CN107954470A - A kind of preparation method and applications of water-soluble titanium dioxide nano particle - Google Patents
A kind of preparation method and applications of water-soluble titanium dioxide nano particle Download PDFInfo
- Publication number
- CN107954470A CN107954470A CN201711194452.8A CN201711194452A CN107954470A CN 107954470 A CN107954470 A CN 107954470A CN 201711194452 A CN201711194452 A CN 201711194452A CN 107954470 A CN107954470 A CN 107954470A
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- Prior art keywords
- water
- nano particle
- ptba
- titanium dioxide
- dioxide nano
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 53
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229920001400 block copolymer Polymers 0.000 claims abstract description 13
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 7
- 101710141544 Allatotropin-related peptide Proteins 0.000 claims abstract description 6
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 6
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 6
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 6
- 239000000693 micelle Substances 0.000 claims abstract description 6
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 5
- 229960004853 betadex Drugs 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 17
- 239000012467 final product Substances 0.000 claims description 17
- 239000003708 ampul Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 230000001699 photocatalysis Effects 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 10
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 10
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 235000015424 sodium Nutrition 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- QHHUCCOZVUZUSR-UHFFFAOYSA-N C=1C=CC=CC=1C([Na])C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C([Na])C1=CC=CC=C1 QHHUCCOZVUZUSR-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 230000005291 magnetic effect Effects 0.000 claims description 7
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- -1 alkynyl Glycol Chemical compound 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 238000010257 thawing Methods 0.000 claims description 6
- 150000001540 azides Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000002790 naphthalenes Chemical class 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 230000003252 repetitive effect Effects 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001427 mPEG Polymers 0.000 claims 4
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 claims 2
- 150000001345 alkine derivatives Chemical class 0.000 claims 1
- 125000006840 diphenylmethane group Chemical class 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 7
- 229940012189 methyl orange Drugs 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000002500 effect on skin Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000009533 lab test Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical group O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000225 lethality Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention discloses a kind of preparation method and applications of water-soluble titanium dioxide nano particle, beta cyclodextrin is used as initial reaction raw material, through modifying synthetic macromolecule initiator, using ATRP technologies, and the technology that ATRP and " link " chemical (Click Chemistry) are combined, multi-arm star block copolymer is made, based on solution phase synthesis, using the multi-arm star block copolymer as unimolecular micelle template, the water-soluble titanium dioxide nano particle of size uniformity and favorable dispersibility is made.TiO produced by the present invention2Nanoparticle mass is stablized, and particle size is homogeneous, and can stablize in nanoscale, can effectively ensure that TiO2The performance of nano particle performance.The present invention is to TiO2The surface of nano particle is modified, it can be made to be uniformly dispersed in water, avoids that reuniting effect occurs.
Description
Technical field
The present invention relates to a kind of preparation method and applications of water-soluble titanium dioxide nano particle, belong to inorganic nano material
Expect synthesis technical field.
Background technology
It in 1-100nm or by them is generally referred to as that the material that elementary cell is formed is nano material to have one-dimensional dimensions above,
This is about as much as the scale that 10-100 atom is arranged closely together.Nano material is due to skin effect, micro-dimension
The effect of the uniqueness such as effect and quantum tunneling effect, thus show electricity, optics, magnetics and the catalytic performance of uniqueness.
Titanium dioxide has greater band gap, good biocompatibility, anti-various chemistry corruption as a kind of typical N-type semiconductor
The characteristics of candle, human body nonhazardous, while there is good optical power, photocatalysis performance, photoelectric conversion rate, antimicrobial efficiency,
Through be widely used in cosmetics, coating, water body purification, air purification, solar cell, dye-sensitized cell, biological medicine and
The multiple fields such as antibiotic and sterilizing.
