CN106040277B - A kind of " vesica string " structural carbon fiber composite material and preparation method of supporting Pt - Google Patents
A kind of " vesica string " structural carbon fiber composite material and preparation method of supporting Pt Download PDFInfo
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- CN106040277B CN106040277B CN201610401904.4A CN201610401904A CN106040277B CN 106040277 B CN106040277 B CN 106040277B CN 201610401904 A CN201610401904 A CN 201610401904A CN 106040277 B CN106040277 B CN 106040277B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 32
- 239000004917 carbon fiber 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
- 239000000463 material Substances 0.000 claims abstract description 24
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002121 nanofiber Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229960003638 dopamine Drugs 0.000 claims abstract description 12
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 229940056319 ferrosoferric oxide Drugs 0.000 claims abstract description 8
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 7
- 238000009987 spinning Methods 0.000 claims abstract description 6
- 238000001802 infusion Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 75
- 239000002134 carbon nanofiber Substances 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 30
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 28
- 239000012528 membrane Substances 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 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
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000005253 cladding Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229920002521 macromolecule Polymers 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 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
- 230000035484 reaction time Effects 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004321 preservation 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
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 239000007853 buffer solution Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 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 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
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229920005575 poly(amic acid) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 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 20
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 9
- 238000003763 carbonization Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000003575 carbonaceous material Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000446 fuel 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 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 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
- 230000000694 effects Effects 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 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
- UMABOEXDTSGDQW-UHFFFAOYSA-L [OH-].[OH-].O.O.O.[Fe+2] Chemical compound [OH-].[OH-].O.O.O.[Fe+2] UMABOEXDTSGDQW-UHFFFAOYSA-L 0.000 description 1
- JLFVIEQMRKMAIT-UHFFFAOYSA-N ac1l9mnz Chemical compound O.O.O JLFVIEQMRKMAIT-UHFFFAOYSA-N 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
- 125000004429 atom Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 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
- 238000001523 electrospinning Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N o-dihydroxy-benzene Natural products OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 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
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 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)
- Inorganic Fibers (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
- Inert Electrodes (AREA)
Abstract
The invention belongs to nano-fiber composite material technical field, the preparation method of " vesica string " structural carbon fiber composite material of specially a kind of supporting Pt.The method of the present invention includes：By spinnability high molecular material spinning solution, nanofiber is obtained by electrostatic spinning technique；By water-bath or hydro-thermal iron oxide hydroxide fusiform nanometer rods are uniformly uploaded in nanofiber surface；The tunica fibrosa that iron oxide hydroxide is modified is soaked in dopamine solution, poly-dopamine clad is prepared；It is handled by high temperature cabonization, realizes the carbonization of fiber；" vesica string " structural carbon fiber material is obtained using acid soak removal ferroso-ferric oxide, Pt nano particle particle is uniformly uploaded to by carbon material surface by infusion process, finally obtains the new structure carbon fibre composite of supporting Pt.The method of the present invention safety and environmental protection, the compound carbon fiber prepared have many advantages, such as that catalytic activity height, large specific surface area, conductivity are high and physical and chemical performance is stablized, can play a significant role in the energy devices such as fuel cell, water-splitting.
Description
Technical field
The invention belongs to nano-fiber composite material technical fields, and in particular to a kind of " vesica string " structural carbon of supporting Pt
Fibrous composite and preparation method thereof.
Background technology
Nanofiber is the Typical Representative of monodimension nanometer material, and electrostatic spinning technique directly can continuously be made as one kind
The method of standby polymer nanofiber, is widely noticed all the time.The nano fibrous membrane being prepared because it is good with stability,
It the advantages that porosity height, large specific surface area, conductivity height and more substance and electron-transport duct, can be widely applied to be catalyzed
The electrode material etc. of agent carrier, hydrogen storage material, sorbing material and ultracapacitor or lithium ion battery, advantageously accounts for current society
The energy crisis and problem of environmental pollution of meeting.
