CN106245158A - The preparation method of nitrogen-doped carbon/dioxide composite nanofiber carrier - Google Patents
The preparation method of nitrogen-doped carbon/dioxide composite nanofiber carrier Download PDFInfo
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- CN106245158A CN106245158A CN201610667633.7A CN201610667633A CN106245158A CN 106245158 A CN106245158 A CN 106245158A CN 201610667633 A CN201610667633 A CN 201610667633A CN 106245158 A CN106245158 A CN 106245158A
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- butyl titanate
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- 239000002131 composite material Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 239000002121 nanofiber Substances 0.000 title claims abstract description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000835 fiber Substances 0.000 claims abstract description 43
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 18
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 18
- 229960000583 acetic acid Drugs 0.000 claims abstract description 14
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 14
- 239000002657 fibrous material Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 91
- 238000013019 agitation Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000005030 aluminium foil Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- -1 polyethylene pyrrole Polymers 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 6
- 238000005255 carburizing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 6
- 238000001523 electrospinning Methods 0.000 claims 3
- 229920002554 vinyl polymer Polymers 0.000 claims 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 50
- 239000003054 catalyst Substances 0.000 abstract description 28
- 239000004408 titanium dioxide Substances 0.000 abstract description 20
- 239000000446 fuel Substances 0.000 abstract description 9
- 239000001569 carbon dioxide Substances 0.000 abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 6
- 238000010041 electrostatic spinning Methods 0.000 abstract description 5
- 230000010354 integration Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 239000012528 membrane Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229920000049 Carbon (fiber) Polymers 0.000 description 7
- 239000004917 carbon fiber Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229920003082 Povidone K 90 Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
-
- 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
-
- B01J35/58—
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- 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
-
- 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
Present invention is disclosed the preparation method of a kind of nitrogen-doped carbon/dioxide composite nanofiber carrier, described preparation method includes: the glacial acetic acid solution of butyl titanate and the ethanol solution of polyvinylpyrrolidone are mixed according to proper proportion, prepare complex fiber material by electrostatic spinning technique, then this material is carried out in ammonia atmosphere high temperature cabonization obtain nitrogen-doped carbon/titanium dioxide composite fibre.The integration system achieving titanium dioxide, carbon and composite nano fiber thereof is standby, and material with carbon element organically blends with titanium dioxide.This composite has higher specific surface and porosity, and the charge characteristic of composite is have adjusted by the doping of nitrogen-atoms, improve corrosion resistance and the electrical conductivity of catalyst carrier, become excellent catalyst carrier, improve material transferring, have a good application prospect in catalyst of fuel batter with proton exchange film.
Description
Technical field
The invention belongs to field of fuel cell technology, relate to the preparation method of a kind of fiber carrier, particularly relate to a kind of nitrogen
The preparation method of doping carbon/dioxide composite nanofiber carrier.
Background technology
Proton Exchange Membrane Fuel Cells is that with chemical energy in oxidant, fuel is converted into electric energy one new-generation
Device, has energy conversion efficiency high, and start-up temperature is low, and the advantage such as quiet noiselessness, simple in construction, clean environment firendly, is electronic
The preferred electrical source of power of automobile, mobile electronic equipment and communication base station.
Catalyst is the critical material of Proton Exchange Membrane Fuel Cells, plays decisive to battery performance, life-span and cost
Effect.At present, conventional platinum based catalyst is that carbon carries Pt series, such as catalyst such as Pt/C, Pt-Ru/C.This catalyst series utilizes
The high-specific surface area of carbon dust, satisfactory electrical conductivity, to improve the stability of catalyst, catalysis activity, reduce catalyst cost.But
During fuel cell long-play, carbon carrier easily corrodes in fuel cell strong acid, high potential environment causes metal
Particle separates with carrier, the reunion of metallic, and the carbon dust reunited has a strong impact on the transmission of material.In order to improve catalysis
The resistance to corrosion of agent carrier, some metal-oxides such as SnO2、WO3、CeO2、TiO2Deng by as carrier material.Wherein, TiO2
Stable chemical performance under strong acid environment, abundance, with low cost, especially TiO2With " the strong phase interaction between noble metal
With " become excellent carrier, some noble metals such as Pt, Ag, Ir, Au, Ru and Pd etc. and TiO2After Fu He, catalysis activity and
Stability significantly improves.For improving the material transferring of carbon carrier and electric conductivity, there is bigger serface and high porosity, structure steady
Fixed carbon fiber also serves as the carrier of catalyst, the site, graphite mould edge that carbon fiber surface exposes, it is possible to make catalyst with
Form the interaction of uniqueness between carrier, be greatly improved activity and stability [De Jong KP, the Geus of catalyst
JW.Catalysis Reviews,2000,42(4):481-510；KunChan Lee,JiuJun Zhang,HaiJiang
Wang,David P.Wilkinson.Journal of Applied Electrochemistry,2006,36:507-522]。
Titanium dioxide is combined with carbon fiber, the unique advantage of the two can be made full use of, the anticorrosive of catalyst carrier can be improved
Ability, optimizes material transferring, and there is polarity Ti-O key in titanium dioxide, and the water of surface adsorption dissociates because of polarization, holds
It is easily formed hydroxyl, beneficially the load of catalyst and surface modification.
