CN114497596B - 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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CN114497596B
CN114497596B CN202011151998.7A CN202011151998A CN114497596B CN 114497596 B CN114497596 B CN 114497596B CN 202011151998 A CN202011151998 A CN 202011151998A CN 114497596 B CN114497596 B CN 114497596B
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platinum
carbon
sulfur
phosphorus
boron
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CN114497596A (en
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赵红
荣峻峰
张云阁
顾贤睿
王厚朋
彭茜
张家康
谢南宏
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

The invention relates to a carbon material, a platinum-carbon catalyst, and a preparation method and application thereof. The carbon material is sulfur-phosphorus-boron doped conductive carbon black, and the platinum-carbon catalyst taking the carbon material as a carrier has good mass specific activity and ECSA and has excellent carbon corrosion resistance.

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. In particular, the invention relates to a sulfur-phosphorus-boron doped carbon material, a platinum-carbon catalyst using the same as a carrier, and preparation methods and applications of the sulfur-phosphorus-boron doped carbon material and the platinum-carbon catalyst.
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 more suitable 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 in the literature that elements such as nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine, iodine and the like are incorporated into a carbon material. Although there are many reports of carbon doped materials directly as fuel cell catalysts and some research results show better activity, there are large differences compared to platinum carbon catalysts and far from commercial applications. On the one hand, the knowledge of the combination mode of the hetero atoms and the carbon materials and the interaction between the hetero atoms and the catalysis mechanism is insufficient in the field; on the other hand, each heteroatom has multiple bonding modes with the carbon material, and multiple roles exist among the heteroatoms, so that the situation is very complex when doping multiple heteroatoms, and therefore, how to control the bonding modes of the heteroatoms and the carbon material and the interaction among the heteroatoms 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.
Up to now, the most effective oxygen reduction catalysts are platinum carbon catalysts, but for large scale commercial applications platinum carbon catalysts have been deficient. On the one hand, platinum resources are scarce and expensive, and the cost thereof is about 40% of the total cost of the fuel cell. On the other hand, the dispersion degree of platinum metal in the currently used commercial platinum-carbon catalyst is not ideal and is easy to agglomerate and deactivate, and the dissolution and agglomeration of platinum at the cathode of the hydrogen fuel cell lead to obvious reduction of the surface area of the platinum with time, thus influencing the service life of the fuel cell. The art is urgent to greatly improve the utilization rate of platinum metal, and improve the catalytic activity and stability of the platinum metal, so as to promote the large-scale commercial application of the platinum metal. 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 improving the performance of platinum carbon catalysts by modifying the carbon support.
The carbon carrier can improve the specific surface area of the catalyst, reduce the agglomeration of metal particles and improve the metal utilization rate. The increase of the platinum carrying capacity of the carbon carrier is beneficial to manufacturing thinner membrane electrodes with better performance, but the increase of the platinum carrying capacity greatly is easier to cause accumulation among platinum metal particles, so that the utilization rate of active sites is greatly 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. In addition, 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 lower than 5 wt%).
The problem of deactivation of platinum carbon catalysts in proton exchange membrane fuel cells caused by carbon corrosion has raised a great deal of attention in the art. It is reported in the literature that, theoretically, when the potential is greater than 0.2V, corrosion of the carbon support occurs. In practice, the problem of carbon corrosion is only evident when the potential is greater than 1.2V. The cathode potential can be higher than 0.9V when the cell is operated in an open circuit, and the local interface potential of the cathode can even reach 1.6V during the starting/stopping process of the cell, which greatly accelerates the carbon corrosion reaction, resulting in the rapid reduction of the catalytic performance of the platinum carbon catalyst. In addition, platinum accelerates the carbon corrosion rate, and the larger the platinum carrying amount, the faster the carbon corrosion. The conductive carbon black has low price and is a platinum-carbon catalyst carrier used in industry, but the conductive carbon black has poor corrosion resistance. It is generally believed in the art that increasing the number of defective sites on the carbon support exacerbates carbon corrosion and reducing the number of defective sites inhibits carbon corrosion, but also renders the surface of the carbon support chemically inert and makes it difficult to uniformly disperse platinum on the carbon support.