Traditional electrostatic spinning nano fiber surface is smooth, and structure is single, it is difficult to meet the needs of practical application.Multistage " capsule
The introducing of bubble " structure, not only increases the roughness of fiber and the surface area of fibrous material, and is conducive to improve material
Surface-active.Present invention firstly provides the preparation methods of " vesica string " structural carbon fiber material, it is intended to novel have by this
The preparation of the fibrous material of multi-stage pore structure can make up the deficiency of traditional fibre material, to be answered in more areas
With.
As modernization development is skyrocketed through energy demand, the limited deposit of traditional fossil energy is in huge consumption
Increasingly deficient under rate, the utilization of new energy become the intractable project of world community facing.Currently, the platinum of high activity
Carbon（Pt/C）Catalyst is energy field master catalyst to be used, and the expensive cost of noble metal platinum and not good enough stability
Limit its further extensive use.Therefore, the Pt supported catalysts that utilization rate is high, stability is good become new energy in recent years
One of goal in research of source domain.It is controllably coated on iron oxide hydroxide table by the present invention using the self-polymeric reaction of poly-dopamine
Face, then the carbon coating iron oxide of nucleocapsid is obtained by high temperature cabonization, it finally removes iron oxide and is prepared with novel " capsule
The high-specific surface area carbon fibre material of bubble string " structure, " vesica string " structural carbon fiber of supporting Pt is prepared as matrix
Composite material.
Invention content
The purpose of the present invention is to provide " vesica string " structural carbon fibers of the simple novel load Pt of preparation process a kind of
Composite material and preparation method.
" vesica string " structural carbon fiber composite material of supporting Pt provided by the present invention, preparing raw material composition includes：
Macromolecule, molysite, dopamine, ammonium hydroxide, chloroplatinic acid can be spun.
" vesica string " structural carbon fiber composite material of supporting Pt provided by the present invention selects " vesica string " structure carbon fiber
Dimension material is substrate, and Pt nano particle particle is uniformly uploaded to vesicle surface by infusion process and is prepared.
The present invention is to provide a kind of high-specific surface area, high porosity, " vesicas " being carbonized by poly-dopamine shell
Uniformly upload the multilevel hierarchy carbon fibre composite of Pt nano particle particle.
" vesica string " structural carbon fiber composite material of supporting Pt provided by the present invention, preparation process include：Pass through
Electrostatic spinning apparatus obtains nano fibrous membrane；By immersion method iron oxide hydroxide fusiform nanometer rods are realized in nanofiber surface
Uniformly upload and the controllable cladding of poly-dopamine；It is handled by high temperature cabonization, a step realizes the carbonization of fiber, hydroxide oxygen
Conversion of the iron to ferroso-ferric oxide and poly-dopamine to nitrogen-doped carbon material；Pass through four oxidations three in hydrochloric acid removal system
Iron prepares the carbon nano-fiber materials with unique " vesica string " structure；Pt nano particle particle is uniformly uploaded by infusion process
" vesica string " structural carbon fiber composite material of supporting Pt is prepared to vesicle surface.It is as follows：
（1）By spinnability macromolecule dissolution in solution, it is configured to spinning solution, is prepared by single needle electrostatic spinning technique
Obtain nano fibrous membrane；
（2）Above-mentioned nano fibrous membrane is placed in convection oven and is dried, and carries out pre-oxidation treatment；
（3）Nano fibrous membrane through pre-oxidation treatment is placed in iron salt solutions, hydro-thermal is carried out（Bath）Reaction, obtains hydrogen-oxygen
Change the nano fibrous membrane of oxygen iron modification；
（4）The nano fibrous membrane that iron oxide hydroxide is modified is placed in dopamine solution and is reacted, the packet of poly-dopamine is obtained
Coating；
（5）The nano fibrous membrane of the iron oxide hydroxide modification of poly-dopamine cladding is subjected to high temperature cabonization, is obtained in vesica
" vesica string " nanofiber containing ferroso-ferric oxide, is denoted as CNF@Fe3O4@NC；
（6）By CNF@Fe3O4@NC are soaked in acid solution, and the ferriferous oxide in removal system is obtained with vesica string structure
Pure carbon fiber, be denoted as CNF@NC；
（7）The CNF@NC of certain mass are placed in platinum acid chloride solution, excessive ammonia is added dropwise and carries out Pt reduction；
（8）It takes out tunica fibrosa obtained above to be washed repeatedly with deionized water, and dry, obtains the CNF NC of supporting Pt,
It is denoted as CNF@NC@Pt.
