CN114122417A - Platinum-carbon catalyst and preparation method and application thereof - Google Patents

Platinum-carbon catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN114122417A
CN114122417A CN202010876790.5A CN202010876790A CN114122417A CN 114122417 A CN114122417 A CN 114122417A CN 202010876790 A CN202010876790 A CN 202010876790A CN 114122417 A CN114122417 A CN 114122417A
Authority
CN
China
Prior art keywords
platinum
carbon
carbon material
phosphorus
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010876790.5A
Other languages
Chinese (zh)
Inventor
谢南宏
荣峻峰
赵红
张家康
彭茜
王厚朋
顾贤睿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN202010876790.5A priority Critical patent/CN114122417A/en
Publication of CN114122417A publication Critical patent/CN114122417A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a platinum-carbon catalyst and a preparation method and application thereof. The platinum-carbon catalyst has higher electrochemical stability when being used for oxygen reduction reaction.

Description

Platinum-carbon catalyst and preparation method and application thereof
Technical Field
The invention relates to a platinum-carbon catalyst and a preparation method and application thereof, in particular to a phosphorus-doped platinum-carbon catalyst and a preparation method and application thereof.
Background
The fuel cell serving as an energy conversion device for converting chemical energy into electric energy has the advantages of high energy conversion efficiency, low working temperature, environmental friendliness and the like, and is expected to be widely applied to various fields, particularly the field of transportation. Hydrogen fuel cells are currently the mainstream fuel cell technology, and catalysts and proton exchange membranes are the core of hydrogen fuel cell technology. In the development of hydrogen fuel cells, it has been a hot topic of scientific research to manufacture a high-efficiency and low-cost electrode catalyst, and since the exchange ac density of the cathode Oxygen Reduction Reaction (ORR) is 4 to 5 orders of magnitude lower than that of the anode Hydrogen Oxidation Reaction (HOR) and the overpotential is large, the cathode oxygen reduction electrode catalyst has been the focus of research.
The carbon material doped with elements can be directly used as an alkaline fuel cell catalyst, and although the literature reports of the catalyst are more, the catalyst has larger difference in catalytic performance compared with a platinum carbon catalyst and is far from practical application. The nitrogen element can dope the carbon material in various structural forms, and is the most commonly used doping element. Phosphorus and nitrogen belong to the same main group, but in the case of a doped carbon material, phosphorus has characteristics that are substantially different from those of nitrogen due to differences in atomic radius and electronegativity. At present, in the literature reports about phosphorus-doped carbon materials, the catalytic performance of the materials is generally low, and the catalytic mechanism is not uniformly and definitely known.
The platinum-carbon catalyst is the most mature hydrogen fuel cell catalyst at present, but the price of platinum is high, and the catalytic activity and the stability are not ideal. Factors influencing the catalytic activity and stability of the platinum-carbon catalyst are many and complicated, and some literatures believe that the quality specific activity and stability of the platinum-carbon catalyst are related to the particle size, morphology and structure of platinum, and the type, property and platinum loading of a carrier. In the prior art, the performance of the platinum-carbon catalyst is improved mainly by controlling the particle size, morphology and structure of platinum, the specific surface area and pore structure of a carrier; there is also a literature report that modifying groups are attached to the carbon surface to improve the performance of platinum-carbon catalysts by modifying the carbon support.
Increasing the amount of platinum loading is beneficial for making thinner and better performing membrane electrodes, but in the prior art, increasing the amount of platinum loading by a large margin results in a significant decrease in catalytic performance in terms of platinum per unit mass.
The chemical reduction method is a commonly used method for preparing the platinum-carbon catalyst, and has the advantages of simple process and low utilization rate and catalytic activity of platinum. The reason for this may be that the platinum nanoparticles are not uniformly dispersed due to irregularities in the pore structure of the carbon support.
The information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and may include information that is not already known to those of ordinary skill in the art.
Disclosure of Invention
It is a first object of the present invention to improve the mass specific activity and electrochemical stability of a platinum-carbon catalyst. It is a second object of the present invention to provide a platinum-carbon catalyst with a higher platinum loading in addition to the aforementioned objects. A third object of the present invention is to improve the aqueous phase chemical reduction process for making platinum carbon catalysts.
In order to achieve the above object, the present invention provides the following technical solutions.
1. A method of preparing a platinum carbon catalyst comprising: (1) mixing a phosphorus source: mixing a carbon material with a phosphorus source to obtain a carbon material mixed with the phosphorus source; (2) a step of producing a phosphorus-doped carbon material: carrying out high-temperature treatment on the carbon material mixed with the phosphorus source in the step (1) in an inert atmosphere to obtain a phosphorus-doped carbon material; (3) loading platinum: and (3) loading platinum by using the phosphorus-doped carbon material obtained in the step (2) as a carrier.
2. A method of preparing a platinum carbon catalyst comprising: (1) mixing a phosphorus source: mixing and impregnating a carbon material with a phosphorus source aqueous solution to obtain a phosphorus source impregnated carbon material; (2) a step of producing a phosphorus-doped carbon material: carrying out high-temperature treatment on the carbon material impregnated with the phosphorus source in the step (1) in an inert atmosphere to obtain a phosphorus-doped carbon material; (3) loading platinum: and (3) loading platinum by using the phosphorus-doped carbon material obtained in the step (2) as a carrier.
3. The process according to any one of the preceding claims, wherein the temperature of the high-temperature treatment in (2) is 300 ℃ to 800 ℃ (preferably 400 ℃ to 600 ℃) and the treatment time is 0.5h to 10 h.
