CN114430046B - Sulfur-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof - Google Patents
Sulfur-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof Download PDFInfo
- Publication number
- CN114430046B CN114430046B CN202011014087.XA CN202011014087A CN114430046B CN 114430046 B CN114430046 B CN 114430046B CN 202011014087 A CN202011014087 A CN 202011014087A CN 114430046 B CN114430046 B CN 114430046B
- Authority
- CN
- China
- Prior art keywords
- platinum
- sulfur
- carbon
- carbon material
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 157
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000003575 carbonaceous material Substances 0.000 title abstract description 187
- YYPYFBVEXBVLBS-UHFFFAOYSA-N [B].[S] Chemical compound [B].[S] YYPYFBVEXBVLBS-UHFFFAOYSA-N 0.000 title abstract description 120
- 238000002360 preparation method Methods 0.000 title abstract description 37
- 238000001228 spectrum Methods 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 118
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 84
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 77
- 229910052717 sulfur Inorganic materials 0.000 claims description 71
- 239000011593 sulfur Substances 0.000 claims description 71
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 56
- 229910052796 boron Inorganic materials 0.000 claims description 56
- 229910052697 platinum Inorganic materials 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 46
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 32
- 238000004458 analytical method Methods 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 239000000446 fuel Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 241000220324 Pyrus Species 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 235000021017 pears Nutrition 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical compound [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 238000002441 X-ray diffraction Methods 0.000 abstract 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 47
- 238000012360 testing method Methods 0.000 description 31
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 22
- 238000006722 reduction reaction Methods 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- 239000011148 porous material Substances 0.000 description 17
- 239000000523 sample Substances 0.000 description 15
- 239000002041 carbon nanotube Substances 0.000 description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 11
- 229910021389 graphene Inorganic materials 0.000 description 11
- 239000003273 ketjen black Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 125000005842 heteroatom Chemical group 0.000 description 9
- 239000000725 suspension Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000002902 bimodal effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a sulfur-boron doped carbon material, a platinum-carbon catalyst, a preparation method and application thereof, wherein the sulfur-boron doped carbon material is analyzed by XPS (X-ray analysis) to obtain B 1s The spectrum peak has characteristic peaks between 189ev and 191 ev. The platinum-carbon catalyst taking the carbon material as the carrier has excellent mass specific activity, ECSA and stability.
Description
Technical Field
The invention relates to a sulfur-boron doped carbon material, a platinum-carbon catalyst, and a preparation method and application thereof.
Background
In the chemical field, carbon materials are both important supports and commonly used catalysts. The bonding mode of the carbon element is rich, and the carbon material can be modified in various modes so as to obtain better performance.
Oxygen Reduction Reactions (ORR) are key reactions in the electrochemical field, such as in fuel cells and metal-air cells, and are a major factor affecting cell performance. The atomic doped carbon material can be used directly as a catalyst for the oxygen reduction reaction. When used as an oxygen reduction catalyst, it has been reported that carbon materials incorporate elements such as nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine, iodine, etc., wherein nitrogen has a radius close to that of carbon atoms and is easily incorporated into carbon lattices, and thus is the most commonly used doping element. Although there are many reports of carbon doped materials as fuel cell catalysts and some research results show better activity, there are large gaps compared to platinum carbon catalysts and far from commercial applications. On one hand, the combination mode of hetero atoms and carbon materials and the catalysis mechanism thereof are not fully known in the field; on the other hand, each heteroatom has multiple bonding modes with the carbon material, and when doping multiple heteroatoms, the situation is more complex, so how to control the bonding modes of the heteroatoms and the carbon material is a difficulty of doping atoms. In addition, such catalysts are generally not suitable for use in acidic environments, particularly Proton Exchange Membrane Fuel Cells (PEMFCs), which are important.
The most effective oxygen reduction catalysts to date are platinum carbon catalysts, and the dispersion of platinum metal in the currently used commercial platinum carbon catalysts is not ideal and is easy to agglomerate and deactivate, on the other hand, platinum dissolution and agglomeration of the cathode of the hydrogen fuel cell lead to obvious reduction of platinum surface area with time, and the service life of the fuel cell is affected. There is a great desire in the art to greatly increase the catalytic activity and stability thereof in an effort to promote its large-scale commercial use. Many factors and complications affect the activity and stability of the platinum carbon catalyst, and some documents believe that the activity and stability of the platinum carbon catalyst are related to the particle size, morphology, structure of the platinum, as well as the type, nature and platinum loading of the support. The prior art mainly improves the performance of the platinum-carbon catalyst by controlling the particle size, morphology, structure and specific surface area of the carrier and pore structure of the platinum; there are also reports of modification groups attached to the carbon surface to improve the performance of platinum carbon catalysts by modifying the carbon support.
The platinum loading of the practically applied hydrogen fuel cell platinum carbon catalyst is at least more than 20wt%, which is much more difficult to manufacture than chemical platinum carbon catalysts (platinum loading is less than 5 wt%). The increase of the platinum carrying amount is beneficial to manufacturing a thinner membrane electrode with better performance, but the increase of the platinum carrying amount greatly is easier to cause accumulation among platinum metal particles, so that the utilization rate of active sites is drastically reduced. How to more effectively utilize the catalytic active sites of platinum metal particles and increase the accessible three-phase catalytic reaction interface, thereby improving the utilization rate of platinum and the comprehensive performance of fuel cells and metal-air cells is a key problem to be solved in the art.
The defect sites of the carbon carrier are more favorable for improving the platinum carrying amount, but at the same time, the carbon corrosion is aggravated, and the stability of the platinum-carbon catalyst is reduced. The improvement of the graphitization degree can effectively relieve carbon corrosion, but the high graphitization degree also makes the surface of the carbon carrier chemically inert, so that platinum is difficult to uniformly disperse on the carbon carrier, and the platinum carrying is particularly difficult when the platinum carrying amount is high.
The chemical reduction method is a common method for manufacturing platinum-carbon catalyst, and has the advantages of simple process, low utilization rate of platinum and low catalytic activity. The reason for this may be that the irregular pore structure of the carbon support causes uneven dispersion of the platinum nanoparticles.
The information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and may include information that is not already known to those of ordinary skill in the art.
Disclosure of Invention
It is a first object of the present invention to provide a new carbon material. The second object of the present invention is to provide a platinum carbon catalyst excellent in comprehensive catalytic performance. A third object of the present invention is to provide a platinum carbon catalyst with a high platinum loading amount in addition to the foregoing object.
In order to achieve the above object, the present invention provides the following technical solutions.
1. A sulfur-boron doped carbon material is characterized in that the material is analyzed by XPS 1s The spectrum peak has characteristic peaks between 189ev and 191 ev.
2. The sulfur-boron doped carbon material of 1, wherein S is analyzed by XPS 2P The spectrum peak is 160 ev-170 ev, and only the characteristic peak of thiophene-type sulfur is included.
3. The sulfur-boron doped carbon material of 1, wherein S is analyzed by XPS 2P Among the spectral peaks, between 162eV and 166eV, there is only a characteristic peak of thiophene-type sulfur, and there is a characteristic peak at 168±1.5 eV.
