CN106861733A - Core shell structure TiOx nano piece/SiC nano fiber and preparation method - Google Patents
Core shell structure TiOx nano piece/SiC nano fiber and preparation method Download PDFInfo
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- CN106861733A CN106861733A CN201710077327.2A CN201710077327A CN106861733A CN 106861733 A CN106861733 A CN 106861733A CN 201710077327 A CN201710077327 A CN 201710077327A CN 106861733 A CN106861733 A CN 106861733A
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 122
- 239000011258 core-shell material Substances 0.000 title claims abstract description 60
- 229910003087 TiOx Inorganic materials 0.000 title claims abstract description 47
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 45
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 32
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 25
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 238000010792 warming Methods 0.000 claims abstract description 10
- 238000009987 spinning Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002134 carbon nanofiber Substances 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000010041 electrostatic spinning Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000006722 reduction reaction Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 235000013312 flour Nutrition 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 238000002242 deionisation method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 238000003763 carbonization Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 110
- 229910010271 silicon carbide Inorganic materials 0.000 description 104
- 239000000835 fiber Substances 0.000 description 31
- 239000007789 gas Substances 0.000 description 11
- 229910021426 porous silicon Inorganic materials 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 206010061592 cardiac fibrillation Diseases 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002600 fibrillogenic effect Effects 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical class NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- 239000005510 Diuron Substances 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention provides a kind of core shell structure TiOx nano piece/SiC nano fiber and preparation method, and core shell structure TiOx nano piece/SiC nano fiber is made in accordance with the following methods：(1) in the aqueous isopropanol of diethylenetriamine, appropriate butyl titanate is added, obtains titaniferous hydro-thermal reaction liquid；(2) SiC nano fiber is added in titaniferous hydro-thermal reaction liquid, is sealed, be placed at 160~240 DEG C, be incubated 16~36 hours, be cooled to room temperature, obtain unannealed TiOx nano piece/SiC nano fiber；(3) clean, dry, be warming up to 300~800 DEG C, be incubated 1~5 hour, be cooled to room temperature, obtain core shell structure TiOx nano piece/SiC nano fiber.The inventive method gained TiOx nano piece/SiC nano fiber has hud typed hierarchy, and specific surface area is big, TiO2Thickness and size can be regulated and controled by synthesis condition, there is huge application potential in fields such as photochemical catalyst, gas sensor and light emitting diodes.
Description
Technical field
The present invention relates to nanofiber technology field, a kind of core shell structure TiOx nano piece/carborundum is specifically related to
Nanofiber and preparation method.
Background technology
Carborundum (SiC) as a kind of wide band gap semiconducter, with breakdown electric field high, critical field strength high, high heat conductance, good
The characteristics such as mechanical performance well, high temperature resistant, radioresistance and corrosion-resistant and high carrier migration rate, it goes back and conventional microelectromechanical
System (MEMS) has good compatibility, and maximum operation (service) temperature can reach 1000 DEG C, be a kind of preferable semiconductor function material
Material.
TiO2It is a kind of important n-type semiconductor, becomes with low cost, nontoxic, automatic cleaning action, relative impedances
Change the excellent physicochemical property such as big and environment-friendly.Particularly under the conditions of 800 DEG C of high temperature above, its microcosmic shape can be still kept
State and chemical constitution do not change, and are with a wide range of applications in fields such as gas sensing, photocatalysis and solar cells.But it is pure
Nano-TiO2There is bad dispersibility in application process, the problem easily reunited, only part TiO2Avtive spot can obtain
To apply, nano-TiO is greatly reduced2Performance.TiO with three-dimensional core shell structure2Avtive spot can be fully exposed to
Plane of crystal, makes reactant and TiO2Can sufficiently and quickly contact, improve reaction rate, thus be greatly improved TiO2Performance.
By active TiO2Nanometer sheet is carried on SiC nanofibers, not only can effectively prevent nano-TiO2Reunion, make
Nano-TiO2It is able to effectively disperse, while TiO2Hetero-junctions can also be formed with SiC, the synergy of hetero-junctions is played, improves fine
The performance of dimension.In recent years, on TiO2The research of/SiC compounds is also increasing, but the TiO for reporting2Mostly particle shape, institute
The SiC for using also is mainly SiC particulate or foamed ceramics, for example, Kouam é etc. (Kouam é A N, Masson R, Robert D,
et al.β-SiC foams as a promising structured photocatalytic support for water
and air detoxification[J].Catalysis Today,2013,209:13~20.) by SiC foam cerdip
In TiO2Precursor sol in, be thermally treated resulting in cladding TiO by gel and 450 DEG C of air2The SiC foam pottery of nano thin-film
Porcelain, gained TiO2/ SiC composite ceramicses can be with the diuron agricultural chemicals of the hypertoxicity in photocatalytic degradation water body；Yamashita etc.
