CN116404181A - Pt-M-P alloy porous nanosphere electrocatalyst and preparation method and application thereof - Google Patents
Pt-M-P alloy porous nanosphere electrocatalyst and preparation method and application thereof Download PDFInfo
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- CN116404181A CN116404181A CN202310311249.3A CN202310311249A CN116404181A CN 116404181 A CN116404181 A CN 116404181A CN 202310311249 A CN202310311249 A CN 202310311249A CN 116404181 A CN116404181 A CN 116404181A
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- 239000002077 nanosphere Substances 0.000 title claims abstract description 103
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 61
- 229910001096 P alloy Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 55
- 239000000956 alloy Substances 0.000 claims abstract description 55
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 29
- 239000011574 phosphorus Substances 0.000 claims abstract description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 238000005275 alloying Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 210000001787 dendrite Anatomy 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 10
- 150000003058 platinum compounds Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 36
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 33
- 229910052723 transition metal Inorganic materials 0.000 claims description 32
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 150000003624 transition metals Chemical class 0.000 claims description 29
- 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 26
- 239000012279 sodium borohydride Substances 0.000 claims description 23
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 23
- 229910052697 platinum Inorganic materials 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000011668 ascorbic acid Substances 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 13
- 235000010323 ascorbic acid Nutrition 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 12
- 210000004027 cell Anatomy 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- -1 polyoxypropylene Polymers 0.000 claims description 7
- 239000005749 Copper compound Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 6
- 150000001869 cobalt compounds Chemical class 0.000 claims description 6
- 150000001880 copper compounds Chemical class 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 150000002344 gold compounds Chemical class 0.000 claims description 6
- 150000002506 iron compounds Chemical class 0.000 claims description 6
- 239000005078 molybdenum compound Substances 0.000 claims description 6
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 6
- 150000002816 nickel compounds Chemical class 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 150000002941 palladium compounds Chemical class 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 229940100890 silver compound Drugs 0.000 claims description 6
- 150000003379 silver compounds Chemical class 0.000 claims description 6
- 150000003658 tungsten compounds Chemical class 0.000 claims description 6
- 150000003752 zinc compounds Chemical class 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 4
- 239000011261 inert gas Substances 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 3
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 3
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 235000001727 glucose Nutrition 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002074 nanoribbon Substances 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229940068041 phytic acid Drugs 0.000 claims description 3
- 235000002949 phytic acid Nutrition 0.000 claims description 3
- 239000000467 phytic acid Substances 0.000 claims description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 claims description 3
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 84
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 abstract description 27
- 239000001301 oxygen Substances 0.000 abstract description 27
- 230000009467 reduction Effects 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- 150000003623 transition metal compounds Chemical class 0.000 abstract 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 28
- 239000000843 powder Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 21
- 229960003280 cupric chloride Drugs 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910000881 Cu alloy Inorganic materials 0.000 description 12
- WBLJAACUUGHPMU-UHFFFAOYSA-N copper platinum Chemical compound [Cu].[Pt] WBLJAACUUGHPMU-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 11
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 10
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 10
- 229920006395 saturated elastomer Polymers 0.000 description 10
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- RSRDBZXFUDSTQP-UHFFFAOYSA-N [P].[Cu].[Pt] Chemical compound [P].[Cu].[Pt] RSRDBZXFUDSTQP-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 description 1
- ZTLQDOYROVYUGM-UHFFFAOYSA-N [P].[Co].[Pt] Chemical compound [P].[Co].[Pt] ZTLQDOYROVYUGM-UHFFFAOYSA-N 0.000 description 1
- PFZHNAXLNCTMNS-UHFFFAOYSA-N [P].[Ni].[Pt] Chemical compound [P].[Ni].[Pt] PFZHNAXLNCTMNS-UHFFFAOYSA-N 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
- H01M4/923—Compounds thereof with non-metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
-
- 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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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses a Pt-M-P alloy porous nanosphere electrocatalyst, a preparation method and application thereof, wherein water is used as a solvent, and a platinum compound and a transition metal compound are reduced simultaneously under the action of a reducing agent to form uniform Pt-M alloy; and then carrying out phosphorus alloying on the Pt-M alloy to form the Pt-M-P alloy porous nanosphere electrocatalyst with a porous nanosphere structure, wherein the particle size is 20-40nm, a three-dimensional network is woven by nano dendrites, the length of the nano dendrites is 2-10nm, and the diameter is 0.5-2nm. The electrocatalyst provided by the invention shows a three-dimensional network structure woven by one-dimensional nano dendrites, and the constructed porous nanosphere electrocatalyst has high-efficiency oxygen reduction catalytic activity. The electrocatalyst of the invention exhibits superior stability compared to commercial Pt/C and the same type of catalysts currently being investigated and reported. The preparation method is simple and feasible, and is suitable for large-scale production.
Description
Technical Field
The invention relates to an electrocatalyst, a preparation method and application thereof, in particular to a platinum-transition metal-phosphorus (Pt-M-P) alloy porous nanosphere electrocatalyst and a preparation method and application thereof, belonging to the technical field of new energy sources and being particularly applied to electrocatalysts for fuel cells and metal-air cell cathodes.
Background
The proton exchange membrane fuel cell has the advantages of high energy density, high conversion efficiency, environmental friendliness and the like. However, the slow kinetics of cathodic oxygen reduction (ORR) is one of the major challenges it faces. Heretofore, carbon supported platinum (Pt/C) has remained the most practical commercial catalyst, but high cost, limited Pt resources, poor durability, etc., have prevented the large-scale use of fuel cells.