4. The sulfur-boron doped carbon material according to 2 or 3, wherein the characteristic peak of the thiophene sulfur is bimodal and is located at 163.4.+ -. 0.5ev and 164.7.+ -. 0.5ev, respectively.
5. The sulfur-boron doped carbon material according to any one of the foregoing, characterized in that B in XPS analysis thereof 1s One or two characteristic peaks exist between 191ev and 193ev in the spectrum peaks.
6. The sulfur-boron doped carbon material according to any one of the foregoing, characterized in that B in XPS analysis thereof 1s There are one or two characteristic peaks between 189ev and 191ev in the spectrum peaks.
7. The sulfur-boron doped carbon material according to any of the preceding claims, characterized in that the resistivity of the sulfur-boron doped carbon material is <10Ω -m, preferably <5Ω -m, more preferably <3Ω -m.
8. The sulfur-boron doped carbon material according to any one of the above, wherein in XPS analysis of the sulfur-boron doped carbon material, the mass fraction of sulfur is 0.1% to 5%, and the mass fraction of boron is 0.1% to 5%; preferably, the mass fraction of sulfur is 0.2-3%, and preferably, the mass fraction of boron is 0.2-3%; more preferably, the sulfur mass fraction is 0.4% to 1%. More preferably, the mass fraction of boron is 0.4% -2%.
9. The sulfur-boron-doped carbon material according to any one of the preceding claims, wherein the specific surface area of the sulfur-boron-doped carbon material is 10m 2 /g～2000m 2 /g, preferably 200m 2 /g～2000m 2 /g; the pore volume is 0.02mL/g to 6.0mL/g, preferably 0.2mL/g to 3.0mL/g.
10. The sulfur-boron doped carbon material according to any one of the preceding claims, characterized in that the sulfur-boron doped carbon material is sulfur-boron doped graphene, sulfur-boron doped carbon nanotubes or sulfur-boron doped conductive carbon black.
11. The sulfur-boron doped carbon material according to any of the preceding claims, wherein said conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
12. A preparation method of a sulfur-boron doped carbon material comprises the following steps: and (3) contacting the carbon material with a boron source and a sulfur source, and treating the carbon material in an inert gas at 300-1500 ℃ for 0.5-10 h to obtain the sulfur-boron doped carbon material.
13. The method for preparing the sulfur-boron doped carbon material according to any one of the above, wherein the mass ratio of the carbon material to the sulfur source is 20: 1-2: 1, a step of; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.
14. the preparation method of the sulfur-boron doped carbon material according to any one of the above, characterized in that the mass ratio of the carbon material to the boron source is 100, based on the mass of boron contained in the boron source: 1 to 5:1, a step of; preferably 60:1 to 15:1.
15. The preparation method of the sulfur-boron doped carbon material is characterized in that the sulfur source is elemental sulfur.
16. The preparation method of the sulfur-boron doped carbon material is characterized in that the boron source is one or more of boric acid and borate.
17. The method for preparing the sulfur-boron doped carbon material according to any one of the above, wherein the temperature is 1000 ℃ to 1500 ℃, preferably 1100 ℃ to 1300 ℃.
18. The method for producing a sulfur-boron doped carbon material according to any one of the above, wherein the treatment time is 1 to 5 hours, preferably 2 to 4 hours.
19. The preparation method of the sulfur-boron doped carbon material is characterized in that the carbon material is graphene, carbon nano tubes or conductive carbon black.
20. The method for preparing the sulfur-boron doped carbon material according to any one of the preceding claims, wherein the carbon material is EC-300J, EC-600JD, ECP-600JD, VVC 72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
21. The method for producing a sulfur-boron doped carbon material according to any one of the above, wherein the carbon material has an oxygen mass fraction of more than 4%, preferably 4% to 15%, in XPS analysis.
22. The method for producing a sulfur-boron doped carbon material according to any one of the above, characterized in that the carbon material has a resistivity of <10Ω·m, preferably <5Ω·m, more preferably <2Ω·m.
23. The method for producing a sulfur-boron-doped carbon material according to any one of the above, characterized in that the specific surface area of the carbon material is 10m 2 /g～2000m 2 /g, preferably 200m 2 /g～2000m 2 /g; the pore volume is 0.02mL/g to 6mL/g, preferably 0.2mL/g to 3mL/g.
24. The sulfur-boron doped carbon material prepared by any one of the methods.
25. The use of any of the foregoing sulfur-boron doped carbon materials as electrode materials in electrochemistry.
26. A platinum carbon catalyst characterized by comprising a carbon support and a platinum metal supported thereon; the carbon support is the sulfur-boron doped carbon material of any one of claims 1 to 11 and 25.
27. The platinum carbon catalyst according to 27, characterized by S in XPS analysis thereof 2P The spectrum peak is 160 ev-170 ev, and only the characteristic peak of thiophene-type sulfur is included.
28. The platinum carbon catalyst according to 27, characterized by S in XPS analysis thereof 2P Among the spectral peaks, between 162eV and 166eV, there is only a characteristic peak of thiophene-type sulfur, and there is a characteristic peak at 168±1.5 eV.
29. The platinum carbon catalyst according to any one of the preceding claims, wherein the characteristic peaks of the thiophene-type sulfur are bimodal and are located at 163.4±0.5ev and 164.7±0.5ev, respectively.
30. The platinum carbon catalyst according to any one of the preceding claims, characterized in that B is analyzed by XPS 1s There are no characteristic peaks between 185ev and 200ev in the spectrum peaks.
31. The platinum carbon catalyst according to any one of the preceding claims, characterized in that the platinum carbon catalyst has a resistivity of <10 Ω -m, preferably <2 Ω -m.
32. The platinum carbon catalyst according to any one of the preceding claims, wherein the sulfur-boron doped carbon material is sulfur-boron doped graphene, sulfur-boron doped carbon nanotubes or sulfur-boron doped conductive carbon black.
33. The platinum carbon catalyst according to any one of the preceding claims, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
34. A method for preparing a platinum carbon catalyst, comprising: (1) a step of manufacturing a sulfur-boron doped carbon material: contacting the carbon material with a boron source and a sulfur source, and treating the carbon material in an inert gas at 300-1500 ℃ for 0.5-10 h to obtain the sulfur-boron doped carbon material; (2) And (3) taking the sulfur-boron doped carbon material obtained in the step (1) as a carrier to load platinum.
35. The method for producing a platinum carbon catalyst according to any one of the preceding claims, wherein in (1), the mass ratio of the carbon material to the sulfur source is 20, based on the mass of sulfur contained therein: 1-2: 1, a step of; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.
36. The method for producing a platinum carbon catalyst according to any one of the preceding methods, wherein in (1), the mass ratio of the carbon material to the boron source is 100, based on the mass of boron contained in the boron source: 1 to 5:1, a step of; preferably 60:1 to 15:1.
37. the process for producing a platinum carbon catalyst according to any one of the preceding claims, wherein in (1), the temperature is 1000℃to 1500℃and preferably 1100℃to 1300 ℃.