(Yamashita H,Nishida Y,Yuan S,et al.Design of TiO2-SiC photocatalyst using
TiC-SiC nanoparticles for degradation of2-propanol diluted in water[J]
.Catalysis Today,2007,120(2):163~167.) first pass through carbon thermal reduction TiO2/SiO2Particle obtains TiC/SiC,
Then graininess TiO is thermally treated resulting in atmosphere2/ SiC hetero-junctions catalyst, catalyst table in catalytic degradation 2- propyl alcohol
Reveal catalyst activity high；(Hao D, Yang Z, Jiang C, the et al.Photocatalytic effect of such as Hao
TiO2coatings and p-type semiconductiveSiC foam supports for degradation of
organic contaminant[J].Applied Catalysis B:Environmental,2014,144(1):196~
202.) porous TiO is prepared for using sol-gel process2/ SiC foam ceramics, the degradation efficiency to 4- aminobenzenesulfonic acids can reach
100%.But the TiO obtained by them2The specific surface area of particle and SiC substrate is smaller, and TiO2Without three-dimensional between SiC
Core shell structure, exposed avtive spot is few, and performance needs further raising.
It is currently used for preparing TiO2Nanometer sheet has document report, or but others is to grow on the carbon nanotubes, or
It is pure TiO2, it is impossible to make TiO2Nanometer sheet grows on SiC nanofibers.
The content of the invention
It is an object of the invention to provide a kind of core shell structure TiOx nano piece/SiC nano fiber and preparation side
Method, it is less that the invention solves preparation-obtained TiOx nano piece/SiC nano fiber core shell structure in the prior art,
Or the technical problem of TiOx nano piece/SiC nano fiber cannot be prepared.
Invention provides a kind of core shell structure TiOx nano piece/SiC nano fiber and preparation method, including following step
Suddenly：
It is with the mass ratio of butyl titanate according to SiC nano fiber by the SiC nano fiber with loose structure
1:Hydrothermal synthesis reaction is carried out in 60~600 addition titaniferous hydro-thermal reaction liquid, core shell structure oxygen is obtained by annealing afterwards
Change titanium nanometer sheet/SiC nano fiber；
Titaniferous hydro-thermal reaction liquid by volume fraction 0.5~2 ‰ diethylenetriamine aqueous isopropanol and butyl titanate, press
The aqueous isopropanol of diethylenetriamine and the volume ratio of butyl titanate are mixed for 1~10%；
Hydrothermal synthesis reaction：SiC nano fiber is added in titaniferous hydro-thermal reaction liquid and is sealed afterwards, 160~240
At DEG C, 16~36 hours are incubated, are subsequently cooled to room temperature, the TiOx nano piece/nanometer silicon carbide for obtaining unannealed treatment is fine
Dimension
Further, the volume fraction of the aqueous isopropanol of diethylenetriamine is 0.6~1.2 ‰.
Further, annealing is comprised the following steps：Clean the TiOx nano piece/nanometer silicon carbide of unannealed treatment
Fiber >=3 time, then dry, and are warming up to 300~800 DEG C, are incubated 1~5 hour, are cooled to room temperature, obtain core shell structure oxidation
Titanium nanometer sheet/SiC nano fiber.
Further, stirred 2~10 minutes when preparing titaniferous hydro-thermal reaction liquid.
Further, cleaning includes first being cleaned with deionized water-alcohol mixeding liquid, then is cleaned with deionized water；Deionization
Water-ethanol mixed liquor is that deionized water and ethanol are by volume 1~5:1 mixes.
Further, SiC nano fiber is obtained according to the following steps：
1) spinning solution is prepared：Carbon nano-fiber precursor polymer is dissolved in solvent to be configured to homogeneous spinning molten
Liquid, concentration of the carbon nano-fiber precursor polymer in homogeneous spinning solution is 5~50wt%；
2) electrostatic spinning：Electrostatic spinning is carried out to homogeneous spinning solution, polymer nanofiber is obtained；
The technological parameter of electrostatic spinning：Shower nozzle used for 0.5~1.5mm of internal diameter metal needle, spinning voltage 12~
30kV, receives 15~25cm of distance, and feeding rate 5~30 μ L/ minutes, spinning temperature is 10~60 DEG C, and relative air humidity is
20~80RH%；
3) pre-oxidation crosslinking：Polymer nanofiber is placed in oxidation furnace, with 0.1~10 DEG C/min of heating rate
200~300 DEG C are warming up to, 0.5~5 hour is incubated, pre-oxidation crosslinking is carried out, non-fusible Nanowire is obtained after being cooled to room temperature
Dimension；
4) high temperature burns till：By non-fusible nanofiber under inert atmosphere protection, with 1~10 DEG C/min of heating rate
600~2500 DEG C are warmed up to, 0.5~3 hour is incubated, pyrolysis obtains carbon nano-fiber；
5) carbon thermal reduction：It is put into corundum crucible after carbon nano-fiber is mixed with silica flour, is 0.1~1.0L/ in flow
Under the inert atmosphere protection of minute, 1250~1600 DEG C are heated to 3~10 DEG C/min of heating rate, insulation 1~10 is small
When, carbothermic reduction reaction is carried out, obtain SiC nano fiber；
Silica flour is more than 1 in molar ratio with carbon nano-fiber:1 mixing.
