CN106040277A - Pt-supported carbon fiber composite adopting 'vesica string' structure and preparation method of carbon fiber composite - Google Patents
Pt-supported carbon fiber composite adopting 'vesica string' structure and preparation method of carbon fiber composite Download PDFInfo
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- CN106040277A CN106040277A CN201610401904.4A CN201610401904A CN106040277A CN 106040277 A CN106040277 A CN 106040277A CN 201610401904 A CN201610401904 A CN 201610401904A CN 106040277 A CN106040277 A CN 106040277A
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- string
- carbon fiber
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- fiber composite
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 33
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920001690 polydopamine Polymers 0.000 claims abstract description 26
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012528 membrane Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002121 nanofiber Substances 0.000 claims abstract description 17
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229960003638 dopamine Drugs 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000009987 spinning Methods 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 72
- 239000002134 carbon nanofiber Substances 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 34
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 150000002505 iron Chemical class 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000005253 cladding Methods 0.000 claims description 6
- 238000010041 electrostatic spinning Methods 0.000 claims description 6
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 235000013980 iron oxide Nutrition 0.000 claims description 5
- 229920002521 macromolecule Polymers 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- 238000001802 infusion Methods 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920005575 poly(amic acid) Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000006174 pH buffer Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 238000003860 storage Methods 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 18
- 238000003763 carbonization Methods 0.000 abstract description 10
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000001523 electrospinning Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 2
- 239000000446 fuel Substances 0.000 abstract 1
- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- 239000002073 nanorod Substances 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 229910002588 FeOOH Inorganic materials 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- JLFVIEQMRKMAIT-UHFFFAOYSA-N ac1l9mnz Chemical compound O.O.O JLFVIEQMRKMAIT-UHFFFAOYSA-N 0.000 description 2
- -1 by infusion process Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
- Inert Electrodes (AREA)
Abstract
The invention belongs to the technical field of nanofiber composites and particularly relates to a preparation method of a Pt-supported carbon fiber composite adopting a 'vesica string' structure. The method comprises steps as follows: nanofibers are prepared from a spinnable high-polymer material spinning solution with an electrospinning technique; fusiform iron oxide hydroxide nanorods are uniformly supported on the surfaces of the nanofibers through water bath or hydrothermal treatment; iron oxide hydroxide modified fibrous membranes are soaked in a dopamine solution, and a polydopamine covering layer is prepared; fiber carbonization is realized through high-temperature carbonization treatment; ferroferric oxide is removed through soaking in an acid liquid, and the carbon fiber composite adopting the 'vesica string' structure is obtained. Pt nanoparticles are uniformly supported on the surface of a carbon material with a soaking method, and finally, the Pt-supported carbon fiber composite adopting the novel structure is obtained. The method is safe and environment-friendly, and the prepared composite carbon fibers have the advantages of high catalytic activity, large specific surface area, high electric conductivity, stable physical and chemical properties and the like and have a great significance in fuel cells, water splitting and other energy devices.
Description
Technical field
The invention belongs to nano-fiber composite material technical field, be specifically related to " vesicle string " structural carbon of a kind of supporting Pt
Fibrous composite and preparation method thereof.
Background technology
Nanofiber is the Typical Representative of monodimension nanometer material, and electrostatic spinning technique can be made the most continuously as one
The method of standby polymer nanofiber, the most concerned.The nano fibrous membrane prepared because of its have good stability,
The advantages such as porosity height, the material that specific surface area is big, conductivity is high and more and electric transmission duct, can be widely applied to catalysis
Agent carrier, hydrogen storage material, adsorbing material and ultracapacitor or the electrode material etc. of lithium ion battery, advantageously account for current society
The energy crisis of meeting and problem of environmental pollution.
Traditional electrostatic spinning nano fiber smooth surface, structure is single, is difficult to meet the demand of reality application.Multistage " capsule
Bubble " introducing of structure, not only increase the roughness of fiber and the surface area of fibrous material, and be conducive to improving material
Surface activity.Present invention firstly provides the preparation method of " vesicle string " structural carbon fiber material, it is intended to by this novel having
The preparation of the fibrous material of multistage pore space structure can make up the deficiency of traditional fibre material, to being answered in more areas
With.
