WO2022042640A1 - 碳载铂族金属催化剂及其制备方法和应用 - Google Patents

碳载铂族金属催化剂及其制备方法和应用 Download PDF

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WO2022042640A1
WO2022042640A1 PCT/CN2021/114752 CN2021114752W WO2022042640A1 WO 2022042640 A1 WO2022042640 A1 WO 2022042640A1 CN 2021114752 W CN2021114752 W CN 2021114752W WO 2022042640 A1 WO2022042640 A1 WO 2022042640A1
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carbon
platinum
nitrogen
group metal
platinum group
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PCT/CN2021/114752
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English (en)
French (fr)
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荣峻峰
赵红
谢南宏
张家康
彭茜
王厚朋
顾贤睿
张云阁
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中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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Priority claimed from CN202010877417.1A external-priority patent/CN114122430B/zh
Priority claimed from CN202010877409.7A external-priority patent/CN114122429B/zh
Priority claimed from CN202011012719.9A external-priority patent/CN114430045B/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司石油化工科学研究院 filed Critical 中国石油化工股份有限公司
Priority to KR1020237010563A priority Critical patent/KR20230058142A/ko
Priority to US18/043,310 priority patent/US20230369609A1/en
Priority to EP21860474.2A priority patent/EP4207394A1/en
Priority to JP2023513711A priority patent/JP2023539876A/ja
Publication of WO2022042640A1 publication Critical patent/WO2022042640A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8817—Treatment of supports before application 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
    • H01M4/9075—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
    • 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
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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

Definitions

  • the invention relates to a carbon-supported platinum group metal catalyst, a preparation method and application thereof, and in particular to a carbon-supported platinum group metal catalyst used in a proton membrane hydrogen fuel cell, and a preparation method and application thereof.
  • Oxygen reduction reaction is a key reaction in the field of electrochemistry, such as in fuel cells and metal-air batteries, the oxygen reduction reaction is a major factor affecting the performance of the cells.
  • Atom-doped carbon materials can be directly used as catalysts for oxygen reduction reactions.
  • carbon materials are doped with elements such as nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine, iodine, etc.
  • nitrogen is close to the atomic radius of carbon and easily enters the carbon lattice. , so it is the most commonly used doping element.
  • the most effective oxygen reduction catalysts are platinum-carbon catalysts, but there are still shortcomings.
  • platinum resources are scarce and expensive.
  • the dispersity of platinum metal in the currently used commercial platinum-carbon catalysts is not ideal and is prone to agglomeration and deactivation.
  • the dissolution and agglomeration of platinum in the cathode of hydrogen fuel cells cause the platinum surface area to decrease significantly over time, which affects the life of the fuel cell.
  • the existing technology mainly improves the performance of platinum-carbon catalysts by controlling the particle size, morphology, structure of platinum, and the specific surface area and pore structure of the carrier; there are also reports in the literature that the performance of platinum-carbon catalysts is improved by modifying the carbon carrier.
  • the carbon support can increase the specific surface area of the catalyst, reduce the agglomeration of metal particles, and improve the metal utilization rate.
  • Increasing the platinum loading of carbon supports is beneficial to the fabrication of thinner membrane electrodes with better performance, but greatly increasing the platinum loading is more likely to cause the accumulation of platinum metal particles, resulting in a sharp decrease in the utilization of active sites.
  • the platinum loading of a practical hydrogen fuel cell platinum-carbon catalyst is at least 20 wt%, which is much more difficult to manufacture than a chemical platinum-carbon catalyst (platinum loading is less than 5 wt%).
  • platinum-carbon catalyst deactivation caused by carbon corrosion in proton exchange membrane fuel cells has attracted a lot of attention in the art.
  • platinum also accelerates the carbon corrosion rate.
  • more defect sites on the carbon support are beneficial to increase the platinum loading, but at the same time aggravate carbon corrosion.
  • increasing the degree of graphitization can alleviate carbon corrosion, but it also makes the surface of the carbon support chemically inert, making it difficult to uniformly disperse platinum on the carbon support.
  • the first object of the present invention is to provide a carbon-supported platinum group metal catalyst, which can significantly improve the mass specific activity and electrochemical area; especially in the case of high platinum loading.
  • the second object of the present invention is to improve the comprehensive performance of the catalyst on the basis of the aforementioned objects, especially to improve the mass specific activity and the stability of the electrochemical area.
  • the third object of the invention is to improve the carbon corrosion resistance of the carbon-supported platinum group metal catalyst on the basis of the aforementioned object.
  • a carbon-supported platinum group metal catalyst characterized in that, in the N 1s spectrum peak of the XPS analysis of the carbon-supported platinum group metal catalyst, there is a characteristic peak between 399ev ⁇ 400.5ev, and between 395ev ⁇ 405ev There is no or basically no other characteristic peaks;
  • the carrier of the carbon-supported platinum group metal catalyst is conductive carbon black doped with nitrogen;
  • the platinum mass fraction of the carbon-supported platinum group metal catalyst is 20% to 70%, preferably 40% to 70%, for example, 45% to 65%.
  • the carbon-supported platinum group metal catalyst according to aspect 1 is characterized in that, in the S 2P spectrum peaks of its XPS analysis, the characteristic peak area between 160ev ⁇ 170ev and between 163ev ⁇ 166ev is greater than 92% , or more than 95%, or more than 98%, or only the characteristic peaks located between 163ev and 166ev.
  • platinum group metal is selected from platinum (pt), palladium (Pd), rhodium (Rh), iridium (Ir), osmium (Os) , and ruthenium (Ru), preferably selected from platinum, palladium, rhodium and iridium, also preferably selected from platinum and palladium, eg platinum.
  • a hydrogen fuel cell wherein the carbon-supported platinum group metal catalyst according to any one of aspects 1 to 11 is used in the anode and/or the cathode of the hydrogen fuel cell.
  • a carbon material characterized in that the carbon material is nitrogen-doped conductive carbon black, and in the N 1s spectral peaks of its XPS analysis, except for characteristic peaks between 399ev and 400.5ev, the peaks are between 395ev and 405ev. There are no other characteristic peaks in between.
  • the step of impregnating the nitrogen source mixing the carbon material with the nitrogen source aqueous solution (wherein, optionally adding a small amount of ethanol as needed, such as dispersing the carbon material in a 20% ethanol aqueous solution), impregnating to obtain a nitrogen impregnated solution source of carbon material;
  • the step of manufacturing the nitrogen-doped carbon material the carbon material impregnated with the nitrogen source obtained in the step (1) is heated to 1000°C to 1500°C at a rate of 8°C/min to 15°C/min in an inert gas, then constant temperature treatment for 0.5h ⁇ 10h to obtain a carbon material doped with nitrogen; and
  • step (3) the step of supporting platinum group metals: the step of supporting platinum group metals by using the nitrogen-doped carbon material obtained in step (2) as a carrier;
  • the carbon material is preferably conductive carbon black.
  • step of loading platinum group metals comprises:
  • step (2) (a) dispersing the nitrogen-doped carbon material obtained in step (2) and the platinum group metal precursor in an aqueous phase, and adjusting the pH to 8-12;
  • the platinum group metal precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum group metal precursor is 0.5 mol/ L ⁇ 5mol/L.
  • step (b) the reducing agent is selected from citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride and glycerol; the molar ratio of the reducing agent to platinum is 2 to 100; the reduction temperature is 50°C to 150°C; and the reduction time is 2h to 15h.
  • characteristic peaks between 163ev and 166ev are characteristic peaks of thiophene-type sulfur.
  • the characteristic peaks of the thiophene-type sulfur are believed to be bimodal.
  • the research of the present invention finds that when the conductive carbon black is doped, a carbon material with unique properties can be produced by controlling the bonding mode of the heteroatom and the conductive carbon black and the interaction between the heteroatoms, so that the mass specific activity and electrical conductivity can be significantly improved.
  • Chemical area improve the comprehensive performance of the catalyst, improve the mass specific activity and the stability of the electrochemical area, and improve the carbon corrosion resistance of the carbon-supported platinum group metal catalyst.
  • the present invention can achieve the following beneficial technical effects.
  • the present invention uses a simple method to manufacture a type of conductive carbon black with unique properties doped with atoms on the surface.
  • the sulfur doped on the surface of the conductive carbon black only exists in the form of thiophene-type sulfur
  • the surface-doped nitrogen can exist only in the form of pyrrolic nitrogen, and these features can significantly improve the mass specific activity and electrochemical area of carbon-supported PGM catalysts.
  • the surface of the conductive carbon black can be doped with phosphorus and/or boron, the phosphorus doped on the surface can only have characteristic peaks between 132.5ev and 134.5ev, and the boron doped on the surface can only have a peak between 189ev and 191ev.
  • the surface of the conductive carbon black can be doped with various (for example, three or four) heteroelements, which is beneficial to improve the carbon corrosion resistance of the carbon-supported platinum group metal catalyst.
  • the doped conductive carbon black of the present invention is suitable for making carbon-supported platinum group metal catalysts with high platinum loading, and still has excellent comprehensive catalytic performance and carbon corrosion resistance when the loading of platinum group metals is as high as 70 wt%.
  • the amount of platinum supported by carbon-supported platinum group metal catalysts in practical hydrogen fuel cells is generally above 20 wt%, and it is very difficult to manufacture catalysts with high platinum group metal content with excellent performance.
  • the chemical reduction method has a simple process, but the utilization rate of platinum group metals is low and the catalytic activity is low.
  • using the doped conductive carbon black produced by the present invention as a carrier and using the chemical reduction method in the aqueous phase a catalyst with high platinum loading with excellent mass specific activity and stability can be easily produced.
  • the present invention provides the following exemplary embodiments, or combinations thereof:
  • a platinum-carbon catalyst characterized in that, in the N 1s spectrum peaks analyzed by XPS, there are no other characteristic peaks between 395ev and 405ev except for characteristic peaks between 399ev and 400.5ev.
  • the platinum-carbon catalyst according to Embodiment 1 characterized in that, based on the mass of the catalyst, the mass fraction of platinum is 20%-70%, preferably 40%-70%.
  • a method for preparing a platinum-carbon catalyst comprising: (1) a step of impregnating a nitrogen source: mixing a carbon material with an aqueous nitrogen source solution, and impregnating it to obtain a carbon material impregnated with a nitrogen source; (2) manufacturing nitrogen-doped carbon Material steps: the carbon material impregnated with a nitrogen source obtained in (1) is heated to 1000°C to 1500°C at a rate of 8°C/min to 15°C/min in an inert gas, and then treated at a constant temperature for 0.5h to 10h , to obtain a nitrogen-doped carbon material; (3) the step of loading platinum: the step of loading platinum with the nitrogen-doped carbon material obtained in (2) as a carrier.
  • step of loading platinum comprises: (a) dispersing the nitrogen-doped carbon material obtained in (2) and the platinum precursor in an aqueous phase, The pH is adjusted to 8-12; (b) reducing agent is added for reduction; (c) solid is separated, and the platinum-carbon catalyst is obtained after post-treatment.
  • the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5 mol/L ⁇ 5mol/L.
  • the reducing agent is citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, and sodium borohydride Or one or more of glycerol; the molar ratio of the reducing agent to platinum is 2 to 100; the reduction temperature is 50°C to 150°C; the reduction time is 2h to 15h.
  • a platinum-carbon catalyst characterized in that the catalyst is prepared by any one of the methods exemplified in Embodiments 6 to 17.
  • a hydrogen fuel cell wherein the anode and/or the cathode of the hydrogen fuel cell uses any one of the platinum-carbon catalysts in the exemplified embodiments 1 to 5 and 18.
  • a platinum-carbon catalyst characterized in that it comprises a carbon support and platinum metal loaded thereon, wherein the carbon support is a sulfur-nitrogen doped carbon material; in the S 2P spectrum peak of the XPS analysis of the catalyst, in Between 160ev and 170ev, there are only characteristic peaks between 163ev and 166ev.
  • the platinum-carbon catalyst according to exemplified embodiment 1 characterized in that, in the N 1s spectrum peaks of the XPS analysis of the catalyst, except for a characteristic peak between 399ev and 400.5ev, there is no peak between 390ev and 410ev. other characteristic peaks.
  • a method for preparing a platinum-carbon catalyst comprising: (1) a step of manufacturing a sulfur-nitrogen-doped carbon material; and (2) a step of supporting platinum with the sulfur-nitrogen-doped carbon material obtained in the step (1) as a carrier ;
  • step (1) includes the operation of doping sulfur and the operation of doping nitrogen
  • the operation of doping sulfur includes: placing the carbon material in an inert gas containing thiophene, and treating it at 1000° C. ⁇ 1500° C. for 0.5 h ⁇ 10 h;
  • the nitrogen doping operation is performed before, after or simultaneously with the sulfur doping operation.
  • the reducing agent is citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, and sodium borohydride Or one or more of glycerol; the molar ratio of the reducing agent to platinum is 2 to 100; the reduction temperature is 60°C to 90°C; and the reduction time is 4h to 15h.
  • a preparation method of a platinum-carbon catalyst comprising:
  • the step of impregnating the nitrogen source the carbon material is mixed with the nitrogen source aqueous solution, and impregnated to obtain the carbon material impregnated with the nitrogen source;
  • step (3) the step of using the sulfur-nitrogen-doped carbon material obtained in step (2) as a carrier to support platinum.
  • a platinum-carbon catalyst characterized in that it is prepared by any one of the methods exemplified in Embodiments 6 to 15.
  • a hydrogen fuel cell wherein the anode and/or the cathode of the hydrogen fuel cell uses any one of the platinum-carbon catalysts in Exemplary Embodiments 1 to 5 and 16.
  • a nitrogen-doped carbon material in the N 1s spectral peaks analyzed by XPS, except for characteristic peaks between 399ev and 400.5ev, there are no other characteristic peaks between 395ev and 405ev.
  • a carbon support for platinum-carbon catalyst characterized in that the carbon support is nitrogen-doped conductive carbon black, and in the N 1s spectrum peaks of XPS analysis, except for characteristic peaks between 399ev and 400.5ev , there are no other characteristic peaks between 395ev ⁇ 405ev; in XPS analysis, the oxygen mass fraction is 4% ⁇ 15%, the nitrogen mass fraction is 0.2% ⁇ 5%; its specific surface area is 200m 2 /g ⁇ 2000m 2 /g .
  • a method for preparing a nitrogen-doped carbon material comprising:
  • the step of impregnating the nitrogen source the carbon material is mixed with the nitrogen source aqueous solution, and impregnated to obtain the carbon material impregnated with the nitrogen source;
  • a fuel cell wherein the nitrogen-doped carbon material or the carbon carrier according to any one of Embodiments 1 to 9 is used in the fuel cell.
  • a metal-air battery characterized in that the nitrogen-doped carbon material or carbon support described in any one of Embodiments 1 to 9 is used in the metal-air battery.
  • Figure I-1 is the XPS spectrum of the nitrogen-doped carbon support of Example 1.
  • Figure I-2 is the XPS spectrum of the nitrogen-doped carbon support of Example 3.
  • Figure I-3 is the XPS spectrum of the platinum-carbon catalyst of Example 5.
  • Figure I-4 is the polarization curve of the platinum-carbon catalyst of Example 5 before and after 5000 cycles.
  • Figures I-5 are the XPS spectra of the platinum-carbon catalyst of Example 6.
  • Figures I-6 are XPS spectra of the platinum-carbon catalyst of Example 7.
  • Figures I-7 are XPS spectra of the platinum-carbon catalyst of Example 8.
  • Figure I-8 is the polarization curve of the platinum-carbon catalyst of Comparative Example 3 before and after 5000 cycles.
  • Figure II-1 is an XPS spectrum of sulfur of the sulfur-nitrogen-doped carbon material of Example II-1.
  • Figure II-2 is an XPS spectrum of nitrogen of the sulfur-nitrogen-doped carbon material of Example II-1.
  • Figure II-3 is an XPS spectrum of sulfur of the sulfur-nitrogen-doped carbon material of Example II-2.
  • Figure II-4 is an XPS spectrum of sulfur of the sulfur-nitrogen-doped carbon material of Example II-3.
  • Figure II-5 is an XPS spectrum of sulfur of the sulfur-nitrogen-doped carbon material of Example II-4.
  • Figure II-6 is a TEM image of the platinum-carbon catalyst of Example II-5.
  • Figure II-7 is the polarization curve of the platinum-carbon catalyst of Example II-5.
  • Figure II-8 is the XPS spectrum of sulfur of the platinum-carbon catalyst of Example II-5.
  • Figure II-9 is an XPS spectrum of nitrogen of the platinum-carbon catalyst of Example II-5.
  • Figure II-10 is the XPS spectrum of sulfur of the platinum-carbon catalyst of Example II-7.
  • Figure II-11 is the XPS spectrum of nitrogen of the platinum-carbon catalyst of Example II-7.
  • Figure II-12 is an XPS spectrum of sulfur of the sulfur-nitrogen-doped carbon material of Comparative Example II-1.
  • Figure II-13 is a TEM image of the platinum-carbon catalyst of Comparative Example II-1.
