CN108160122A - Composite material and composite material are the catalyst of carrier and its preparation and application - Google Patents
Composite material and composite material are the catalyst of carrier and its preparation and application Download PDFInfo
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- CN108160122A CN108160122A CN201611115302.9A CN201611115302A CN108160122A CN 108160122 A CN108160122 A CN 108160122A CN 201611115302 A CN201611115302 A CN 201611115302A CN 108160122 A CN108160122 A CN 108160122A
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- polymer
- electrostatic spinning
- catalyst
- composite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 41
- 239000002121 nanofiber Substances 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 238000009987 spinning Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 229910000510 noble metal Inorganic materials 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 11
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 6
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 6
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 5
- 229940113088 dimethylacetamide Drugs 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002071 nanotube Substances 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000002322 conducting polymer Substances 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 4
- -1 polypropylene Polymers 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 claims 1
- 229910021393 carbon nanotube Inorganic materials 0.000 claims 1
- 239000002041 carbon nanotube Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical class CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 239000000835 fiber Substances 0.000 abstract description 10
- 239000010411 electrocatalyst Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 229910002462 C-Pt Inorganic materials 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000969 carrier Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 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 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- UKKGMDDPINLFIY-UHFFFAOYSA-N [C+4].[O-2].[Ti+4].[O-2].[O-2].[O-2] Chemical compound [C+4].[O-2].[Ti+4].[O-2].[O-2].[O-2] UKKGMDDPINLFIY-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 1
- FSDZFKWCTBMYDV-UHFFFAOYSA-N platinum;propan-2-one Chemical compound [Pt].CC(C)=O FSDZFKWCTBMYDV-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- JTTXECQCCPZGII-UHFFFAOYSA-M sodium;ethane-1,2-diol;hydroxide Chemical compound [OH-].[Na+].OCCO JTTXECQCCPZGII-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/58—
-
- B01J35/60—
-
- 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
-
- 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
Abstract
It is the catalyst of carrier and its preparation and application the present invention relates to a kind of composite material and composite material, specifically based on electrostatic spinning technique and solwution method, prepares based on metal conductive oxide Material cladding fiber/MO2C and using its elctro-catalyst N/MO as carrier2‑C.Its electro-catalyst carrier/MO2C is metal conductive oxide carbon material composite fibre, catalyst carrier can be distributed in solution then reduction method introducing Pt catalyst granules by being introduced into for catalyst Pt, it can also be by adding Pt salt precursors in spinning solution, then one-step method prepares Pt base elctro-catalysts.The present invention passes through the addition of conductive carbon material and a step low-temperature treatment of later stage polymer nanofiber, both the loose and porous structure of prepared carrier had been ensure that, it ensure that carbon material in the electric conductivity of carrier and the stability of structure simultaneously, in addition the step low-temperature treatment under air or oxygen atmosphere both ensure that the oxidation of metal precursor salt, while ensure that the decomposition of polymer precursor and being stabilized for carbon material.
Description
Technical field
The present invention relates to field of fuel cell technology, more particularly to a kind of composite material and the catalysis that composite material is carrier
Agent and its preparation and application.
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.Studies have reported that using doping novel carriers such as SiC, TiO2, CeO2Deng and C hydridization
As carrier to improve the electro catalytic activity and stability of Pt base catalyst.Numerous studies show Pt/TiO2- C has than Pt/C
Higher electro catalytic activity and more preferably stability.Qing Lv et al. are by TiO2After nano particle is mixed with carbon black ultrasonic disperse,
It immerses in the ethylene glycol solution of chloroplatinic acid, Pt/TiO is prepared by ultrasonic radiation2- C elctro-catalysts, relative to Pt/C electro-catalysis
Agent, activity and stability improve (J.Power Sources, 2012,218:93), but the carrier of Nanoparticulate, electric conductivity
It is poor, and specific surface area is smaller.Then, Xu-Le i Sui et al. use TiO2The mixed system of nanotube (TNTs) and carbon dust
Pt/C-TNTs elctro-catalysts are prepared, further improved stability active (J.Power Sources, 2014,255:43.),
But preparation method is more complicated, needs first by the degreasing of Ti foils, the anodization by two electrode systems, then roasted through high temperature
Burning obtains TNTs, then TNTs and carbon black ultrasonic disperse, then introduce Pt by microwave radiation in the Pt salting liquids of ethylene glycol.
