CN114497599B - Sulfur-nitrogen-phosphorus-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof - Google Patents
Sulfur-nitrogen-phosphorus-boron doped carbon material, platinum-carbon catalyst, and preparation methods and applications thereof Download PDFInfo
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- CN114497599B CN114497599B CN202011152364.3A CN202011152364A CN114497599B CN 114497599 B CN114497599 B CN 114497599B CN 202011152364 A CN202011152364 A CN 202011152364A CN 114497599 B CN114497599 B CN 114497599B
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- platinum
- carbon
- sulfur
- phosphorus
- nitrogen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 175
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 title claims abstract description 155
- UUOVEQAKKMIYCT-UHFFFAOYSA-N [N].[B].[P].[S] Chemical compound [N].[B].[P].[S] UUOVEQAKKMIYCT-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000003575 carbonaceous material Substances 0.000 title abstract description 219
- 238000002360 preparation method Methods 0.000 title abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 110
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 105
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 66
- 239000011593 sulfur Substances 0.000 claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 61
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 46
- 238000004458 analytical method Methods 0.000 claims abstract description 28
- 239000000446 fuel Substances 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 126
- 238000000034 method Methods 0.000 claims description 87
- 229910052796 boron Inorganic materials 0.000 claims description 66
- 229910052698 phosphorus Inorganic materials 0.000 claims description 66
- 229910052757 nitrogen Inorganic materials 0.000 claims description 63
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 62
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 58
- 239000011574 phosphorus Substances 0.000 claims description 58
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 38
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 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
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000003595 spectral effect Effects 0.000 claims description 10
- 238000001228 spectrum Methods 0.000 claims description 10
- 241000220324 Pyrus Species 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 235000021017 pears Nutrition 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 239000004202 carbamide Substances 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
- 239000002243 precursor Substances 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 5
- 229920000388 Polyphosphate Polymers 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 5
- 235000011180 diphosphates Nutrition 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 5
- 235000011007 phosphoric acid Nutrition 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 239000001205 polyphosphate Substances 0.000 claims description 5
- 235000011176 polyphosphates Nutrition 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 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
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 4
- 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
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000011068 loading method Methods 0.000 abstract description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract 2
- -1 sulfur nitrogen phosphorus boron carbon Chemical compound 0.000 abstract 2
- 229930192474 thiophene Natural products 0.000 abstract 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 46
- 238000012360 testing method Methods 0.000 description 35
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 32
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
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- 229910052760 oxygen Inorganic materials 0.000 description 15
- 239000003273 ketjen black Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000002041 carbon nanotube Substances 0.000 description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 description 13
- 229910021389 graphene Inorganic materials 0.000 description 13
- 238000012512 characterization method Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 4
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical group [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 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
- 230000005540 biological transmission Effects 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002923 metal particle Substances 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
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000002902 bimodal 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
- 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
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002791 soaking Methods 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
- 208000016057 CHAND syndrome Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- DBQBWZSDXNFYJI-UHFFFAOYSA-N [B].[N].[P] Chemical compound [B].[N].[P] DBQBWZSDXNFYJI-UHFFFAOYSA-N 0.000 description 1
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical group [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
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- 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
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 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
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 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
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- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
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- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/32—Specific surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- 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
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- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a sulfur-nitrogen-phosphorus-boron doped carbon material, a platinum-carbon catalyst, a preparation method and application thereof. In XPS analysis of the sulfur nitrogen phosphorus boron carbon doped carbon material, only characteristic peaks of thiophene type sulfur exist between 160ev and 170 ev. The fuel cell platinum-carbon catalyst using the sulfur-nitrogen-phosphorus-boron-carbon doped carbon material as a carrier, in particular to a platinum-carbon catalyst with high platinum loading amount, has excellent catalytic performance and carbon corrosion resistance.
Description
Technical Field
The invention relates to a carbon material doped with sulfur, nitrogen, phosphorus and boron, a platinum-carbon catalyst using the carbon material as a carrier, and preparation methods and applications of the carbon material and the platinum-carbon catalyst.
Background
In the chemical field, carbon materials are both important supports and commonly used catalysts. The bonding mode of the carbon element is rich, and the carbon material can be modified in various modes so as to obtain more suitable performance.
Oxygen Reduction Reactions (ORR) are key reactions in the electrochemical field, such as in fuel cells and metal-air cells, and are a major factor affecting cell performance. The atomic doped carbon material can be used directly as a catalyst for the oxygen reduction reaction. When used as an oxygen reduction catalyst, it has been reported 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 directly as fuel cell catalysts and some research results show better activity, there are large differences compared to platinum carbon catalysts and far from commercial applications. On the one hand, the knowledge of the combination mode of the hetero atoms and the carbon materials and the interaction between the hetero atoms and the catalysis mechanism is insufficient in the field; on the other hand, each heteroatom has multiple bonding modes with the carbon material, and multiple roles exist among the heteroatoms, so that the situation is very complex when doping multiple heteroatoms, and therefore, how to control the bonding modes of the heteroatoms and the carbon material and the interaction among the heteroatoms is a difficulty of doping atoms. In addition, such catalysts are generally not suitable for use in acidic environments, particularly Proton Exchange Membrane Fuel Cells (PEMFCs), which are important.
Up to now, the most effective oxygen reduction catalysts are platinum carbon catalysts, but for large scale commercial applications platinum carbon catalysts have been deficient. On the one hand, platinum resources are scarce and expensive, and the cost thereof is about 40% of the total cost of the fuel cell. On the other hand, the dispersion degree of platinum metal in the currently used commercial platinum-carbon catalyst is not ideal and is easy to agglomerate and deactivate, and the dissolution and agglomeration of platinum at the cathode of the hydrogen fuel cell lead to obvious reduction of the surface area of the platinum with time, thus influencing the service life of the fuel cell. The art is urgent to greatly improve the utilization rate of platinum metal, and improve the catalytic activity and stability of the platinum metal, so as to promote the large-scale commercial application of the platinum metal. Many factors and complications affect the activity and stability of the platinum carbon catalyst, and some documents believe that the activity and stability of the platinum carbon catalyst are related to the particle size, morphology, structure of the platinum, as well as the type, nature and platinum loading of the support. The prior art mainly improves the performance of the platinum-carbon catalyst by controlling the particle size, morphology, structure and specific surface area of the carrier and pore structure of the platinum; there are also reports of improving the performance of platinum carbon catalysts by modifying the carbon support.
The carbon carrier can improve the specific surface area of the catalyst, reduce the agglomeration of metal particles and improve the metal utilization rate. The increase of the platinum carrying capacity of the carbon carrier is beneficial to manufacturing thinner membrane electrodes with better performance, but the increase of the platinum carrying capacity greatly is easier to cause accumulation among platinum metal particles, so that the utilization rate of active sites is greatly reduced. How to more effectively utilize the catalytic active sites of platinum metal particles and increase the accessible three-phase catalytic reaction interface, thereby improving the utilization rate of platinum and the comprehensive performance of fuel cells and metal-air cells is a key problem to be solved in the art. In addition, the platinum loading of the practically applied hydrogen fuel cell platinum carbon catalyst is at least more than 20wt%, which is much more difficult to manufacture than chemical platinum carbon catalysts (platinum loading is lower than 5 wt%).