38. The process for producing a platinum carbon catalyst according to any one of the above (1), wherein the treatment time is 1 to 5 hours, preferably 2 to 4 hours.
39. The method for preparing a platinum carbon catalyst according to any one of the preceding claims, wherein in (1), the carbon material is graphene, carbon nanotubes or conductive carbon black.
40. The preparation method of any one of the platinum carbon catalysts is characterized in that the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLASK 40B2.
41. The method for producing a platinum carbon catalyst according to any one of the above (1), wherein in the XPS analysis of the carbon material, the mass fraction of oxygen is more than 4%, preferably 4% to 15%.
42. The method for producing a platinum carbon catalyst according to any one of the above (1), wherein in (1), the specific resistance of the carbon material is <10Ω·m, preferably <5Ω·m, and more preferably <2Ω·m.
43. The process for producing a platinum carbon catalyst according to any one of the preceding (1), wherein in (1), the specific surface area of the carbon material is 10m 2 /g～2000m 2 /g, preferably 200m 2 /g～2000m 2 /g; the pore volume is 0.02mL/g to 6mL/g, preferably 0.2mL/g to 3mL/g.
44. The method for preparing the platinum-carbon catalyst according to any one of the preceding claims, wherein the step of supporting platinum comprises the steps of:
(a) Dispersing the sulfur-boron doped carbon material obtained in the step (1) and a platinum precursor in an aqueous phase, and adjusting the pH to 8-12 (preferably adjusting the pH to 10+/-0.5);
(b) Reducing agent is added for reduction;
(c) Separating out solid, and post-treating to obtain the platinum carbon catalyst.
45. The method for preparing the platinum carbon catalyst according to any one of the preceding methods, wherein in (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate or sodium chloroplatinate; the concentration of the platinum precursor is 0.5 mol/L-5 mol/L.
46. The preparation method of any platinum-carbon catalyst is characterized in that in the step (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the mol ratio of the reducing agent to the platinum is 2-100; the reduction temperature is 60-90 ℃; the reduction time is 4-15 h.
47. A platinum carbon catalyst, characterized by being prepared by any one of the aforementioned platinum carbon catalyst preparation methods.
48. A hydrogen fuel cell characterized in that any one of the platinum carbon catalysts described above is used for an anode and/or a cathode of the hydrogen fuel cell.
The hetero atoms and the carbon materials have various combination modes, the doping method and the raw materials are different, and the operation steps and the conditions of the doping process are different, so that the combination modes of the hetero atoms and the carbon materials are influenced, the property differences of the hetero atoms and the carbon materials are caused, and the functions of the hetero atoms and the carbon materials are changed. How to control the way heteroatoms are bound to carbon materials is a difficulty in the art when doping atoms. Controlling impuritiesThe manner in which atoms are bonded to the carbon material may result in a carbon material that is uniquely characterized, thereby rendering it suitable for a particular application. The research of the invention shows that the carbon material can be obtained by doping the sulfur source and the boron source simultaneously, and in the XPS analysis of the carbon material, the boron B 1s The characteristic peak of 190.0+/-1 ev exists in the map, S of sulfur 2p In the spectrogram, by controlling the doping conditions, only the characteristic peak of the thiophene-type sulfur can be provided, and the characteristic peaks of the thiophene-type sulfur and the oxidized sulfur can be provided at the same time. Further research has also found that the sulfur-boron doped carbon material of the present invention is suitable as a carrier for a platinum carbon catalyst of a hydrogen fuel cell.
Compared with the prior art, the invention can realize the following beneficial technical effects.
1. The invention prepares a sulfur-boron doped carbon material, B of boron 1s Characteristic peaks exist between 189ev and 191ev in the map; furthermore, the combination mode of sulfur and carbon materials can be controlled, and the carbon material with thiophene sulfur doped on the surface of the carbon material or the carbon material with both thiophene sulfur and oxidized sulfur doped on the surface of the carbon material can be obtained by a simple method.
2. The carbon material manufactured by the invention is suitable for being used as a carrier of a platinum-carbon catalyst, in particular to a platinum-carbon catalyst with high platinum loading.
3. The platinum-carrying amount of the practically applied platinum-carbon catalyst of the hydrogen fuel cell is generally more than 20 weight percent, and the difficulty in manufacturing the high-platinum-carrying catalyst with excellent performance is great. The chemical reduction method has simple process, but the utilization rate of platinum is low and the catalytic activity is low. However, the sulfur-boron doped carbon material prepared by the method is used as a carrier, and a high-load platinum catalyst with good mass specific activity and stability can be easily prepared by adopting a water phase chemical reduction method.
4. The platinum-carbon catalyst prepared by the invention has excellent mass specific activity, ECSA and stability.
5. Sulfur is generally believed to have an irreversible deleterious effect on platinum catalysts, however, the present inventors have discovered that by modifying carbon materials with sulfur doping, the catalytic activity of platinum carbon catalysts and their stability are significantly improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Fig. 1 is an XPS spectrum of sulfur of the sulfur-boron doped carbon material of example 1.
Fig. 2 is an XPS spectrum of boron of the sulfur-boron doped carbon material of example 1.
Fig. 3 is an XPS spectrum of sulfur of the sulfur-boron doped carbon material of example 2.
Fig. 4 is an XPS spectrum of sulfur of the sulfur-boron doped carbon material of example 3.
Fig. 5 is an XPS spectrum of boron of the sulfur-boron doped carbon material of example 3.
Fig. 6 is an XPS spectrum of sulfur of the sulfur-boron doped carbon material of example 4.
Fig. 7 is an XPS spectrum of boron of the sulfur-boron doped carbon material of example 4.
Fig. 8 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 5.
Fig. 9 is a polarization (LSV) curve before and after 5000 turns of the platinum carbon catalyst of example 5.
FIG. 10 is a CV curve before and after 5000 cycles of the Pt-C catalyst of example 5.
Fig. 11 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 6.
Fig. 12 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 7.
Fig. 13 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 8.
Fig. 14 is a polarization curve before and after 5000 turns for the commercial platinum carbon catalyst of comparative example 4.
Detailed Description
The invention is described in detail below in connection with the embodiments, but it should be noted that the scope of the invention is not limited by these embodiments and the principle explanation, but is defined by the claims.
In the present invention, any matters or matters not mentioned are directly applicable to those known in the art without modification except for those explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all considered as part of the original disclosure or description of the present invention, and should not be considered as new matters not disclosed or contemplated herein unless such combination would obviously be unreasonable to one skilled in the art.
All of the features disclosed in this invention may be combined in any combination which is known or described in the present invention and should be interpreted as specifically disclosed and described in the present invention unless the combination is obviously unreasonable by those skilled in the art. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the embodiments but also the end points of each numerical range in the specification, and any combination of these numerical points should be considered as a disclosed or described range of the present invention.
Technical and scientific terms used in the present invention are defined to have their meanings, and are not defined to have their ordinary meanings in the art.
The "doping element" in the present invention means nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine.
In the present invention, reference to "carbon material" refers to carbon material that does not contain a doping element, except that it may be uniquely determined to be "carbon material containing a doping element" depending on the context or definition itself. The same is true of the underlying concept of carbon materials.