Photocatalysis oxidation technique has outstanding advantages of efficient, energy saving, cleaning is nontoxic, and being one has wide application prospect
New air pollution and water pollution treatment technology.Optically catalytic TiO 2 research origin in Fujishima in 1979 and
Honda decomposes the experiment of water with luminous energy using titanium deoxid film as electrode.Since then, optically catalytic TiO 2 technology just causes
The extensive concern of scientist.Titanium dioxide can produce substantial amounts of electron hole and extremely strong oxygen under sunlight and radiation of visible light
The active oxygen of change effect, can be the nonhazardous materials such as water and carbon dioxide by the oxidation operation adsorbed on the titanium dioxide,
Secondary pollution will not be caused, thus is a kind of environment-friendly materials very with application prospect.Further, good light will urges
The nano-titanium dioxide for changing performance is added in coating, forms photo-catalytic coating.The photo-catalytic coating new clothes that can effectively degrade are repaired the house
Between formaldehyde, the TVOCs such as toluene, purify the air of a room.Photo-catalytic coating can also effectively kill the various bacteria in air,
It can suppress various bacteria growth at the same time, bring glad tidings for newly-decorated family.
The synthetic method of titania nanoparticles has many kinds, can be generally divided into liquid phase method and vapor phase method.Vapor phase method
Mainly gas phase TiCl4Oxidizing process.Liquid phase method mainly includes sol-gal process, chemical precipitation method and hydrothermal synthesis method etc..Tradition
Method synthesis titania nanoparticles usually have the shortcomings that size and be distributed it is uncontrollable, and the property of titanium dioxide and answer
With the size and dispersiveness depended greatly in particle, therefore find that a kind of grain size is homogeneous and favorable dispersibility
The simple and convenient process for preparing of titania nanoparticles be very crucial.
The content of the invention
The technical problems to be solved by the invention be to provide a kind of water-soluble titanium dioxide nano particle preparation method and
It is applied, titania nanoparticles size uniformity prepared by this method, favorable dispersibility.
To achieve these goals, the technical solution adopted in the present invention is：
A kind of preparation method of water-soluble titanium dioxide nano particle, comprises the following steps：
(1) beta-cyclodextrin is dissolved in 1-methyl-2-pyrrolidinone, 2- bromine isobutyl acylbromides, room temperature is added under the conditions of being placed in 0 DEG C
Reaction, is made starlike macromole evocating agent 21Br- β-CD；
(2) reacting starlike macromole evocating agent 21Br- β-CD by ATRP polymerization triggers tert-butyl acrylate monomer to gather
Close, multi-arm star β-CD-g-PtBA are made；
(3) multi-arm star β-CD-g-PtBA are subjected to Azide processing, then using end group modification as the mono methoxy with alkynyl
Polyethylene glycol is the presoma of outermost section block, prepares radial block polymer β-CD-g- [PtBA-b-PEG]；
(4) by radial block polymer β-CD-g- [PtBA-b-PEG] dissolvings in methylene chloride, trifluoroacetic acid is added,
Hydrolysis obtains multi-arm star block copolymer β-CD-g- [PAA-b-PEG] under normal temperature condition；
(5) using multi-arm star block copolymer β-CD-g- [PAA-b-PEG] as unimolecular micelle template, then with solvable
Property containing titanium oxide compounds be presoma, water-soluble titanium dioxide nano particle is made.
The beta-cyclodextrin and the molar ratio of 2- bromine isobutyl acylbromides are 1：42.
The specific method of step (2) is：In ampoule bottle add 0.0707g CuBr, 0.1707g PMDETA,
0.1g21Br- β-CD, 20mL tert-butyl acrylates monomer, 20mL butanone, be placed in liquid nitrogen by freeze-vacuumize degassing-
Defrosting is de-gassed, and circulation three times, is put into ampoule bottle in 60 DEG C of oil baths, magnetic agitation 12-24h after closed；Take out ampoule bottle,
Put into mixture of ice and water, terminate reaction；Acetone dilution is added, is splined on neutral alumina column, collects efflux ,-
For 20 DEG C of methanol with being precipitated in the mixed liquor of 4 DEG C of water, the volume ratio of methanol and water is 1：1, after repeating dissolution/precipitation operation twice,
Gained white powder product is dried in vacuo 12h at 50 DEG C, to obtain the final product.