Further, carbon nano-fiber precursor polymer is polyacrylonitrile, phenolic resin or pitch；Step 1) in, it is molten
Agent is dimethylformamide or dimethyl sulfoxide (DMSO)；Step 4) in, inert atmosphere is the high-purity argon gas or height of purity >=99.999%
Pure nitrogen gas.
Further, the mass fraction of butyl titanate is 1wt%~10wt%.
Another aspect of the present invention additionally provides a kind of core shell structure TiOx nano piece/SiC nano fiber, by such as
Above-mentioned core shell structure TiOx nano piece/SiC nano fiber preparation method is obtained.
Technique effect of the invention：
The present invention provides core shell structure TiOx nano piece/SiC nano fiber preparation method, is carbonized with porous nano
Silica fibre and butyl titanate are raw material, and under the collective effect of diethylenetriamine and isopropanol, titanium oxide is preferentially in carborundum
Nanofiber surface forming core and gradually different growth, formed in nanometer plate shape, and sintering process after titanium oxide by
Gradually crystallize, form TiOx nano piece and the TiO with core shell structure is prepared by hydrothermal synthesis reaction2Nanometer sheet/SiC receives
Rice fiber.
The present invention provides core shell structure TiOx nano piece/SiC nano fiber preparation method, and technical process is simple, bar
Part is gentle, is easy to implement large-scale production.
The present invention provides core shell structure TiOx nano piece/SiC nano fiber, with a large amount of three dimensions nucleocapsid knots
Structure, the specific surface area of gained nanofiber is high, is attached to the TiO on SiC nano fiber2Nanometer sheet thickness and size, can lead to
Cross hydrothermal condition regulation.
Specifically refer to core shell structure TiOx nano piece/SiC nano fiber of the invention and preparation method is carried
The various embodiments for going out it is described below, will cause that above and other of the invention aspect is apparent.
Brief description of the drawings
Fig. 1 schemes for the SEM of the gained core shell structure TiOx nano piece of the preferred embodiment of the present invention 1/SiC nano fiber；
Fig. 2 is the XRD of the gained core shell structure TiOx nano piece of the preferred embodiment of the present invention 1/SiC nano fiber；
Fig. 3 is the photocatalysis of the gained core shell structure TiOx nano piece of the preferred embodiment of the present invention 1/SiC nano fiber
Decomposition water-hydrogen output performance schematic diagram.
Specific embodiment
The accompanying drawing for constituting the part of the application is used for providing a further understanding of the present invention, schematic reality of the invention
Apply example and its illustrate, for explaining the present invention, not constitute inappropriate limitation of the present invention.
Core shell structure TiOx nano piece/SiC nano fiber preparation method that the present invention is provided, comprises the following steps：
According to the mass ratio of SiC nano fiber and butyl titanate it is 1 by the SiC nano fiber with loose structure:60~600
Hydrothermal synthesis reaction is carried out in addition titaniferous hydro-thermal reaction liquid, core shell structure TiOx nano is obtained by annealing afterwards
Piece/SiC nano fiber, titaniferous hydro-thermal reaction liquid by volume fraction 0.5~2 ‰ diethylenetriamine aqueous isopropanol with
Butyl titanate is mixed for 1~10% by the aqueous isopropanol of diethylenetriamine and the volume ratio of butyl titanate；
Hydrothermal synthesis reaction：Sealing after SiC nano fiber is added in titaniferous hydro-thermal reaction liquid, it is placed in 160~
At 240 DEG C, 16~36 hours are incubated, are subsequently cooled to room temperature, obtain the TiOx nano piece/nanometer silicon carbide of unannealed treatment
Fiber.
Diethylenetriamine aqueous isopropanol is configured in a conventional manner.Butyl titanate used herein can be by existing conventional titanium
Acid butyl ester solution, preferably mass fraction are the solution of 1wt%~10wt%.
By controlling mass ratio, the hydro-thermal that butyl titanate reacts with porous silicon carbide nanofiber in titaniferous hydro-thermal reaction liquid
Reaction temperature and soaking time are in order that obtaining regular nano-sheet TiO2Energy homoepitaxial is in porous silicon carbide nanofiber
Surface.
The present invention provides core shell structure TiOx nano piece/SiC nano fiber preparation method, it is raw materials used in SiC
Fiber is porous nano-fibre, small with diameter, the features such as specific surface area is big, prepared TiO2Nanometer sheet/SiC nanofibers
With three-dimensional hud typed hierarchy, as shown in figure 1, three-dimensional core shell structure causes TiO2Nanometer sheet/SiC nanofibers have compared with
Big specific surface area, because SiC fiber surfaces Direct Uniform grows TiO2Nanometer sheet, fully exposes TiO2The activity of nanometer sheet
Site, is conducive to improving TiO2The performance such as the air-sensitive of nanometer sheet/SiC nanofibers and photocatalysis.Gained core shell structure titanium oxide
TiO in nanometer sheet/SiC nano fiber2Nanometer sheet is evenly distributed in SiC fiber surfaces, can completely be coated on SiC Nanowires
Dimension table face, with significant hierarchy.