In the present invention, "carbon black" and "carbon black" are interchangeable terms of art.
The "inert gas" in the present invention refers to a gas that does not have any appreciable effect on the properties of the sulfur-boron doped carbon material in the preparation process of the present invention. The same is true of the underlying concept of carbon materials.
In the present invention, other references to "pore volume" refer to P/P unless otherwise clear from context or definition of the same 0 The single point adsorption total pore volume at maximum.
The invention provides a sulfur-boron doped carbon material, which is characterized in that the material is analyzed by XPS 1s The spectrum peak has characteristic peaks between 189ev and 191 ev.
The sulfur-boron doped carbon material according to the present invention does not contain other doping elements than sulfur and boron.
The sulfur-boron doped carbon material according to the present invention is free of metal elements.
According to the sulfur-boron doped carbon material of the present invention, in some embodiments, the S of XPS analysis thereof 2P The spectrum peak is 160 ev-170 ev, and only the characteristic peak of thiophene-type sulfur is included.
According to the sulfur-boron doped carbon material of the present invention, in some embodiments, the S of XPS analysis thereof 2P Of the spectral peaks, only the characteristic peak of thiophene-type sulfur is present.
According to the sulfur-boron doped carbon material of the present invention, in some embodiments, there is no characteristic peak between 166ev and 170ev in XPS analysis thereof.
According to the sulfur-boron doped carbon material of the present invention, in some embodiments, the XPS analysis thereof 2P In the spectrum peaks, between 162ev and 166ev, only the characteristic peak of thiophene sulfur exists, and the characteristic peak exists at 168+/-1.5 ev; in addition to that, S was analyzed in its XPS 2P There are no other characteristic peaks between 160ev and 170ev in the spectrum peaks.
According to the sulfur-boron doped carbon material, characteristic peaks of the thiophene sulfur are bimodal and are respectively located at 163.4+/-0.5 ev and 164.7+/-0.5 ev.
The sulfur-boron doped carbon material according to the invention has been analyzed by XPS analysis of B 1s One or two characteristic peaks exist between 191ev and 193ev in the spectrum peaks.
The sulfur-boron doped carbon material according to the invention has been analyzed by XPS analysis of B 1s There are one or two characteristic peaks between 189ev and 191ev in the spectrum peaks.
The boron-sulfur doped carbon material according to the present invention has a resistivity of <10.0 Ω -m, preferably <5.0 Ω -m, more preferably <3.0 Ω -m.
In XPS analysis, the sulfur-boron doped carbon material has the mass fraction of sulfur of 0.1-5% and the mass fraction of boron of 0.1-5%; preferably, the mass fraction of sulfur is 0.2-3%, and the mass fraction of boron is 0.2-3%; more preferably, the sulfur mass fraction is 0.4% -1%. The mass fraction of the boron is 0.4-2%.
The sulfur-boron doped carbon material according to the present invention is not particularly limited in oxygen content. Generally, the mass fraction of oxygen analyzed by XPS is 2% -15%.
The specific surface area and the pore volume of the sulfur-boron doped carbon material according to the invention can be changed within a wide range, for example, the specific surface area can be 10m 2 /g～2000m 2 The pore volume may be 0.02mL/g to 6.0mL/g. In one embodiment, the specific surface area is 200m 2 /g～2000m 2 Per gram, the pore volume is 0.2 mL/g-3.0 mL/g.
According to the sulfur-boron doped carbon material, the sulfur-boron doped carbon material is sulfur-boron doped graphene, sulfur-boron doped carbon nanotubes or sulfur-boron doped conductive carbon black. The conductive carbon black can be common conductive carbon black (Conductive Blacks), super conductive carbon black (Super Conductive Blacks) or special conductive carbon black (Extra Conductive Blacks), for example, the conductive carbon black can be one or more of Ketjen black series super conductive carbon black, cabot series conductive carbon black and series conductive carbon black produced by Yingchang solid Saint Co; preferably Ketjen Black EC-300J, ketjen Black EC-600JD, ketjen Black ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
According to the sulfur-boron doped carbon material, the preparation method and the source of the conductive carbon black are not limited. The conductive carbon black can be acetylene black, furnace black and the like.
According to the sulfur-boron doped carbon material, the carbon nanotube or the graphene can be oxidized carbon nanotube or graphene or non-oxidized carbon nanotube or graphene.
According to the sulfur-boron doped carbon material of the present invention, the sulfur and boron are chemically bonded to the carbon material.
The invention also provides a preparation method of the sulfur-boron doped carbon material, which comprises the following steps: and (3) contacting the carbon material with a boron source and a sulfur source, and treating (preferably carrying out constant temperature treatment) in an inert gas at 300-1500 ℃ for 0.5-10 h to obtain the sulfur-boron doped carbon material.
According to the method for preparing the sulfur-boron doped carbon material of the present invention, the carbon material is contacted with a boron source and a sulfur source in a mixed manner. The order and manner in which the carbon material is mixed with the boron source and the sulfur source is not limited by the present invention, and those skilled in the art can select an appropriate order and manner based on the teachings and/or prior knowledge of the present invention. The invention provides a preferred mixing mode: the carbon material is first mixed with a boron source solution (preferably an aqueous solution), impregnated, dried, and then mixed with a sulfur source.
According to the preparation method of the sulfur-boron doped carbon material, the carbon material can be conductive carbon black, carbon nano tubes or graphene. The conductive carbon black can be one or more of Ketjen black series superconducting carbon black, cabot series conductive carbon black and series conductive carbon black produced by Yingchang De Guest company; preferably EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
According to the preparation method of the sulfur-boron doped carbon material, I of the carbon material D /I G The value is generally from 0.8 to 5, preferably from 1 to 4. In Raman spectrum, at 1320cm -1 The nearby peak is D peak, which is located at 1580cm -1 The nearby peak is G peak, I D Representing the intensity of the D peak, I G Representing the intensity of the G peak.
According to the preparation method of the sulfur-boron doped carbon material, the sulfur source is elemental sulfur.
According to the preparation method of the sulfur-boron doped carbon material, the mass ratio of the carbon material to the sulfur source is 20: 1-2: 1, a step of; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.
according to the preparation method of the sulfur-boron doped carbon material, the boron source is one or more of boric acid and borate.
According to the preparation method of the sulfur-boron doped carbon material, the mass ratio of the carbon material to the boron source is 100, wherein the mass ratio of the boron source to the boron contained in the carbon material is as follows: 1 to 5:1, a step of; preferably 60:1 to 15:1.
according to the preparation method of the sulfur-boron doped carbon material, the inert gas is nitrogen or argon.
According to the preparation method of the sulfur-boron doped carbon material, if the temperature is required to be raised, the temperature raising rate can be 1-20 ℃ per minute, preferably 3-15 ℃ per minute, and more preferably 8-15 ℃ per minute.
According to the preparation method of the sulfur-boron doped carbon material, the temperature can be 500-1500 ℃, 700-1500 ℃, 1000-1500 ℃ or 1000-1300 ℃.
