in XPS analysis of the conductive carbon black, the mass fraction of oxygen is generally more than 4%, and preferably 4% -15%.
According to the preparation method of the carbon material, the specific surface area of the conductive carbon black can be changed in a wide range. Generally, the specific surface area is 10m 2 /g～2000m 2 /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, in (1), the conductive carbon black is contacted with the boron source by immersing in an aqueous solution of the boron source and then drying.
The use of any of the foregoing carbon materials as electrode materials in electrochemistry.
A platinum-carbon catalyst comprises a carbon carrier and platinum metal loaded on the carbon carrier, wherein the carbon carrier is sulfur and boron doped conductive carbon black.
The platinum carbon catalyst according to the present invention does not contain other doping elements except 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 conductive carbon black in the carbon support.
The platinum carbon catalyst according to the present invention has a specific molecular sieve in S of XPS analysis 2P Among the spectral peaks, between 162eV and 166eV, there is only a characteristic peak of thiophene-type sulfur, and there is a characteristic peak at 168±1 eV.
According to the platinum carbon catalyst of the present invention, the characteristic peaks of the thiophene sulfur are bimodal, and are located at 163.6.+ -. 0.5ev and 164.8.+ -. 0.5ev, respectively.
The platinum carbon catalyst according to the present invention has a specific molecular sieve in S of XPS analysis 2P In the spectrum peak, the peak area ratio of the characteristic peak of thiophene-type sulfur to the characteristic peak at 168+/-1 eV is more than 10.
The platinum carbon catalyst according to the invention, in its XPS analysis B 1s There are no characteristic peaks between 185ev and 200ev in the spectrum peaks.
According to the platinum carbon catalyst of the present invention, a boron signal (B) was detected in a TG-MS (thermogravimetric-mass spectrometry) test 2 O 3 And B) a method for producing a polymer.
The platinum carbon catalyst according to the present invention has a mass fraction of platinum of 0.1 to 80%, preferably 20 to 70%, 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 80m 2 /g～1500m 2 /g, preferably 100m 2 /g～200m 2 /g。
The platinum carbon catalyst according to 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 manufactured by wining dezaocys company; preferably Ketjen Black EC-300J, ketjen Black EC-600JD, ketjen Black ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
The platinum carbon catalyst according to the present invention is not limited in the production method and source of the conductive carbon black. The conductive carbon black can be acetylene black, furnace black and the like.
The invention provides a preparation method of a platinum-carbon catalyst, which comprises the following steps:
(1) The method comprises the following steps of: the conductive carbon black is contacted with a boron source, and is treated (preferably, is treated at constant temperature) for 0.5 to 10 hours at 300 to 800 ℃ in inert gas, so as 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 carrying out constant temperature treatment) in an inert gas at 400-1500 ℃ for 0.5-10 h to obtain the sulfur-boron doped conductive carbon black;
(3) And (3) taking the sulfur-boron doped conductive carbon black obtained in the step (2) as a carrier to load platinum.
According to the preparation method of the platinum carbon catalyst, the temperature is required to be raised as in (1) and/or (2), and the temperature raising rate is 1 ℃/min-20 ℃/min, preferably 3 ℃/min-15 ℃/min, and more preferably 8 ℃/min-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 (1), the mass ratio of the conductive carbon black to the boron source is 100:1 to 5:1, a step of; preferably 60:1 to 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 (2), the mass ratio of the conductive carbon black to the sulfur source is 20: 1-2: 1, a step of; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.
according to the preparation method of the platinum carbon catalyst, in the (1), the temperature is 400-600 ℃.
According to the method for preparing a platinum carbon catalyst of the present invention, (2) the temperature is 1000 to 1500 ℃, preferably 1100 to 1300 ℃.
According to the method for preparing a platinum carbon catalyst of the present invention, the treatment time in (1) and/or (2) is 1 to 5 hours, preferably 2 to 4 hours.
According to the preparation method of the platinum carbon catalyst, the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLASK 40B2.
According to the preparation method of the platinum carbon catalyst, in (1), the mass fraction of oxygen in XPS analysis of the conductive carbon black is more than 4%, preferably 4% -15%.
According to the method for producing a platinum carbon catalyst of the present invention, in (1), the resistivity of the conductive carbon black is <10Ω·m, preferably <5Ω·m, more preferably <2Ω·m.
According to the method for preparing a platinum carbon catalyst of the present invention, (1) wherein the specific surface area of the conductive carbon black is 10m 2 /g～2000m 2 /g, preferably 200m 2 /g～2000m 2 /g; the pore volume is 0.02mL/g to 6mL/g, preferably 0.2mL/g to 3mL/g.