In the present invention, step（1）Described in spinnability macromolecule be selected from polyacrylonitrile（PAN）, polyamic acid（PAA）,
Polyamide（PA）And polystyrene（PS）, preferably PAN.The spinning solution range of solid content separately configured is 8% ~ 20%, preferably 10-
12%。
In the present invention, step（2）Described in the pre-oxidation treatment program of nanofiber be：（1）It slowly rises in air
To 200-300 DEG C, heating rate controls within the scope of 2 ~ 10 DEG C/min temperature；（2）1-3 h are kept at such a temperature.
In the present invention, step（3）Described in molysite be selected from iron chloride, ferric nitrate, ferric sulfate and ferric acetate, preferably chlorine
Change iron.The concentration of iron salt solutions is controlled in 10 ~ 50 mg/mL, preferably 25 mg/mL.Hydro-thermal（Bath）Reaction temperature control 60 ~
120℃（It is preferred that 80 DEG C）, the reaction time is 6-12 h.
In the present invention, step（4）Described in dopamine solution concentration range be 0.5 ~ 3 mg/mL, wherein use pH
Buffer solution Tris/TrisHCl, a concentration of 10 mM/L；Reaction temperature is 55-65 DEG C（It is preferred that 60 DEG C）, reaction time 3-
12 h（It is preferred that 3-6 h）.
In the present invention, step（5）Described in high temperature cabonization, process is：The hydrogen that obtained poly-dopamine is coated
Oxidation oxygen iron modification nano fibrous membrane be placed in tube furnace, temperature programming is controlled in nitrogen atmosphere, i.e., from room temperature to
400-500 DEG C of heating, time are 1-2 h, heat preservation 0.5-1 h；Then it is warming up to 600-800 DEG C again, the heating-up time is 1-3 h,
1-2 h are kept the temperature, preferably carburizing temperature is 700 DEG C ~ 800 DEG C.
In the present invention, step（6）Described in removal system in ferriferous oxide acid solution, selected from hydrochloric acid, nitric acid, sulfuric acid,
Or their mixtures for centainly matching.Preferred concentration is 8-15% hydrochloric acid solutions.
In the present invention, step（7）Described in a concentration of 1 ~ 30 mg/mL of platinum acid chloride solution, ammonium hydroxide is added dropwise to slightly mistake
Amount.
In the present invention, step（7）The CNF@NC are placed in platinum acid chloride solution, and soaking time is 3-12 h.