At present, existing part is about the patent [CN103816884A of titanium dioxide Yu carbon fibre composite；
CN103696235A；CN103100378A；CN101250811；CN105268400A；CN102465442A；CN103055835A；
CN103566917A], titanium dioxide and carbon composite fibre are used for the field such as new forms of energy, environmental protection.These patents all use multistep
Method prepares composite, first prepares the carbon fibre carrier of molding, and then the employing means such as chemical deposition or physics coating will
Titania supported is on carbon fiber.In such preparation technology, titanium dioxide is the most weak with the interphase interaction of carbon fiber,
And titanium dioxide is distributed the most uneven on carbon fibre carrier.Additionally, titanium dioxide decreases in the covering of carbon fiber surface
The avtive spot of carbon fiber surface, necessarily reduces the activity of catalyst, electric conductivity.
In view of problem above, nowadays in the urgent need to designing the preparation method of a kind of new fiber carrier, in order to overcome existing
The drawbacks described above that preparation method exists.
Summary of the invention
The technical problem to be solved is: provide a kind of nitrogen-doped carbon/dioxide composite nanofiber carrier
Preparation method, prepared composite has higher specific surface and a porosity, and be have adjusted multiple by the doping of nitrogen-atoms
The charge characteristic of condensation material, improves corrosion resistance and the electrical conductivity of catalyst carrier, improves material transferring.
For solving above-mentioned technical problem, the present invention adopts the following technical scheme that
A kind of preparation method of nitrogen-doped carbon/dioxide composite nanofiber carrier, described preparation method includes:
The preparation of step S1. butyl titanate solution: under low-humidity environment, butyl titanate is joined in glacial acetic acid,
Seal stirring, wiring solution-forming；Wherein, butyl titanate concentration range, 0.01～0.5g/ml, seals stirring 15～60min；
The preparation of step S2. polyvinylpyrrolidonesolution solution: under room temperature, polyvinylpyrrolidone is dissolved in ethanol, is made into
Transparent sticky shape solution；Wherein polyvinylpyrrolidone ethanol solution concentration is 10～20wt.%, magnetic agitation 6～8h, poly-second
The average molecular weight range of alkene pyrrolidone is 40000～1500000, and joined solution concentration regards the polyvinylpyrrolidone selected
Depending on molecular weight, the highest solution concentration of molecular weight is the lowest；
Step S3. mixed solution is prepared: the polyethylene that butyl titanate solution step S1 obtained obtains with step S2
Pyrrolidone solution mixes by a certain percentage；Wherein, butyl titanate solution and the mixing of polyvinylpyrrolidonesolution solution
Volume ratio is 0.01:1～0.5:1；
The preparation of step S4. composite fibre: the mixed solution that step S3 obtains is joined in syringe, and is fixed on electricity
Spin and inject on pump, rotating bolus injection pump, adjust process variable, make syringe needle direction horizontal by 10～15 degree, use rolling
Cylinder attached aluminium foil receive, negative pressure-5～-7kV, malleation 11～15kV, receiving range 12～18cm, syringe pump flow velocity 0.01～
0.15mm/min, the spinning time is 9～11 hours；Composite fibre diameter range is 200～800nm；
The carbonization of step S5. composite fibre: the composite fibre that step S4 obtains is placed in tube furnace, is continually fed into ammonia
Gas, makes composite fibre high temperature cabonization under ammonia atmosphere, obtains nitrogen-doped carbon/dioxide composite nanofiber；Carburizing temperature
At 600～800 DEG C, heating rate is not higher than 5 DEG C/min, calcines 6～8h, keeps ammonia atmosphere in calcination process.