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-doped material having unique properties and a simple process for preparing the same. A second object of the present invention is to improve the carbon corrosion resistance of platinum carbon catalysts based on the carbon doped material. A third object of the present invention is to provide a platinum carbon catalyst having more excellent overall properties and a simple process for producing the same, in addition to the foregoing objects. A fourth object of the present invention is to provide a platinum carbon catalyst of higher platinum carrying amount in which platinum is uniformly dispersed, in addition to the foregoing object.
In order to achieve the above object, the present invention provides the following technical solutions.
1. A carbon material is sulfur phosphorus boron doped conductive carbon black.
2. The carbon material according to any one of the foregoing, characterized by S in XPS analysis thereof 2P The characteristic peak area of the thiophene-type sulfur in the spectrum peak is 70% or more, preferably 80% or more, more preferably 90% or more of the total characteristic peak area of 160ev to 170 ev.
3. The carbon material according to any one of the foregoing, characterized by P analyzed by XPS 2P Of the spectral peaks, there was a characteristic peak at 135.9.+ -. 0.5 ev.
4. The carbon material according to any one of the foregoing, characterized by P analyzed by XPS 2P There are two characteristic peaks between 134.5ev and 136.5ev in the spectrum peak.
5. Pressing the buttonA carbon material according to any one of the above, characterized in that B is analyzed by XPS 1s Of the spectral peaks, there is a characteristic peak at 190.8.+ -. 0.5 ev.
6. The carbon material according to any one of the foregoing, characterized in that B is analyzed by XPS 1s Four characteristic peaks exist between 190ev and 195ev in the spectrum peaks.
7. The carbon material according to any one of the above, characterized in that in XPS analysis, the mass fraction of sulfur is 0.01% to 4%, the mass fraction of phosphorus is 0.01% to 4%, and the mass fraction of boron is 0.01% to 4%; preferably, the mass fraction of sulfur is 0.1-2.5%, the mass fraction of phosphorus is 0.1-3%, and the mass fraction of boron is 0.1-3.5%.
8. 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.
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: the conductive carbon black is contacted with a sulfur source, a phosphorus source and a boron source, and is treated (preferably, is treated at a constant temperature) for 0.5 to 10 hours at the temperature of 400 to 900 ℃ in inert gas, so that the carbon material is obtained.
12. The method for producing a carbon material according to any one of the above, wherein the sulfur source is elemental sulfur.
13. The method for preparing a carbon material according to any one of the preceding claims, wherein 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, a step of; more preferably 8:1 to 4:1.
14. the method for preparing the carbon material according to any one of the preceding claims, wherein the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.
15. The method for preparing the carbon material according to any one of the preceding claims, wherein the mass ratio of the conductive carbon black to the phosphorus source is 10000, based on the mass of phosphorus contained in the carbon material: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
16. the method for preparing the carbon material according to any one of the above, wherein the boron source is one or more of boric acid and borate.
17. The method for preparing a carbon material according to any one of the preceding claims, wherein the mass ratio of the conductive carbon black to the boron source is 10000, based on the mass of boron contained in the boron source: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
18. the method for producing a carbon material according to any one of the above, wherein the treatment time is 1 to 5 hours, preferably 2 to 4 hours.
19. The method for producing a carbon material according to any one of the above, wherein the temperature is 500 to 900 ℃.
20. The method for preparing 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 HIBLASK 40B2.
21. The method for producing a carbon material according to any one of the above, wherein the mass fraction of oxygen in XPS analysis of the conductive carbon black is more than 4%, preferably 4% to 15%.
22. The method for producing a carbon material according to any one of the above, characterized in that the conductive carbon black has a resistivity of <10Ω·m, preferably <5Ω·m, more preferably <2Ω·m.
23. The method for producing a carbon material according to any one of the above, characterized in that 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.
24. A carbon material produced by the method for producing a carbon material of any one of the foregoing.
25. The use of any of the foregoing carbon materials as electrode materials in electrochemistry.
26. A platinum-carbon catalyst comprises a carbon carrier and platinum metal loaded on the carbon carrier, and is characterized in that the carbon carrier is sulfur-phosphorus-boron doped conductive carbon black.
27. S in XPS analysis of the platinum carbon catalyst according to any one of the above 2P The characteristic peak area of the thiophene-type sulfur in the spectrum peak is 70% or more, preferably 80% or more, more preferably 90% or more of the total characteristic peak area of 160ev to 170 ev.