The problem of deactivation of platinum carbon catalysts in proton exchange membrane fuel cells caused by carbon corrosion has raised a great deal of attention in the art. It is reported in the literature that, theoretically, when the potential is greater than 0.2V, corrosion of the carbon support occurs. In practice, the problem of carbon corrosion is only evident when the potential is greater than 1.2V. The cathode potential can be higher than 0.9V when the cell is operated in open circuit, and the local interface potential of the cathode can even reach 1.6V during the starting/stopping process of the cell, which greatly accelerates the carbon corrosion reaction, resulting in the drastic reduction of the performance of the platinum carbon catalyst. In addition, platinum accelerates the carbon corrosion rate, and the larger the platinum carrying amount, the faster the carbon corrosion. The conductive carbon black has low price and is a platinum-carbon catalyst carrier used in industry, but the conductive carbon black has poor corrosion resistance. On the one hand, the defect sites of the carbon carrier are more beneficial to increasing the platinum carrying capacity, but at the same time, the carbon corrosion is aggravated. On the other hand, increasing the graphitization degree can alleviate carbon corrosion, but also makes the surface of the carbon carrier chemically inert, and it is difficult to uniformly disperse platinum on the carbon carrier.
The chemical reduction method is a common method for manufacturing platinum-carbon catalyst, and has the advantages of simple process, low utilization rate of platinum and low catalytic activity. The reason for this may be that the irregular pore structure of the carbon support causes uneven dispersion of the platinum nanoparticles.
The information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and may include information that is not already known to those of ordinary skill in the art.
Disclosure of Invention
It is a first object of the present invention to provide a carbon material having unique properties and a simple method for preparing the same. A second object of the present invention is to improve the resistance of platinum carbon catalysts to carbon corrosion on the basis of the carbon material. A third object of the present invention is to provide a platinum carbon catalyst having more excellent overall properties and a simple process for producing the same, in addition to the foregoing objects. A fourth object of the present invention is to provide a platinum carbon catalyst with a higher platinum-carrying 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 nitrogen phosphorus boron doped carbon material is characterized in that S is analyzed by XPS 2P The spectral peaks were characterized by thiophene-type sulfur only between 160ev and 170 ev.
2. The sulfur-nitrogen-phosphorus-boron doped carbon material according to any one of the above, characterized in that N in XPS analysis thereof 1s Of the spectral peaks, the characteristic peak area between 399ev and 400.5ev is 70% or more, preferably 80% or more, more preferably 90% or more of the total characteristic peak area between 390ev and 410 ev.
3. The sulfur-nitrogen-phosphorus-boron doped carbon material according to any one of the above, characterized in that B is analyzed by XPS 1s The spectrum peak has a characteristic peak between 189ev and 191.5 ev.
4. The sulfur-nitrogen-phosphorus-boron doped carbon material according to any one of the above, characterized in that B is analyzed by XPS 1s In the spectrum peak, between 189ev and 191.5evThere are two characteristic peaks.
5. The sulfur-nitrogen-phosphorus-boron doped carbon material according to any one of the above, characterized by P analyzed by XPS 2P There are two characteristic peaks between 133.5ev and 135.5ev in the spectrum peak.
6. The sulfur-nitrogen-phosphorus-boron doped carbon material according to any one of the above is characterized in that in XPS analysis, the mass fraction of sulfur is 0.01-6%, the mass fraction of nitrogen is 0.01-8%, the mass fraction of phosphorus is 0.01-6%, and the mass fraction of boron is 0.01-6%; preferably, the sulfur mass fraction is 0.1-2%, preferably, the nitrogen mass fraction is 0.1-4%, preferably, the phosphorus mass fraction is 0.1-4%, preferably, the boron mass fraction is 0.1-4%.
7. The sulfur-nitrogen-phosphorus-boron doped carbon material according to any one of the preceding claims, characterized in that its resistivity is <10Ω·m, preferably <5Ω·m, more preferably <3Ω·m.
8. The sulfur-nitrogen-phosphorus-boron-doped carbon material according to any one of the above, which is characterized by having a specific surface area of 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.
9. The sulfur nitrogen phosphorus 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.
10. A method of doping a carbon material, comprising: (1) Firstly, contacting a carbon material with a phosphorus source and a boron source, and treating (preferably, constant temperature treatment) the carbon material in inert gas at 300-800 ℃ for 0.5-10 h; (2) Then the mixture is contacted with a sulfur source and a nitrogen source and treated (preferably at a constant temperature) for 0.5 to 10 hours at a temperature of between 400 and 1000 ℃ in an inert gas.
11. The method for doping a 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, a step of; more preferably 8:1 to 4:1.
12. the method for doping a carbon material according to any one of the above, wherein the mass ratio of the carbon material to the nitrogen source, based on the mass of nitrogen contained therein, is 500:1 to 5:1, a step of; preferably 200:1 to 10:1.
13. the doping method of a carbon material according to any one of the above, wherein the mass ratio of the carbon material to the phosphorus source is 10000, based on the mass of phosphorus contained in the carbon material: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
14. The doping method of a carbon material according to any one of the above, characterized in that the mass ratio of the carbon material to the boron source is 10000, based on the mass of boron contained therein: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
15. the method for doping a carbon material according to any one of the above, wherein the sulfur source is elemental sulfur.
16. The method for doping a carbon material according to any one of the above, wherein the nitrogen source is ammonia water and/or urea.
17. The doping method of the carbon material according to any one of the preceding claims, wherein the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.
18. The method for doping a carbon material according to any one of the above, wherein the boron source is one or more of boric acid and a borate.
19. The method for doping a carbon material according to any one of the above, wherein in (1) and (2), the treatment time is 1 to 5 hours, preferably 2 to 4 hours, independently of each other.
20. The method for doping a carbon material according to any one of the above, wherein in (1), the temperature is 450 to 700 ℃.
21. The method for doping a carbon material according to any one of the above, wherein in (2), the temperature is 550 to 900 ℃.
22. The doping method of the carbon material according to any one of the above, wherein the carbon material is graphene, carbon nanotubes or conductive carbon black; the conductive carbon Black is preferably EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
23. The method for doping a carbon material according to any one of the above, wherein the mass fraction of oxygen in XPS analysis of the carbon material is greater than 4%, preferably 4% to 15%.
24. The method for doping a carbon material according to any one of the above, wherein the carbon material has a resistivity of <10Ω·m, preferably <5Ω·m, more preferably <2Ω·m.
25. The method for doping a carbon material according to any one of the above, wherein 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.
26. The sulfur-nitrogen-phosphorus-boron doped carbon material prepared by the doping method of any one of the carbon materials.
27. The application of any one of the sulfur-nitrogen-phosphorus-boron doped carbon materials as an electrode material in electrochemistry.
28. A platinum-carbon catalyst comprises a carbon carrier and a platinum metal loaded on the carbon carrier, and is characterized in that the carbon carrier is a sulfur-nitrogen-phosphorus-boron doped carbon material, and the platinum-carbon catalyst is analyzed by XPS 2P The spectral peaks were characterized by thiophene-type sulfur only between 160ev and 170 ev.
29. N in XPS analysis of platinum carbon catalyst according to any one of the above 1s The spectral peak has no other characteristic peak between 390ev and 410ev except for the characteristic peak area between 399ev and 400.5 ev.
30. The platinum carbon catalyst according to any one of the preceding claims, wherein in XPS analysis thereof, there is no B between 185ev and 200ev 1s And no P between 125ev and 145ev 2p Is a characteristic peak of (2).
31. The platinum carbon catalyst according to any one of the preceding claims, characterized in that the carbon material is graphene, carbon nanotubes or conductive carbon black; the conductive carbon Black is preferably EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
32. 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.