The treatment time is preferably 1 to 5 hours, more preferably 2 to 4 hours.
According to the method for preparing the sulfur-boron doped carbon material, the resistivity of the carbon material is <10Ω -m, preferably <5Ω -m, more preferably <2Ω -m.
According to the preparation method of the sulfur-boron doped carbon material, in XPS analysis of the carbon material, the mass fraction of oxygen is generally more than 4%, preferably 4% -15%.
According to the preparation method of the sulfur-boron doped carbon material, the specific surface area of the carbon material can be changed in a large range. Generally, the specific surface area is 10m 2 /g～2000m 2 /g; the pore volume is 0.02 mL/g-6 mL/g.
According to the preparation method of the sulfur-boron doped carbon material, in one embodiment, the carbon material impregnated with the boron source is mixed with the sulfur source, placed in a tube furnace, heated to 300 ℃ -1500 ℃ (preferably 700 ℃ -1500 ℃, more preferably 1000 ℃ -1500 ℃) in inert gas at a speed of 8 ℃/min-15 ℃/min, and then subjected to constant temperature treatment for 0.5 h-10 h, thus obtaining the sulfur-boron co-doped carbon material.
The inert gas is nitrogen or argon.
According to the preparation method of the sulfur-boron doped carbon material, a metal-containing catalyst is not used in the process of preparing the sulfur-boron doped carbon material.
The invention also provides the sulfur-boron doped carbon material prepared by any one of the methods.
The use of any of the foregoing sulfur-boron doped carbon materials as electrode materials in electrochemistry.
A platinum carbon catalyst comprising a carbon support and a platinum metal supported thereon, the carbon support being any one of the carbon materials described above.
The platinum carbon catalyst according to the present invention does not contain other doping elements except sulfur and boron.
The platinum carbon catalyst according to the present invention does not contain other metal elements than platinum.
According to the platinum carbon catalyst of the present invention, the sulfur and boron are chemically bonded to the carbon material.
According to the platinum carbon catalyst of the present invention, in some examples, S was analyzed by XPS 2P Among the spectral peaks, between 162ev and 166ev, there is only a characteristic peak of thiophene-type sulfur, and there is a characteristic peak at 168±1.5 ev. In addition to that, S was analyzed in its XPS 2P There are no other characteristic peaks between 160ev and 170ev in the spectrum peaks.
According to the platinum carbon catalyst of the present invention, in some examples, S was analyzed by XPS 2P The spectrum peak is 160 ev-170 ev, and only the characteristic peak of thiophene-type sulfur is included.
According to the platinum carbon catalyst of the present invention, the characteristic peaks of the thiophene sulfur are bimodal, and are located at 163.4.+ -. 0.5ev and 164.7.+ -. 0.5ev, respectively.
The platinum carbon catalyst according to the present invention has no B in its XPS analysis between 185ev and 200ev 1s Is a characteristic peak of (2).
According to the platinum carbon catalyst of the present invention, a boron signal (B) was detected in a TG-MS (thermogravimetric-mass spectrometry) test 2 O 3 And B) a method for producing a polymer.
The platinum carbon catalyst according to the present invention has a mass fraction of platinum of 0.1 to 80%, preferably 20 to 70%, more preferably 40 to 70%, based on the mass of the catalyst.
The platinum carbon catalyst according to the invention has a resistivity of <10.0 Ω -m, preferably <2.0 Ω -m.
According to the platinum carbon catalyst of the present invention, the specific surface area of the platinum carbon catalyst is 80m 2 /g～1500m 2 /g, preferably 100m 2 /g～200m 2 /g。
According to the platinum carbon catalyst of the present invention, the carbon material may be conductive carbon black, graphene or carbon nanotubes. The conductive carbon black can be one or more of Ketjen black series superconducting carbon black, cabot series conductive carbon black and series conductive carbon black produced by Yingchangzhucai company; preferably Ketjen Black EC-300J, ketjen Black EC-600JD, ketjen Black ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
The invention provides a preparation method of a platinum-carbon catalyst, which comprises the following steps: comprising the following steps: (1) a step of manufacturing a sulfur-boron doped carbon material: contacting the carbon material with a boron source and a sulfur source, and treating (preferably carrying out constant temperature treatment) the carbon material in inert gas at 300-1500 ℃ for 0.5-10 h to obtain the sulfur-boron doped carbon material; (2) And (3) taking the sulfur-boron doped carbon material obtained in the step (1) as a carrier to load platinum.
According to the preparation method of the platinum carbon catalyst, the contact mode of the carbon material with the boron source and the sulfur source is the same as the corresponding part in the previous description, and the invention is not repeated.
According to the preparation method of the platinum carbon catalyst, in (1), the mass ratio of the carbon material to the sulfur source is 20: 1-2: 1, a step of; preferably 10:1 to 4:1, more preferably 8:1 to 4:1.
According to the preparation method of the platinum carbon catalyst, in the (1), the mass ratio of the carbon material to the boron source is 100:1 to 5:1, a step of; preferably 60:1 to 15:1.
according to the preparation method of the platinum carbon catalyst, the sulfur source is elemental sulfur.
According to the preparation method of the platinum carbon catalyst, the boron source is one or more of boric acid and borate.
According to the preparation method of the platinum carbon catalyst, if heating is needed in the step (1), the heating rate can be 1-20 ℃ per minute, preferably 3-15 ℃ per minute, and more preferably 8-15 ℃ per minute.
According to the method for preparing a platinum carbon catalyst of the present invention, in (1), the temperature is 700 to 1500 ℃, preferably 1000 to 1500 ℃, more preferably 1100 to 1300 ℃.
According to the method for preparing a platinum carbon catalyst of the present invention, in (1), the treatment time is 1 to 5 hours, preferably 2 to 4 hours.
According to the preparation method of the platinum carbon catalyst, in the (1), the carbon material is graphene, conductive carbon black or carbon nano tube. The conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
According to the preparation method of the platinum carbon catalyst, in (1), the mass fraction of oxygen in XPS analysis of the carbon material is more than 4%, preferably 4% -15%.
According to the method for producing a platinum carbon catalyst of the present invention, in (1), the specific resistance of the carbon material is <10Ω·m, preferably <5Ω·m, more preferably <2Ω·m.
According to the method for producing a platinum carbon catalyst of the present invention, (1) the specific surface area of the carbon material is 10m 2 /g～2000m 2 /g, preferably 200m 2 /g～2000m 2 /g; the pore volume is 0.02mL/g to 6mL/g, preferably 0.2mL/g to 3mL/g.
A platinum carbon catalyst prepared by any one of the methods for preparing a platinum carbon catalyst described above.
A hydrogen fuel cell uses any one of the platinum carbon catalysts described above in the anode and/or cathode of the hydrogen fuel cell.
The platinum-carbon catalyst according to the present invention has a mass specific activity decrease rate of <10% after 5000 cycles and an ECSA decrease rate of <15% after 5000 cycles when used in an oxygen reduction reaction.