28. The platinum carbon catalyst according to any one of the above, wherein the XPS analysis thereof shows no B in the range of 185 to 200ev 1s And no P between 125ev and 145ev 2p Is a characteristic peak of (2).
29. The platinum carbon catalyst according to any one of the preceding claims, characterized in that the carbon support is any one of the preceding doped carbon materials.
30. 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.
31. 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.
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 sulfur source, a phosphorus source and a boron source, and is treated (preferably treated at constant temperature) for 0.5 to 10 hours at 400 to 900 ℃ in inert gas to obtain a sulfur-phosphorus-boron doped carbon material;
(2) And (3) taking the sulfur-phosphorus-boron doped carbon material obtained in the step (1) as a carrier to load platinum.
33. The method for producing a platinum carbon catalyst according to any one of the above (1), wherein the sulfur source is elemental sulfur.
34. The method for producing 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 sulfur source is 20: 1-2: 1, a step of; preferably 10:1 to 4:1, a step of; preferably 8:1 to 4:1.
35. the method for preparing a platinum carbon catalyst according to any one of the above (1), wherein the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.
36. 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 phosphorus source is 10000, based on the mass of phosphorus contained in the phosphorus source: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
37. The method for preparing a platinum carbon catalyst according to any one of the above (1), wherein the boron source is one or more of boric acid and a borate.
38. 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 10000, based on the mass of boron contained in the boron source: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
39. the process for producing a platinum carbon catalyst according to any one of the above (1), wherein the temperature is 500℃to 900 ℃.
40. The process for producing a platinum carbon catalyst according to any one of the above (1), wherein the treatment time is 1 to 5 hours, preferably 2 to 4 hours.
41. The method for preparing a platinum carbon catalyst according to any one of the preceding methods, wherein in (1), the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
42. 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%.
43. 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.
44. 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.
45. The method for preparing a platinum carbon catalyst according to any one of the preceding claims, wherein the step (2) of supporting platinum comprises:
(a) Dispersing the sulfur-phosphorus-boron doped carbon material obtained in the step (1) and a platinum precursor in a water phase, and adjusting the pH value to 8-12 (preferably adjusting the pH value to 10+/-0.5);
(b) Reducing agent is added for reduction;
(c) Separating out solid, and post-treating to obtain the platinum carbon catalyst.
46. 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.
47. 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.
48. A platinum carbon catalyst, characterized by being prepared by any one of the aforementioned platinum carbon catalyst preparation methods.
49. 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 hetero atoms and the carbon materials have various combination modes, the hetero atoms have various interactions, the preparation method and the raw materials are different, and the operation steps and the conditions of the doping process are different, so that the combination modes of the hetero atoms and the carbon materials and the interactions among the hetero atoms can be influenced, the property differences of the hetero atoms and the carbon materials are caused, and the functions of the hetero atoms and the carbon materials are changed. In the art, how to control the binding mode of heteroatoms to carbon materials and the interactions between heteroatoms are difficulties in doping atoms. Controlling the manner in which heteroatoms are bound to the carbon material and the interactions between the heteroatoms may result in a carbon material that is uniquely characterized, thereby rendering it suitable for a particular application. The research of the invention finds that the carbon corrosion resistance of the platinum-carbon catalyst is more favorable to be improved when the carbon material is doped more. After the carbon material is subjected to sulfur, phosphorus and boron triple doping by a simple method, the carbon material with unique properties can be obtained, and an XPS analysis map of the carbon material shows that sulfur doped on the surface of the carbon material mainly exists in a thiophene sulfur form, the phosphorus doped on the surface has a characteristic peak at 135.9+/-0.5 ev, and the boron doped on the surface has a characteristic peak at 190.8+/-0.5 ev. The inventor researches and discovers that the characteristics are beneficial to improving the 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. Compared with the existing doped carbon material, the surface doped sulfur mainly exists in the form of thiophene sulfur, the surface doped phosphorus has a characteristic peak at 135.9+/-0.5 ev, and the surface doped boron has a characteristic peak at 190.8+/-0.5 ev. The present invention has found that these features are beneficial for improving the catalytic performance of platinum carbon catalysts.