  • Figure II-14 is the polarization curve of the platinum-carbon catalyst of Comparative Example II-1.
  • Figure II-15 is an XPS spectrum of sulfur of the sulfur-nitrogen-doped carbon material of Comparative Example II-2.
  • Figure II-16 is the polarization curve of the platinum-carbon catalyst of Comparative Example II-3.
  • any matters or matters that are not mentioned are directly applicable to those known in the art without any change, except for those explicitly stated.
  • any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are regarded as part of the original disclosure or record of the present invention, and should not be It is regarded as new content not disclosed or expected herein, unless those skilled in the art consider that the combination is obviously unreasonable.
  • the "doping element" in the present invention includes nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine, or is selected from these elements.
  • a material "doped with" an element means that the one or more elements specifically mentioned are doped into the material, but the material can also be doped with the one or more specifically mentioned elements. Elements other than the various elements, especially those commonly used in the art.
  • a material "doped" with an element means that the one or more elements specifically mentioned are doped into the material; wherein in one embodiment, the material may also be doped with a specific other elements than the one or more elements mentioned; and preferably, the material is free of other doping elements than the one or more elements specifically mentioned. .
  • carbon material containing doping elements In the present invention, except that it can be uniquely defined as "carbon material containing doping elements" according to the context or self-definition, other "carbon materials” mentioned refer to carbon materials that do not contain doping elements. The same is true for the subordinate concept of carbon materials.
  • carbon black and “carbon black” are interchangeable technical terms.
  • the graphene, carbon nanotubes and conductive carbon black that can be used for the carbon material of the present invention respectively have concepts well known in the art, and belong to different concepts from each other.
  • a carbon material may contain a lower content of one or more other carbon materials, as long as it still belongs to the type of carbon material recognized by those skilled in the art.
  • “graphene” may contain trace amounts (eg, less than 1%, or less than 0.1% by weight) of conductive carbon black and/or carbon nanotubes for various reasons.
  • the conductive carbon black comprises less than 5% by weight, preferably less than 2% by weight of graphene and/or carbon nanotubes.
  • in the present invention refers to a gas that does not cause any appreciable effect on the properties of the doped carbon material in the preparation method of the present invention. The same is true for the subordinate concept of carbon materials.
  • Numerical ranges defined herein include the endpoints of the numerical ranges.
  • a "range” disclosed herein is given in the form of lower and upper limits, eg, one or more lower limits and one or more upper limits.
  • a given range can be defined by selecting a lower limit and an upper limit that define the boundaries of the given range. All ranges defined in this manner are inclusive and combinable, ie any lower limit can be combined with any upper limit to form a range.
  • ranges of 60-110 and 80-120 are listed for certain parameters, with the understanding that ranges of 60-120 and 80-110 are also contemplated.
  • the lower limits are listed as 1 and 2 and the upper limits are listed as 3, 4 and 5, the following ranges are contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.
  • pore volume refers to the total pore volume of single-point adsorption when P/P 0 is the maximum.
  • characteristic peaks between 395ev and 405ev means that except for characteristic peaks between 399ev and 400.5ev (such as characteristic peaks of preferably pyrrole nitrogen), the peak area of any other characteristic peak is less than 10%, preferably less than 5%.
  • Embodiment I of the present invention provides a carbon-supported platinum group metal catalyst, in the N 1s spectrum peaks of XPS analysis, except for characteristic peaks between 399ev and 400.5ev, there are no other characteristics between 395ev and 405ev. peak.
  • the carbon-supported platinum group metal catalyst according to the present invention contains no doping elements other than nitrogen.
  • the platinum group metal is platinum
  • the carbon-supported platinum group metal catalyst according to the present invention does not contain other metal elements other than platinum.
  • the mass fraction of platinum is 0.1%-80%, preferably 20%-70%, more preferably 40% to 70%.
  • the resistivity of the carbon-supported platinum group metal catalyst according to the present invention is ⁇ 10.0 ⁇ m, preferably ⁇ 2 ⁇ m.
  • the carbon-supported platinum group metal catalyst according to the present invention has a specific surface of 80 m 2 /g to 1500 m 2 /g, preferably 100 m 2 /g to 200 m 2 /g.
  • the support of the carbon-supported platinum group metal catalyst according to the present invention is nitrogen-doped conductive carbon black, nitrogen-doped graphene or nitrogen-doped carbon nanotubes.
  • the conductive carbon black may be Ketjen black (Ketjen black) series superconducting carbon black, Cabot series conductive carbon black and Evonik One or more of the series of conductive carbon blacks produced by Degussa; preferably Ketjen black EC-300J, Ketjen black EC-600JD, Ketjen black ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
  • Ketjen black Ketjen black
  • Embodiment 1 of the present invention also provides a preparation method of a carbon-supported platinum group metal catalyst, comprising:
  • the step of impregnating the nitrogen source the carbon material is mixed with the nitrogen source aqueous solution, and impregnated to obtain the carbon material impregnated with the nitrogen source;
  • step (2) The step of manufacturing nitrogen-doped carbon material: the carbon material impregnated with nitrogen source obtained in step (1) is heated to 1000°C ⁇ 1500°C at a rate of 8°C/min ⁇ 15°C/min in an inert gas °C, and then constant temperature treatment for 0.5h ⁇ 10h to obtain nitrogen-doped carbon material;
  • Step of supporting platinum group metal eg platinum: the step of supporting platinum group metal (eg platinum) by using the nitrogen-doped carbon material obtained in step (2) as a carrier.
  • the temperature of the constant temperature treatment may be 1000°C to 1500°C, preferably 1150°C to 1450°C; the treatment time may be 0.5h to 10h, preferably 1h to 5h, more preferably 2h to 4h.
  • the nitrogen source can be ammonia water/or urea.
  • the mass of the nitrogen source is calculated by the mass of the nitrogen-containing element, and the mass ratio of the carbon material to the nitrogen source is 30:1 to 1:2; preferably It is 25:1 ⁇ 1:1.5.
  • the carbon material may be conductive carbon black, graphene or carbon nanotubes.
  • the conductive carbon black can be ordinary conductive carbon black (Conductive Blacks), superconductive carbon black (Super Conductive Blacks) or extra conductive carbon black (Extra Conductive Blacks) Blacks), for example, the conductive carbon black can be one or more of Ketjen black (Ketjen black) series superconducting carbon black, Cabot series conductive carbon black and series conductive carbon black produced by Evonik Degussa; Preferably Ketjen black EC-300J, Ketjen black EC-600JD, Ketjen black ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
  • the preparation method and source of the conductive carbon black are not limited.
  • the conductive carbon black can be acetylene black, furnace carbon black and the like.
  • the ID/ IG value of the conductive carbon black is generally 0.8-5 , preferably 1-4.
  • the peak located near 1320 cm -1 is the D peak
  • the peak located near 1580 cm -1 is the G peak
  • ID represents the intensity of the D peak
  • IG represents the intensity of the G peak.
  • the graphene or carbon nanotubes may be either unoxidized graphene or carbon nanotubes, or oxidized graphite. alkene or carbon nanotubes.
  • the oxygen mass fraction is greater than 4%, preferably 4% to 15%.
  • the resistivity of the carbon material is ⁇ 10 ⁇ m, preferably ⁇ 5 ⁇ m, more preferably ⁇ 2 ⁇ m.
  • the carbon material in step (1) has a specific surface area of 10m 2 /g ⁇ 2000m 2 /g, and a pore volume of 0.2mL/g ⁇ 6.0mL /g.
  • the carbon material is mixed with a nitrogen source aqueous solution, impregnated (generally 12h ⁇ 72h) and then dried ( Generally 70 °C ⁇ 120 °C), and then placed in a tube furnace, heating the tube furnace (the heating rate can be 8 °C / min ⁇ 15 °C /min), and then at a high temperature (1000 °C ⁇ 1500 °C, preferably 1150 °C ⁇ 1450°C) for a period of time (may be 0.5h ⁇ 10h, generally 1h ⁇ 5h), then the nitrogen-doped carbon material can be obtained.
  • a nitrogen source aqueous solution generally 12h ⁇ 72h
  • the heating rate can be 8 °C / min ⁇ 15 °C /min
  • a high temperature 1000 °C ⁇ 1500 °C, preferably 1150 °C ⁇ 1450°C
  • a period of time may be 0.5h ⁇ 10h, generally 1h ⁇ 5h
  • the nitrogen-doped carbon material prepared in step (2) can be easily dispersed in the water phase.
  • some carbon materials such as Ketjen Black, it is difficult to directly disperse in the water phase.
  • the step of supporting the platinum group metal comprises:
  • step (2) Disperse the nitrogen-doped carbon material obtained in step (2) and a platinum group metal precursor (eg, platinum precursor) in an aqueous phase, and adjust the pH to 8-12 (preferably adjust the pH to 10 ⁇ 0.5) ;
  • a platinum group metal precursor eg, platinum precursor
  • the platinum group metal precursor eg, platinum precursor
  • the platinum group metal precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the platinum group metal
  • the concentration of the precursor is 0.5 mol/L to 5 mol/L.
  • step (a) the pH value of the aqueous phase is adjusted with sodium carbonate aqueous solution, potassium carbonate aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution or ammonia water.
  • the reducing agent is citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, hydrogen borohydride One or more of sodium or glycerol.
  • step (b) the molar ratio of the reducing agent to platinum is 2-100.
  • the reduction temperature is 50°C to 150°C, preferably 60°C to 90°C; the reduction time is 4h to 15h, preferably 8h ⁇ 12h.
  • the post-treatment includes: washing, filtering and drying.
  • Embodiment I of the present invention also provides a carbon-supported platinum group metal catalyst, which is prepared by the method of any of the foregoing embodiments of the present invention.
  • Embodiment I of the present invention also provides a hydrogen fuel cell, in which the anode and/or the cathode of the hydrogen fuel cell uses the carbon-supported platinum group metal catalyst in any of the foregoing embodiments of the present invention.
  • the present invention adopts a simple method to dope nitrogen on the surface of carbon material in the form of pyrrole nitrogen, thereby producing a platinum-carbon electrode catalyst for hydrogen fuel cell anode oxidation reaction or cathode oxygen reduction reaction, with the same carbon material and platinum loading amount Compared with other catalysts, it has a higher half-wave potential, especially the ECSA and mass specific activity of the catalyst and its stability are significantly improved.
  • the carbon-supported platinum group metal catalyst (eg, platinum-carbon catalyst) according to the present invention, when used in an oxygen reduction reaction, in some embodiments, has an ECSA > 55 m 2 g -1 -Pt, such as At 55m 2 g -1 -Pt to 140m 2 g -1 -Pt.
  • the mass specific activity decrease rate is ⁇ 10% after 5000 cycles .
  • the half-wave potential is >0.88V, such as 0.88V ⁇ 0.92V.
  • the carbon-supported platinum group metal catalyst (eg, platinum-carbon catalyst) according to the present invention, when used in an oxygen reduction reaction, in some embodiments, has a mass specific activity > 0.11 A mg -1 -Pt , such as 0.11A mg -1 -Pt to 0.44A mg -1 -Pt.
  • the carbon-supported platinum group metal catalyst of the present invention is a platinum-carbon catalyst.
  • Embodiment II of the present invention provides a carbon-supported platinum group metal catalyst, which comprises a carbon support and platinum metal supported thereon, wherein the carbon support is a sulfur-nitrogen-doped carbon material; the XPS analysis of the catalyst shows Among the peaks of S 2P spectrum, there are only characteristic peaks between 163ev and 166ev between 160ev and 170ev.
  • the carbon-supported platinum group metal catalyst eg, platinum carbon catalyst
  • the carbon-supported platinum group metal catalyst is free of other doping elements other than sulfur and nitrogen.
  • the platinum group metal is platinum
  • the carbon-supported platinum group metal catalyst eg, platinum-carbon catalyst
  • Embodiment II there are no characteristic peaks between 166ev and 170ev in XPS analysis of a carbon-supported platinum group metal catalyst (eg, platinum-carbon catalyst) according to the present invention.
  • a carbon-supported platinum group metal catalyst eg, platinum-carbon catalyst
  • Embodiment II there are one or two characteristic peaks between 399ev and 400.5ev in the N 1s spectrum peak of the XPS analysis of the carbon-supported platinum group metal catalyst (eg, platinum-carbon catalyst) according to the present invention .
  • the carbon-supported platinum group metal catalyst eg, platinum-carbon catalyst
  • the mass fraction of platinum is 0.1% to 80%, preferably 20% ⁇ 70%, more preferably 40% to 70%.
  • the resistivity of the carbon-supported platinum group metal catalyst (eg, platinum carbon catalyst) according to the present invention is ⁇ 10.0 ⁇ m, preferably ⁇ 2.0 ⁇ m.
  • the specific surface area of the carbon-supported platinum group metal catalyst (eg, platinum-carbon catalyst) according to the present invention is 80 m 2 /g to 1500 m 2 /g, preferably 100 m 2 /g to 200 m 2 /g .
  • the sulfur-nitrogen-doped carbon material is sulfur-nitrogen-doped conductive carbon black, sulfur-nitrogen-doped graphite alkene or sulfur nitrogen doped carbon nanotubes.
  • the conductive carbon black can be one or more of Ketjen black (Ketjen black) series superconducting carbon black, Cabot series conductive carbon black and series conductive carbon black produced by Evonik Degussa; preferably EC- 300J, EC-600JD, ECP-600JD, VXC72, Black pearls 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
  • the graphene or carbon nanotube can be oxidized or unoxidized graphene or carbon nanotube.
  • the characteristic peak between 163ev and 166ev is a doublet, and in some Examples II-, The double peaks are located at 163.4 ⁇ 0.5ev and 164.7 ⁇ 0.5ev, respectively.
  • the mass of sulfur is 0.2% to 3%, and the mass fraction of nitrogen is 0.1% to 5%.
  • Embodiment II of the present invention also provides a preparation method of a carbon-supported platinum group metal catalyst (such as a platinum-carbon catalyst), comprising:
  • step (1) includes the operation of doping sulfur and the operation of doping nitrogen
  • the operation of doping sulfur includes: placing the carbon material in an inert gas containing thiophene, and treating it at 1000°C-1500°C (preferably constant temperature treatment) for 0.5h-10h;
  • the nitrogen doping operation is performed before, after or simultaneously with the sulfur doping operation.
  • the heating rate is not lower than 8°C/min, and may be 8°C/min ⁇ 15°C/min. min.
  • the operation of doping nitrogen when the operation of doping nitrogen is performed before or after the operation of doping sulfur, it can adopt any known doping nitrogen Methods.
  • the carbon material when the operation of doping nitrogen is performed before the operation of doping sulfur, the carbon material is mixed with a nitrogen source, and treated in an inert gas at 300° C. to 1500° C. (preferably constant temperature treatment) for 0.5 h ⁇ 10h.
  • the sulfur-doped carbon material is mixed with a nitrogen source, and treated in an inert gas at 300° C. to 1500° C. (preferably Constant temperature treatment) 0.5h ⁇ 10h.
  • the operating conditions of doping with sulfur are adopted.
  • the carbon material is first mixed with the nitrogen source, and then the carbon material is simultaneously subjected to nitrogen doping and sulfur doping operations under the operating conditions of sulfur doping.
  • the mass of thiophene is calculated as the mass of sulfur, and the mass ratio of the carbon material to thiophene is 20:1-2:1; preferably 10:1-4 : 1, more preferably 8:1 to 4:1.
  • the temperature is preferably 1100°C to 1400°C, more preferably 1200°C to 1400°C.
  • the treatment time is independently 1h-5h, preferably 2h-4h.
  • the mass ratio of the carbon material to the nitrogen source is 30:1 to 1:2 in terms of the mass of the nitrogen source based on the mass of the nitrogen it contains; preferably It is 25:1 ⁇ 1:1.5.
  • the sulfur-nitrogen-doped carbon material described in step (1) in the S 2P spectrum peak of its XPS analysis, is between 160ev and 170ev, There are only characteristic peaks between 163ev and 166ev.
  • the sulfur-nitrogen-doped carbon material described in step (1) has a characteristic peak between 163ev and 166ev, which is a double peak.
  • the double peaks are at 163.7 ⁇ 0.5ev and 165.0 ⁇ 0.5ev, respectively.
  • the carbon material is conductive carbon black, graphene or carbon nanotube.
  • the conductive carbon black can be ordinary conductive carbon black (Conductive Blacks), superconductive carbon black (Super Conductive Blacks) or extra conductive carbon black (Extra Conductive Blacks), such as the conductive carbon black can be Ketjen black (Ketjen black).
  • the graphene or carbon nanotubes can be either unoxidized graphene or carbon nanotubes, or oxidized graphene or carbon nanotubes.
  • the preparation method and source of the conductive carbon black are not limited.
  • the conductive carbon black can be acetylene black, furnace carbon black and the like.
  • the ID/ IG value of the carbon material is generally 0.8-5 , preferably 1-4.
  • the peak located near 1320 cm -1 is the D peak
  • the peak located near 1580 cm -1 is the G peak
  • ID represents the intensity of the D peak
  • IG represents the intensity of the G peak.