A kind of preparation method of nitrogen-doped carbon/dioxide composite nanofiber carrier, described preparation method includes:
The glacial acetic acid solution of butyl titanate and the ethanol solution of polyvinylpyrrolidone are mixed according to proper proportion, logical
Cross electrostatic spinning technique and prepare complex fiber material, then this material is carried out in ammonia atmosphere high temperature cabonization obtain N doping
Carbon/titanium dioxide composite fibre.
As a preferred embodiment of the present invention, the preparation of step S1. butyl titanate solution: will under low-humidity environment
Butyl titanate joins in glacial acetic acid, seals stirring, wiring solution-forming；
The preparation of step S2. polyvinylpyrrolidonesolution solution: under room temperature, polyvinylpyrrolidone is dissolved in ethanol, is made into
Transparent sticky shape solution；
Step S3. mixed solution is prepared: the polyethylene that butyl titanate solution step S1 obtained obtains with step S2
Pyrrolidone solution mixes by a certain percentage；
The preparation of step S4. composite fibre: the mixed solution that step S3 obtains is joined in syringe, and is fixed on electricity
Spin and inject on pump, rotating bolus injection pump, adjust process variable, make syringe needle direction horizontal by 10～15 degree, use rolling
Cylinder attached aluminium foil receive, negative pressure-5～-7kV, malleation 11～15kV, receiving range 12～18cm, syringe pump flow velocity 0.01～
0.15mm/mi n, the spinning time is 9～11 hours；
The carbonization of step S5. composite fibre: the composite fibre that step S4 obtains is placed in tube furnace, is continually fed into ammonia
Gas, makes composite fibre high temperature cabonization under ammonia atmosphere, obtains nitrogen-doped carbon/dioxide composite nanofiber.
As a preferred embodiment of the present invention, in step S1, butyl titanate concentration range 0.01～0.5g/ml,
Seal stirring 15～60min.
As a preferred embodiment of the present invention, in step S2, polyvinylpyrrolidone ethanol solution concentration 10～
20wt.%, magnetic agitation 6～8h, the average molecular weight range of polyvinylpyrrolidone 40000～1500000 (K30～
K90), joined solution concentration is depending on the polyvinylpyrrolidonemolecules molecules amount selected, and the highest solution concentration of molecular weight is the lowest.
As a preferred embodiment of the present invention, in step S3, butyl titanate solution and polyvinylpyrrolidonesolution solution
Mixed volume than for 0.01:1～0.5:1.
As a preferred embodiment of the present invention, in step S4, composite fibre diameter range is 200～800nm.
As a preferred embodiment of the present invention, in step S5, carburizing temperature is at 600～800 DEG C, and heating rate is not higher than
5 DEG C/min, calcine 6～8h, calcination process keeps ammonia atmosphere.
The beneficial effects of the present invention is: nitrogen-doped carbon/dioxide composite nanofiber carrier that the present invention proposes
Preparation method, mixes the glacial acetic acid solution of butyl titanate and the ethanol solution of polyvinylpyrrolidone according to proper proportion,
Prepare complex fiber material by electrostatic spinning technique, then this material is carried out in ammonia atmosphere high temperature cabonization obtain N doping
Carbon/titanium dioxide composite fibre, it is achieved that the integration system of titanium dioxide, carbon and composite nano fiber thereof is standby, material with carbon element and two
Organically blending of titanium oxide.This composite has higher specific surface and porosity, and be have adjusted by the doping of nitrogen-atoms
The charge characteristic of composite, improves corrosion resistance and the electrical conductivity of catalyst carrier, becomes excellent catalyst carrier,
Improve material transferring, have a good application prospect in catalyst of fuel batter with proton exchange film.