2. The carbon-doped material is suitable for being used as a carrier of a platinum-carbon catalyst, and the platinum-carbon catalyst manufactured by the carbon-doped material still has excellent comprehensive catalytic performance and carbon corrosion resistance when the platinum loading reaches 70 wt%.
3. 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, when the platinum-carbon catalyst is produced by using the carbon material produced by the present invention as a carrier and adopting a chemical reduction method using an aqueous phase, platinum is uniformly distributed on the carbon carrier, and a high-supported platinum catalyst excellent in specific activity and stability can be easily produced.
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 sulfur of the sulfur phosphorus boron doped carbon material of example 1.
Fig. 2 is an XPS spectrum of phosphorus of the sulfur phosphorus boron doped carbon material of example 1.
Fig. 3 is an XPS spectrum of boron of the sulfur phosphorus boron doped carbon material of example 1.
Fig. 4 is an XPS spectrum of sulfur of the sulfur phosphorus boron doped carbon material of example 2.
Fig. 5 is an XPS spectrum of phosphorus of the sulfur phosphorus boron doped carbon material of example 2.
Fig. 6 is an XPS spectrum of boron of the sulfur phosphorus boron doped carbon material of example 2.
Fig. 7 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 3.
Fig. 8 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 5.
Fig. 9 is a TEM image of the platinum carbon catalyst of example 5.
Fig. 10 is an XPS spectrum of phosphorus of the phosphorus-doped carbon material of comparative example 4.
Fig. 11 is an XPS spectrum of boron of the boron doped carbon material of comparative example 5.
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.
The numerical ranges defined in the present invention include the endpoints of the numerical ranges.
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 cause any appreciable influence on the properties of the boron-parathion-doped carbon material in the preparation method 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 sulfur-phosphorus-boron doped conductive carbon black.
According to the carbon material of the present invention, sulfur, phosphorus and boron are chemically bonded to conductive carbon black.
The carbon material according to the present invention does not contain other doping elements than sulfur, phosphorus 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 The characteristic peak area of the thiophene-type sulfur in the spectrum peak is 70% or more, preferably 80% or more, more preferably 90% or more of the total characteristic peak area of 160ev to 170 ev.
According to the carbon material of the present invention, P in XPS analysis thereof 2P Of the spectral peaks, there was a characteristic peak at 135.9.+ -. 0.5 ev.
According to the carbon material of the present invention, P in XPS analysis thereof 2P There are two characteristic peaks between 134.5ev and 136.5ev in the spectrum peak.
B of the carbon Material according to the invention in its XPS analysis 1s Of the spectral peaks, there is a characteristic peak at 190.8.+ -. 0.5ev.
B of the carbon Material according to the invention in its XPS analysis 1s Four characteristic peaks exist between 190ev and 195ev in the spectrum peaks.
According to the carbon material of the present invention, the characteristic peak of the thiophene-type sulfur is located between 162ev and 166 ev.
According to the carbon material of the present invention, the characteristic peaks of the thiophene-type sulfur are bimodal, and are located at 163.5.+ -. 0.5ev and 164.7.+ -. 0.5ev, respectively.
In XPS analysis, the carbon material of the invention has the mass fraction of sulfur of 0.01-4%, the mass fraction of phosphorus of 0.01-4% and the mass fraction of boron of 0.01-4%; preferably, the mass fraction of sulfur is 0.1-2.5%, the mass fraction of phosphorus is 0.1-3%, and the mass fraction of boron is 0.1-3.5%.
According to the carbon material of the present invention, in some embodiments, the mass fraction of sulfur in the XPS analysis is 0.1% to 1.2%, the mass fraction of phosphorus is 0.1% to 2%, and the mass fraction of boron is 0.1% to 2.5%.
The carbon material according to the present invention has a resistivity of <10Ω·m, preferably <5Ω·m, more preferably <3Ω·m.
The carbon material according to the present invention is not particularly limited in its oxygen content. Generally, the mass fraction of oxygen analyzed by XPS is 2% -15%.
The carbon material according to the invention has a specific surface area andthe pore volume can vary over a wide range, for example, the specific 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.
The invention also provides a preparation method of the carbon material, which comprises the following steps: the conductive carbon black is contacted with a sulfur source, a phosphorus source and a boron source, and is treated (preferably, is treated at a constant temperature) for 0.5 to 10 hours at the temperature of 400 to 900 ℃ in inert gas, so that the carbon material is obtained.