Commercial Pt/C catalysts are Pt nano-particles with the size of about 3nm loaded on the surface of carbon black with a high specific surface area, and in practical application, the Pt nano-particles are often dissolved, aged in Walder, and the like to influence the catalytic activity of ORR. Therefore, the structural design of the catalyst is the focus of research in this field. For example: the core-shell structure is designed to improve the Pt utilization rate so as to improve the catalytic activity and enhance the stability; the preparation of the one-dimensional nanowire enables the catalyst to have rapid electron conduction capability, high stability and rich active sites; the porous/hollow form is constructed, mass transfer is improved by means of rich pore canal structures, and catalytic performance is improved. Therefore, developing nanostructures of a particular morphology is an effective means of improving catalyst performance.
Further, by alloying Pt with other transition metals (m=fe, co, ni, cu, etc.), the strain effect, ligand effect, etc. can be adjusted, and not only the catalyst activity can be improved, but also the amount of Pt used can be reduced. Further alloying it with non-metals (x=n, P, S, etc.), more active sites can be induced to form on the Pt surface. In recent years, phosphorus (P) alloying with Pt-M has received increasing attention. P has a rich valence electron: on one hand, strong metal-nonmetal bonds can be formed, and the adsorption energy of the oxygen-containing intermediate on the Pt surface is changed through the synergistic effect among a plurality of elements; on the other hand, the electronic structure of the Pt-M alloy can be effectively regulated and controlled, so that the oxygen reduction activity and stability of the catalyst are improved.
The existing catalyst has unsatisfactory performance and high cost, and the electrochemical performance of the catalyst is still to be improved. Patent document with publication number of CN114759204A discloses a platinum-based alloy porous nanosphere electrocatalyst with high oxygen reduction performance and a preparation method thereof, which do not comprise alloying of phosphorus in Pt-M alloy, have unobvious advantage of electronic synergistic effect, and limit the application of the catalyst in fuel cells and metal-air cell cathodes. Publication number CN110911697a discloses a transition metal/nitrogen doped porous carbon nanosphere electrocatalyst and a preparation method thereof, the method comprises: placing a precursor solution consisting of a template agent, a carbon source and a nitrogen source into a reaction kettle, and heating to obtain nitrogen-doped carbon nanosphere powder; carrying out vacuum drying after ultrasonic treatment on the nitrogen-doped carbon nanospheres and the transition metal salt solution to obtain transition metal/nitrogen-doped carbon nanosphere powder; carbonizing the transition metal/nitrogen doped carbon nanosphere powder in inert gas to obtain the transition metal/nitrogen doped porous carbon nanosphere electrocatalyst. The porous carbon nanosphere electrocatalyst has the advantages that the performance is not dominant, the catalytic activity of the electrocatalyst can be improved by adjusting the content of transition metal adsorbed by the nitrogen-doped carbon nanosphere by adjusting the content of nitrogen source, the prepared catalyst has the advantages of insignificant electronic synergy effect although the half-wave potential can reach 0.86V (vs. RHE), high-temperature treatment is required, the energy consumption is higher, the steps are complex, noble metal is not adopted, the cost is reduced by replacing noble metal, the integral performance improvement brought by noble metal elements to the catalyst is weakened, and the catalyst is unfavorable for industrial application and needs to be further improved and developed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide a Pt-M-P alloy porous nanosphere electrocatalyst, a preparation method and application thereof. The electrocatalyst of the invention exhibits superior stability compared to commercial Pt/C and the same type of catalysts currently being investigated and reported. The preparation method is simple and feasible, and is suitable for large-scale production.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a Pt-M-P alloy porous nanosphere electrocatalyst takes water as a solvent, forms a nanosphere structure of a three-dimensional porous network under the induction of a surfactant, and simultaneously reduces a platinum compound and a transition metal (M) compound under the action of a reducing agent to form uniform Pt-M alloy; and then carrying out phosphorus alloying on the Pt-M alloy to form the Pt-M-P alloy porous nanosphere electrocatalyst with a porous nanosphere structure, wherein the particle size of the Pt-M-P alloy porous nanosphere is 20-40nm, a three-dimensional network is woven by nano dendrites, the length of the nano dendrites is 2-10nm, and the diameter is 0.5-2nm.
Preferably, the Pt-M-P alloy porous nanospheres have Pt (111) crystal planes and form a porous structure.
Preferably, the transition metal (M) compound is at least one of a palladium compound, a silver compound, a gold compound, a molybdenum compound, a tungsten compound, an iron compound, a cobalt compound, a nickel compound, a copper compound, and a zinc compound.
The preparation method of the Pt-M-P alloy porous nanosphere electrocatalyst comprises the following steps:
1) Preparing a precursor solution:
dissolving surfactant in water, continuously dissolving platinum (Pt) compound and transition metal (M) compound, introducing protective gas to saturation, and sealing precursor solution for later use;
2) Preparing Pt-M alloy porous nanospheres:
heating and maintaining the precursor solution at a constant temperature under the condition of protective gas atmosphere, injecting a reducing reagent A, and standing for reaction to obtain the Pt-M alloy porous nanospheres;
3) Constructing a Pt-M-P alloy porous nanosphere electrocatalyst:
adding a reducing agent B and a phosphorus (P) source into the prepared Pt-M alloy porous nanospheres to perform a phosphorus alloying reaction to obtain the Pt-M-P alloy porous nanosphere electrocatalyst;
the reducing agent A and the reducing agent B are respectively at least one of ascorbic acid, glucose, oxalic acid, citric acid, hydrazine hydrate, sodium borohydride and potassium borohydride.
Preferably, in the step 1), the surfactant is at least one of cationic surfactant, anionic surfactant and nonionic surfactant with different carbon chain lengths.
Preferably, in the step 1), the platinum (Pt) compound is at least one of chloroplatinic acid, potassium chloroplatinate, platinum acetylacetonate, and platinum chloride.
Preferably, in the step 1), the transition metal (M) compound is at least one of a palladium compound, a silver compound, a gold compound, a molybdenum compound, a tungsten compound, an iron compound, a cobalt compound, a nickel compound, a copper compound, and a zinc compound.
Preferably, in the step 1), the shielding gas is at least one of inert gas, oxidizing gas, reducing gas, and air.