Invention content
The present invention develops a kind of microcosmic upper with the loose of nanofiber intertexture for problems of the prior art
The MO of porous structure2The method of C composite (wherein M is one or both of Ti, Ce, Ru, Sn) and its electrostatic spinning
It prepares.N/MO prepared by the present invention2- C elctro-catalysts are microcosmic upper with 1-dimention nano fibre structure, and the nanofiber interweaves
Into loose and porous structure, which is provided with larger specific surface area, improves the specific activity of elctro-catalyst, and reticular structure promotes
Mass transfer, relatively low radius of curvature are conducive to improve the stability of catalyst.
A kind of MO2C composite, the MO2M is one or more of for Ti, Ce, Ru, Sn in C composite,
The MO2The microcosmic upper loose and porous structure to interweave for nanofiber of C composite, a diameter of 50- of the nanofiber
500nm, porosity are more than 70%.
The MO2The preparation method of C composite, includes the following steps,
1) preparation of electrostatic spinning solution：The dispersion liquid of prepared polymer solution and conductive carbon material, and mix the two
It is uniform to obtain mixed liquor, the precursor salt of metal M is added in gained mixed liquor and obtains electrostatic spinning solution after mixing again,
The M is one or both of Ti, Ce, Ru, Sn；
2) electrostatic spinning prepares the polymer nanofiber of doping：Step 1) the electrostatic spinning solution is placed in Static Spinning
The polymer nanofiber precursor that spinning must be adulterated is carried out in silk equipment；
3)MO2The preparation of C composite；By the polymer nanofiber precursor adulterated obtained by step 2) in air and/or
It carries out being heat-treated to obtain MO under certain temperature in oxygen atmosphere2C composite, the certain temperature start to decompose temperature for polymer
More than degree and to start below oxidation of coal temperature.
Polymer described in step 1) is polyacrylonitrile 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 quality of conducting polymer point in the polymer solution
Number is 5-20%；In the dispersion liquid of the conductive carbon material, solvent is n,N-dimethylacetamide, N-Methyl pyrrolidone, N,
One or more of dinethylformamide, dimethyl sulfoxide (DMSO)；Conductive carbon material is carbon black, carbon fiber, activated carbon, carbon
The mixture of one or more of nanotube, carbon nano-fiber, carbosphere or graphite powder；The conductive carbon material in point
Mass fraction in dispersion liquid is 1-5%；The precursor salt of the M is one in butyl titanate, cerous nitrate, ruthenic chloride, stannic chloride
Kind or two or more mixtures.
The mass ratio of polymer and conductive carbon material is 10 in step 1) electrostatic spinning solution:1-1:1；Conductive carbon material with
The ratio of the amount of the substance of metal M is 0.2:1-1:1.
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.
Step 3) the polymer decomposition starting temperature is 200-380 DEG C；It is 450 DEG C to start oxidation of coal temperature.
One kind is with MO2C composite is catalyst n/MO of carrier2- C, in the catalyst N be precious metals pt, Pd,
One or more of Ru, Au, Ph, noble metal N quality carrying capacity in catalyst is 10-40%；M for Ti, Ce,
One or more of Ru, Sn；The MO2The microcosmic upper loose and porous structure to interweave for nanofiber of C composite,
A diameter of 50-500nm of the nanofiber.