Prepared TiO2The average thickness of nanometer sheet is 1~15nm, and width is 10~100nm, is compared to body phase material
Middle most of atom is in material internal, and the method provided by the present invention institute nanofiber surface product/volume ratio is big, i.e., atom mainly divides
Cloth is in material surface, so as to realize making full use of the most active reaction sites on gained nanofiber, TiO2Size
Adjustment can be realized by the regulation and control to synthesis condition, so as to be conducive to being easy to batch production.In photochemical catalyst, gas sensing
The field such as device and light emitting diode has huge application potential.
Obtained porous silicon carbide nanofiber has specific surface area big as stated above, it is easy to prepare with scale.
Especially gained nanofiber surface titanium oxide is can guarantee that in the ratio hybrid silicon carbide nanofiber and butyl titanate
In the adhesion amount on SiC nano fiber surface, it is to avoid excessively wrapping attached causes active reduction.Make in titaniferous hydro-thermal reaction liquid used
With the aqueous isopropanol of the diethylenetriamine of the volume fraction, be conducive to the dispersion of butyl titanate, while hydro-thermal conjunction can be improved
Titanium dioxide fiber forms core shell structure into course of reaction, improves the activity of gained nanofiber.The amount of butyl titanate is too many then
TiO2Can be deposited on fiber, nanometer sheet thickness can also increase, and TiO2Very little, then nanometer sheet can not be completely covered SiC to nanometer sheet
NFs。
Preferably, the volume fraction of the aqueous isopropanol of diethylenetriamine is 0.6~1.2 ‰.By this configuration, gained it is molten
Liquid, can improve the dissolution dispersity of titanium, so that the titanium for improving gained fiber surface is uniformly dispersed.
Preferably, make annealing treatment：TiOx nano piece/SiC nano fiber >=3 time of unannealed treatment are cleaned, then
Dry, be finally warming up to 300~800 DEG C, be incubated 1~5 hour, be cooled to room temperature, obtain core shell structure TiOx nano piece/carbon
SiClx nanofiber.The TiO that can be crystallized under annealing temperature and soaking time2, and may cause if temperature exceedes
Changes in crystal structure.And the nanofiber with a large amount of core shell structures cannot be obtained.
Preferably, cleaning includes first being cleaned with deionized water-alcohol mixeding liquid, then is cleaned with deionized water；Deionized water-
The volume ratio of alcohol mixeding liquid is 1~5:1.Deionized water-alcohol mixeding liquid can simultaneously remove inorganic salts and generation in product
Organic impurities such as butanol etc..Drying is to be dried 6~24 hours at 80~120 DEG C.
Preferably, stirred 2~10 minutes when preparing titaniferous hydro-thermal reaction liquid.Butyl titanate can be made sufficiently to dissolve, formed
Uniform titaniferous reaction solution.
Existing other SiC nano fibers can be used for the inventive method, it is preferred that porous silicon carbide nanofiber
Preparation method comprise the following steps：
1) spinning solution is prepared：Carbon nano-fiber precursor polymer is dissolved in solvent to be configured to homogeneous spinning molten
Liquid, concentration of the carbon nano-fiber precursor polymer in homogeneous spinning solution is 5~50wt%；
2) electrostatic spinning：By step 1) homogeneously spinning solution carries out electrostatic spinning to gained, and the shower nozzle used by electrostatic spinning is
Internal diameter size is the metal needle of 0.5~1.5mm, 12~30kV of spinning voltage, receives 15~25cm of distance, feeding rate 5~
30 μ L/ minutes, spinning temperature was 10~60 DEG C, and relative air humidity is 20~80RH%；Under electric field force effect, spinning solution
Gradually drawing-off refinement, while solvent volatilizees, forms polymer nanofiber and collects on the receiver；
3) pre-oxidation crosslinking：By step 2) polymer nanofiber that obtains is placed in oxidation furnace, with 0.1~10 DEG C/minute
The heating rate of clock is warming up to 200~300 DEG C, is incubated 0.5~5 hour, carries out pre-oxidation crosslinking, is obtained not after being cooled to room temperature
Fusing nanofiber；
4) high temperature burns till：By step 3) the non-fusible nanofiber that obtains under inert atmosphere protection, with 1~10 DEG C/minute
The heating rate of clock is warmed up to 600~2500 DEG C, is incubated 0.5~3 hour, and pyrolysis obtains carbon nano-fiber；
5) carbon thermal reduction：By step 4) carbon nano-fiber that obtains is put into corundum crucible together with silica flour, be in flow
Under the inert atmosphere protection of 0.1~1.0L/ minutes, 1250~1600 DEG C are heated to 3~10 DEG C/min of heating rate, protected
Temperature 1~10 hour, carries out carbothermic reduction reaction, obtains porous silicon carbide nanofiber；Silica flour is big with the mol ratio of carbon nano-fiber
In 1:1.