Use SEM（Scanning electron microscope）, X-ray diffraction analysis, electrochemical workstation come characterize the present invention obtained
Supporting Pt " vesica string " structural carbon fiber composite material structure and morphology and chemical property as electrochemical catalyst,
Its result is as follows：
（1）The test result of SEM shows：Polyacrylonitrile（PAN）With excellent spinnability.By to concentration of dope,
The optimization of the various aspects condition such as electrospinning processes, the PAN fiber surface that the present invention is prepared is smooth, and diameter is more uniform
It is distributed between 300-400 nm.In addition, PAN fiber is in random distribution, higher porosity is shown, is follow-up FeOOH particles
Growth with vesica provides space.PAN nanofiber membrane is immersed in iron salt solutions, FeOOH fusiform nano particles are in
It is radial to be grown in fiber surface, almost cover entire fiber surface.Further upload poly-dopamine（PDA）Afterwards, FeOOH receives
Rice grain surface forms one layer of uniform PDA clad.One step of high temperature cabonization realizes the carbonization of fiber, iron oxide hydroxide to
Ferroso-ferric oxide and poly-dopamine form the carbon fibre material of multilevel hierarchy to the conversion process of nitrogen-doped carbon material, referring to
Attached drawing 1.Further by the ferroso-ferric oxide in hydrochloric acid removal system, that is, prepares the carbon with unique " vesica string " structure and receive
Rice fibrous material, referring to attached drawing 2." vesica string " structural carbon fiber composite material of supporting Pt is prepared by the precipitation method, joins
See attached drawing 3；
（2）X-ray diffraction characterization result shows：" vesica string " carbon nano-fiber preparation-obtained in the present invention is shown
There is the diffraction pattern of platinum after supporting Pt, referring to attached drawing 4 on collection of illustrative plates in the diffraction curve of pure carbon material；
（3）Hydrogen reduction Electrochemical results show：" vesica string " carbon Nanowire of prepared supporting Pt in the present invention
Dimension composite material is a kind of good oxygen reduction catalyst, and take-off potential is down to 100 mV (Vs. RHE) and is catalyzed participation and is
The reaction process of four electronics.Separately in terms of cyclical stability, prepared supporting Pt " vesica string " carbon nano-fiber in the present invention
Also clear superiority is shown, referring to attached drawing 5, Fig. 6；
（4）Liberation of hydrogen Electrochemical results show：" vesica string " carbon nano-fiber of prepared supporting Pt in the present invention
Composite material is also a kind of good liberation of hydrogen catalyst, its Hydrogen Evolution Performance is better than business platinum carbon, take-off potential after supporting Pt
Down to 30 mV (Vs. RHE), referring to attached drawing 7.
The present invention relates to four basic principles：
（1）Contain a large amount of cyano on polyacrylonitrile nanofiber, hydroxyl, carboxyl isoreactivity are introduced by preoxidation process
Functional group.These functional groups can be used as active site, be sent out under certain conditions with macromolecular, small molecule, ion, nano particle etc.
Raw further reaction.In the present invention in a heated condition, iron ion has an effect with polyacrylonitrile surface group and generates hydroxide
Oxygen iron particle realizes the specific surface area of fusiform FeOOH particles being uniformly distributed and composite material has also been significantly greatly increased；
（2）Dopamine is amino-containing pyrocatechol small molecule, can aoxidize autohemagglutination in a mild condition substantially any
Material surface forms a strata dopamine modified membrane.Poly-dopamine has certain reactivity, with reducing metal ion or can connect
Other active groups of branch.The oxidation self-polymeric reaction that dopamine is utilized in the present invention realizes poly-dopamine in fusiform FeOOH particles
The controllable cladding on surface is the committed step of " vesica string " carbon nano-fiber preparation process；
（3）It prepares poly-dopamine cladding FeOOH and uploads PAN by high temperature cabonization, a step realizes the carbonization of fiber, hydrogen
Oxygen iron is aoxidized to ferroso-ferric oxide and poly-dopamine to the conversion process of nitrogen-doped carbon material, forms the carbon fiber of multilevel hierarchy
Material；
（4）Successfully solves the group of Pt nano particles using " vesica string " carbon nano-fiber being prepared as matrix supporting Pt
Poly- problem gives full play to its catalytic activity；The carbon nano vesicle obtained after poly-dopamine carbonization has the atom knot of class graphene
Structure, the high doped of electroactive N atoms make the conductive energy that there is " vesica " carbon lower impedance therefore to enhance carbon fibre material
Power.
The present invention supporting Pt " vesica string " structural carbon fiber composite material, can be used as catalyst carrier, hydrogen storage material,
The application of the electrode material of sorbing material and ultracapacitor or lithium ion battery.