The inventive method is easy, quick, the method achieves the integration system of titanium dioxide, carbon and composite nano fiber thereof
Standby, prepared composite fibre has high specific surface area and porosity, and have adjusted composite by the doping of nitrogen-atoms
Charge characteristic, improve catalyst carrier corrosion resistance, electric conductivity and material transferring ability.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of nitrogen-doped carbon of the present invention/dioxide composite nanofiber carrier.
Fig. 2 is the electromicroscopic photograph of nitrogen-doped carbon/dioxide composite nanofiber prepared by present example 4, amplifies
2000 times.
Fig. 3 is the electromicroscopic photograph of nitrogen-doped carbon/dioxide composite nanofiber prepared by present example 4, amplifies
10000 times.
Fig. 4 is the Electronic Speculum that nitrogen-doped carbon/dioxide composite nanofiber prepared by present example 3 supports Pt catalyst
Photo.
Detailed description of the invention
Describe the preferred embodiments of the present invention below in conjunction with the accompanying drawings in detail.
Embodiment one
Refer to Fig. 1, present invention is disclosed the preparation side of a kind of nitrogen-doped carbon/dioxide composite nanofiber carrier
Method, described preparation method includes:
The preparation of step S1. butyl titanate solution: under low-humidity environment, butyl titanate is joined in glacial acetic acid,
Seal stirring, wiring solution-forming；Wherein, butyl titanate concentration range, 0.01～0.5g/ml, seals stirring 15～60min；
The preparation of step S2. polyvinylpyrrolidonesolution solution: under room temperature, polyvinylpyrrolidone is dissolved in ethanol, is made into
Transparent sticky shape solution；Wherein polyvinylpyrrolidone ethanol solution concentration is 10～20wt.%, magnetic agitation 6～8h, poly-second
The average molecular weight range of alkene pyrrolidone regards, in 40000～1500000 (K30～K90), joined solution concentration, the poly-second selected
Depending on alkene pyrrolidone molecular weight, the highest solution concentration of molecular weight is the lowest；
Step S3. mixed solution is prepared: the polyethylene that butyl titanate solution step S1 obtained obtains with step S2
Pyrrolidone solution mixes by a certain percentage；Wherein, butyl titanate solution and the mixing of polyvinylpyrrolidonesolution solution
Volume ratio is 0.01:1～0.5:1；
The preparation of step S4. composite fibre: the mixed solution that step S3 obtains is joined in syringe, and is fixed on electricity
Spin and inject on pump, rotating bolus injection pump, adjust process variable, make syringe needle direction horizontal by 10～15 degree, use rolling
Cylinder attached aluminium foil receive, negative pressure-5～-7kV, malleation 11～15kV, receiving range 12～18cm, syringe pump flow velocity 0.01～
0.15mm/min, the spinning time is 9～11 hours；Composite fibre diameter range is 200～800nm；
The carbonization of step S5. composite fibre: the composite fibre that step S4 obtains is placed in tube furnace, is continually fed into ammonia
Gas, makes composite fibre high temperature cabonization under ammonia atmosphere, obtains nitrogen-doped carbon/dioxide composite nanofiber；Carburizing temperature
At 600～800 DEG C, heating rate is not higher than 5 DEG C/min, calcines 6～8h, keeps ammonia atmosphere in calcination process.
Embodiment two
A kind of preparation method of nitrogen-doped carbon/dioxide composite nanofiber carrier, described preparation method includes:
The glacial acetic acid solution of butyl titanate and the ethanol solution of polyvinylpyrrolidone are mixed according to proper proportion, logical
Cross electrostatic spinning technique and prepare complex fiber material, then this material is carried out in ammonia atmosphere high temperature cabonization obtain N doping
Carbon/titanium dioxide composite fibre.
