CN108193500A - Catalyst that composite nano fiber and composite nano fiber support and its preparation and application - Google Patents
Catalyst that composite nano fiber and composite nano fiber support and its preparation and application Download PDFInfo
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- CN108193500A CN108193500A CN201611120356.4A CN201611120356A CN108193500A CN 108193500 A CN108193500 A CN 108193500A CN 201611120356 A CN201611120356 A CN 201611120356A CN 108193500 A CN108193500 A CN 108193500A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention provides the catalyst that a kind of composite nano fiber and composite nano fiber support and its preparation and application, the present invention is based on electrostatic spinning techniques and solwution method, prepare the elctro-catalyst of high activity and high stability, the carrier of its elctro-catalyst is the composite fibre based on metal conductive oxide polymer material, and Pt precursor salt is reduced to Pt while solwution method introduces conducting polymer modified metal-oxide fiber surface, improve dispersion degrees of the Pt on carrier, gained metal conductive oxide polymer P t elctro-catalysts are expected to improve the activity and stability of elctro-catalyst.
Description
Technical field
The present invention relates to field of fuel cell technology, more particularly to a kind of fuel cell composite fibre elctro-catalyst and its
Preparation method.
Background technology
Pt is presently the most the elctro-catalyst of common Proton Exchange Membrane Fuel Cells, and it is the most that wherein carbon, which carries Pt (Pt/C),
Widely applied, still, Pt nanoparticles and the Interaction Force of carbon carrier are weaker, and carbon carrier is in high-temperature strong acid highfield
Under it is perishable, seriously affected fuel cell longtime running stability.
To alleviate these problems, generally use novel carriers prepare catalyst.Metal oxide, particularly low d electronics
Metal oxide such as TiO2And CeO2Deng in addition to excellent electricity/chemical stability and acid-alkali-corrosive-resisting, also showing to be catalyzed
Increasing action inhibits Pt to reunite between metallic catalyst Pt there are strong interaction, is preparing high stable and high catalysis work
Property catalyst in terms of be concerned.But TiO2Poorly conductive, characteristic of semiconductor make electronics in Pt/TiO2HOMO orbital energies begin
It is lower than Pt/C eventually, cause electronics transfer difficult.
Invention content
The present invention in view of the deficiencies of the prior art, has invented a kind of metal oxide and conducting polymer composite nano fiber
And preparation method thereof, and thereby invented using the composite nano fiber as catalyst of carrier and preparation method thereof.
A kind of composite nano fiber, the composite nano fiber are received for the metal oxide that surface deposition has conducting polymer
Rice fiber, the composite nano fiber are microcosmic upper for the netted pilotaxitic texture of nanofiber, a diameter of 50- of the nanofiber
500nm；The mass content of metal oxide is 50-90% in the composite nano fiber.
The conducting polymer is one or more of polyaniline, polypyrrole, polythiophene；The metal oxide
For TiO2、CeO2、RuO2、SnO2One or more of mixture.
The preparation method of the composite nano fiber, includes the following steps,
1) preparation of electrostatic spinning solution：Prepared polymer solution adds in the metal oxygen in resulting polymers solution
The precursor salt of compound obtains electrostatic spinning solution after mixing；
2) preparation of metal oxide nanofibres：Step 1) the electrostatic spinning solution is placed in electrospinning device
It carries out spinning and obtains metal oxide-polymer nanofiber precursor；By metal oxide-polymer nanofiber precursor in air
Or carrying out heat treatment under certain temperature in oxygen atmosphere makes polymer decompose to obtain metal oxide nanofibres, the certain temperature
Decomposition temperature for the polymer；
3) preparation of composite nano fiber；Metal oxide nanofibres obtained by step 2) are scattered in dilute acid soln and are obtained
Dispersion liquid, sequentially add conducting polymer monomer solution in gained dispersion liquid and oxidant be placed on 0-4 DEG C under the conditions of react,
Dry composite nano fiber is washed after reaction.
