CN114426268B - Sulfur-phosphorus doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof - Google Patents

Sulfur-phosphorus doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof Download PDF

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CN114426268B
CN114426268B CN202011012749.XA CN202011012749A CN114426268B CN 114426268 B CN114426268 B CN 114426268B CN 202011012749 A CN202011012749 A CN 202011012749A CN 114426268 B CN114426268 B CN 114426268B
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sulfur
platinum
phosphorus
carbon material
phosphorus doped
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CN114426268A (en
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赵红
王厚朋
荣峻峰
谢南宏
张家康
彭茜
顾贤睿
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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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Priority to PCT/CN2021/114870 priority patent/WO2022042667A1/en
Priority to US18/043,307 priority patent/US20230364587A1/en
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    • 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
    • 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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • 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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • 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
    • 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

Abstract

The invention relates to a sulfur-phosphorus doped carbon material, a platinum-carbon catalyst and a preparation method and application thereof, wherein in XPS analysis of the sulfur-phosphorus doped carbon material, only one characteristic peak of sulfur exists between 160ev and 170 ev; there is only one characteristic peak of phosphorus between 125ev and 145 ev. The platinum carbon catalyst prepared from the sulfur-phosphorus doped carbon material has high mass specific activity, ECSA and stability.

Description

Sulfur-phosphorus doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof
Technical Field
The invention relates to a sulfur-phosphorus doped carbon material, a platinum-carbon catalyst, and a preparation method and application thereof.
Background
The carbon material has wide sources and rich properties, and is widely used in various technical fields. 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 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. Phosphorus and nitrogen belong to the same main group, but in the case of carbon-doped materials, phosphorus has a characteristic that is essentially different from nitrogen due to the difference in atomic radius and electronegativity. At present, in literature reports on phosphorus-doped carbon materials, the catalytic performance of the materials is generally low, and the catalytic mechanism is not uniformly and clearly known. 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 the situation when doping multiple heteroatoms 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 doped carbon material in which the doping element and carbon are combined in a more uniform manner. A second object of the present invention is to provide a platinum carbon catalyst with better overall performance. 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 sulfur-phosphorus doped carbon material is characterized by S analyzed by XPS 2P The spectrum peak is 160 ev-170 ev, and only the characteristic peak of thiophene-type sulfur is included.
2. The sulfur-phosphorus doped carbon material as described in 1, wherein P is analyzed by XPS 2p There is a characteristic peak between 125ev and 145ev in the spectrum peak.
3. The sulfur-phosphorus doped carbon material according to claim 2, wherein the characteristic peaks of the thiophene-type sulfur are bimodal and are located at 163.5.+ -. 0.5ev and 164.7.+ -. 0.5ev, respectively.
4. The sulfur-phosphorus doped carbon material according to any of the preceding claims, characterized in that its resistivity is <10Ω·m, preferably <5Ω·m, more preferably <3Ω·m.
5. The sulfur-phosphorus doped carbon material according to any one of the above, characterized in that in the XPS analysis thereof, the mass fraction of sulfur is 0.1% to 5%, and the mass fraction of phosphorus is 0.01% to 5%; preferably, the mass fraction of sulfur is 0.2-3%, and preferably, the mass fraction of phosphorus is 0.02-3%; more preferably, the sulfur mass fraction is 0.3% to 2%. More preferably, the mass fraction of phosphorus is 0.05% -2%.
6. The sulfur-phosphorus doped 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.
7. The sulfur-phosphorus doped carbon material according to any one of the preceding claims, characterized in that the sulfur-phosphorus doped carbon material is sulfur-phosphorus doped graphene, sulfur-phosphorus doped carbon nanotubes or sulfur-phosphorus doped conductive carbon black.
8. The sulfur-phosphorus doped carbon material according to any of the preceding claims, wherein said conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
9. A preparation method of a sulfur-phosphorus doped carbon material comprises the following steps:
(1) A step of doping phosphorus: contacting the carbon material with a phosphorus source, and treating the carbon material in inert gas at 300-800 ℃ for 0.5-10 h to obtain a phosphorus doped carbon material; and
(2) A step of doping sulfur: and (3) contacting the phosphorus-doped carbon material in the step (1) with a sulfur source, and treating the carbon material in an inert gas at 400-1500 ℃ for 0.5-10 h to obtain the sulfur-phosphorus-doped carbon material.