According to the method for producing a 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.
According to the preparation method of the carbon material, the preparation method and the source of the conductive carbon black are not limited. The conductive carbon black can be acetylene black, furnace black and the like.
According to the preparation method of the carbon material, the conductive carbon black has I 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 method for producing a carbon material of the present invention, the conductive carbon black is contacted with a sulfur source, a phosphorus source and a boron source in a mixed manner. The order and manner in which the conductive carbon black is mixed with the sulfur source, the phosphorus source, and the boron source is not limited by the present invention, and those skilled in the art can select an appropriate order and manner based on the teachings of the present invention and/or the prior knowledge. The invention provides a preferred mixing mode: the conductive carbon black is first mixed with a phosphorus source and a boron source solution (preferably an aqueous solution), impregnated and dried, and then mixed with a sulfur source (e.g., elemental sulfur).
According to the preparation method of the carbon material, if heating is needed, the heating rate can be 1-20 ℃ per minute, preferably 3-15 ℃ per minute, and more preferably 3-7 ℃ per minute.
According to the method for producing a carbon material of the present invention, the temperature is preferably 500 to 900 ℃.
According to the method for producing a carbon material of the present invention, the treatment time is preferably 1 to 5 hours, more preferably 2 to 4 hours.
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, a step of; more preferably 8:1 to 4:1.
according to the preparation method of the carbon material, the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphates, polyphosphates, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.
According to the preparation method of the carbon material, the mass ratio of the conductive carbon black to the phosphorus source is 10000, based on the mass of phosphorus contained in the carbon material: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
According to the preparation method of the carbon material, the boron source is one or more of boric acid and borate.
According to the preparation method of the carbon material, the mass ratio of the conductive carbon black to the boron source is 10000, based on the mass of boron contained in the boron source: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
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 conductive carbon black has a resistivity of <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%, preferably 4% -15%.
According to the preparation method of the carbon material of the present invention, the specific surface area of the conductive carbon black may vary within 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 preparation method of the carbon material, in one embodiment, the conductive carbon black which is immersed with a phosphorus source and a boron source in an aqueous solution is dried, then is uniformly mixed with sulfur powder, is placed in a tube furnace, is heated to 400 ℃ -900 ℃ (preferably 500 ℃ -900 ℃) in inert gas at a speed of 3 ℃/min-7 ℃/min, and is subjected to constant temperature treatment for 0.5 h-10 h, so that the carbon material is obtained.
The inert gas is nitrogen or argon.
According to the method for preparing a carbon material of the present invention, a metal-containing catalyst is not used in the process of doping conductive carbon black.
The invention also provides the carbon material prepared by any one of the methods.
The carbon material of the present invention of any one of the foregoing is used in electrochemistry as an electrode material.
The invention provides a platinum-carbon catalyst, which comprises a carbon carrier and platinum metal loaded on the carbon carrier, wherein the carbon carrier is sulfur-phosphorus-boron doped conductive carbon black.
The platinum carbon catalyst according to the present invention does not contain other doping elements except sulfur, phosphorus and boron.
The platinum carbon catalyst according to the present invention does not contain other metal elements than platinum.
The platinum carbon catalyst according to the present invention, wherein sulfur, phosphorus and boron are chemically bonded to conductive carbon black.
The platinum carbon catalyst according to the present invention has a specific molecular sieve in S of XPS analysis 2P The characteristic peak area of the thiophene-type sulfur in the spectrum peak is 70% or more, preferably 80% or more, more preferably 90% or more of the total characteristic peak area of 160ev to 170 ev.
The platinum carbon catalyst according to the present invention has no B in its XPS analysis between 185ev and 200ev 1s And no P between 125ev and 145ev 2p Is a characteristic peak of (2).
According to the platinum carbon catalyst of the invention, P was detected in the TG-MS test 2 O 3 And P 2 O 5 Is a signal of (a).
According to the platinum carbon catalyst of the present invention, boron signals (B and B) were detected in TG-MS (thermogravimetric-mass spectrometry) test 2 O 3 )。
According to the platinum carbon catalyst of the present invention, the characteristic peak of the thiophene-type sulfur is located between 162ev and 166 ev.