Polymer solution described in step 1) is polyacrylonitrile or is polyvinylpyrrolidone, polymer is polyacrylonitrile
When solvent can be DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N,N-dimethylformamide, one kind in dimethyl sulfoxide (DMSO)
It is or two or more；Solvent can be ethyl alcohol, DMAC N,N' dimethyl acetamide, N- crassitudes when polymer is polyvinylpyrrolidone
One or more of ketone, N,N-dimethylformamide, dimethyl sulfoxide (DMSO)；The quality of polymer in the polymer solution
Score is 5-20%；The precursor salt of the metal oxide is butyl titanate, one kind in cerous nitrate, ruthenic chloride, stannic chloride
Or two or more mixture；The mass fraction of metal oxide precursor salt is 5-20% in spinning solution；
The condition of the step 2) electrostatic spinning is that the charging rate of electrostatic spinning solution is 0.03-1.0mm/min, electrostatic
The operating voltage of spinning is 10-30kV, and the distance of spinning syringe needle and receiving part is 5-15cm；The polymer decomposition temperature is
200-380℃；
Step 3) the dilute acid soln is hydrochloric acid, sulfuric acid, phosphoric acid, one or more of perchloric acid, a concentration of
0.5-2mol/L；The conducting polymer monomer is one or more kinds of in aniline, pyrroles, thenoic acid；The oxidant is
One kind in ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, iron chloride；The molar ratio of monomer and oxidant is 1:1-3.
The active component for the catalyst that the composite nano fiber supports is precious metals pt, one kind in Pd, Ru, Au, Ph
Or two kinds, mass content of the active component in catalyst is 10-40%.
The active component noble metal is supported in the form of nano-particle in composite nano fiber surface, and the noble metal is received
The grain size of rice corpuscles is 1-5nm.
The preparation method of the composite nano fiber elctro-catalyst, includes the following steps,
1) preparation of electrostatic spinning solution：Prepared polymer solution adds in the metal oxygen in resulting polymers solution
The precursor salt of compound obtains electrostatic spinning solution after mixing；
2) preparation of metal oxide nanofibres：Step 1) the electrostatic spinning solution is placed in electrospinning device
It carries out spinning and obtains metal oxide-polymer nanofiber precursor；By metal oxide-polymer nanofiber precursor in air
Or carrying out heat treatment under certain temperature in oxygen atmosphere makes polymer decompose to obtain metal oxide nanofibres, the certain temperature
Decomposition temperature for the polymer；
3) preparation of composite nano fiber；Metal oxide nanofibres obtained by step 2) are scattered in dilute acid soln and are obtained
Dispersion liquid, sequentially add conducting polymer monomer solution in gained dispersion liquid and oxidant be placed on 0-4 DEG C under the conditions of react,
Wash dry metal oxide-conducting polymer composite nano fiber；
4) preparation for the catalyst that composite nano fiber supports：Metal oxide-conducting polymer obtained by step 3) is multiple
Nanofiber dispersion is closed in ethylene glycol and adds in noble metal precursor body salt and obtains catalyst precarsor mixed liquor, adjusting solution ph is
12~14, and react 1-5h at 100~150 DEG C；It is 3~5 to cool down and adjust solution ph, filtered successively, washing, vacuum
The catalyst that dry composite nano fiber supports；The noble metal precursor body salt for chloroplatinic acid, acetylacetone,2,4-pentanedione platinum, ruthenic chloride,
One or more of iridium chloride, palladium bichloride, gold chloride.
The preparation method of another composite nano fiber elctro-catalyst, includes the following steps,
1) preparation of electrostatic spinning solution：Prepared polymer solution adds in the metal oxygen in resulting polymers solution
The precursor salt of compound obtains electrostatic spinning solution after mixing；
2) preparation of metal oxide nanofibres：Step 1) the electrostatic spinning solution is placed in electrospinning device
It carries out spinning and obtains metal oxide-polymer nanofiber precursor；By metal oxide-polymer nanofiber precursor in air
Or carrying out heat treatment under certain temperature in oxygen atmosphere makes polymer decompose to obtain metal oxide nanofibres, the certain temperature
Decomposition temperature for the polymer；
3) preparation for the catalyst that composite nano fiber supports；Metal oxide nanofibres obtained by step 2) are scattered in
Dispersion liquid is obtained in dilute acid soln, conducting polymer monomer solution is sequentially added in gained dispersion liquid and noble metal precursor body salt is molten
It after liquid, is reacted under the conditions of being placed in 10-40 DEG C, the catalyst that dry the composite nano fiber of washing supports.