4. The preparation method according to any one of the preceding claims, characterized in that the high temperature treatment time is 1h to 5h, preferably 1.5h to 4 h.
5. The preparation method according to any one of the preceding claims, characterized in that the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite, preferably phosphoric acid.
6. The preparation method according to any one of the preceding claims, characterized in that the mass ratio of the carbon material to the phosphorus source is 100:0.1 to 100: 8; preferably 100: 0.5-100: 5.
7. a process according to any one of the preceding claims, characterized in that the carbon material is a conductive carbon Black, preferably EC-300J, EC-600JD, ECP-600JD, VXC72, Black pearls2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXAXK 40B 2.
8. The production method according to any one of the preceding claims, characterized in that the carbon material has an oxygen mass fraction of more than 4%, preferably 4% to 15%, in XPS analysis.
9. A production method according to any one of the preceding claims, characterized in that the carbon material has a resistivity of <10 Ω · m, preferably <5 Ω · m, more preferably <2 Ω · m.
10. A production method according to any one of the preceding claims, characterized in that the carbon material has a specific surface area of 10m2/g～2000m2/g。
11. The production method according to any one of the preceding claims, wherein the mass fraction of phosphorus in the XPS analysis of the phosphorus-doped carbon material is 0.1% to 6%, preferably 0.2% to 4%, more preferably 0.3% to 3%.
12. A production method according to any one of the preceding claims, characterized in that XPS analysis of P for the phosphorus-doped carbon material2pAmong the peaks, there are characteristic peaks of C-P and P-O.
13. A production method according to any one of the preceding claims, characterized in that XPS analysis of P for the phosphorus-doped carbon material2pIn the spectrum peaks, the peak is a double peak between 125ev and 145ev, and the peak is respectively positioned at 133.3ev +/-0.5 ev and 134.2ev +/-0.5ev。
14. The production method according to any one of the preceding claims, characterized in that the step of supporting platinum comprises:
(a) dispersing the phosphorus-doped carbon material obtained in the step (1) and a platinum precursor in a water phase, and adjusting the pH to 8-12 (preferably, adjusting the pH to 10 +/-0.5);
(b) adding a reducing agent for reduction;
(c) separating out solid, and post-treating to obtain the platinum-carbon catalyst.
15. The preparation method according to any one of the preceding claims, characterized in that the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5-5 mol/L.
16. The process according to any one of the preceding claims, wherein in (a), the pH of the aqueous phase is adjusted with an aqueous solution of sodium carbonate, an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydroxide or aqueous ammonia.
17. The preparation method according to any one of the preceding claims, characterized in that in (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the molar ratio of the reducing agent to the platinum is 2-100; the reduction temperature is 50-150 ℃, and preferably 60-90 ℃; the reduction time is 2 to 15 hours, preferably 8 to 12 hours.
18. The method of any one of the preceding claims, wherein said post-treatment comprises: washing, filtering and drying.
19. A platinum carbon catalyst, characterized in that the catalyst is prepared by any of the methods described above.
20. A platinum-carbon catalyst comprises a carbon support and platinum metal loaded thereon, wherein the carbon support is a phosphorus-doped carbon material.
21. A platinum-carbon catalyst according to any one of the preceding claims, characterised in that P is analysed in its XPS2pAmong the spectral peaks, there was a characteristic peak between 125 to 145.
22. The platinum-carbon catalyst according to any one of the preceding claims, characterized in that XPS score of said carbon supportAnalysis of P2pAmong the peaks, there are characteristic peaks of C-P and P-O.
23. The platinum-carbon catalyst according to any one of the above, characterized in that the mass fraction of platinum is 0.1% to 80%, preferably 20% to 70%, more preferably 40% to 70%, based on the mass of the catalyst.
24. The platinum-carbon catalyst according to any of the preceding claims, characterized in that the platinum-carbon catalyst has a resistivity of <10 Ω · m, preferably <2 Ω · m.
25. The platinum-carbon catalyst according to any one of the preceding claims, characterized in that the platinum-carbon catalyst has a specific surface area of 80m2/g～1500m2A/g, preferably of 100m2/g～200m2/g。
26. A platinum carbon catalyst according to any one of the preceding claims characterised in that the carbon material is a conductive carbon Black, preferably EC-300J, EC-600JD, ECP600JD, VXC72, Black pearls2000, PRINTEX XE2-B, PRINTEX L6 or hilblaxk 40B 2.
27. A hydrogen fuel cell characterized in that any one of 19 to 26 of platinum-carbon catalysts is used for an anode and/or a cathode of the hydrogen fuel cell.
28. A carbon material characterized by P analyzed in its XPS2pAmong the peaks, there are two peaks at 125 to 145eV, which are respectively 133.3eV + -0.5 eV and 134.2eV + -0.5 eV.
29. The carbon material according to 20, wherein the carbon material is conductive carbon black.
Compared with the prior art, the invention has the following beneficial technical effects.
Firstly, the carbon material is doped with phosphorus to manufacture a novel carbon carrier, and the platinum carbon catalyst manufactured by the carbon carrier can obviously improve the electrochemical stability of the catalyst, for example, after 5000 circles of stability test, half-wave potential is not reduced, and ECSA is not reduced by more than 10%.