The specific method of step (3) is：
(a) synthesis of star end group Azide PtBA
Above-mentioned gained β-CD-g-PtBA 3.60g are taken, are dissolved in 15mL DMF, add sodium azide, sodium azide and β-
The molar ratio of Br atoms is 10 in CD-g-PtBA：1,24h is stirred in sealing at ambient temperature；Acetone dilution is added, is splined on
Neutral alumina column, collects efflux, and in -20 DEG C of methanol with being precipitated in the mixed liquor of 4 DEG C of water, the volume ratio of methanol and water is 1：
1, after repeating dissolution/precipitation operation twice, gained white powder product is placed at 50 DEG C and is dried in vacuo 12h to obtain the final product, name
For β-CD-g-PtBA-N3；
(b) synthesis of benzhydryl sodium DPMNa
100mL tetrahydrofurans and 7.7g naphthalenes are added in 250mL three-necked flasks, open stirring, after waiting naphthalene to be completely dissolved,
1.38g metallic sodiums are added under the protection of inert gas argon gas, 4h is reacted under the conditions of 40 DEG C, then add 11.1g hexichol first
Alkane, flow back 24h under the conditions of 80 DEG C, obtains the THF solution of the wine-colored sodium containing benzhydryl；
(c) synthesis of the mPEG of alkynyl end-blocking
In dry three-necked flask, 10g mPEG and 150mL tetrahydrofurans are added, then add the sodium containing benzhydryl
THF solution, benzhydryl sodium molal quantity are 5 times of mPEG, and solution colour is changed into brownish red；It is then placed in ice-water bath, is added dropwise
Propargyl bromide, propargyl bromide molal quantity are 5 times of mPEG, react 24h at ambient temperature；Dichloromethane dilution is added, is splined on
Neutral alumina column, collects efflux, is concentrated with Rotary Evaporators, precipitated in -20 DEG C of ether, sediment is in vacuum drying oven
50 DEG C of dry 5h to obtain the final product, are named as mPEG-propargyl；
(d) synthesis of multi-arm star block copolymer β-CD-g- [PtBA-b-PEG]
CuBr, PMDETA, β-CD-g-PtBA-N are added in ampoule bottle3, mPEG-propargyl, their molar ratio
For CuBr：PMDETA：β-CD-g-PtBA-N3：MPEG-propargyl=10：10：1：1.2, and DMF is added as solvent, make
β-CD-g-PtBA-N3Concentration be 1g/10mL；It is subsequently placed in liquid nitrogen and is taken off by freezing-vacuumizing degassing-defrosting
Gas, circulation three times, are put into ampoule bottle in 90 DEG C of oil baths, magnetic agitation 24h after closed；Room temperature is cooled to, adds dichloromethane
Alkane dilutes, and is splined on neutral alumina column, collects efflux, is precipitated in -20 DEG C of methanol, repeats dissolution/precipitation operation twice
Afterwards, gained white powder product is placed at 60 DEG C and is dried in vacuo 12h, to obtain the final product.
The specific method of step (4) is：0.3g β-CD-g- [PtBA-b-PEG] are dissolved in 30mL dichloromethane, 0
DEG C stirring is lower adds trifluoroacetic acid, and trifluoroacetic acid addition is that tert-butyl acrylate monomer rubs in β-CD-g- [PtBA-b-PEG]
5 times of that amount, after 0 DEG C is continued to keep 3h, continue stirring reaction 21h, generation white depositions, filtering, with two at room temperature
Chloromethanes washing precipitate, and vacuum freeze drying, to obtain the final product.
The specific method of step (5) is：β-CD-g- [PAA-b-PEG] are dissolved in DMF, unimolecular micelle mould is made
Plate solution；Presoma isopropyl titanate is added, back flow reaction, is made water-soluble titanium dioxide nano particle.
The molar ratio of the presoma isopropyl titanate and acrylic acid repetitive unit in β-CD-g- [PAA-b-PEG] is not small
In 5：1.