Preferably, carbon nano-fiber precursor polymer is the one kind or any in polyacrylonitrile, phenolic resin or pitch
Kind；Step 1) in, solvent is dimethylformamide or dimethyl sulfoxide (DMSO)；Step 4) in, inert atmosphere is purity >=99.999%
High-purity argon gas or high pure nitrogen.The entrance of oxygen is prevented, carbon is reacted with oxygen under the high temperature conditions and is lost.
Specifically, the method that the present invention is provided is comprised the following steps：
(1) in the aqueous isopropanol of the diethylenetriamine of volume fraction 0.5~2 ‰, addition mass fraction be 1wt%~
In the butyl titanate of 10wt%, the two is by volume 1~10% mixing, continues to stir 2~10 minutes, obtains titaniferous hydro-thermal reaction
Liquid；
(2) according to the mass ratio of SiC nano fiber and butyl titanate it is 1 by porous silicon carbide nanofiber:60~
600 ratio is added in step (1) gained titaniferous hydro-thermal reaction liquid, and sealing is placed at 160~240 DEG C, and insulation 16~36 is small
When, room temperature is subsequently cooled to, obtain unannealed TiOx nano piece/SiC nano fiber；
(3) unannealed TiOx nano piece/SiC nano fiber >=3 time of cleaning step (2) gained, then dry,
300~800 DEG C are finally warming up to, 1~5 hour is incubated, room temperature is cooled to, core shell structure TiOx nano piece/carborundum are obtained and is received
Rice fiber.
Another aspect of the present invention additionally provide a kind of core shell structure TiOx nano piece that use above method prepares/
SiC nano fiber.The fiber has substantial amounts of three-dimensional core shell structure, and the structure is in nanofiber surface, referring to Fig. 1.
Preferably, cleaning includes first being cleaned with deionized water-alcohol mixeding liquid, then is cleaned with deionized water；Deionization water-ethanol mixes
The volume ratio of liquid is 1~5:1.The inorganic salts that deionized water-alcohol mixeding liquid can be removed in product simultaneously are organic miscellaneous with generation
Matter such as butanol etc..Drying is to be dried 6~24 hours at 80~120 DEG C.
Core shell structure TiOx nano piece/SiC nano fiber that the present invention is provided can be used for gas sensing or light is urged
Change field.
Embodiment
Purity >=99.999% of high-purity argon gas used and high pure nitrogen in following examples and comparative example, concentrated hydrochloric acid used
Mass concentration is 37wt%, and density is 1.18g/mL, other chemical reagent for being used, unless otherwise specified, by routine
Commercial sources are obtained.
Embodiment 1
(1) in the diethylenetriamine aqueous isopropanol of 30ml volume fractions 0.6 ‰, the isopropanol by diethylenetriamine is molten
Liquid and the butyl titanate that the volume ratio of butyl titanate is that 1% addition mass fraction is 5wt%, continue to stir 5 minutes, obtain titaniferous water
Thermal response liquid；
(2) the gained porous silicon carbide Nanowire of 0.005g reference examples 2 is placed in the polytetrafluoroethyllining lining bottom of water heating kettle
Dimension, SiC nano fiber is 1 with the mass ratio of butyl titanate:300, step (1) gained titaniferous hydro-thermal reaction liquid is added to
In polytetrafluoroethyllining lining, then be placed in water heating kettle in 200 DEG C of insulating box by sealing, is incubated 20 hours, is subsequently cooled to room
Temperature, obtains unannealed TiO2Nanometer sheet/SiC nanofibers；
(3) deionized water-ethanol (v/v=3 is first used:1) mixed liquor cleaning step (2) gained TiO2Nanometer sheet/SiC nanometers
Fiber 3 times, is then cleaned 3 times with deionized water, then in 80 DEG C of drying boxes, is dried 12 hours, is finally placed in Muffle furnace and is risen
Temperature is incubated 2 hours to 400 DEG C, is cooled to room temperature, obtains core shell structure TiO2Nanometer sheet/SiC nanofibers.
As shown in figure 1, the present embodiment gained core shell structure TiO2In nanometer sheet/SiC nanofibers, TiO2Nanometer sheet is average
Thickness≤5nm, surface area/volume ratio is big, fully exposes avtive spot, and mean breadth is 50nm, TiO2Nanometer sheet is in SiC fibers
Surface distributed is uniform, SiC nanofiber surfaces can be completely coated on, with significant hierarchy.Avtive spot is crystal
Certain point for chemically reacting of surface, whole plane of crystal exposure is more, and active site is more.