  • the resistivity of the carbon material may be ⁇ 10.0 ⁇ m, preferably ⁇ 5.0 ⁇ m, more preferably ⁇ 2.0 ⁇ m.
  • the oxygen mass fraction is greater than 2%, which may be 2%-15%, preferably 2.5%-12%.
  • the specific surface area and pore volume of the carbon material can be varied within a wide range.
  • the specific surface area is 10 m 2 /g to 2000 m 2 /g
  • the pore volume is 0.02 mL/g to 6 mL/g.
  • the carbon material in step (1) is conductive carbon black, and its specific surface area is 200m 2 /g ⁇ 2000m 2 /g.
  • the inert gas may be nitrogen or argon.
  • the carbon material is placed in a tube furnace, and a carrier gas containing thiophene is passed into it, and the temperature is 8 °C/
  • the tube furnace is heated to 1000°C ⁇ 1500°C at a rate of min ⁇ 15°C/min, and then treated at a constant temperature for 0.5h ⁇ 10h.
  • the carrier gas can be nitrogen or argon.
  • the volume fraction of thiophene may be 0.1% to 5.0%.
  • the step of supporting a platinum group metal includes:
  • step (1) Disperse the sulfur-nitrogen-doped carbon material obtained in step (1) and a platinum group metal precursor (such as a platinum precursor) in an aqueous phase, and adjust the pH to 8-12 (preferably adjust the pH to 10 ⁇ 0.5 );
  • a platinum group metal precursor such as a platinum precursor
  • the platinum group metal precursor eg, platinum precursor
  • the platinum group metal precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate ;
  • the concentration of the platinum group metal precursor is 0.5 mol/L to 5 mol/L.
  • step (a) the pH value of the aqueous phase is adjusted with sodium carbonate aqueous solution, potassium carbonate aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution or ammonia water.
  • the reducing agent is citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, hydrogen borohydride One or more of sodium or glycerol.
  • step (b) the molar ratio of the reducing agent to platinum is 2-100.
  • the reduction temperature is 50°C to 150°C, preferably 60°C to 90°C; the reduction time is 4h to 15h, preferably 8h ⁇ 12h.
  • the sulfur-nitrogen-doped carbon material prepared in step (1) can be easily dispersed in the water phase.
  • some carbon materials, such as Ketjen Black it is difficult to directly disperse them in the water phase.
  • the post-treatment includes: washing, filtering and drying.
  • Embodiment II of the present invention also provides a preparation method of a carbon-supported platinum group metal catalyst (such as a platinum-carbon catalyst), comprising:
  • the step of impregnating the nitrogen source the carbon material is mixed with the nitrogen source aqueous solution, and impregnated to obtain the carbon material impregnated with the nitrogen source;
  • the step of manufacturing the sulfur-nitrogen-doped carbon material the carbon material impregnated with the nitrogen source obtained in the step (1) is placed in an inert gas containing thiophene, and treated at 1000°C to 1500°C (preferably constant temperature treatment) for 0.5 h ⁇ 10h, the sulfur-nitrogen doped carbon material is obtained;
  • step (1) the carbon material impregnated with the nitrogen source in step (1) is first dried, and then step (2) is performed.
  • the carbon-supported platinum-group metal catalyst (eg, platinum-carbon catalyst) described in this embodiment is prepared by the preparation method of the carbon-supported platinum-group-metal catalyst (eg, platinum-carbon catalyst).
  • Embodiment II of the present invention also provides a hydrogen fuel cell, wherein the anode and/or the cathode of the hydrogen fuel cell uses the carbon-supported platinum group metal catalyst of any of the foregoing embodiments II of the present invention.
  • the mass specific activity decrease rate is ⁇ 10% after 5000 cycles.
  • the carbon-supported platinum group metal catalysts (eg, platinum-carbon catalysts) of the present invention when used in oxygen reduction reactions, have ECSA > 68.93 m 2 g -1 -Pt in some embodiments II- , for example, in 60.0m 2 g -1 -Pt ⁇ 100.0m 2 g -1 -Pt.
  • the half-wave potential is >0.890V, such as 0.89V ⁇ 0.91V.
  • the mass specific activity is >0.15A mg -1 - Pt, such as 0.15A mg -1 -Pt to 0.35A mg -1 -Pt.
  • the existing carbon-supported platinum group metal catalysts for hydrogen fuel cells have the shortcomings of low mass specific activity and poor stability.
  • the mass specific activity and stability of the supported platinum group metal catalyst, especially the mass specific activity and stability of the carbon-supported platinum group metal catalyst with a high platinum loading amount are improved.
  • the carbon-supported platinum group metal catalyst of the present invention is a platinum-carbon catalyst.
  • the reagents used in the present invention are all analytically pure, and all reagents used are commercially available.
  • the present invention detects elements on the surface of the material by means of X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the X-ray photoelectron spectrometer used is ESCALab220i-XL ray electron spectrometer equipped with Avantage V5.926 software produced by VG Scientific.
  • the power is 330W
  • the basic vacuum is 3 ⁇ 10 -9 mbar during the analysis and test.
  • the electron binding energy was corrected by the C1s peak (284.3 eV) of elemental carbon, and the late-stage peak-splitting processing software was XPSPEAK.
  • elemental analyzer Vario EL Cube
  • reaction temperature 1150°C weigh 5 mg of sample
  • reduction temperature 850°C carrier gas helium flow rate 200mL/min
  • oxygen flow rate 30mL/min oxygen flow Time 70s.
  • Instruments, methods and conditions for testing platinum mass fraction in platinum-carbon catalyst take 30 mg of the prepared Pt/C catalyst, add 30 mL of aqua regia, condense and reflux at 120 °C for 12 h, cool to room temperature, take the supernatant and dilute it with ICP - AES test for Pt content.
  • the model of the high-resolution transmission electron microscope (HRTEM) used in the present invention is JEM-2100 (HRTEM) (Japan Electronics Co., Ltd.), and the test conditions of the high-resolution transmission electron microscope are: the acceleration voltage is 200kV.
  • the particle size of the nanoparticles in the samples was measured by electron microscope images.
  • BET test method In the present invention, the pore structure of the sample is measured by a Quantachrome AS-6B analyzer, the specific surface area and pore volume of the catalyst are obtained by the Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is obtained according to the Barrett-Joyner- The desorption curve was calculated by Halenda (BJH) method.
  • BET Brunauer-Emmett-Taller
  • the Raman detection of the present invention adopts the LabRAM HR UV-NIR laser confocal Raman spectrometer produced by Japan HORIBA company, and the laser wavelength is 532 nm.
  • Electrochemical performance test instrument model Solartron analytical EnergyLab and Princeton Applied Research (Model 636A), method and test conditions:
  • the polarization curve LSV of the catalyst was tested in 0.1M HClO 4 saturated with O 2 at a rotating speed of 1600 rpm, and the CV curve was in
  • the electrochemical active area ECSA was calculated by testing in 0.1 M HClO 4 under Ar atmosphere.
  • the stability test in 0.1 M HClO 4 saturated with O 2 , after scanning for 5000 cycles in the range of 0.6 V to 0.95 V, LSV and ECSA were tested as above.
  • the catalyst was prepared into a uniformly dispersed slurry and coated on a glassy carbon electrode with a diameter of 5 mm.
  • the platinum content of the catalyst on the electrode was 3 ⁇ g to 4 ⁇ g.
  • Resistivity test Four-probe resistivity tester, instrument model KDY-1, method and test conditions: the applied pressure is 3.9 ⁇ 0.03MPa, and the current is 500 ⁇ 0.1mA.
  • VXC72 Vulcan XC72, produced by Cabot Corporation, USA, production batch number
  • the results show that the specific surface area is 258m 2 /g, the pore volume is 0.388mL / g , the oxygen mass fraction is 8.72%, the ID/IG is 1.02, and the resistivity is 1.22 ⁇ m.
  • Ketjenblack ECP600JD (Ketjen black, produced by Lion Company in Japan, production batch number) was purchased from Suzhou Yilongsheng Energy Technology Co., Ltd. Tested by the aforementioned instrument method, the results show that the specific surface area is 1362m 2 /g, the pore volume is 2.29mL / g , the oxygen mass fraction is 6.9%, the ID/IG is 1.25, and the resistivity is 1.31 ⁇ m.
  • This example is used to illustrate the preparation of the nitrogen-doped carbon carrier of the present invention.
  • the nitrogen mass fraction of XPS analysis was 1.43%; the oxygen mass fraction of XPS analysis was 9.31%; the specific surface area was 239 m 2 /g; and the resistivity was 1.28 ⁇ m.
  • FIG. 1 is an XPS spectrum of carbon support A of Example 1.
  • FIG. 1 is an XPS spectrum of carbon support A of Example 1.
  • This example is used to illustrate the preparation of the nitrogen-doped carbon carrier of the present invention.
  • the nitrogen mass fraction of XPS analysis was 0.68%; the oxygen mass fraction of XPS analysis was 8.92%; the resistivity was 1.25 ⁇ m.
  • This example is used to illustrate the preparation of the nitrogen-doped carbon carrier of the present invention.
  • the nitrogen mass fraction of XPS analysis was 1.48%; the oxygen mass fraction of XPS analysis was 11.22%; the specific surface area was 1369 m 2 /g, and the resistivity was 1.36 ⁇ m.
  • FIG. 2 is an XPS spectrum of the carbon support C of Example 3.
  • FIG. 2 is an XPS spectrum of the carbon support C of Example 3.
  • This example is used to illustrate the preparation of the nitrogen-doped carbon carrier of the present invention.
  • the nitrogen mass fraction of XPS analysis was 1.31%; the oxygen mass fraction of XPS analysis was 9.54%; the resistivity was 1.34 ⁇ m.
  • This example is used to illustrate the preparation of the platinum-carbon catalyst of the present invention.
  • the carbon carrier A was dispersed in deionized water, 3.4 mmol of chloroplatinic acid was added per gram of carbon carrier, ultrasonically dispersed to form a suspension, and 1 mol/L sodium carbonate aqueous solution was added to make the pH of the system
  • the value is 10; the above suspension is heated to 80°C, and formic acid is added under stirring to carry out the reduction reaction.
  • the molar ratio of formic acid and chloroplatinic acid is 50:1, and the reaction is continued for 10h; the reaction mixture is filtered and deionized water is used. Wash until the pH value of the filtrate is neutral, filter, and then dry at 100° C. to obtain a platinum-carbon catalyst.
  • the platinum mass fraction of the platinum-carbon catalyst is 39.7%.
  • FIG. 4 is the polarization curve of the platinum-carbon catalyst of Example 5 before and after 5000 cycles.
  • This example is used to illustrate the preparation of platinum carbon catalyst.
  • the platinum-carbon catalyst was prepared according to the method of Example 5, except that the carbon carrier B prepared in Example 2 was used, and 1.3 mmol of chloroplatinic acid was added per gram of carbon carrier.
  • the platinum mass fraction of the platinum-carbon catalyst is 20.1%.
  • FIG. 5 is the XPS spectrum of the platinum-carbon catalyst of Example 6.
  • This example is used to illustrate the preparation of the platinum-carbon catalyst of the present invention.
  • the platinum mass fraction of the platinum-carbon catalyst is 70.0%.
  • FIG. 6 is the XPS spectrum of the platinum-carbon catalyst of Example 7.
  • FIG. 6 is the XPS spectrum of the platinum-carbon catalyst of Example 7.
  • This example is used to illustrate the preparation of platinum carbon catalyst.
  • the platinum-carbon catalyst was prepared according to the method of Example 7, except that the carbon support D prepared in Example 4 was used, and 1.3 mmol of chloroplatinic acid was added per gram of carbon support.
  • the platinum mass fraction of the platinum-carbon catalyst is 20.1%.
  • FIG. 7 is the XPS spectrum of the platinum-carbon catalyst of Example 8.
  • the platinum-carbon catalyst was prepared according to the method of Example 5, except that the carrier was Vulcan XC72.
  • the platinum mass fraction of the platinum-carbon catalyst is 40.1%.
  • the platinum-carbon catalyst was manufactured and tested in the same manner as in Example 7, except that the carbon support was Ketjenblack ECP600JD, and when Pt was loaded, each gram of carbon support was dispersed with 200 mL of water and 50 mL of ethanol.
  • the platinum mass fraction of the platinum-carbon catalyst is 69.7%.
  • the platinum-carbon catalyst was a commercial catalyst purchased under the designation HISPEC4000.
  • the platinum mass fraction of the platinum-carbon catalyst is 40.2%.
  • FIG. 8 is the polarization curve of the platinum-carbon catalyst of Comparative Example 3 before and after 5000 cycles.
  • the present invention detects elements on the surface of the material by means of X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • the X-ray photoelectron spectrometer used is ESCALab220i-XL ray electron spectrometer equipped with Avantage V5.926 software produced by VG Scientific.
  • the power is 330W
  • the basic vacuum is 3 ⁇ 10 -9 mbar during the analysis and test.
  • the electron binding energy was corrected by the C1s peak (284.3 eV) of elemental carbon
  • the late-stage peak-splitting processing software was XPSPEAK.
  • the characteristic peaks of thiophene sulfur and nitrogen in the spectrum are the characteristic peaks after peak separation.
  • elemental analyzer Vario EL Cube
  • reaction temperature 1150°C weigh 5 mg of sample
  • reduction temperature 850°C carrier gas helium flow rate 200mL/min
  • oxygen flow rate 30mL/min oxygen flow Time 70s.
  • Instruments, methods and conditions for testing platinum mass fraction in platinum-carbon catalyst take 30 mg of the prepared Pt/C catalyst, add 30 mL of aqua regia, condense and reflux at 120 °C for 12 h, cool to room temperature, take the supernatant and dilute it with ICP - AES test for Pt content.
  • the model of the high-resolution transmission electron microscope (HRTEM) used in the present invention is JEM-2100 (HRTEM) (Japan Electronics Co., Ltd.), and the test conditions of the high-resolution transmission electron microscope are: the acceleration voltage is 200kV.
  • the particle size of the nanoparticles in the samples was measured by electron microscope images.
  • BET test method In the present invention, the pore structure properties of the sample are measured by Quantachrome AS-6B analyzer, the specific surface area and pore volume of the catalyst are obtained by the Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is obtained according to the Barrett-Joyner- The desorption curve was calculated by Halenda (BJH) method.
  • BET Brunauer-Emmett-Taller
  • the Raman detection of the present invention adopts the LabRAM HR UV-NIR laser confocal Raman spectrometer produced by Japan HORIBA company, and the laser wavelength is 532 nm.
  • Electrochemical performance test instrument model Solartron analytical EnergyLab and Princeton Applied Research (Model 636A), method and test conditions:
  • the polarization curve LSV of the catalyst was tested in 0.1M HClO 4 saturated with O 2 at a rotating speed of 1600 rpm, and the CV curve was in
  • the electrochemical active area ECSA was calculated by testing in 0.1 M HClO 4 under Ar atmosphere.
  • LSV and ECSA were tested as described above.
  • the catalyst was prepared into a uniformly dispersed slurry and coated on a glassy carbon electrode with a diameter of 5 mm.
  • the platinum content of the catalyst on the electrode was 3 ⁇ g to 4 ⁇ g.
  • Resistivity test Four-probe resistivity tester, instrument model KDY-1, method and test conditions: the applied pressure is 3.9 ⁇ 0.03MPa, and the current is 500 ⁇ 0.1mA.
  • VXC72 Vulcan XC72, produced by Cabot Corporation, USA, production batch number
  • the results show that the specific surface area is 258m 2 /g, the pore volume is 0.388mL / g , the oxygen mass fraction is 8.72%, the ID/IG is 1.02, and the resistivity is 1.22 ⁇ m.
  • Ketjenblack ECP600JD (Ketjen black, produced by Lion Company in Japan, production batch number) was purchased from Suzhou Yilongsheng Energy Technology Co., Ltd. Tested by the aforementioned instrument method, the results show that the specific surface area is 1362m 2 /g, the pore volume is 2.29mL / g , the oxygen mass fraction is 6.9%, the ID/IG is 1.25, and the resistivity is 1.31 ⁇ m.
  • This example is used to illustrate the preparation of sulfur-nitrogen-doped carbon materials.
  • Vulcan XC72 1g was immersed in 20mL of 2wt% ammonia solution for 24h, dried in an oven at 100°C and placed in a tubular furnace.
  • the carrier gas (being nitrogen) entered the tubular furnace after passing through a bubbling bottle containing thiophene.
  • the tube furnace was heated to 1200°C at a rate of 10°C/min, then treated at a constant temperature for 3 hours, and naturally cooled to obtain a sulfur-nitrogen-doped carbon material, numbered as carrier A.
  • the mass of thiophene is based on the mass of sulfur it contains, and the mass ratio of Vulcan XC72 to thiophene is 3:1.
  • the amount of thiophene is controlled by the carrier gas ventilation rate, and the carrier gas ventilation rate corresponding to different thiophene amounts is calibrated in advance according to the ventilation time.