Embodiment three
The preparation method of a kind of nitrogen-doped carbon/dioxide composite nanofiber carrier, described preparation method includes as follows
Step:
(1) preparation of butyl titanate solution: take in the glacial acetic acid that 0.1g butyl titanate joins 2ml, prepares adult
Long-pending mass fraction is the solution of 0.05g/ml, magnetic agitation 15min；
(2) preparation of polyvinylpyrrolidonesolution solution: take 1g PVP K90 and be dissolved in 8ml ethanol, be configured to
Volume mass mark is the solution of 13.5wt.%, magnetic agitation 6h, it is thus achieved that transparent solution；
(3) preparation of composite solution: the polyethylene that butyl titanate solution step (1) obtained and step (2) obtain
Pyrrolidone solution mixes, magnetic agitation 20min under room temperature, it is thus achieved that pale yellow transparent thick liquid；
(4) preparation of composite nano-fiber membrane: the composite solution that step (3) obtains is joined in syringe, and fixes
In injecting on pump, syringe needle direction is higher than horizontal plane 15 degree, meanwhile, pastes aluminium foil on cylinder, and level receives, negative pressure-5kV, just
Pressure 11kV, speed 0.04mm/min, receiving range 15cm, spinning 10 hours, it is thus achieved that a diameter of 260～the fibrous membrane of 300nm；
(5) carbonization of composite fibre: be placed in tube furnace by the fibrous membrane that step (4) obtains, under ammonia atmosphere, with 2
DEG C/min, and rising to 800 DEG C of calcining 6h from room temperature, the final nitrogen-doped carbon/titanium dioxide obtaining a diameter of 190～220nm is combined
Nanofiber.
(6) the supporting of precious metals platinum catalyst: weigh the carbon fibre 400mg obtained in step (5), be infiltrated on 27ml's
In ethylene glycol, supersound process 5～10min, make fiber surface complete wetting；By the ethylene glycol solution of 3ml chloroplatinic acid, (platinum concentration is
7.4mg Pt/ml) and it is added dropwise to above-mentioned solution；With the NaOH/ ethylene glycol solution regulation mixed solution PH that concentration is 1M/ml
It is 13, magnetic agitation 30min, in 130 DEG C of oil baths, keep 2h subsequently, be then cooled to room temperature；50ml is added in mixture
Regulating its PH with aqueous hydrochloric acid solution under deionized water, and magnetic agitation is 4.0, stands 2h after stirring 30min；Take out catalyst also
Repeatedly rinse with deionized water, be finally placed in 70 DEG C dry 12 hours in vacuum drying oven, it is thus achieved that nitrogen-doped carbon/titania fiber
Supported platinum catalyst, platinum carrying capacity is 5wt.%.
Embodiment four
The preparation method of a kind of nitrogen-doped carbon/dioxide composite nanofiber carrier, described preparation method includes as follows
Step:
(1) preparation of butyl titanate solution: take in the glacial acetic acid that 0.5g butyl titanate joins 2ml, prepares adult
Long-pending mass fraction is the solution of 0.2g/ml, magnetic agitation 15min；
(2) preparation of polyvinylpyrrolidonesolution solution: take 1g PVP K90 and be dissolved in 7ml ethanol, be configured to
Volume mass mark is the solution of 15.2wt.%, magnetic agitation 6h, it is thus achieved that transparent solution；
(3) preparation of composite solution: the polyethylene that butyl titanate solution step (1) obtained and step (2) obtain
Pyrrolidone solution mixes, magnetic agitation 20min under room temperature, it is thus achieved that pale yellow transparent thick liquid；
(4) preparation of composite nano-fiber membrane: the composite solution that step (3) obtains is joined in syringe, and fixes
In injecting on pump, syringe needle direction is higher than horizontal plane 15 degree, meanwhile, pastes aluminium foil on cylinder, and level receives, negative pressure-5kV, just
Pressure 11kV, speed 0.06mm/min, receiving range 15cm, spinning 10 hours, it is thus achieved that a diameter of 300～the fibrous membrane of 350nm；
(5) fibrous membrane that step (4) obtains is placed in tube furnace, under ammonia atmosphere, with 2 DEG C/min, from room temperature liter
To 800 DEG C of calcining 6h, the nitrogen-doped carbon/carbon dioxide composite nano fiber of final acquisition a diameter of 200～240nm.