Catalyst n/the MO2The preparation method of-C, including foregoing MO2The preparation of C composite and following step
Suddenly：
By gained MO2C composite, which is scattered in ethylene glycol and adds in the precursor salt of noble metal N, obtains catalyst precarsor
Mixed liquor, it is 12~14 to adjust solution ph, and reacts 1-5h at 100~150 DEG C；Cool down and adjust solution ph for 3~
5, it is filtered successively, wash, be dried in vacuo to obtain catalyst n/MO2-C；The precursor salt of the noble metal N is chloroplatinic acid, acetyl
One or more of acetone platinum, ruthenic chloride, iridium chloride, palladium bichloride, gold chloride.
Another catalyst n/the MO2The preparation method of-C, includes the following steps：
1) preparation of electrostatic spinning solution：The dispersion liquid of prepared polymer solution and conductive carbon material, and mix the two
It is uniform to obtain mixed liquor, the precursor salt of metal M and the precursor salt of noble metal N are added in gained mixed liquor, and mix again
Electrostatic spinning solution is obtained after uniformly；The M is one or more of Ti, Ce, Ru, Sn；The forerunner that the noble metal N is
Body salt is one or more of chloroplatinic acid, acetylacetone,2,4-pentanedione platinum, ruthenic chloride, iridium chloride, palladium bichloride, gold chloride；
Step 2) and step 3) MO as described above2The preparation method of C composite.
Catalyst n/the MO2In the preparation method of-C, the precursor salt of the noble metal N is chloroplatinic acid, acetylacetone,2,4-pentanedione
One or more of platinum, ruthenic chloride, iridium chloride, palladium bichloride, gold chloride；The addition of the precursor salt of the noble metal N
The ratio of amount and the amount of substance of the precursor salt of M in electrostatic spinning solution is 0.05:1-0.3:1.
The present invention is based on electrostatic spinning technique and solwution method, prepare based on metal oxide-conductive material composite fibre/
MO2- C and using its elctro-catalyst N/MO as carrier2-C.Its electro-catalyst carrier/MO2- C is metal oxide-conductive carbon material
Catalyst carrier can be distributed in solution then reduction method introducing Pt catalyst particles by composite fibre, being introduced into for catalyst Pt
Grain, can also be by adding Pt salt precursors in spinning solution, and then one-step method prepares Pt base elctro-catalysts.The present invention is by leading
The addition of electrical carbon material and a step low-temperature treatment of later stage polymer nanofiber, both ensure that the loose of prepared carrier
Porous structure, while carbon material is ensure that in the electric conductivity of carrier and the stability of structure, in addition under air or oxygen atmosphere
One step low-temperature treatment both ensure that the oxidation of Ti, Ce, Ru, Sn precursor salt, while ensure that decomposition and the carbon of polymer precursor
Material is stabilized.Preparation method simple and flexible proposed by the invention, MO2The loose porous nano fibre carriers of-C, which are used as, urges
Agent carrier is conducive to improve the specific surface area of catalyst, and then improves the activity and stability of catalyst, improves simultaneously
Using its mass-transfer performance as electrode catalyst.
Description of the drawings
TiO prepared by Fig. 1 embodiments 12The electron microscope of-C composite nano fibers；
TiO prepared by Fig. 2 embodiments 12The electron microscope of-C-Pt elctro-catalysts；
TiO prepared by Fig. 3 embodiments 12- C and TiO2The XRD characterization of-C-Pt fibers；
TiO prepared by Fig. 4 embodiments 22The XRF characterizations of-C-Pt elctro-catalysts；
TiO obtained by electrostatic spinning in Fig. 5 comparative examples2The electron microscope of nanofiber.
Specific embodiment
Embodiment 1：
It weighs in 0.2g carbon dusts (XC-72R carbon dusts) ultrasonic disperse to 8g ethyl alcohol, is then added to polyvinylpyrrolidone
In ethanol solution (polyvinylpyrrolidone content is 7.4wt.%), stirred in ultrasound, then add in 2g acetic acid, then again
1g butyl titanates are added in, black spinning solution is obtained after stirring 2h, is moved into syringe after standing and defoaming, be then attached to electrostatic
On the workbench of spinning, workbench is 10cm apart from the distance of idler wheel or stainless steel flat plate, and the charging rate of spinning solution is
0.02mm/min applies the operating voltage of 20kV, aluminium-foil paper is fixed on idler wheel to collect fiber, idler wheel rotary speed is
120rpm or 100~300rpm.Finally fiber from aluminium-foil paper is removed, 400 DEG C of calcining 4h in Muffle furnace is put into and obtains
Titanium oxide-carbon (TiO2- C) nanofiber.Fig. 1 is prepared TiO2The electron microscope of-C.