The back flow reaction temperature is 150-200 DEG C, time 2-4h.
Sodium dioxide nano particle prepared by a kind of method is preparing the photocatalytic degradation of organic pollution and conjunction
Into the application in photo-catalytic coating.
Beneficial effect：
1st, the present invention uses beta-cyclodextrin as initial reaction raw material, through modifying synthetic macromolecule initiator, using ATRP skills
Art, and the technology that ATRP and " link " chemical (Click Chemistry) are combined, are made multi-arm star block copolymer,
Based on solution phase synthesis, using the multi-arm star block copolymer as unimolecular micelle template, size uniformity is made and divides
Dissipate the good water-soluble titanium dioxide nano particle of property.
2、TiO2For nano particle since its surface is the unordered noncrystalline layer of short distance, inside is complete crystallization, cycle row
The atom of cloth, therefore it is special with small-size effect, skin effect, quantum size effect, macro quanta tunnel effect etc.
Property：
(1)TiO2Nano particle has a photocatalysis, and the electronics in valence band is excited, and transits to conduction band, produces high living
Property light induced electron (e-), while can produce corresponding photohole (h+) in valence band.Light induced electron and photohole can be with absorption
- OH, O in nano grain surface2And H2O reacts, generation activity hydroxy (- OH), hydroperoxyl (- OOH), superoxide ion (- O2)
With hydrogen peroxide (H2O2)。TiO2This performance of nano particle has extremely strong lethality to microorganism, has in emulsion paint
Important function.
(2)TiO2The particle diameter of nano particle is small, specific surface area is big, in the composite, is produced very between meeting and basis material
Strong combination power, therefore, can improve the intensity and toughness of material at the same time, this is that nano material is most aobvious to high molecular polymer modification
One of effect of work.
(3)TiO2The size of nano particle drops to nanoscale, and surface area can significantly increase, and cause surface energy to increase rapidly
Add, be easily combined and settle out with other atoms, therefore there is very high chemism, it is easy to absorb small point of ambient gas etc.
Son, these small molecules gas membrane stable equivalent to one layer, makes You Heshui can not be in the unfolded surface of material, therefore nanometer material
Expect that double thin property are presented in surface, referred to as super parents' interfacial characteristics.
(4) reunion is also easy to produce in nano material preparation process, the actual particle size of material is more than nanoscale, under various performances
Drop does not have the function that nano material even.Therefore it must be uniformly dispersed, avoid reuniting, this is exactly the innovative point of the present invention
One of.The present invention is to TiO2The surface of nano particle is modified, it can be made to be uniformly dispersed in water, avoids reuniting
Effect.
(5)TiO2Nano-particle has good visible light catalytic performance.
3rd, TiO produced by the present invention2Nanoparticle mass is stablized, and particle size is homogeneous, and can stablize in nanometer
Level, can effectively ensure that TiO2The performance of nano particle performance.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with attached drawing.
Fig. 1 is the TEM image of titania nanoparticles.
Fig. 2 is the dissolubility result of titania nanoparticles.
Fig. 3 is the formaldehyde removal effect figure of photo-catalytic coating prepared by titania nanoparticles.
Fig. 4 is titania nanoparticles photo-catalytic degradation of methyl-orange design sketch.
Embodiment
The embodiment of the present invention is described in further detail with reference to embodiments.