The platinum carbon catalyst of the present invention, when used in an oxygen reduction reaction, in some examples, ECSA>46m 2 g -1 Pt, e.g. at 46m 2 g -1 -Pt～88m 2 g -1 -Pt。
The platinum carbon catalyst of the present invention, when used in an oxygen reduction reaction, in some examples, has a mass specific activity>0.139A mg -1 Pt, e.g. 0.139A mg -1 -Pt～0.282A mg -1 -Pt。
The platinum carbon catalyst of the present invention, when used in an oxygen reduction reaction, has a half-wave potential of >0.88V, such as 0.88V to 0.91V, in some examples.
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way.
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the present invention are analytically pure and commercially available.
The invention detects the elements on the surface of the material by an X-ray photoelectron spectroscopy (XPS). The X-ray photoelectron spectroscopy analyzer used was an ESCALab220i-XL type radiation electron spectroscopy manufactured by VG scientific company and equipped with Avantage V5.926 software, and the X-ray photoelectron spectroscopy analysis test conditions were: the excitation source is monochromized A1K alpha X-ray with power of 330W and basic vacuum of 3X 10 during analysis and test -9 mbar. In addition, the electron binding energy was corrected by the C1s peak (284.3 eV) of elemental carbon, and the post-peak splitting treatment software was XPSPEAK. Characteristic peaks of thiophene sulfur and boron in the spectrogram are characteristic peaks after peak separation.
Instrument and method for elemental analysis, conditions: elemental analyzer (Vario EL Cube), reaction temperature 1150 ℃, 5mg of sample, reduction temperature 850 ℃, carrier gas helium flow rate 200mL/min, oxygen flow rate 30mL/min, and oxygen introduction time 70s.
Apparatus, method, conditions for testing mass fraction of platinum in platinum carbon catalyst: 30mg of the prepared Pt/C catalyst is taken, 30mL of aqua regia is added, the mixture is condensed and refluxed for 12 hours at 120 ℃, cooled to room temperature, and the supernatant is taken for dilution, and then the content of Pt in the mixture is tested by ICP-AES.
The model of the high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100 (HRTEM) (Japanese electronics Co., ltd.) and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200kV. The particle size of the nano particles in the sample is measured by an electron microscope picture.
BET test method: in the invention, the pore structure property of a sample is measured by a Quantachrome AS-6B type analyzer, the specific surface area and the pore volume of the catalyst are obtained by a Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
The Raman detection of the invention adopts a LabRAM HR UV-NIR laser confocal Raman spectrometer manufactured by HORIBA company of Japan, and the laser wavelength is 532nm.
Electrochemical performance testing, instrument models Solartron analytical EnergyLab and Princeton Applied Research (Model 636A), methods and test conditions: polarization curve LSV of catalyst O at 1600rpm 2 Saturated 0.1M HClO 4 CV Curve 0.1M HClO under Ar atmosphere 4 The electrochemically active area ECSA was calculated therefrom. Stability test at O 2 Saturated 0.1M HClO 4 After 5000 cycles of scanning in the range of 0.6V to 0.95V, LSV and ECSA were tested as described above. The catalyst is prepared into slurry which is uniformly dispersed during the test, and the slurry is coated on a glassy carbon electrode with the diameter of 5mm, wherein the platinum content of the catalyst on the electrode is 3-4 mug.
Resistivity test four-probe resistivity tester, instrument model KDY-1, method and test conditions: the applied pressure was 3.9.+ -. 0.03MPa and the current was 500.+ -. 0.1mA.
TG-MS test method: testing by using a German relaxation-resistant STA449F5-QMS403D type thermogravimetric-mass spectrometer, wherein an ion source is an EI source, a four-stage rod mass spectrometer is in an MID mode, a transmission pipeline is a 3-meter long capillary, and the temperature is 260 ℃; the temperature is 55-1000 ℃ and the heating rate is 10 ℃/min.
VXC72 (Vulcan XC72, manufactured by cabot corporation, usa) is available from energy technologies limited in wing Long, su. The test by the instrument method shows that: specific surface area 258m 2 Per gram, pore volume 0.388mL/g, oxygen mass fraction 8.72% by XPS analysis, I D /I G The resistivity was 1.02. Omega. M, which was 1.22. Omega. M.
Ketjenback ECP600JD (Ketjen Black, manufactured by Lion corporation, japan) was purchased from Suzhou wing Long energy technologies Co. The test by the instrument method shows that: specific surface area 1362m 2 Oxygen mass fraction analyzed by XPS, per gram, pore volume 2.29mL/g6.9％，I D /I G 1.25, and the resistivity was 1.31. Omega. M.
Black Pearls 2000 (manufactured by Kabot corporation, U.S.A.) was purchased from energy technologies Inc. of Suzhou wing Long. The test by the instrument method shows that: specific surface area 1479m 2 Oxygen mass fraction of XPS analysis of 9.13% per gram, I D /I G The resistivity was 1.14 and 1.19Ω·m.
Commercial platinum carbon catalyst (trade name HISPEC4000, manufactured by Johnson Matthey Co.) was purchased from Alfa Aesar. The test results show that: the mass fraction of platinum was 40.2%.
Example 1
This example is intended to illustrate the sulfur-boron doped carbon material of the present invention.
1g of Vulcan XC72 is immersed in 15mL of 3wt% sodium borate aqueous solution for 16h; drying in an oven at 100deg.C; then evenly mixing the mixture with 0.167g of elemental sulfur, putting the mixture into a tube furnace, heating the tube furnace to 1000 ℃ at the speed of 8 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the sulfur-boron doped carbon material, wherein the number of the carbon carrier A.
Sample characterization and testing
1. Sulfur-boron doped carbon material
The mass fraction of sulfur analyzed by XPS is 0.61%; the mass fraction of boron analyzed by XPS is 0.5%; specific surface area of 232m 2 And/g, the resistivity is 1.27. Omega. M.
Fig. 1 is an XPS spectrum of sulfur of the sulfur-boron doped carbon material of example 1.
Fig. 2 is an XPS spectrum of boron of the sulfur-boron doped carbon material of example 1.
Example 2
This example is intended to illustrate the sulfur-boron doped carbon material of the present invention.
Prepared in the same manner as in example 1 except that: the temperature of the constant temperature treatment was 500 ℃. Naturally cooling to obtain the sulfur-boron doped carbon material, wherein the number of the carbon carrier B is the number.
Sample characterization and testing
1. Sulfur-boron doped carbon material
The mass fraction of sulfur analyzed by XPS is that0.82%; the mass fraction of boron analyzed by XPS is 1.7%; specific surface area of 251m 2 /g; the resistivity was 1.30Ω·m.
Fig. 3 is an XPS spectrum of sulfur of the sulfur-boron doped carbon material of example 2.
Example 3
This example is intended to illustrate the sulfur-boron doped carbon material of the present invention.
10mL of absolute ethanol was added to 1g Ketjenblack ECP600JD, followed by 25mL of 3.5wt% sodium borate aqueous solution for 24 hours; drying in an oven at 100deg.C; then evenly mixing with 0.25g of elemental sulfur, placing the mixture in a tube furnace, heating the tube furnace to 1300 ℃ at the speed of 10 ℃/min, then carrying out constant temperature treatment for 3 hours, and naturally cooling to obtain the sulfur-boron doped carbon material with the number of carbon carrier C.