Then, the TiO of 60mg is weighed2C nano fiber is distributed in the ethylene glycol solution of 50mL, then adds in 5.3mL's
Chloroplatinic acid/ethylene glycol solution (7.5mgPt/mL), and it is 13 to adjust pH value with sodium hydroxide ethylene glycol solution, then at 130 DEG C
3h is stirred to react, 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, is obtained
TiO2- C-Pt elctro-catalysts.Fig. 2 show gained TiO2The electron microscope of-C-Pt elctro-catalysts.Fig. 3 is prepared TiO2- C and
TiO2The XRD spectra of-C-Pt.
Embodiment 2：
TiO is prepared using electrostatic spinning one-step method2- C-Pt elctro-catalysts：Weigh 0.2g carbon dusts (XC-72R carbon dusts) ultrasound
It is distributed in 10g ethyl alcohol, is then added in polyvinylpyrrolidone ethanol solution that (polyvinylpyrrolidone content is
10wt.%), it is stirred in ultrasound, then adds in 2g acetic acid, then add 1g butyl titanates, after stirring 2h, then again will
The chloroplatinic acid ethanol solution (platinum acid chloride solution concentration 0.15g/mL) of 0.15g is added drop-wise in above-mentioned dark solution, finally obtains spinning
Silk solution.Then, it will be moved into syringe after spinning solution standing and defoaming and carry out electrostatic spinning, with embodiment 1, finally by gained
Fiber is put into 350 DEG C of roasting 2h in Muffle furnace, and Ti salt and Pt salt are separately disassembled into TiO while polymer decomposes2And Pt, finally
Obtain TiO2- C-Pt elctro-catalysts.Fig. 4 is that the XRF of gained pile catalyst is characterized, and shows to succeed using this one-step method
Introduce Pt.
Comparative example：
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, electrostatic spinning is carried out with embodiment 1, finally fiber from aluminium-foil paper is removed, is put into Muffle furnace 600 DEG C
Calcining 4h obtains titanium oxide (TiO2) nanofiber.Fig. 5 is gained TiO2The electron microscope of nanofiber.Compare TiO2And TiO2-C
Nanofiber electron microscope, in spinning solution after addition conductive carbon material, gained TiO2Fiber C is more loose porous, and TiO2Fiber
It is dense.
The conductivity of electro-catalyst carrier is tested with four probe method, wherein, the conductivity of TiO2 nanofibers in comparative example<
10-10S/cm, and the conductivity of the TiO2-C nano fibre carriers of embodiment 1 is 2.84S/cm.In addition, using cyclic voltammetry
The electrochemistry specific surface area (ECSA) of catalyst is tested, the ECSA of TiO2-Pt catalyst prepared by comparative example is about 22m2g-
1Pt, the ECSA of the TiO2-C-Pt elctro-catalysts prepared by embodiment 1 is about 90m2g-1Pt, the TiO2- prepared by embodiment 2
The ECSA of C-Pt elctro-catalysts is about 82m2g-1Pt.The raising of elctro-catalyst performance prepared by the present invention be on the one hand due to
The doping of carbon black improves the electric conductivity of carrier, is on the other hand since the carrier of loose and porous structure improves the dispersion of Pt.
Claims (10)
1. a kind of composite material, it is characterised in that：The composite material is MO2C composite, MO2M is in C composite
One or more of Ti, Ce, Ru, Sn, the MO2The microcosmic upper porous knot to interweave for nanofiber of C composite
Structure, a diameter of 50-500nm of the nanofiber.