Along with energy demand is skyrocketed through by modernization development, limited the laying in huge consumption of traditional fossil energy
Under speed day by day deficient, the exploitation of new forms of energy become the thorny problem of world community facing.At present, highly active platinum
Carbon (Pt/C) catalyst is the catalyst that energy field mainly uses, and the expensive cost of noble metal platinum and not good enough stability
Limit its most extensively application.Therefore, utilization rate height, the Pt supported catalyst of good stability become new energy in recent years
One of goal in research of source domain.The present invention utilizes the self-polymeric reaction of poly-dopamine that controlled it is coated on iron oxide hydroxide table
Face, then the carbon coated iron oxide of nucleocapsid structure is obtained by high temperature cabonization, finally removal ferrum oxide prepares and has novel " capsule
Bubble string " the high-specific surface area carbon fibre material of structure, " vesicle string " structural carbon fiber of supporting Pt is prepared as matrix
Composite.
Summary of the invention
It is an object of the invention to provide " vesicle string " structural carbon fiber of a kind of preparation process simple novel load Pt
Composite and preparation method thereof.
" vesicle string " structural carbon fiber composite of supporting Pt provided by the present invention, its prepare raw material composition include:
Macromolecule, iron salt, dopamine, ammonia, chloroplatinic acid can be spun.
" vesicle string " structural carbon fiber composite of supporting Pt provided by the present invention, selects " vesicle string " structural carbon fine
Dimension material is substrate, by infusion process, Pt nano particle granule is uniformly uploaded to vesicle surface and prepares.
The present invention is to provide a kind of high-specific surface area, high porosity, " vesicle " that obtained by poly-dopamine shell carbonization
Uniformly upload the multilevel hierarchy carbon fibre composite of Pt nano particle granule.
" vesicle string " structural carbon fiber composite of supporting Pt provided by the present invention, its preparation process includes: pass through
Electrostatic spinning apparatus obtains nano fibrous membrane；Iron oxide hydroxide fusiform nanometer rods is realized at nanofiber surface by immersion method
Uniformly upload and the controlled cladding of poly-dopamine；Being processed by high temperature cabonization, a step realizes the carbonization of fiber, hydroxide oxygen
Ferrum to ferroso-ferric oxide and poly-dopamine to the conversion of nitrogen-doped carbon material；By four oxidations three in hydrochloric acid removal system
Ferrum, prepares the carbon nano-fiber materials with uniqueness " vesicle string " structure；By infusion process, Pt nano particle granule is uniformly uploaded
" vesicle string " structural carbon fiber composite of supporting Pt is prepared to vesicle surface.Specifically comprise the following steps that
(1) by spinnability macromolecule dissolution in solution, it is configured to spinning liquid, is prepared by single needle electrostatic spinning technique
Nano fibrous membrane；
(2) above-mentioned nano fibrous membrane is placed in convection oven drying, and carries out pre-oxidation treatment；
(3) nano fibrous membrane through pre-oxidation treatment is placed in iron salt solutions, carries out hydro-thermal (bath) reaction, obtain hydroxide oxygen
The nano fibrous membrane that ferrum is modified；
(4) nano fibrous membrane that iron oxide hydroxide is modified is placed in dopamine solution reaction, obtains the clad of poly-dopamine；
(5) nano fibrous membrane that the iron oxide hydroxide being coated with by poly-dopamine is modified carries out high temperature cabonization, obtains vesicle and is contained within
" vesicle string " nanofiber of ferroso-ferric oxide, is denoted as CNF@Fe3O4@NC；
(6) by CNF@Fe3O4@NC is soaked in acid solution, the iron oxides in removal system, obtains having the pure of vesicle string structure
Carbon fiber, is denoted as CNF@NC；
(7) being placed in platinum acid chloride solution by the CNF@NC of certain mass, dropping excessive ammonia carries out Pt reduction；
(8) take out fibrous membrane deionized water cyclic washing obtained above, and be dried, obtain the CNF NC of supporting Pt, be designated as
CNF@NC@Pt。
In the present invention, the spinnability macromolecule described in step (1) be selected from polyacrylonitrile (PAN), polyamic acid (PAA),
Polyamide (PA) and polystyrene (PS), preferably PAN.The spinning liquid range of solid content of another configuration is 8% ~ 20%, preferably 10-
12%。
In the present invention, the pre-oxidation treatment program of the nanofiber described in step (2) is: (1) the most slowly rises
Temperature is to 200-300 DEG C, and heating rate controls in the range of 2 ~ 10 DEG C/min；(2) 1-3 h is kept at such a temperature.