Preferably, in the step 1), the molar ratio of the transition metal (M) compound to the platinum (Pt) compound is 0 to 10:1, and the content of the transition metal (M) compound is not 0.
Preferably, in the step 1), the molar ratio of the surfactant to the platinum compound is 0 to 100:1, and the amount of the surfactant is not 0.
Further preferably, the cationic surfactants of different carbon chain lengths are cetyl trimethylammonium bromide or cetyl trimethylammonium chloride.
Further preferably, the anionic surfactant is sodium dodecyl benzene sulfonate or sodium hexadecyl sulfate.
Further preferably, the nonionic surfactant is at least one of polyvinylpyrrolidone, polyoxypropylene polyoxyethylene copolymer, and the like.
Preferably, in the step 2), the precursor solution is heated at a temperature of 25-100 ℃, and the standing reaction time is not less than 0.5h. Further preferably, the precursor solution is heated at a temperature of 80 to 100℃and allowed to stand for a reaction time of not less than 6 hours.
Preferably, in said step 2), reducing agent a is added in an amount other than 0.
Preferably, in the step 3), the phosphorus (P) source is at least one of sodium hypophosphite, phytic acid, sodium hypophosphite monohydrate, and sodium hypophosphite hexahydrate.
Preferably, in the step 3), the molar ratio of the reducing agent B, the phosphorus (P) source and the Pt-M alloy porous nanospheres is 0-2:0-10:1, and the amounts of reducing agent B and transition metal (M) compound are respectively different from 0.
Preferably, in the step 3), the alloying reaction time of phosphorus is not less than 5min, and the heating temperature of the reaction is not higher than 60 ℃. Further preferably, the alloying reaction time of phosphorus is 5-30 min, and the heating temperature of the reaction is 0-60 ℃.
Preferably, in the step 3), after the alloying reaction of phosphorus is completed, the Pt-M-P alloy porous nanosphere electrocatalyst material without the carrier is obtained through centrifugation, washing and drying.
The invention relates to application of a Pt-M-P alloy porous nanosphere electrocatalyst, which is formed by loading the Pt-M-P alloy porous nanosphere on a conductive carrier;
the conductive carrier is at least one of spherical, linear or sheet/block carbon black, oxide, nitride, carbide and sulfide; the mass ratio of the conductive carrier to the Pt-M-P alloy porous nanospheres is 0-1000:1, and the mass of the conductive carrier is not 0.
Preferably, the spherical carbon black is at least one of EC600JD, EC300J, vulcan XC72R, BP 2000.
Preferably, the linear carbon black is at least one of carbon nanotubes, carbon fibers and carbon nanorods.
Preferably, the sheet/block carbon black is at least one of graphene, nanoribbons, and activated carbon.
Compared with the prior art, the invention has the following obvious prominent substantive features and obvious advantages:
1. the preparation method does not need to react in organic solvents such as oleylamine, oleic acid and the like, does not need to be heated and reduced in a high-temperature furnace under a reducing atmosphere, only adopts chemical reduction in a water solvent, has simple operation and low energy consumption, is environment-friendly, and is suitable for large-scale production;
2. compared with a commercial Pt/C catalyst, the electrocatalyst provided by the invention has the advantages that the Pt consumption is reduced, and the catalyst cost is reduced;
3. the electrocatalyst provided by the invention is subjected to induction growth by a common surfactant, and the catalyst has a stronger electron synergistic effect due to the introduction of P, so that a Pt (111) crystal face with abundant high catalytic activity is exposed and a porous structure is formed, and the electrocatalyst shows excellent oxygen reduction activity compared with commercial Pt/C and the catalysts of the same type which are researched and reported at present; the introduction of P further reduces the Pt consumption, thereby further reducing the catalyst cost;
4. the electrocatalyst provided by the invention is of a network structure assembled by a one-dimensional structure, has a stable bulk structure, and shows excellent electrochemical performance compared with commercial Pt/C and catalysts of the same type which are reported in current research.
Drawings
FIG. 1 is a TEM image of porous nanospheres of platinum-copper-phosphorus alloy (PtCuP-NSs) prepared in example 1 of the present invention;
FIG. 2 is a powder X-ray diffraction (XRD) spectrum of a platinum copper phosphorus alloy porous nanosphere catalyst (PtCuP-NSs/C) prepared in example 1 of the present invention versus a platinum copper alloy porous nanosphere catalyst (PtCu-NSs/C) and a commercial Pt/C catalyst;
FIG. 3 is a Cyclic Voltammetry (CV) diagram of a platinum copper phosphorus alloy porous nanosphere catalyst (PtCuP-NSs/C) prepared in example 1 of the present invention versus a platinum copper alloy porous nanosphere catalyst (PtCu-NSs/C) versus a commercial Pt/C catalyst;
FIG. 4 is a graph showing the polarization of oxygen reduction (ORR) for a platinum copper phosphorus alloy porous nanosphere catalyst (PtCuP-NSs/C) prepared in example 1 of the present invention versus a platinum copper alloy porous nanosphere catalyst (PtCu-NSs/C) versus a commercial Pt/C catalyst;
FIG. 5 is a graph of current versus time for a platinum copper phosphorus porous nanosphere catalyst (PtCuP-NSs/C) prepared in example 1 of the present invention versus a commercial Pt/C catalyst at 0.7V (vs. RHE) constant potential.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrative of the present invention, but the contents of the present invention are not limited to the following examples only.