2. a kind of preparation method of composite material described in claim 1, it is characterised in that：Include the following steps,
1) preparation of electrostatic spinning solution：The dispersion liquid of prepared polymer solution and conductive carbon material, and it is uniformly mixed the two
Mixed liquor is obtained, the precursor salt of metal M is added in gained mixed liquor and obtains electrostatic spinning solution after mixing again, it is described
M is one or more of Ti, Ce, Ru, Sn；
2) electrostatic spinning prepares the polymer nanofiber of doping：Step 1) the electrostatic spinning solution is placed in electrostatic spinning to set
The polymer nanofiber precursor that standby middle progress spinning must be adulterated；
3)MO2The preparation of C composite；By the polymer nanofiber precursor adulterated obtained by step 2) in air and/or oxygen
It carries out being heat-treated to obtain MO under certain temperature in atmosphere2C composite, the certain temperature for polymer decomposition starting temperature with
Temperature upper and to start below oxidation of coal temperature.
3. the preparation method of composite material as claimed in claim 2, it is characterised in that：Polymer described in step 1) is polypropylene
Nitrile or polyvinylpyrrolidone；When polymer is polyacrylonitrile solvent can be DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone,
One or more of N,N-dimethylformamide, dimethyl sulfoxide (DMSO)；Solvent can when polymer is polyvinylpyrrolidone
For one kind in ethyl alcohol, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide (DMSO) or
It is two or more；The mass fraction of polymer is 5-20% in the polymer solution；
In the dispersion liquid of the conductive carbon material, solvent is n,N-dimethylacetamide, N-Methyl pyrrolidone, N, N- dimethyl
One or more of formamide, dimethyl sulfoxide (DMSO)；Conductive carbon material for carbon black, carbon fiber, activated carbon, carbon nanotube,
The mixture of one or more of carbon nano-fiber, carbosphere or graphite powder；The conductive carbon material is in dispersion liquid
Mass fraction be 1-5%；
The precursor salt of the M is the mixture of one or more of butyl titanate, cerous nitrate, ruthenic chloride, stannic chloride.
4. the preparation method of composite material as claimed in claim 2, it is characterised in that：Polymer in step 1) electrostatic spinning solution
Mass ratio with conductive carbon material is 10:1-1:1；Conductive carbon material and the ratio of the amount of the substance of metal M are 0.2:1-1:1.
5. the preparation method of composite material as claimed in claim 2, it is characterised in that：The condition of the step 2) electrostatic spinning is
The charging rate of electrostatic spinning solution is 0.03-1.0mm/min, and the operating voltage of electrostatic spinning is 10~30kV, spinning syringe needle
Distance with receiving part is 5~15cm；
Step 3) the polymer decomposition starting temperature is 200-380 DEG C；It is 450 DEG C to start oxidation of coal temperature.
It is 6. a kind of using composite material as the catalyst of carrier, it is characterised in that：Catalyst n/the MO2In-C N for precious metals pt,
One or more of Pd, Ru, Au, Ph, noble metal N quality carrying capacity in catalyst is 10-40%；M for Ti,
One or more of Ce, Ru, Sn；The MO2The microcosmic upper porous structure to interweave for nanofiber of C composite, institute
State a diameter of 50-500nm of nanofiber.
7. a kind of catalyst n/MO described in claim 62The preparation method of-C, it is characterised in that：Include the following steps,
1) preparation of electrostatic spinning solution：The dispersion liquid of prepared polymer solution and conductive carbon material, and it is uniformly mixed the two
Mixed liquor is obtained, the precursor salt of metal M is added in gained mixed liquor and obtains electrostatic spinning solution after mixing again, it is described
M is one or more of Ti, Ce, Ru, Sn；
2) electrostatic spinning prepares the polymer nanofiber of doping：Step 1) the electrostatic spinning solution is placed in electrostatic spinning to set
The polymer nanofiber precursor that standby middle progress spinning must be adulterated；
3)MO2The preparation of C composite；By the polymer nanofiber precursor adulterated obtained by step 2) in air and/or oxygen
It carries out being heat-treated to obtain MO under certain temperature in atmosphere2C composite, the certain temperature for polymer decomposition starting temperature with
Above and to start below oxidation of coal temperature；
4) by MO obtained by step 3)2C composite be scattered in ethylene glycol and add in noble metal N precursor salt obtain catalyst before
Body mixed liquor, it is 12~14 to adjust solution ph, and reacts 1-5h at 100~150 DEG C；It is 3 to cool down and adjust solution ph
~5, it is filtered successively, wash, be dried in vacuo to obtain catalyst n/MO2-C；The precursor salt of the noble metal N is chloroplatinic acid, second
One or more of acyl acetone platinum, ruthenic chloride, iridium chloride, palladium bichloride, gold chloride.