Embodiment 1
A kind of preparation method of water-soluble titanium dioxide nano particle, comprises the following steps：
(1) synthesis of starlike macromole evocating agent 21Br- β-CD：
6.82g beta-cyclodextrins are taken, under vacuum in 80 DEG C of dry 12h, are then dissolved in 60mL under normal temperature condition
1-methyl-2-pyrrolidinone, then be placed in ice-water bath, be cooled to 0 DEG C, under this condition, 58g 2- bromine isobutyryls are added dropwise in 2h
Bromine, room temperature is warming up to after completion of dropwise addition, the reaction was continued 24h, obtains brown solution, vacuum distillation concentration, adds 100mL dichloromethanes
Alkane dilutes, and is respectively washed three times with 100mL saturated sodium bicarbonate aqueous solutions and 100mL deionized waters respectively, obtained organic phase
Dried with anhydrous magnesium sulfate, then concentrated with Rotary Evaporators, finally precipitated in the n-hexane below -20 DEG C, obtain white
Sediment, 50 DEG C of dry 12h in vacuum drying oven, to obtain the final product；
(2) synthesis of multi-arm star β-CD-g-PtBA
0.0707g CuBr, 0.1707g PMDETA (pentamethyl-diethylenetriamine), 0.1g are added in ampoule bottle
21Br- β-CD, 20mL tert-butyl acrylates monomer, 20mL butanone, are placed in liquid nitrogen by freezing-vacuumizing degassing-defrosting
It is de-gassed, circulation three times, is put into ampoule bottle in 60 DEG C of oil baths, magnetic agitation 24h after closed；Ampoule bottle is taken out, is thrown
Enter in mixture of ice and water, terminate reaction；Acetone (50mL) dilution is added, is splined on neutral alumina column, collects efflux ,-
For 20 DEG C of methanol with being precipitated in the mixed liquor of 4 DEG C of water, the volume ratio of methanol and water is 1：1, after repeating dissolution/precipitation operation twice,
Gained white powder product is dried in vacuo 12h at 50 DEG C, to obtain the final product；
(3) synthesis of star end group Azide PtBA
Above-mentioned gained β-CD-g-PtBA 3.60g are taken, are dissolved in 15mL DMF, add sodium azide, sodium azide and β-
The molar ratio of Br atoms is 10 in CD-g-PtBA：1,24h is stirred in sealing at ambient temperature；The dilution of 50mL acetone is added, on
Sample collects efflux, in -20 DEG C of methanol with being precipitated in the mixed liquor of 4 DEG C of water, the volume ratio of methanol and water in neutral alumina column
For 1：1, after repeating dissolution/precipitation operation twice, gained white powder product is placed at 50 DEG C and is dried in vacuo 12h to obtain the final product,
It is named as β-CD-g-PtBA-N3；
(4) synthesis of benzhydryl sodium DPMNa
100mL tetrahydrofurans and 7.7g naphthalenes are added in 250mL three-necked flasks, open stirring, after waiting naphthalene to be completely dissolved,
1.38g metallic sodiums are added under the protection of inert gas argon gas, 4h is reacted under the conditions of 40 DEG C, then add 11.1g hexichol first
Alkane, flow back 24h under the conditions of 80 DEG C, obtains the THF solution of the wine-colored sodium containing benzhydryl；Gained benzhydryl sodium solution is used
0.1M hydrochloric acid solutions are demarcated, and concentration is about 0.56M.
(5) synthesis of the mPEG of alkynyl end-blocking
In dry three-necked flask, 10g mono methoxy polyethylene glycols (mPEG) and 150mL tetrahydrofurans are added, then
The THF solution of the sodium containing benzhydryl is added, benzhydryl sodium molal quantity is 5 times of mPEG, and solution colour is changed into brownish red；Then
It is put into ice-water bath, propargyl bromide is added dropwise, propargyl bromide molal quantity is 5 times of mPEG, reacts 24h at ambient temperature；Add
100mL dichloromethane dilutes, and is splined on neutral alumina column, collects efflux, is concentrated with Rotary Evaporators, in -20 DEG C of ether
Middle precipitation, sediment 50 DEG C of dry 5h in vacuum drying oven to obtain the final product, are named as mPEG-propargyl；
(6) synthesis of multi-arm star block copolymer β-CD-g- [PtBA-b-PEG]
CuBr, PMDETA, β-CD-g-PtBA-N are added in ampoule bottle3, mPEG-propargyl, their molar ratio
For CuBr：PMDETA：β-CD-g-PtBA-N3：MPEG-propargyl=10：10：1：1.2, and DMF is added as solvent, make
β-CD-g-PtBA-N3Concentration be 1g/10mL；It is subsequently placed in liquid nitrogen and is taken off by freezing-vacuumizing degassing-defrosting
Gas, circulation three times, are put into ampoule bottle in 90 DEG C of oil baths, magnetic agitation 24h after closed；Room temperature is cooled to, adds dichloromethane