33. The platinum carbon catalyst according to any one of the preceding claims, characterized in that the carbon carrier is any one of the preceding sulfur nitrogen phosphorus boron doped carbon materials.
34. A method for preparing a platinum carbon catalyst, comprising:
(1) A step of manufacturing a carbon carrier: firstly, contacting a carbon material with a phosphorus source and a boron source, and treating (preferably, constant temperature treatment) the carbon material in inert gas at 300-800 ℃ for 0.5-10 h; then contacting with a sulfur source and a nitrogen source, and treating (preferably constant temperature treatment) in an inert gas at 400-1000 ℃ for 0.5-10 h to obtain the carbon carrier;
(2) A step of supporting platinum with the carbon support obtained in (1).
35. The method for producing a platinum carbon catalyst according to any one of the above (1), wherein the sulfur source is elemental sulfur.
36. 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, a step of; preferably 8:1 to 4:1.
37. the process for producing a platinum carbon catalyst according to any one of the preceding claims, wherein in (1), the nitrogen source is ammonia and/or urea.
38. 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 nitrogen source is 500, based on the mass of the nitrogen contained therein: 1 to 5:1.
39. The method for preparing a platinum carbon catalyst according to any one of the above (1), wherein the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.
40. The method for preparing a platinum carbon catalyst according to any one of the preceding claims, wherein in (1), the mass ratio of the carbon material to the phosphorus source is 10000, based on the mass of phosphorus contained in the phosphorus source: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
41. the method for preparing a platinum carbon catalyst according to any one of the above (1), wherein the boron source is one or more of boric acid and a borate.
42. The method for preparing 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 10000, based on the mass of boron contained in the boron source: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
43. the method for preparing the platinum-carbon catalyst according to any one of the above methods, wherein the temperature is 450 ℃ to 700 ℃ in the phosphorus-boron doping operation.
44. The method for preparing the platinum carbon catalyst according to any one of the above methods, wherein the temperature is 550 ℃ to 900 ℃ in the sulfur-nitrogen doping operation.
45. The method for preparing a platinum-carbon catalyst according to any one of the above methods, wherein the treatment time is 1 to 5 hours, preferably 2 to 4 hours, independently of each other in the phosphorus-boron doping operation and the sulfur-nitrogen doping operation.
46. The preparation method of any one of the platinum carbon catalysts is characterized in that in the step (1), the carbon material is graphene, carbon nano tube or conductive carbon black; the conductive carbon Black is preferably EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
47. 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%.
48. 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.
49. 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.
50. The method for preparing a platinum carbon catalyst according to any one of the preceding claims, wherein the step (2) of supporting platinum comprises:
(a) Dispersing the carbon carrier 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.
51. 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.
52. 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.
53. A platinum carbon catalyst, characterized by being prepared by any one of the aforementioned platinum carbon catalyst preparation methods.
54. A hydrogen fuel cell characterized in that any one of the platinum carbon catalysts described above is used for an anode and/or a cathode of the hydrogen fuel cell.
The hetero atoms and the carbon materials have various combination modes, the hetero atoms have various interactions, the preparation method and the raw materials are different, and the operation steps and the conditions of the doping process are different, so that the combination modes of the hetero atoms and the carbon materials and the interactions among the hetero atoms can be influenced, the property differences of the hetero atoms and the carbon materials are caused, and the functions of the hetero atoms and the carbon materials are changed. In the art, how to control the binding mode of heteroatoms to carbon materials and the interactions between heteroatoms are difficulties in doping atoms. Controlling the manner in which heteroatoms are bound to the carbon material and the interactions between the heteroatoms may result in a carbon material that is uniquely characterized, thereby rendering it suitable for a particular application. The research of the invention finds that the multi-element co-doping of the carbon carrier is more beneficial to improving the carbon corrosion resistance of the platinum-carbon catalyst. After the carbon material is subjected to sulfur-nitrogen-phosphorus-boron four-doping by a relatively simple method, the carbon material with uniform doping element combination mode can be prepared, and XPS analysis spectrum of the carbon material shows that sulfur doped on the surface of the carbon material exists in a thiophene sulfur form, nitrogen doped on the surface mainly exists in a pyrrole nitrogen form, boron doped on the surface only has characteristic peaks between 189ev and 191ev, and phosphorus doped on the surface only has characteristic peaks between 133.5ev and 135.5 ev. The inventor researches and discovers that the characteristics are beneficial to improving the performance of the platinum-carbon catalyst of the hydrogen fuel cell, in particular to improving the performance of the platinum-carrying platinum-carbon catalyst.
Compared with the prior art, the invention can realize the following beneficial technical effects.
1. Compared with the existing carbon material, the sulfur doped on the surface of the carbon material only exists in the form of thiophene sulfur, the nitrogen doped on the surface mainly exists in the form of pyrrole nitrogen, the boron doped on the surface only has characteristic peaks between 189ev and 191ev, and the phosphorus doped on the surface only has characteristic peaks between 133.5ev and 135.5ev, which are found by the invention to be beneficial to improving the catalytic performance of the platinum-carbon catalyst of the fuel cell.
2. The carbon material is suitable for manufacturing platinum-carbon catalysts with high platinum loading, and has excellent comprehensive catalytic performance and carbon corrosion resistance when the platinum loading is up to 70 wt%.
3. The platinum-carrying amount of the practically applied platinum-carbon catalyst of the hydrogen fuel cell is generally more than 20 weight percent, and the difficulty in manufacturing the high-platinum-carrying catalyst with excellent performance is great. The chemical reduction method has simple process, but the utilization rate of platinum is low and the catalytic activity is low. However, the carbon material produced by the present invention is used as a carrier, and a high-platinum-carrying catalyst having excellent mass specific activity and stability can be easily produced by a chemical reduction method using an aqueous phase.
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 nitrogen phosphorus boron doped carbon material of example 1.
Fig. 2 is an XPS spectrum of nitrogen of the sulfur nitrogen phosphorus boron doped carbon material of example 1.
Fig. 3 is an XPS spectrum of phosphorus of the sulfur nitrogen phosphorus boron doped carbon material of example 1.
Fig. 4 is an XPS spectrum of boron of the sulfur nitrogen phosphorus boron doped carbon material of example 1.
Fig. 5 is an XPS spectrum of sulfur of the sulfur nitrogen phosphorus boron doped carbon material of example 2.
Fig. 6 is an XPS spectrum of nitrogen of the sulfur nitrogen phosphorus boron doped carbon material of example 2.
Fig. 7 is an XPS spectrum of phosphorus of the sulfur nitrogen phosphorus boron doped carbon material of example 2.
Fig. 8 is an XPS spectrum of boron of the sulfur nitrogen phosphorus boron doped carbon material of example 2.
Fig. 9 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 3.
Fig. 10 is an XPS spectrum of nitrogen of the platinum carbon catalyst of example 3.
Fig. 11 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 5.
Fig. 12 is an XPS spectrum of nitrogen of the platinum carbon catalyst of example 5.
Fig. 13 is a TEM image of the platinum carbon catalyst of example 5.
Fig. 14 is an XPS spectrum of phosphorus of the phosphorus-doped carbon material of comparative example 4.
Fig. 15 is an XPS spectrum of boron of the boron doped carbon material of comparative example 5.
Fig. 16 is an XPS spectrum of sulfur of the sulfur-doped carbon material of comparative example 6.
Fig. 17 is an XPS spectrum of nitrogen of the nitrogen-doped carbon material of comparative example 7.