10. The method for preparing the sulfur-phosphorus doped carbon material according to any one of the above, wherein the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.
11. The preparation method of the sulfur-phosphorus doped carbon material according to any one of the above, wherein the mass ratio of the carbon material to the phosphorus source is 10000, based on the mass of phosphorus contained in the carbon material: 1-20: 1, a step of; preferably 2500: 1-30: 1.
12. the preparation method of the sulfur-phosphorus doped carbon material is characterized in that the sulfur source is elemental sulfur.
13. The preparation method of the sulfur-phosphorus doped carbon material according to any one of the above, wherein the mass ratio of the carbon material 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.
14. the method for producing a sulfur-phosphorus doped carbon material according to any one of the above, wherein the temperature in (1) is 400℃to 600 ℃.
15. The method for producing a sulfur-phosphorus doped carbon material according to any one of the above, characterized in that the temperature in (2) is 1000 to 1500 ℃, preferably 1100 to 1300 ℃.
16. The method for producing a sulfur-phosphorus doped carbon material 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.
17. The preparation method of the sulfur-phosphorus doped carbon material is characterized in that the carbon material is graphene, carbon nano tube or conductive carbon black.
18. The method for preparing the sulfur-phosphorus doped carbon material according to any one of the above, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VVC 72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
19. The method for producing a sulfur-phosphorus doped carbon material according to any one of the above, wherein the carbon material in (1) has an oxygen mass fraction of more than 4%, preferably 4% to 15% in XPS analysis.
20. The method for producing a sulfur-phosphorus doped carbon material according to any one of the above, wherein the carbon material has a resistivity of <10Ω·m, preferably <5Ω·m, more preferably <2Ω·m in (1).
21. The method for producing a sulfur-phosphorus doped carbon material according to any one of the foregoing, characterized in that the specific surface area of the carbon material in (1) 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.
22. The method for preparing the sulfur-phosphorus doped carbon material according to any one of the above, wherein in (1), the contact mode of the carbon material and the phosphorus source is as follows: the carbon material is dried after being immersed in an aqueous solution of a phosphorus source.
23. The method for preparing a sulfur-phosphorus doped carbon material according to any one of the above, wherein in (2), the contact mode between the phosphorus doped carbon material and the sulfur source is as follows: the phosphorus doped carbon material is mixed with elemental sulfur.
24. A sulfur-phosphorus doped carbon material, characterized by being prepared by any of the methods described above.
25. The use of any of the foregoing sulfur-phosphorus doped 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 a sulfur-phosphorus doped carbon material; s analyzed by XPS of the platinum carbon catalyst 2P The spectrum peak is 160 ev-170 ev, and only the characteristic peak of thiophene-type sulfur is included.
27. The platinum carbon catalyst according to any one of the preceding claims, characterized in that P is analyzed by XPS 2p There are no characteristic peaks between 125ev and 145ev in the spectrum peaks.
28. 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.
29. The platinum carbon catalyst according to any one of the preceding claims, wherein the sulfur-phosphorus doped carbon material is sulfur-phosphorus doped graphene, sulfur-phosphorus doped carbon nanotubes or sulfur-phosphorus doped conductive carbon black.
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. A method for preparing a platinum carbon catalyst, comprising:
(1) The steps of manufacturing the phosphorus-doped carbon material: contacting the carbon material with a phosphorus source, and treating the carbon material in inert gas at 300-800 ℃ for 0.5-10 h to obtain a phosphorus doped carbon material;
(2) The method comprises the steps of: contacting the phosphorus-doped carbon material in the step (1) with a sulfur source, and treating the carbon material in an inert gas at 400-1500 ℃ for 0.5-10 h to obtain the sulfur-phosphorus-doped carbon material;
(3) And (3) taking the sulfur-phosphorus doped carbon material obtained in the step (2) as a carrier to load platinum.
32. The method for preparing a platinum carbon catalyst according to any one of the preceding methods, wherein in (1), the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.
33. The method for preparing a platinum carbon catalyst according to any one of the preceding claims, wherein in (1), the mass ratio of the carbon material to the phosphorus source is 10000, based on the mass of phosphorus contained in the phosphorus source: 1-20: 1, a step of; preferably 2500: 1-30: 1.