Secondly, the platinum carrying amount of the industrial hydrogen fuel cell platinum-carbon catalyst is at least more than 20 wt%, and the technology in the field is expected to greatly improve the platinum carrying amount and keep the platinum utilization rate still good, but the difficulty in manufacturing the high platinum carrying amount catalyst with excellent performance is very large. The chemical reduction method has simple process, but the stability of the prepared catalyst is still to be improved. However, when the phosphorus-doped carbon material produced by the present invention is used as a carrier, a high-platinum-loading catalyst having good specific activity and electrochemical stability can be easily produced by an aqueous chemical reduction method. Some carbon materials are difficult to disperse in water, such as ketjen black, and must be pretreated or use an organic solvent, however, the phosphorus-doped carbon material of the present invention can be easily dispersed in water.
When the platinum carrying amount is similar, the performance of the catalyst is obviously superior to that of a commercial catalyst, even if the platinum carrying amount is far higher than that of the commercial catalyst, the performances of the catalyst, such as half-wave potential, ECSA, specific mass activity and the like, are still equivalent to those of the commercial catalyst, and the stability is obviously higher than that of the commercial catalyst.
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 a phosphorus doped carbon support of example 1.
Fig. 2 is an XPS spectrum of a phosphorus doped carbon support of example 2.
Fig. 3 is an XPS spectrum of a phosphorus doped carbon support of example 3.
Fig. 4 is an XPS spectrum of a phosphorus doped carbon support of example 4.
Fig. 5 is a plot of polarization (LSV) before and after 5000 cycles of the platinum-carbon catalyst of example 5.
Fig. 6 is a CV curve before and after 5000 cycles of the platinum-carbon catalyst of example 5.
Fig. 7 is an XPS spectrum of the platinum-carbon catalyst of example 6.
Detailed Description
The present invention will be described in detail with reference to the following embodiments, but it should be understood that the scope of the present invention is not limited by these embodiments and the principle of the present invention, but is defined by the claims.
In the present invention, anything or matters not mentioned is directly applicable to those known in the art without any change except those explicitly described. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.
All of the features disclosed in this application can be combined in any combination which is understood to be disclosed or described in this application and which, unless clearly considered to be too irrational by a person skilled in the art, is to be considered as being specifically disclosed and described in this application. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the examples but also the endpoints of each numerical range in the specification, and ranges in which any combination of the numerical points is disclosed or recited should be considered as ranges of the present invention.
Technical and scientific terms used herein are to be defined only in accordance with their definitions, and are to be understood as having ordinary meanings in the art without any definitions.
The "doping element" in the present invention means nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine.
In the present invention, unless otherwise specified as "carbon material containing a doping element" according to the context or self-restriction, the other references to "carbon material" refer to a carbon material containing no doping element; so does the underlying concept of carbon material.
In the present invention, "carbon black" and "carbon black" are terms of art that can be substituted for each other.
The "inert gas" in the present invention means a gas which does not have any appreciable influence on the properties of the phosphorus-doped carbon material in the production process of the present invention.
In the present invention, other references to "pore volume" are to P/P, except where the context or limitations may dictate0The maximum single point adsorption total pore volume.
The invention provides a preparation method of a platinum-carbon catalyst, which comprises the following steps:
(1) mixing a phosphorus source: mixing a carbon material with a phosphorus source to obtain a carbon material mixed with the phosphorus source;
(2) a step of producing a phosphorus-doped carbon material: carrying out high-temperature treatment on the carbon material mixed with the phosphorus source in the step (1) in an inert atmosphere to obtain a phosphorus-doped carbon material;
(3) loading platinum: and (3) loading platinum by using the phosphorus-doped carbon material obtained in the step (2) as a carrier.
As a preferred embodiment of the present invention, the preparation method comprises:
(1) mixing a phosphorus source: mixing and impregnating a carbon material with a phosphorus source aqueous solution to obtain a phosphorus source impregnated carbon material;
(2) a step of producing a phosphorus-doped carbon material: carrying out high-temperature treatment on the carbon material impregnated with the phosphorus source in the step (1) in an inert atmosphere to obtain a phosphorus-doped carbon material;
(3) loading platinum: and (3) loading platinum by using the phosphorus-doped carbon material obtained in the step (2) as a carrier.
According to the preparation method of the platinum-carbon catalyst of the present invention, for the high temperature treatment in (2), those skilled in the art can determine the appropriate temperature and time according to the teaching of the present invention or by simple experiment. The temperature of the high-temperature treatment can be 300-800 ℃, and is preferably 400-600 ℃; the treatment time may be 0.5 to 10 hours, preferably 1 to 5 hours.
According to the preparation method of the platinum-carbon catalyst, the phosphorus source can be one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite, and phosphoric acid is preferred.
According to the preparation method of the platinum-carbon catalyst, the mass ratio of the carbon material to the phosphorus source is 100:0.1 to 100: 8; preferably 100: 0.5-100: 5.
according to the preparation method of the platinum-carbon catalyst, the carbon material can be conductive carbon black, carbon nanotubes or graphene.
According to the preparation method of the platinum-carbon catalyst, the carbon nanotube or the graphene can be carbon nanotube or graphene which is not subjected to oxidation treatment, and can also be carbon nanotube or graphene which is subjected to oxidation treatment.
According to the preparation method of the platinum carbon catalyst, the Conductive carbon black can be common Conductive carbon black (Conductive Blacks), Super Conductive carbon black (Super Conductive Blacks) or special Conductive carbon black (Extra Conductive Blacks), for example, the Conductive carbon black can be one or more of Ketjen black series superconducting carbon black, Cabot series Conductive carbon black and series Conductive carbon black produced by Wingda Degussa; preferably EC-300J, EC-600JD, ECP-600JD, VXC72, Black pearls2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B 2.