It is illustrated in figure 2 the present embodiment gained core shell structure TiO2The XRD spectra of nanometer sheet/SiC nanofibers, as a result table
Contain anatase structured TiO in light fibers2With Emission in Cubic SiC.
By the present embodiment gained hierarchy TiO2Nanometer sheet/SiC nanofibers are simulated with xenon lamp (300W) at normal temperatures
Sunshine carries out photochemical catalyzing and prepares experiments Hydrogen.Understand as shown in Figure 3, core shell structure TiO2Nanometer sheet/SiC Nanowires
The hydrogen output in 4 hours is tieed up more than 14 μm of ol, and the hydrogen output of pure SiC nanofibers is about 10 μm of ol, illustrates the nucleocapsid knot
Structure TiO2Nanometer sheet/SiC nanofibers have photocatalysis performance higher.Therefore, gained core shell structure TiO2Nanometer sheet/SiC receives
Rice fiber has huge application potential in fields such as photochemical catalyst, gas sensor and light emitting diodes.
Embodiment 2
(1) in the diethylenetriamine aqueous isopropanol of 30ml volume fractions 1.2 ‰, the isopropanol by diethylenetriamine is molten
Liquid and the butyl titanate that the volume ratio of butyl titanate is that 10% addition mass fraction is 1wt%, continue to stir 5 minutes, obtain titaniferous
Hydro-thermal reaction liquid；
(2) the gained porous silicon carbide Nanowire of 0.005g reference examples 2 is placed in the polytetrafluoroethyllining lining bottom of water heating kettle
Dimension, SiC nano fiber is 1 with the mass ratio of butyl titanate:60, step (1) gained titaniferous hydro-thermal reaction liquid is added to poly-
In tetrafluoroethene liner, then be placed in water heating kettle in 160 DEG C of insulating box by sealing, is incubated 16 hours, is subsequently cooled to room
Temperature, obtains TiO2Nanometer sheet/SiC nanofibers；
(3) deionized water-ethanol (v/v=3 is first used:1) mixed liquor cleaning step (2) gained TiO2Nanometer sheet/SiC nanometers
Fiber 3 times, is then cleaned 3 times with deionized water, then in 80 DEG C of drying boxes, is dried 12 hours, is finally placed in Muffle furnace and is risen
Temperature is incubated 5 hours to 800 DEG C, is cooled to room temperature, obtains core shell structure TiO2Nanometer sheet/SiC nanofibers.
The present embodiment gained core shell structure TiO2In nanometer sheet/SiC nanofibers, TiO2Nanometer sheet average thickness for≤
5nm, mean breadth is 30~60nm, TiO2Nanometer sheet is evenly distributed to form core shell structure in SiC fiber surfaces, but can not be complete
Coated Si/C nanofiber.
Embodiment 3
(1) in the diethylenetriamine aqueous isopropanol of 30ml volume fractions 0.5 ‰, the isopropanol by diethylenetriamine is molten
Liquid and the butyl titanate that the volume ratio of butyl titanate is that 5% addition mass fraction is 10wt%, continue to stir 2 minutes, obtain titaniferous
Hydro-thermal reaction liquid；
(2) the gained porous silicon carbide Nanowire of 0.005g reference examples 2 is placed in the polytetrafluoroethyllining lining bottom of water heating kettle
Dimension, SiC nano fiber is 1 with the mass ratio of butyl titanate:600, step (1) gained titaniferous hydro-thermal reaction liquid is added to
In polytetrafluoroethyllining lining, then be placed in water heating kettle in 240 DEG C of insulating box by sealing, is incubated 36 hours, is subsequently cooled to room
Temperature, obtains TiO2Nanometer sheet/SiC nanofibers；
(3) deionized water-ethanol (v/v=5 is first used:1) mixed liquor cleaning step (2) gained TiO2Nanometer sheet/SiC nanometers
Fiber 3 times, is then cleaned 3 times with deionized water, then in 80 DEG C of drying boxes, is dried 12 hours, is finally placed in Muffle furnace and is risen
Temperature is incubated 1 hour to 300 DEG C, is cooled to room temperature, obtains core shell structure TiO2Nanometer sheet/SiC nanofibers.
The present embodiment gained core shell structure TiO2In nanometer sheet/SiC nanofibers, TiO2Nano-sheet pattern it is unobvious,
Size is≤30nm, and mean breadth is 30~60nm, TiO2Nanometer sheet is evenly distributed to form nucleocapsid knot in SiC fiber surfaces
Structure, on complete coated Si/C nanofiber.