Alkane (50-100mL) dilutes, and is splined on neutral alumina column, collects trickle, is precipitated in -20 DEG C of methanol, and repetition dissolving/
Precipitation operation twice after, gained white powder product is placed at 60 DEG C and is dried in vacuo 12h, to obtain the final product；
(7) synthesis of multi-arm star block copolymer β-CD-g- [PAA-b-PEG]
0.3g β-CD-g- [PtBA-b-PEG] are dissolved in 30mL dichloromethane, trifluoro second is added under 0 DEG C of stirring
Acid, trifluoroacetic acid addition are 5 times of tert-butyl acrylate monomer molar amount in β-CD-g- [PtBA-b-PEG], in 0 DEG C of continuation
After keeping 3h, continue stirring reaction 21h at room temperature, produce white depositions, filtering, with dichloromethane washing precipitate, and
Vacuum freeze drying (- 10 DEG C, 30min), to obtain the final product；
(8) synthesis of titania nanoparticles
20mg multi-arm star block copolymer β-CD-g- [PAA-b-PEG] are dissolved in 30mL DMF, unimolecule is made
Micellar Gel solution；Presoma isopropyl titanate 0.1758g is added, the back flow reaction 3h under the conditions of 170 DEG C, finally with centrifugation
(rotating speed 1000rpm, centrifuges 5min) removes accessory substance, to obtain the final product.
TiO2The TEM figures of nano particle are as shown in Figure 1, the nanoparticle size for preparing of the present invention is homogeneous, and average grain diameter is about
For 10nm.
To TiO2The solubility of nano particle in water is detected, and the results are shown in Figure 2, it is known that prepared by the present invention
TiO2Nano particle has good dissolubility.
Application examples performance evaluation
1st, the formaldehyde removal effect test of photo-catalytic coating
Particle diameter is added to (titania nanoparticles quality in commercially available common coating for 10nm titania nanoparticles
Fraction is 3%) to prepare photo-catalytic coating, is then squeegeed onto onto the test plate (panel) of 300 × 500mm.In 1m3Sealing experiment cabin
Formaldehyde removal effect under middle test LED light irradiation, formaldehyde test use national standard phenol reagent process.Parallel laboratory test result table three times
Bright, after 24h, the removal rate of formaldehyde reaches 90% or so (as shown in Figure 3).
2nd, methyl orange measure of merit in titania nanoparticles degradation of dye
Catalyst using particle diameter as 10nm titania nanoparticles as methyl orange degradation, with the methyl orange of 20mg/L
Organic solution is target contaminant, and titania nanoparticles are added the (nano titania into the organic solution of methyl orange
Granular mass fraction is 3%), to test the methyl orange degradation efficiency under sunlight conditions.Three times parallel laboratory test the result shows that, 4h
Afterwards, the degradation rate of methyl orange reaches 90% or so (as shown in Figure 4).
The foregoing is merely the embodiment that the present invention is optimal, for those skilled in the art, the present invention can have
Various modifications and variations.Within the spirit and principles of the invention, any modification, equivalent replacement, improvement and so on, should all
Within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of water-soluble titanium dioxide nano particle, it is characterised in that comprise the following steps：
(1) beta-cyclodextrin is dissolved in 1-methyl-2-pyrrolidinone, addition 2- bromine isobutyl acylbromides under the conditions of being placed in 0 DEG C, normal-temperature reaction,
Starlike macromole evocating agent 21Br- β-CD are made；
(2) starlike macromole evocating agent 21Br- β-CD are reacted by ATRP polymerization and triggers tert-butyl acrylate monomer polymerization, system
Obtain multi-arm star β-CD-g-PtBA；
(3) multi-arm star β-CD-g-PtBA are subjected to Azide processing, then using end group modification as the poly- second of the mono methoxy with alkynyl
Glycol is the presoma of outermost section block, prepares radial block polymer β-CD-g- [PtBA-b-PEG]；
(4) by radial block polymer β-CD-g- [PtBA-b-PEG] dissolvings in methylene chloride, trifluoroacetic acid, room temperature are added
Under the conditions of hydrolysis obtain multi-arm star block copolymer β-CD-g- [PAA-b-PEG]；
(5) multi-arm star block copolymer β-CD-g- [PAA-b-PEG] are contained as unimolecular micelle template, then with solubility
Titanium oxide compounds are presoma, and water-soluble titanium dioxide nano particle is made.