  • the mass fraction of sulfur by XPS analysis was 1.25%; the mass fraction of nitrogen by XPS analysis was 0.54%; the specific surface area was 211m 2 /g, the pore volume was 0.421mL/g, and the resistivity was 1.31 ⁇ m.
  • Figure II-1 is an XPS spectrum of sulfur of the sulfur-nitrogen-doped carbon material of Example II-1.
  • Figure II-2 is an XPS spectrum of nitrogen of the sulfur-nitrogen-doped carbon material of Example II-1.
  • Vulcan XC72 Immerse 1g of Vulcan XC72 in 20mL of 20wt% ammonia solution for 24h, dry it in a 100°C oven, and place it in a tubular furnace.
  • the carrier gas nitrogen
  • the mass of thiophene is based on the mass of sulfur contained, and the mass ratio of Vulcan XC72 to thiophene is 9:1.
  • the amount of thiophene is controlled by the carrier gas ventilation rate, and the carrier gas ventilation rate corresponding to different thiophene amounts is calibrated in advance according to the ventilation time.
  • the mass fraction of sulfur in XPS analysis was 0.91%; the mass fraction of nitrogen in XPS analysis was 0.62%; and the resistivity was 1.29 ⁇ m.
  • Figure II-3 is an XPS spectrum of sulfur of the sulfur-nitrogen-doped carbon material of Example II-2.
  • Ketjenblack ECP600JD Add 10 mL of absolute ethanol to 1 g of Ketjenblack ECP600JD, then add 20 mL of 20 wt% ammonia solution for immersion for 24 hours, dry it in an oven at 100 °C and place it in a tube furnace. Enter the tube furnace, heat the tube furnace to 1200 °C at a rate of 10 °C/min, then treat at a constant temperature for 3 hours, and naturally cool down to obtain a sulfur-nitrogen doped carbon material, numbered as carrier C.
  • the mass of thiophene is based on the mass of sulfur contained, and the mass ratio of Ketjenblack ECP600JD to thiophene is 8:1.
  • the amount of thiophene is controlled by the carrier gas ventilation rate, and the carrier gas ventilation rate corresponding to different thiophene amounts is calibrated in advance according to the ventilation time.
  • the mass fraction of sulfur by XPS analysis was 0.72%; the mass fraction of nitrogen by XPS analysis was 1.84%; the specific surface area was 1317m 2 /g; and the resistivity was 1.38 ⁇ m.
  • Figure II-4 is an XPS spectrum of sulfur of the sulfur-nitrogen-doped carbon material of Example II-3.
  • This example is used to illustrate the preparation of sulfur-nitrogen-doped carbon materials.
  • the mass of thiophene is based on the mass of sulfur it contains, and the mass ratio of Vulcan XC72 to thiophene is 3:1.
  • the amount of thiophene is controlled by the carrier gas ventilation rate, and the carrier gas ventilation rate corresponding to different thiophene amounts is calibrated in advance according to the ventilation time.
  • the mass fraction of sulfur by XPS analysis was 1.14%; the mass fraction of nitrogen by XPS analysis was 0.14%.
  • Figure II-5 is an XPS spectrum of sulfur of the sulfur-nitrogen-doped carbon material of Example II-4.
  • This example is used to illustrate the preparation of the platinum-carbon catalyst of the present invention.
  • the carbon carrier A was dispersed in deionized water, 3.4 mmol of chloroplatinic acid was added per gram of carbon carrier, ultrasonically dispersed to form a suspension, and 1 mol/L sodium carbonate aqueous solution was added to make the pH of the system
  • the value is 10; the above suspension is heated to 80°C, and formic acid is added under stirring to carry out the reduction reaction.
  • the molar ratio of formic acid and chloroplatinic acid is 50:1, and the reaction is continued for 10h; the reaction mixture is filtered and deionized water is used. Wash until the pH value of the filtrate is neutral, filter, and then dry at 100° C. to obtain a platinum-carbon catalyst.
  • the platinum mass fraction of the platinum-carbon catalyst is 39.9%.
  • Figure II-6 is a TEM image of the platinum-carbon catalyst of Example II-5.
  • Figure II-7 is the polarization curve of the platinum-carbon catalyst of Example II-5.
  • Figure II-8 is the XPS spectrum of sulfur of the platinum-carbon catalyst of Example II-5.
  • Figure II-9 is an XPS spectrum of nitrogen of the platinum-carbon catalyst of Example II-5.
  • This example is used to illustrate the preparation of the platinum-carbon catalyst of the present invention.
  • the platinum-carbon catalyst was prepared according to the method of Example II-5, except that the carbon support B prepared in Example II-2 was used, and 1.3 mmol of chloroplatinic acid was added per gram of carbon support.
  • the platinum mass fraction of the platinum-carbon catalyst is 20.3%.
  • This example is used to illustrate the preparation of the platinum-carbon catalyst of the present invention.
  • the platinum mass fraction of the platinum-carbon catalyst is 69.8%.
  • Figure II-10 is the XPS spectrum of sulfur of the platinum-carbon catalyst of Example II-7.
  • Figure II-11 is the XPS spectrum of nitrogen of the platinum-carbon catalyst of Example II-7.
  • This example is used to illustrate the preparation of the platinum-carbon catalyst of the present invention.
  • the platinum-carbon catalyst was prepared according to the method of Example II-5, except that the carbon support D prepared in Example II-4 was used.
  • the platinum mass fraction of the platinum-carbon catalyst is 39.9%.
  • the sulfur-nitrogen-doped carbon material was prepared in the same manner as in Example II-1, except that the tube furnace was heated to 1200°C at a rate of 3°C/min.
  • the platinum-carbon catalyst was prepared in the same manner as in Example II-5, except that the carbon support was the sulfur-nitrogen doped carbon material prepared in Comparative Example II-1.
  • the mass fraction of sulfur in XPS analysis was 1.29%; the mass fraction of nitrogen in XPS analysis was 0.58%; and the resistivity was 1.32 ⁇ m.
  • Figure II-12 is an XPS spectrum of sulfur of the sulfur-nitrogen-doped carbon material of Comparative Example II-1.
  • the platinum mass fraction of the platinum-carbon catalyst is 40.1%.
  • Figure II-13 is a TEM image of the platinum-carbon catalyst of Comparative Example II-1.
  • Figure II-14 is the polarization curve of the platinum-carbon catalyst of Comparative Example II-1.
  • the sulfur-nitrogen-doped carbon material was prepared in the same manner as in Example II-1, except that the temperature of the constant temperature treatment was 700° C. when manufacturing the sulfur-nitrogen-doped carbon material.
  • the sulfur mass fraction of XPS analysis is 0.967%; the nitrogen mass fraction of XPS analysis is 0.92%.
  • Figure II-15 is an XPS spectrum of sulfur of the sulfur-nitrogen-doped carbon material of Comparative Example II-2.
  • the platinum-carbon catalyst was a commercial catalyst purchased under the designation HISPEC4000.
  • the platinum mass fraction of the platinum-carbon catalyst is 40.2%.
  • Figure II-16 is the polarization curve of the platinum-carbon catalyst of Comparative Example II-3.
  • the aforementioned nitrogen-doped carbon carrier was dispersed in deionized water, 12 mmol of chloroplatinic acid was added per gram of carbon carrier, ultrasonically dispersed to form a suspension, and 1 mol/L potassium hydroxide aqueous solution was added to adjust
  • the pH value of the system is 10; the above suspension is heated to 80°C, sodium borohydride is added under stirring to carry out the reduction reaction, the molar ratio of reducing agent and platinum precursor is 5:1, and the reaction is maintained for 12h; the reaction mixture is filtered , washed until the pH of the solution was neutral, and dried at 100 °C to obtain a carbon-supported platinum catalyst.
  • the nitrogen mass fraction of the nitrogen-doped carbon support was 1.48% by XPS analysis.
  • the platinum mass fraction of the platinum-carbon catalyst is 70.0%.
  • the Ketjenblack ECP600JD was placed in a tube furnace, and the carrier gas (nitrogen) entered the tube furnace after passing through a bubbling bottle containing thiophene. After natural cooling, the sulfur-doped carbon support was obtained.
  • Thiophene is based on the mass of sulfur, and the mass ratio of Ketjenblack ECP600JD to thiophene is 20:1.
  • the amount of thiophene is controlled by the carrier gas ventilation rate, and the carrier gas ventilation rate corresponding to different thiophene amounts is calibrated in advance according to the ventilation time.