According to the platinum carbon catalyst of the present invention, the characteristic peaks of the thiophene sulfur are bimodal, and are located at 163.5.+ -. 0.5ev and 164.9.+ -. 0.5ev, respectively.
The platinum carbon catalyst according to the present invention has a carbon carrier which is the carbon material of the present invention as described above.
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 produced by wining schrader corporation; 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 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.
The platinum carbon catalyst according to the invention has a specific surface area of 80m 2 /g～1500m 2 /g, preferably 100m 2 /g～200m 2 /g。
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 sulfur source, a phosphorus source and a boron source, and is treated (preferably treated at constant temperature) for 0.5 to 10 hours at 400 to 900 ℃ in inert gas to obtain a sulfur-phosphorus-boron doped carbon material;
(2) And (3) taking the sulfur-phosphorus-boron doped carbon material obtained in the step (1) as a carrier to load platinum.
According to the preparation method of the platinum carbon catalyst of the present invention, in (1), the "contact mode of the conductive carbon black with the sulfur source, the phosphorus source and the boron source" is the same as the corresponding parts in the foregoing, and the present invention will not be repeated.
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 (1), 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, a step of; preferably 8:1 to 4:1.
according to the preparation method of the platinum carbon catalyst, the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.
According to the preparation method of the platinum carbon catalyst, in the (1), the mass ratio of the conductive carbon black to the phosphorus source is 10000 based on the mass of phosphorus contained in the phosphorus source: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
according to the preparation method of the platinum carbon catalyst, the boron source is one or more of boric acid and borate.
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 10000, based on the mass of boron contained in the boron source: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
according to the preparation method of the platinum carbon catalyst, if heating is needed in the step (1), the heating rate can be 1-20 ℃ per minute, preferably 3-15 ℃ per minute, and more preferably 3-7 ℃ per minute.
According to the method for producing a platinum carbon catalyst of the present invention, in (1), the temperature is preferably 500 to 900 ℃.
According to the method for preparing a platinum carbon catalyst of the present invention, in (1), the treatment time is 1 to 5 hours, preferably 2 to 4 hours.
According to the preparation method of the platinum carbon catalyst, in the (1), the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
According to the preparation method of the platinum carbon catalyst, the sulfur-phosphorus-boron doped carbon material prepared in the step (1) can be easily dispersed in an aqueous phase. For some carbon materials, such as ketjen black, it is difficult to disperse directly in the aqueous phase.
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 preparation method of the platinum carbon catalyst, TEM image of the prepared platinum carbon catalyst shows that platinum metal particles are uniformly distributed on a carbon carrier.
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 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, phosphorus 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 1.0V to 1.5V, 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 method: 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 cabot corporation, usa) is available from energy technologies limited in wing Long, su. 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% by XPS analysis, 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% by XPS analysis, I D /I G 1.25, resistanceThe ratio was 1.31. Omega. M.
Black Pearls 2000 (manufactured by Kabot corporation, U.S.A.) was purchased from energy technologies Inc. of Suzhou wing Long. The test by the instrument method shows that: specific surface area 1479m 2 Oxygen mass fraction of XPS analysis of 9.13% per gram, I D /I G The resistivity was 1.14 and 1.19Ω·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 used to illustrate the preparation of the sulfur phosphorus boron doped carbon material of the present invention.
1g of Vulcan XC72 is immersed in 15mL of aqueous solution with sodium borate concentration of 1.0wt% and phosphoric acid concentration of 0.3wt% for 20h; drying in an oven at 100 ℃; then evenly mixing the mixture with 0.167g of elemental sulfur, putting the mixture into a tube furnace, heating the tube furnace to 900 ℃ at the speed of 8 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the sulfur-phosphorus-boron doped carbon material, wherein the number of the carbon carrier A.
Sample characterization and testing
The mass fraction of sulfur analyzed by XPS is 0.6%; the mass fraction of phosphorus analyzed by XPS is 0.7%; the mass fraction of boron analyzed by XPS is 2.2%; specific surface area of 233m 2 /g; the resistivity was 1.28Ω·m.
Fig. 1 is an XPS spectrum of sulfur of the sulfur phosphorus boron doped carbon material of example 1.
In FIG. 1, the ratio of the characteristic peak area of thiophene-type sulfur to the characteristic peak area at 168.+ -. 1ev was 16.1.