The present invention remarkable advantage be：
（1）Preparation process is mild, environmentally friendly, easily operated, is a kind of Green Chemistry preparation method；
（2）Mentality of designing is ingenious：It is logical as substrate using the pre-oxidized acrylonitrile polymer fiber for containing abundant oxygen-containing functional group
The multilevel hierarchy nanofiber that FeOOH modifications are prepared in ion-exchange is crossed, the property of dopamine is further utilized, it is real
Controllable cladding of the existing poly-dopamine in fusiform FeOOH particle surfaces.Poly-dopamine after carbonization still keeps fusoid structure,
The carbon nano-fiber of this novel " vesica string " structure is prepared in the oxides-containing iron that its cladding is removed by ion exchange；
The agglomeration traits for successfully solving Pt nano particles as matrix supporting Pt give full play to its catalytic activity, height are prepared
The composite material of catalytic activity.
Description of the drawings
After Fig. 1 is pure PAN fiber prepared in the present invention, PAN@FeOOH, PAN@FeOOH@PDA and carbonization
CNF@Fe3O4@NC。
Fig. 2 is prepared " vesica 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 diagram of material prepared in the present invention, corresponds respectively to pure PAN, PAN@FeOOH, PAN@FeOOH@
CNF@Fe after PDA, carbonization3O4The@NC and CNF@NC and CNF@NC@Pt for removing iron oxide.
Fig. 5 is the hydrogen reduction LSV curves of CNF@NC@Pt prepared in the present invention.
Fig. 6 is the stable circulation performance comparison diagram of CNF@NC@Pt and business Pt/C prepared in the present invention.
Fig. 7 is the liberation of hydrogen LSV curves of pure CNF@NC prepared in the present invention, CNF@NC@Pt and business Pt/C.
Specific implementation mode
With reference to specific example, the present invention is further explained, it should be appreciated that these embodiments be merely to illustrate the present invention and
It is not used in and limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Various changes or modification can be made to the present invention, such equivalent forms are equally fallen within defined by the application the appended claims
Range.
Embodiment 1
The present embodiment includes the following steps：
（1）Polyacrylonitrile is dissolved in dimethylformamide and is configured to spinning solution, passes through single needle electrostatic spinning technique
Polyacrylonitrile nanofiber film is prepared；
（2）Polyacrylonitrile fibre membrane is placed in convection oven and is pre-oxidized；
（3）Polyacrylonitrile after pre-oxidation is placed in 25mg/mL FeCl3·6H2Iron oxide hydroxide modification is obtained in O salting liquids
Polyacrylonitrile fibre, be denoted as PAN@FeOOH；
（4）PAN@FeOOH are placed in 3 h in 1mg/mL dopamine solutions and obtain the clad of poly-dopamine, are denoted as PAN@
FeOOH@PDA；
（5）PAN FeOOH PDA are subjected to high temperature cabonization, obtain " vesica string " nanometer containing ferroso-ferric oxide in vesica
Fiber is denoted as CNF@Fe3O4@NC；
（6）By CNF@Fe3O4@NC are soaked in acid solution, and the ferriferous oxide in removal system obtains having vesica string structure
Pure carbon fiber is denoted as CNF@NC；
（7）The CNF@NC of certain mass are placed in 5 mg/mL platinum acid chloride solutions, excessive ammonia is added dropwise and carries out Pt reduction；
（8）Tunica fibrosa is taken out after a certain period of time and washs simultaneously drying for standby repeatedly with deionized water, obtains the CNF of supporting Pt
NC is denoted as CNF@NC@Pt-5.