In the present invention, the iron salt described in step (3) is selected from iron chloride, ferric nitrate, iron sulfate and ferric acetate, preferably chlorine
Change ferrum.The concentration of iron salt solutions controls at 10 ~ 50 mg/mL, preferably 25 mg/mL.Hydro-thermal (bath) reaction temperature controls 60 ~
120 DEG C (preferably 80 DEG C), the response time is 6-12 h.
In the present invention, the concentration range of the dopamine solution described in step (4) is 0.5 ~ 3 mg/mL, wherein uses pH
Buffer Tris/Tris HCl, its concentration is 10 mM/L；Reaction temperature is 55-65 DEG C (preferably 60 DEG C), and the response time is 3-
12 preferred 3-6 h of h().
In the present invention, the high temperature cabonization described in step (5), its process is: by the hydrogen of obtained poly-dopamine cladding
Oxidation oxygen ferrum modify nano fibrous membrane be placed in tube furnace, in nitrogen atmosphere control temperature programming, i.e. from room temperature to
400-500 DEG C of intensification, the time is 1-2 h, is incubated 0.5-1 h；Being warmed up to 600-800 DEG C the most again, the heating-up time is 1-3 h,
Insulation 1-2 h, preferably carburizing temperature are 700 DEG C ~ 800 DEG C.
In the present invention, the acid solution of iron oxides in the removal system described in step (6), selected from hydrochloric acid, nitric acid, sulphuric acid,
Or the mixture of their certain proportioning.Preferred concentration is 8-15% hydrochloric acid solution.
In the present invention, the platinum acid chloride solution concentration described in step (7) is 1 ~ 30 mg/mL, ammonia be added dropwise to little over
Amount.
In the present invention, the CNF@NC described in step (7) is placed in platinum acid chloride solution, and soak time is 3-12 h.
Use SEM(scanning electron microscope), X-ray diffraction analysis, electrochemical workstation characterize the present invention and obtained
Supporting Pt " vesicle string " structural carbon fiber composite structure and morphology and be used as electrochemical catalyst chemical property,
Its result is as follows:
(1) test result of SEM shows: polyacrylonitrile (PAN) has the spinnability of excellence.By to concentration of dope, electrospinning
The optimization of each side conditions such as technique, the PAN fiber smooth surface that the present invention prepares is smooth, and the most homogeneous distribution of diameter
Between 300-400 nm.Additionally, PAN fiber is random, show higher porosity, for follow-up FeOOH granule and capsule
The growth of bubble provides space.PAN nanofiber membrane being immersed in iron salt solutions, FeOOH fusiform nano-particle is radiation
Shape is grown in fiber surface, almost covers whole fiber surface.After uploading poly-dopamine (PDA) further, FeOOH nanometer
Grain surface defines one layer of uniform PDA clad.High temperature cabonization one step achieves the carbonization of fiber, and iron oxide hydroxide is to four oxygen
Change three-iron and poly-dopamine, to the conversion process of nitrogen-doped carbon material, form the carbon fibre material of multilevel hierarchy, see accompanying drawing
1.Further by the ferroso-ferric oxide in hydrochloric acid removal system, i.e. prepare the carbon Nanowire with uniqueness " vesicle string " structure
Dimension material, sees accompanying drawing 2.Prepared " vesicle string " structural carbon fiber composite of supporting Pt by the sedimentation method, see attached
Fig. 3；
(2) X-ray diffraction characterization result shows: preparation-obtained in the present invention " vesicle string " carbon nano-fiber shows pure carbon
, there is the diffraction pattern of platinum in the diffraction curve of material on collection of illustrative plates after supporting Pt, see accompanying drawing 4；
(3) hydrogen reduction Electrochemical results shows: " vesicle string " carbon nano-fiber of supporting Pt prepared in the present invention is multiple
Condensation material is a kind of good oxygen reduction catalyst, its take-off potential as little as 100 mV (Vs. RHE) and be catalyzed participation be four electricity
The course of reaction of son.Another in terms of cyclical stability, supporting Pt " vesicle string " carbon nano-fiber also table prepared in the present invention
Reveal clear superiority, see accompanying drawing 5, Fig. 6；
(4) liberation of hydrogen Electrochemical results shows: " vesicle string " carbon nano-fiber of supporting Pt prepared in the present invention is combined
Material is also a kind of good liberation of hydrogen catalyst, and after supporting Pt, its Hydrogen Evolution Performance is better than business platinum carbon, and its take-off potential is as little as
30 mV (Vs. RHE), see accompanying drawing 7.