Detailed Description
The invention is described in detail below in connection with the embodiments, but it should be noted that the scope of the invention is not limited by these embodiments and the principle explanation, but is defined by the claims.
In the present invention, any matters or matters not mentioned are directly applicable to those known in the art without modification except for those explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all considered as part of the original disclosure or description of the present invention, and should not be considered as new matters not disclosed or contemplated herein unless such combination would obviously be unreasonable to one skilled in the art.
All of the features disclosed in this invention may be combined in any combination which is known or described in the present invention and should be interpreted as specifically disclosed and described in the present invention unless the combination is obviously unreasonable by those skilled in the art. The numerical points disclosed in the present specification include not only the numerical points specifically disclosed in the embodiments but also the end points of each numerical range in the specification, and any combination of these numerical points should be considered as a disclosed or described range of the present invention.
Technical and scientific terms used in the present invention are defined to have their meanings, and are not defined to have their ordinary meanings in the art.
The "doping element" in the present invention means nitrogen, phosphorus, boron, sulfur, fluorine, chlorine, bromine and iodine.
The numerical ranges defined in the present invention include the endpoints of the numerical ranges.
In the present invention, reference to "carbon material" refers to carbon material that does not contain a doping element, except that it may be uniquely determined to be "carbon material containing a doping element" depending on the context or definition itself. The same is true of the underlying concept of carbon materials.
In the present invention, "carbon black" and "carbon black" are interchangeable terms of art.
The "inert gas" in the present invention refers to a gas that does not have any appreciable effect on the properties of the sulfur-nitrogen-phosphorus-boron-doped carbon material in the preparation method of the present invention. The same is true of the underlying concept of carbon materials.
In the present invention, other references to "pore volume" refer to P/P unless otherwise clear from context or definition of the same 0 The single point adsorption total pore volume at maximum.
The invention providesSulfur nitrogen phosphorus boron doped carbon material analyzed in XPS S 2P The spectral peaks were characterized by thiophene-type sulfur only between 160ev and 170 ev.
According to the sulfur-nitrogen-phosphorus-boron doped carbon material of the present invention, sulfur, nitrogen, phosphorus and boron are chemically bonded to the carbon material.
The sulfur-nitrogen-phosphorus-boron doped carbon material according to the present invention does not contain other doping elements except sulfur, nitrogen, phosphorus and boron.
The sulfur-nitrogen-phosphorus-boron doped carbon material according to the present invention is free of metal elements.
According to the sulfur-nitrogen-phosphorus-boron doped carbon material, the characteristic peak of the thiophene-type sulfur is between 162ev and 166 ev.
According to the sulfur-nitrogen-phosphorus-boron doped carbon material, characteristic peaks of the thiophene-type sulfur are bimodal and are respectively located at 163.4+/-0.5 ev and 164.6+/-0.5 ev.
The sulfur-nitrogen-phosphorus-boron doped carbon material according to the invention has N analyzed in XPS 1s Of the spectral peaks, the characteristic peak area between 399ev and 400.5ev is 70% or more, preferably 80% or more, more preferably 90% or more of the total characteristic peak area between 390ev and 410 ev.
According to the sulfur-nitrogen-phosphorus-boron doped carbon material of the present invention, in some embodiments, N is analyzed in XPS 1s Of the spectrum peaks, the characteristic peak area between 399ev and 400.5ev accounts for 90% -99% of the total characteristic peak area between 390ev and 410 ev.
The sulfur-nitrogen-phosphorus-boron doped carbon material according to the invention has N analyzed in XPS 1s Of the spectral peaks, there were two characteristic peaks between 399ev and 400.5ev, one at 401.5 ev.+ -. 0.5ev, and no other characteristic peak between 390ev and 410 ev.
According to the sulfur-nitrogen-phosphorus-boron doped carbon material, P is analyzed by XPS 2P Of the spectral peaks, there are two characteristic peaks between 133ev and 135ev, and there are no other characteristic peaks between 125ev and 145 ev.
The sulfur-nitrogen-phosphorus-boron doped carbon material according to the invention has XPS analysis of B 1s In the spectrum peak, there are two characteristic peaks between 189ev and 191.5ev, and between 185ev and 200evWithout other characteristic peaks in between.
The sulfur-nitrogen-phosphorus-boron doped carbon material according to the invention has XPS analysis of B 1s Of the peaks, there was a characteristic peak at 189.6 ev.+ -. 0.5 ev.
In XPS analysis, the sulfur, nitrogen, phosphorus and boron doped carbon material has the mass fraction of 0.01-6%, the mass fraction of nitrogen of 0.01-6%, the mass fraction of phosphorus of 0.01-6% and the mass fraction of boron of 0.01-6%; preferably, the sulfur mass fraction is 0.1-2%, preferably, the nitrogen mass fraction is 0.1-4%, preferably, the phosphorus mass fraction is 0.1-4%, preferably, the boron mass fraction is 0.1-4%.
In some embodiments, the sulfur-nitrogen-phosphorus-boron doped carbon material according to the invention has a mass fraction of sulfur of 0.1-1.5%, a mass fraction of nitrogen of 0.1-3.5%, a mass fraction of phosphorus of 0.01-2.5%, and a mass fraction of boron of 0.1-2.5% in XPS analysis
The carbon material doped with sulfur, nitrogen, phosphorus and boron according to the present invention has a resistivity of <10Ω·m, preferably <5Ω·m, more preferably <3Ω·m.
The sulfur-nitrogen-phosphorus-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-nitrogen-phosphorus-boron doped carbon material can be changed in 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 nitrogen phosphorus boron doped carbon material, the sulfur nitrogen phosphorus boron doped carbon material can be sulfur nitrogen phosphorus boron doped graphene, sulfur nitrogen phosphorus boron doped carbon nano tube or sulfur nitrogen phosphorus boron doped conductive carbon black. The conductive carbon black may be a general conductive carbon black (Conductive Blacks), a super conductive carbon black (Super Conductive Blacks) or a special conductive carbon black (Extra Conductive Blacks), for example, the conductive carbon black may be one or more of Ketjen black (Ketjen black) series of superconducting carbon black, cabot series of conductive carbon black, and series of conductive carbon black produced by qin-chand solid race 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.
According to the sulfur-nitrogen-phosphorus-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-nitrogen-phosphorus-boron doped carbon material, the carbon nanotube or the graphene can be oxidized carbon nanotube or graphene or non-oxidized carbon nanotube or graphene.
The invention also provides a doping method of the carbon material, which comprises the following steps: (1) Firstly, contacting a carbon material with a phosphorus source and a boron source, and treating (preferably, carrying out constant temperature treatment) in an inert gas at 300-800 ℃ for 0.5-10 h to obtain a phosphorus-boron doped carbon material (intermediate product); (2) Then contacts with sulfur source and nitrogen source, and is treated for 0.5h to 10h at 400 ℃ to 1000 ℃ in inert gas, thus obtaining the sulfur-nitrogen-phosphorus-boron doped carbon material.
According to the doping method of the carbon material of the present invention, the carbon material may be graphene, carbon nanotubes or conductive carbon black. 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 solid Saint Co; preferably EC-300J, EC-600JD, ECP-600JD, VXC72, black pears 2000, PRINTEX XE2-B, PRINTEX L6 or HIBLAXK 40B2.
According to the doping method of the 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 doping method of the carbon material of the present invention, there is no limitation on the preparation method and source of the conductive carbon black. The conductive carbon black can be acetylene black, furnace black and the like.