34. the method for producing a platinum carbon catalyst according to any one of the above (2), wherein the sulfur source is elemental sulfur.
35. The method for producing a platinum carbon catalyst according to any one of the preceding claims, wherein in (2), the mass ratio of the carbon material to the sulfur source is 20, based on the mass of sulfur contained therein: 1-2: 1, a step of; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.
36. The process for producing a platinum carbon catalyst according to any one of the above (1), wherein the temperature is 400℃to 600 ℃.
37. 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 ℃.
38. 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.
39. The preparation method of any one of the platinum carbon catalysts is characterized in that the carbon material is graphene, conductive carbon black or carbon nanotubes.
40. 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.
41. The method for producing a platinum carbon catalyst according to any one of the above (1), wherein in the XPS analysis of the carbon material, the mass fraction of oxygen is more than 4%, preferably 4% to 15%.
42. The method for producing a platinum carbon catalyst according to any one of the above (1), wherein in (1), the specific resistance of the carbon material is <10Ω·m, preferably <5Ω·m, and more preferably <2Ω·m.
43. The process for producing a platinum carbon catalyst according to any one of the preceding (1), wherein in (1), the specific surface area of the carbon material 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.
44. 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-phosphorus doped carbon material 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.
45. 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.
46. 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.
47. A platinum carbon catalyst, characterized by being prepared by any one of the aforementioned platinum carbon catalyst preparation methods.
48. 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 doping 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 are 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. 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. When a platinum catalyst is produced using a carbon material as a carrier, not only the functions of dispersing the carbon material, fixing platinum particles, and the like, but also the functions of electron transfer, reactant molecule diffusion, and the like of the carbon material are considered. The invention discovers that the carbon material with unique property can be obtained in a wide sulfur doping temperature range by doping phosphorus and then sulfur into the carbon material, and in XPS analysis of the carbon material, S of sulfur 2p In the spectrogram, only one characteristic peak of sulfur exists between 160ev and 170 ev. Further research also finds that the sulfur-phosphorus doped carbon material of the inventionThe comprehensive performance of the platinum-carbon catalyst of the hydrogen fuel cell can be improved.
Compared with the prior art, the invention can realize the following beneficial technical effects.
1. The preparation method is simple, and the carbon material with uniform combination mode of sulfur and carbon can be obtained in a wide temperature range, and S of sulfur is analyzed in XPS of the carbon material 2p In the spectra, only the characteristic peak of thiophenic sulfur exists.
2. 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 carbon material is particularly suitable for being used as a platinum carbon catalyst, can improve the comprehensive performance of the platinum carbon catalyst, and particularly can manufacture the platinum carbon catalyst with excellent performance and high platinum loading.
3. 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.
4. 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 phosphorus of the sulfur-phosphorus doped carbon material of example 1.
Fig. 2 is an XPS spectrum of sulfur of the sulfur-phosphorus doped carbon material of example 1.
Fig. 3 is an XPS spectrum of oxygen of the sulfur-phosphorus doped carbon material of example 1.
Fig. 4 is an XPS spectrum of phosphorus of the sulfur-phosphorus doped carbon material of example 2.
Fig. 5 is an XPS spectrum of sulfur of the sulfur-phosphorus doped carbon material of example 2.
Fig. 6 is an XPS spectrum of phosphorus of the sulfur-phosphorus doped carbon material of example 3.
Fig. 7 is an XPS spectrum of sulfur of the sulfur-phosphorus doped carbon material of example 3.
Fig. 8 is an XPS spectrum of phosphorus of the sulfur-phosphorus doped carbon material of example 4.
Fig. 9 is an XPS spectrum of sulfur of the sulfur-phosphorus doped carbon material of example 4.
Fig. 10 is an XPS spectrum of oxygen of the sulfur-phosphorus doped carbon material of example 4.
Fig. 11 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 5.
Fig. 12 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 6.
Fig. 13 is an XPS spectrum of sulfur of the sulfur-doped carbon material of comparative example 4.
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 cause any appreciable effect on the properties of the 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 sulfur-phosphorus doped carbon material, S analyzed in XPS 2P The spectrum peak is 160 ev-170 ev, and only the characteristic peak of thiophene-type sulfur is included.
The sulfur-phosphorus doped carbon material according to the present invention does not contain other doping elements except sulfur and phosphorus.
The sulfur-phosphorus doped carbon material according to the present invention is free of metal elements.