8. another catalyst n/MO as claimed in claim 62The preparation method of-C, it is characterised in that：Include the following steps,
1) preparation of electrostatic spinning solution：The dispersion liquid of prepared polymer solution and conductive carbon material, and it is uniformly mixed the two
Mixed liquor is obtained, the precursor salt of metal M and the precursor salt of noble metal N are added in gained mixed liquor, and again after mixing
Obtain electrostatic spinning solution；The M is one or more of Ti, Ce, Ru, Sn；The precursor salt of the noble metal N is chlorine
One or more of platinic acid, acetylacetone,2,4-pentanedione platinum, ruthenic chloride, iridium chloride, palladium bichloride, gold chloride；
2) electrostatic spinning prepares the polymer nanofiber of doping：Step 1) the electrostatic spinning solution is placed in electrostatic spinning to set
The polymer nanofiber precursor that standby middle progress spinning must be adulterated；
3)MO2The preparation of C composite；By the polymer nanofiber precursor adulterated obtained by step 2) in air and/or oxygen
It carries out being heat-treated to obtain MO under certain temperature in atmosphere2C composite, the certain temperature for polymer decomposition starting temperature with
Above and to start below oxidation of coal temperature.
9. catalyst n/MO as described in claim 7 or 82The preparation method of-C, it is characterised in that：
Polymer described in step 1) is polyacrylonitrile or polyvinylpyrrolidone, and solvent can be N when polymer is polyacrylonitrile,
One or more of N- dimethylacetylamides, N-Methyl pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide (DMSO)；
Solvent can be ethyl alcohol, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, N when polymer is polyvinylpyrrolidone, N- diformazans
One or more of base formamide, dimethyl sulfoxide (DMSO)；The mass fraction of conducting polymer is in the polymer solution
5-20%；
In the dispersion liquid of conductive carbon material described in step 1), solvent is n,N-dimethylacetamide, N-Methyl pyrrolidone, N,
One or more of dinethylformamide, dimethyl sulfoxide (DMSO), conductive carbon material is carbon black, carbon fiber, activated carbon, carbon
The mixture of one or more of nanotube, carbon nano-fiber, carbosphere or graphite powder；The conductive carbon material in point
Mass fraction in dispersion liquid is 1-5%；
The precursor salt of M described in step 1) is one or more of butyl titanate, cerous nitrate, ruthenic chloride, stannic chloride
Mixture；
The mass ratio of polymer and conductive carbon material is 10 in step 1) electrostatic spinning solution:1-1:1；Conductive carbon material and metal
The ratio of the amount of the substance of M is 0.2:1-1:1；
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；
Step 3) the polymer decomposition starting temperature is 200-380 DEG C；It is 450 DEG C to start carbon decomposition temperature；
The precursor salt of the noble metal N is chloroplatinic acid, in acetylacetone,2,4-pentanedione platinum, ruthenic chloride, iridium chloride, palladium bichloride, gold chloride
It is one or more kinds of；The substance of the precursor salt of M in the addition and electrostatic spinning solution of the precursor salt of the noble metal N
The ratio of amount is 0.05:1-0.3:1.
10. a kind of application of 1 and 6 catalyst of claim, it is characterised in that：The catalyst is fuel cell catalyst
Agent.
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