According to the doping method of the carbon material of the invention, the carbon material is I D /I G The value is generally from 0.8 to 5, preferably1 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 doping method of the carbon material of the present invention, the carbon material is preferably contacted with the phosphorus source and the boron source in a mixed manner. The order and manner in which the carbon material is mixed with the phosphorus source and the boron source is not limited by the present invention, and those skilled in the art can select an appropriate order and manner based on the teachings and/or prior knowledge of the present invention. The invention provides a preferred mixing mode: the carbon material is mixed with a phosphorus source and a boron source solution (preferably an aqueous solution), impregnated and dried.
According to the doping method of the carbon material of the present invention, the phosphorus-boron doped carbon material (intermediate product) is preferably contacted with a sulfur source and a nitrogen source in a mixed manner. The order and manner in which the intermediate product is mixed with the sulfur source and the nitrogen 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 intermediate product is first mixed with a nitrogen source solution, preferably an aqueous solution, impregnated and dried, and then mixed with a sulfur source, such as elemental sulfur.
According to the doping method of the carbon material, if the temperature is required to be raised in any operation process, the temperature raising rate can be 1-20 ℃ per minute, preferably 3-15 ℃ per minute; more preferably, the phosphorus and boron are doped at 3-7 deg.C/min and the sulfur and nitrogen are doped at 5-10 deg.C/min.
According to the doping method of a carbon material of the present invention, in (1) and (2), the time of the treatment is each independently 1 to 5 hours, preferably 2 to 4 hours.
According to the doping method of a carbon material of the present invention, in (1), the temperature is 450 to 700 ℃.
According to the doping method of a carbon material of the present invention, in (2), the temperature is 550 to 900 ℃.
According to the doping method of the carbon material, the sulfur source is elemental sulfur.
According to the doping method of the carbon material, the mass ratio of the carbon material to the sulfur source is 20, wherein the mass ratio of the sulfur source to the sulfur source is calculated according to the mass of sulfur contained in the sulfur source: 1-2: 1, a step of; preferably 10:1 to 4:1, a step of; more preferably 8:1 to 4:1.
according to the doping method of the carbon material, the nitrogen source is ammonia water and/or urea.
According to the doping method of the carbon material, the mass ratio of the carbon material to the nitrogen source is 500, based on the mass of nitrogen contained in the carbon material: 1 to 5:1, preferably 200:1 to 10:1.
According to the doping method of the carbon material, the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphates, polyphosphates, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.
According to the doping method of the carbon material, the mass ratio of the carbon material to the phosphorus source is 10000, based on the mass of phosphorus contained in the carbon material: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
according to the doping method of the carbon material, the boron source is one or more of boric acid and borate.
According to the doping method of the carbon material, the mass ratio of the carbon material to the boron source is 10000, based on the mass of boron contained in the carbon material: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
according to the doping method of the carbon material, the inert gas is nitrogen or argon.
According to the doping method of the 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 doping method of the carbon material of the present invention, the resistivity of the carbon material is <10Ω·m, preferably <5Ω·m, more preferably <2Ω·m.
According to the doping method of the carbon material of the present invention, the specific surface area of the carbon material may vary within a wide range. Generally, the specific surface area is 10m 2 /g～2000m 2 /g; the pore volume is 0.02 mL/g-6 mL/g.
According to the doping method of the carbon material of the present invention, in one embodiment, (1) the carbon material impregnated with the phosphorus source and the boron source in the aqueous solution is dried, placed in a tube furnace, and the tube furnace is heated to 300 ℃ to 800 ℃ (preferably 450 ℃ to 700 ℃) at a rate of 3 ℃/min to 7 ℃/min in an inert gas, and then is subjected to constant temperature treatment for 0.5h to 10h, thereby obtaining a phosphorus-boron doped carbon material (intermediate product); (2) Drying an intermediate product immersed with a nitrogen source in an aqueous solution, uniformly mixing the intermediate product with sulfur powder, placing the mixture in a tube furnace, heating the tube furnace to 400-1000 ℃ at a speed of 5-10 ℃/min in inert gas (preferably 550-900 ℃), and then performing constant temperature treatment for 0.5-10 hours to obtain the sulfur-nitrogen-phosphorus-boron doped carbon material.
The inert gas is nitrogen or argon.
According to the doping method of the carbon material of the present invention, a metal-containing catalyst is not used in the process of doping the carbon material.
The invention also provides the sulfur-nitrogen-phosphorus-boron doped carbon material prepared by any one of the methods.
The sulfur nitrogen phosphorus boron doped carbon material of the invention of any one of the foregoing is used as an electrode material in electrochemistry.
The invention provides a platinum carbon catalyst, which comprises a carbon carrier and platinum metal loaded on the carbon carrier, wherein the carbon carrier is a sulfur nitrogen phosphorus boron doped carbon material, and the platinum carbon catalyst is analyzed by XPS 2P The spectral peaks were characterized by thiophene-type sulfur only between 160ev and 170 ev.
According to the platinum carbon catalyst of the present invention, the characteristic peak of the thiophene-type sulfur is located between 162ev and 166 ev.
According to the platinum carbon catalyst of the present invention, the characteristic peaks of the thiophene sulfur are bimodal, and are located at 163.4.+ -. 0.5ev and 164.6.+ -. 0.5ev, respectively.
According to the platinum carbon catalyst of the present invention, N analyzed in XPS thereof 1s The spectrum peak has a characteristic peak between 399ev and 400.5ev, and has no other characteristic peak between 390ev and 410 ev.
According to the platinum carbon catalyst of the present invention, in some embodiments, N is analyzed in XPS thereof 1s In the spectrum peak, at 399evThere are two characteristic peaks between about 400.5ev and no other characteristic peaks between 390ev and 410 ev.
The platinum carbon catalyst according to the present invention has no B in its XPS analysis between 185ev and 200ev 1s And no P between 125ev and 145ev 2p Is a characteristic peak of (2).
According to the platinum carbon catalyst of the present invention, P, P was detected in a TG-MS (thermogravimetric-mass spectrometry) test 2 O 3 And P 2 O 5 Is a signal of (a).
According to the platinum carbon catalyst of the present invention, boron signals (B and B) were detected in TG-MS (thermogravimetric-mass spectrometry) test 2 O 3 )。
The platinum carbon catalyst according to the present invention does not contain other doping elements except sulfur, nitrogen, phosphorus and boron.
The platinum carbon catalyst according to the present invention does not contain other metal elements than platinum.
The platinum carbon catalyst according to the present invention, wherein sulfur, nitrogen, phosphorus and boron are chemically bonded to a carbon material.
The platinum carbon catalyst according to the invention has a carbon carrier which is any one of the sulfur nitrogen phosphorus boron doped carbon materials of the invention.
According to the platinum carbon catalyst of the present invention, the carbon material may be graphene, carbon nanotubes or conductive carbon black. 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 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.
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 ratio of the platinum carbon catalyst is as followsThe surface is 80m 2 /g～1500m 2 /g, preferably 100m 2 /g～200m 2 /g。
The invention provides a preparation method of a platinum-carbon catalyst, which comprises the following steps:
(1) A step of manufacturing a carbon carrier: firstly, contacting a carbon material with a phosphorus source and a boron source, and treating (preferably, constant temperature treatment) the carbon material in inert gas at 300-800 ℃ for 0.5-10 h; then contacting with a sulfur source and a nitrogen source, and treating (preferably constant temperature treatment) in an inert gas at 400-1000 ℃ for 0.5-10 h to obtain the carbon carrier;
(2) A step of supporting platinum with the carbon support obtained in (1).