Fig. 2 is an XPS spectrum of phosphorus of the sulfur phosphorus boron doped carbon material of example 1.
Fig. 3 is an XPS spectrum of boron of the sulfur phosphorus boron doped carbon material of example 1.
Example 2
This example is used to illustrate the preparation of the sulfur phosphorus boron doped carbon material of the present invention.
10mL of absolute ethanol was added to 1g Ketjenblack ECP600JD, followed by soaking in 25mL of an aqueous solution having a boric acid concentration of 0.3wt% and a sodium dihydrogen phosphate concentration of 1.2wt% for 24 hours; drying in an oven at 100 ℃; then evenly mixing with 0.25g of elemental sulfur, putting into a tube furnace, heating the tube furnace to 500 ℃ at a speed of 5 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the sulfur-phosphorus-boron doped carbon material, wherein the number of the carbon carrier B is the number of the carbon carrier B.
Sample characterization and testing
The mass fraction of sulfur analyzed by XPS is 0.7%; the mass fraction of phosphorus analyzed by XPS is 1.8%; the mass fraction of boron analyzed by XPS is 0.6%; specific surface area 1351m 2 /g; the resistivity was 1.36. Omega. M.
Fig. 4 is an XPS spectrum of sulfur of the sulfur phosphorus boron doped carbon material of example 2.
In FIG. 4, the ratio of the characteristic peak area of thiophene-type sulfur to the characteristic peak area at 168.+ -. 1ev is 12.4.
Fig. 5 is an XPS spectrum of phosphorus of the sulfur phosphorus boron doped carbon material of example 2.
Fig. 6 is an XPS spectrum of boron of the sulfur phosphorus boron doped carbon material of example 2.
Example 3
This example illustrates the preparation of 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 40.2%.
Fig. 7 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 3.
In FIG. 7, the ratio of the characteristic peak area of thiophene-type sulfur to the characteristic peak area at 168.+ -. 1ev is 10.4.
XPS analysis of Pt-C catalyst is between 125ev and 145evWithout P 2p Is a characteristic peak of (2).
P, P was detected in TG-MS test of platinum carbon catalyst 2 O 3 And P 2 O 5 Is a signal of (a).
In XPS analysis of the platinum carbon catalyst, there was no B between 185ev and 200ev 1s Is a characteristic peak of (2).
B and B were detected in TG-MS test of platinum carbon catalyst 2 O 3 Is a signal of (a).
The results of the performance test of the platinum carbon catalyst are shown in table 1.
Example 4
This example illustrates the preparation of a platinum carbon catalyst.
A platinum carbon catalyst was prepared according to the method of example 3, except that: 1.3mmol of chloroplatinic acid per gram of carbon support are added.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 20.4%.
P, P was detected in TG-MS test of platinum carbon catalyst 2 O 3 And P 2 O 5 Is a signal of (a).
B and B were detected in TG-MS test of platinum carbon catalyst 2 O 3 Is a signal of (a).
The results of the performance test of the platinum carbon catalyst are shown in table 1.
Example 5
This example illustrates the preparation of the platinum carbon catalyst of the present invention.
Dispersing a carbon carrier B in a solution according to the proportion of 600mL of water and 600mL of ethylene glycol used for each gram of carbon carrier, adding 12mmol of chloroplatinic acid into each gram of carbon carrier, adding sodium acetate into the solution according to the molar ratio of sodium acetate to chloroplatinic acid being 2:1, 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 sodium borohydride under stirring to perform reduction reaction, wherein the molar ratio of the sodium borohydride to chloroplatinic acid is 5:1, 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 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 69.9%.
Fig. 8 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 5.
In FIG. 8, the ratio of the characteristic peak area of thiophene-type sulfur to the characteristic peak area at 168.+ -. 1ev was 10.4.
Fig. 9 is a TEM image of the platinum carbon catalyst of example 5.
In XPS analysis of the Pt-C catalyst, there was no P between 125ev and 145ev 2p Is a characteristic peak of (2).
P, P was detected in TG-MS test of platinum carbon catalyst 2 O 3 And P 2 O 5 Is a signal of (a).
In XPS analysis of the platinum carbon catalyst, there was no B between 185ev and 200ev 1s Is a characteristic peak of (2).