According to the method for producing a platinum carbon catalyst of the present invention, (1) the conductive carbon black is contacted with the boron source by immersing in an aqueous solution of the boron source and then drying.
According to the preparation method of the platinum carbon catalyst of the present invention, (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, the platinum loading step comprises the following steps:
(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 to 10+/-0.5);
(b) Reducing agent is added for reduction;
(c) Separating out solid, and post-treating to obtain the platinum carbon catalyst.
According to the preparation method of the platinum carbon catalyst, in the (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5 mol/L-5 mol/L.
According to the preparation method of the platinum carbon catalyst, in the (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 mol 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 prepared by any one of the methods for preparing a platinum carbon catalyst described above.
A hydrogen fuel cell uses any one of the platinum carbon catalysts described above in the anode and/or cathode of the hydrogen fuel cell.
The platinum-carbon catalyst according to the present invention has a mass specific activity decrease rate of <10% after 5000 cycles and an ECSA decrease rate of <10% after 5000 cycles when used in an oxygen reduction reaction.
The platinum carbon catalyst of the present invention, when used in an oxygen reduction reaction, in some embodiments, ECSA>42m 2 g -1 Pt, e.g. at 42m 2 g -1 -Pt～74m 2 g -1 -Pt。
The platinum carbon catalysts of the invention, when used in oxygen reduction reactions, in some embodiments, have a mass specific activity>0.14A mg -1 Pt, e.g. 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, has a half-wave potential of >0.88V, such as 0.88V to 0.91V, in some embodiments.
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 present invention, but are not intended to limit the invention in any way.
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the present invention are analytically pure and commercially available.
The invention detects the elements on the surface of the material by an X-ray photoelectron spectroscopy (XPS). The X-ray photoelectron spectroscopy analyzer used was an ESCALab220i-XL type radiation electron spectroscopy manufactured by VG scientific company and equipped with Avantage V5.926 software, and the X-ray photoelectron spectroscopy analysis test conditions were: the excitation source is monochromized A1K alpha X-ray with power of 330W and basic vacuum of 3X 10 during analysis and test -9 mbar. In addition, the electron binding energy was corrected by the C1s peak (284.3 eV) of elemental carbon, and the post-peak splitting treatment software was XPSPEAK. Characteristic peaks of thiophene sulfur and boron in the spectrogram are characteristic peaks after peak separation.
Instrument and method for elemental analysis, conditions: elemental analyzer (Vario EL Cube), reaction temperature 1150 ℃, 5mg of sample, reduction temperature 850 ℃, carrier gas helium flow rate 200mL/min, oxygen flow rate 30mL/min, and oxygen introduction time 70s.
Apparatus, method, conditions for testing mass fraction of platinum in platinum carbon catalyst: 30mg of the prepared Pt/C catalyst is taken, 30mL of aqua regia is added, the mixture is condensed and refluxed for 12 hours at 120 ℃, cooled to room temperature, and the supernatant is taken for dilution, and then the content of Pt in the mixture is tested by ICP-AES.
The model of the high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100 (HRTEM) (Japanese electronics Co., ltd.) and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200kV. The particle size of the nano particles 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 of the invention adopts a LabRAM HR UV-NIR laser confocal Raman spectrometer manufactured by HORIBA company of Japan, and the laser wavelength is 532nm.
Electrochemical performance testing, instrument models Solartron analytical EnergyLab and Princeton Applied Research (Model 636A), methods and test conditions: polarization curve LSV of catalyst O at 1600rpm 2 Saturated 0.1M HClO 4 CV Curve 0.1M HClO under Ar atmosphere 4 The electrochemically active area ECSA was calculated therefrom. Stability test at O 2 Saturated 0.1M HClO 4 After 5000 cycles of scanning in the range of 0.6V to 0.95V, LSV and ECSA were tested as described above. The catalyst is prepared into slurry which is uniformly dispersed during the test, and the slurry is coated on a glassy carbon electrode with the diameter of 5mm, wherein the platinum content of the catalyst on the electrode is 3-4 mug.
Resistivity test four-probe resistivity tester, instrument model KDY-1, method and test conditions: the applied pressure was 3.9.+ -. 0.03MPa and the current was 500.+ -. 0.1mA.
TG-MS test: testing by using a German relaxation-resistant STA449F5-QMS403D type thermogravimetric-mass spectrometer, wherein an ion source is an EI source, a four-stage rod mass spectrometer is in an MID mode, a transmission pipeline is a 3-meter long capillary, and the temperature is 260 ℃; the temperature is 55-1000 ℃ and the heating rate is 10 ℃/min.