The foregoing aspects are further described in conjunction with specific embodiments, and the following detailed description of preferred embodiments of the present invention is provided:
example 1
In this example, preparation of a platinum copper phosphorus alloy porous nanosphere catalyst (PtCuP-NSs/C):
according to the mole ratio of cetyl trimethyl ammonium bromide to chloroplatinic acid of 53:1 and the mole ratio of cupric chloride to chloroplatinic acid of 0.5:1, weighing cetyl trimethyl ammonium bromide powder with certain mass, dissolving in water, and then continuously dissolving chloroplatinic acid and cupric chloride; injecting ascorbic acid in air atmosphere, and reacting at 80 ℃ for 6 hours to prepare a platinum-transition metal alloy; then, centrifuging and washing the platinum-transition metal alloy, dispersing in ultrapure water, adding sodium hypophosphite and sodium borohydride, and reacting for 20min at 25 ℃; the molar ratio of the platinum copper alloy porous nanospheres to the sodium hypophosphite is 1:2.25, sodium hypophosphite to sodium borohydride in a molar ratio of 1:2; and then centrifuging and washing, and compositing with Vulcan XC-72R conductive carbon black to obtain the PtCuP-NSs/C catalyst.
Test characterization
TEM results are shown in figure 1, which shows a porous nanosphere structure with a particle size of about 30nm, and a three-dimensional network is woven from nano dendrites with a length of 2-10nm and a diameter of 0.5-2nm. From XRD test patterns (shown in FIG. 2), it is seen that the characteristic diffraction peak of PtCuP-NSs/C catalyst shifts to high angles, indicating that Pt forms an alloy with Cu, and to low angles, indicating that P further forms an alloy with PtCu, as compared to commercial Pt/C catalysts. The particles of the Pt-M-P alloy porous nanosphere electrocatalyst of this example have Pt (111) crystal planes and form a porous structure.
Next, the electrochemical performance of the PtCuP-NSs/C catalyst was tested. Using a standard three-electrode system, counter electrodesThe electrode is a platinum sheet, and the reference electrode is a saturated calomel electrode. As can be seen from the Cyclic Voltammetry (CV) shown in fig. 3, P-alloying contributes to the improvement of the electrochemically active area of the catalyst. Further, oxygen reduction test was performed on oxygen saturated 0.1M HClO 4 The electrode rotation speed is 1600rpm, the scanning speed is 5mV/s, and the polarization curve (as shown in figure 4) result shows that the half-wave potential of the PtCuP-NSs/C catalyst is 0.923V (vs. RHE) and is obviously superior to that of the commercial Pt/C catalyst. The current loss of the PtCuP-NSs/C catalyst was nearly 45% as seen by the current versus time curve of FIG. 5 at 0.7V (vs. RHE) constant potential, whereas the commercial Pt/C catalyst lost nearly 85%.
Example 2
This embodiment is substantially the same as embodiment 1, except that:
in this example, the molar ratio of the platinum copper alloy porous nanospheres to the phosphorus source is 1: preparation of PtCuP-NSs/C catalyst at 1:
according to the mole ratio of cetyl trimethyl ammonium bromide to chloroplatinic acid of 53:1 and the mole ratio of cupric chloride to chloroplatinic acid of 0.5:1, weighing a certain mass of cetyl trimethyl ammonium bromide powder, dissolving the solution in water, then continuously dissolving chloroplatinic acid and cupric chloride, injecting ascorbic acid in air atmosphere, and reacting for 6 hours at 80 ℃ to prepare the platinum-transition metal alloy; then, after centrifugation and washing, dispersing in ultrapure water, adding sodium hypophosphite and sodium borohydride, and reacting for 20min at 25 ℃; the molar ratio of the platinum copper alloy porous nanospheres to the sodium hypophosphite is 1:1, the molar ratio of sodium hypophosphite to sodium borohydride is 1:2; and then centrifuging and washing, and compositing with Vulcan XC-72R conductive carbon black to obtain the PtCuP-NSs/C catalyst.
Test characterization
The electrochemical performance of the PtCuP-NSs/C catalyst is characterized by adopting a standard three-electrode system, wherein a counter electrode is a platinum sheet, and a reference electrode is a saturated calomel electrode. Oxygen reduction test 0.1M HClO saturated with oxygen 4 The electrolyte was used at an electrode rotation speed of 1600rpm and a scan speed of 5mV/s. The half-wave potential of the PtCuP-NSs/C catalyst under example 2 was-0.918V (vs. RHE).
Example 3
This embodiment is substantially identical to the previous embodiment, except that:
in this example, the molar ratio of the platinum copper alloy porous nanospheres to the phosphorus source is 1: preparation of PtCuP-NSs/C catalyst at 9:
according to the mole ratio of cetyl trimethyl ammonium bromide to chloroplatinic acid of 53:1 and the mole ratio of cupric chloride to chloroplatinic acid of 0.5:1, weighing cetyl trimethyl ammonium bromide powder with certain mass, dissolving the cetyltrimethylammonium bromide powder in water, then continuously dissolving chloroplatinic acid and cupric chloride, injecting ascorbic acid in air atmosphere, and reacting for 6 hours at 80 ℃; then, after centrifugation and washing, dispersing in ultrapure water, adding sodium hypophosphite and sodium borohydride, and reacting for 20min at 25 ℃; the molar ratio of the platinum copper alloy porous nanospheres to the sodium hypophosphite is 1:9, the molar ratio of sodium hypophosphite to sodium borohydride is 1:2; and then centrifuging and washing, and compositing with Vulcan XC-72R conductive carbon black to obtain the PtCuP-NSs/C catalyst.
Test characterization
The electrochemical performance of the PtCuP-NSs/C catalyst is characterized by adopting a standard three-electrode system, wherein a counter electrode is a platinum sheet, and a reference electrode is a saturated calomel electrode. Oxygen reduction test 0.1M HClO saturated with oxygen 4 The electrolyte was used at an electrode rotation speed of 1600rpm and a scan speed of 5mV/s. The half-wave potential of the PtCuP-NSs/C catalyst under example 3 was-0.901V (vs. RHE).