The present invention relates to four ultimate principles:
(1) containing a large amount of cyano group on polyacrylonitrile nanofiber, hydroxyl, carboxyl isoreactivity official's energy are introduced by preoxidation process
Group.These functional groups can enter with macromole, little molecule, ion, nano-particle etc. under certain conditions as avtive spot
Single step reaction.In the present invention in a heated condition, iron ion and polyacrylonitrile surface group are had an effect generation iron oxide hydroxide
Granule, it is achieved that the specific surface area being uniformly distributed and being also significantly greatly increased composite of fusiform FeOOH granule；
(2) dopamine is the catechol micromolecular containing amino, can aoxidize autohemagglutination in a mild condition at substantially any material
Surface forms a strata dopamine modified membrane.Poly-dopamine has certain reactivity, can be with reducing metal ion or be grafted it
His active group.The present invention utilizes the oxidation self-polymeric reaction of dopamine, it is achieved poly-dopamine is at fusiform FeOOH particle surface
Controlled cladding, for the committed step of " vesicle string " carbon nano-fiber preparation process；
(3) prepare poly-dopamine cladding FeOOH to upload PAN and achieve the carbonization of fiber, hydroxide through high temperature cabonization, a step
Oxygen ferrum to the conversion process of nitrogen-doped carbon material, forms the carbon fiber material of multilevel hierarchy to ferroso-ferric oxide and poly-dopamine
Material；
(4) it is that matrix supporting Pt successfully solves the reunion of Pt nano-particle and asks with " vesicle string " carbon nano-fiber prepared
Topic, gives full play to its catalysis activity；The carbon nano vesicle obtained after poly-dopamine carbonization has the atomic structure of class Graphene, electricity
The high doped of activity atom N makes " vesicle " carbon have lower impedance and therefore enhances the conductive capability of carbon fibre material.
" vesicle string " structural carbon fiber composite of the supporting Pt of the present invention, can as catalyst carrier, hydrogen storage material,
The application of the electrode material of adsorbing material and ultracapacitor or lithium ion battery.
The remarkable advantage of the present invention is:
(1) preparation process gentleness, environmental protection, it is easy to operation, is a kind of Green Chemistry preparation method；
(2) mentality of designing is ingenious: use pre-oxidized acrylonitrile polymer fiber containing abundant oxygen-containing functional group as substrate by from
Sub-exchange process prepares the multilevel hierarchy nanofiber that FeOOH modifies, further with the property of dopamine, it is achieved poly-
Dopamine is in the controlled cladding of fusiform FeOOH particle surface.Poly-dopamine after carbonization still keeps fusoid structure, passes through
Ion exchange removes its oxides-containing iron being coated with and i.e. prepares the carbon nano-fiber of this novel " vesicle string " structure；With this
Successfully solve the agglomeration traits of Pt nano-particle for matrix supporting Pt, give full play to its catalysis activity, prepare high catalysis
The composite of activity.
Accompanying drawing explanation
After Fig. 1 is pure PAN fiber, PAN@FeOOH, PAN@FeOOH@PDA and carbonization prepared in the present invention
CNF@Fe3O4@NC。
Fig. 2 is prepared " vesicle string " structure pure carbon fiber in the present invention.
Fig. 3 is the CNF@NC@Pt of different Pt load capacity prepared in the present invention.
Fig. 4 is the XRD figure of material prepared in the present invention, corresponds respectively to pure PAN, PAN@FeOOH, PAN@FeOOH@
CNF@Fe after PDA, carbonization3O4@NC and CNF@NC and the CNF@NC@Pt of removing ferrum oxide.
Fig. 5 is the hydrogen reduction LSV curve of CNF@NC@Pt prepared in the present invention.
Fig. 6 is CNF NC Pt prepared in the present invention and the stable circulation performance comparison diagram of business Pt/C.
Fig. 7 is pure CNF@NC, CNF@NC@Pt and the liberation of hydrogen LSV curve of business Pt/C prepared in the present invention.
Detailed description of the invention
Below in conjunction with instantiation, the present invention is expanded on further, it should be appreciated that these embodiments be merely to illustrate the present invention and
It is not used in restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art
The present invention can make various change or amendment, and these equivalent form of values fall within what the application appended claims was limited equally
Scope.