Above two is prepared in the method for the catalyst that composite nano fiber supports,
Polymer solution described in step 1) is polyacrylonitrile or is polyvinylpyrrolidone, when polymer is polyacrylonitrile
Solvent can be DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N,N-dimethylformamide, one kind in dimethyl sulfoxide (DMSO) or
It is two or more；Solvent can be ethyl alcohol, DMAC N,N' dimethyl acetamide, N- crassitudes when polymer is polyvinylpyrrolidone
One or more of ketone, N,N-dimethylformamide, dimethyl sulfoxide (DMSO)；The quality of polymer in the polymer solution
Score is 5-20%；The precursor salt of the metal oxide is butyl titanate, one kind in cerous nitrate, ruthenic chloride, stannic chloride
Or two or more mixture；The mass fraction of metal oxide precursor salt is 5-20% in spinning solution；
The condition of the step 2) electrostatic spinning is that the charging rate of electrostatic spinning solution is 0.03-1.0mm/min, electrostatic
The operating voltage of spinning is 10-30kV, and the distance of spinning syringe needle and receiving part is 5-15cm；The polymer decomposition temperature is
200-380℃；
Step 3) the dilute acid soln is hydrochloric acid, sulfuric acid, phosphoric acid, one or more of perchloric acid, a concentration of
0.5-2mol/L；The conducting polymer monomer solution is one or more kinds of in aniline, pyrroles, thenoic acid；The oxidation
Agent is that the molar ratio of a kind of monomer and oxidant in ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, iron chloride is 1:1-3.
The present invention in view of the deficiencies of the prior art, has invented a kind of metal oxide and conducting polymer composite Nano is fine
Dimension, and thereby invented the catalyst using the composite nano fiber as carrier.The catalyst is urged as fuel cell electrode
The shortcomings that carbon carrier is perishable in the prior art and metal oxide carrier electric conductivity is insufficient is overcome during agent.It is in addition, described
Composite fibre combination electrostatic spinning technique and solwution method are prepared, and then further use ethylene glycol by the catalyst that it is supported
Two methods of reduction method and solwution method direct-reduction are prepared, and the method is simply easily achieved, and elctro-catalyst obtained is lived
Property and performance increase.
Description of the drawings
TiO obtained by 1 electrostatic spinning of Fig. 1 embodiments2The electron microscope of nanofiber；
The electron microscope of elctro-catalyst prepared by Fig. 2 embodiments 1；
The electron microscope of elctro-catalyst prepared by Fig. 3 embodiments 2；
The XRF characterizations of elctro-catalyst prepared by Fig. 4 embodiments 2.
Specific embodiment
The preparation of metal oxide-conducting polymer-Pt elctro-catalysts prepared by the present invention：First, method of electrostatic spinning
Prepare metal-oxide fiber substrate；Then conducting polymer and Pt are introduced there are two types of mode：One kind is in metal oxide table
Face deposits conducting polymer, and subsequent spent glycol solution reduction obtains Pt；Another kind is to introduce conducting polymer modified metal
Pt precursors salt is reduced to Pt while oxide fibre surface.
The present invention is implemented, but the present invention is not limited to detailed description below using scheme in detail below.
Embodiment 1
It weighs 1g polyvinylpyrrolidone to be dissolved in 10g ethyl alcohol, then adds in 3g acetic acid, then add 1.5g titaniums
Acid butyl ester obtains light yellow clear spinning solution after stirring 1h, is moved into syringe after standing and defoaming, be then attached to Static Spinning
On the workbench of silk, workbench is 10cm apart from the distance of idler wheel or stainless steel flat plate, and the charging rate of spinning solution is
0.04mm/min applies the operating voltage of 20kV, aluminium-foil paper is fixed on idler wheel to collect fiber, idler wheel rotary speed is
120rpm.Finally fiber from aluminium-foil paper is removed, 600 DEG C of calcining 4h in Muffle furnace is put into and obtains titanium oxide (TiO2) Nanowire
Dimension.Fig. 1 is gained TiO2The electron microscope of nanofiber.