Embodiment 4
(1) in the diethylenetriamine aqueous isopropanol of 30ml volume fractions 1.2 ‰, the isopropanol by diethylenetriamine is molten
Liquid and the butyl titanate that the volume ratio of butyl titanate is that 9% addition mass fraction is 5wt%, continue to stir 10 minutes, obtain titaniferous
Hydro-thermal reaction liquid；
(2) the gained porous silicon carbide Nanowire of 0.01g reference examples 2 is placed in the polytetrafluoroethyllining lining bottom of water heating kettle
Dimension, SiC nano fiber is 1 with the mass ratio of butyl titanate:150, step (1) gained titaniferous hydro-thermal reaction liquid is added to
In polytetrafluoroethyllining lining, then be placed in water heating kettle in 200 DEG C of insulating box by sealing, is incubated 20 hours, is subsequently cooled to room
Temperature, obtains TiO2Nanometer sheet/SiC nanofibers；
(3) deionized water-ethanol (v/v=1 is first used:1) mixed liquor cleaning step (2) gained TiO2Nanometer sheet/SiC nanometers
Fiber 3 times, is then cleaned 3 times with deionized water, then in 80 DEG C of drying boxes, is dried 12 hours, is finally placed in Muffle furnace and is risen
Temperature is incubated 2 hours to 600 DEG C, is cooled to room temperature, obtains core shell structure TiO2Nanometer sheet/SiC nanofibers.
The present embodiment gained core shell structure TiO2In nanometer sheet/SiC nanofibers, TiO2Nanometer sheet is significantly thicker, and size is big
It is small for≤15nm, but crystallinity are significantly improved, gained nanometer sheet width be 30~60nm, TiO2Nanometer sheet is in SiC fiber surfaces
It is evenly distributed to form core shell structure, on complete coated Si/C nanofiber.
The nanometer silicon carbide fiber with loose structure used is by the method below with reference to being provided in example in above example
Prepare.
Reference example 1
1) spinning solution is prepared：Polyacrylonitrile powder is added in dimethylformamide (DMF), polyacrylonitrile powder with
DMF mass ratioes are 1.2:10 (i.e. the mass concentration of polyacrylonitrile is 10.7wt%), stirring is completely dissolved polyacrylonitrile, obtains
Phase spinning solution；
2) electrostatic spinning：By step 1) homogeneously spinning solution carries out electrostatic spinning to gained, and the shower nozzle used by electrostatic spinning is
The metal needle of internal diameter 0.8mm, spinning voltage is 16kV, and it is 20cm to receive distance, and feeding rate is 10 μ L/ minutes, spinning temperature
20 DEG C of degree, relative air humidity is 60RH%, using flat board aluminium foil receiver, nano polypropylene nitrile fibrillation is obtained；
3) pre-oxidation crosslinking：By step 2) the nano polypropylene nitrile fibrillation that obtains is placed in oxidation furnace, with 5 DEG C/min
Speed be warming up to 280 DEG C, be incubated 1 hour, after being cooled to room temperature, obtain non-fusible polyacrylonitrile fibre；
4) high temperature burns till：By step 3) in the high temperature furnace that is placed under high pure nitrogen protection of the fusion-free fibre that obtains, with 5
DEG C/min speed be warming up to 1000 DEG C, be incubated 1 hour, pyrolysis obtains carbon nano-fiber；
5) carbon thermal reduction：By step 4) (silica flour is with the mol ratio of carbon nano-fiber for the carbon nano-fiber that obtains and silica flour
2:1) it is placed in corundum crucible, under protection of the flow for the high pure nitrogen of 0.15L/ minutes, is heated up with 5 DEG C/min of speed
To 1300 DEG C, 3 hours are incubated, obtain porous silicon carbide nanofiber.
Gained porous nano silicon carbide fibre average diameter is 200nm, and uniform diameter, fiber is loose structure, specific surface
Product is 65.8m2/g。
Reference example 2
With differing only in for reference example 1：Step 3) in, the temperature of insulation is 260 DEG C；Step 5) in, the temperature after intensification
It is 1500 DEG C to spend, and soaking time is 2 hours, and protection gas is high-purity argon gas.
Gained porous nano silicon carbide fibre average diameter is 200nm, and uniform diameter, fiber is loose structure, specific surface
Product is 24.6m2/g。
Reference example 3
With differing only in for reference example 1：Step 5) in, the temperature after intensification is 1400 DEG C, and soaking time is 5 hours,
Protection gas is high-purity argon gas.
Gained porous nano silicon carbide fibre average diameter is 200nm, and uniform diameter, fiber is loose structure, specific surface
Product is 19.6m2/g。
Those skilled in the art will be clear that the scope of the present invention is not restricted to example discussed above, it is possible to which it is carried out
Some changes and modification, without deviating from the scope of the present invention that appended claims are limited.Although oneself is through in accompanying drawing and explanation
The present invention is illustrated and described in book in detail, but such explanation and description are only explanations or schematical, and it is nonrestrictive.
The present invention is not limited to the disclosed embodiments.
By to accompanying drawing, the research of specification and claims, when the present invention is implemented, those skilled in the art can be with
Understand and realize the deformation of the disclosed embodiments.In detail in the claims, term " including " be not excluded for other steps or element,
And indefinite article " one " or " one kind " are not excluded for multiple.Some measures quoted in mutually different dependent claims
The fact does not mean that the combination of these measures can not be advantageously used.It is right that any reference marker in claims is not constituted
The limitation of the scope of the present invention.