Embodiment 1
The present embodiment comprises the following steps:
(1) polyacrylonitrile is dissolved in dimethylformamide it is configured to spinning liquid, prepared by single needle electrostatic spinning technique
Obtain polyacrylonitrile nanofiber film；
(2) polyacrylonitrile fibre membrane is placed in convection oven pre-oxidizes；
(3) polyacrylonitrile after pre-oxidation is placed in 25mg/mL FeCl3·6H2O saline solution obtains what iron oxide hydroxide was modified
Polyacrylonitrile fibre, is denoted as PAN@FeOOH；
(4) PAN@FeOOH is placed in 3 h in 1mg/mL dopamine solution and obtains the clad of poly-dopamine, be denoted as PAN@
FeOOH@PDA；
(5) PAN@FeOOH@PDA is carried out high temperature cabonization, obtain vesicle and be contained within " vesicle string " Nanowire of ferroso-ferric oxide
Dimension, is denoted as CNF@Fe3O4@NC；
(6) by CNF@Fe3O4@NC is soaked in acid solution, and the iron oxides in removal system obtains having the pure of vesicle string structure
Carbon fiber, is denoted as CNF@NC；
(7) being placed in 5 mg/mL platinum acid chloride solutions by the CNF@NC of certain mass, dropping excessive ammonia carries out Pt reduction；
(8) take out fibrous membrane deionized water cyclic washing drying for standby after certain time, obtain the CNF NC of supporting Pt, note
For CNF@NC@Pt-5.
Embodiment 2
Platinum acid chloride solution solubility in embodiment 1 is become 10 mg/mL, and remaining is all with embodiment 1, and finally obtained is compound
Material is designated as CNF@NC@Pt-10, and this material also shows good oxygen reduction catalytic activity, its take-off potential as little as 100 mV
(Vs. RHE), steady-state current density reaches 12.3 mA cm-2。
Embodiment 3
Platinum acid chloride solution solubility in embodiment 1 is become 20 mg/mL, and remaining is all with embodiment 1, and finally obtained is compound
Material is designated as CNF@NC@Pt-20, and this material also shows good oxygen reduction catalytic activity, its take-off potential as little as 100 mV
(Vs. RHE), steady-state current density reaches 17.8 mA cm-2。
Embodiment 4
Platinum acid chloride solution solubility in embodiment 1 is become 30 mg/mL, and remaining is all with embodiment 1, and finally obtained is compound
Material is designated as CNF@NC@Pt-30, and this material is slightly inferior to the oxygen of CNF@NC@Pt-10 also owing to the reunion of Pt nano-particle shows
Former catalysis activity, its take-off potential as little as 100 mV (Vs. RHE), steady-state current density reaches 8.2 mA cm-2。
In electro-chemical test, use three electrode test systems, with the platinum carbon electrode that prepared hybrid material is modified be
Working electrode, Ag/AgCl electrode is reference electrode, and graphite rod is to electrode.Before testing, in advance electrolyte is led to nitrogen or
Oxygen 30 min.Use hydridization prepared in cyclic voltammetry curve (CV) and linear sweep voltammetry (LSV) the research present invention
The electrocatalytic oxidation reduction reaction activity of material.Technological parameter relevant in above-mentioned electrochemical test method is as follows:
(1) pretreatment of platinum carbon electrode: platinum carbon electrode polishes with the alumina powder of 1.0,0.3,0.05 micron successively, makes into mirror
Face.Clean with deionized water and EtOH Sonicate after polishing every time, then dry up with nitrogen standby；
(2) preparation of modified electrode: use direct drop-coating made in the surface present invention of the platinum carbon electrode through pretreatment
Standby hybrid material is modified.It is specially and prepared hybrid material is dispersed in molten than for 1:1 of deionized water and ethanol
In agent, make the solution of 2 mg/mL, after supersound process 1 h, take 5 Al of Solution and drop on platinum carbon electrode, in the baking oven of 70 DEG C
It is dried 0.5 h.