According to the preparation method of the platinum-carbon catalyst, the preparation method and the source of the conductive carbon black are not limited. The conductive carbon black may be acetylene black, furnace black, or the like.
Preparation of platinum-carbon catalyst according to the invention, I of the carbon MaterialD/IGThe value is generally 0.8 to 5, preferably 1 to 4. In the Raman spectrum, it is located at 1320cm-1The nearby peak is the D peak and is located at 1580cm-1The nearby peak is the G peak, IDRepresents the intensity of the D peak, IGRepresenting the intensity of the G peak.
According to the preparation method of the platinum-carbon catalyst, the carbon material has an oxygen mass fraction of more than 4%, preferably 4-15% in XPS analysis.
According to the method for producing a platinum-carbon catalyst of the present invention, the carbon material has a resistivity of <10 Ω · m, preferably <5 Ω · m, and more preferably <2 Ω · m.
According to the preparation method of the platinum-carbon catalyst of the present invention, the carbon material in (1) has a specific surface area of 10m2/g～2000m2(ii)/g; the pore volume is 0.2mL/g to 6.0 mL/g.
According to the preparation method of the platinum-carbon catalyst, the impregnation operation further comprises a drying operation, preferably a drying operation, and the phosphorus-doped carbon material is obtained after drying.
According to the preparation method of the platinum-carbon catalyst, in XPS analysis of the phosphorus-doped carbon-carbon material, the mass fraction of phosphorus is 0.1-6%, preferably 0.2-4%, and more preferably 0.3-3%.
According to the preparation method of the platinum-carbon catalyst, the XPS analysis P of the phosphorus-doped carbon material2pAmong the peaks, there are characteristic peaks of C-P and P-O.
According to the preparation method of the platinum-carbon catalyst, the XPS analysis P of the phosphorus-doped carbon material2pAmong the peaks, there are two peaks at 125 to 145eV, which are respectively 133.3eV + -0.5 eV and 134.2eV + -0.5 eV. In some embodiments, XPS analysis of P for the phosphorus doped carbon material2pAmong the peaks, there are two peaks between 125eV and 145eV, which are respectively 133.3eV + -0.3 eV and 134.2eV + -0.3 eV.
According to the preparation method of the platinum-carbon catalyst, in one embodiment of the preparation method of the phosphorus-doped carbon material, the carbon material is mixed with a phosphorus source aqueous solution, the mixture is soaked (generally for 12-72 hours) and dried (generally for 70-120 ℃), then the mixture is placed in a tube furnace, the temperature of the tube furnace is raised (the temperature raising rate can be 4-15 ℃/min, generally for 5 ℃/min) under the protection of inert gas, and then the tube furnace is treated at high temperature (generally for 300-800 ℃, preferably for 400-600 ℃) for a period of time (which can be 0.5-10 hours, generally for 1-5 hours), so that the phosphorus-doped carbon material is obtained.
According to the preparation method of the platinum-carbon catalyst of the present invention, the phosphorus-doped carbon material prepared in (2) can be easily dispersed in an aqueous phase. However, it is difficult to directly disperse the carbon material in the aqueous phase, such as ketjen black.
According to the preparation method of the platinum-carbon catalyst, the inert gas is nitrogen or argon.
According to the preparation method of the platinum-carbon catalyst of the present invention, the step of supporting platinum comprises:
(a) dispersing the phosphorus-doped carbon material obtained in the step (1) and a platinum precursor in a water phase, and adjusting the pH to 8-12 (preferably, adjusting the pH to 10 +/-0.5);
(b) adding a reducing agent 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, the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5-5 mol/L.
According to the preparation method of the platinum-carbon catalyst of the present invention, in (a), the pH of the aqueous phase is adjusted with an aqueous solution of sodium carbonate, an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydroxide, or aqueous ammonia.
According to the preparation method of the platinum-carbon catalyst, in the step (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol.
According to the preparation method of the platinum-carbon catalyst, in the step (b), the molar ratio of the reducing agent to platinum is 2-100.
According to the preparation method of the platinum-carbon catalyst, in the step (b), the reduction temperature is 50-150 ℃, and preferably 60-90 ℃; the reduction time is 4 to 15 hours, preferably 8 to 12 hours.
According to the preparation method of the platinum-carbon catalyst, the post-treatment comprises the following steps: washing, filtering and drying.
According to the method for producing a platinum-carbon catalyst of the present invention, in the step of producing a phosphorus-doped carbon material in (2), a metal-containing catalyst is not used.
A platinum carbon catalyst for a battery, which is prepared by any one of the methods.
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 a phosphorus-doped carbon material.
The platinum-carbon catalyst according to the invention is free of doping elements other than phosphorus.
The platinum-carbon catalyst according to the present invention does not contain other metal elements than platinum.
P of platinum-carbon catalyst according to the invention, analyzed in XPS thereof2pAmong the spectral peaks, there was a characteristic peak between 125 to 145. In some embodiments, XPS analysis P of the platinum carbon catalyst2pAmong the peaks, there are two peaks between 125eV and 145eV, which are respectively at 132.9 eV. + -. 0.3eV and 134.1 eV. + -. 0.3 eV.
According to the bookInventive platinum-carbon catalyst, XPS analysis of P on said carbon support2pAmong the peaks, there are characteristic peaks of C-P and P-O.
According to the platinum-carbon catalyst of the present invention, the mass fraction of platinum is 0.1% to 80%, preferably 20% to 70%, and more preferably 40% to 70% based on the mass of the catalyst.
According to the platinum-carbon catalyst of the present invention, the platinum-carbon catalyst has a resistivity of <10.0 Ω · m, preferably <2 Ω · m.
