CN107233877A - A kind of preparation method of titanium dioxide CNT composite porous microspheres - Google Patents
A kind of preparation method of titanium dioxide CNT composite porous microspheres Download PDFInfo
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- CN107233877A CN107233877A CN201710578035.7A CN201710578035A CN107233877A CN 107233877 A CN107233877 A CN 107233877A CN 201710578035 A CN201710578035 A CN 201710578035A CN 107233877 A CN107233877 A CN 107233877A
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- titanium dioxide
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- carbon nano
- cnt
- composite porous
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000004005 microsphere Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000004408 titanium dioxide Substances 0.000 title abstract description 15
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 36
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 6
- 239000012798 spherical particle Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 38
- 239000010936 titanium Substances 0.000 claims description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 18
- 239000013049 sediment Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 230000004044 response Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000003916 acid precipitation Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 claims description 6
- 239000002048 multi walled nanotube Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 150000003608 titanium Chemical class 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 4
- -1 amino silicane Chemical compound 0.000 claims description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims description 2
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical group C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical group CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 2
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 230000035935 pregnancy Effects 0.000 claims description 2
- 235000011078 sorbitan tristearate Nutrition 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- PFJFNQUFMTYCHB-UHFFFAOYSA-N C[SiH2]N[SiH3] Chemical compound C[SiH2]N[SiH3] PFJFNQUFMTYCHB-UHFFFAOYSA-N 0.000 claims 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000007822 coupling agent Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000011806 microball Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 10
- 239000008131 herbal destillate Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia Species 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002109 single walled nanotube Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 description 1
- CYKMNKXPYXUVPR-UHFFFAOYSA-N [C].[Ti] Chemical compound [C].[Ti] CYKMNKXPYXUVPR-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910000062 azane Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical class CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000001652 electrophoretic deposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/653—500-1000 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of preparation method of titanium dioxide CNT composite porous microspheres, this method mixes titania hydrosol with CNT, under binding agent, hydrophobic modifier and low surface tension solvent collective effect, by constant pressure and dry and high-temperature activation, the synthetically prepared of the titanium dioxide carbon nano tube compound material with porous property is realized.The inventive method has technological process simple, and raw materials for production are cheap, and solvent is easily reclaimed, and production cost is low, the characteristics of yield is high.Titanium dioxide CNT composite porous microspheres prepared by the present invention are regular spherical particle, and with typical nano-porous structure, can be applied to the fields such as hydrogen manufacturing, dye-sensitized solar cells and photocatalysis.
Description
Technical field
The present invention relates to field of material preparation, and in particular to a kind of system of titanium dioxide-CNT composite porous microspheres
Preparation Method.
Background technology
Titanium dioxide（TiO2）Nano material has that good weatherability, chemical resistance, photocatalytic be high, chemistry with
The characteristic advantages such as optical stability is good, harmless, especially disappear in solar cell and organic pollution processing, sterilization
The field of Environment Protection such as poison have a wide range of applications.Particularly in recent years, nano-TiO2In catalysis, air cleaning, Water warfare etc.
Research and application in field of Environment Protection are increasingly subject to the attention of people.
CNT is a kind of One-dimensional Quantum material with special construction, can regard flake graphite alkene volume as in theory
Into cylinder, multi-walled carbon nanotube and single-walled carbon nanotube can be divided into.It is outstanding due to possessing from it since 1991 are found
Physical and chemical performance, mechanical property and heat endurance, cause the widely studied of scientific circles.CNT has unique sky
The excellent performances such as core structure, nano-scale, abnormal high aspect ratio and larger specific surface area so that it is in numerous areas
Such as high sensor, transistor electronic equipment, solar cell, catalysis, environmental area and biotechnology industry etc. have
Various applications.
With the development of science and technology, single functional material far can not meet the demand of people, Composite
The development trend of material is only, by compound on two kinds or more of material functions, mutually making up in performance and is optimized, from
And prepare the more excellent composite of performance.CNT and TiO2Nano material is respectively provided with excellent functional characteristic, will
CNT and titanium dioxide nano material, which are combined, prepares CNT-composite titania material, is expected to titanium dioxide
（Photocatalytic activity and oxidability）And CNT（High adsorption, high-specific surface area and electric conductivity）The advantages of combine one
Rise.Such as because CNT has good electric conductivity, the transmission of electronics can be strengthened, promote light induced electron and point in hole
From the photo-quantum efficiency of raising titanium dioxide；And CNT there is unique hollow structure and higher specific surface area with
And very strong adsorption capacity, it is preferable titania support.The method for preparing titanium dioxide/carbon nano tube compound material at present
Mainly there are sol/gel method, chemical vapour deposition technique, hydro-thermal method, electrophoretic deposition etc..