Claims (10)
1. the preparation method of " vesicle string " structural carbon fiber composite of a supporting Pt, it is characterised in that with " vesicle string "
Structural carbon fiber is load matrix, uses infusion process growth in situ Pt nanoparticle on carbon skeleton；It is prepared raw material and includes: one
Plant or multiple spinnability macromolecular material, dopamine, iron salt, ammonia, chloroplatinic acid；Specifically comprise the following steps that
(1) by spinnability macromolecule dissolution in solution, it is configured to spinning liquid, is prepared by single needle electrostatic spinning technique
Nano fibrous membrane；
(2) nano fibrous membrane is placed in convection oven drying, and carries out pre-oxidation treatment；
(3) nano fibrous membrane is placed in iron salt solutions, carries out hydro-thermal reaction, obtain the nanofiber that iron oxide hydroxide is modified
Film；
(4) nano fibrous membrane that iron oxide hydroxide is modified is placed in dopamine solution reaction, obtains the clad of poly-dopamine；
(5) nano fibrous membrane that the iron oxide hydroxide being coated with by poly-dopamine is modified carries out high temperature cabonization, obtains vesicle and is contained within
" vesicle string " nanofiber of ferroso-ferric oxide, is denoted as CNF@Fe3O4@NC；
(6) by CNF@Fe3O4@NC is soaked in acid solution, the iron oxides in removal system, obtains having the pure of vesicle string structure
Carbon fiber, is denoted as CNF@NC；
(7) being placed in platinum acid chloride solution by the CNF@NC of certain mass, dropping excessive ammonia carries out Pt reduction；
(8) take out fibrous membrane, use deionized water cyclic washing, and be dried, obtain the CNF NC of supporting Pt, be designated as CNF NC Pt.
The preparation method of " vesicle string " structural carbon fiber composite of supporting Pt the most according to claim 1, its feature
Being, the spinnability macromolecule described in step (1) is selected from polyacrylonitrile, polyamic acid, polyamide and polystyrene；Configuration
Spinning liquid range of solid content be 8% ~ 20%.
The preparation method of " vesicle string " structural carbon fiber composite of supporting Pt the most according to claim 1 and 2, its
Being characterised by, the pre-oxidation treatment of the nanofiber described in step (2), its program is: (a) is to slowly warm up in atmosphere
200-300 DEG C, heating rate controls in the range of 2 ~ 10 DEG C/min；B () keeps 1-3 h at such a temperature.
The preparation method of " vesicle string " structural carbon fiber composite of supporting Pt the most according to claim 3, its feature
Being, the iron salt described in step (3) is selected from iron chloride, ferric nitrate, iron sulfate and ferric acetate；The concentration of iron salt solutions controls
At 10 ~ 50 mg/mL；Hydrothermal temperature controls at 60 ~ 120 DEG C, and the response time is 6-12 h.
5. according to the preparation method of " vesicle string " structural carbon fiber composite of the supporting Pt described in claim 1,2 or 4,
It is characterized in that, the concentration of the dopamine solution described in step (4) is 0.5 ~ 3 mg/mL, wherein, uses pH buffer
Tris/Tris HCl, its concentration is 10 mM/L；Reaction temperature is 55-65 DEG C, and the response time is 3-12 h.
The preparation method of " vesicle string " structural carbon fiber composite of supporting Pt the most according to claim 5, its feature
Being, the high temperature cabonization described in step (5), its process is: modified by the iron oxide hydroxide of obtained poly-dopamine cladding
Nano fibrous membrane be placed in tube furnace, nitrogen atmosphere controls temperature programming, i.e. from room temperature to 400-500 DEG C, rises
The temperature time is 1-2 h, is incubated 0.5-1 h；Being warmed up to 600-800 DEG C the most again, the heating-up time is 1-3 h, is incubated 1-2 h.
7. according to the preparation method of " vesicle string " structural carbon fiber composite of the supporting Pt described in claim 1,2,4 or 6,
It is characterized in that, the acid solution described in step (6) is selected from hydrochloric acid, nitric acid, sulphuric acid, or the mixture of their certain proportioning.
The preparation method of " vesicle string " structural carbon fiber composite of supporting Pt the most according to claim 7, its feature
Being, the platinum acid chloride solution concentration described in step (7) is 1 ~ 30 mg/mL, and ammonia is added dropwise to little over amount；CNF@NC puts
In platinum acid chloride solution, soak time is 3-12 h.
9. " vesicle string " the structural carbon fiber composite wood of the supporting Pt that the preparation method as described in one of claim 1-8 obtains
Material.
10. " vesicle string " structural carbon fiber composite of supporting Pt as claimed in claim 9 is as catalyst carrier, hydrogen storage
The application of the electrode material of material, adsorbing material and ultracapacitor or lithium ion battery.
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Granted publication date: 20181026 Termination date: 20210608 |