According to the sulfur-phosphorus doped carbon material, characteristic peaks of the thiophene sulfur are bimodal and are respectively located at 163.5+/-0.5 ev and 164.7+/-0.5 ev.
According to the sulfur-phosphorus doped carbon material of the invention, P is analyzed in XPS 2p There is a characteristic peak between 125ev and 145ev in the spectrum peak, which is located at 133.5ev + -0.5 ev.
The sulphur-phosphorus doped carbon material according to the invention has a resistivity of <10.0 Ω -m, preferably <5.0 Ω -m, more preferably <3.0 Ω -m.
According to the sulfur-phosphorus doped carbon material, in XPS analysis, the mass fraction of sulfur is 0.1-5%, and the mass fraction of phosphorus is 0.01-5%; preferably, the mass fraction of sulfur is 0.2-3%, and the mass fraction of phosphorus is 0.02-3%; more preferably, the sulfur mass fraction is 0.3% -2%. The mass fraction of the phosphorus is 0.05-2%.
The specific surface area and the pore volume of the sulfur-phosphorus doped carbon material according to the invention can be changed within 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 sulfur-phosphorus doped carbon material, the sulfur-phosphorus doped carbon material is sulfur-phosphorus doped graphene, sulfur-phosphorus doped carbon nanotubes or sulfur-phosphorus doped conductive carbon black.
According to the sulfur-phosphorus doped 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 qin-bax 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.
According to the sulfur-phosphorus doped 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 sulfur-phosphorus doped carbon material of the present invention, sulfur and phosphorus are combined with the carbon material in the form of chemical bonds.
According to the sulfur-phosphorus doped carbon material of the invention, O analyzed in XPS thereof 1s There is a symmetrical peak between 530ev and 535ev in the spectrum peak.
The invention also provides a preparation method of the sulfur-phosphorus doped carbon material, which comprises the following steps:
(1) A step of doping phosphorus: contacting the carbon material with a phosphorus source, and treating the carbon material in inert gas at 300-800 ℃ for 0.5-10 h to obtain a phosphorus doped carbon material; and
(2) A step of doping sulfur: and (3) contacting the phosphorus-doped carbon material in the step (1) with a sulfur source, and treating the carbon material in an inert gas at 400-1500 ℃ for 0.5-10 h to obtain the sulfur-phosphorus-doped carbon material.
According to the preparation method of the sulfur-phosphorus doped carbon material, in the (1) and the (2), if heating is needed, the heating rate is respectively and independently 1-20 ℃ per minute, preferably 3-15 ℃ per minute, and more preferably 8-15 ℃ per minute.
According to the method for preparing a sulfur-phosphorus doped carbon material of the present invention, there is no particular limitation on the phosphorus source, and any phosphorus source that can be used in the art to dope a carbon material can be used in the present invention. The phosphorus source can be one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.
According to the preparation method of the sulfur-phosphorus doped carbon material, the mass ratio of the carbon material to the phosphorus source is 10000 based on the mass of phosphorus contained in the carbon material: 1-20: 1, a step of; preferably 2500: 1-30: 1.
according to the preparation method of the sulfur-phosphorus doped carbon material, the sulfur source is elemental sulfur.
According to the preparation method of the sulfur-phosphorus doped carbon material, the mass ratio of the carbon material 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 sulfur-phosphorus doped carbon material, in the (1), the temperature is 400-600 ℃.
According to the preparation method of the sulfur-phosphorus doped carbon material of the present invention, in (2), the temperature may be 400 to 600 ℃, 600 to 1000 ℃, or 1000 to 1500 ℃.
According to the preparation method of the sulfur-phosphorus doped carbon material, in the steps (1) and (2), the treatment time is 1 to 5 hours, preferably 2 to 4 hours.
According to the preparation method of the sulfur-phosphorus doped carbon material, the carbon material can be carbon nano tubes, conductive carbon black or graphene. The conductive carbon black is one or more of Ketjen black series superconducting carbon black, cabot series conductive carbon black and series conductive carbon black produced by Yingchangzhucai company; preferably EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
According to the method for preparing the sulfur-phosphorus doped carbon material of the present invention, I of the carbon material in (1) 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 sulfur-phosphorus doped carbon material, the inert gas is nitrogen or argon.