CNT-composite titania material is prepared into porous material, can be further by titanium dioxide and carbon nanometer
The advantage of pipe is combined and maximized, but such compound porous material of titanium dioxide-CNT of rare document and patent report at present
The preparation and application of material.If CNT-titanium dioxide composite porous material can be prepared into profile rule and particle can
The microballoon of control, on the one hand improves the use function of CNT-composite titania material, on the other hand can solve composite
The problem of being difficult to separation and recovery, this will greatly extend this nano composite material in hydrogen manufacturing, dye-sensitized solar cells and light
The application in the fields such as catalysis.
The content of the invention
The present invention is directed to prior art problem, it is therefore intended that a kind of cost of offer is low, technique is simple and can realize scale
The preparation method of the titanium dioxide of production-CNT composite porous microspheres.
The purpose of the present invention is completed in the following manner：
A kind of preparation method for titanium dioxide and silicon dioxide composite Nano porous microsphere that the present invention is provided, it includes following step
Suddenly：
A kind of TiO2-SiO2The preparation method of composite Nano porous microsphere, comprises the following steps：
（1）The preparation of titania hydrosol
Titanium salt presoma and deionized water are mixed at room temperature, stirs, is fully hydrolyzed reaction, metatitanic acid precipitation is obtained；To inclined
Concentrated acid and hydrogen peroxide are added in metatitanic acid precipitation, ultrasound obtains yellow sol；Then stabilizer is added toward yellow sol, backflow is anti-
Should, the titania hydrosol stablized.
（2）The preparation of carbon nano tube dispersion liquid
Carboxylic carbon nano-tube dry powder is dissolved in deionized water, it is ultrasonically treated it is uniform be configured to mass fraction for 0.5%~
10% carbon nano tube dispersion liquid.
（3）The preparation of titanium dioxide-CNT composite porous microspheres
Titania hydrosol, carbon nano tube dispersion liquid, binding agent and deionized water are well mixed at room temperature, regulation and control pH is extremely
1 ~ 2, obtain mixed sols；Low surface tension solvent, hydrophobic modifier and surfactant are added in mixed sols, passes through height
Speed stirring makes after System forming emulsion, and heating response treats that solution is layered and removes water layer, obtains sediment；Sediment is entered
Row washing, constant pressure and dry, high-temperature activation, obtain titanium dioxide-CNT composite porous microspheres.
In the step（1）In, titanium salt presoma, deionized water, concentrated acid, the mass ratio of hydrogen peroxide and stabilizer are 1：
（10~200）：（0.1~1）：（1~20）：（0.01~1）.
In the step（3）In, titania hydrosol, carbon nano tube dispersion liquid, binding agent, deionized water, low surface
The mass ratio of tension solvent is 1：（0.1~10）：（0.01~1）：（0.1~10）：（1~10）；Hydrophobic modifier and titanium dioxide water
The mass ratio of colloidal sol is（0.01~1）：1；The mass ratio of surfactant and titania hydrosol is（0.001~0.2）：1.
In order to which the present invention is better achieved, in the step（1）In, described titanium salt presoma is titanyl sulfate, tetrachloro
Change at least one of titanium, tetraisopropyl titanate, the n-propyl of metatitanic acid four, tetraethyl titanate or butyl titanate；Described stabilization
Agent is at least one of isopropanol or acetylacetone,2,4-pentanedione；Described concentrated acid is at least one of concentrated nitric acid and the concentrated sulfuric acid；It is described
The mass concentration of concentrated nitric acid is 69%；The mass concentration of the concentrated sulfuric acid is 98%；The mass concentration of described hydrogen peroxide be 30 ~
50%。
In order to which the present invention is better achieved, in the step（2）In, described carboxylic carbon nano-tube is many walls of carboxylated
At least one of CNT and carboxylated single-walled carbon nanotube；The preferred carboxyl-content of carboxylic carbon nano-tube is 0 ~ 10wt%, carboxylic
Base carbon nano tube preferred length is 0.01 ~ 10 μm.