According to the preparation method of the platinum carbon catalyst of the present invention, in (1), the "contact mode of the carbon material with the sulfur source, the nitrogen source, the phosphorus source and the boron source" is the same as the corresponding parts in the foregoing, and the present invention will not be repeated.
According to the preparation method of the platinum carbon catalyst, the sulfur source is elemental sulfur.
According to the preparation method of the platinum carbon catalyst, in (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, a step of; preferably 8:1 to 4:1.
According to the preparation method of the platinum carbon catalyst, the nitrogen source is ammonia water and/or urea.
According to the preparation method of the platinum carbon catalyst, in the (1), the mass ratio of the carbon material to the nitrogen source is 500:1 to 5:1, preferably 200:1 to 10:1.
according to the preparation method of the platinum carbon catalyst, the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite.
According to the preparation method of the platinum carbon catalyst, in the (1), the mass ratio of the carbon material to the phosphorus source is 10000 based on the mass of phosphorus contained in the phosphorus source: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
according to the preparation method of the platinum carbon catalyst, the boron source is one or more of boric acid and borate.
According to the preparation method of the platinum carbon catalyst, in (1), the mass ratio of the carbon material to the boron source is 10000 based on the mass of boron contained in the boron source: 1 to 10:1, a step of; preferably 2000: 1-20: 1.
according to the preparation method of the platinum carbon catalyst, if heating is needed in the step (1), the heating rate can be 1-20 ℃ per minute, preferably 3-15 ℃ per minute; more preferably, the phosphorus and boron are doped at 3-7 deg.C/min and the sulfur and nitrogen are doped at 5-10 deg.C/min.
According to the preparation method of the platinum carbon catalyst, in the phosphorus-boron doped operation in the step (1), the temperature is 450-700 ℃.
According to the preparation method of the platinum carbon catalyst, in the sulfur-nitrogen doped operation in the step (1), the temperature is 550-900 DEG C
According to the preparation method of the platinum carbon catalyst, in the phosphorus-boron doping operation in the step (1), the treatment time is 1 to 5 hours, preferably 2 to 4 hours.
According to the preparation method of the platinum carbon catalyst of the present invention, in the sulfur-nitrogen doped operation of (2), 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 can be graphene, carbon nano tube or conductive carbon black; the conductive carbon Black is 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 platinum carbon catalyst, the sulfur-nitrogen-phosphorus-boron doped carbon material prepared in the step (1) can be easily dispersed in an aqueous phase. For some carbon materials, such as ketjen black, it is difficult to disperse directly in the aqueous phase.
According to the preparation method of the platinum carbon catalyst, in (1), the mass fraction of oxygen in XPS analysis of the 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 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, nitrogen, phosphorus and boron in the spectrogram are characteristic peaks after peak separation.
Instrument and method for elemental analysis, conditions: elemental analyzer (Vario EL Cube), reaction temperature 1150 ℃, 5mg of sample, reduction temperature 850 ℃, carrier gas helium flow rate 200mL/min, oxygen flow rate 30mL/min, and oxygen introduction time 70s.
Apparatus, method, conditions for testing mass fraction of platinum in platinum carbon catalyst: 30mg of the prepared Pt/C catalyst is taken, 30mL of aqua regia is added, the mixture is condensed and refluxed for 12 hours at 120 ℃, cooled to room temperature, and the supernatant is taken for dilution, and then the content of Pt in the mixture is tested by ICP-AES.
The model of the high-resolution transmission electron microscope (HRTEM) adopted by the invention is JEM-2100 (HRTEM) (Japanese electronics Co., ltd.) and the test conditions of the high-resolution transmission electron microscope are as follows: the acceleration voltage was 200kV. The particle size of the nano particles in the sample is measured by an electron microscope picture.
BET test method: in the invention, the pore structure property of a sample is measured by a Quantachrome AS-6B type analyzer, the specific surface area and the pore volume of the catalyst are obtained by a Brunauer-Emmett-Taller (BET) method, and the pore distribution curve is obtained by calculating a desorption curve according to a Barrett-Joyner-Halenda (BJH) method.
The Raman detection of the invention adopts a LabRAM HR UV-NIR laser confocal Raman spectrometer manufactured by HORIBA company of Japan, and the laser wavelength is 532nm.
Electrochemical performance testing, instrument models Solartron analytical EnergyLab and Princeton Applied Research (Model 636A), methods and test conditions: polarization curve LSV of catalyst O at 1600rpm 2 Saturated 0.1M HClO 4 CV Curve 0.1M HClO under Ar atmosphere 4 The electrochemically active area ECSA was calculated therefrom. Stability test at O 2 Saturated 0.1M HClO 4 After 5000 cycles of scanning in the range of 1.0V to 1.5V, LSV and ECSA were tested as described above. The catalyst is prepared into slurry which is uniformly dispersed during the test, and the slurry is coated on a glassy carbon electrode with the diameter of 5mm, wherein the platinum content of the catalyst on the electrode is 3-4 mug.
Resistivity test four-probe resistivity tester, instrument model KDY-1, method and test conditions: the applied pressure was 3.9.+ -. 0.03MPa and the current was 500.+ -. 0.1mA.
TG-MS test method: testing by using a German relaxation-resistant STA449F5-QMS403D type thermogravimetric-mass spectrometer, wherein an ion source is an EI source, a four-stage rod mass spectrometer is in an MID mode, a transmission pipeline is a 3-meter long capillary, and the temperature is 260 ℃; the temperature is 55-1000 ℃ and the heating rate is 10 ℃/min.
VXC72 (Vulcan XC72, manufactured by cabot corporation, usa) is available from energy technologies limited in wing Long, su. Using the aforementioned instrumentationThe test shows that: specific surface area 258m 2 Per gram, pore volume 0.388mL/g, oxygen mass fraction 8.72% by XPS analysis, I D /I G The resistivity was 1.02. Omega. M, which was 1.22. Omega. M.
Ketjenback ECP600JD (Ketjen Black, manufactured by Lion corporation, japan) was purchased from Suzhou wing Long energy technologies Co. The test by the instrument method shows that: specific surface area 1362m 2 Per gram, pore volume 2.29mL/g, oxygen mass fraction 6.9% by XPS analysis, I D /I G 1.25, 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 used to illustrate the preparation of sulfur nitrogen phosphorus boron doped carbon materials of the present invention.
1g of Vulcan XC72 is immersed for 16h in 15mL of aqueous solution with sodium borate concentration of 0.5wt% and phosphoric acid concentration of 2.5 wt%; drying in an oven at 100 ℃; then placing the mixture into a tube furnace, heating the tube furnace to 450 ℃ at a speed of 5 ℃/min, and carrying out constant temperature treatment for 2 hours; naturally cooling to obtain the phosphorus-boron doped carbon material.
Immersing the phosphorus-boron doped carbon material in 20mL of ammonia water solution with the ammonia concentration of 1.2wt% for 24h; drying in an oven at 100 ℃; then evenly mixing the mixture with 0.167g of elemental sulfur, putting the mixture into a tube furnace, heating the tube furnace to 900 ℃ at the speed of 8 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the sulfur-nitrogen-phosphorus-boron doped carbon material, wherein the number of the carbon carrier A.
Sample characterization and testing
The mass fraction of sulfur analyzed by XPS is 0.6%; the mass fraction of nitrogen analyzed by XPS is 2.7%; the mass fraction of phosphorus analyzed by XPS is 1.9%; boron analysis by XPSThe amount fraction was 1.8%; specific surface area of 236m 2 /g; the resistivity was 1.32Ω·m.