According to the method for producing a sulfur-phosphorus doped carbon material of the present invention, the carbon material has a resistivity of <10Ω·m, preferably <5Ω·m, more preferably <2Ω·m in (1).
According to the preparation method of the sulfur-phosphorus doped carbon material, in XPS analysis of the carbon material in the step (1), the mass fraction of oxygen is generally more than 4%, preferably 4% -15%.
According to the method for preparing the sulfur-phosphorus doped carbon material of the present invention, the specific surface area of the carbon material in (1) 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 sulfur-phosphorus doped carbon material, in the (1), the contact mode of the carbon material and a phosphorus source is as follows: the carbon material is dried after being immersed in an aqueous solution of a phosphorus source.
According to the preparation method of the sulfur-phosphorus doped carbon material, in the (2), the contact mode of the phosphorus doped carbon material and a sulfur source is as follows: the phosphorus doped carbon material is mixed with elemental sulfur.
According to the preparation method of the sulfur-phosphorus doped carbon material, a metal-containing catalyst is not used in the process of manufacturing the sulfur-phosphorus doped carbon material.
A sulfur-phosphorus doped carbon material made by any of the methods described above.
The use of any of the foregoing sulfur-phosphorus doped 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 a sulfur-phosphorus doped carbon material; s analyzed by XPS in the platinum carbon catalyst 2P The spectrum peak is 160 ev-170 ev, and only the characteristic peak of thiophene-type sulfur is included.
The platinum carbon catalyst according to the present invention does not contain other doping elements than sulfur and phosphorus.
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 phosphorus are chemically bonded to a carbon material in the carbon support.
The platinum carbon catalyst according to the invention has P analyzed by XPS 2p There are no characteristic peaks between 125ev and 145ev in the spectrum peaks.
According to the platinum carbon catalyst, the sulfur-phosphorus doped carbon material is sulfur-phosphorus doped graphene, sulfur-phosphorus doped carbon nanotubes or sulfur-phosphorus doped conductive carbon black.
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 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 platinum carbon catalystThe specific surface area of the chemical agent is 80m 2 /g～1500m 2 /g, preferably 100m 2 /g～200m 2 /g。
According to the platinum carbon catalyst of the present invention, a phosphorus signal was detected in a TG-MS (thermogravimetry-Mass Spectrometry) test (P, P) 2 O 3 And P 2 O 5 )。
The invention provides a preparation method of a platinum-carbon catalyst, which comprises the following steps:
(1) The steps of manufacturing the phosphorus-doped carbon material: contacting the carbon material with a phosphorus source, and treating the carbon material in inert gas at 300-800 ℃ for 0.5-10 h to obtain a phosphorus doped carbon material;
(2) The method comprises the steps of: contacting the phosphorus-doped carbon material in the step (1) with a sulfur source, and treating the carbon material in an inert gas at 400-1500 ℃ for 0.5-10 h to obtain the sulfur-phosphorus-doped carbon material;
(3) And (3) taking the sulfur-phosphorus doped carbon material obtained in the step (2) as a carrier to load platinum.
According to the preparation method of the platinum carbon catalyst, the temperature is increased in the steps (1) and (2) if required, and the temperature increasing rate is respectively and independently 1-20 ℃/min, preferably 3-15 ℃/min, and more preferably 8-15 ℃/min.
According to the preparation method of the platinum carbon catalyst, 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 platinum carbon catalyst, in the (1), the mass ratio of the carbon material to the phosphorus source is 10000 based on the mass of phosphorus contained in the phosphorus source: 1-20: 1, a step of; preferably 2500: 1-30: 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 of the present invention, (2) the mass ratio of the carbon material 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, in (2), the temperature may be 400 to 600 ℃, 600 to 1000 ℃, or 1000 to 1500 ℃.
According to the preparation method of the platinum carbon catalyst of the present invention, in (1) and (2), the treatment time is 1 to 5 hours, preferably 2 to 4 hours, independently of each other.
According to the preparation method of the platinum carbon catalyst, the carbon material is graphene, conductive carbon black or carbon nano tube. 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, in (1), the mass fraction of oxygen in XPS analysis of the carbon material is more than 4%, preferably 4% -15%.
According to the method for producing a platinum carbon catalyst of the present invention, in (1), the specific resistance of the carbon material is <10Ω·m, preferably <5Ω·m, more preferably <2Ω·m.