VXC72 (Vulcan XC72, manufactured by Kabot Co., USA) is available from Suzhou wing Long energy technologies Company limited. The test by the instrument method shows that: specific surface area 258m 2 Per gram, pore volume 0.388mL/g, oxygen mass fraction 8.72%, I D /I G The resistivity was 1.02. Omega. M, which was 1.22. Omega. M.
Ketjenback ECP600JD (Ketjen Black, manufactured by Lion corporation, japan) was purchased from Suzhou wing Long energy technologies Co. The test by the instrument method shows that: specific surface area 1362m 2 Per gram, pore volume 2.29mL/g, oxygen mass fraction 6.9%, I D /I G 1.25, and the resistivity was 1.31. Omega. M.
Commercial platinum carbon catalyst (trade name HISPEC4000, manufactured by Johnson Matthey Co.) was purchased from Alfa Aesar. The test results show that: the mass fraction of platinum was 40.2%.
Example 1
This example is intended to illustrate the sulfur-boron doped conductive carbon black of the present invention.
1g of Vulcan XC72 is immersed in 15mL of 4.0wt% sodium borate aqueous solution for 16h; drying in an oven at 100deg.C; 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 3 hours, and naturally cooling to obtain the boron doped conductive carbon black.
Uniformly mixing the boron doped conductive carbon black and 0.167g of elemental sulfur, putting the mixture into a tube furnace, heating the tube furnace to 1100 ℃ at the speed of 8 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the sulfur-boron doped conductive carbon black, wherein the number of the sulfur-boron doped conductive carbon black is a carbon carrier A.
Sample characterization and testing
The sulfur-boron doped conductive carbon black of the embodiment has the mass fraction of sulfur of 0.93% in XPS analysis; the mass fraction of boron analyzed by XPS is 0.95%; specific surface area of 245m 2 /g; the resistivity was 1.28Ω·m.
Fig. 1 is an XPS spectrum of boron of the sulfur-boron doped conductive carbon black of example 1.
Fig. 2 is an XPS spectrum of sulfur of the sulfur-boron doped conductive carbon black of example 1.
In FIG. 2, the peak area ratio of the characteristic peak of thiophene-type sulfur to the characteristic peak at 168.+ -. 1eV was 11.16.
Example 2
This example is intended to illustrate the sulfur-boron doped conductive carbon black of the present invention.
1g of Vulcan XC72 is immersed in 15mL of 4.8wt% sodium borate aqueous solution for 24h; drying in an oven at 100deg.C; then placing the mixture into a tube furnace, heating the tube furnace to 400 ℃ at the speed of 8 ℃/min, carrying out constant temperature treatment for 3 hours, and naturally cooling to obtain the boron doped conductive carbon black.
Uniformly mixing the boron doped conductive carbon black and 0.2g of elemental sulfur, putting the mixture into a tube furnace, heating the tube furnace to 400 ℃ at the speed of 8 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the sulfur-boron doped conductive carbon black, wherein the number of the sulfur-boron doped conductive carbon black is carbon carrier B.
Sample characterization and testing
Sulfur-boron doped conductive carbon black in the embodiment has a mass fraction of sulfur of 1.09% in XPS analysis; the mass fraction of boron analyzed by XPS is 1.56%; specific surface area of 259m 2 /g; the resistivity was 1.31. Omega. M.
Fig. 3 is an XPS spectrum of boron of the sulfur-boron doped conductive carbon black of example 2.
Fig. 4 is an XPS spectrum of sulfur of the sulfur-boron doped conductive carbon black of example 2.
Example 3
This example is intended to illustrate the sulfur-boron doped conductive carbon black of the present invention.
10mL of absolute ethanol was added to 1g Ketjenblack ECP600JD, followed by impregnation with 25mL of 3.8wt% sodium borate aqueous solution for 24 hours; drying in an oven at 100deg.C; 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 3 hours, and naturally cooling to obtain the boron doped conductive carbon black.
Uniformly mixing the boron doped conductive carbon black and 0.25g of elemental sulfur, putting the mixture into a tube furnace, heating the tube furnace to 1300 ℃ at the speed of 10 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the sulfur-boron doped conductive carbon black, wherein the number of the carbon black is carbon carrier C.
Sample characterization and testing
The sulfur-boron doped conductive carbon black has the mass fraction of sulfur analyzed by XPS of 0.96%; the mass fraction of boron analyzed by XPS is 1.43%; specific surface area of 1311m 2 /g; the resistivity was 1.36. Omega. M.