In order to which the present invention is better achieved, in the step（3）In, described binding agent is zirconium carbonate ammonium, 2D resins, ammonia
At least one of base silane coupling agent, water soluble hydroxy acrylate；Described hydrophobic modifier is dimethyl diethoxy
Base silane, dimethyldimethoxysil,ne, HMDO, HMDS, MTES, methyl
Trimethoxy silane, dodecyltrimethoxysilane, dodecyl triethoxysilane, hexadecyl trimethoxy silane,
At least one of hexadecyl, octamethylcy-clotetrasiloxane, hexamethyl cyclotrisiloxane；Described low table
Face tension solvent is at least one of n-hexane and normal heptane；Described surfactant be Tween-20, Tween-80, Span-
60, at least one of Span -65.
In order to which the present invention is better achieved, in the step（1）In, the ultrasonic power be 10 ~ 200W, the time be 5 ~
100min；The condition of the backflow is 40 ~ 90 DEG C of temperature, 3 ~ 100h of time.
In order to which the present invention is better achieved, in the step（2）In, the ultrasonically treated power is 5 ~ 200W, time
For 1 ~ 200min.
In order to which the present invention is better achieved, in the step（3）In, the high-speed stirred, refer to mixing speed for 400 ~
1200 revs/min；Described heating response, reaction temperature is 30 ~ 70 DEG C, and the reaction time is 0.5h ~ 5h；The drying process
Refer to and 1 ~ 6h is handled at 70 ~ 150 DEG C；Described high-temperature activation refers to 1 ~ 5h of processing at 200 ~ 600 DEG C.
Prepared titanium dioxide-CNT composite porous microspheres are regular spherical particle, and particle diameter is 1 ~ 3000 μm, pine
Dress density is 0.01 ~ 0.8 g/cm3, specific surface area is 100 ~ 1200 m2/ g, aperture is 5 ~ 1000nm.
The present invention is using titania hydrosol is mixed with CNT, on binding agent, hydrophobic modifier and low surface
Under tension solvent collective effect, by constant pressure and dry and high-temperature activation, realize that one-step synthesis method goes out the dioxy with porous matter
Change titanium-carbon nano tube compound material.Loose structure formation mechenism is：After titania hydrosol is mixed with CNT,
Realized using binding agent and covalent bond is carried out between TiO 2 particles and CNT, form gel skeleton；Changed by hydrophobic
Property agent surface hydrophobicity modification is carried out to TiO 2 particles and CNT；Solvent displacement is carried out using low-surface-energy solvent, is led to
Cross the constant pressure and dry of low-surface-energy solvent, it is ensured that the gel skeleton pore space structure of TiO 2 particles and CNT formation not by
Destruction；Surfactant primarily serves to form microballoon and promote solvent replacement result, i.e., under Action of Surfactant, by aqueous phase
（Titanium dioxide+CNT+water）Composition dispersed with stirring increases solvent into countless tiny microgels（Water and low-surface-energy are molten
Agent）Between replacement result.In the preparation process of titanium dioxide-CNT composite porous microspheres, surface-hydrophobicized modification,
The processes such as solvent displacement are synchronously carried out, i.e., so-called " one-step method " is substantially shorter the reaction time.
Relative to prior art, the invention has the advantages that and beneficial effect：
1st, the preparation method of titanium dioxide of the present invention-CNT composite porous microspheres, by titania hydrosol
Mixed with CNT, under binding agent, hydrophobic modifier and low surface tension solvent collective effect, realize that one-step synthesis method goes out
Titanium dioxide-carbon nano tube compound material with porous property, simple with technological process, raw materials for production are cheap, molten
Agent is easily reclaimed, and production cost is low, the characteristics of yield is high.
2nd, titanium dioxide-CNT composite porous microspheres prepared by the present invention are regular spherical particle, average grain diameter
It can regulate and control in 1 ~ 3000 μ m, and with typical nano-porous structure, can be applied to hydrogen manufacturing, dye-sensitized solar cells
With the field such as photocatalysis.
Brief description of the drawings
Fig. 1 is the structural representation of titanium dioxide-CNT composite porous microspheres prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscopic picture of titanium dioxide-CNT composite porous microspheres prepared by the embodiment of the present invention 1.