  • the aforementioned sulfur-doped carbon carrier was dispersed in deionized water, 12 mmol of chloroplatinic acid was added per gram of carbon carrier, ultrasonically dispersed to form a suspension, and 1 mol/L aqueous potassium hydroxide solution was added to make a
  • the pH of the system is 10; the above suspension is heated to 80°C, sodium borohydride is added under stirring to carry out the reduction reaction, the molar ratio of the reducing agent to the platinum precursor is 5:1, and the reaction is maintained for 12h; the reacted mixture is filtered and washed When the pH of the solution is neutral, the carbon-supported platinum catalyst is obtained after drying at 100°C.
  • the sulfur mass fraction of the sulfur-doped carbon support by XPS analysis was 0.76%.
  • the platinum mass fraction of the platinum-carbon catalyst is 70.2%.
  • the sulfur-doped carbon material not only contains characteristic peaks between 163ev and 166ev (according to analysis, it is speculated that it is the characteristic peak of thiophene sulfur). characteristic peaks), also including oxidized sulfur.
  • Example II-7 compared with Comparative Examples II-4 and II-5, compared with the conductive carbon black with characteristic peaks only between 163ev and 166ev or a single pyrrole nitrogen doped, and at the same time Conductive carbon black with characteristic peaks or single pyrrole nitrogen between 163ev and 166ev improves the comprehensive properties of platinum-carbon catalysts, such as the mass specific activity and its stability.

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Abstract

本发明涉及铂碳催化剂及其制备方法和应用，在该铂碳催化剂的XPS分析的N1s谱峰中，除399ev～400.5ev之间有特征峰外，在395ev～405ev之间没有其他的特征峰；所述铂碳催化剂的载体为氮掺杂导电炭黑。本发明对铂碳催化剂的载体导电炭黑进行改性，通过控制掺杂元素的掺杂形式，显著提高了铂碳催化剂的质量比活性、电化学面积；进一步地，还可以提高铂碳催化剂的稳定性以及抗碳腐蚀能力。另外，本发明还提供了上述铂碳催化剂的简单制法。

Description

碳载铂族金属催化剂及其制备方法和应用 技术领域
本发明涉及碳载铂族金属催化剂及其制备方法和应用，特别涉及用于质子膜氢燃料电池的碳载铂族金属催化剂及其制备方法和应用。
背景技术
氧还原反应(ORR)是电化学领域的关键反应，例如在燃料电池和金属空气电池中，氧还原反应是影响电池性能的主要因素。掺杂原子的碳材料可直接用作氧还原反应的催化剂。在用作氧还原催化剂时，已有文献报道在碳材料中掺入氮、磷、硼、硫、氟、氯、溴、碘等元素，其中氮与碳原子半径接近，容易进入碳晶格中，因此是最常用的掺杂元素。尽管将掺杂碳材料直接作为燃料电池催化剂的文献报道较多，但与铂碳催化剂相比尚有较大差距。
到目前为止，最有效的氧还原催化剂是铂碳催化剂，但仍有不足之处。一方面，铂资源稀缺、价格昂贵。另一方面，目前使用的商业铂碳催化剂中铂金属的分散度还不理想且易团聚失活，氢燃料电池阴极的铂溶解和团聚导致铂表面积随时间下降明显，影响燃料电池寿命。现有技术主要是通过控制铂的粒径、形貌、结构以及载体的比表面积、孔结构来改进铂碳催化剂的性能；也有文献报道，通过对碳载体改性来提高铂碳催化剂的性能。
碳载体可提髙催化剂的比表面积，减少金属颗粒团聚，提高金属利用率。提高碳载体的载铂量有利于制造更薄、性能更好的膜电极，但大幅度提高载铂量更容易造成铂金属颗粒间的堆积，导致活性位点利用率急剧下降。另外，实际应用的氢燃料电池铂碳催化剂的铂载量至少在20wt％以上，其比化工铂碳催化剂(铂载量低于5wt％)的制造难度大很多。
质子交换膜燃料电池中由碳腐蚀引起的铂碳催化剂失活问题已引发本领域的大量关注。另外，铂还会加速碳腐蚀速率，载铂量越大，碳腐蚀越快。一方面，碳载体缺陷位多有利于提高载铂量，但同时加剧碳腐蚀。另一方面，提高石墨化程度能缓解碳腐蚀，但也使碳载体表面呈化学惰性，很难将铂均匀分散在碳载体上。
前述背景技术部分所公开的信息仅用于加强对本发明的背景理解，它可以包括不属于本领域普通技术人员已知的信息。
发明内容
本发明的第一个目的是提供一种碳载铂族金属催化剂，其能够显著提高质量比活性和电化学面积；特别是在高载铂量的情况下。本发明的第二个目的是在前述目的的基础上，改进催化剂的综合性能，特别是提高质量比活性和电化学面积的稳定性。发明的第三个目的是在前述目的的基础上，提高碳载铂族金属催化剂抗碳腐蚀性能。本发明的第四个目的是在前述目的的基础上提供碳载铂族金属催化剂的简单制法。本发明的其它目的通过本发明的详细讨论和示例得以体现。
为了实现前述目的中的一个或多个，本发明提供了如下方面的技术方案。
1.一种碳载铂族金属催化剂，其特征在于，在该碳载铂族金属催化剂的XPS分析的N 1s谱峰中，在399ev～400.5ev之间有特征峰，并且在395ev～405ev之间没有或基本没有其他的特征峰；所述碳载铂族金属催化剂的载体为掺杂有氮的导电炭黑；所述碳载铂族金属催化剂的铂质量分数为20％～70％，优选40％～70％，例如可以为45％～65％。
2.按照方面1所述的碳载铂族金属催化剂，其特征在于，所述碳载铂族金属催化剂的载体为硫氮掺杂导电炭黑。
3.按照方面1所述的碳载铂族金属催化剂，其特征在于，在其XPS分析的S 2P谱峰中，在160ev～170ev之间，位于163ev～166ev之间的特征峰面积大于92％，或大于95％，或大于98％，或只有位于163ev～166ev之间的特征峰。
4.按照方面1所述的碳载铂族金属催化剂，其特征在于，所述导电炭黑为普通导电炭黑、超导电炭黑或特导电炭黑。
5.按照方面1所述的碳载铂族金属催化剂，其特征在于，所述铂族金属选自铂(pt)、钯(Pd)、铑(Rh)、铱(Ir)、锇(Os)、和钌(Ru)，优选选自铂、钯、铑和铱，还优选选自铂和钯，例如为铂。
6.按照方面1所述的碳载铂族金属催化剂，其特征在于，所述碳载铂族金属催化剂的电阻率<10Ω·m，优选<2Ω·m。
7.一种氢燃料电池，其特征在于，所述氢燃料电池的阳极和/或阴极中，使用了方面1～11中任一所述的碳载铂族金属催化剂。
8.一种碳材料，其特征在于，所述碳材料为氮掺杂导电炭黑，在其XPS分析的N 1s谱峰中，除399ev～400.5ev之间有特征峰外，在395ev～405ev之间没有其他的特征峰。
9.如方面1-6中任一项所述碳载铂族金属催化剂的制备方法，包括以下步骤：
(1)浸渍氮源的步骤：将碳材料与氮源水溶液混合(其中，视需要任选地另外添加少量乙醇，如将碳材料分散在20％的乙醇水溶液中)，浸渍，得到浸渍有氮源的碳材料；
(2)制造氮掺杂碳材料的步骤：将步骤(1)中所得浸渍有氮源的碳材料在惰性气体中以8℃/min～15℃/min的速率升温至1000℃～1500℃，然后恒温处理0.5h～10h，得到掺杂有氮的碳材料；和
(3)负载铂族金属的步骤：以步骤(2)中所得掺杂有氮的碳材料为载体，负载铂族金属的步骤；
其中所述碳材料优选为导电炭黑。
10.按照方面9所述的制备方法，其特征在于，(2)中，所述恒温处理的温度为1150℃～1450℃。
11.按照方面9所述的制备方法，其特征在于，所述氮源为氨水/或尿素。
12.按照方面9所述的制备方法，其特征在于，氮源质量按其所含氮元素的质量计，所述碳材料与氮源的质量比为30：1～1：2。
13.按照方面6所述的制备方法，其特征在于，所述碳材料的XPS分析中，氧质量分数大于4％。
14.按照方面9所述的制备方法，其特征在于，所述负载铂族金属的步骤包括：
(a)将步骤(2)中得到的掺杂有氮的碳材料与铂族金属前驱体分散在水相中，调节pH为8～12；
(b)加入还原剂进行还原；和
(c)分离出固体，经后处理得到所述的铂碳催化剂。
15.按照方面14所述的制备方法，其特征在于，所述铂族金属前驱体为氯铂酸、氯铂酸钾或氯铂酸钠；所述铂族金属前驱体的浓度为0.5mol/L～5mol/L。
16.按照方面14所述的制备方法，其特征在于，步骤(b)中，所述还原剂选自柠檬酸、抗坏血酸、甲醛、甲酸、乙二醇、柠檬酸钠、水合肼、硼氢化钠和丙三醇；所述还原剂与铂的摩尔比为2～100；还原温度为50℃～150℃；还原时间为2h～15h。
不受限于任何已知理论，优选地，基于对位于163ev～166ev之间的特征峰的实验数据的分析，例如如本发明中的例示公开和讨论的那样，据信所述位于163ev～166ev之间的特征峰为噻吩型硫的特征峰。在一个实施方案中，优选地，据信所述噻吩型硫的特征峰为双峰。
杂原子与碳材料有多种结合方式，杂原子间有多种相互作用，制备方法和原料不同以及掺杂过程的操作步骤和条件不同，都会影响杂原子与碳材料的结合方式以及杂原子间的相互作用，导致杂原子及碳材料的性质差异很大，使二者的功能发生显著变化。在本领域，如何控制杂原子与碳材料的结合方式及杂原子间的相互作用是掺杂原子时的难点。本发明的研究发现，对导电炭黑掺杂时，通过控制杂原子与导电炭黑的结合方式及杂原子间的相互作用能够制造出性质独特的碳材料，从而能够显著提高质量比活性和电化学面积，改进催化剂的综合性能，提高质量比活性和电化学面积的稳定性，提高碳载铂族金属催化剂的抗碳腐蚀性能等。
与现有技术相比，本发明可实现以下有益技术效果。
一、本发明用简单方法制造了一类性质独特的表面掺杂原子的导电炭黑，与现有掺杂碳材料相比，该导电炭黑表面掺杂的硫仅以噻吩型硫的形式存在，表面掺杂的氮可以仅以吡咯型氮的形式存在，这些特点可以显著提高是碳载铂族金属催化剂的质量比活性和电化学面积。进一步地，该导电炭黑表面可以掺杂磷和/或硼，表面掺杂的磷可以只在132.5ev～134.5ev之间有特征峰，表面掺杂的硼可以只在189ev～191ev之间有特征峰，这些特点可以改进碳载铂族金属催化剂的综合性能，特别是提高质量比活性和电化学面积的稳定性。进一步地，该导电炭黑表面可以进行多种(例如三种或四种)杂元素的多掺杂，这一特点有利于提高碳载铂族金属催化剂抗碳腐蚀性能。
二、本发明的掺杂导电炭黑适合用于制造高载铂量的碳载铂族金属催化剂，在载铂族金属量高达70wt％时仍具有优异的综合催化性能和抗碳腐蚀能力。
三、实际应用的氢燃料电池碳载铂族金属催化剂的载铂量一般在20wt％以上，制造性能优异的高载铂族金属量催化剂难度很大。化学还原法工艺简单，但是铂族金属的利用率低，催化活性较低。然而，以本发明制造的掺杂导电炭黑为载体，采用水相的化学还原法，可容易地制造出质量比活性和稳定性俱佳的高载铂量催化剂。
作为例子，本发明提供了以下的例示实施方式，或它们之间的组合：
本发明第一系列的例示实施方式包括：
1、一种铂碳催化剂，其特征在于，在其XPS分析的N 1s谱峰中，除399ev～400.5ev之间有特征峰外，在395ev～405ev之间没有其他的特征峰。
2、照例示实施方式1所述的铂碳催化剂，其特征在于，以催化剂的质量为基准，铂的质量分数为20％～70％，优选为40％～70％。
3、按照例示实施方式1所述的铂碳催化剂，其特征在于，所述铂碳催化剂的电阻率<10Ω·m。
4、按照例示实施方式1所述的铂碳催化剂，其特征在于，所述铂碳催化剂的载体为氮掺杂导电炭黑、氮掺杂石墨烯或氮掺杂碳纳米管。
5、按照例示实施方式4所述的铂碳催化剂，其特征在于，所述导电炭黑为EC-300J、EC-600JD、ECP600JD、VXC72、Black pearls 2000、PRINTEX XE2-B、PRINTEX L6或HIBLAXK 40B2。
6、一种铂碳催化剂的制备方法，包括：(1)浸渍氮源的步骤：将碳材料与氮源水溶液混合，浸渍，得到浸渍上氮源的碳材料；(2)制造氮掺杂碳材料的步骤：将(1)中所得浸渍上氮源的碳材料，在惰性气体中，以8℃/min～15℃/min的速率升温至1000℃～1500℃，然后恒温处理0.5h～10h，得到氮掺杂碳材料；(3)负载铂的步骤：以(2)中所得氮掺杂碳材料为载体，负载铂的步骤。
7、按照例示实施方式6所述的制备方法，其特征在于，(2)中，所述恒温处理的温度为1150℃～1450℃。
8、按照例示实施方式6所述的制备方法，其特征在于，所述氮源为氨水/或尿素。
9、按照例示实施方式6所述的制备方法，其特征在于，氮源质 量按其所含氮元素的质量计，所述碳材料与氮源的质量比为30：1～1：2。
10、按照例示实施方式6所述的制备方法，其特征在于，所述碳材料为导电炭黑、石墨烯或碳纳米管。
11、按照例示实施方式10所述的制备方法，其特征在于，所述导电炭黑为EC-300J、EC-600JD、ECP-600JD、VXC72、Black pearls 2000、PRINTEX XE2-B、PRINTEX L6或HIBLAXK 40B2。
12、按照例示实施方式6所述的制备方法，其特征在于，所述碳材料的XPS分析中，氧质量分数大于4％。
13、按照例示实施方式6所述的制备方法，其特征在于，所述碳材料的电阻率<10Ω·m。
14、按照例示实施方式6所述的制备方法，其特征在于，所述碳材料的比表面积为10m 2/g～2000m 2/g。
15、按照例示实施方式6所述的制备方法，其特征在于，所述负载铂的步骤包括：(a)将(2)中得到的氮掺杂碳材料与铂前驱体分散在水相中，调节pH为8～12；(b)加入还原剂进行还原；(c)分离出固体，经后处理得到所述的铂碳催化剂。
16、按照例示实施方式15所述的制备方法，其特征在于，所述铂前驱体为氯铂酸、氯铂酸钾或氯铂酸钠；所述铂前驱体的浓度为0.5mol/L～5mol/L。
17、按照例示实施方式15所述的制备方法，其特征在于，(b)中，所述还原剂为柠檬酸、抗坏血酸、甲醛、甲酸、乙二醇、柠檬酸钠、水合肼、硼氢化钠或丙三醇中的一种或几种；所述还原剂与铂的摩尔比为2～100；还原温度为50℃～150℃；还原时间为2h～15h。
18、一种铂碳催化剂，其特征在于，该催化剂由例示实施方式6～17中的任一方法制得。
19、一种氢燃料电池，其特征在于，所述氢燃料电池的阳极和/或阴极中，使用了例示实施方式1～5和18中的任一铂碳催化剂。
本发明第二系列的例示实施方式包括：
1、一种铂碳催化剂，其特征在于，包括碳载体和负载于其上的铂金属，所述碳载体为硫氮掺杂碳材料；所述催化剂的XPS分析的S 2P 谱峰中，在160ev～170ev之间，只有位于163ev～166ev之间的特征峰。
2、按照例示实施方式1所述的铂碳催化剂，其特征在于，所述催化剂的XPS分析的N 1s谱峰中，除399ev～400.5ev之间有特征峰外，在390ev～410ev之间没有其他的特征峰。
3、按照例示实施方式1所述的铂碳催化剂，其特征在于，以催化剂的质量为基准，铂的质量分数为20％～70％，优选为40％～70％。
4、按照例示实施方式1所述的铂碳催化剂，其特征在于，所述位于163ev～166ev之间的特征峰位于163.4±0.5ev和164.7±0.5ev。
5、按照例示实施方式1所述的铂碳催化剂，其特征在于，所述硫氮掺杂碳材料为硫氮掺杂导电炭黑、硫氮掺杂石墨烯或硫氮掺杂碳纳米管。
6、一种铂碳催化剂的制备方法，包括：(1)制造硫氮掺杂碳材料的步骤；和(2)以步骤(1)中所得硫氮掺杂碳材料为载体，负载铂的步骤；
其中的步骤(1)包括掺杂硫的操作和掺杂氮的操作；
所述掺杂硫的操作包括：将碳材料置于含噻吩的惰性气体中，于1000℃～1500℃处理0.5h～10h；
所述的掺杂氮的操作在所述掺杂硫的操作之前、之后或同时进行。
7、按照例示实施方式6所述的制备方法，其特征在于，噻吩的质量以其所含硫的质量计，所述碳材料与噻吩的质量比为20：1～2：1。
8、按照例示实施方式6所述的制备方法，其特征在于，所述掺杂硫的操作中，所述温度为1150℃～1450℃。
9、按照例示实施方式6所述的制备方法，其特征在于，氮源的质量以其所含氮元素的质量计，所述碳材料与氮源的质量比为30：1～1：2。
10、按照例示实施方式6所述的制备方法，其特征在于，所述碳材料为导电炭黑、石墨烯或碳纳米管。
11、按照例示实施方式6所述的制备方法，其特征在于，所述碳材料的电阻率<10Ω·m，比表面积为10m 2/g～2000m 2/g。
12、按照例示实施方式6所述的制备方法，其特征在于，所述负载铂的步骤包括：
(a)将(1)中得到的硫氮掺杂碳材料与铂前驱体分散在水相中，调节pH为8～12；
(b)加入还原剂进行还原；
(c)分离出固体，经后处理得到所述的铂碳催化剂。
13、按照例示实施方式12所述的制备方法，其特征在于，(a)中，所述铂前驱体为氯铂酸、氯铂酸钾或氯铂酸钠；所述铂前驱体的浓度为0.5mol/L～5mol/L。
14、按照例示实施方式12所述的制备方法，其特征在于，(b)中，所述还原剂为柠檬酸、抗坏血酸、甲醛、甲酸、乙二醇、柠檬酸钠、水合肼、硼氢化钠或丙三醇中的一种或几种；所述还原剂与铂的摩尔比为2～100；还原温度为60℃～90℃；还原时间为4h～15h。
15、一种铂碳催化剂的制备方法，包括：
(1)浸渍氮源的步骤：将碳材料与氮源水溶液混合，浸渍，得到浸渍上氮源的碳材料；
(2)制造硫氮掺杂碳材料的步骤：将(1)中所得浸渍上氮源的碳材料，置于含噻吩的惰性气体中，于1000℃～1500℃处理0.5h～10h，得到硫氮掺杂碳材料；
(3)以步骤(2)中所得硫氮掺杂碳材料为载体，负载铂的步骤。