B and B were detected in TG-MS test of platinum carbon catalyst 2 O 3 Is a signal of (a).
The results of the performance test of the platinum carbon catalyst 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 in a solution according to the proportion of 600mL of water and 600mL of ethylene glycol used for each gram of carbon carrier, adding 12mmol of chloroplatinic acid into each gram of carbon carrier, adding sodium acetate into the solution according to the molar ratio of sodium acetate to chloroplatinic acid being 2:1, 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 sodium borohydride under stirring to perform reduction reaction, wherein the molar ratio of the sodium borohydride to chloroplatinic acid is 5:1, 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 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 69.9%.
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.
Comparative example 4
This comparative example is used to illustrate the preparation of phosphorus doped carbon materials.
1g Vulcan XC72 is immersed in 15mL of 0.8wt% phosphoric acid aqueous solution for 16h; drying in an oven at 100 ℃; then placing 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 2 hours; naturally cooling to obtain the phosphorus-doped carbon material.
Sample characterization and testing
Fig. 10 is an XPS spectrum of phosphorus of the phosphorus-doped carbon material of comparative example 4.
Comparative example 5
This comparative example is used to illustrate the preparation of boron doped carbon materials.
1g of Vulcan XC72 is immersed in 15mL of 4.5wt% sodium borate aqueous solution for 16h; drying in an oven at 100 ℃; then placing the mixture into a tube furnace, heating the tube furnace to 400 ℃ at a speed of 10 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the boron doped carbon material.
Sample characterization and testing
Fig. 11 is an XPS spectrum of boron of the boron doped carbon material of comparative example 5.
TABLE 1
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Claims (9)

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, characterized in that the carbon support is a sulfur phosphorus boron doped conductive carbon black, the carbon support being prepared by a process comprising: drying the conductive carbon black which is immersed with a phosphorus source and a boron source in an aqueous solution, mixing the dried conductive carbon black with a sulfur source, placing the mixture in a tube furnace, heating the tube furnace to 400-900 ℃ in an inert gas at a speed of 3-7 ℃/min, and then performing constant temperature treatment for 0.5-10 h; 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; the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite, the mass of the phosphorus source is counted by the mass of phosphorus contained in the phosphorus source, and the mass ratio of the conductive carbon black to the phosphorus source is 10000:1 to 10:1, a step of; 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 10000:1 to 10:1, a step of; XPS analysis of S on the carbon support 2P In the spectrum peak, the characteristic peak area of the thiophene sulfur accounts for more than 90% of the total characteristic peak area between 160ev and 170 ev; XPS analyzed P on the carbon support 2P Of the spectral peaks, there is a characteristic peak at 135.9.+ -. 0.5 ev; XPS analysis of B on the carbon Carrier 1s Of the spectral peaks, there is a characteristic peak at 190.8.+ -. 0.5 ev; the carbon carrier does not contain other doping elements except sulfur, phosphorus and boron, and the doping elements are nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine; based on the mass of the catalyst, the mass fraction of platinum is 40% -70%.
2. 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.
3. The platinum carbon catalyst according to claim 1, wherein in XPS analysis of the carbon support, the mass fraction of sulfur is 0.01 to 5%, the mass fraction of phosphorus is 0.01 to 4%, and the mass fraction of boron is 0.01 to 4%.
4. The platinum carbon catalyst according to claim 1, wherein the catalyst has no B in XPS analysis of 185ev to 200ev 1s And no P between 125ev and 145ev 2p Is a characteristic peak of (2).
5. The method for preparing a platinum carbon catalyst according to claim 1, comprising:
(1) The step of manufacturing a carbon support as described in claim 1;
(2) And (3) supporting platinum on the carbon carrier obtained in (1).
6. The method for producing a platinum carbon catalyst according to claim 5, wherein said platinum supporting step (2) comprises:
(a) Dispersing the carbon carrier and the platinum precursor obtained in the step (1) 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.
7. The method of preparing a platinum carbon catalyst according to claim 6, 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.
8. The method for preparing a platinum carbon catalyst according to claim 6, 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.
9. A hydrogen fuel cell, wherein the platinum carbon catalyst according to any one of claims 1 to 4 is used in an anode and/or a cathode of the hydrogen fuel cell.
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