According to the platinum-carbon catalyst of the present invention, the specific surface area of the platinum-carbon catalyst is 80m2/g～1500m2A/g, preferably of 100m2/g～200m2/g。
According to the platinum carbon catalyst of the invention, the conductive carbon black can be one or more of Ketjen black series superconducting carbon black, Cabot series conductive carbon black and series conductive carbon black produced by Wingda Gusai company; preferred are Ketjen Black EC-300J, Ketjen Black EC-600JD, Ketjen Black ECP-600JD, VXC72, Black pearls2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B 2.
A hydrogen fuel cell comprising an anode and/or a cathode, wherein any one of the platinum-carbon catalysts described above is used.
Carbon material, P analyzed by XPS2pAmong the peaks, there are two peaks at 125 to 145eV, which are respectively 133.3eV + -0.5 eV and 134.2eV + -0.5 eV.
The carbon material according to the invention is free of doping elements other than phosphorus.
The carbon material according to the present invention contains no metal element.
Carbon materials according to the present disclosure, in some embodiments, XPS analysis P of the carbon materials2pAmong the peaks, there are two peaks between 125eV and 145eV, which are respectively 133.3eV + -0.3 eV and 134.2eV + -0.3 eV.
A method of producing a carbon material, comprising:
(1) mixing a phosphorus source: mixing a carbon material with a phosphorus source to obtain a carbon material mixed with the phosphorus source;
(2) a step of manufacturing a carbon support: and (2) performing high-temperature treatment on the carbon material mixed with the phosphorus source obtained in the step (1) in an inert gas to obtain the carbon material.
Other features of the preparation method of the carbon material are the same as the corresponding features of the preparation method of the platinum-carbon catalyst, and the invention is not repeated herein.
The invention adopts a simple method to firmly combine the phosphorus and the surface of the carbon material to prepare a novel carrier which is beneficial to platinum metal loading and dispersion, thereby preparing the platinum-carbon electrode catalyst for hydrogen fuel cell anode hydrogen oxidation reaction or cathode oxygen reduction reaction.
The platinum-carbon catalyst according to the invention, when used in an oxygen reduction reaction, ECSA>35m2 g-1Pt, e.g. at 35m2g-1-Pt～75m2 g-1-Pt。
When the platinum-carbon catalyst is used for oxygen reduction reaction, the reduction rate of specific mass activity is less than or equal to 10 percent after 5000 circles.
The platinum-carbon catalyst according to the present invention, when used in an oxygen reduction reaction, has a half-wave potential >0.88V, such as 0.88V to 0.91V.
The platinum-carbon catalyst according to the present invention has a specific mass activity when used in an oxygen reduction reaction>0.14Amg-1-Pt, such as 0.14A mg-1-Pt～0.20A mg-1-Pt。
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way.
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the invention are analytically pure, and all reagents are commercially available.
The analytical tests in the invention are all carried out by the following instruments and methods.
The invention detects the material by X-ray photoelectron spectrum analyzer (XPS)Elements of the surface. The adopted X-ray photoelectron spectrum analyzer is an ESCALB 220i-XL type ray photoelectron spectrum analyzer which is manufactured by VG scientific company and is provided with Avantage V5.926 software, and the X-ray photoelectron spectrum analysis test conditions are as follows: the excitation source is monochromatized A1K alpha X-ray, the power is 330W, and the basic vacuum is 3X 10 during analysis and test-9mbar. In addition, the electron binding energy was corrected with the C1s peak (284.3eV) of elemental carbon, and the late peak processing software was XPSPEAK.
Apparatus and method of elemental analysis, conditions: an element analyzer (Vario EL Cube), the reaction temperature is 1150 ℃, 5mg of the sample is weighed, the reduction temperature is 850 ℃, the flow rate of carrier gas helium is 200mL/min, the flow rate of oxygen is 30mL/min, and the oxygen introducing time is 70 s.
The instrument, the method and the conditions for testing the mass fraction of platinum in the platinum-carbon catalyst are as follows: and (3) adding 30mL of aqua regia into 30mg of the prepared Pt/C catalyst, condensing and refluxing for 12h at 120 ℃, cooling to room temperature, taking supernatant liquid for dilution, and testing the Pt content in the supernatant liquid by using ICP-AES (inductively coupled plasma-atomic emission Spectrometry).
The high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100(HRTEM) (Nippon electronics Co., Ltd.), and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200 kV. The particle size of the nanoparticles in the sample is measured by an electron microscope picture.
BET test method: in the invention, the pore structure property of a sample is measured by a Quantachrome AS-6B type analyzer, the specific surface area and the pore volume of the catalyst are obtained by a Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
The Raman detection adopts a LabRAM HR UV-NIR laser confocal Raman spectrometer produced by HORIBA company of Japan, and the laser wavelength is 532 nm.
Electrochemical performance test, instrument Model Solartron analytical energy lab and Princeton Applied Research (Model 636A), methods and test conditions: polarization curve LSV of catalyst at 1600rpm2Saturated 0.1M HClO4Test in (1), CV Curve under Ar atmosphere 0.1M HClO4To calculate the electrochemically active area ECSA. In the stability test atO2Saturated 0.1M HClO4After 5000 cycles of scanning in the range of 0.6V to 0.95V, LSV and ECSA were tested as described above. During the test, the catalyst is prepared into evenly dispersed slurry and coated on a glassy carbon electrode with the diameter of 5mm, and the platinum content of the catalyst on the electrode is 3-4 mu g.