16、一种铂碳催化剂，其特征在于，由例示实施方式6～15中的任一方法制得。
17、一种氢燃料电池，其特征在于，所述氢燃料电池的阳极和/或阴极使用了例示实施方式1～5和16中的任一铂碳催化剂。
本发明第三系列的例示实施方式包括：
1、一种氮掺杂碳材料，在其XPS分析的N 1s谱峰中，除399ev～400.5ev之间有特征峰外，在395ev～405ev之间没有其他的特征峰。
2、按照例示实施方式1所述的氮掺杂碳材料，其特征在于，所述氮掺杂碳材料的XPS分析中，氮质量分数为0.1％～10％。
3、按照例示实施方式1所述的氮掺杂碳材料，其特征在于，所述氮掺杂碳材料的XPS分析中，氧质量分数>4％。
4、按照例示实施方式1所述的氮掺杂碳材料，其特征在于，所述氮掺杂碳材料的电阻率<10Ω·m。
5、按照例示实施方式1所述的氮掺杂碳材料，其特征在于，所 述氮掺杂碳材料的比表面10m 2/g～2000m 2/g。
6、按照例示实施方式1所述的氮掺杂碳材料，其特征在于，所述氮掺杂碳材料为氮掺杂的导电炭黑、氮掺杂的石墨烯或氮掺杂的碳纳米管。
7、按照例示实施方式6所述的氮掺杂碳材料，其特征在于，所述导电炭黑为EC-300J、EC-600JD、ECP600JD、VXC72、Black pearls2000、PRINTEX XE2-B、PRINTEX L6或HIBLAXK 40B2。
8、一种铂碳催化剂的碳载体，其特征在于，所述碳载体为氮掺杂的导电炭黑，在其XPS分析的N 1s谱峰中，除399ev～400.5ev之间有特征峰外，在395ev～405ev之间没有其他的特征峰；其XPS分析中，氧质量分数4％～15％，氮质量分数为0.2％～5％；其比表面积为200m 2/g～2000m 2/g。
9、按照例示实施方式8所述的碳载体，其特征在于，所述导电炭黑为EC-300J、EC-600JD、ECP-600JD、VXC72、Black pearls 2000、PRINTEX XE2-B、PRINTEX L6或HIBLAXK 40B2。
10、一种氮掺杂碳材料的制备方法，包括：
(1)浸渍氮源的步骤：将碳材料与氮源水溶液混合，浸渍，得到浸渍上氮源的碳材料；
(2)制造氮掺杂碳材料的步骤：将(1)中所得浸渍上氮源的碳材料，在惰性气体中，以8℃/min～15℃/min的速率升温至1000℃～1500℃，然后恒温处理0.5h～10h。
11、按照例示实施方式10所述的制备方法，其特征在于，(2)中，所述恒温处理的温度为1150℃～1450℃。
12、按照例示实施方式10所述的制备方法，其特征在于，所述氮源为氨水/或尿素。
13、按照例示实施方式10所述的制备方法，其特征在于，氮源的质量以其所含氮的质量计，所述碳材料与氮源的质量比为30：1～1：2；优选为25：1～1：1.5。
14、例示实施方式1～9中任一所述的氮掺杂碳材料或碳载体作为电极材料在电化学中的应用。
15、一种燃料电池，其特征在于，所述燃料电池中使用了例示实施方式1～9中任一所述的氮掺杂碳材料或碳载体。
16、按照例示实施方式15所述的燃料电池，其特征在于，所述的燃料电池为氢燃料电池。
17、一种金属空气电池，其特征在于，所述金属空气电池中使用了例示实施方式1～9中任一所述的氮掺杂碳材料或碳载体。
18、按照例示实施方式17所述的金属空气电池，其特征在于，所述金属空气电池为锂空气电池。
本发明的其他特征和优点将在具体实施方式部分中详细说明。
附图说明
实施方式Ⅰ
图Ⅰ-1为实施例1的氮掺杂碳载体的XPS谱图。
图Ⅰ-2为实施例3的氮掺杂碳载体的XPS谱图。
图Ⅰ-3为实施例5的铂碳催化剂的XPS谱图。
图Ⅰ-4为实施例5的铂碳催化剂5000圈前后的极化曲线。
图Ⅰ-5为实施例6的铂碳催化剂的XPS谱图。
图Ⅰ-6为实施例7的铂碳催化剂的XPS谱图。
图Ⅰ-7为实施例8的铂碳催化剂的XPS谱图。
图Ⅰ-8为对比例3的铂碳催化剂5000圈前后的极化曲线。
实施方式Ⅱ
图Ⅱ-1为实施例Ⅱ-1的硫氮掺杂碳材料的硫的XPS谱图。
图Ⅱ-2为实施例Ⅱ-1的硫氮掺杂碳材料的氮的XPS谱图。
图Ⅱ-3为实施例Ⅱ-2的硫氮掺杂碳材料的硫的XPS谱图。
图Ⅱ-4为实施例Ⅱ-3的硫氮掺杂碳材料的硫的XPS谱图。
图Ⅱ-5为实施例Ⅱ-4的硫氮掺杂碳材料的硫的XPS谱图。
图Ⅱ-6为实施例Ⅱ-5的铂碳催化剂的TEM图。
图Ⅱ-7为实施例Ⅱ-5的铂碳催化剂的极化曲线。
图Ⅱ-8为实施例Ⅱ-5的铂碳催化剂的硫的XPS谱图。
图Ⅱ-9为实施例Ⅱ-5的铂碳催化剂的氮的XPS谱图。
图Ⅱ-10为实施例Ⅱ-7的铂碳催化剂的硫的XPS谱图。
图Ⅱ-11为实施例Ⅱ-7的铂碳催化剂的氮的XPS谱图。
图Ⅱ-12为对比例Ⅱ-1的硫氮掺杂碳材料的硫的XPS谱图。
图Ⅱ-13为对比例Ⅱ-1的铂碳催化剂的TEM图。
图Ⅱ-14为对比例Ⅱ-1的铂碳催化剂的极化曲线。
图Ⅱ-15为对比例Ⅱ-2的硫氮掺杂碳材料的硫的XPS谱图。
图Ⅱ-16为对比例Ⅱ-3的铂碳催化剂的极化曲线。
具体实施方式
以下结合具体实施方式详述本发明，但需说明的是，本发明的保护范围不受这些具体实施方式和原理性解释的限制，而是由权利要求书来确定。
本发明中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此形成的技术方案或技术思想均视为本发明原始公开或记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合明显不合理。
本发明所公开的所有特征可以任意组合，这些组合应被理解为本发明所公开或记载的内容，除非本领域技术人员认为该组合明显不合理，均应被视为被本发明所具体公开和记载。本说明书所公开的数值点，不仅包括实施例中具体公开的数值点，还包括说明书中各数值范围的端点，这些数值点所任意组合的范围都应被视为本发明已公开或记载的范围。
本发明中的技术和科学术语，给出定义的以其定义为准，未给出定义的则按本领域的通常含义理解。
本发明中的“掺杂元素”包括氮、磷、硼、硫、氟、氯、溴和碘，或选自这些元素。
本发明中，材料“掺杂有”某元素是指具体提及的该一种或多种元素被掺杂至所述材料中，但该材料还可以掺杂有具体提及的该一种或多种元素之外的其它元素，尤其是本领域常用的那些。
本发明中，某元素“掺杂的”材料是指具体提及的该一种或多种元素被掺杂至所述材料中；其中在一种实施方案中，该材料还可以掺杂有具体提及的该一种或多种元素之外的其它元素；以及优选地，该材料不含除具体提及的该一种或多种元素外的其他掺杂元素。。
本发明中，除了根据上下文或自身限定可以唯一确定为“含掺杂元素的碳材料”，其他提及的“碳材料”均指不含掺杂元素的碳材料。碳材料的下位概念也如此。
本发明中，“炭黑”与“碳黑”为可相互替换的技术术语。在本发明中，本发明所述碳材料可用的石墨烯、碳纳米管和导电炭黑分别具有本领域公知的概念，且彼此属于不同的概念。但是，根据本发明，一种碳材料可以包含较低含量的一种或多种其它碳材料，只要其仍旧属于本领域技术人员公认的该种碳材料。例如，“石墨烯”可以因各种原因而包含微量(例如低于1％，或低于0.1％重量)的导电炭黑和/或碳纳米管。优选地，例如，对于本发明目的，所述导电炭黑包含小于5％重量，优选小于2％重量的石墨烯和/或碳纳米管。
本发明中的“惰性气体”是指，在本发明的制备方法中，对掺杂碳材料的性能不造成任何可察觉影响的气体。碳材料的下位概念也如此。
本发明中限定的数值范围包括数值范围的端点。本文所公开的“范围”以下限和上限的形式，例如一个或多个下限与一个或多个上限的形式给出。给定范围可通过选择一个下限和一个上限来进行限定，选定的下限和上限限定了给定范围的边界。所有以这种方式限定的范围是包含和可组合的，即任何下限可与任何上限组合形成一个范围。例如，针对特定参数列出了60-110和80-120的范围，理解为60-120和80-110的范围也是可预料到的。此外，如果列出的下限为1和2而列出的上限为3，4和5，则下面的范围都是可预料到的：1-3、1-4、1-5、2-3、2-4和2-5。
在本发明中，除非有其他说明，术语“包括”、“包含”、“含有”、“具有”和类似措词表示开放式，但是也应当理解为同时明确公开了封闭式的情形。例如，“包括”表示还可以包含没有列出的其他要素，但是也同时明确公开了仅包括所列出的要素的情形。此外，如本文所用，将“包含/包括”解释为明确说明存在提及的所述特征、整数、步骤或组分，但是不排除一种或多种其它特征、整数、步骤、组分或其组的存在或添加。另外，术语“包含”旨在包括由术语“基本上由…组成”和“由…组成”涵盖的实施方式。相似地，术语“基本上由…组成”旨在包括由术语“由…组成”涵盖的实施方式。
在本发明中，除非有其他说明，本文所提到的所有实施方式以及优选实施方式可以相互组合形成新的技术方案。特别地，例如对于本发明所涵盖的实施方式I和II，它们之中提到的技术特征和技术方案可 以在内部和相互之间进行组合，除非这样的组合对于本发明的目的而言是相悖的。
在本发明中，除非有其他说明，本文所提到的所有技术特征以及优选特征可以相互组合形成新的技术方案。
本发明中，除了根据上下文或自身限定可以明确的之外，其他提及的“孔体积”均指P/P 0最大时的单点吸附总孔容。
本发明中，“395ev～405ev之间基本没有其他的特征峰”是指除399ev～400.5ev之间有特征峰(例如优选为吡咯型氮的特征峰)外，任何其他特征峰的峰面积小于10％，优选小于5％。
实施方式Ⅰ
本发明的实施方式I提供了一种碳载铂族金属催化剂，在其XPS分析的N 1s谱峰中，除399ev～400.5ev之间有特征峰外，在395ev～405ev之间没有其他的特征峰。
在实施方式I的一个实施方案中，根据本发明的碳载铂族金属催化剂不含除氮外的其他掺杂元素。
在实施方式I的一个实施方案中，所述铂族金属为铂。
在实施方式I的一个实施方案中，根据本发明的碳载铂族金属催化剂不含除铂外的其他金属元素。
在实施方式I的一个实施方案中，根据本发明的碳载铂族金属催化剂，以催化剂的质量为基准，铂的质量分数为0.1％～80％，优选为20％～70％，更优选为40％～70％。
在实施方式I的一个实施方案中，根据本发明的碳载铂族金属催化剂的电阻率<10.0Ω·m，优选<2Ω·m。
在实施方式I的一个实施方案中，根据本发明的碳载铂族金属催化剂的比表面为80m 2/g～1500m 2/g，优选为100m 2/g～200m 2/g。
在实施方式I的一个实施方案中，根据本发明的碳载铂族金属催化剂的载体为氮掺杂导电炭黑、氮掺杂石墨烯或氮掺杂碳纳米管。
在实施方式I的一个实施方案中，对于根据本发明的碳载铂族金属催化剂，所述导电炭黑可为Ketjen black(科琴黑)系列超导碳黑、Cabot系列导电碳黑和赢创德固赛公司生产的系列导电碳黑中的一种或几种；优选为Ketjen black EC-300J、Ketjen black EC-600JD、Ketjen black ECP-600JD、VXC72、Black pearls 2000、PRINTEX XE2-B、PRINTEX  L6或HIBLAXK 40B2。
本发明的实施方式I还提供了一种碳载铂族金属催化剂的制备方法，包括：
(1)浸渍氮源的步骤：将碳材料与氮源水溶液混合，浸渍，得到浸渍有氮源的碳材料；
(2)制造氮掺杂碳材料的步骤：将步骤(1)中所得浸渍有氮源的碳材料，在惰性气体中，以8℃/min～15℃/min的速率升温至1000℃～1500℃，然后恒温处理0.5h～10h，得到氮掺杂碳材料；
(3)负载铂族金属(例如铂)的步骤：以步骤(2)中所得氮掺杂碳材料为载体，负载铂族金属(例如铂)的步骤。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，所述恒温处理的温度可为1000℃～1500℃，优选为1150℃～1450℃；处理时间可以为0.5h～10h，优选为1h～5h，更优选为2h～4h。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，所述氮源可以为氨水/或尿素。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，氮源质量按所其含氮元素的质量计，所述碳材料与氮源的质量比为30：1～1：2；优选为25：1～1：1.5。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，所述碳材料可以为导电炭黑、石墨烯或碳纳米管。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，所述导电炭黑可以是普通导电炭黑(Conductive Blacks)、超导电炭黑(Super Conductive Blacks)或特导电炭黑(Extra Conductive Blacks)，比如所述导电炭黑可以为Ketjen black(科琴黑)系列超导碳黑、Cabot系列导电碳黑和赢创德固赛公司生产的系列导电炭黑中的一种或几种；优选为Ketjen black EC-300J、Ketjen black EC-600JD、Ketjen black ECP-600JD、VXC72、Black pearls 2000、PRINTEX XE2-B、PRINTEX L6或HIBLAXK 40B2。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，对导电炭黑的制法、来源没有限制。所述导电炭黑可以为乙炔黑、炉法炭黑等。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，所述导 电炭黑的I D/I G值一般为0.8～5，优选为1～4。在拉曼光谱中，位于1320cm -1附近的峰为D峰，位于1580cm -1附近的峰为G峰，I D代表D峰的强度，I G代表G峰的强度。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，所述的石墨烯或碳纳米管既可以是未经氧化处理的石墨烯或碳纳米管，也可以是经过氧化处理后的石墨烯或碳纳米管。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，所述碳材料的XPS分析中，氧质量分数大于4％，优选为4％～15％。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，所述碳材料的电阻率<10Ω·m，优选<5Ω·m，更优选<2Ω·m。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，步骤(1)中的碳材料，其比表面积为10m 2/g～2000m 2/g；孔体积为0.2mL/g～6.0mL/g。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，一种制造氮掺杂碳材料的实施方式中，将碳材料与氮源水溶液混合，浸渍(一般12h～72h)后烘干(一般70℃～120℃)，然后置于管式炉中，将管式炉升温(升温速率可以为8℃/min～15℃/min)，然后在高温(1000℃～1500℃，优选为1150℃～1450℃)下处理一段时间(可以0.5h～10h，一般为1h～5h)，即得所述的氮掺杂碳材料。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，步骤(2)中制得的氮掺杂碳材料可以容易的分散于水相。而对于某些碳材料，比如科琴黑，很难直接分散于水相。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，所述负载铂族金属(例如铂)的步骤包括：
(a)将步骤(2)中得到的氮掺杂碳材料与铂族金属前驱体(例如铂前驱体)分散在水相中，调节pH为8～12(优选调节pH值为10±0.5)；
(b)加入还原剂进行还原；
(c)分离出固体，经后处理得到所述的碳载铂族金属(例如碳载铂)催化剂。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，所述铂族金属前驱体(例如铂前驱体)为氯铂酸、氯铂酸钾或氯铂酸钠；所述铂族金属前驱体(例如铂前驱体)的浓度为0.5mol/L～5mol/L。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，步骤(a)中，用碳酸钠水溶液、碳酸钾水溶液、氢氧化钾水溶液、氢氧化钠水溶液或氨水调节水相的pH值。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，步骤(b)中，所述还原剂为柠檬酸、抗坏血酸、甲醛、甲酸、乙二醇、柠檬酸钠、水合肼、硼氢化钠或丙三醇中的一种或几种。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，步骤(b)中，所述还原剂与铂的摩尔比为2～100。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，步骤(b)中，还原温度为50℃～150℃，优选为60℃～90℃；还原时间为4h～15h，优选为8h～12h。
根据本发明实施方式I的碳载铂族金属催化剂的制备方法，所述的后处理包括：洗涤、过滤和烘干。
本发明的实施方式I还提供了一种碳载铂族金属催化剂，该催化剂由前述中本发明实施方式I任一的方法制得。
本发明的实施方式I还提供了一种氢燃料电池，该氢燃料电池的阳极和/或阴极中，使用了前述中本发明实施方式I任一的碳载铂族金属催化剂。
本发明采用简单方法使氮以吡咯氮的形式掺杂于碳材料表面，由此制造用于氢燃料电池阳极氢氧化反应或阴极氧还原反应的铂碳电极催化剂，与相同碳材料和载铂量的催化剂相比，具有更高的半波电位，尤其是显著提高了催化剂的ECSA和质量比活性及其稳定性。
在实施方式I的一个实施方案中，根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)在用于氧还原反应时，一些实施例中，ECSA>55m 2g -1-Pt，比如在55m 2g -1-Pt～140m 2g -1-Pt。
在实施方式I的一个实施方案中，根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)在用于氧还原反应时，一些实施例中，5000圈后质量比活性下降率<10％。
在实施方式I的一个实施方案中，根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)在用于氧还原反应时，一些实施例中，半波电位>0.88V，比如0.88V～0.92V。
在实施方式I的一个实施方案中，根据本发明的碳载铂族金属催化 剂(例如铂碳催化剂)在用于氧还原反应时，一些实施例中，质量比活性>0.11A mg -1-Pt，比如0.11A mg -1-Pt～0.44A mg -1-Pt。
在实施方式I的一个实施方案中，本发明的碳载铂族金属催化剂为铂碳催化剂。
实施方式Ⅱ
本发明的实施方式II提供了一种碳载铂族金属催化剂，该催化剂包括碳载体和负载于其上的铂金属，所述碳载体为硫氮掺杂碳材料；所述催化剂的XPS分析的S 2P谱峰中，在160ev～170ev之间，只有位于163ev～166ev之间的特征峰。
在实施方式II的一个实施方案中，根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)不含除硫和氮外的其他掺杂元素。
在实施方式I的一个实施方案中，所述铂族金属为铂。