Example 4
This embodiment is substantially identical to the previous embodiment, except that:
in this example, ptCuP-NSs/C catalyst preparation at a reaction time of 10 min:
according to the mole ratio of cetyl trimethyl ammonium bromide to chloroplatinic acid of 53:1 and the mole ratio of cupric chloride to chloroplatinic acid of 0.5:1, weighing cetyl trimethyl ammonium bromide powder with certain mass, dissolving the cetyltrimethylammonium bromide powder in water, then continuously dissolving chloroplatinic acid and cupric chloride, injecting ascorbic acid in air atmosphere, and reacting for 6 hours at 80 ℃; then, after centrifugation and washing, dispersing in ultrapure water, adding sodium hypophosphite and sodium borohydride, and reacting for 10min at 25 ℃; the molar ratio of the platinum copper alloy porous nanospheres to the sodium hypophosphite is 1:2.25, sodium hypophosphite to sodium borohydride in a molar ratio of 1:2; and then centrifuging and washing, and compositing with Vulcan XC-72R conductive carbon black to obtain the PtCuP-NSs/C catalyst.
Test characterization
The electrochemical performance of the PtCuP-NSs/C catalyst is characterized by adopting a standard three-electrode system, wherein a counter electrode is a platinum sheet, and a reference electrode is a saturated calomel electrode. Oxygen reduction test 0.1M HClO saturated with oxygen 4 The electrolyte was used at an electrode rotation speed of 1600rpm and a scan speed of 5mV/s. The half-wave potential of the PtCuP-NSs/C catalyst under example 4 was-0.911V (vs. RHE).
Example 5
This embodiment is substantially identical to the previous embodiment, except that:
in this example, ptCuP-NSs/C catalyst preparation at 30min reaction time
According to the mole ratio of cetyl trimethyl ammonium bromide to chloroplatinic acid of 53:1 and the mole ratio of cupric chloride to chloroplatinic acid of 0.5:1, weighing cetyl trimethyl ammonium bromide powder with certain mass, dissolving the cetyltrimethylammonium bromide powder in water, then continuously dissolving chloroplatinic acid and cupric chloride, injecting ascorbic acid in air atmosphere, and reacting for 6 hours at 80 ℃; then, after centrifugation and washing, dispersing in ultrapure water, adding sodium hypophosphite and sodium borohydride, and reacting for 30min at 25 ℃; the molar ratio of the platinum copper alloy porous nanospheres to the sodium hypophosphite is 1:2.25, sodium hypophosphite to sodium borohydride in a molar ratio of 1:2; and then centrifuging and washing, and compositing with Vulcan XC-72R conductive carbon black to obtain the PtCuP-NSs/C catalyst.
Test characterization
The electrochemical performance of the PtCuP-NSs/C catalyst is characterized by adopting a standard three-electrode system, wherein a counter electrode is a platinum sheet, and a reference electrode is a saturated calomel electrode. Oxygen reduction test 0.1M HClO saturated with oxygen 4 The electrolyte was used at an electrode rotation speed of 1600rpm and a scan speed of 5mV/s. The half-wave potential of the PtCuP-NSs/C catalyst under example 5 was-0.919V (vs. RHE).
Example 6
This embodiment is substantially identical to the previous embodiment, except that:
in this example, ptCuP-NSs/C catalyst preparation at a reaction temperature of 0deg.C:
according to the mole ratio of cetyl trimethyl ammonium bromide to chloroplatinic acid of 53:1 and the mole ratio of cupric chloride to chloroplatinic acid of 0.5:1, weighing cetyl trimethyl ammonium bromide powder with certain mass, dissolving the cetyltrimethylammonium bromide powder in water, then continuously dissolving chloroplatinic acid and cupric chloride, injecting ascorbic acid in air atmosphere, and reacting for 6 hours at 80 ℃; then, after centrifugation and washing, dispersing in ultrapure water, adding sodium hypophosphite and sodium borohydride, and reacting for 20min at 0 ℃; the molar ratio of the platinum copper alloy porous nanospheres to the sodium hypophosphite is 1:2.25, sodium hypophosphite to sodium borohydride in a molar ratio of 1:2; and then centrifuging and washing, and compositing with Vulcan XC-72R conductive carbon black to obtain the PtCuP-NSs/C catalyst.
Test characterization
The electrochemical performance of the PtCuP-NSs/C catalyst is characterized by adopting a standard three-electrode system, wherein a counter electrode is a platinum sheet, and a reference electrode is a saturated calomel electrode. Oxygen reduction test 0.1M HClO saturated with oxygen 4 The electrolyte was used at an electrode rotation speed of 1600rpm and a scan speed of 5mV/s. The half-wave potential of the PtCuP-NSs/C catalyst under example 6 was-0.906V (vs. RHE).
Example 7
This embodiment is substantially identical to the previous embodiment, except that:
in this example, ptCuP-NSs/C catalyst preparation at a reaction temperature of 80℃was used:
according to the mole ratio of cetyl trimethyl ammonium bromide to chloroplatinic acid of 53:1 and the mole ratio of cupric chloride to chloroplatinic acid of 0.5:1, weighing cetyl trimethyl ammonium bromide powder with certain mass, dissolving the cetyltrimethylammonium bromide powder in water, then continuously dissolving chloroplatinic acid and cupric chloride, injecting ascorbic acid in air atmosphere, and reacting for 6 hours at 80 ℃; then, after centrifugation and washing, dispersing in ultrapure water, adding sodium hypophosphite and sodium borohydride, and reacting for 20min at 60 ℃; the molar ratio of the platinum copper alloy porous nanospheres to the sodium hypophosphite is 1:2.25, sodium hypophosphite to sodium borohydride in a molar ratio of 1:2; and then centrifuging and washing, and compositing with Vulcan XC-72R conductive carbon black to obtain the PtCuP-NSs/C catalyst.
Test characterization
The electrochemical performance of the PtCuP-NSs/C catalyst is characterized by adopting a standard three-electrode system, wherein a counter electrode is a platinum sheet, and a reference electrode is a saturated calomel electrode. Oxygen reduction test 0.1M HClO saturated with oxygen 4 The electrolyte was used at an electrode rotation speed of 1600rpm and a scan speed of 5mV/s. The half-wave potential of the PtCuP-NSs/C catalyst under example 7 was-0.919V (vs. RHE).
Example 8
This embodiment is substantially identical to the previous embodiment, except that:
in this example, preparation of a platinum iron phosphorus alloy porous nanosphere catalyst (PtFeP-NSs/C):
according to the mole ratio of cetyl trimethyl ammonium bromide to chloroplatinic acid of 53:1 and the mole ratio of ferric chloride to chloroplatinic acid of 0.5:1, weighing a certain mass of cetyl trimethyl ammonium bromide powder, dissolving the cetyltrimethylammonium bromide powder in water, then continuously dissolving chloroplatinic acid and ferric chloride, injecting ascorbic acid in air atmosphere, and reacting for 6 hours at 80 ℃; then, after centrifugation and washing, dispersing in ultrapure water, adding sodium hypophosphite and sodium borohydride, and reacting for 20min at 25 ℃; the mole ratio of the platinum-iron alloy porous nanospheres to the sodium hypophosphite is 1:2.25, sodium hypophosphite to sodium borohydride in a molar ratio of 1:2; and then centrifuging and washing, and compositing with Vulcan XC-72R conductive carbon black to obtain the PtFeP-NSs/C catalyst.
Test characterization
And (3) carrying out electrochemical performance characterization on the prepared PtFeP-NSs/C catalyst by adopting a standard three-electrode system, wherein a counter electrode is a platinum sheet, and a reference electrode is a saturated calomel electrode. Oxygen reduction test 0.1M HClO saturated with oxygen 4 The electrolyte was used at an electrode rotation speed of 1600rpm and a scan speed of 5mV/s. The half-wave potential of the PtFeP-NSs/C catalyst under example 8 was 0.871V (vs. RHE).
Example 9
This embodiment is substantially identical to the previous embodiment, except that:
in this example, a platinum cobalt phosphorus alloy porous nanosphere catalyst (PtCoP-NSs/C) was prepared:
according to the mole ratio of cetyl trimethyl ammonium bromide to chloroplatinic acid of 53:1 and the mole ratio of cobalt chloride to chloroplatinic acid of 0.5:1, weighing cetyl trimethyl ammonium bromide powder with certain mass, dissolving the cetyltrimethylammonium bromide powder in water, then continuously dissolving chloroplatinic acid and cobalt chloride, injecting ascorbic acid in air atmosphere, and reacting for 6 hours at 80 ℃; then, after centrifugation and washing, dispersing in ultrapure water, adding sodium hypophosphite and sodium borohydride, and reacting for 20min at 25 ℃; the mole ratio of the platinum cobalt alloy porous nanospheres to the sodium hypophosphite is 1:2.25, sodium hypophosphite to sodium borohydride in a molar ratio of 1:2; and then centrifuging, washing, and compositing with Vulcan XC-72R conductive carbon black to obtain the PtCoP-NSs/C catalyst.
Test characterization
The electrochemical performance of the prepared PtCoP-NSs/C catalyst is characterized by adopting a standard three-electrode system, wherein a counter electrode is a platinum sheet, and a reference electrode is a saturated calomel electrode. Oxygen reduction test 0.1M HClO saturated with oxygen 4 The electrolyte was used at an electrode rotation speed of 1600rpm and a scan speed of 5mV/s. The half-wave potential of the PtCoP-NSs/C catalyst under example 9 was-0.882V (vs. RHE).
Example 10
This embodiment is substantially identical to the previous embodiment, except that:
in this example, preparation of a platinum nickel phosphorus alloy porous nanosphere catalyst (PtNiP-NSs/C):
according to the mole ratio of cetyl trimethyl ammonium bromide to chloroplatinic acid of 53:1 and the mole ratio of nickel chloride to chloroplatinic acid of 0.5:1, weighing cetyl trimethyl ammonium bromide powder with certain mass, dissolving the cetyltrimethylammonium bromide powder in water, then continuously dissolving chloroplatinic acid and nickel chloride, injecting ascorbic acid in air atmosphere, and reacting for 6 hours at 80 ℃; then, after centrifugation and washing, dispersing in ultrapure water, adding sodium hypophosphite and sodium borohydride, and reacting for 20min at 25 ℃; the mole ratio of the platinum nickel alloy porous nanospheres to the sodium hypophosphite is 1:2.25, sodium hypophosphite to sodium borohydride in a molar ratio of 1:2; and then centrifuging, washing, and compositing with Vulcan XC-72R conductive carbon black to obtain the PtNiP-NSs/C catalyst.
Test characterization
The electrochemical performance of the prepared PtNiP-NSs/C catalyst is characterized by adopting a standard three-electrode system, wherein a counter electrode is a platinum sheet, and a reference electrode is a saturated calomel electrode. Oxygen reduction test 0.1M HClO saturated with oxygen 4 The electrolyte was used at an electrode rotation speed of 1600rpm and a scan speed of 5mV/s. The half-wave potential of the PtNiP-NSs/C catalyst under example 10 was-0.892V (vs. RHE).
The half-wave potential of the PtNiP-NSs/C catalyst in the above examples 1-10 is 0.871-0.923V (vs. RHE), which is 0.86V (vs. RHE) higher than that of the transition metal/nitrogen doped porous carbon nanosphere electrocatalyst disclosed in publication No. CN110911697A, which is significantly better than that of the commercial Pt/C catalyst. The current loss for the PtCuP-NSs/C catalyst of the above example was less than 45%, while the commercial Pt/C catalyst lost nearly 85%. The electrocatalyst of the above embodiment exhibits a three-dimensional network structure woven from one-dimensional nano dendrites, and the particles of the Pt-M-P alloy porous nanosphere electrocatalyst have Pt (111) crystal planes and form a porous structure; electrocatalysts exhibit superior stability properties over commercial Pt/C and the same types of catalysts currently being investigated and reported. The preparation method of the embodiment is simple and feasible, and is suitable for large-scale production.
Example 11
This embodiment is substantially identical to the previous embodiment, except that:
in this embodiment, the following alternative technical solutions or parameter conditions of the foregoing embodiments may also be adopted, and the preparation method of the Pt-M-P alloy porous nanosphere electrocatalyst includes the following steps:
1) Preparing a precursor solution:
dissolving surfactant in water, continuously dissolving platinum (Pt) compound and transition metal (M) compound, introducing protective gas to saturation, and sealing precursor solution for later use;
2) Preparing Pt-M alloy porous nanospheres:
heating and maintaining the precursor solution at a constant temperature under the condition of protective gas atmosphere, injecting a reducing reagent A, and standing for reaction to obtain the Pt-M alloy porous nanospheres;
3) Constructing a Pt-M-P alloy porous nanosphere electrocatalyst:
adding a reducing agent B and a phosphorus (P) source into the prepared Pt-M alloy porous nanospheres to perform a phosphorus alloying reaction to obtain the Pt-M-P alloy porous nanosphere electrocatalyst;
the reducing agent A and the reducing agent B are respectively at least one of ascorbic acid, glucose, oxalic acid, citric acid, hydrazine hydrate, sodium borohydride and potassium borohydride.
In the step 1), the surfactant is at least one of cationic surfactant, anionic surfactant and nonionic surfactant with different carbon chain lengths;
in the step 1), the platinum (Pt) compound is at least one of chloroplatinic acid, potassium chloroplatinate, platinum acetylacetonate and platinum chloride;
in the step 1), the transition metal (M) compound is at least one of a palladium compound, a silver compound, a gold compound, a molybdenum compound, a tungsten compound, an iron compound, a cobalt compound, a nickel compound, a copper compound, and a zinc compound;
in the step 1), the shielding gas is at least one of inert gas, oxidizing gas, reducing gas and air;
in the step 1), the molar ratio of the transition metal (M) compound to the platinum (Pt) compound is 0-10:1, and the content of the transition metal (M) compound is not 0;
in the step 1), the molar ratio of the surfactant to the platinum compound is 0-100:1, and the dosage of the surfactant is not 0.
The cationic surfactants with different carbon chain lengths are cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride;
the anionic surfactant is sodium dodecyl benzene sulfonate or sodium hexadecyl sulfate;
the nonionic surfactant is at least one of polyvinylpyrrolidone, polyoxypropylene polyoxyethylene copolymer, etc.
In the step 2), the precursor solution is heated at 25-100 ℃, and the standing reaction time is not less than 0.5h;
in said step 2), reducing agent A is added in an amount other than 0.
In the step 3), the phosphorus (P) source is at least one of sodium hypophosphite, phytic acid, sodium hypophosphite monohydrate and sodium hypophosphite hexahydrate;
in the step 3), the molar ratio of the reducing agent B, the phosphorus (P) source and the Pt-M alloy porous nanospheres is 0-2:0-10:1, and the amounts of the reducing agent B and the transition metal (M) compound are respectively different from 0;
in the step 3), the alloying reaction time of the phosphorus is not less than 5min, and the heating temperature of the reaction is not higher than 60 ℃;
in the step 3), after the alloying reaction of phosphorus is completed, the Pt-M-P alloy porous nanosphere electrocatalyst material without the carrier is obtained through centrifugation, washing and drying.
The application of the Pt-M-P alloy porous nanosphere electrocatalyst comprises the step of loading the Pt-M-P alloy porous nanosphere electrocatalyst particles by a conductive carrier to form an electrocatalyst composite material for a fuel cell or a metal-air cell cathode;
the conductive carrier is at least one of spherical, linear or sheet/block carbon black, oxide, nitride, carbide and sulfide; the mass ratio of the conductive carrier to the Pt-M-P alloy porous nanosphere electrocatalyst particles is 0-1000:1, and the mass of the conductive carrier is not 0.
The spherical carbon black is at least one of EC600JD, EC300J and Vulcan XC72R, BP 2000;
the linear carbon black is at least one of carbon nano tubes, carbon fibers and carbon nano rods;
the sheet/block carbon black is at least one of graphene, nanoribbon and activated carbon.
In a word, the porous nanosphere electrocatalyst of Pt-M-P alloy of this example takes water as solvent, form the nanosphere structure of the three-dimensional porous network under the induction of surfactant, reduce platinum compound and transition metal (M) compound and form the homogeneous Pt-M alloy at the same time under the action of reducing agent; and then carrying out phosphorus alloying on the Pt-M alloy to form the Pt-M-P alloy porous nanosphere electrocatalyst with a porous nanosphere structure, wherein the particle size of the Pt-M-P alloy porous nanosphere electrocatalyst is 30-40nm, a three-dimensional network is woven by nano dendrites, and the length of the nano dendrites is 2-10nm and the diameter is 0.5-2nm.
The particles of the Pt-M-P alloy porous nanosphere electrocatalyst of this example have Pt (111) crystal planes and form a porous structure.
The transition metal (M) compound is at least one of palladium compound, silver compound, gold compound, molybdenum compound, tungsten compound, iron compound, cobalt compound, nickel compound, copper compound, and zinc compound. The electrocatalyst of the embodiment shows a three-dimensional network structure woven by one-dimensional nano dendrites, and compared with commercial Pt/C and the catalysts of the same type which are reported in the current research, the electrocatalyst has excellent stability. The preparation method of the embodiment is simple and feasible, and is suitable for large-scale production.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the embodiments described above, and various changes, modifications, substitutions, combinations or simplifications made under the spirit and principles of the technical solution of the present invention can be made according to the purpose of the present invention, and all the changes, modifications, substitutions, combinations or simplifications should be equivalent to the substitution, so long as the purpose of the present invention is met, and all the changes are within the scope of the present invention without departing from the technical principles and the inventive concept of the present invention.