Resistivity test four-probe resistivity tester, instrument model KDY-1, method and test conditions: the applied pressure is 3.9 plus or minus 0.03MPa, and the current is 500 plus or minus 0.1 mA.
VXC72(Vulcan XC72, produced by Kabot, USA) was purchased from Suzhou wingong sandisk energy science and technology, Inc. The results of the tests by the instrument method show that: specific surface area 258m2Per g, pore volume 0.388mL/g, oxygen mass fraction 8.72%, ID/IG1.02, and a resistivity of 1.22. omega. m.
Ketjenblack ECP600JD (manufactured by Lion corporation, japan) was purchased from tsuzhou wingong sandisk energy science and technology limited. The results of the tests by the instrument method show that: specific surface area 1362m2G, pore volume 2.29mL/g, oxygen mass fraction 6.9%, ID/IG1.25, and resistivity of 1.31. omega. m.
Commercial platinum carbon catalyst (trade name HISPEC4000, manufactured by Johnson Matthey corporation) was purchased from Alfa Aesar. And (3) testing results: the mass fraction of platinum was 40.2%.
Example 1
This example illustrates the preparation of a phosphorus-doped carbon support according to the invention.
1g of Vulcan XC72 was immersed in 15mL of a 0.8 wt% aqueous phosphoric acid solution for 16 h; drying in an oven at 100 ℃; then placing the tube furnace into a tube furnace, heating the tube furnace to 400 ℃ at the speed of 8 ℃/min, and carrying out constant temperature treatment for 2 h; and naturally cooling to obtain the phosphorus-doped carbon carrier, which is numbered as carbon carrier A.
Sample characterization and testing
The mass fraction of phosphorus analyzed by XPS was 2.8%; the oxygen mass fraction by XPS analysis was 13.9%; specific surface area of 253m2(ii)/g; the resistivity was 1.23. omega. m.
Fig. 1 is an XPS spectrum of a phosphorus doped carbon support of example 1.
Example 2
This example illustrates the preparation of a phosphorus-doped carbon support according to the invention.
1g of Vulcan XC72 was immersed in 15mL of a 0.6 wt% aqueous phosphoric acid solution for 24 h; drying in an oven at 100 ℃; then placing the tube furnace into a tube furnace, heating the tube furnace to 500 ℃ at the speed of 10 ℃/min, and carrying out constant temperature treatment for 2 h; and naturally cooling to obtain the phosphorus-doped carbon carrier, which is numbered as carbon carrier B.
Sample characterization and testing
The mass fraction of phosphorus analyzed by XPS was 2.4%; the oxygen mass fraction by XPS analysis was 13.6%; specific surface area of 259m2(ii)/g; the resistivity was 1.22. omega. m.
Fig. 2 is an XPS spectrum of a phosphorus doped carbon support of example 2.
Example 3
This example illustrates the preparation of a phosphorus-doped carbon support according to the invention.
Adding 10mL of absolute ethanol into 1g of Ketjenblack ECP600JD, and then adding 25mL of 0.1 wt% phosphoric acid aqueous solution for impregnation for 24 h; drying in an oven at 100 ℃; then placing the tube furnace into a tube furnace, heating the tube furnace to 600 ℃ at the speed of 8 ℃/min, and carrying out constant temperature treatment for 3 h; and naturally cooling to obtain the phosphorus-doped carbon carrier, which is numbered as carbon carrier C.
Sample characterization and testing
The mass fraction of phosphorus analyzed by XPS is 0.2%; the oxygen mass fraction by XPS analysis was 9.5%; the specific surface area is 1315m2(ii)/g; resistivity of 1.32. omega. m.
Fig. 3 is an XPS spectrum of a phosphorus doped carbon support of example 3.
Example 4
This example illustrates the preparation of a phosphorus-doped carbon support according to the invention.
Adding 10mL of absolute ethanol into 1g of Ketjenblack ECP600JD, and then adding 25mL of 0.25wt% phosphoric acid aqueous solution for soaking for 24 h; drying in an oven at 100 ℃; then placing the tube furnace into a tube furnace, heating the tube furnace to 600 ℃ at the speed of 10 ℃/min, and carrying out constant temperature treatment for 3 h; and naturally cooling to obtain the phosphorus-doped carbon carrier, wherein the number of the phosphorus-doped carbon carrier is carbon carrier D.
Sample characterization and testing
The mass fraction of phosphorus analyzed by XPS was 0.9%; the oxygen mass fraction by XPS analysis was 10.2%; the specific surface area is 1309m2(ii)/g; resistivity of 1.32. omega. m.
Fig. 4 is an XPS spectrum of a phosphorus doped carbon support of example 4.
Example 5
This example illustrates the preparation of a platinum carbon catalyst according to the invention.
Dispersing a carbon carrier A into deionized water according to the proportion that 250mL of water is used for each gram of carbon carrier, adding 3.4mmol of chloroplatinic acid into each gram of carbon carrier, performing ultrasonic dispersion to form a suspension, and adding 1mol/L of sodium carbonate aqueous solution to enable the pH value of the system to be 10; heating the suspension to 80 ℃, adding formic acid to carry out reduction reaction while stirring, wherein the molar ratio of the formic acid to the chloroplatinic acid is 50:1, and continuously maintaining the reaction for 10 hours; and filtering the reacted mixture, washing the mixture by deionized water until the pH value of the filtrate is neutral, filtering the mixture, and drying the filtrate at 100 ℃ to obtain the platinum-carbon catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 39.9%.
XPS analyzed P for platinum carbon catalyst2pAmong the spectral peaks, there was no characteristic peak between 125 to 145 eV.