Fig. 5 is an XPS spectrum of boron of the sulfur-boron doped conductive carbon black of example 3.
Fig. 6 is an XPS spectrum of sulfur of the sulfur-boron doped conductive carbon black of example 3.
In FIG. 6, the peak area ratio of the characteristic peak of thiophene-type sulfur to the characteristic peak at 168.+ -. 1eV was 11.45.
Example 4
This example is intended to illustrate the sulfur-boron doped conductive carbon black of the present invention.
10mL of absolute ethanol was added to 1g Ketjenblack ECP600JD, followed by soaking in 25mL of 1wt% sodium borate aqueous solution for 16h; drying in an oven at 100deg.C; 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 3 hours, and naturally cooling to obtain the boron doped conductive carbon black.
Uniformly mixing the boron doped conductive carbon black and 0.15g of elemental sulfur, putting the mixture into a tube furnace, heating the tube furnace to 700 ℃ at the speed of 10 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the sulfur-boron doped conductive carbon black, wherein the number of the sulfur-boron doped conductive carbon black is a carbon carrier D.
Sample characterization and testing
The sulfur-boron doped conductive carbon black has the mass fraction of sulfur analyzed by XPS of 0.72%; the mass fraction of boron analyzed by XPS is 0.58%; specific surface area 1344m 2 /g; the resistivity was 1.35. Omega. M.
Fig. 7 is an XPS spectrum of the boron doped conductive carbon black of example 4.
Fig. 8 is an XPS spectrum of boron of the 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.
Example 5
This example is intended to illustrate the platinum carbon catalyst of the present invention.
Dispersing the carbon carrier A in deionized water according to the proportion of 250mL of water used per gram of carbon carrier, adding 3.4mmol of chloroplatinic acid per gram of carbon carrier, performing ultrasonic dispersion to form 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 under stirring to perform reduction reaction, wherein the molar ratio of the formic acid to the chloroplatinic acid is 50:1, and continuously maintaining the reaction for 10 hours; filtering the reacted mixture, washing the mixture with deionized water until the pH value of the filtrate is neutral, filtering the mixture, and then drying the mixture at 100 ℃ to obtain the platinum-carbon catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 40.0%.
In XPS analysis of the platinum carbon catalyst, there was no B between 185ev and 200ev 1s Is a characteristic peak of (2).
Detection of B in TG-MS test 2 O 3 And B.
Fig. 10 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 5.
In FIG. 10, the peak area ratio of the characteristic peak of thiophene-type sulfur to the characteristic peak at 168.+ -. 1eV was 10.8.
Fig. 11 is a polarization (LSV) curve before and after 5000 turns of the platinum carbon catalyst of example 5.
FIG. 12 is a CV curve before and after 5000 cycles of the Pt-C catalyst of example 5.
The results of the platinum carbon catalyst performance test are shown in table 1.
Example 6
This example is intended to illustrate the platinum carbon catalyst of the present invention.
A platinum carbon catalyst was prepared according to the method of example 5, except that: 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%.
In XPS analysis of the platinum carbon catalyst, there was no B between 185ev and 200ev 1s Is a characteristic peak of (2).
Detection of B in TG-MS test 2 O 3 And B.
Fig. 13 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 6.
In FIG. 13, the peak area ratio of the characteristic peak of thiophene-type sulfur to the characteristic peak at 168.+ -. 1eV was 5.8.
The results of the platinum carbon catalyst performance test are shown in table 1.
Example 7
This example is intended to illustrate the platinum carbon catalyst of the present invention.
Dispersing the carbon carrier C in deionized water according to the proportion of 250mL of water used per gram of carbon carrier, adding 12mmol of chloroplatinic acid per gram of carbon carrier, performing ultrasonic dispersion to form 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 under stirring to perform 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%.
In XPS analysis of the platinum carbon catalyst, there was no B between 185ev and 200ev 1s Is a characteristic peak of (2).
Detection of B in TG-MS test 2 O 3 And B.
Fig. 14 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 7.
In FIG. 14, the peak area ratio of the characteristic peak of thiophene-type sulfur to the characteristic peak at 168.+ -. 1eV was 11.4.
The results of the platinum carbon catalyst performance test are shown in table 1.
Example 8
This example is intended to illustrate the platinum carbon catalyst of the present invention.
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 were added.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 20.6%.
In XPS analysis of the platinum carbon catalyst, there was no B between 185ev and 200ev 1s Is a characteristic peak of (2).
Detection of B in TG-MS test 2 O 3 And B.
Fig. 15 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 8.