在实施方式II的一个实施方案中，根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)不含除铂外的其他金属元素。
在实施方式II的一个实施方案中，根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)的XPS分析的S 2P谱峰中，只有位于163ev～166ev之间的特征峰。
在实施方式II的一个实施方案中，根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)的XPS分析中，在166ev～170ev之间没有特征峰。
在实施方式II的一个实施方案中，根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)的XPS分析的N 1s谱峰中，除399ev～400.5ev之间有特征峰外，在390ev～410ev之间没有其他的特征峰。
在实施方式II的一个实施方案中，根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)的XPS分析的N 1s谱峰中，在399ev～400.5ev之间有一个或两个特征峰。
在实施方式II的一个实施方案中，对于根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)，以催化剂的质量为基准，铂的质量分数为0.1％～80％，优选为20％～70％，更优选为40％～70％。
在实施方式II的一个实施方案中，根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)的电阻率<10.0Ω·m，优选<2.0Ω·m。
在实施方式II的一个实施方案中，根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)的比表面80m 2/g～1500m 2/g，优选为100m 2/g～ 200m 2/g。
在实施方式II的一个实施方案中，对于根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)，所述硫氮掺杂碳材料为硫氮掺杂导电炭黑、硫氮掺杂石墨烯或硫氮掺杂碳纳米管。所述导电炭黑可为Ketjen black(科琴黑)系列超导碳黑、Cabot系列导电碳黑和赢创德固赛公司生产的系列导电碳黑中的一种或几种；优选为EC-300J、EC-600JD、ECP-600JD、VXC72、Black pearls 2000、PRINTEX XE2-B、PRINTEX L6或HIBLAXK 40B2。所述的石墨烯或碳纳米管可以是经过氧化处理或未经氧化处理的石墨烯或碳纳米管。
在实施方式II的一个实施方案中，对于根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)，所述位于163ev～166ev之间的特征峰为双峰，一些实施例Ⅱ-中，该双峰分别位于163.4±0.5ev和164.7±0.5ev。
在实施方式II的一个实施方案中，对于根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)，以所述碳载铂族金属催化剂的载体质量为基准，XPS测试时，硫的质量分数为0.2％～3％，氮的质量分数为0.1％～5％。
本发明的实施方式II还提供了一种碳载铂族金属催化剂(例如铂碳催化剂)的制备方法，包括：
(1)制造硫氮掺杂碳材料的步骤；和
(2)以步骤(1)中所得硫氮掺杂碳材料为载体，负载铂族金属(例如铂)的步骤；
其中的步骤(1)包括掺杂硫的操作和掺杂氮的操作；
所述掺杂硫的操作包括：将碳材料置于含噻吩的惰性气体中，于1000℃～1500℃处理(优选恒温处理)0.5h～10h；
所述掺杂氮的操作在所述掺杂硫的操作之前、之后或同时进行。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述掺杂硫的操作中，如需升温，升温速率不低于8℃/min，可以为8℃/min～15℃/min。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述掺杂氮的操作在所述掺杂硫的操作之前或之后进行时，其可以采用任何现有已知的掺杂氮的方法。一种实施方式是，所述掺杂氮的操作在所述掺杂硫的操作之前进行时，将碳材料与氮源混合，在惰性气体中于 300℃～1500℃处理(优选恒温处理)0.5h～10h。另一种实施方式是，所述掺杂氮的操作在所述掺杂硫的操作之后进行时，将硫掺杂碳材料与氮源混合，在惰性气体中于300℃～1500℃处理(优选恒温处理)0.5h～10h。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述掺杂氮的操作在所述掺杂硫的同时进行时，采用所述掺杂硫的操作条件。一种实施方式是，先将碳材料与氮源混合，然后在所述掺杂硫的操作条件下，同时对碳材料进行掺杂氮和掺杂硫的操作。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，噻吩质量以硫的质量计，所述碳材料与噻吩的质量比为20：1～2：1；优选为10：1～4：1，更优选为8：1～4：1。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述掺杂硫的操作中，所述温度优选为1100℃～1400℃，更优选为1200℃～1400℃。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述掺杂硫的操作与掺杂氮的操作中，处理的时间各自独立为1h～5h，优选为2h～4h。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，氮源的质量以其所含氮的质量计，所述碳材料与氮源的质量比为30：1～1：2；优选为25：1～1：1.5。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，步骤(1)中所述的硫氮掺杂碳材料，在其XPS分析的S 2P谱峰中，在160ev～170ev之间，只有位于163ev～166ev之间的特征峰。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，步骤(1)中所述的硫氮掺杂碳材料，其位于163ev～166ev之间的特征峰为双峰，一些实施例Ⅱ-中，该双峰分别为于163.7±0.5ev和165.0±0.5ev。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述的碳材料为导电炭黑、石墨烯或碳纳米管。所述导电炭黑可以是普通导电炭黑(Conductive Blacks)、超导电炭黑(Super Conductive Blacks)或特导电炭黑(Extra Conductive Blacks)，比如所述导电炭黑可以为Ketjen black(科琴黑)系列超导碳黑、Cabot系列导电碳黑和赢创德固赛公司生产的系列导电炭黑中的一种或几种；优选为Ketjen black  EC-300J、Ketjen blackEC-600JD、Ketjen blackECP-600JD、VXC72、Black pearls 2000、PRINTEX XE2-B、PRINTEX L6或HIBLAXK 40B2。所述的石墨烯或碳纳米管既可以是未经氧化处理的石墨烯或碳纳米管，也可以是经过氧化处理后的石墨烯或碳纳米管。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，对导电炭黑的制法、来源没有限制。所述导电炭黑可以为乙炔黑、炉法炭黑等。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述碳材料的I D/I G值一般为0.8～5，优选为1～4。在拉曼光谱中，位于1320cm -1附近的峰为D峰，位于1580cm -1附近的峰为G峰，I D代表D峰的强度，I G代表G峰的强度。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述碳材料的电阻率可以<10.0Ω·m，优选为<5.0Ω·m，更优选<2.0Ω·m。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述碳材料的XPS分析中，氧质量分数大于2％，可以为2％～15％，优选为2.5％～12％。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述碳材料的比表面积和孔体积可以在较大范围内变化。一般地，比表面积为10m 2/g～2000m 2/g，孔体积为0.02mL/g～6mL/g。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，一种实施方式中，步骤(1)中的碳材料为导电炭黑，其比表面积为200m 2/g～2000m 2/g。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述惰性气体可以为氮气或氩气。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，一种实施方式的掺杂硫操作中，将碳材料置于管式炉中，通入含噻吩的载气，以8℃/min～15℃/min的速率将管式炉升温至1000℃～1500℃，然后恒温处理0.5h～10h。
所述载气可以为氮气或氩气。
所述载气中，噻吩的体积分数可以为0.1％～5.0％。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述负载铂族金属(例如铂)的步骤包括：
(a)将步骤(1)中得到的硫氮掺杂碳材料与铂族金属前驱体(例如铂前驱体)分散在水相中，调节pH为8～12(优选调节pH值为10±0.5)；
(b)加入还原剂进行还原；
(c)分离出固体，经后处理得到所述的碳载铂族金属(例如碳载铂)催化剂。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，步骤(a)中，所述铂族金属前驱体(例如铂前驱体)为氯铂酸、氯铂酸钾或氯铂酸钠；所述铂族金属前驱体(例如铂前驱体)的浓度为0.5mol/L～5mol/L。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，步骤(a)中，用碳酸钠水溶液、碳酸钾水溶液、氢氧化钾水溶液、氢氧化钠水溶液或氨水调节水相的pH值。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，步骤(b)中，所述还原剂为柠檬酸、抗坏血酸、甲醛、甲酸、乙二醇、柠檬酸钠、水合肼、硼氢化钠或丙三醇中的一种或几种。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，步骤(b)中，所述还原剂与铂的摩尔比为2～100。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，步骤(b)中，还原温度为50℃～150℃，优选为60℃～90℃；还原时间为4h～15h，优选为8h～12h。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，步骤(1)中制得的硫氮掺杂碳材料可以容易的分散于水相。而对于某些碳材料，比如科琴黑，很难直接将其分散于水相。
根据本发明实施方式II的碳载铂族金属催化剂的制备方法，所述的后处理包括：洗涤、过滤和干燥。
本发明的实施方式II还提供了一种碳载铂族金属催化剂(例如铂碳催化剂)的制备方法，包括：
(1)浸渍氮源的步骤：将碳材料与氮源水溶液混合，浸渍，得到浸渍有氮源的碳材料；
(2)制造硫氮掺杂碳材料的步骤：将步骤(1)中所得浸渍有氮源的碳材料，置于含噻吩的惰性气体中，于1000℃～1500℃处理(优选恒温处理)0.5h～10h，得到硫氮掺杂碳材料；
(3)以步骤(2)中所得硫氮掺杂碳材料为载体，负载铂族金属(例如铂)的步骤。
根据前述碳载铂族金属催化剂的制备方法，先将步骤(1)中的浸渍有氮源的碳材料干燥，然后再进行步骤(2)。
在实施方式II的一个实施方案中，通过该碳载铂族金属催化剂(例如铂碳催化剂)的制备方法制得本实施方式所述的碳载铂族金属催化剂(例如铂碳催化剂)。
本发明的实施方式II还提供了一种氢燃料电池，该氢燃料电池的阳极和/或阴极使用了前述中本发明实施方式II任一的碳载铂族金属催化剂。
在实施方式II的一个实施方案中，根据本发明的碳载铂族金属催化剂(例如铂碳催化剂)在用于氧还原反应时，5000圈后质量比活性下降率<10％。
在实施方式II的一个实施方案中，本发明的碳载铂族金属催化剂(例如铂碳催化剂)在用于氧还原反应时，一些实施例Ⅱ-中，ECSA>68.93m 2g -1-Pt，比如在60.0m 2g -1-Pt～100.0m 2g -1-Pt。
在实施方式II的一个实施方案中，本发明的碳载铂族金属催化剂(例如铂碳催化剂)在用于氧还原反应时，一些实施例Ⅱ-中，半波电位>0.890V，比如0.89V～0.91V。
在实施方式II的一个实施方案中，本发明的碳载铂族金属催化剂(例如铂碳催化剂)在用于氧还原反应时，一些实施例Ⅱ-中，质量比活性>0.15A mg -1-Pt，比如0.15A mg -1-Pt～0.35A mg -1-Pt。
现有的氢燃料电池碳载铂族金属催化剂存在着质量比活性较低、其稳定性较差的不足，本发明通过将硫氮以特定的形式掺杂在碳载体表面，进而显著提高了碳载铂族金属催化剂的质量比活性及其稳定性，尤其是提高了高载铂量的碳载铂族金属催化剂的质量比活性及其稳定性。
在实施方式II的一个实施方案中，本发明的碳载铂族金属催化剂为铂碳催化剂。
实施例部分
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。
如无特殊说明，本发明所采用试剂均为分析纯，所用试剂均为市售可得。
实施方式Ⅰ
试剂、仪器与测试
本发明通过X射线光电子能谱分析仪(XPS)检测材料表面的元素。所采用X射线光电子能谱分析仪为VG Scientifc公司生产配备有Avantage V5.926软件的ESCALab220i-XL型射线电子能谱仪，X射线光电子能谱分析测试条件为：激发源为单色化A1KαX射线，功率为330W，分析测试时基础真空为3×10 -9mbar。另外，电子结合能用单质碳的C1s峰(284.3eV)校正，后期分峰处理软件为XPSPEAK。
元素分析的仪器和方法、条件：元素分析仪(Vario EL Cube),反应温度1150℃，称取样品5mg，还原温度850℃，载气氦气流速200mL/min，氧气流速30mL/min，通氧时间70s。
测试铂碳催化剂中铂质量分数的仪器、方法、条件：取30mg制备好的Pt/C催化剂，加入30mL王水，120℃冷凝回流12h，冷却至室温后，取上清液稀释后，用ICP-AES测试其中Pt含量。
本发明所采用高分辨透射电镜(HRTEM)的型号为JEM-2100(HRTEM)(日本电子株式会社)，高分辨透射电镜测试条件为：加速电压为200kV。样品中纳米颗粒的粒径通过电镜图片测量得到。
BET测试方法：本发明中，样品的孔结构性质由Quantachrome AS-6B型分析仪测定，催化剂的比表面积和孔体积由Brunauer-Emmett-Taller(BET)方法得到，孔分布曲线根据Barrett-Joyner-Halenda(BJH)方法对脱附曲线进行计算得到。
本发明的拉曼检测采用的是日本HORIBA公司生产的LabRAM HR UV-NIR型激光共聚焦拉曼光谱仪，激光波长为532nm。
电化学性能测试，仪器型号Solartron analytical EnergyLab和Princeton Applied Research(Model 636A)，方法及测试条件：催化剂的极化曲线LSV在1600rpm的转速下，O 2饱和的0.1M HClO 4中测试，CV曲线在Ar气氛下0.1M HClO 4中测试，以此计算电化学活性面积ECSA。稳定性测试时在O 2饱和的0.1M HClO 4中，0.6V～0.95V范围内扫描5000个循环后，按上述方法测试LSV和ECSA。以上测试时将催化剂配成均匀分散的浆液，涂于直径5mm的玻碳电极上，电极上催化剂的铂含量 为3μg～4μg。
电阻率测试四探针电阻率测试仪，仪器型号KDY-1，方法及测试条件：施加压力3.9±0.03MPa，电流为500±0.1mA。
VXC72(Vulcan XC72，美国卡博特公司生产，生产批号)购自苏州翼隆晟能源科技有限公司。采用前述的仪器方法测试，结果表明：比表面积258m 2/g，孔体积0.388mL/g，氧质量分数8.72％，I D/I G为1.02,电阻率为1.22Ω·m。
Ketjenblack ECP600JD(科琴黑，日本Lion公司生产，生产批号)购自苏州翼隆晟能源科技有限公司。采用前述的仪器方法测试，结果表明：比表面积1362m 2/g，孔体积2.29mL/g，氧质量分数6.9％，I D/I G为1.25,电阻率为1.31Ω·m。
商业铂碳催化剂(牌号HISPEC4000，Johnson Matthey公司生产)购自Alfa Aesar。测试结果表明：铂的质量分数为40.2％。
实施例1
本实施例用于说明本发明氮掺杂碳载体的制备。
将1g Vulcan XC72在20mL 2.5wt％的氨水溶液中浸渍24h；在100℃下于烘箱中烘干；然后放入管式炉内，以8℃/min的速率将管式炉升温至1100℃，恒温处理3h；自然降温后得到氮掺杂碳载体，编号为碳载体A。
样品表征及测试
XPS分析的氮质量分数为1.43％；XPS分析的氧质量分数为9.31％；比表面积为239m 2/g；电阻率1.28Ω·m。
图1为实施例1的碳载体A的XPS谱图。
实施例2
本实施例用于说明本发明氮掺杂碳载体的制备。
将1g Vulcan XC72在15mL 0.7wt％的尿素水溶液中浸渍24h；在100℃下于烘箱中烘干；然后放入管式炉内，以10℃/min的速率将管式炉升温至1200℃，恒温处理3h；自然降温后得到氮掺杂碳载体，编号为碳载体B。
样品表征及测试
XPS分析的氮质量分数为0.68％；XPS分析的氧质量分数为8.92％；电阻率为1.25Ω·m。
实施例3
本实施例用于说明本发明氮掺杂碳载体的制备。
向1g Ketjenblack ECP600JD中加入10mL无水乙醇，然后加入25mL10wt％的氨水溶液浸渍24h；在100℃下于烘箱中烘干；然后放入管式炉内，以8℃/min的速率将管式炉升温至1100℃，恒温处理3h；自然降温后得到氮掺杂碳载体，编号为碳载体C。
样品表征及测试
XPS分析的氮质量分数为1.48％；XPS分析的氧质量分数为11.22％；比表面积为1369m 2/g，电阻率为1.36Ω·m。
图2为实施例3的碳载体C的XPS谱图。
实施例4
本实施例用于说明本发明氮掺杂碳载体的制备。
向1g Ketjenblack ECP600JD中加入10mL无水乙醇，然后加入20mL1wt％的尿素水溶液浸渍24h；在100℃下于烘箱中烘干；然后放入管式炉内，以10℃/min的速率将管式炉升温至1300℃，恒温处理3h；自然降温后得到氮掺杂碳载体，编号为碳载体D。
样品表征及测试