Fig. 1 is an XPS spectrum of sulfur of the sulfur nitrogen phosphorus boron doped carbon material of example 1.
Fig. 2 is an XPS spectrum of nitrogen of the sulfur nitrogen phosphorus boron doped carbon material of example 1.
In fig. 2, the ratio of the sum of the characteristic peak areas between 399ev and 400.5ev to the other characteristic peak area between 390ev and 410ev is 10.8.
Fig. 3 is an XPS spectrum of phosphorus of the sulfur nitrogen phosphorus boron doped carbon material of example 1.
Fig. 4 is an XPS spectrum of boron of the sulfur nitrogen phosphorus boron doped carbon material of example 1.
Example 2
This example is used to illustrate the preparation of sulfur nitrogen phosphorus boron doped carbon materials of the present invention.
10mL of absolute ethanol was added to 1g Ketjenblack ECP600JD, followed by soaking in 25mL of an aqueous solution having a boric acid concentration of 0.8wt% and a sodium dihydrogen phosphate concentration of 0.4wt% for 20 hours; drying in an oven at 100 ℃; then placing the mixture into a tube furnace, heating the tube furnace to 700 ℃ at a speed of 5 ℃/min, and carrying out constant temperature treatment for 2 hours; naturally cooling to obtain the boron-phosphorus doped carbon material.
Adding the boron-phosphorus doped carbon material into 35mL of aqueous solution with urea concentration of 0.1wt% for soaking for 20h, and drying in an oven at 100 ℃; then evenly mixing with 0.25g of elemental sulfur and nitrogen, putting into a tube furnace, heating the tube furnace to 550 ℃ at a speed of 6 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the sulfur-nitrogen-boron-phosphorus doped carbon material, wherein the number of the carbon carrier B is the number of the carbon carrier B.
Sample characterization and testing
The mass fraction of sulfur analyzed by XPS is 0.9%; the mass fraction of nitrogen analyzed by XPS is 1.7%; the mass fraction of phosphorus analyzed by XPS is 0.4%; the mass fraction of boron analyzed by XPS is 2.1 percent; specific surface area 1341m 2 /g; the resistivity was 1.39Ω·m.
Fig. 5 is an XPS spectrum of sulfur of the sulfur nitrogen phosphorus boron doped carbon material of example 2.
Fig. 6 is an XPS spectrum of nitrogen of the sulfur nitrogen phosphorus boron doped carbon material of example 2.
In fig. 6, the ratio of the sum of the characteristic peak areas between 399ev and 400.5ev to the other characteristic peak area between 390ev and 410ev is 13.7.
Fig. 7 is an XPS spectrum of phosphorus of the sulfur nitrogen phosphorus boron doped carbon material of example 2.
Fig. 8 is an XPS spectrum of boron of the sulfur nitrogen phosphorus boron doped carbon material of example 2.
Example 3
This example illustrates the preparation of the platinum carbon catalyst of the present invention.
Dispersing the carbon carrier A in deionized water according to the proportion of 250mL of water used per gram of carbon carrier, adding 3.4mmol of chloroplatinic acid per gram of carbon carrier, performing ultrasonic dispersion to form suspension, and adding 1mol/L of sodium carbonate aqueous solution to enable the pH value of the system to be 10; heating the suspension to 80 ℃, adding formic acid under stirring to perform reduction reaction, wherein the molar ratio of the formic acid to the chloroplatinic acid is 50:1, and continuously maintaining the reaction for 10 hours; filtering the reacted mixture, washing the mixture with deionized water until the pH value of the filtrate is neutral, filtering the mixture, and then drying the mixture at 100 ℃ to obtain the platinum-carbon catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 39.7%.
Fig. 9 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 3.
Fig. 10 is an XPS spectrum of nitrogen of the platinum carbon catalyst of example 3.
In XPS analysis of the Pt-C catalyst, there was no P between 125ev and 145ev 2p Is a characteristic peak of (2).
P, P was detected in TG-MS test of platinum carbon catalyst 2 O 3 And P 2 O 5 Is a signal of (a).
In XPS analysis of the platinum carbon catalyst, there was no B between 185ev and 200ev 1s Is a characteristic peak of (2).
B and B were detected in TG-MS test of platinum carbon catalyst 2 O 3 Is a signal of (a).
The results of the performance test of the platinum carbon catalyst are shown in table 1.
Example 4
This example illustrates the preparation of a platinum carbon catalyst.
A platinum carbon catalyst was prepared according to the method of example 3, except that: 1.3mmol of chloroplatinic acid per gram of carbon support are added.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 20.3%.
P, P was detected in TG-MS test of platinum carbon catalyst 2 O 3 And P 2 O 5 Is a signal of (a).
B and B were detected in TG-MS test of platinum carbon catalyst 2 O 3 Is a signal of (a).
The results of the performance test of the platinum carbon catalyst are shown in table 1.
Example 5
This example illustrates the preparation of the platinum carbon catalyst of the present invention.
Dispersing a carbon carrier B in a solution according to the proportion of 600mL of water and 600mL of ethylene glycol used for each gram of carbon carrier, adding 12mmol of chloroplatinic acid into each gram of carbon carrier, adding sodium acetate into the solution according to the molar ratio of sodium acetate to chloroplatinic acid being 2:1, performing ultrasonic dispersion to form a suspension, and adding 1mol/L of sodium carbonate aqueous solution to enable the pH value of the system to be 10; heating the suspension to 80 ℃, adding sodium borohydride under stirring to perform reduction reaction, wherein the molar ratio of the sodium borohydride to chloroplatinic acid is 5:1, and continuously maintaining the reaction for 10 hours; filtering the reacted mixture, washing the mixture with deionized water until the pH value of the filtrate is neutral, filtering the mixture, and drying the mixture at 100 ℃ to obtain the platinum-carbon catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 70.2%.
Fig. 11 is an XPS spectrum of sulfur of the platinum carbon catalyst of example 5.
Fig. 12 is an XPS spectrum of nitrogen of the platinum carbon catalyst of example 5.
Fig. 13 is a TEM image of the platinum carbon catalyst of example 5.
In XPS analysis of the Pt-C catalyst, there was no P between 125ev and 145ev 2p Is a characteristic peak of (2).
P, P was detected in TG-MS test of platinum carbon catalyst 2 O 3 And P 2 O 5 Is a signal of (a).
In XPS analysis of the platinum carbon catalyst, there was no B between 185ev and 200ev 1s Is a characteristic peak of (2).
B and B were detected in TG-MS test of platinum carbon catalyst 2 O 3 Is a signal of (a).
The results of the performance test of the platinum carbon catalyst are shown in table 1.
Comparative example 1
Dispersing Vulcan XC72 in deionized water according to the proportion of 250mL of water used for each gram of carbon carrier, adding 3.4mmol of chloroplatinic acid for each gram of carbon carrier, performing ultrasonic dispersion to form suspension, and adding 1mol/L of sodium carbonate aqueous solution to enable the pH value of the system to be 10; heating the suspension to 80 ℃, adding formic acid under stirring to perform reduction reaction, wherein the molar ratio of the formic acid to the chloroplatinic acid is 50:1, and continuously maintaining the reaction for 10 hours; filtering the reacted mixture, washing the mixture with deionized water until the pH value of the filtrate is neutral, filtering the mixture, and then drying the mixture at 100 ℃ to obtain the platinum-carbon catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 40.1%.
The results of the platinum carbon catalyst performance test are shown in table 1.