Titanium dioxide-CNT composite porous microspheres internal microstructure prepared by Fig. 3 embodiment of the present invention 1 is swept
Retouch electron microscopic picture.
Fig. 4 is the EDS elementary analyses test that the embodiment of the present invention 1 prepares titanium dioxide-CNT composite porous microspheres
Figure.
Embodiment
Son is described in further detail to the embodiment of the present invention with reference to the accompanying drawings and examples, but this hair
Bright embodiment not limited to this.
Embodiment 1
（1）The preparation of titania hydrosol
10g titanium tetrachlorides and 1000g deionized waters are mixed at room temperature, stirs, is fully hydrolyzed reaction, metatitanic acid is obtained and sinks
Form sediment；The concentrated nitric acid that 3g mass concentrations are 69% and the hydrogen peroxide that 200g mass concentrations are 50% are added in being precipitated to metatitanic acid, 10W surpasses
Ultrasonic reaction 5min under the conditions of sound, obtains yellow sol；Then added toward yellow sol under 3g acetylacetone,2,4-pentanediones, 90 DEG C of counterflow conditions
React 48h, the titania hydrosol stablized；
（2）The preparation of carbon nano tube dispersion liquid
Functionalized multi-wall carbonnanotubes dry powder is dissolved in deionized water, ultrasonically treated 100min, is obtained under 200W ultrasound conditions
It is uniform to be configured to the carbon nano tube dispersion liquid that mass fraction is 2%；
（3）The preparation of titanium dioxide-CNT composite porous microspheres
100g titania hydrosols, 100g carbon nano tube dispersion liquids, 50g zirconium carbonate ammoniums and 100g water are mixed at room temperature
Even, pH is to 1.2 for regulation and control, obtains mixed sols；1000g n-hexanes, 50g dimethyldiethoxysilanes are added in mixed sols
With 50g Tween-20 surfactants, under the conditions of 400 revs/min of high-speed stirreds, the heating response 5h under the conditions of 50 DEG C treats molten
Liquid is layered and removes water layer, obtains sediment；After sediment is washed, in 70 DEG C of dry 6h, then locate at 500 DEG C
4h is managed, titanium dioxide-CNT composite porous microspheres are obtained.
Accompanying drawing 1 is the structural representation of titanium dioxide-CNT composite porous microspheres prepared by the embodiment of the present invention 1.
Accompanying drawing 4 is the EDS elementary analysis test charts of titanium dioxide-CNT composite porous microspheres prepared by the present embodiment, from figure
As can be seen that containing Ti and C element in nanoporous microballoon prepared by the present invention, titanium dioxide and CNT are illustrated
Success is compound.From accompanying drawing 2 and accompanying drawing 3 it can be seen that, prepared titanium dioxide-CNT composite porous microsphere material
Average grain diameter is 30 μm, and apparent density is 0.2g/cm3, specific surface area is 300 m2/ g, average pore size is 10nm.
Embodiment 2
（1）The preparation of titania hydrosol
10g tetraethyl titanates and 800g deionized waters are mixed at room temperature, stirs, is fully hydrolyzed reaction, metatitanic acid precipitation is obtained；
The concentrated sulfuric acid that 5g mass concentrations are 98% and the hydrogen peroxide that 15g mass concentrations are 50%, 200W ultrasounds are added in being precipitated to metatitanic acid
Under the conditions of ultrasonic reaction 30min, obtain yellow sol；Then added toward yellow sol under 0.1g isopropanols, 80 DEG C of counterflow conditions
React 100h, the titania hydrosol stablized；
（2）The preparation of carbon nano tube dispersion liquid
Functionalized multi-wall carbonnanotubes dry powder is dissolved in deionized water, ultrasonically treated 200min under 5W ultrasound conditions, obtained
It is even to be configured to the carbon nano tube dispersion liquid that mass fraction is 0.5%；
（3）The preparation of titanium dioxide-CNT composite porous microspheres
100g titania hydrosols, 10g carbon nano tube dispersion liquids, 1g2D resins and 1000g water are well mixed at room temperature,
Regulate and control pH to 1, obtain mixed sols；500g normal heptanes, 20g HMDOs and 0.1g is added in mixed sols to tell
Warm -80 surfactants, under the conditions of 1200 revs/min of high-speed stirreds, the heating response 5h under the conditions of 30 DEG C treats that solution is layered
And water layer is removed, obtain sediment；After sediment is washed, in 150 DEG C of dry 1h, then at 400 DEG C processing 1 ~
5h, obtains titanium dioxide-CNT composite porous microspheres.