Embodiment 2
Platinum acid chloride solution solubility in embodiment 1 is become into 10 mg/mL, remaining with embodiment 1, is finally obtained
Composite material is denoted as CNF@NC@Pt-10, which also shows good oxygen reduction catalytic activity, and take-off potential is down to 100
MV (Vs. RHE), steady-state current density reach 12.3 mA cm-2。
Embodiment 3
Platinum acid chloride solution solubility in embodiment 1 is become into 20 mg/mL, remaining with embodiment 1, is finally obtained
Composite material is denoted as CNF@NC@Pt-20, which also shows good oxygen reduction catalytic activity, and take-off potential is down to 100
MV (Vs. RHE), steady-state current density reach 17.8 mA cm-2。
Embodiment 4
Platinum acid chloride solution solubility in embodiment 1 is become into 30 mg/mL, remaining with embodiment 1, is finally obtained
Composite material is denoted as CNF@NC@Pt-30, which shows slightly to be inferior to CNF@NC@Pt-10's due to the reunion of Pt nano particles
Oxygen reduction catalytic activity, take-off potential reach 8.2 mA cm down to 100 mV (Vs. RHE), steady-state current density-2。
In electro-chemical test, using three electrode test systems, it is with the platinum carbon electrode that prepared hybrid material is modified
Working electrode, Ag/AgCl electrodes are reference electrode, and graphite rod is to electrode.Before testing, in advance by electrolyte lead to nitrogen or
30 min of oxygen.Using cyclic voltammetry curve（CV）And linear sweep voltammetry（LSV）Prepared hydridization in the research present invention
The electrocatalytic oxidation reduction reaction activity of material.Relevant technological parameter is as follows in above-mentioned electrochemical test method：
（1）The pretreatment of platinum carbon electrode：Platinum carbon electrode is polished with 1.0,0.3,0.05 microns of alumina powder successively, is made
At minute surface.It is cleaned, is then dried up with nitrogen spare with deionized water and EtOH Sonicate after polishing every time；
（2）The preparation of modified electrode：Using direct drop-coating in the surface present invention by pretreated platinum carbon electrode
Prepared hybrid material is modified.It is 1 that prepared hybrid material, which is specially dispersed in deionized water and ethyl alcohol ratio,:1
Solvent in, be made the solution of 2 mg/mL, after being ultrasonically treated 1 h, take 5 microlitres of solution to drop on platinum carbon electrode, in 70 DEG C of baking
Dry 0.5 h in case.
Claims (10)
1. a kind of preparation method of " vesica string " structural carbon fiber composite material of supporting Pt, which is characterized in that with " vesica string "
Structural carbon fiber be load matrix, using infusion process on carbon skeleton growth in situ Pt nano-particles；It prepares raw material：One
Kind or a variety of spinnability high molecular materials, dopamine, molysite, ammonium hydroxide, chloroplatinic acid；It is as follows：
（1）By spinnability macromolecule dissolution in solution, it is configured to spinning solution, is prepared by single needle electrostatic spinning technique
Nano fibrous membrane；
（2）Nano fibrous membrane is placed in convection oven and is dried, and carries out pre-oxidation treatment；
（3）Nano fibrous membrane is placed in iron salt solutions, hydro-thermal reaction is carried out, obtains the nanofiber of iron oxide hydroxide modification
Film；
（4）The nano fibrous membrane that iron oxide hydroxide is modified is placed in dopamine solution and is reacted, the clad of poly-dopamine is obtained；
（5）The nano fibrous membrane of the iron oxide hydroxide modification of poly-dopamine cladding is subjected to high temperature cabonization, obtains containing in vesica
" vesica string " nanofiber of ferroso-ferric oxide, is denoted as CNF@Fe3O4@NC；
（6）By CNF@Fe3O4@NC are soaked in acid solution, the ferriferous oxide in removal system, obtain having the pure of vesica string structure
Carbon fiber is denoted as CNF@NC；
（7）The CNF@NC of certain mass are placed in platinum acid chloride solution, excessive ammonia is added dropwise and carries out Pt reduction；
（8）Tunica fibrosa is taken out, is washed repeatedly with deionized water, and is dry, the CNF NC of supporting Pt is obtained, is denoted as CNF NC Pt；
Step（1）Described in spinnability macromolecule be selected from polyacrylonitrile, polyamic acid, polyamide and polystyrene.