Comparative example 2
Dispersing Ketjenback ECP600JD in a solution according to the proportion of 600mL of water and 600mL of ethylene glycol used for each gram of carbon carrier, adding 12mmol of chloroplatinic acid into each gram of carbon carrier, adding sodium acetate into the solution according to the molar ratio of sodium acetate to chloroplatinic acid being 2:1, performing ultrasonic dispersion to form a suspension, and adding 1mol/L of sodium carbonate aqueous solution to enable the pH value of the system to be 10; heating the suspension to 80 ℃, adding sodium borohydride under stirring to perform reduction reaction, wherein the molar ratio of the sodium borohydride to chloroplatinic acid is 5:1, and continuously maintaining the reaction for 10 hours; filtering the reacted mixture, washing the mixture with deionized water until the pH value of the filtrate is neutral, filtering the mixture, and drying the mixture at 100 ℃ to obtain the platinum-carbon catalyst.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 69.9%.
The results of the platinum carbon catalyst performance test are shown in table 1.
Comparative example 3
The platinum carbon catalyst is a commercially available catalyst, under the trade designation HISPEC4000.
Sample characterization and testing
The platinum mass fraction of the platinum carbon catalyst was 40.2%.
The results of the platinum carbon catalyst performance test are shown in table 1.
Comparative example 4
This comparative example is used to illustrate the preparation of phosphorus doped carbon materials.
1g Vulcan XC72 is immersed in 15mL of 0.8wt% phosphoric acid aqueous solution for 16h; drying in an oven at 100 ℃; then placing the mixture into a tube furnace, heating the tube furnace to 400 ℃ at the speed of 8 ℃/min, and carrying out constant temperature treatment for 2 hours; naturally cooling to obtain the phosphorus-doped carbon material.
Sample characterization and testing
Fig. 14 is an XPS spectrum of phosphorus of the phosphorus-doped carbon material of comparative example 4.
Comparative example 5
This comparative example is used to illustrate the preparation of boron doped carbon materials.
1g of Vulcan XC72 is immersed in 15mL of 4.5wt% sodium borate aqueous solution for 16h; drying in an oven at 100 ℃; then placing the mixture into a tube furnace, heating the tube furnace to 400 ℃ at a speed of 10 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the boron doped carbon material.
Sample characterization and testing
Fig. 15 is an XPS spectrum of boron of the boron doped carbon material of comparative example 5.
Comparative example 6
This comparative example is used to illustrate the preparation of sulfur-doped carbon materials.
1g Ketjenblack ECP600JD and 0.25g of elemental sulfur and nitrogen are uniformly mixed, the mixture is put into a tube furnace, the tube furnace is heated to 500 ℃ at the speed of 5 ℃/min, and the constant temperature treatment is carried out for 3 hours; naturally cooling to obtain the sulfur-doped carbon material.
Sample characterization and testing
Fig. 16 is an XPS spectrum of sulfur of the sulfur-doped carbon material of comparative example 6.
Comparative example 7
This comparative example is used to illustrate the preparation of nitrogen-doped carbon materials.
1g Vulcan XC72 is immersed in 20mL of 2.5wt% ammonia water solution for 24h; drying in an oven at 100 ℃; then placing the mixture into a tube furnace, heating the tube furnace to 1100 ℃ at a speed of 8 ℃/min, and carrying out constant temperature treatment for 3 hours; naturally cooling to obtain the nitrogen-doped carbon material.
Sample characterization and testing
Fig. 17 is an XPS spectrum of nitrogen of the nitrogen-doped carbon material of comparative example 7.
TABLE 1
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Claims (9)
1. A platinum carbon catalyst for an anode and/or a cathode of a hydrogen fuel cell, comprising a carbon support and a platinum metal supported thereon, wherein the carbon support is a sulfur nitrogen phosphorus boron doped conductive carbon black, the carbon support being prepared by a method comprising: firstly, the conductive carbon black is contacted with a phosphorus source and a boron source, and is treated for 0.5 to 10 hours at the temperature of 300 to 800 ℃ in inert gas; then contacts with a sulfur source and a nitrogen source, and is treated for 0.5 to 10 hours at the temperature of 400 to 1000 ℃ in inert gas; the sulfur source is elemental sulfur, the mass of the sulfur source is calculated by the mass of sulfur contained in the sulfur source, and the mass ratio of the conductive carbon black to the sulfur source is 20: 1-2: 1, a step of; the nitrogen source is ammonia water and/or urea, the mass of the nitrogen source is calculated by the mass of nitrogen contained in the nitrogen source, and the mass ratio of the conductive carbon black to the nitrogen source is 500:1 to 5:1, a step of; the phosphorus source is one or more of phosphoric acid, phosphate, pyrophosphate, polyphosphate, hydrogen phosphate, dihydrogen phosphate, phosphite and hypophosphite, the mass of the phosphorus source is counted by the mass of phosphorus contained in the phosphorus source, and the mass ratio of the conductive carbon black to the phosphorus source is 10000:1 to 10:1, a step of; the boron source is one or more of boric acid and borate, the mass of the boron source is calculated by the mass of boron contained in the boron source, and the mass ratio of the conductive carbon black to the boron source is 10000:1 to 10:1, a step of; s analyzed by XPS of the platinum carbon catalyst 2P In the spectrum peak, 160 ev-170 eV has only characteristic peaks of thiophene-type sulfur, and the platinum carbon catalyst is analyzed by XPS 1s In the spectrum peak, besides the characteristic peak between 399ev and 400.5ev, there is no other characteristic peak between 390ev and 410ev, and the XPS analysis B of the carbon carrier 1s Of the spectral peaks, there was one characteristic peak at 189.6 ev.+ -. 0.5 ev; 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 in its XPS analysis, there is no B between 185ev and 200ev 1s And no P between 125ev and 145ev 2p Is a characteristic peak of (2).
3. 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.
4. The platinum carbon catalyst according to claim 1, wherein in XPS analysis of the carbon support, the mass fraction of sulfur is 0.01 to 6%, the mass fraction of nitrogen is 0.01 to 6%, the mass fraction of phosphorus is 0.01 to 6%, and the mass fraction of boron is 0.01 to 6%.
5. The method for preparing a platinum carbon catalyst according to claim 1, comprising:
(1) The carbon support manufacturing step of claim 1;
(2) A step of supporting platinum with the carbon support obtained in (1).
6. The method for producing a platinum carbon catalyst according to claim 5, wherein said platinum supporting step (2) comprises:
(a) Dispersing the carbon carrier and the platinum precursor obtained in the step (1) in a water phase, and regulating the pH to 8-12;
(b) Reducing agent is added for reduction;
(c) Separating out solid, and post-treating to obtain the platinum carbon catalyst.
7. The method of preparing a platinum carbon catalyst according to claim 6, wherein in (a), the platinum precursor is chloroplatinic acid, potassium chloroplatinate, or sodium chloroplatinate; the concentration of the platinum precursor is 0.5 mol/L-5 mol/L.
8. The method for preparing a platinum carbon catalyst according to claim 6, wherein in (b), the reducing agent is one or more of citric acid, ascorbic acid, formaldehyde, formic acid, ethylene glycol, sodium citrate, hydrazine hydrate, sodium borohydride or glycerol; the mol ratio of the reducing agent to the platinum is 2-100; the reduction temperature is 60-90 ℃; the reduction time is 4-15 h.
9. A hydrogen fuel cell, wherein the platinum carbon catalyst according to any one of claims 1 to 4 is used in an anode and/or a cathode of the hydrogen fuel cell.
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