Metal-oxide fiber prepared by above-mentioned method of electrostatic spinning is immersed in the dilute hydrochloric acid solution of 1M, then thereto
It the acid solution of aniline is added in, then adds the acid solution of oxidant ammonium persulfate, wherein the substance of aniline and ammonium persulfate
The ratio between amount is 1：1, two solution are put into after quickly mixing in refrigerator to react for 24 hours at 4 DEG C, is subsequently washed with water products therefrom removing
Acid is to neutrality, and dry 12h removes moisture at 80 DEG C in vacuum drying oven, finally obtains TiO2- PANI composite fibres.
Then, by the TiO of 60mg2- PANI composite nano fibers are distributed in the ethylene glycol solution of 100mL, are then added in
Chloroplatinic acid/ethylene glycol solution (7.5mgPt/mL) of 3mL, and it is 13, then 130 to adjust pH value with sodium hydroxide ethylene glycol solution
3h is stirred to react at DEG C, is cooled down, it is 4 to adjust pH with hydrochloric acid solution, continues after stirring 1h, is down to room temperature, filter, washs, dry,
Obtain TiO2- PANI-Pt elctro-catalysts.Fig. 2 is the electron microscope of last gained elctro-catalyst.
Embodiment 2
TiO is first obtained using the method electrostatic spinning identical with embodiment 12Then nanofiber weighs 100mg TiO2Fiber
It is distributed in the perchloric acid solution of 1M, adding 5mL aniline monomers solution, (aniline monomer is dissolved in perchloric acid, 0.05mol/
L), stir, then add the chloroplatinic acid (5mg chloroplatinic acids are dissolved in 50mg water) of 5mL, lower reaction is finally stirred at room temperature for 24 hours.With
After products therefrom is washed with water to neutrality, and dry 12h removes moisture at 80 DEG C in vacuum drying oven.Gained TiO2-PANI-Pt
Pattern projection electron microscope as shown in Figure 3, Pt nano particles are evenly distributed in carrier surface.It is urged for further characterization gained
Agent carries out x-ray fluorescence analysis, as shown in figure 4, proving the presence of surface Pt.
Comparative example
It weighs 60mg TiO2 nano particles to be distributed in the ethylene glycol solution of 100mL, using the second identical with embodiment 1
Glycol reduction method introduces Pt nano particles in TiO2 nano grain surfaces and prepares TiO2-Pt catalyst.
The conductivity of electro-catalyst carrier is tested with four probe method, wherein, the conductivity of TiO2 nano particles<10-11S/
Cm, and the conductivity of the TiO2-PANI nano fibre carriers of embodiment 1 is 0.16S/cm.In addition, it is tested using cyclic voltammetry
The electrochemistry specific surface area (ECSA) of catalyst, the ECSA of TiO2-Pt nanoparticle catalysts prepared by conventional method are about
18m2g-1Pt, the ECSA of elctro-catalyst prepared by embodiment 1 are about 44m2g-1Pt, the elctro-catalyst prepared by embodiment 2
ECSA is about 56m2g-1Pt.On the one hand the raising of elctro-catalyst performance prepared by the present invention is carrying due to carrier conductivity
On the other hand height is since conducting polymer modified TiO2 nano-carriers improve the dispersion of Pt.
Claims (10)
1. a kind of composite nano fiber, it is characterised in that：The composite nano fiber has the gold of conducting polymer for surface deposition
Belong to oxide nanofiber, the microcosmic composite nano fiber is above nanofiber interwoven mesh structure, the nanofiber
A diameter of 50-500nm；The mass content of metal oxide is 50-90% in the composite nano fiber.
2. composite nano fiber as described in claim 1, it is characterised in that：The conducting polymer is polyaniline, polypyrrole, is gathered
One or more of thiophene；The metal oxide is TiO2、CeO2、RuO2、SnO2One or more of
Mixture.