Sample characterization and testing
1. Sulfur-boron doped carbon material
The mass fraction of sulfur analyzed by XPS is 0.86%; the mass fraction of boron analyzed by XPS is 1.6%; specific surface area of 1256m 2 /g; the resistivity was 1.38Ω·m.
Fig. 4 is an XPS spectrum of sulfur of the sulfur-boron doped carbon material of example 3.
Fig. 5 is an XPS spectrum of boron of the sulfur-boron doped carbon material of example 3.
Example 4
This example is intended to illustrate the sulfur-boron doped carbon material of the present invention.
Prepared in the same manner as in example 3 except that: the carbon Black was Black pears 2000, the temperature of the constant temperature treatment was 700℃and the temperature raising rate was 5℃per minute. Naturally cooling to obtain the sulfur-boron doped carbon material, wherein the number of the carbon carrier is D.
Sample characterization and testing
1. Sulfur-boron doped carbon material
The mass fraction of sulfur analyzed by XPS is 0.70%; the mass fraction of boron analyzed by XPS is 1.8%; specific surface area of 1389m 2 /g; the resistivity was 1.32Ω·m.
Fig. 6 is an XPS spectrum of sulfur of the sulfur-boron doped carbon material of example 4.
Fig. 7 is an XPS spectrum of boron of the sulfur-boron doped carbon material of example 4.
Example 5
This example is intended to illustrate the platinum carbon catalyst of the present invention.
Dispersing the carbon carrier A in deionized water according to the proportion of 250mL of water used per gram of carbon carrier, adding 3.4mmol of chloroplatinic acid per gram of carbon carrier, performing ultrasonic dispersion to form suspension, and adding 1mol/L of sodium carbonate aqueous solution to enable the pH value of the system to be 10; heating the suspension to 80 ℃, adding formic acid under stirring to perform reduction reaction, wherein the molar ratio of the formic acid to the chloroplatinic acid is 50:1, and continuously maintaining the reaction for 10 hours; filtering the reacted mixture, washing the mixture with deionized water until the pH value of the filtrate is neutral, filtering the mixture, and then drying the mixture at 100 ℃ to obtain the platinum-carbon catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 39.8%.
In XPS analysis of the platinum carbon catalyst, no B is present between 185ev and 200ev 1s Is a characteristic peak of (2).
Fig. 8 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 5.
Fig. 9 is a polarization (LSV) curve before and after 5000 turns of the platinum carbon catalyst of example 5.
FIG. 10 is a CV curve before and after 5000 cycles of the Pt-C catalyst of example 5.
Detection of B in TG-MS test 2 O 3 And B.
The results of the platinum carbon catalyst performance test are shown in table 1.
Example 6
This example is intended to illustrate the platinum carbon catalyst of the present invention.
A platinum carbon catalyst was prepared according to the method of example 5, except that: carbon support B prepared in example 2 was used.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 39.6%.
In XPS analysis of the platinum carbon catalyst, no B is present between 185ev and 200ev 1s Is a characteristic peak of (2).
Fig. 11 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 6.
Detection of B in TG-MS test 2 O 3 And B.
The results of the platinum carbon catalyst performance test are shown in table 1.
Example 7
This example is intended to illustrate the platinum carbon catalyst of the present invention.
Dispersing the carbon carrier C in deionized water according to the proportion of 250mL of water used per gram of carbon carrier, adding 12mmol of chloroplatinic acid per gram of carbon carrier, performing ultrasonic dispersion to form suspension, and adding 1mol/L of potassium hydroxide aqueous solution to adjust the pH value of the system to 10; heating the suspension to 80 ℃, adding sodium borohydride under stirring to perform reduction reaction, wherein the molar ratio of the reducing agent to the platinum precursor is 5:1, and maintaining the reaction for 12 hours; and filtering the reacted mixture, washing until the pH value of the solution is neutral, and drying at 100 ℃ to obtain the carbon-supported platinum catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 69.6%.
In XPS analysis of the platinum carbon catalyst, no B is present between 185ev and 200ev 1s Is a characteristic peak of (2).
Fig. 12 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 7.
Detection of B in TG-MS test 2 O 3 And B.
The results of the platinum carbon catalyst performance test are shown in table 1.
Example 8
This example is intended to illustrate the platinum carbon catalyst of the present invention.
A platinum carbon catalyst was prepared according to the method of example 7, except that: using the carbon support D prepared in example 4, 1.3mmol of chloroplatinic acid per gram of carbon support were added.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 20.3%.
In XPS analysis of the platinum carbon catalyst, no B is present between 185ev and 200ev 1s Is a characteristic peak of (2).
Fig. 13 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 8.
Detection of B in TG-MS test 2 O 3 And B.
The results of the platinum carbon catalyst performance test are shown in table 1.
Comparative example 1
Dispersing Vulcan XC72 in deionized water according to the proportion of 250mL of water used for each gram of carbon carrier, adding 3.4mmol of chloroplatinic acid for each gram of carbon carrier, performing ultrasonic dispersion to form suspension, and adding 1mol/L of sodium carbonate aqueous solution to enable the pH value of the system to be 10; heating the suspension to 80 ℃, adding formic acid under stirring to perform reduction reaction, wherein the molar ratio of the formic acid to the chloroplatinic acid is 50:1, and continuously maintaining the reaction for 10 hours; filtering the reacted mixture, washing the mixture with deionized water until the pH value of the filtrate is neutral, filtering the mixture, and then drying the mixture at 100 ℃ to obtain the platinum-carbon catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 40.1%.
The results of the platinum carbon catalyst performance test are shown in table 1.
Comparative example 2
Dispersing Ketjenback ECP600JD by using 200mL of water and 50mL of ethanol per gram of carbon carrier, adding 12mmol of chloroplatinic acid per gram of carbon carrier, performing ultrasonic dispersion to form a suspension, and adding 1mol/L of potassium hydroxide aqueous solution to adjust the pH value of the system to 10; heating the suspension to 80 ℃, adding sodium borohydride under stirring to perform reduction reaction, wherein the molar ratio of the reducing agent to the platinum precursor is 5:1, and maintaining the reaction for 12 hours; and filtering the reacted mixture, washing until the pH value of the solution is neutral, and drying at 100 ℃ to obtain the carbon-supported platinum catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 69.7%.
The results of the platinum carbon catalyst performance test are shown in table 1.
Comparative example 3
The platinum carbon catalyst is a commercially available catalyst, under the trade designation HISPEC4000.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 40.2%.
The results of the platinum carbon catalyst performance test are shown in table 1.
Fig. 14 is a polarization curve before and after 5000 turns for the commercial platinum carbon catalyst of comparative example 3.