According to the method for producing a platinum carbon catalyst of the present invention, (1) the specific surface area of the carbon material 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, in the (1), the contact mode of the carbon material and the phosphorus source is as follows: the carbon material is dried after being immersed in an aqueous solution of a phosphorus source.
According to the preparation method of the platinum carbon catalyst, in the (2), the contact mode of the phosphorus doped carbon material and the sulfur source is as follows: the phosphorus doped carbon material is mixed with elemental sulfur.
According to the preparation method of the platinum carbon catalyst, the platinum loading step comprises the following steps:
(a) Dispersing the sulfur-phosphorus doped carbon material 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, wherein a sulfur-phosphorus doped carbon material of any one of the above or a platinum carbon catalyst of any one of the above is used in an anode and/or a 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. The characteristic peak of thiophene sulfur in the spectrogram is the characteristic peak 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 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%, 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-phosphorous doped carbon material of the present invention.
1g Vulcan XC72 is immersed in 15mL of 4.0wt% phosphoric acid 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 phosphorus-doped carbon material.
Uniformly mixing the phosphorus-doped carbon material with 0.167g of elemental sulfur, 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 3 hours; naturally cooling to obtain the sulfur-phosphorus doped carbon material.
Sample characterization and testing
The sulfur-phosphorus doped carbon material of the embodiment has a mass fraction of sulfur of 1.44% by XPS analysis; the mass fraction of phosphorus analyzed by XPS is 1.57%; specific surface area of 239m 2 /g; the resistivity was 1.31. Omega. M.
Fig. 1 is an XPS spectrum of phosphorus of the sulfur-phosphorus doped carbon material of example 1.
Fig. 2 is an XPS spectrum of sulfur of the sulfur-phosphorus doped carbon material of example 1.
Fig. 3 is an XPS spectrum of oxygen of the sulfur-phosphorus doped carbon material of example 1.
Example 2
This example is intended to illustrate the sulfur-phosphorous doped carbon material of the present invention.
1g of Vulcan XC72 is immersed in 15mL of 4.8wt% sodium phosphate 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 phosphorus-doped carbon material.
Uniformly mixing the phosphorus-doped carbon material with 0.2g of elemental sulfur, placing the mixture into a tube furnace, heating the tube furnace to 1400 ℃ at the speed of 8 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the sulfur-phosphorus doped carbon material, wherein the number of the carbon carrier A.
Sample characterization and testing
In the sulfur-phosphorus doped carbon material in the embodiment, the mass fraction of sulfur analyzed by XPS is 0.97%; the mass fraction of phosphorus analyzed by XPS is 0.55%; specific surface area of 231m 2 /g; the resistivity was 1.27. Omega. M.
Fig. 4 is an XPS spectrum of phosphorus of the sulfur-phosphorus doped carbon material of example 2.
Fig. 5 is an XPS spectrum of sulfur of the sulfur-phosphorus doped carbon material of example 2.
Example 3
This example is intended to illustrate the sulfur-phosphorous doped carbon material of the present invention.
10mL of absolute ethanol was added to 1g Ketjenblack ECP600JD, followed by impregnation with 25mL of 1.8wt% phosphoric acid 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 a speed of 10 ℃/min, carrying out constant temperature treatment for 3 hours, and naturally cooling to obtain the phosphorus-doped carbon material.
Uniformly mixing the phosphorus-doped carbon material with 0.15g of elemental sulfur, placing 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-phosphorus doped carbon material.
Sample characterization and testing
The sulfur-phosphorus doped carbon material has the mass fraction of sulfur analyzed by XPS of 1.41%; the mass fraction of phosphorus analyzed by XPS is 0.18%; a specific surface area of 1325m 2 /g; the resistivity was 1.37Ω·m.
Fig. 6 is an XPS spectrum of phosphorus of the sulfur-phosphorus doped carbon material of example 3.
Fig. 7 is an XPS spectrum of sulfur of the sulfur-phosphorus doped carbon material of example 3.
Example 4
This example is intended to illustrate the sulfur-phosphorous doped carbon material of the present invention.
10mL of absolute ethanol was added to 1g Ketjenblack ECP600JD, followed by soaking in 25mL of 1wt% sodium phosphate 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 a speed of 10 ℃/min, carrying out constant temperature treatment for 3 hours, and naturally cooling to obtain the phosphorus-doped carbon material.