XPS分析的氮质量分数为1.31％；XPS分析的氧质量分数为9.54％；电阻率为1.34Ω·m。
实施例5
本实施例用于说明本发明铂碳催化剂的制备。
按每克碳载体使用250mL水的比例，将碳载体A分散于去离子水中，按每克碳载体加入3.4mmol氯铂酸，超声分散形成悬浮液，加入1mol/L碳酸钠水溶液使体系的pH值为10；将上述悬浮液加热至80℃，搅拌下加入甲酸进行还原反应，甲酸与氯铂酸的摩尔比为50:1，继续维持反应10h；将反应后的混合物过滤，用去离子水洗涤至滤液的pH值为中性，过滤，然后在100℃烘干，得到铂碳催化剂。
样品表征及测试
铂碳催化剂的铂质量分数为39.7％。
图3为实施例5的铂碳催化剂的XPS谱图。
图4为实施例5的铂碳催化剂5000圈前后的极化曲线。
铂碳催化剂性能测试结果见表1。
实施例6
本实施例用于说明铂碳催化剂的制备。
按照实施例5的方法制备铂碳催化剂，区别仅在于：使用实施例2制备的碳载体B，每克碳载体加入1.3mmol氯铂酸。
样品表征及测试
铂碳催化剂的铂质量分数为20.1％。
图5为实施例6的铂碳催化剂的XPS谱图。
铂碳催化剂性能测试结果见表1。
实施例7
本实施例用于说明本发明铂碳催化剂的制备。
按每克碳载体使用250mL水的比例，将碳载体C分散于去离子水中，按每克碳载体加入12mmol氯铂酸，超声分散形成悬浮液，加入1mol/L氢氧化钾水溶液调节体系的pH值为10；将上述悬浮液加热至80℃，搅拌下加入硼氢化钠进行还原反应，还原剂与铂前驱体的摩尔比为5:1，维持反应12h；将反应后的混合物过滤，洗涤至溶液pH为中性，100℃烘干后得到碳载铂催化剂。
样品表征及测试
铂碳催化剂的铂质量分数为70.0％。
图6为实施例7的铂碳催化剂的XPS谱图。
铂碳催化剂性能测试结果见表1。
实施例8
本实施例用于说明铂碳催化剂的制备。
按照实施例7的方法制备铂碳催化剂，区别仅在于：使用实施例4制备的碳载体D，每克碳载体加入1.3mmol氯铂酸。
样品表征及测试
铂碳催化剂的铂质量分数为20.1％。
图7为实施例8的铂碳催化剂的XPS谱图。
铂碳催化剂性能测试结果见表1。
对比例1
按照实施例5的方法制备铂碳催化剂，区别仅在于：载体为Vulcan XC72。
样品表征及测试
铂碳催化剂的铂质量分数为40.1％。
铂碳催化剂性能测试结果见表1。
对比例2
按照实施例7相同的方法制造铂碳催化剂并进行测试，不同之处仅在于：碳载体为Ketjenblack ECP600JD,负载Pt时每克碳载体用200mL水和50mL乙醇进行分散。
样品表征及测试
铂碳催化剂的铂质量分数为69.7％。
铂碳催化剂性能测试结果见表1。
对比例3
铂碳催化剂为购买的商业催化剂，牌号HISPEC4000。
样品表征及测试
铂碳催化剂的铂质量分数为40.2％。
图8为对比例3的铂碳催化剂5000圈前后的极化曲线。
铂碳催化剂性能测试结果见表1。
表1
Figure PCTCN2021114752-appb-000001
实施方式Ⅱ
试剂、仪器与测试
本发明通过X射线光电子能谱分析仪(XPS)检测材料表面的元素。 所采用X射线光电子能谱分析仪为VG Scientifc公司生产配备有Avantage V5.926软件的ESCALab220i-XL型射线电子能谱仪，X射线光电子能谱分析测试条件为：激发源为单色化A1KαX射线，功率为330W，分析测试时基础真空为3×10 -9mbar。另外，电子结合能用单质碳的C1s峰(284.3eV)校正，后期分峰处理软件为XPSPEAK。谱图中噻吩硫和氮的特征峰为分峰后的特征峰。
元素分析的仪器和方法、条件：元素分析仪(Vario EL Cube),反应温度1150℃，称取样品5mg，还原温度850℃，载气氦气流速200mL/min，氧气流速30mL/min，通氧时间70s。
测试铂碳催化剂中铂质量分数的仪器、方法、条件：取30mg制备好的Pt/C催化剂，加入30mL王水，120℃冷凝回流12h，冷却至室温后，取上清液稀释后，用ICP-AES测试其中Pt含量。
本发明所采用高分辨透射电镜(HRTEM)的型号为JEM-2100(HRTEM)(日本电子株式会社)，高分辨透射电镜测试条件为：加速电压为200kV。样品中纳米颗粒的粒径通过电镜图片测量得到。
BET测试方法：本发明中，样品的孔结构性质由Quantachrome AS-6B型分析仪测定，催化剂的比表面积和孔体积由Brunauer-Emmett-Taller(BET)方法得到，孔分布曲线根据Barrett-Joyner-Halenda(BJH)方法对脱附曲线进行计算得到。
本发明的拉曼检测采用的是日本HORIBA公司生产的LabRAM HR UV-NIR型激光共聚焦拉曼光谱仪，激光波长为532nm。
电化学性能测试，仪器型号Solartron analytical EnergyLab和Princeton Applied Research(Model 636A)，方法及测试条件：催化剂的极化曲线LSV在1600rpm的转速下，O 2饱和的0.1M HClO 4中测试，CV曲线在Ar气氛下0.1M HClO 4中测试，以此计算电化学活性面积ECSA。稳定性测试时在O 2饱和的0.1M HClO 4中，0.6V～0.95V范围内扫描5000个循环后，按上述方法测试LSV和ECSA。以上测试时将催化剂配成均匀分散的浆液，涂于直径5mm的玻碳电极上，电极上催化剂的铂含量为3μg～4μg。
电阻率测试四探针电阻率测试仪，仪器型号KDY-1，方法及测试条件：施加压力3.9±0.03MPa，电流为500±0.1mA。
VXC72(Vulcan XC72，美国卡博特公司生产，生产批号)购自苏 州翼隆晟能源科技有限公司。采用前述的仪器方法测试，结果表明：比表面积258m 2/g，孔体积0.388mL/g，氧质量分数8.72％，I D/I G为1.02,电阻率为1.22Ω·m。
Ketjenblack ECP600JD(科琴黑，日本Lion公司生产，生产批号)购自苏州翼隆晟能源科技有限公司。采用前述的仪器方法测试，结果表明：比表面积1362m 2/g，孔体积2.29mL/g，氧质量分数6.9％，I D/I G为1.25,电阻率为1.31Ω·m。
商业铂碳催化剂(牌号HISPEC4000，Johnson Matthey公司生产)购自Alfa Aesar。测试结果表明：铂的质量分数为40.2％。
实施例Ⅱ-1
本实施例用于说明硫氮掺杂碳材料的制备。
将1g Vulcan XC72浸渍于20mL 2wt％的氨水溶液中24h，于100℃烘箱中烘干后置于管式炉内，载气(为氮气)经过装有噻吩的鼓泡瓶后进入管式炉，以10℃/min的速率将管式炉升温至1200℃，然后恒温处理3h，自然降温后得到硫氮掺杂碳材料，编号为载体A。噻吩质量以其所含硫的质量计，Vulcan XC72与噻吩的质量比为3:1。噻吩用量通过载气通气速率控制，预先根据通气时间，标定好不同的噻吩用量所对应的载气通气速率。
样品表征及测试
一、硫氮掺杂碳材料
XPS分析的硫质量分数为1.25％；XPS分析的氮质量分数为0.54％；比表面积为211m 2/g，孔体积0.421mL/g；电阻率为1.31Ω·m。
图Ⅱ-1为实施例Ⅱ-1的硫氮掺杂碳材料的硫的XPS谱图。
图Ⅱ-2为实施例Ⅱ-1的硫氮掺杂碳材料的氮的XPS谱图。
实施例Ⅱ-2
将1g Vulcan XC72浸渍于20mL 20wt％的氨水溶液中24h，于100℃烘箱中烘干后置于管式炉内，载气(氮气)经过装有噻吩的鼓泡瓶后进入管式炉，以10℃/min的速率将管式炉升温至1300℃，然后恒温处理3h，自然降温后得到硫氮掺杂碳材料，编号为载体B。噻吩质量以所含的硫的质量计，Vulcan XC72与噻吩的质量比为9:1。噻吩用量通过载气通气速率控制，预先根据通气时间，标定好不同的噻吩用量所对应的载气通气速率。
样品表征及测试
XPS分析的硫质量分数为0.91％；XPS分析的氮质量分数为0.62％；电阻率为1.29Ω·m。
图Ⅱ-3为实施例Ⅱ-2的硫氮掺杂碳材料的硫的XPS谱图。
实施例Ⅱ-3
向1g Ketjenblack ECP600JD中加入10mL无水乙醇，后加入20mL20wt％的氨水溶液浸渍24h，于100℃烘箱中烘干后置于管式炉内，载气(氮气)经过装有噻吩的鼓泡瓶后进入管式炉，以10℃/min的速率将管式炉升温至1200℃，然后恒温处理3h，自然降温后得到硫氮掺杂碳材料，编号为载体C。噻吩质量以所含硫的质量计，Ketjenblack ECP600JD与噻吩的质量比为8:1。噻吩用量通过载气通气速率控制，预先根据通气时间，标定好不同的噻吩用量所对应的载气通气速率。
样品表征及测试
一、硫氮掺杂碳材料
XPS分析的硫质量分数为0.72％；XPS分析的氮质量分数为1.84％；比表面积为1317m 2/g；电阻率1.38Ω·m。
图Ⅱ-4为实施例Ⅱ-3的硫氮掺杂碳材料的硫的XPS谱图。
实施例Ⅱ-4
本实施例用于说明硫氮掺杂碳材料的制备。
将1g Vulcan XC72浸渍于20mL 2wt％的氨水溶液中24h，于100℃烘箱中烘干后置于管式炉内，在氮气保护下，以10℃/min的速率将管式炉升温至1200℃恒温处理3h；然后，载气(为氮气)经过装有噻吩的鼓泡瓶后进入管式炉，继续在1200℃下恒温处理3h，自然降温后得到硫氮掺杂碳材料，编号为载体D。噻吩质量以其所含硫的质量计，Vulcan XC72与噻吩的质量比为3:1。噻吩用量通过载气通气速率控制，预先根据通气时间，标定好不同的噻吩用量所对应的载气通气速率。
样品表征及测试
一、硫氮掺杂碳材料
XPS分析的硫质量分数为1.14％；XPS分析的氮质量分数为0.14％。
图Ⅱ-5为实施例Ⅱ-4的硫氮掺杂碳材料的硫的XPS谱图。
实施例Ⅱ-5
本实施例用于说明本发明铂碳催化剂的制备。
按每克碳载体使用250mL水的比例，将碳载体A分散于去离子水中，按每克碳载体加入3.4mmol氯铂酸，超声分散形成悬浮液，加入1mol/L碳酸钠水溶液使体系的pH值为10；将上述悬浮液加热至80℃，搅拌下加入甲酸进行还原反应，甲酸与氯铂酸的摩尔比为50:1，继续维持反应10h；将反应后的混合物过滤，用去离子水洗涤至滤液的pH值为中性，过滤，然后在100℃烘干，得到铂碳催化剂。
样品表征及测试
铂碳催化剂的铂质量分数为39.9％。
图Ⅱ-6为实施例Ⅱ-5的铂碳催化剂的TEM图。
图Ⅱ-7为实施例Ⅱ-5的铂碳催化剂的极化曲线。
图Ⅱ-8为实施例Ⅱ-5的铂碳催化剂的硫的XPS谱图。
图Ⅱ-9为实施例Ⅱ-5的铂碳催化剂的氮的XPS谱图。
铂碳催化剂性能测试结果见表Ⅱ-1。
实施例Ⅱ-6
本实施例用于说明本发明铂碳催化剂的制备。
按照实施例Ⅱ-5的方法制备铂碳催化剂，区别仅在于：使用实施例Ⅱ-2制备的碳载体B，每克碳载体加入1.3mmol氯铂酸。
样品表征及测试
铂碳催化剂的铂质量分数为20.3％。
铂碳催化剂性能测试结果见表Ⅱ-1。
实施例Ⅱ-7
本实施例用于说明本发明铂碳催化剂的制备。
按每克碳载体使用250mL水的比例，将碳载体C分散于去离子水中，按每克碳载体加入12mmol氯铂酸，超声分散形成悬浮液，加入1mol/L氢氧化钾水溶液调节体系的pH值为10；将上述悬浮液加热至80℃，搅拌下加入硼氢化钠进行还原反应，还原剂与铂前驱体的摩尔比为5:1，维持反应12h；将反应后的混合物过滤，洗涤至溶液pH为中性，100℃烘干后得到碳载铂催化剂。
样品表征及测试
铂碳催化剂的铂质量分数为69.8％。
图Ⅱ-10为实施例Ⅱ-7的铂碳催化剂的硫的XPS谱图。
图Ⅱ-11为实施例Ⅱ-7的铂碳催化剂的氮的XPS谱图。
铂碳催化剂性能测试结果见表Ⅱ-1。
实施例Ⅱ-8
本实施例用于说明本发明铂碳催化剂的制备。
按照实施例Ⅱ-5的方法制备铂碳催化剂，区别仅在于：使用实施例Ⅱ-4制备的碳载体D。
样品表征及测试
铂碳催化剂的铂质量分数为39.9％。
铂碳催化剂性能测试结果见表Ⅱ-1。
对比例Ⅱ-1
按实施例Ⅱ-1相同的方法制备硫氮掺杂碳材料，区别仅在于：以3℃/min的速率将管式炉升温至1200℃。
按实施例Ⅱ-5相同的方法制备铂碳催化剂，区别仅在于：碳载体为本对比例Ⅱ-1制备的硫氮掺杂碳材料。
样品表征及测试
一、硫氮掺杂碳材料
XPS分析的硫质量分数为1.29％；XPS分析的氮质量分数为0.58％；电阻率为1.32Ω·m。
图Ⅱ-12为对比例Ⅱ-1的硫氮掺杂碳材料的硫的XPS谱图。
二、铂碳催化剂
铂碳催化剂的铂质量分数为40.1％。
图Ⅱ-13为对比例Ⅱ-1的铂碳催化剂的TEM图。
图Ⅱ-14为对比例Ⅱ-1的铂碳催化剂的极化曲线。
对比例Ⅱ-2
按实施例Ⅱ-1相同的方法制备硫氮掺杂碳材料，区别仅在于：制造硫氮掺杂碳材料时，恒温处理的温度为700℃。
样品表征及测试
本对比例Ⅱ-2的硫氮掺杂碳材料，XPS分析的硫质量分数为0.967％；XPS分析的氮质量分数为0.92％。
图Ⅱ-15为对比例Ⅱ-2的硫氮掺杂碳材料的硫的XPS谱图。
对比例Ⅱ-3
铂碳催化剂为购买的商业催化剂，牌号HISPEC4000。
样品表征及测试
铂碳催化剂的铂质量分数为40.2％。
图Ⅱ-16为对比例Ⅱ-3的铂碳催化剂的极化曲线。
对比例Ⅱ-4
向1g Ketjenblack ECP600JD中加入10mL无水乙醇，然后加入25mL10wt％的氨水溶液浸渍24h；在100℃下于烘箱中烘干；然后放入管式炉内，以8℃/min的速率将管式炉升温至1100℃，恒温处理3h；自然降温后得到氮掺杂碳载体。
按每克碳载体使用250mL水的比例，将前述氮掺杂碳载体分散于去离子水中，按每克碳载体加入12mmol氯铂酸，超声分散形成悬浮液，加入1mol/L氢氧化钾水溶液调节体系的pH值为10；将上述悬浮液加热至80℃，搅拌下加入硼氢化钠进行还原反应，还原剂与铂前驱体的摩尔比为5:1，维持反应12h；将反应后的混合物过滤，洗涤至溶液pH为中性，100℃烘干后得到碳载铂催化剂。
样品表征及测试
氮掺杂碳载体的XPS分析的氮质量分数为1.48％。
铂碳催化剂的铂质量分数为70.0％。
铂碳催化剂性能测试结果见表Ⅱ-1。
对比例Ⅱ-5
将Ketjenblack ECP600JD置于管式炉内，载气(氮气)经过装有噻吩的鼓泡瓶后进入管式炉，以10℃/min的速率将管式炉升温至1200℃，然后恒温处理3h，自然降温后得到硫掺杂碳载体。噻吩以硫的质量计，Ketjenblack ECP600JD与噻吩的质量比为20:1。噻吩用量通过载气通气速率控制，预先根据通气时间，标定好不同的噻吩用量所对应的载气通气速率。
按每克碳载体使用250mL水的比例，将前述硫掺杂碳载体分散于去离子水中，按每克碳载体加入12mmol氯铂酸，超声分散形成悬浮液，加入1mol/L氢氧化钾水溶液使体系pH为10；将上述悬浮液加热至80℃，搅拌下加入硼氢化钠进行还原反应，还原剂与铂前驱体的摩尔比为5:1，维持反应12h；将反应后的混合物过滤，洗涤至溶液pH为中性，100℃烘干后得到碳载铂催化剂。
样品表征及测试
硫掺杂碳载体的XPS分析的硫质量分数为0.76％。
铂碳催化剂的铂质量分数为70.2％。
铂碳催化剂性能测试结果见表Ⅱ-1。
表Ⅱ-1
Figure PCTCN2021114752-appb-000002
由图Ⅱ-12和图Ⅱ-15所示，不按本发明的制造方法，硫掺杂的碳材料中，不仅包含了163ev～166ev之间的特征峰(据分析，推测其为噻吩硫的特征峰)，还包括了氧化态硫。
如表Ⅱ-1，“各实施例”与“对比例Ⅱ-3”相比可知，以硫氮掺杂的导电炭黑明显提高了铂碳催化剂的ECSA和质量比活性及其稳定性。
如表Ⅱ-1，实施例Ⅱ-7与对比例Ⅱ-4和Ⅱ-5相比可知，与仅在163ev～166ev之间具有特征峰或单一吡咯氮掺杂的导电炭黑相比，同时在163ev～166ev之间具有特征峰或单一吡咯氮的导电炭黑提高了铂碳催化剂的综合性能，比如质量比活性及其稳定性都进一步提高。

Claims (16)

  1. 一种碳载铂族金属催化剂，其特征在于，在该碳载铂族金属催化剂的XPS分析的N 1s谱峰中，在399ev～400.5ev之间有特征峰，并且在395ev～405ev之间没有或基本没有其他的特征峰；所述碳载铂族金属催化剂的载体为掺杂有氮的导电炭黑；所述碳载铂族金属催化剂的铂质量分数为20％～70％，优选40％～70％。
  2. 按照权利要求1所述的碳载铂族金属催化剂，其特征在于，所述碳载铂族金属催化剂的载体为硫氮掺杂导电炭黑。
  3. 按照权利要求1所述的碳载铂族金属催化剂，其特征在于，在其XPS分析的S 2P谱峰中，在160ev～170ev之间，位于163ev～166ev之间的特征峰面积大于92％，或大于95％，或大于98％，或只有位于163ev～166ev之间的特征峰。
  4. 按照权利要求1所述的碳载铂族金属催化剂，其特征在于，所述导电炭黑为普通导电炭黑、超导电炭黑或特导电炭黑。
  5. 按照权利要求1所述的碳载铂族金属催化剂，其特征在于，所述铂族金属选自铂(pt)、钯(Pd)、铑(Rh)、铱(Ir)、锇(Os)、和钌(Ru)，优选选自铂、钯、铑和铱，还优选选自铂和钯，例如为铂。
  6. 按照权利要求1所述的碳载铂族金属催化剂，其特征在于，所述碳载铂族金属催化剂的电阻率<10Ω·m，优选<2Ω·m。
  7. 一种氢燃料电池，其特征在于，所述氢燃料电池的阳极和/或阴极中，使用了权利要求1～11中任一所述的碳载铂族金属催化剂。
  8. 一种碳材料，其特征在于，所述碳材料为氮掺杂导电炭黑，在其XPS分析的N 1s谱峰中，除399ev～400.5ev之间有特征峰外，在395ev～405ev之间没有其他的特征峰。
  9. 如权利要求1-6中任一项所述碳载铂族金属催化剂的制备方法，包括以下步骤：
    (1)浸渍氮源的步骤：将碳材料与氮源水溶液混合，浸渍，得到浸渍有氮源的碳材料；
    (2)制造氮掺杂碳材料的步骤：将步骤(1)中所得浸渍有氮源的碳材料在惰性气体中以8℃/min～15℃/min的速率升温至1000℃～1500℃，然后恒温处理0.5h～10h，得到掺杂有氮的碳材料；和
    (3)负载铂族金属的步骤：以步骤(2)中所得掺杂有氮的碳材料为载体，负载铂族金属的步骤；
    其中所述碳材料优选为导电炭黑。
  10. 按照权利要求9所述的制备方法，其特征在于，(2)中，所述恒温处理的温度为1150℃～1450℃。
  11. 按照权利要求9所述的制备方法，其特征在于，所述氮源为氨水/或尿素。
  12. 按照权利要求9所述的制备方法，其特征在于，氮源质量按其所含氮元素的质量计，所述碳材料与氮源的质量比为30：1～1：2。
  13. 按照权利要求6所述的制备方法，其特征在于，所述碳材料的XPS分析中，氧质量分数大于4％。
  14. 按照权利要求9所述的制备方法，其特征在于，所述负载铂族金属的步骤包括：
    (a)将步骤(2)中得到的掺杂有氮的碳材料与铂族金属前驱体分散在水相中，调节pH为8～12；
    (b)加入还原剂进行还原；和
    (c)分离出固体，经后处理得到所述的铂碳催化剂。
  15. 按照权利要求14所述的制备方法，其特征在于，所述铂族金属前驱体为氯铂酸、氯铂酸钾或氯铂酸钠；所述铂族金属前驱体的浓度为0.5mol/L～5mol/L。
  16. 按照权利要求14所述的制备方法，其特征在于，步骤(b)中，所述还原剂选自柠檬酸、抗坏血酸、甲醛、甲酸、乙二醇、柠檬酸钠、水合肼、硼氢化钠和丙三醇；所述还原剂与铂的摩尔比为2～100；还原温度为50℃～150℃；还原时间为2h～15h。
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