The average grain diameter of prepared titanium dioxide-CNT composite Nano porous microsphere material is 1 μm, apparent density
For 0.01g/cm3, specific surface area is 900 m2/ g, average pore size is 1000nm.
Embodiment 3
（1）The preparation of titania hydrosol
10g butyl titanates and 500g deionized waters are mixed at room temperature, stirs, is fully hydrolyzed reaction, metatitanic acid is obtained and sinks
Form sediment；The concentrated nitric acid that 1g mass concentrations are 69% and the hydrogen peroxide that 50g mass concentrations are 50% are added in being precipitated to metatitanic acid, 100W surpasses
Ultrasonic reaction 20min under the conditions of sound, obtains yellow sol；Then 0.5g acetylacetone,2,4-pentanediones, 50 DEG C of reflux conditions are added toward yellow sol
8h is reacted under part, the titania hydrosol stablized；
（2）The preparation of carbon nano tube dispersion liquid
Carboxylated single-walled carbon nanotube dry powder is dissolved in deionized water, ultrasonically treated 1min under 200W ultrasound conditions, obtained
It is even to be configured to the carbon nano tube dispersion liquid that mass fraction is 10%；
（3）The preparation of titanium dioxide-CNT composite porous microspheres
100g titania hydrosols, 1000g carbon nano tube dispersion liquids, 100g aminopropyl triethoxysilanes and 300g water are existed
It is well mixed at room temperature, pH is to 2 for regulation and control, obtains mixed sols；1000g n-hexanes, 100g dodecanes are added in mixed sols
Base trimethoxy silane and the surfactant of 3g Spans -65, under the conditions of 600 revs/min of high-speed stirreds, add under the conditions of 50 DEG C
Thermal response 1h, treats that solution is layered and removes water layer, obtains sediment；After sediment is washed, in 100 DEG C of dry 2h,
Then 1 ~ 5h is handled at 300 DEG C, titanium dioxide-CNT composite porous microspheres are obtained.
The average grain diameter of prepared titanium dioxide-CNT composite Nano porous microsphere material is 500 μm, and pine fills close
Spend for 0.8g/cm3, specific surface area is 100 m2/ g, average pore size is 500nm.
Embodiment 4
（1）The preparation of titania hydrosol
The n-propyl of 10g metatitanic acids four and 1500g deionized waters are mixed at room temperature, is stirred, is fully hydrolyzed reaction, obtains metatitanic acid
Precipitation；The concentrated nitric acid that 10g mass concentrations are 69% and the hydrogen peroxide that 70g mass concentrations are 30%, 70W are added in being precipitated to metatitanic acid
Ultrasonic reaction 80min under ultrasound condition, obtains yellow sol；Then 1g isopropanols, 50 DEG C of counterflow conditions are added toward yellow sol
Lower reaction 3h, the titania hydrosol stablized；
（2）The preparation of carbon nano tube dispersion liquid
Functionalized multi-wall carbonnanotubes dry powder is dissolved in deionized water, ultrasonically treated 50min under 150W ultrasound conditions, obtained
It is even to be configured to the carbon nano tube dispersion liquid that mass fraction is 1%；
（3）The preparation of titanium dioxide-CNT composite porous microspheres
By 100g titania hydrosols, 1000g carbon nano tube dispersion liquids, 100g water soluble hydroxies acrylate and 10g
Water is well mixed at room temperature, and pH is to 1.5 for regulation and control, obtains mixed sols；100g normal heptanes, 1g pregnancy are added in mixed sols
Basic ring trisiloxanes and 10g Tween-20 surfactants, under the conditions of 800 revs/min of high-speed stirreds, add under the conditions of 40 DEG C
Thermal response 3h, treats that solution is layered and removes water layer, obtains sediment；After sediment is washed, in 120 DEG C of dry 4h,
Then 1 ~ 5h is handled at 450 DEG C, titanium dioxide-CNT composite porous microspheres are obtained.