In FIG. 15, the peak area ratio of the characteristic peak of thiophene-type sulfur to the characteristic peak at 168.+ -. 1eV was 3.6.
The results of the platinum carbon catalyst performance test are shown in table 1.
Comparative example 1
Dispersing Vulcan XC72 in deionized water according to the proportion of 250mL of water used for each gram of carbon carrier, adding 3.4mmol of chloroplatinic acid for each gram of carbon carrier, performing ultrasonic dispersion to form 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 under stirring to perform reduction reaction, wherein the molar ratio of the formic acid to the chloroplatinic acid is 50:1, and continuously maintaining the reaction for 10 hours; filtering the reacted mixture, washing the mixture with deionized water until the pH value of the filtrate is neutral, filtering the mixture, and then drying the mixture at 100 ℃ to obtain the platinum-carbon catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 40.1%.
The results of the platinum carbon catalyst performance test are shown in table 1.
Comparative example 2
Dispersing Ketjenback ECP600JD by using 200mL of water and 50mL of ethanol per gram of carbon carrier, adding 12mmol of chloroplatinic acid per 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 under stirring to perform 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%.
The results of the platinum carbon catalyst performance test are shown in table 1.
Comparative example 3
The platinum carbon catalyst is a commercially available catalyst, under the trade designation HISPEC4000.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 40.2%.
The results of the platinum carbon catalyst performance test are shown in table 1.
Fig. 16 is a polarization curve before and after 5000 turns for the commercial platinum carbon catalyst of comparative example 3.
TABLE 1
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Claims (8)

1. A platinum carbon catalyst for an anode and/or a cathode of a hydrogen fuel cell, comprising a carbon support and a platinum metal supported thereon, wherein the carbon support is a sulfur-and boron-doped conductive carbon black; the carbon carrier is prepared by the following method: (1) The conductive carbon black is contacted with a boron source in a manner of drying after being immersed in a boron source aqueous solution, and is treated for 0.5 to 10 hours at the temperature of 300 to 800 ℃ in inert gas, so as to obtain boron doped conductive carbon black; (2) Contacting the boron doped conductive carbon black in the step (1) with a sulfur source, and treating the carbon black in an inert gas at 1000-1500 ℃ for 0.5-10 h to obtain the carbon carrier; the boron source is one or more of boric acid and borate, 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 to 5:1, a step of; the sulfur source is elemental sulfur, 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, a step of; XPS analysis of the carbon Carrier B 1s Two characteristic peaks exist between 191ev and 193ev, and other characteristic peaks exist between 185ev and 200 ev; XPS analysis S of the carbon Carrier 2P In the spectrum peak, between 162eV and 166eV, only the characteristic peak of thiophene sulfur exists, and the characteristic peak exists at 168+/-1 eV; s of XPS analysis of the catalyst 2P In the spectrum peak, the peak area ratio of the characteristic peak of the thiophene sulfur to the characteristic peak at 168+/-1 eV is more than 10; the catalyst does not contain other doping elements except sulfur and boron, wherein the other doping elements are nitrogen, phosphorus, fluorine, chlorine, bromine and iodine; based on the mass of the catalyst, the mass fraction of platinum is 20-70%.
2. The platinum carbon catalyst according to claim 1, wherein the carbon carrier has a mass fraction of sulfur of 0.1 to 5% and a mass fraction of boron of 0.1 to 5% in XPS analysis.
3. The platinum carbon catalyst according to claim 1, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
4. The method for preparing a platinum carbon catalyst according to claim 1, comprising: the step of producing sulfur-and boron-doped conductive carbon black as claimed in claim 1 and the step of supporting platinum with the sulfur-and boron-doped conductive carbon black obtained in (2) thereof as a carbon support.
5. The method for preparing a platinum carbon catalyst according to claim 4, wherein said step of supporting platinum comprises:
(a) Dispersing the carbon carrier and the platinum precursor in a water phase, and regulating the pH to 8-12;
(b) Reducing agent is added for reduction;
(c) Separating out solid, and post-treating to obtain the platinum carbon catalyst.
6. The method of preparing a platinum carbon catalyst according to claim 5, wherein in (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate, or sodium chloroplatinate; the concentration of the platinum precursor is 0.5 mol/L-5 mol/L.
7. The method for preparing a platinum carbon catalyst according to claim 5, 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 mol ratio of the reducing agent to the platinum is 2-100; the reduction temperature is 60-90 ℃; the reduction time is 4-15 h.
8. A hydrogen fuel cell characterized in that the platinum carbon catalyst according to any one of claims 1 to 3 is used in an anode and/or a cathode of the hydrogen fuel cell.
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