Claims (9)
1. a kind of core shell structure TiOx nano piece/SiC nano fiber preparation method, it is characterised in that including following step
Suddenly：
According to the mass ratio of SiC nano fiber and butyl titanate it is 1 by the SiC nano fiber with loose structure:60
Hydrothermal synthesis reaction is carried out in~600 addition titaniferous hydro-thermal reaction liquid, the core shell structure oxygen is obtained by annealing afterwards
Change titanium nanometer sheet/SiC nano fiber；
The titaniferous hydro-thermal reaction liquid by volume fraction 0.5~2 ‰ diethylenetriamine aqueous isopropanol and butyl titanate, press
The volume ratio of the aqueous isopropanol of the diethylenetriamine and the butyl titanate is mixed for 1~10%；
The hydrothermal synthesis reaction：The SiC nano fiber is added in the titaniferous hydro-thermal reaction liquid and is sealed afterwards,
At 160~240 DEG C, 16~36 hours are incubated, are subsequently cooled to room temperature, obtain the TiOx nano piece/carbonization of unannealed treatment
Silicon nanofiber.
2. core shell structure TiOx nano piece/SiC nano fiber preparation method according to claim 1, its feature exists
In the volume fraction of the aqueous isopropanol of the diethylenetriamine is 0.6~1.2 ‰.
3. core shell structure TiOx nano piece/SiC nano fiber preparation method according to claim 2, its feature exists
In the annealing is comprised the following steps：Clean the TiOx nano piece/SiC nano fiber of the unannealed treatment >=
3 times, then dry, be warming up to 300~800 DEG C, be incubated 1~5 hour, be cooled to room temperature, obtain the core shell structure titanium oxide
Nanometer sheet/SiC nano fiber.
4. core shell structure TiOx nano piece/SiC nano fiber preparation method according to claim 3, its feature exists
In stirring 2~10 minutes when preparing the titaniferous hydro-thermal reaction liquid.
5. core shell structure TiOx nano piece/SiC nano fiber preparation method according to claim 3, its feature exists
In the cleaning includes first being cleaned with deionized water-alcohol mixeding liquid, then is cleaned with deionized water；The deionization water-ethanol
Mixed liquor is that deionized water and ethanol are by volume 1~5:1 mixes.
6. core shell structure TiOx nano piece/SiC nano fiber preparation method according to claim 1, its feature exists
In the SiC nano fiber is obtained according to the following steps：
1) spinning solution is prepared：Carbon nano-fiber precursor polymer is dissolved in homogeneous spinning solution is configured in solvent, institute
Concentration of the carbon nano-fiber precursor polymer in the homogeneous spinning solution is stated for 5~50wt%；
2) electrostatic spinning：Electrostatic spinning is carried out to the homogeneous spinning solution, polymer nanofiber is obtained；
The technological parameter of the electrostatic spinning：Shower nozzle used for 0.5~1.5mm of internal diameter metal needle, spinning voltage 12~
30kV, receives 15~25cm of distance, and feeding rate 5~30 μ L/ minutes, spinning temperature is 10~60 DEG C, and relative air humidity is
20~80RH%；
3) pre-oxidation crosslinking：The polymer nanofiber is placed in oxidation furnace, with 0.1~10 DEG C/min of heating rate
200~300 DEG C are warming up to, 0.5~5 hour is incubated, pre-oxidation crosslinking is carried out, non-fusible Nanowire is obtained after being cooled to room temperature
Dimension；
4) high temperature burns till：By the non-fusible nanofiber under inert atmosphere protection, with 1~10 DEG C/min of heating rate
600~2500 DEG C are warmed up to, 0.5~3 hour is incubated, pyrolysis obtains carbon nano-fiber；
5) carbon thermal reduction：It is put into corundum crucible after the carbon nano-fiber is mixed with silica flour, is 0.1~1.0L/ in flow
Under the inert atmosphere protection of minute, 1250~1600 DEG C are heated to 3~10 DEG C/min of heating rate, insulation 1~10 is small
When, carbothermic reduction reaction is carried out, obtain the SiC nano fiber；
The silica flour is more than 1 in molar ratio with the carbon nano-fiber:1 mixing.
7. core shell structure TiOx nano piece/SiC nano fiber preparation method according to claim 6, its feature exists
In the carbon nano-fiber precursor polymer is polyacrylonitrile, phenolic resin or pitch；
The step 1) in, the solvent is dimethylformamide or dimethyl sulfoxide (DMSO).
8. core shell structure TiOx nano piece/SiC nano fiber preparation method according to claim 1, its feature exists
In the mass fraction of the butyl titanate is 1wt%~10wt%.
9. a kind of core shell structure TiOx nano piece/SiC nano fiber, it is characterised in that appoint by such as claim 1~8
Core shell structure TiOx nano piece/SiC nano fiber preparation method described in one is obtained.
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