2. the preparation method of " vesica string " structural carbon fiber composite material of supporting Pt according to claim 1, feature
It is, step（1）Described in spinnability macromolecule configuration spinning solution range of solid content be 8% ~ 20%.
3. the preparation method of " vesica string " structural carbon fiber composite material of supporting Pt according to claim 1 or 2, special
Sign is, step（2）Described in nanofiber pre-oxidation treatment, program is：（a）It is to slowly warm up to 200- in air
300 DEG C, heating rate controls within the scope of 2 ~ 10 DEG C/min；（b）1-3 h are kept at such a temperature.
4. the preparation method of " vesica string " structural carbon fiber composite material of supporting Pt according to claim 3, feature
It is, step（3）Described in molysite be selected from iron chloride, ferric nitrate, ferric sulfate and ferric acetate；The concentration of iron salt solutions controls
In 10 ~ 50 mg/mL；At 60 ~ 120 DEG C, the reaction time is 6-12 h for hydrothermal temperature control.
5. the preparation method of " vesica string " structural carbon fiber composite material of supporting Pt according to claim 1,2 or 4,
It is characterized in that, step（4）Described in dopamine solution a concentration of 0.5 ~ 3 mg/mL, wherein use pH buffer solutions Tris/
TrisHCl, a concentration of 10 mM；Reaction temperature is 55-65 DEG C, and the reaction time is 3-12 h.
6. the preparation method of " vesica string " structural carbon fiber composite material of supporting Pt according to claim 5, feature
It is, step（5）Described in high temperature cabonization, process is：The iron oxide hydroxide modification that obtained poly-dopamine is coated
Nano fibrous membrane be placed in tube furnace, temperature programming is controlled in nitrogen atmosphere, i.e., from room temperature to 400-500 DEG C, is risen
The warm time is 1-2 h, heat preservation 0.5-1 h；Then it is warming up to 600-800 DEG C again, the heating-up time is 1-3 h, heat preservation 1-2 h.
7. the preparation method of " vesica string " structural carbon fiber composite material of the supporting Pt according to claim 1,2,4 or 6,
It is characterized in that, step（6）The acid solution is selected from hydrochloric acid, nitric acid, sulfuric acid or mixture that they centainly match.
8. the preparation method of " vesica string " structural carbon fiber composite material of supporting Pt according to claim 7, feature
It is, step（7）Described in a concentration of 1 ~ 30 mg/mL of platinum acid chloride solution, ammonium hydroxide is added dropwise to slightly excessive；CNF@NC are set
In platinum acid chloride solution, soaking time is 3-12 h.
9. " vesica string " the structural carbon fiber composite wood for the supporting Pt that preparation method as described in one of claim 1-8 obtains
Material.
10. " vesica string " structural carbon fiber composite material of supporting Pt as claimed in claim 9 is as catalyst carrier, hydrogen storage
The application of the electrode material of material, sorbing material and ultracapacitor or lithium ion battery.
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| CN112206824A (en) * | 2020-10-30 | 2021-01-12 | 江西维邦生物科技有限公司 | Preparation method of polydopamine-mediated magnetic bimetallic nanoenzyme |
| CN113235300B (en) * | 2021-05-06 | 2022-07-26 | 甘肃省民翔新能源科技有限公司 | Preparation method of high-temperature-resistant lithium ion battery composite diaphragm |
| CN113751014B (en) * | 2021-09-16 | 2023-12-01 | 福州大学 | Monodisperse spindle-shaped monoatomic catalyst for denitration and sulfur resistance and preparation method thereof |
| CN114672845A (en) * | 2022-04-27 | 2022-06-28 | 桂林电子科技大学 | Carbon nanofiber-based metal sulfide self-supporting composite material and preparation method and application thereof |
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