Fig. 5 is a plot of polarization (LSV) before and after 5000 cycles of the platinum-carbon catalyst of example 5.
Fig. 6 is a CV curve before and after 5000 cycles of the platinum-carbon catalyst of example 5.
The results of the platinum carbon catalyst performance tests are shown in table 1.
Example 6
This example illustrates the preparation of a platinum carbon catalyst.
A platinum carbon catalyst was prepared according to the method of example 5, except that: using the carbon support B prepared in example 2, 1.3mmol of chloroplatinic acid per gram of carbon support was added.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 20.1%.
Fig. 7 is an XPS spectrum of the platinum-carbon catalyst of example 6.
The results of the platinum carbon catalyst performance tests are shown in table 1.
Example 7
This example illustrates the preparation of a platinum carbon catalyst according to the invention.
Dispersing a carbon carrier C in deionized water according to the proportion that 250mL of water is used for each gram of carbon carrier, adding 12mmol of chloroplatinic acid into each gram of carbon carrier, performing ultrasonic dispersion to form a suspension, and adding 1mol/L of potassium hydroxide aqueous solution to adjust the pH value of the system to 10; heating the suspension to 80 ℃, adding sodium borohydride while stirring for reduction reaction, wherein the molar ratio of the reducing agent to the platinum precursor is 5:1, and maintaining the reaction for 12 hours; and filtering the reacted mixture, washing until the pH value of the solution is neutral, and drying at 100 ℃ to obtain the carbon-supported platinum catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 69.8%.
XPS analyzed P for platinum carbon catalyst2pAmong the spectral peaks, there was no characteristic peak between 125 to 145 eV.
The results of the platinum carbon catalyst performance tests are shown in table 1.
Example 8
This example illustrates the preparation of a platinum carbon catalyst.
A platinum carbon catalyst was prepared according to the method of example 7, except that: using the carbon support D prepared in example 4, 3.4mmol of chloroplatinic acid per gram of carbon support was added.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 40.1%.
XPS analyzed P for platinum carbon catalyst2pAmong the spectral peaks, there was no characteristic peak between 125 to 145 eV.
The results of the platinum carbon catalyst performance tests are shown in table 1.
Comparative example 1
A platinum carbon catalyst was prepared according to the method of example 5, except that: the carrier was Vulcan XC 72.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 40.0%.
The results of the platinum carbon catalyst performance tests are shown in table 1.
Comparative example 2
A platinum-carbon catalyst was produced and tested in the same manner as in example 7, except that: the carbon support was Ketjenblack ECP600JD, and was dispersed with 200mL water and 50mL ethanol per gram of carbon support when Pt was supported.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 69.7%.
The results of the platinum carbon catalyst performance tests are shown in table 1.
Comparative example 3
The platinum carbon catalyst was a commercial catalyst purchased under the designation HISPEC 4000.
Sample characterization and testing
The platinum mass fraction of the platinum-carbon catalyst was 40.2%.
The results of the platinum carbon catalyst performance tests are shown in table 1.
TABLE 1
Figure BDA0002652833600000191

Claims (21)

1. A method of preparing a platinum carbon catalyst comprising: (1) mixing a phosphorus source: mixing a carbon material with a phosphorus source to obtain a carbon material mixed with the phosphorus source; (2) a step of producing a phosphorus-doped carbon material: carrying out high-temperature treatment on the carbon material mixed with the phosphorus source in the step (1) in an inert atmosphere to obtain a phosphorus-doped carbon material; (3) and (3) loading platinum by using the phosphorus-doped carbon material obtained in the step (2) as a carrier.
2. The process according to claim 1, wherein in (2), the temperature of the high-temperature treatment is 300 ℃ to 800 ℃ and the treatment time is 0.5h to 10 h.
3. The method according to claim 1, wherein the phosphorus source is one or more selected from phosphoric acid, phosphates, pyrophosphates, polyphosphates, hydrogenphosphates, dihydrogenphosphates, phosphites and hypophosphites.
4. The method according to claim 1, wherein the mass ratio of the carbon material to the phosphorus source is 100:0.1 to 100:8 in terms of the mass of the phosphorus element contained.
5. The process according to claim 1, wherein the carbon material is a conductive carbon Black, preferably EC-300J, EC-600JD, ECP-600JD, VXC72, Black pearls2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXAXK 40B 2.
6. The production method according to claim 1, wherein the carbon material has an oxygen mass fraction of more than 4% in XPS analysis.
7. The production method according to claim 1, wherein the carbon material has a resistivity of <10 Ω -m.
8. The production method according to claim 1, wherein the carbon material has a specific surface area of 10m2/g～2000m2/g。
9. The method according to claim 1, wherein the step of supporting platinum comprises: (a) dispersing the phosphorus-doped carbon material obtained in the step (1) and a platinum precursor in a water phase, and adjusting the pH to 8-12; (b) adding a reducing agent for reduction; (c) separating out solid, and post-treating to obtain the platinum-carbon catalyst.
10. The method according to claim 9, wherein the platinum precursor is chloroplatinic acid, potassium chloroplatinate, or sodium chloroplatinate; the concentration of the platinum precursor is 0.5-5 mol/L.
11. The method according to claim 9, wherein in (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the molar ratio of the reducing agent to the platinum is 2-100; the reduction temperature is 50-150 ℃; the reduction time is 2-15 h.