TABLE 1
/>
Claims (9)
1. A platinum carbon catalyst for an anode and/or a cathode of a hydrogen fuel cell, characterized by comprising a carbon support and a platinum metal supported thereon; the carbon carrier is prepared by the following method: mixing the conductive carbon black impregnated with the boron source with a sulfur source, placing the mixture in a tube furnace, heating the tube furnace to 1000-1500 ℃ at a speed of 8-15 ℃/min in inert gas, and then performing constant temperature treatment for 0.5-10 h; the sulfur source is elemental sulfur, and the mass ratio of the conductive carbon black to the sulfur source is 20: 1-2: 1, a step of; the boron source is one or more of boric acid and borate, the mass of the boron source is calculated by the mass of boron contained in the boron source, and the mass ratio of the conductive carbon black to the boron source is 100:1 to 5:1, a step of; XPS analysis of B on the carbon Carrier 1s The spectrum peak has characteristic peak between 189ev and 191 ev; XPS analysis of S on the carbon support 2P The spectrum peak is 160 ev-170 ev, only the characteristic peak of thiophene sulfur; based on the mass of the catalyst, the mass fraction of platinum is 20-70%.
2. The platinum carbon catalyst according to claim 1, wherein the conductive carbon Black is EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
3. The platinum carbon catalyst according to claim 1, wherein the carbon carrier has a mass fraction of sulfur of 0.1 to 5% and a mass fraction of boron of 0.1 to 5% in XPS analysis.
4. According to claim1, wherein the platinum carbon catalyst is characterized by XPS-analyzed B 1s There are no characteristic peaks between 185ev and 200ev in the spectrum peaks.
5. The method for preparing a platinum carbon catalyst according to claim 1, comprising: (1) the step of manufacturing a carbon support according to claim 1; (2) a step of supporting platinum with the carbon support obtained in (1).
6. The method for preparing a platinum carbon catalyst according to claim 5, wherein said step of supporting platinum comprises:
(a) Dispersing the carbon carrier and the platinum precursor obtained in the step (1) in a water phase, and regulating the pH to 8-12;
(b) Reducing agent is added for reduction;
(c) Separating out solid, and post-treating to obtain the platinum carbon catalyst.
7. The method of preparing a platinum carbon catalyst according to claim 6, wherein in (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate, or sodium chloroplatinate; the concentration of the platinum precursor is 0.5 mol/L-5 mol/L.
8. The method for preparing a platinum carbon catalyst according to claim 6, wherein in (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the mol ratio of the reducing agent to the platinum is 2-100; the reduction temperature is 60-90 ℃; the reduction time is 4-15 h.
9. A hydrogen fuel cell characterized in that the platinum carbon catalyst according to any one of claims 1 to 4 is used in an anode and/or a cathode of the hydrogen fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011014087.XA CN114430046B (en) | 2020-09-24 | 2020-09-24 | Sulfur-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011014087.XA CN114430046B (en) | 2020-09-24 | 2020-09-24 | Sulfur-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114430046A CN114430046A (en) | 2022-05-03 |
| CN114430046B true CN114430046B (en) | 2024-04-02 |
Family
ID=81309432
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011014087.XA Active CN114430046B (en) | 2020-09-24 | 2020-09-24 | Sulfur-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114430046B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111007118A (en) * | 2018-02-06 | 2020-04-14 | 红河学院 | Boron-sulfur co-doped graphene, preparation method and application thereof in preparing AFB1Electrochemical sensor of |
| CN111111637A (en) * | 2019-12-31 | 2020-05-08 | 太原理工大学 | Boron-doped non-metallic catalyst and preparation method and application thereof |
| CN111170306A (en) * | 2020-01-10 | 2020-05-19 | 南昌大学 | Boron/nitrogen double-doped porous carbon nanosheet and lithium-sulfur battery positive electrode material thereof |
| CN111285354A (en) * | 2020-02-19 | 2020-06-16 | 东华大学 | Boron-doped carbon nanotube and preparation and application thereof |
-
2020
- 2020-09-24 CN CN202011014087.XA patent/CN114430046B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111007118A (en) * | 2018-02-06 | 2020-04-14 | 红河学院 | Boron-sulfur co-doped graphene, preparation method and application thereof in preparing AFB1Electrochemical sensor of |
| CN111111637A (en) * | 2019-12-31 | 2020-05-08 | 太原理工大学 | Boron-doped non-metallic catalyst and preparation method and application thereof |
| CN111170306A (en) * | 2020-01-10 | 2020-05-19 | 南昌大学 | Boron/nitrogen double-doped porous carbon nanosheet and lithium-sulfur battery positive electrode material thereof |
| CN111285354A (en) * | 2020-02-19 | 2020-06-16 | 东华大学 | Boron-doped carbon nanotube and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Glycerol and formic acid electro-oxidation over Pt on S-doped carbon nanotubes: Effect of carbon support and synthesis method on the metal-support interaction";Xiaomei Ning et al.;《Electrochimica Acta》;第第 319 卷卷;第 129-137 页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114430046A (en) | 2022-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20230369609A1 (en) | Carbon-supported platinum group metal catalyst, preparation method therefor and application thereof | |
| CN114497593B (en) | Phosphorus-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof | |
| CN114479521B (en) | Carbon material, platinum-carbon catalyst, and preparation method and application thereof | |
| CN114426267B (en) | Carbon material, platinum-carbon catalyst, and preparation method and application thereof | |
| CN114426268B (en) | Sulfur-phosphorus doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof | |
| CN114122428B (en) | Platinum-carbon catalyst and preparation method and application thereof | |
| CN114122426B (en) | Platinum-carbon catalyst and preparation method and application thereof | |
| CN114430046B (en) | Sulfur-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof | |
| CN114497595A (en) | Nitrogen-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof | |
| CN114497601B (en) | Carbon-doped material, platinum-carbon catalyst, and preparation methods and applications thereof | |
| CN114430047B (en) | Carbon material, platinum-carbon catalyst, and preparation method and application thereof | |
| CN114497602B (en) | Carbon material, platinum-carbon catalyst, and preparation method and application thereof | |
| CN114497599B (en) | Sulfur-nitrogen-phosphorus-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof | |
| CN114497596B (en) | Carbon material, platinum-carbon catalyst, and preparation method and application thereof | |
| CN114477123B (en) | Carbon-doped material, platinum-carbon catalyst, and preparation methods and applications thereof | |
| CN114430045B (en) | Platinum-carbon catalyst and preparation method and application thereof | |
| CN114430049B (en) | Platinum-carbon catalyst, carbon material, preparation method and application thereof | |
| CN114105122B (en) | Sulfur-doped carbon material and preparation method and application thereof | |
| CN114122427B (en) | Platinum-carbon catalyst and preparation method and application thereof | |
| CN114426266B (en) | Sulfur-nitrogen doped carbon material and preparation method and application thereof | |
| CN114122430B (en) | Platinum-carbon catalyst and preparation method and application thereof | |
| CN114122429B (en) | Application of nitrogen-doped carbon material as carbon carrier of platinum-carbon catalyst in hydrogen fuel cell | |
| CN114497602A (en) | Carbon material, platinum-carbon catalyst, and preparation method and application thereof | |
| CN114426272A (en) | Sulfur-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof | |
| CN114497598A (en) | Sulfur-nitrogen-phosphorus doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |