CN103545536A - Carbon fiber supported metal catalyst as well as preparation method and application thereof - Google Patents
Carbon fiber supported metal catalyst as well as preparation method and application thereof Download PDFInfo
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- CN103545536A CN103545536A CN201310500935.1A CN201310500935A CN103545536A CN 103545536 A CN103545536 A CN 103545536A CN 201310500935 A CN201310500935 A CN 201310500935A CN 103545536 A CN103545536 A CN 103545536A
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- carbon fiber
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- fiber
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 62
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 49
- 238000005087 graphitization Methods 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 28
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 22
- 238000003763 carbonization Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 83
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 57
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- 229910052697 platinum Inorganic materials 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000003863 metallic catalyst Substances 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 18
- 238000009987 spinning Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000005255 carburizing Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000013528 metallic particle Substances 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 10
- -1 actinide metals Chemical class 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052768 actinide Inorganic materials 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000011232 storage material Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 239000002077 nanosphere Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 7
- 230000001988 toxicity Effects 0.000 abstract description 7
- 231100000419 toxicity Toxicity 0.000 abstract description 7
- 239000002127 nanobelt Substances 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 5
- 238000002166 wet spinning Methods 0.000 abstract description 2
- 238000000970 chrono-amperometry Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- 239000002121 nanofiber Substances 0.000 description 11
- 239000010453 quartz Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- 239000002048 multi walled nanotube Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 230000005518 electrochemistry Effects 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 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 description 2
- 150000007513 acids Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical class Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000013139 quantization Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 239000011357 graphitized carbon fiber Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
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- 230000007306 turnover Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a carbon fiber supported metal catalyst as well as a preparation method and an application thereof. The materials such as graphene nano belt, a multi-arm carbon nano tube and graphene are adopted as graphitization template-based additives, and composite carbon fiber with high graphitization degree and high conductivity is obtained by electrostatic spinning and wet spinning processes and a high-temperature carbonization process, wherein the preferential amount of the template-based additives is 0.5-5% by weight; the high-graphitization composite carbon fiber is used as a carrier of the catalyst, and a metal/carbon nano fiber catalyst for a fuel cell is obtained by reduction; the catalyst has a large initial electrochemical-activity surface area and strong CO toxicity resistance; the current density attenuation is reduced in a 30 minutes of chronoamperometry test, and the catalyst shows higher electrochemical activity, higher current density and better electrochemical stability; and moreover, the catalyst taking the high-graphitization carbon fiber as a carrier shows remarkably high durability.
Description
Technical field
The present invention relates to fuel cell carbon fiber nanometer metal supported catalyst, especially relate to a kind of carbon fiber loaded metallic catalyst and its preparation method and application.
Background technology
Fuel cell is a kind ofly without burning, directly the chemical energy of fuel to be changed into the energy conversion device of electric energy, at sustainable energy, utilizes and in link, has critical role.Catalyst carrier is one of critical material of low-temperature fuel cell Catalytic Layer, is also the focus of scientific research.Prepare catalytic performance high, anti-carbon monoxide (CO) toxicity is good, electrochemical stability, and the catalyst of good endurance is one of business-like key factor of fuel cell.Wherein, catalyst carrier has a great impact even decisive action for the performance tool of catalyst, is one of critical material of Low-Temperature Fuel Cell Catalysts, is also problem important in fuel cell studies, and catalyst carrier mainly be take material with carbon element as main at present.Wherein activated carbon, ketjenblack EC, carbon nano-fiber, carbon nano-tube (CNTs) etc. all have certain application.At present, the carbon carrier extensively adopting is the Vulcan XC-72 carbon black of Cabot company etc.But, as easy as rolling off a log can corrosion under the condition of dimethyl formamide Cs peracidity, high potential and higher temperature, surface is oxidized to CO or CO
2.For the polymer-membrane fuel battery 100 ℃ of following operations, only 100,000/several CO will cause Pt catalyst based seriously poisoning; The Pt that the corrosion of carbon carrier also can be accelerated high degree of dispersion assembles.When battery brings into operation and be out of service, electrode local voltage can reach 1.2V; The corrosion rate of carbon carrier obviously increases, thereby causes the electrochemical surface area of precious metals pt to reduce loss or the reunion with Pt, and durability is poor.This is the active one of the main reasons reducing with electrode life of eelctro-catalyst.In order to improve electrode durability and useful life, one of method is exactly to adopt more stable carbon carrier.Therefore, people begun one's study carbon nano-tube, mesoporous carbon, carbon fiber, carbon nano-fiber, the corrosion-resistant carrier such as carbon nanohorn, however these carbon carrier surfaces are stronger inertia, dispersion (the Jiang Yulin that is unfavorable for catalyst metal particles, He great Ping, in the wood soil spring, carbon nano-tube supports the method for nano-noble metal catalyst, battery, 2012,42, (5); HalderA, Sharma S, Hegde M, et al.An timicrobial activity of single walled carbon nanotubes.J Phys Chem C, 2009,113 (4): 1466-1473).
Mesoporous carbon is the novel non-silicon-based mesoporous material of a class of recent findings, because it has huge specific area, (can reach 2500m
2/ g) and pore volume (can reach 2.25cm
3/ g), be expected to very much be applied in the aspects such as catalyst carrier, hydrogen storage material, electrode material, be therefore subject to people and pay much attention to.Conventional synthetic method is hard template method, and utilizing the mesopore molecular sieves such as MCM-48, SBA-15 is template, selects suitable predecessor, makes predecessor carbonization under acid catalysis, is deposited in the duct of mesoporous material, then with NaOH or HF etc., dissolves away mesoporous SiO
2, obtain mesoporous carbon
[13].But as fuel-cell catalyst carrier, from cost angle, say and be not suitable for, and complicated preparation technology also makes its application be restricted.
Graphene is a kind of by the tightly packed bi-dimensional cellular shape lattice structure carbonaceous material forming of monolayer carbon atom, the current outstanding material of electric conductivity, has huge specific area, very high carrier mobility speed and compared with characteristics such as high Young's modulus, ferromagnetism.The nanostructure that it is special and performance impel grapheme material at numerous areas such as electronics, optics, magnetics, biomedicine, catalysis, transducer, energy storage, to demonstrate huge application potential.Graphene is to have the material with carbon element that is less than 10 layers of graphite molecule layer structure, and the theoretical specific area of single-layer graphene can reach 2620m2/g, and more Metal Supported position can be provided; Graphene shows very strong quantum effect, has excellent electronic conduction ability.Graphene can be used as the excellent candidate materials of fuel-cell catalyst carrier.Carbon magazine reported adopt ethylene glycol be reducing agent prepare Graphene platinum catalyst platinum grain footpath in 5nm, its electrochemically active specific surface area is about 36.27m2/g, compared with the electrochemistry specific surface of carbon nano-tube platinum catalyst 33.43m2/g, wants bigger and has shown the ability of higher resisting CO poisoning.ACS Appl.Mater.Interfaces2012 has reported that Graphene parcel multi-wall carbon nano-tube composite material carries platinum and makees fuel battery cathode with proton exchange film catalyst than doing carrier with Graphene and carbon pipe has higher energy density merely.
Carbon fiber is the novel carrier material of a class of recent findings, because it has huge specific area, (can reach 2000m
2/ g) and pore volume (can reach 2.25cm
3/ g), be expected to very much be applied in the aspects such as catalyst carrier, hydrogen storage material, electrode material, be therefore subject to people and pay much attention to.But obtain high graphitization degree, the carbon fiber of high conductivity, needs extremely high temperature (for example: 3000 ℃), not only needs special instrument configuration, also has danger, from cost angle, says and is not suitable for.
In sum, carrier material affects distribution of sizes and the catalytic activity that is prepared into metal nanoparticle, and the degree of graphitization of carrier is one of shocking key issue to be solved of fuel cell commercial applications with becoming to produce cost.
Summary of the invention
The object of the invention is to prepare cheaply a kind of high graphitization carbon fiber supported metal catalyst, its preferred compound carrying capacity is 10～90wt%.This catalyst is used the graphene oxide band of high graphitization, graphene oxide, Graphene, carbon nano-tube, graphite flakes etc. are the graphitized carbon additive of PAN solution, adopt static or wet spinning and the resulting high graphitization carbon fiber of follow-up carbonisation as catalyst carrier, utilize the distinctive quantization effect of nanofiber carbon and high graphitization, highly electron conductive, to improve the catalytic activity of catalyst, utilize template additive to introduce defect, better dispersed metal nano particle, utilize metal alloy to have higher anti-carbon monoxide toxicity to improve the stability in use of catalyst than single noble metal platinum.By by high graphitization carbon fiber and single metal or the blend of metal alloy presoma, take sodium borohydride, methyl alcohol or ethylene glycol as reducing agent, obtain a kind of composition metal/highly-graphitized carbon fiber catalyst for fuel cell, the ratio of the spinning conditions such as the concentration by regulator solution, voltage strength, acceptance distance and carburizing temperature and programming rate and composition metal presoma and material with carbon element, control catalytic activity and stability, and then prepare high activity, high stability, cheaply catalyst.
Another object of the present invention is to provide the preparation method of fuel-cell catalyst.
Object of the present invention can be achieved through the following technical solutions:
A metallic catalyst, is mixed to get for 100:0.01:0.01～100:50:90 in mass ratio by carbon fiber, graphitization additive, metallic particles,
The diameter of described carbon fiber is for being 50nm～5 μ m, and porosity is 20～80%, and specific area is 2～2500m
2g
-1, pore volume is 0.1～15mL g
-1;
Described graphitization additive is the material with carbon element that degree of graphitization is high, is selected from stannic oxide/graphene nano band, single armed, one or more in both arms or multi-arm carbon nano-tube, graphene oxide, graphene nanometer sheet or graphene nanospheres,
Described metallic particles is the platinum of diameter 0.1～50nm, rhodium, palladium, gold, silver, copper, manganese, the transition metals such as iron, lanthanide series metal, the mixture metallic particles of one or more in the single metal of actinide metals, metal alloy, metal oxide, slaine.
As preferred embodiment, the mass ratio of described carbon fiber, graphitization additive, metallic particles is 100:0.5:10～100:5:60,
The diameter of carbon fiber is 50-500nm, and porosity is 50～70%, specific area is 1000～1500m
2g
-1, pore volume is 6～10mL g
-1,
The diameter of metallic particles is 1～10nm,
Graphitization additive is oxidation state material with carbon element or reduction-state material with carbon element.
Described graphitization additive preferential oxidation state material with carbon element.
The preparation method of carbon fiber loaded metallic catalyst adopts following steps:
(1) 1 part of weight portion polyacrylonitrile and 0.0001～0.5 part of wt carbon meterial additive are dissolved in dimethyl formamide or dimethylacetylamide, polyacrylonitrile concentration is 7～20wt%, at 20～100 ℃, stirs 0.5～24h;
(2) mixed solution step (1) being obtained carries out electrostatic spinning, and spinning gained tunica fibrosa is placed in reacting furnace to carry out carbonization and obtain the carbon nano-fiber that contains material with carbon element additive;
(3) carbon nano-fiber is dissolved to the carbon fiber reinforce plastic dispersion liquid that forms 0.05～1wt%, add metal precursor to stir and form uniform dispersion, the carrying capacity of metal precursor in dispersion liquid is 1～99wt%, with 0.5～4M potassium hydroxide aqueous solution, regulating pH value is 9～13, stir and carry out reduction reaction, again after filtration, vacuumize obtains carbon fiber loaded metallic catalyst.
The voltage range that described electrostatic spinning is used is 5～30KV, and flow velocity is 0.02～0.5ml/h, and spinning receiving range is 5～30cm.
The process of described carbonization is divided pre-oxidation and two stages of carbonization, and Pre oxidation is that 180～320 ℃, heating rate are 1～10 ℃/min; Carburizing temperature is 600～2200 ℃, and programming rate is 1～20 ℃/min.
Described metal precursor is one or more the mixture in single metal in transition metal, lanthanide series metal, actinide metals, metal alloy, metal oxide, slaine, carbon fiber is 100:0.01～100:99 with metal quality ratio, preferably 100:10～100:60.
As preferred embodiment, carbon fiber is 100:10～100:60 with the metal quality ratio in metal precursor.
The reducing agent that reduction reaction adopts is sodium borohydride, ethylene glycol or methyl alcohol, and reaction temperature is 10～180 ℃.
Furthermore, carbon fiber loaded metallic catalyst can adopt sodium borohydride reduction, Reduction of methanol method or reduction of ethylene glycol method to prepare, and below respectively three kinds of diverse ways is described, and below all with mass parts, represents:
Sodium borohydride reduction:
(1) by 1 weight portion polyacrylonitrile, the template based additive material of 0.001-0.5 weight portion is placed in dimethyl formamide, at 30～60 ℃, more than stirring 0.5-12h, prepares uniform polyacrylonitrile-template sill mixed solution;
(2) polyacrylonitrile-template sill mixed solution is injected to disposable syringe, carry out spinning, voltage is 10-30KV, and flow velocity is 0.01-0.45ml/h, and receiving range is 8-15cm, and reception material is aluminium flake.
(3) polyacrylonitrile-template sill composite fibre is inserted to 45-90 ℃ of vacuum drying oven, dry 6h.
(4) dry polyacrylonitrile-template sill composite fibre is packed in ceramic boat, be placed in the Muffle furnace of 200-300 ℃ and carry out pre-oxidation and stablize 0.5-6h, heating rate is 1-10 ℃/min.
(5) polyacrylonitrile nanofiber is placed in quartz tube furnace and carries out carbonization 0.5-6h, carburizing temperature is 700-2200 ℃, and atmosphere is nitrogen, argon gas, or hydrogen-argon-mixed etc., heating rate is 1-10 ℃/min, obtains the carbon fiber reinforce plastic of high graphitization.
(6) carbon fiber reinforce plastic of high graphitization is inserted in deionized water, form carbon nano-fiber dispersion liquid 1000-2000 part of 0.05wt-1wt%, ultrasonic certain hour, add again 2.66-15.93 part gold chloride or other platinum based composite metal presoma to mix, making the carrying capacity of platinum in composition metal/carbon nano-fiber is 1wt-99wt%, with 0.5M-4M potassium hydroxide aqueous solution, regulate PH to 9-13, after stirred for several minute, add 160-640 part sodium borohydride and 5000-10000 part deionized water, at 20-80 ℃, reduce 1-18h, suction filtration, vacuumize at 60-100 ℃, coolingly under room temperature obtain carbon fiber loaded metallic catalyst.
Reduction of methanol method:
(1) by 1 weight portion polyacrylonitrile, the template based additive material of 0.001-0.5 weight portion is placed in dimethyl formamide, at 30～60 ℃, more than stirring 0.5-12h, prepares uniform polyacrylonitrile-template sill mixed solution;
(2) polyacrylonitrile-template sill mixed solution is injected to disposable syringe, carry out spinning, voltage is 10-30KV, and flow velocity is 0.01-0.45ml/h, and receiving range is 8-15cm, and reception material is aluminium flake.
(3) polyacrylonitrile-template sill fiber is inserted to 45-90 ℃ of vacuum drying oven, dry 6h.
(4) dry polyacrylonitrile-template sill fiber is packed in ceramic boat, be placed in the Muffle furnace of 250 ℃ and carry out pre-oxidation and stablize 0.5-6h, heating rate is 1-10 ℃/min.
(5) polyacrylonitrile-template sill fiber is placed in quartz tube furnace and carries out carbonization 0.5-6h, carburizing temperature is 700-2200 ℃, and atmosphere is nitrogen, argon gas, or hydrogen-argon-mixed etc., heating rate is 1-10 ℃/min, has both obtained the carbon fiber reinforce plastic of high graphitization.
(6) carbon fiber reinforce plastic of high graphitization is inserted in methyl alcohol, carbon fiber methyl alcohol dispersion liquid 1000-2000 part that formation contains 0.05wt-1wt%, ultrasonic certain hour, add again 2.66-15.93 part platinum based composite metal presoma to mix, making the carrying capacity of composition metal in composition metal/carbon nano-fiber is 1wt-99wt%, with 0.5M-4M potassium hydroxide aqueous solution, regulate PH to 9-13, after stirred for several minute, at 60-180 ℃, reduce 1-18h, suction filtration, vacuumize at 60-100 ℃, coolingly under room temperature obtain carbon fiber loaded metallic catalyst.
Reduction of ethylene glycol method:
(1) by 1 weight portion polyacrylonitrile, the template based additive material of 0.001-0.5 weight portion is placed in dimethyl formamide, at 30～60 ℃, more than stirring 0.5-12h, prepares uniform polyacrylonitrile-template sill mixed solution;
(2) polyacrylonitrile-template sill mixed solution is injected to disposable syringe, carry out spinning, voltage is 10-30KV, and flow velocity is 0.01-0.45ml/h, and receiving range is 8-15cm, and reception material is aluminium flake.
(3) polyacrylonitrile-template sill fiber is inserted to 45-90 ℃ of vacuum drying oven, dry 6h.
(4) dry polyacrylonitrile-template sill fiber is packed in ceramic boat, be placed in the Muffle furnace of 250 ℃ and carry out pre-oxidation and stablize 0.5-6h, heating rate is 1-10 ℃/min.
(5) polyacrylonitrile-template sill fiber is placed in quartz tube furnace and carries out carbonization 0.5-6h, carburizing temperature is 700-2200 ℃, and atmosphere is nitrogen, argon gas, or hydrogen-argon-mixed etc., heating rate is 1-10 °/min, has both obtained the carbon fiber reinforce plastic of high graphitization.
(6) carbon fiber reinforce plastic of high graphitization is inserted in ethylene glycol, carbon fiber ethylene glycol dispersion liquid 1000-2000 part that formation contains 0.05wt-1wt%, ultrasonic certain hour, add again 2.66-15.93 part platinum based composite metal presoma to mix, making the carrying capacity of composition metal in composition metal/carbon nano-fiber is 1wt-99wt%, with 0.5M-4M potassium hydroxide aqueous solution, regulate PH to 9-13, after stirred for several minute, at 60-180 ℃, reduce 1-18h, suction filtration, vacuumize at 60-100 ℃, coolingly under room temperature obtain carbon fiber loaded metallic catalyst.
In the method for the invention, add graphitization template sill and improve carbon fiber and graphite degree except being used as the agent of graphitization template-mediated in spinning process, also as defect, carry out spread loads metal pore creating material, consumption and proportion requirement have strict restriction.During carried metal, object is to improve load capacity and the catalytic capability of metal, and consumption and proportion requirement have strict restriction.Aluminium flake is mainly used to receive fiber, the not strict restriction of thickness and shape, and potassium hydroxide is used for regulating pH value, so have no particular limits on consumption, those skilled in the art can easily determine their consumption.
Carbon fiber loaded metallic catalyst can be applied to fuel cell, lithium ion battery, in ultracapacitor hydrogen storage material.Preferably, fuel-cell catalyst of the present invention comprises template based additive material, contains oxygen-containing functional group on it.
Compared with prior art, the present invention has the following advantages:
(1) the high graphitization carbon fiber that the present invention adopts is as catalyst carrier, because electron conduction is high, quantization effect is strong, adsorbing metal particles in catalyst preparation process, make metallic more stable be adsorbed on carrier surface, be difficult for migration, its larger specific area has also effectively stoped metallic particles reunion, more be conducive to Metal Supported, improved catalytic activity and the stability of catalyst; The one-dimentional structure itself that fiber is elongated is difficult for reuniting, and than carbon nano-tube, carbon dust is more suitable for doing metallic particles carrier;
(2) the high graphitization carbon fiber that the present invention adopts is as catalyst carrier, and because degree of graphitization is high, corrosion-resistant strong, carbon turnover rate is low, and durability of catalyst is strong.
(3) the high graphitization carbon fiber that the present invention adopts is as catalyst carrier, due to the interpolation of template base, carbon fiber surface evenly produces defect, is conducive to the load of platinum based metal catalysts, when being conducive to improve catalytic activity, the oxygen-containing functional group energy of template primary surface and the similar bimetallic alloy of effect between platinum, improve the resisting CO poisoning ability of platinum, extended the life-span of catalyst, effectively reduce catalyst cost, realize that it is efficient, antitoxin, cheaply target.
Accompanying drawing explanation
Fig. 1 is the product of comparative example 1 and the embodiment 5 electrochemistry cyclic voltammogram in sulfuric acid solution;
Fig. 2 is the product of comparative example 1 and the embodiment 5 electrochemistry cyclic voltammogram in sulfuric acid methyl alcohol blend solution;
Fig. 3 is the product of comparative example 1 and embodiment 5 chronoa mperometric plot in the blend solution of sulfuric acid and methyl alcohol.
Embodiment
Below, with embodiment, further illustrate content of the present invention, but protection scope of the present invention is not limited in embodiment.Other variation and modification that those skilled in the art is made in the situation that not deviating from the present invention's spirit and protection range, within being still included in protection range of the present invention.
The raw material using in embodiments of the invention, except special instruction, is commercially available prod.
The fuel cell that the present invention obtains completes by carry out electro-chemical test in standard three-electrode system by the electro-chemical activity surface area of metal/carbon fiber and the inspection method of methanol tolerance toxicity and stability.Adopt platinum filament to do electrode, silver/silver chlorate is done reference electrode, and the glass-carbon electrode of diameter 3mm is work electrode, the sulfuric acid solution that electrolyte is 0.5mol/L or 0.5mol/L sulfuric acid and 1mol/L methyl alcohol mixed solution.Test is carried out in the AutoLab system of Switzerland Wan Tong company, and specific operation process is: accurately weigh 5mg catalyst fines, add 50 μ L5wt%Nafion (Eastern Mountain group) solution, ultrasonic being scattered in 1ml deionized water.Pipetting 6 μ L drips in glass-carbon electrode surface, drying at room temperature.Cyclic voltammetry method is surveyed electro-chemical activity surface area: before test, first in the sulfuric acid solution that immerses three-electrode system, pass into nitrogen more than half an hour, with the sweep speed of 50mV/s, at-0.25V, to 1V interval, carry out repeatedly cyclic voltammetry scan, to stable to curve, according to cyclic voltammetry curve, calculate catalyst electro-chemical activity surface area.Cyclic voltammetry method is surveyed platinum catalyst anti-carbon monoxide toxicity: before test, first in immersing three-electrode system sulfuric acid methyl alcohol mixed solution, pass into nitrogen more than half an hour, with the sweep speed of 50mV/s, at-0.25V, to 1V interval, carry out repeatedly cyclic voltammetry scan, to stable to curve, according to the peak current numerical value of the forward scan of cyclic voltammetry curve, scan peak current numerical value (I with negative sense
f/ I
b) calculate catalyst anti-carbon monoxide toxicity.Electrochemical stability test utilizes timing electric current to send out at this three-electrode system to carry out, and its electrolyte is sulfuric acid methyl alcohol mixed solution, and timing time is 120 minutes.
(1) by 1 gram of PAN, 0.02 gram of carbon nano-tube (MWCNT) is placed in 10 milliliters of DMF, at 30 ℃, stirs 3h, prepares uniform manganese acetate/PAN mixed solution;
(2) the MWCNT/PAN mixed solution solution of (1) gained is injected to disposable syringe, carry out spinning, voltage is 12KV, and flow velocity is 0.15ml/h, and receiving range is 10cm, and reception material is aluminium flake;
(3) the MWCNT/PAN nanofiber of (2) gained is inserted to the dry 6h of 50 ℃ of vacuum drying ovens;
(4) the MWCNT/PAN nanofiber of (3) gained is packed in ceramic boat, be placed in the Muffle furnace of 250 ℃ and carry out pre-oxidation and stablize 1h, heating rate is 1 ℃/min;
(5) the MWCNT/PAN nanofiber of (4) gained is placed in quartz tube furnace and carries out carbonization 0.5h, carburizing temperature is 900 ℃, and heating rate is 1 ℃/min, has both obtained pure MWCNT/ carbon fiber;
(6) the MWCNT/ carbon fiber dimension of 100 milligrams is inserted in deionized water, 100 milliliters of the MWCNT/ carbon fiber dimension dispersion liquids of formation 0.1%, ultrasonic even, add again 40 milligrams of gold chlorides to mix, making the carrying capacity of platinum in platinum/carbon nano fiber is 28wt%, with 0.5～4M potassium hydroxide aqueous solution, regulate pH to 9～13, after stirred for several minute, add 150 milligrams of sodium borohydrides and 50 ml deionized water, under room temperature, reduce 8h, suction filtration, vacuumize at 60 ℃, coolingly under room temperature obtain described catalyst; Its electro catalytic activity area and positive negative direction peak current ratio I
f/ I
blist in table 1.
(1) by 1.2 grams of PAN, the Graphene of 0.024 gram is placed in 10 milliliters of DMF, more than stirring 20h, prepares uniform Graphene/PAN solution at 40 ℃;
(2) Graphene/PAN solution of (1) gained is injected to disposable syringe, carry out spinning, voltage is 18KV, and flow velocity is 0.18ml/h, and receiving range is 13cm, and reception material is aluminium flake;
(3) Graphene/PAN nanofiber of (2) gained is inserted to the dry 6h of 50 ℃ of vacuum drying ovens;
(4) Graphene/PAN fiber of (3) gained is packed in ceramic boat, directly enter in the Muffle furnace of 250 ℃, to carry out pre-oxidation and stablize 4h, heating rate is 2 ℃/min;
(5) Graphene/PAN fiber of (4) gained is placed in quartz tube furnace and carries out carbonization 2h, carburizing temperature is 900 ℃, and heating rate is 2 ℃/min, has both obtained the described carbon nano-fiber that contains Graphene;
(6) described certain 100 milligrams of carbon nano-fibers that contain Graphene are inserted in methyl alcohol, 100 milliliters of the carbon nano-fiber dispersion liquids of formation 0.1%, ultrasonic certain hour, add again 40 milligrams of chloroplatinic acids, manganese chloride mixes, platinum content is 30wt% than the carrying capacity in platinum/manganese/carbon nano-fiber, manganese content is 5wt% than the carrying capacity in platinum/manganese/carbon nano-fiber, with 0.5～4M potassium hydroxide aqueous solution, regulate pH to 9～13, reductase 12 4h under 85 degree, suction filtration, vacuumize at 45 ℃, coolingly under room temperature obtain described catalyst; Its electro catalytic activity area and positive negative direction peak current ratio I
f/ I
blist in table 1.
Embodiment 3
(1) by 1.2 grams of PAN, the graphite of 0.06 gram is placed in 10 milliliters of DMF, more than stirring 20h, prepares uniform graphite/PAN solution at 40 ℃;
(2) graphite/PAN solution of (1) gained is injected to disposable syringe, carry out spinning, voltage is 18KV, and flow velocity is 0.18ml/h, and receiving range is 13cm, and reception material is aluminium flake;
(3) graphite/PAN nanofiber of (2) gained is inserted to the dry 6h of 50 ℃ of vacuum drying ovens;
(4) graphite/PAN fiber of (3) gained is packed in ceramic boat, directly enter in the Muffle furnace of 250 ℃, to carry out pre-oxidation and stablize 4h, heating rate is 2 ℃/min;
(5) graphite/PAN fiber of (4) gained is placed in quartz tube furnace and carries out carbonization 2h, carburizing temperature is 900 ℃, and heating rate is 2 ℃/min, has both obtained the described carbon nano-fiber that contains graphite;
(6) described certain 100 milligrams of carbon nano-fibers that contain graphite are inserted in methyl alcohol, 100 milliliters of the carbon nano-fiber dispersion liquids of formation 0.1%, ultrasonic certain hour, add again 40 milligrams of chloroplatinic acids, ferric sulfate, cobalt chloride mixes, the carrying capacity of platinum content in platinum/carbon nano fiber is 40wt%, the carrying capacity of iron cobalt in platinum/carbon nano fiber is that 10wt% regulates pH to 9～13 with 0.5～4M potassium hydroxide aqueous solution,, under 120 degree, reduce 8h, suction filtration, vacuumize at 45 ℃, coolingly under room temperature obtain described catalyst; Its electro catalytic activity area and positive negative direction peak current ratio I
f/ I
blist in table 1.
Embodiment 4
(1) by 1.2 grams of PAN, the stannic oxide/graphene nano band of 0.06 gram is placed in 10 milliliters of DMF, more than stirring 20h, prepares uniform stannic oxide/graphene nano band/PAN solution at 40 ℃;
(2) stannic oxide/graphene nano band/PAN solution of (1) gained is injected to disposable syringe, carry out spinning, voltage is 18KV, and flow velocity is 0.18ml/h, and receiving range is 13cm, and reception material is aluminium flake;
(3) stannic oxide/graphene nano band/PAN nanofiber of (2) gained is inserted to the dry 6h of 50 ℃ of vacuum drying ovens;
(4) stannic oxide/graphene nano band/PAN fiber of (3) gained is packed in ceramic boat, directly enter in the Muffle furnace of 250 ℃, to carry out pre-oxidation and stablize 4h, heating rate is 2 ℃/min;
(5) stannic oxide/graphene nano band/PAN fiber of (4) gained is placed in quartz tube furnace and carries out carbonization 2h, carburizing temperature is 900 ℃, and heating rate is 2 ℃/min, has both obtained the described carbon nano-fiber that contains graphene nanobelt;
(6) described certain 100 milligrams of carbon nano-fibers that contain graphene nanobelt are inserted in ethylene glycol, 100 milliliters of the carbon nano-fiber dispersion liquids of formation 0.1%, ultrasonic certain hour, add again 40 milligrams of chloroplatinic acid/gold chlorides to mix, the carrying capacity of platinum in platinum/gold/carbon nano-fiber is 36wt%, the carrying capacity of gold in platinum/gold/carbon nano-fiber is that 4wt% regulates pH to 9～13 with 0.5～4M potassium hydroxide aqueous solution, under 135 degree, reduce 8h, suction filtration, vacuumize at 45 ℃, coolingly under room temperature obtain described catalyst; Its electro catalytic activity area and positive negative direction peak current ratio I
f/ I
blist in table 1.
Embodiment 5
(1), by 1 gram of PAN, 0.02 gram of stannic oxide/graphene nano band (GNR), is placed in 10 milliliters of DMF, at 30 ℃, stirs 10h, prepares uniform GNR/PAN mixed solution;
(2) the GNR/PAN mixed solution of (1) gained is injected to disposable syringe, carry out spinning, voltage is 12KV, and flow velocity is 0.15ml/h, and receiving range is 12cm, and reception material is aluminium flake;
(3) the GNR/PAN fiber of (2) gained is inserted to the dry 6h of 50 ℃ of vacuum drying ovens;
(4) the GNR/PAN fiber of (3) gained is packed in ceramic boat, directly enter in the Muffle furnace of 250 ℃, to carry out pre-oxidation and stablize 2h, heating rate is 2 ℃/min;
(5) the GNR/PAN composite fibre of (4) gained is placed in quartz tube furnace and carries out carbonization 0.5h, carburizing temperature is 900 ℃, and heating rate is 2 ℃/min, has both obtained the described carbon nano-fiber that contains GNR;
(6) carbon nano-fiber of described 100 milligrams of GNR is inserted in deionized water, 100 milliliters of the carbon nano-fiber dispersion liquids that formation contains GNR, ultrasonic certain hour, add again 40 milligrams of gold chlorides to mix, making the carrying capacity of platinum in platinum/carbon nano fiber is 28wt%, with 0.5～4M potassium hydroxide aqueous solution, regulate pH to 9～13, after stirred for several minute, add 150 milligrams of sodium borohydrides and 50 ml deionized water, under room temperature, reduce 8h, suction filtration, vacuumize at 60 ℃, coolingly under room temperature obtain described catalyst; Its electro catalytic activity area and positive negative direction peak current ratio I
f/ I
blist in table 1.
Embodiment 6
(1) by 1.2 grams of PAN, the multi-arm carbon nano-tube of 0.048 gram is placed in 10 milliliters of DMF, more than stirring 20h, prepares uniform multi-arm carbon nano-tube/PAN solution at 40 ℃;
(2) multi-arm carbon nano-tube/PAN solution of (1) gained is injected to disposable syringe, carry out spinning, voltage is 12KV, and flow velocity is 0.12ml/h, and receiving range is 15cm, and reception material is aluminium flake;
(3) multi-arm carbon nano-tube/PAN nanofiber of (2) gained is inserted to the dry 6h of 50 ℃ of vacuum drying ovens;
(4) multi-arm carbon nano-tube/PAN fiber of (3) gained is packed in ceramic boat, directly enter in the Muffle furnace of 250 ℃, to carry out pre-oxidation and stablize 4h, heating rate is 2 ℃/min;
(5) multi-arm carbon nano-tube/PAN fiber of (4) gained is placed in quartz tube furnace and carries out carbonization 2h, carburizing temperature is 900 ℃, and heating rate is 2 ℃/min, has both obtained the described carbon nano-fiber that contains multi-arm carbon nano-tube;
(6) described certain 100 milligrams of carbon nano-fibers that contain multi-arm carbon nano-tube are inserted in ethylene glycol, 100 milliliters of the carbon nano-fiber dispersion liquids of formation 0.1%, ultrasonic certain hour, add again 40 milligrams of chloroplatinic acid/cobalt chlorides to mix, the carrying capacity of platinum in platinum/gold/carbon nano-fiber is 27wt%, the carrying capacity of cobalt in platinum/gold/carbon nano-fiber is that 3wt% regulates pH to 9～13 with 0.5～4M potassium hydroxide aqueous solution, under 135 degree, reduce 8h, suction filtration, vacuumize at 45 ℃, coolingly under room temperature obtain described catalyst; Its electro catalytic activity area and positive negative direction peak current ratio I
f/ I
blist in table 1.
Embodiment 7
(1) by 1 gram of PAN, the Graphene of 0.036 gram is placed in 10 milliliters of DMF, more than stirring 20h, prepares uniform Graphene/PAN solution at 40 ℃;
(2) Graphene/PAN solution of (1) gained is injected to disposable syringe, carry out spinning, voltage is 12KV, and flow velocity is 0.12ml/h, and receiving range is 15cm, and reception material is aluminium flake;
(3) Graphene/PAN nanofiber of (2) gained is inserted to the dry 6h of 50 ℃ of vacuum drying ovens;
(4) Graphene/PAN fiber of (3) gained is packed in ceramic boat, directly enter in the Muffle furnace of 250 ℃, to carry out pre-oxidation and stablize 4h, heating rate is 2 ℃/min;
(5) Graphene/PAN fiber of (4) gained is placed in quartz tube furnace and carries out carbonization 2h, carburizing temperature is 900 ℃, and heating rate is 2 ℃/min, has both obtained the described carbon nano-fiber that contains Graphene;
(6) described certain 100 milligrams of carbon nano-fibers that contain Graphene are inserted in methyl alcohol, 100 milliliters of the carbon nano-fiber dispersion liquids that contains Graphene of formation 0.1%, ultrasonic certain hour, add again 40 milligrams of chloroplatinic acid/palladium to mix, the carrying capacity of platinum in platinum/palladium/carbon nano-fiber is 42wt%, the carrying capacity of palladium in platinum/palladium/carbon nano-fiber is that 8wt% regulates pH to 9～13 with 0.5～4M potassium hydroxide aqueous solution, under 110 degree, reduce 12h, suction filtration, vacuumize at 45 ℃, coolingly under room temperature obtain described catalyst; Its electro catalytic activity area and positive negative direction peak current ratio I
f/ I
blist in table 1.
Embodiment 8
(1) by 1 gram of PAN, the multi-arm carbon nano-tube of 0.072 gram is placed in 10 milliliters of DMF, more than stirring 20h, prepares uniform multi-arm carbon nano-tube/PAN solution at 40 ℃;
(2) multi-arm carbon nano-tube/PAN solution of (1) gained is injected to disposable syringe, carry out spinning, voltage is 12KV, and flow velocity is 0.12ml/h, and receiving range is 15cm, and reception material is aluminium flake;
(3) multi-arm carbon nano-tube/PAN nanofiber of (2) gained is inserted to the dry 6h of 50 ℃ of vacuum drying ovens;
(4) multi-arm carbon nano-tube/PAN fiber of (3) gained is packed in ceramic boat, directly enter in the Muffle furnace of 250 ℃, to carry out pre-oxidation and stablize 4h, heating rate is 2 ℃/min;
(5) multi-arm carbon nano-tube/PAN fiber of (4) gained is placed in quartz tube furnace and carries out carbonization 2h, carburizing temperature is 900 ℃, and heating rate is 2 ℃/min, has both obtained the described carbon nano-fiber that contains multi-arm carbon nano-tube;
(6) described certain 100 milligrams of carbon nano-fibers that contain multi-arm carbon nano-tube are inserted in methyl alcohol, 100 milliliters of the carbon nano-fiber dispersion liquids that contains multi-arm carbon nano-tube of formation 0.1%, ultrasonic certain hour, add again 40 milligrams of chloroplatinic acid/copper sulphate/nickelous sulfates to mix, the carrying capacity of platinum in platinum/nickel/carbon nano-fiber is 48wt%, the carrying capacity of copper nickel in platinum/copper/nickel/carbon nano-fiber is that 12wt% regulates pH to 9～13 with 0.5～4M potassium hydroxide aqueous solution, , under 150 degree, reduce 6h, suction filtration, vacuumize at 45 ℃, coolingly under room temperature obtain described catalyst, its electro catalytic activity area and positive negative direction peak current ratio I
f/ I
blist in table 1.
Comparative example 1,2
Platinum/many carbon nano-fibers (platinum content is 28%) that catalyst in comparative example 1 is carrier for the carbon nano-fiber that obtained by virgin pp nitrile calcining, catalyst in comparative example 2 is commercial catalysts platinum/C catalyst, its carrier is that XC-72, platinum content are 40%, electro catalytic activity area and the positive negative direction peak current ratio I of using said method to measure
f/ I
blist in table 1.
Table 1
Wherein, the carrier continuous phase of embodiment 1～8 is carbon nano-fiber.
Fig. 1 is embodiment 5 and the electrochemistry cyclic voltammogram of comparative example 1 product in sulfuric acid solution; Fig. 2 is embodiment 5 and the electrochemistry cyclic voltammogram of comparative example 1 product in sulfuric acid methyl alcohol blend solution; Fig. 3 is embodiment 5 and the chronoa mperometric plot of comparative example 1 product in the blend solution of sulfuric acid and methyl alcohol.
Compare with pure carbon nano-fiber (comparative example 1), the catalyst (embodiment 5) that has added graphene nanobelt has larger electrochemical surface area, higher peak current and the I of Geng Gao
f/ I
b, and, in whole electrochemistry timing testing current, maintain a current curve the highest, illustrated that to have added the catalyst activity of graphene nanobelt higher, anti-CO toxicity is stronger, and electrochemical stability is also better.
Claims (10)
1. a carbon fiber loaded metallic catalyst, is characterized in that, this catalyst is mixed to get for 100:0.01:0.01～100:50:90 in mass ratio by carbon fiber, graphitization additive, metallic particles,
The diameter of described carbon fiber is for being 50nm～5 μ m, and porosity is 20～80%, and specific area is 2～2500m
2g
-1, pore volume is 0.1～15mL g
-1;
Described graphitization additive is the material with carbon element that degree of graphitization is high, is selected from stannic oxide/graphene nano band, single armed, one or more in both arms or multi-arm carbon nano-tube, graphene oxide, graphene nanometer sheet or graphene nanospheres,
Described metallic particles is one or more the mixture in single metal in the transition metal, lanthanide series metal, actinide metals of diameter 0.1～50nm, metal alloy, metal oxide, slaine.
2. a kind of carbon fiber loaded metallic catalyst according to claim 1, is characterized in that,
Preferred 100:0.5:10～the 100:5:60 of mass ratio of described carbon fiber, graphitization additive, metallic particles,
The preferred 50-500nm of diameter of carbon fiber, porosity preferably 50～70%, the preferred 1000～1500m of specific area
2g
-1, the preferred 6～10mLg of pore volume
-1,
The diameter of metallic particles is 1～10nm preferably, and described transition metal is platinum, rhodium, palladium, gold, silver, copper, manganese or iron.
Graphitization additive is oxidation state material with carbon element or reduction-state material with carbon element.
3. a kind of carbon fiber loaded metallic catalyst according to claim 2, is characterized in that, described graphitization additive preferential oxidation state material with carbon element.
4. the preparation method of carbon fiber loaded metallic catalyst as described in any one in claim 1-3, is characterized in that, the method adopts following steps:
(1) 1 part of weight portion polyacrylonitrile and 0.0001～0.5 part of wt carbon meterial additive are dissolved in dimethyl formamide or dimethylacetylamide, polyacrylonitrile concentration is 7～20wt%, stirs 0.5～24h at 20～100 ℃:
(2) mixed solution step (1) being obtained carries out electrostatic spinning, and spinning gained tunica fibrosa is placed in reacting furnace to carry out carbonization and obtain the carbon nano-fiber that contains material with carbon element additive;
(3) carbon nano-fiber is dissolved to the carbon fiber reinforce plastic dispersion liquid that forms 0.05～1wt%, add metal precursor to stir and form uniform dispersion, the carrying capacity of metal precursor in dispersion liquid is 1～99wt%, with 0.5～4M potassium hydroxide aqueous solution, regulating pH value is 9～13, stir and carry out reduction reaction, again after filtration, vacuumize obtains carbon fiber loaded metallic catalyst.
5. the preparation method of a kind of carbon fiber loaded metallic catalyst according to claim 4, is characterized in that, the voltage range that described electrostatic spinning is used is 5～30KV, and flow velocity is 0.02～0.5ml/h, and spinning receiving range is 5～30cm.
6. the preparation method of a kind of carbon fiber loaded metallic catalyst according to claim 4, is characterized in that, the process of described carbonization is divided pre-oxidation and two stages of carbonization, and Pre oxidation is that 180～320 ℃, heating rate are 1～10 ℃/min; Carburizing temperature is 600～2200 ℃, and programming rate is 1～20 ℃/min.
7. the preparation method of a kind of carbon fiber loaded metallic catalyst according to claim 4, it is characterized in that, described metal precursor is one or more the mixture in single metal in transition metal, lanthanide series metal, actinide metals, metal alloy, metal oxide, slaine, carbon nano-fiber is 100:0.01～100:99 with metal quality ratio, preferably 100:10～100:60.
8. the preparation method of a kind of carbon fiber loaded metallic catalyst according to claim 4, is characterized in that, the metal quality in described carbon nano-fiber and metal precursor is than preferred 100:10～100:60.
9. the preparation method of a kind of carbon fiber loaded metallic catalyst according to claim 4, is characterized in that, the reducing agent that reduction reaction adopts is sodium borohydride, ethylene glycol or methyl alcohol, and reaction temperature is 10～180 ℃.
10. the application of carbon fiber loaded metallic catalyst as claimed in any one of claims 1-9 wherein, is characterized in that, this carbon fiber loaded metallic catalyst is applied to fuel cell, lithium ion battery, in ultracapacitor hydrogen storage material.
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