The average grain diameter of prepared titanium dioxide-CNT composite Nano porous microsphere material is 1000 μm, pine dress
Density is 0.01g/cm3, specific surface area is 1200 m2/ g, average pore size is 5nm.
Embodiment 5
（1）The preparation of titania hydrosol
10g tetraisopropyl titanates and 2000g deionized waters are mixed at room temperature, is stirred, is fully hydrolyzed reaction, obtains metatitanic acid
Precipitation；The concentrated nitric acid that 2g mass concentrations are 69% and the hydrogen peroxide that 80g mass concentrations are 30%, 150W are added in being precipitated to metatitanic acid
Ultrasonic reaction 50min under ultrasound condition, obtains yellow sol；Then 10g acetylacetone,2,4-pentanediones, 60 DEG C of reflux conditions are added toward yellow sol
20h is reacted under part, the titania hydrosol stablized；
（2）The preparation of carbon nano tube dispersion liquid
Carboxylated single-walled carbon nanotube dry powder is dissolved in deionized water, ultrasonically treated 100min, is obtained under 100W ultrasound conditions
It is uniform to be configured to the carbon nano tube dispersion liquid that mass fraction is 5%；
（3）The preparation of titanium dioxide-CNT composite porous microspheres
By 100g titania hydrosols, 500g carbon nano tube dispersion liquids, 1g aminopropyl triethoxysilanes and 1000g water in room
Temperature is lower well mixed, regulates and controls pH to 2, obtains mixed sols；600g n-hexanes, the silicon of 20g hexamethyls two are added in mixed sols
Azane and the surfactant of 5g Spans -65, under the conditions of 1000 revs/min of high-speed stirreds, the heating response under the conditions of 60 DEG C
0.5h, treats that solution is layered and removes water layer, obtains sediment；After sediment is washed, in 80 DEG C of dry 5h, then exist
1 ~ 5h is handled at 500 DEG C, titanium dioxide-CNT composite porous microspheres are obtained.
The average grain diameter of prepared titanium dioxide-CNT composite Nano porous microsphere material is 3000 μm, pine dress
Density is 0.5g/cm3, specific surface area is 100m2/ g, average pore size is 1000nm.
Embodiment 6
（1）The preparation of titania hydrosol
10g titanyl sulfates and 100g deionized waters are mixed at room temperature, stirs, is fully hydrolyzed reaction, metatitanic acid precipitation is obtained；
The concentrated sulfuric acid that 4g mass concentrations are 98% and the hydrogen peroxide that 10g mass concentrations are 50%, 50W ultrasound bars are added in being precipitated to metatitanic acid
Ultrasonic reaction 100min under part, obtains yellow sol；Then added toward yellow sol anti-under 2g acetylacetone,2,4-pentanediones, 40 DEG C of counterflow conditions
60h is answered, the titania hydrosol stablized；
（2）The preparation of carbon nano tube dispersion liquid
Functionalized multi-wall carbonnanotubes dry powder is dissolved in deionized water, ultrasonically treated 150min, is obtained under 100W ultrasound conditions
It is uniform to be configured to the carbon nano tube dispersion liquid that mass fraction is 3%；
（3）The preparation of titanium dioxide-CNT composite porous microspheres
100g titania hydrosols, 800g carbon nano tube dispersion liquids, 20g zirconium carbonate ammoniums and 1000g water are mixed at room temperature
Uniformly, regulation and control pH obtains mixed sols to 1；Added in mixed sols 1000g n-hexanes, 50g MTESs and
The surfactant of 20g Spans -60, under the conditions of 600 revs/min of high-speed stirreds, heating response 5h, treats solution under the conditions of 70 DEG C
It is layered and removes water layer, obtains sediment；After sediment is washed, in 90 DEG C of dry 6h, then handled at 600 DEG C
1 ~ 5h, obtains titanium dioxide-CNT composite porous microspheres.
The average grain diameter of prepared titanium dioxide-CNT composite Nano porous microsphere material is 1 μm, apparent density
For 0.01g/cm3, specific surface area is 1200 m2/ g, average pore size is 5nm.