12. A method of preparing a platinum carbon catalyst comprising: (1) mixing a phosphorus source: mixing and impregnating a carbon material with a phosphorus source aqueous solution to obtain a phosphorus source impregnated carbon material; (2) a step of producing a phosphorus-doped carbon material: carrying out high-temperature treatment on the carbon material impregnated with the phosphorus source in the step (1) in an inert atmosphere to obtain a phosphorus-doped carbon material; (3) loading platinum: and (3) loading platinum by using the phosphorus-doped carbon material obtained in the step (2) as a carrier.
13. A platinum carbon catalyst, characterised in that it is obtainable by a process according to any one of claims 1 to 12.
14. A platinum-carbon catalyst is characterized by comprising a carbon carrier and platinum metal loaded on the carbon carrier, wherein the carbon carrier is a phosphorus-doped carbon material.
15. Platinum-carbon catalyst according to claim 14, characterised in that P is analysed in its XPS2pAmong the spectral peaks, there was no characteristic peak between 125 to 145 eV.
16. Platinum-carbon catalyst according to claim 14, characterized in that the mass fraction of platinum is between 20% and 70%, preferably between 40% and 70%, based on the mass of the catalyst.
17. Platinum-carbon catalyst according to claim 14, characterized in that it has a resistivity <10 Ω -m.
18. A platinum carbon catalyst according to claim 14, characterised in that the carbon material is a conductive carbon Black, preferably EC-300J, EC-600JD, ECP600JD, VXC72, Black pearls2000, PRINTEX XE2-B, PRINTEX L6 or hilblaxk 40B 2.
19. A hydrogen fuel cell characterized in that the platinum-carbon catalyst of claim 13 or 14 is used in the anode and/or the cathode of the hydrogen fuel cell.
20. A carbon material characterized by P analyzed in its XPS2pAmong the peaks, there are two peaks at 125 to 145eV, which are respectively 133.3eV + -0.5 eV and 134.2eV + -0.5 eV.
21. The carbon material according to claim 20, wherein the carbon material is conductive carbon black.
CN202010876790.5A 2020-08-27 2020-08-27 Platinum-carbon catalyst and preparation method and application thereof Pending CN114122417A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010876790.5A CN114122417A (en) 2020-08-27 2020-08-27 Platinum-carbon catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010876790.5A CN114122417A (en) 2020-08-27 2020-08-27 Platinum-carbon catalyst and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN114122417A true CN114122417A (en) 2022-03-01

Family

ID=80374279

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010876790.5A Pending CN114122417A (en) 2020-08-27 2020-08-27 Platinum-carbon catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114122417A (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180272320A1 (en) * 2017-03-22 2018-09-27 Tda Research, Inc Nitrogen and phosphorous doped carbon supported nanoparticle platinum electrocatalyst and method of making

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180272320A1 (en) * 2017-03-22 2018-09-27 Tda Research, Inc Nitrogen and phosphorous doped carbon supported nanoparticle platinum electrocatalyst and method of making

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MEICHEN AN 等: "Phosphorus-doped graphene support to enhance electrocatalysis of methanol oxidation reaction on platinum nanoparticles", 《CHEMICAL PHYSICS LETTERS》 *
VIVIANE SANTOS PEREIRA 等: "PtRu Nanoparticles Supported on Phosphorous-Doped Carbon as Electrocatalysts for Methanol Electro-Oxidation", 《ELECTROCATALYSIS》 *
周丹 等: "磷掺杂碳材料的制备、表征及应用进展", 《工业催化》 *

Similar Documents

Publication Publication Date Title
CN114122426B (en) Platinum-carbon catalyst and preparation method and application thereof
CN114497600B (en) Nitrogen-phosphorus doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof
CN114497593B (en) Phosphorus-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof
CN114426267B (en) Carbon material, platinum-carbon catalyst, and preparation method and application thereof
CN114426268B (en) Sulfur-phosphorus doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof
CN114122428B (en) Platinum-carbon catalyst and preparation method and application thereof
CN114497595B (en) Nitrogen-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof
CN114479521B (en) Carbon material, platinum-carbon catalyst, and preparation method and application thereof
CN114122430B (en) Platinum-carbon catalyst and preparation method and application thereof
CN114122417A (en) Platinum-carbon catalyst and preparation method and application thereof
CN114497594B (en) Carbon-doped material, platinum-carbon catalyst, and preparation methods and applications thereof
CN114430049B (en) Platinum-carbon catalyst, carbon material, preparation method and application thereof
CN114430045B (en) Platinum-carbon catalyst and preparation method and application thereof
CN114122427B (en) Platinum-carbon catalyst and preparation method and application thereof
CN114430047B (en) Carbon material, platinum-carbon catalyst, and preparation method and application thereof
CN114477123B (en) Carbon-doped material, platinum-carbon catalyst, and preparation methods and applications thereof
CN114497599B (en) Sulfur-nitrogen-phosphorus-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof
CN114122429B (en) Application of nitrogen-doped carbon material as carbon carrier of platinum-carbon catalyst in hydrogen fuel cell
CN114497596B (en) Carbon material, platinum-carbon catalyst, and preparation method and application thereof
CN114497602B (en) Carbon material, platinum-carbon catalyst, and preparation method and application thereof
CN114426266B (en) Sulfur-nitrogen doped carbon material and preparation method and application thereof
CN114105122B (en) Sulfur-doped carbon material and preparation method and application thereof
CN114497598A (en) Sulfur-nitrogen-phosphorus doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof
CN114426273A (en) Preparation method of sulfur-phosphorus doped carbon material, product and application thereof
CN114477124A (en) Carbon material, platinum-carbon catalyst, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20220301