Embodiment five
The preparation method of a kind of nitrogen-doped carbon/dioxide composite nanofiber carrier, described preparation method includes as follows
Step:
(1) preparation of butyl titanate solution: take in the glacial acetic acid that 1.5g butyl titanate joins 2ml, prepares adult
Long-pending mass fraction is the solution of 0.43g/ml, magnetic agitation 15min；
(2) preparation of polyvinylpyrrolidonesolution solution: take 1g PVP K90 and be dissolved in 6ml ethanol, be configured to
Volume mass mark is the solution of 17.2wt.%, magnetic agitation 6h, it is thus achieved that transparent solution；
(3) preparation of composite solution: the polyethylene that butyl titanate solution step (1) obtained and step (2) obtain
Pyrrolidone solution mixes, magnetic agitation 20min under room temperature, it is thus achieved that pale yellow transparent thick liquid；
(4) preparation of composite nano-fiber membrane: the composite solution that step (3) obtains is joined in syringe, and fixes
In injecting on pump, syringe needle direction is higher than horizontal plane 15 degree, meanwhile, pastes aluminium foil on cylinder, and level receives, negative pressure-5kV, just
Pressure 11kV, speed 0.09mm/min, receiving range 15cm, spinning 10 hours, it is thus achieved that a diameter of 370～the fibrous membrane of 430nm；
(5) fibrous membrane that step (4) obtains is placed in tube furnace, under ammonia atmosphere, with 2 DEG C/min, from room temperature liter
To 800 DEG C of calcining 6h, the nitrogen-doped carbon/dioxide composite nanofiber of final acquisition a diameter of 220～260nm.
In sum, the preparation method of nitrogen-doped carbon/dioxide composite nanofiber carrier that the present invention proposes, by titanium
The acid glacial acetic acid solution of four butyl esters and the ethanol solution of polyvinylpyrrolidone mix according to proper proportion, by electrostatic spinning skill
Art prepares complex fiber material, then this material carries out in ammonia atmosphere high temperature cabonization, and to obtain nitrogen-doped carbon/titanium dioxide multiple
Condensating fiber, it is achieved that the integration system of titanium dioxide, carbon and composite nano fiber thereof is standby, material with carbon element melts with the organic of titanium dioxide
Close.This composite has higher specific surface and porosity, and be have adjusted the electric charge of composite by the doping of nitrogen-atoms
Characteristic, improves corrosion resistance and the electrical conductivity of catalyst carrier, becomes excellent catalyst carrier, improves material and passes
Defeated, have a good application prospect in catalyst of fuel batter with proton exchange film.
The inventive method is easy, quick, the method achieves the integration system of titanium dioxide, carbon and composite nano fiber thereof
Standby, prepared composite fibre has high specific surface area and porosity, and have adjusted composite by the doping of nitrogen-atoms
Charge characteristic, improve catalyst carrier corrosion resistance, electric conductivity and material transferring ability.
Here description of the invention and application is illustrative, is not wishing to limit the scope of the invention to above-described embodiment
In.The deformation of embodiments disclosed herein and change are possible, real for those skilled in the art
The various parts with equivalence of replacing executing example are known.It should be appreciated by the person skilled in the art that without departing from the present invention
Spirit or essential characteristics in the case of, the present invention can in other forms, structure, layout, ratio, and with other assembly,
Material and parts realize.In the case of without departing from scope and spirit of the present invention, embodiments disclosed herein can be entered
Other deformation of row and change.
Claims (8)
1. the preparation method of nitrogen-doped carbon/dioxide composite nanofiber carrier, it is characterised in that described preparation method
Including:
The preparation of step S1. butyl titanate solution: join in glacial acetic acid by butyl titanate under low-humidity environment, seals
Stirring, wiring solution-forming；Wherein, butyl titanate concentration range, 0.01～0.5g/ml, seals stirring 15～60min；
The preparation of step S2. polyvinylpyrrolidonesolution solution: under room temperature, polyvinylpyrrolidone is dissolved in ethanol, is made into transparent
Sticky shape solution；Wherein polyvinylpyrrolidone ethanol solution concentration is 10～20wt.%, magnetic agitation 6～8h, polyethylene pyrrole
The average molecular weight range of pyrrolidone is 40000～1500000, and joined solution concentration regards the polyvinylpyrrolidonemolecules molecules selected
Depending on amount, the highest solution concentration of molecular weight is the lowest；
Step S3. mixed solution is prepared: the polyvinyl pyrrole that butyl titanate solution step S1 obtained obtains with step S2
Alkanone solution mixes by a certain percentage；Wherein, butyl titanate solution and the mixed volume of polyvinylpyrrolidonesolution solution
Ratio is 0.01:1～0.5:1；
The preparation of step S4. composite fibre: the mixed solution that step S3 obtains is joined in syringe, and is fixed on electrospinning and pushes away
On note pump, rotating bolus injection pump, adjust process variable, make syringe needle direction horizontal by 10～15 degree, use cylinder attached
Aluminium foil receives, negative pressure-5～-7kV, malleation 11～15kV, receiving range 12～18cm, syringe pump flow velocity 0.01～0.15mm/
Min, the spinning time is 9～11 hours；Composite fibre diameter range is 200～800nm；
The carbonization of step S5. composite fibre: the composite fibre that step S4 obtains is placed in tube furnace, is continually fed into ammonia, makes
Composite fibre is high temperature cabonization under ammonia atmosphere, obtains nitrogen-doped carbon/dioxide composite nanofiber；Carburizing temperature is 600
～800 DEG C, heating rate is not higher than 5 DEG C/min, calcines 6～8h, keeps ammonia atmosphere in calcination process.