Claims (5)
1. the preparation method of a kind of titanium dioxide-CNT composite porous microspheres, it is characterised in that comprise the following steps：
（1）The preparation of titania hydrosol
Titanium salt presoma and deionized water are mixed at room temperature, stirs, is fully hydrolyzed reaction, metatitanic acid precipitation is obtained；To inclined
Concentrated acid and hydrogen peroxide are added in metatitanic acid precipitation, ultrasound obtains yellow sol；Then stabilizer is added toward yellow sol, backflow is anti-
Should, the titania hydrosol stablized；
（2）The preparation of carbon nano tube dispersion liquid
Carboxylic carbon nano-tube dry powder is dissolved in deionized water, it is ultrasonically treated it is uniform be configured to mass fraction for 0.5%~
10% carbon nano tube dispersion liquid；
（3）The preparation of titanium dioxide-CNT composite porous microspheres
Titania hydrosol, carbon nano tube dispersion liquid, binding agent and deionized water are well mixed at room temperature, regulation and control pH is extremely
1 ~ 2, obtain mixed sols；Low surface tension solvent, hydrophobic modifier and surfactant are added in mixed sols, passes through height
Speed stirring makes after System forming emulsion, and heating response treats that solution is layered and removes water layer, obtains sediment；Sediment is entered
Row washing, constant pressure and dry, high-temperature activation, obtain titanium dioxide-CNT composite porous microspheres.
2. preparation method according to claim 1, it is characterised in that：
In the step（1）In, titanium salt presoma, deionized water, concentrated acid, the mass ratio of hydrogen peroxide and stabilizer are 1：（10~
200）：（0.1~1）：（1~20）：（0.01~1）；
In the step（3）In, titania hydrosol, carbon nano tube dispersion liquid, binding agent, deionized water, low surface tension
The mass ratio of solvent is 1：（0.1~10）：（0.01~1）：（0.1~10）：（1~10）；Hydrophobic modifier and titania hydrosol
Mass ratio be（0.01~1）：1；The mass ratio of surfactant and titania hydrosol is（0.001~0.2）：1.
3. preparation method according to claim 1, it is characterised in that：
In the step（1）In, described titanium salt presoma for titanyl sulfate, titanium tetrachloride, tetraisopropyl titanate, metatitanic acid four just
At least one of propyl ester, tetraethyl titanate or butyl titanate；Described stabilizer is in isopropanol or acetylacetone,2,4-pentanedione
It is at least one；Described concentrated acid is at least one of concentrated nitric acid and the concentrated sulfuric acid；The mass concentration of described hydrogen peroxide is 30 ~ 50%；
In the step（2）In, described carboxylic carbon nano-tube is that functionalized multi-wall carbonnanotubes and carboxylated single wall carbon are received
At least one of mitron；
In the step（3）In, described binding agent is zirconium carbonate ammonium, 2D resins, amino silicane coupling agent, water soluble hydroxy third
At least one of alkene acid ester resin；
Described hydrophobic modifier is dimethyldiethoxysilane, dimethyldimethoxysil,ne, HMDO, six
Methyl disilazane, MTES, MTMS, dodecyltrimethoxysilane, dodecyl
Triethoxysilane, hexadecyl trimethoxy silane, hexadecyl, octamethylcy-clotetrasiloxane, pregnancy
At least one of basic ring trisiloxanes；
Described low surface tension solvent is at least one of n-hexane and normal heptane；
Described surfactant is Tween-20, Tween-80, Span -60, at least one of Span -65.
4. according to the method described in claim 1, it is characterised in that：
In the step（1）In, the ultrasonic power is 10 ~ 200W, and the time is 5 ~ 100min；The condition of the backflow is temperature
40 ~ 90 DEG C of degree, 3 ~ 100h of time；
In the step（2）In, the ultrasonically treated power is 5 ~ 200W, and the time is 1 ~ 200min；
In the step（3）In, the high-speed stirred refers to mixing speed for 400 ~ 1200 revs/min；Described heating response,
Reaction temperature is 30 ~ 70 DEG C, and the reaction time is 0.5h ~ 5h；The drying process refers to 1 ~ 6h of processing at 70 ~ 150 DEG C；Described
High-temperature activation refers to 1 ~ 5h of processing at 200 ~ 600 DEG C.
5. according to the method described in claim 1, it is characterised in that：Prepared titanium dioxide-CNT is compound porous micro-
Ball is regular spherical particle, and particle diameter is 1 ~ 3000 μm, and apparent density is 0.01 ~ 0.8 g/cm3, specific surface area is 100 ~ 1200
m2/ g, aperture is 5 ~ 1000nm.
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