3. a kind of preparation method of composite nano fiber as claimed in claim 1 or 2, it is characterised in that：Include the following steps,
1) preparation of electrostatic spinning solution：Prepared polymer solution adds in the metal oxide in resulting polymers solution
Precursor salt after mixing electrostatic spinning solution；
2) preparation of metal oxide nanofibres：Step 1) the electrostatic spinning solution is placed in electrospinning device and is carried out
Spinning obtains metal oxide-polymer nanofiber precursor；By metal oxide-polymer nanofiber precursor in air and/
Or carrying out heat treatment under certain temperature in oxygen atmosphere makes polymer decompose to obtain metal oxide nanofibres, the certain temperature
Decomposition temperature for the polymer；
3) preparation of composite nano fiber；Metal oxide nanofibres obtained by step 2) are scattered in dilute acid soln and must disperseed
Liquid, sequentially add conducting polymer monomer solution in gained dispersion liquid and oxidant be placed on 0-4 DEG C under the conditions of react, react
After wash dry composite nano fiber.
4. the preparation method of composite nano fiber as claimed in claim 3, it is characterised in that：
Polymer described in step 1) is polyacrylonitrile solution or polyvinylpyrrolidone, and solvent can when polymer is polyacrylonitrile
For one or both of DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide (DMSO) with
On；Solvent can be ethyl alcohol, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N when polymer is polyvinylpyrrolidone, N-
One or more of dimethylformamide, dimethyl sulfoxide (DMSO)；The mass fraction of polymer is in the polymer solution
5-20%；The precursor salt of the metal oxide is butyl titanate, solvent is ethyl alcohol, DMAC N,N' dimethyl acetamide, N- methyl
One or more of pyrrolidones, N,N-dimethylformamide, dimethyl sulfoxide (DMSO)；In spinning solution before metal oxide
The mass fraction for driving body salt is 5-20%；
The condition of the step 2) electrostatic spinning is that the charging rate of electrostatic spinning solution is 0.03-1.0mm/min, electrostatic spinning
Operating voltage for 10-30kV, the distance of spinning syringe needle and receiving part is 5-15cm；The polymer decomposition starting temperature is
200-380℃；
Step 3) the dilute acid soln is hydrochloric acid, sulfuric acid, phosphoric acid, one or more of perchloric acid, a concentration of 0.5-
2mol/L；The conducting polymer monomer is one or more of aniline, pyrroles, thenoic acid；The oxidant was
One kind in ammonium sulfate, potassium peroxydisulfate, hydrogen peroxide, iron chloride；The molar ratio of monomer and oxidant is 1:1-3.
5. a kind of catalyst supported with composite nano fiber described in claims 1 or 2, it is characterised in that：The composite Nano
The active component for the catalyst that fiber supports is precious metals pt, one or more of Pd, Ru, Au, Ph, the activearm
The mass content divided in catalyst is 10-40%.
6. the catalyst that composite nano fiber as claimed in claim 5 supports, it is characterised in that：The active component noble metal with
The form of nano-particle is supported in composite nano fiber surface, and the grain size of the noble metal nano particles is 1-5nm.
7. a kind of preparation method of the composite nano fiber elctro-catalyst of claim 5 or 6, it is characterised in that：Including following
Step,
1) preparation of electrostatic spinning solution：Prepared polymer solution adds in the metal oxide in resulting polymers solution
Precursor salt after mixing electrostatic spinning solution；
2) preparation of metal oxide nanofibres：Step 1) the electrostatic spinning solution is placed in electrospinning device and is carried out
Spinning obtains metal oxide-polymer nanofiber precursor；By metal oxide-polymer nanofiber precursor in air and/
Or carrying out heat treatment under certain temperature in oxygen atmosphere makes polymer decompose to obtain metal oxide nanofibres, the certain temperature
Decomposition temperature for the polymer；
3) preparation of composite nano fiber；Metal oxide nanofibres obtained by step 2) are scattered in dilute acid soln and must disperseed
Liquid, sequentially add conducting polymer monomer solution in gained dispersion liquid and oxidant be placed on 0-4 DEG C under the conditions of react, wash
Dry metal oxide-conducting polymer composite nano fiber；
4) preparation for the catalyst that composite nano fiber supports：It receives metal oxide-conducting polymer is compound obtained by step 3)
Rice fiber, which is scattered in ethylene glycol and adds in noble metal precursor body salt, obtains catalyst precarsor mixed liquor, adjust solution ph for 12~
14, and react 1-5h at 100~150 DEG C；It is 3~5 to cool down and adjust solution ph, filtered successively, washing, vacuum drying
Obtain the catalyst that composite nano fiber supports；The noble metal precursor body salt is chloroplatinic acid, acetylacetone,2,4-pentanedione platinum, ruthenic chloride, chlorination
One or more of iridium, palladium bichloride, gold chloride.