2. the preparation method of nitrogen-doped carbon/dioxide composite nanofiber carrier, it is characterised in that described preparation method
Including:
The glacial acetic acid solution of butyl titanate and the ethanol solution of polyvinylpyrrolidone are mixed according to proper proportion, by quiet
Electrospinning prepares complex fiber material, then this material carries out in ammonia atmosphere high temperature cabonization obtains nitrogen-doped carbon/bis-
Titanium oxide composite fibre.
The preparation method of nitrogen-doped carbon the most according to claim 2/dioxide composite nanofiber carrier, its feature exists
Following steps are specifically included in, described preparation method:
The preparation of step S1. butyl titanate solution: join in glacial acetic acid by butyl titanate under low-humidity environment, seals
Stirring, wiring solution-forming；
The preparation of step S2. polyvinylpyrrolidonesolution solution: under room temperature, polyvinylpyrrolidone is dissolved in ethanol, is made into transparent
Sticky shape solution；
Step S3. mixed solution is prepared: the polyvinyl pyrrole that butyl titanate solution step S1 obtained obtains with step S2
Alkanone solution mixes by a certain percentage；
The preparation of step S4. composite fibre: the mixed solution that step S3 obtains is joined in syringe, and is fixed on electrospinning and pushes away
On note pump, rotating bolus injection pump, adjust process variable, make syringe needle direction horizontal by 10～15 degree, use cylinder attached
Aluminium foil receives, negative pressure-5～-7kV, malleation 11～15kV, receiving range 12～18cm, syringe pump flow velocity 0.01～0.15mm/
Min, the spinning time is 9～11 hours；
The carbonization of step S5. composite fibre: the composite fibre that step S4 obtains is placed in tube furnace, is continually fed into ammonia, makes
Composite fibre is high temperature cabonization under ammonia atmosphere, obtains nitrogen-doped carbon/dioxide composite nanofiber.
The preparation method of nitrogen-doped carbon the most according to claim 3/dioxide composite nanofiber carrier, its feature exists
In:
In step S1, butyl titanate concentration range, 0.01～0.5g/ml, seals stirring 15～60min.
The preparation method of nitrogen-doped carbon the most according to claim 3/dioxide composite nanofiber carrier, its feature exists
In:
In step S2, polyvinylpyrrolidone ethanol solution concentration 10～20wt.%, magnetic agitation 6～8h, polyvinyl pyrrole
The average molecular weight range of alkanone is 40000～1500000, and joined solution concentration regards the polyvinylpyrrolidonemolecules molecules amount selected
Depending on, the highest solution concentration of molecular weight is the lowest.
The preparation method of nitrogen-doped carbon the most according to claim 3/dioxide composite nanofiber carrier, its feature exists
In:
In step S3, the mixed volume of butyl titanate solution and polyvinylpyrrolidonesolution solution is than for 0.01:1～0.5:1.
The preparation method of nitrogen-doped carbon the most according to claim 3/dioxide composite nanofiber carrier, its feature exists
In:
In step S4, composite fibre diameter range is 200～800nm.
The preparation method of nitrogen-doped carbon the most according to claim 3/dioxide composite nanofiber carrier, its feature exists
In:
In step S5, carburizing temperature is at 600～800 DEG C, and heating rate is not higher than 5 DEG C/min, calcines 6～8h, in calcination process
Keep ammonia atmosphere.
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