Uniformly mixing the phosphorus-doped carbon material with 0.25g of elemental sulfur, placing the mixture into a tube furnace, heating the tube furnace to 1200 ℃ at the speed of 10 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the sulfur-phosphorus doped carbon material, wherein the number of the carbon carrier B is the number.
Sample characterization and testing
The sulfur-phosphorus doped carbon material has the mass fraction of sulfur analyzed by XPS of 1.06%; the mass fraction of phosphorus analyzed by XPS is 0.11%; specific surface area of 1306m 2 /g; the resistivity was 1.35. Omega. M.
Fig. 8 is an XPS spectrum of phosphorus of the sulfur-phosphorus doped carbon material of example 4.
Fig. 9 is an XPS spectrum of sulfur of the sulfur-phosphorus doped carbon material of example 4.
Fig. 10 is an XPS spectrum of oxygen of the sulfur-phosphorus doped carbon material 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 40.2%.
In XPS analysis of the Pt-C catalyst, there was no P between 125ev and 145ev 2p Is a characteristic peak of (2).
Fig. 11 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 5.
P, P was detected in TG-MS test 2 O 3 And P 2 O 5 Is a signal of (a).
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.
Dispersing the carbon carrier B 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 69.8%.
In XPS analysis of the Pt-C catalyst, there was no P between 125ev and 145ev 2p Is a characteristic peak of (2).
Fig. 12 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 6.
P, P was detected in TG-MS test 2 O 3 And P 2 O 5 Is a signal of (a).
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.
Comparative example 4
Uniformly mixing Vulcan XC72 with elemental sulfur, wherein the mass ratio of the Vulcan XC72 to the elemental sulfur is 6:1, placing the mixture into a tube furnace, heating the tube furnace to 400 ℃ at the speed of 8 ℃/min, then carrying out constant temperature treatment for 3 hours, and naturally cooling to obtain the sulfur-doped carbon material.
Sample characterization and testing
Fig. 13 is an XPS spectrum of sulfur of the sulfur-doped carbon material of comparative example 4.
TABLE 1
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Claims (7)

1. A platinum carbon catalyst for an anode 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-phosphorus doped conductive carbon black, and is prepared by the following method: soaking conductive carbon black in a phosphorus source water solution, drying, and treating in inert gas at 300-800 ℃ for 0.5-10 h to obtain phosphorus doped conductive carbon black; mixing the phosphorus doped conductive carbon black with a sulfur source, and treating the mixture in inert gas at 400-1500 ℃ for 0.5-10 h to obtain the sulfur-phosphorus doped conductive carbon black; the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphates, polyphosphates, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite, the mass ratio of the conductive carbon black to the phosphorus source is 2500 based on the mass of phosphorus contained in the phosphorus source: 1-30: 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 8:1 to 4:1, a step of; XPS analyzed S of sulfur-phosphorus doped conductive carbon black 2P In the spectrum peak, between 160ev and 170ev, only the characteristic peak of thiophene sulfur exists, and the P of the sulfur-phosphorus doped conductive carbon black 2p A characteristic peak exists between 125ev and 145ev in the spectrum peak; the sulfur-phosphorus doped conductive carbon black does not contain other doping elements except sulfur and phosphorus, wherein the doping elements are nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine; s analyzed by XPS of the platinum carbon catalyst 2P The spectrum peak is 160 ev-170 ev, only the characteristic peak of thiophene sulfur; in the platinum carbon catalyst, based on the mass of the catalyst, platinumThe mass fraction of (2) 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. A method of preparing the platinum carbon catalyst according to claim 1, comprising: the process for producing sulfur-phosphorus doped conductive carbon black as claimed in claim 1, and the process for supporting platinum by using said sulfur-phosphorus doped conductive carbon black as a carrier.
4. A method of preparing a platinum carbon catalyst according to claim 3, wherein said step of supporting platinum comprises:
(a) Dispersing the sulfur-phosphorus doped conductive carbon black and a 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.
5. The method of preparing a platinum carbon catalyst according to claim 4, 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.
6. The method for preparing a platinum carbon catalyst according to claim 4, 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.
7. A hydrogen fuel cell, characterized in that the platinum carbon catalyst according to claim 1 or 2 is used in the anode and/or the cathode of the hydrogen fuel cell.
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