Claims (10)
1. A Pt-M-P alloy porous nanosphere electrocatalyst is characterized in that: forming a three-dimensional porous network nanosphere structure under the induction of a surfactant by taking water as a solvent, and simultaneously reducing a platinum compound and a transition metal (M) compound under the action of a reducing agent to form a uniform Pt-M alloy; and then carrying out phosphorus alloying on the Pt-M alloy to form the Pt-M-P alloy porous nanosphere electrocatalyst with a porous nanosphere structure, wherein the particle size of the Pt-M-P alloy porous nanosphere is 20-40nm, a three-dimensional network is woven by nano dendrites, the length of the nano dendrites is 2-10nm, and the diameter is 0.5-2nm.
2. The Pt-M-P alloy porous nanosphere electrocatalyst according to claim 1, wherein: the Pt-M-P alloy porous nanospheres have Pt (111) crystal faces and form a porous structure.
3. The Pt-M-P alloy porous nanosphere electrocatalyst according to claim 1, wherein: the transition metal (M) compound is at least one of palladium compound, silver compound, gold compound, molybdenum compound, tungsten compound, iron compound, cobalt compound, nickel compound, copper compound, and zinc compound.
4. A method for preparing the Pt-M-P alloy porous nanosphere electrocatalyst according to claim 1, comprising the steps of:
1) Preparing a precursor solution:
dissolving surfactant in water, continuously dissolving platinum (Pt) compound and transition metal (M) compound, introducing protective gas to saturation, and sealing precursor solution for later use;
2) Preparing Pt-M alloy porous nanospheres:
heating and maintaining the precursor solution at a constant temperature under the condition of protective gas atmosphere, injecting a reducing reagent A, and standing for reaction to obtain the Pt-M alloy porous nanospheres;
3) Constructing a Pt-M-P alloy porous nanosphere electrocatalyst:
adding a reducing agent B and a phosphorus (P) source into the prepared Pt-M alloy porous nanospheres to perform a phosphorus alloying reaction to obtain the Pt-M-P alloy porous nanosphere electrocatalyst;
the reducing agent A and the reducing agent B are respectively at least one of ascorbic acid, glucose, oxalic acid, citric acid, hydrazine hydrate, sodium borohydride and potassium borohydride.
5. The method for preparing the Pt-M-P alloy porous nanosphere electrocatalyst according to claim 4, wherein the method comprises the following steps: in the step 1), the surfactant is at least one of cationic surfactant, anionic surfactant and nonionic surfactant with different carbon chain lengths;
in the step 1), the platinum (Pt) compound is at least one of chloroplatinic acid, potassium chloroplatinate, platinum acetylacetonate and platinum chloride;
in the step 1), the transition metal (M) compound is at least one of a palladium compound, a silver compound, a gold compound, a molybdenum compound, a tungsten compound, an iron compound, a cobalt compound, a nickel compound, a copper compound, and a zinc compound;
in the step 1), the shielding gas is at least one of inert gas, oxidizing gas, reducing gas and air;
in the step 1), the molar ratio of the transition metal (M) compound to the platinum (Pt) compound is 0-10:1, and the content of the transition metal (M) compound is not 0;
in the step 1), the molar ratio of the surfactant to the platinum compound is 0-100:1, and the dosage of the surfactant is not 0.
6. The method for preparing the Pt-M-P alloy porous nanosphere electrocatalyst according to claim 5, wherein the method comprises the steps of: the cationic surfactants with different carbon chain lengths are cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride;
the anionic surfactant is sodium dodecyl benzene sulfonate or sodium hexadecyl sulfate;
the nonionic surfactant is at least one of polyvinylpyrrolidone, polyoxypropylene polyoxyethylene copolymer, etc.
7. The method for preparing the Pt-M-P alloy porous nanosphere electrocatalyst according to claim 4, wherein the method comprises the following steps: in the step 2), the precursor solution is heated at 25-100 ℃, and the standing reaction time is not less than 0.5h;
in said step 2), reducing agent A is added in an amount other than 0.
8. The method for preparing the Pt-M-P alloy porous nanosphere electrocatalyst according to claim 4, wherein the method comprises the following steps: in the step 3), the phosphorus (P) source is at least one of sodium hypophosphite, phytic acid, sodium hypophosphite monohydrate and sodium hypophosphite hexahydrate;
in the step 3), the molar ratio of the reducing agent B, the phosphorus (P) source and the Pt-M alloy porous nanospheres is 0-2:0-10:1, and the amounts of the reducing agent B and the transition metal (M) compound are respectively different from 0;
in the step 3), the alloying reaction time of the phosphorus is not less than 5min, and the heating temperature of the reaction is not higher than 60 ℃;
in the step 3), after the alloying reaction of phosphorus is completed, the Pt-M-P alloy porous nanospheres without the carrier are obtained through centrifugation, washing and drying.
9. Use of the Pt-M-P alloy porous nanospheres electrocatalyst according to claim 1, wherein the Pt-M-P alloy porous nanospheres are supported by a conductive support to form an electrocatalyst for a fuel cell or metal-air cell cathode;
the conductive carrier is at least one of spherical, linear or sheet/block carbon black, oxide, nitride, carbide and sulfide; the mass ratio of the conductive carrier to the Pt-M-P alloy porous nanospheres is 0-1000:1, and the mass of the conductive carrier is not 0.
10. The use of the Pt-M-P alloy porous nanosphere electrocatalyst according to claim 9, wherein: the spherical carbon black is at least one of EC600JD, EC300J and Vulcan XC72R, BP 2000;
the linear carbon black is at least one of carbon nano tubes, carbon fibers and carbon nano rods;
the sheet/block carbon black is at least one of graphene, nanoribbon and activated carbon.
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