8. the preparation method of another claim 5 or 6 composite nano fiber elctro-catalyst, it is characterised in that：Including with
Lower step,
1) preparation of electrostatic spinning solution：Prepared polymer solution adds in the metal oxide in resulting polymers solution
Precursor salt after mixing electrostatic spinning solution；
2) preparation of metal oxide nanofibres：Step 1) the electrostatic spinning solution is placed in electrospinning device and is carried out
Spinning obtains metal oxide-polymer nanofiber precursor；By metal oxide-polymer nanofiber precursor in air and/
Or carrying out heat treatment under certain temperature in oxygen atmosphere makes polymer decompose to obtain metal oxide nanofibres, the certain temperature
Decomposition temperature for the polymer；
3) preparation for the catalyst that composite nano fiber supports；Metal oxide nanofibres obtained by step 2) are scattered in diluted acid
Dispersion liquid is obtained in solution, conducting polymer monomer solution and noble metal precursor body salting liquid are sequentially added in gained dispersion liquid
Afterwards, it is reacted under the conditions of being placed in 10-40 DEG C, the catalyst that dry the composite nano fiber of washing supports.
9. the preparation method of composite nano fiber elctro-catalyst as described in claim 7 or 8, it is characterised in that：
Polymer solution described in step 1) is polyacrylonitrile or is polyvinylpyrrolidone, solvent when polymer is polyacrylonitrile
Can be one or both of DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide (DMSO)
More than；Solvent can be ethyl alcohol, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N when polymer is polyvinylpyrrolidone,
One or more of dinethylformamide, dimethyl sulfoxide (DMSO)；The mass fraction of polymer in the polymer solution
For 5-20%；The precursor salt of the metal oxide is butyl titanate, cerous nitrate, ruthenic chloride, one kind in stannic chloride or two
Kind or more mixture；The mass fraction of metal oxide precursor salt is 5-20% in spinning solution；
The condition of the step 2) electrostatic spinning is that the charging rate of electrostatic spinning solution is 0.03-1.0mm/min, electrostatic spinning
Operating voltage for 10-30kV, the distance of spinning syringe needle and receiving part is 5-15cm；The polymer decomposition temperature is 200-
380℃；
Step 3) the dilute acid soln is hydrochloric acid, sulfuric acid, one or more of phosphoric acid, perchloric acid, a concentration of 0.5-
2mol/L；The conducting polymer monomer solution is one or more kinds of in aniline, pyrroles, thenoic acid；The oxidant is
One kind in ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, iron chloride；The molar ratio of monomer and oxidant is 1:1-3.
10. a kind of application of catalyst that composite nano fiber of claim 5 or 6 supports, it is characterised in that：The catalysis
Agent is fuel-cell catalyst.
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| CN108914249A (en) * | 2018-06-26 | 2018-11-30 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of fluorine-doped tin oxide fiber |
| CN110424063A (en) * | 2019-08-25 | 2019-11-08 | 天津大学 | A kind of preparation method of the chemical fibre in the atom level site of constant temperature catalyzing foul gas |
| CN111560665A (en) * | 2020-04-24 | 2020-08-21 | 中国科学院化学研究所 | Pt-loaded B and N co-doped In2O3/TiO2Nano fiber and preparation method and application thereof |
| CN112853751A (en) * | 2021-01-14 | 2021-05-28 | 天津大学 | Phenanthroline palladium functionalized fiber and preparation method and application thereof |
| CN113413894A (en) * | 2021-06-24 | 2021-09-21 | 兰州交通大学 | Preparation method of zinc ferrite electrostatic spinning membrane with photocatalytic antibacterial performance |
| CN114534797A (en) * | 2022-03-09 | 2022-05-27 | 东南大学 | Continuous flow purification and separation method of nanofiber supported catalyst |
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