2. the preparation method of water-soluble titanium dioxide nano particle according to claim 1, it is characterised in that the β-
The molar ratio of cyclodextrin and 2- bromine isobutyl acylbromides is 1：42.
3. the preparation method of water-soluble titanium dioxide nano particle according to claim 1, it is characterised in that step (2)
Specific method be：0.0707g CuBr, 0.1707g PMDETA, 0.1g 21Br- β-CD, 20mL third are added in ampoule bottle
Enoic acid ter-butyl ester monomer, 20mL butanone, are placed in liquid nitrogen and are de-gassed by freezing-vacuumizing degassing-defrosting, circulation three
It is secondary, ampoule bottle is put into 60 DEG C of oil baths after closed, magnetic agitation 12-24h；Ampoule bottle is taken out, is put into mixture of ice and water
In, terminate reaction；Acetone dilution is added, is splined on neutral alumina column, collects efflux, in mixing for -20 DEG C of methanol and 4 DEG C of water
Close and precipitated in liquid, the volume ratio of methanol and water is 1：1, gained white powder product is dried in vacuo 12h at 50 DEG C, to obtain the final product.
4. the preparation method of water-soluble titanium dioxide nano particle according to claim 1, it is characterised in that step (3)
Specific method be：
(a) synthesis of star end group Azide PtBA
Above-mentioned gained β-CD-g-PtBA 3.60g are taken, are dissolved in 15mL DMF, add sodium azide, sodium azide and β-CD-g-
The molar ratio of Br atoms is 10 in PtBA：1,24h is stirred in sealing at ambient temperature；Acetone dilution is added, is splined on neutrality
Alumina column, collects efflux, and in -20 DEG C of methanol with being precipitated in the mixed liquor of 4 DEG C of water, the volume ratio of methanol and water is 1：1, institute
White powder product be placed at 50 DEG C be dried in vacuo 12h to obtain the final product, be named as β-CD-g-PtBA-N3；
(b) synthesis of benzhydryl sodium DPMNa
100mL tetrahydrofurans and 7.7g naphthalenes are added in 250mL three-necked flasks, stirring is opened, after waiting naphthalene to be completely dissolved, lazy
Property gases argon protection under add 1.38g metallic sodiums, 4h is reacted under the conditions of 40 DEG C, then add 11.1g diphenyl-methanes,
Flow back 24h under the conditions of 80 DEG C, obtains the THF solution of the wine-colored sodium containing benzhydryl；
(c) synthesis of the mPEG of alkynyl end-blocking
In dry three-necked flask, 10g mPEG and 150mL tetrahydrofurans are added, then add the THF of the sodium containing benzhydryl
Solution, benzhydryl sodium molal quantity are 5 times of mPEG, and solution colour is changed into brownish red；It is then placed in ice-water bath, bromine third is added dropwise
Alkynes, propargyl bromide molal quantity are 5 times of mPEG, react 24h at ambient temperature；Dichloromethane dilution is added, is splined on neutrality
Alumina column, collects efflux, is concentrated with Rotary Evaporators, precipitated in -20 DEG C of ether, sediment is 50 DEG C in vacuum drying oven
Dry 5h to obtain the final product, is named as mPEG-propargyl；
(d) synthesis of multi-arm star block copolymer β-CD-g- [PtBA-b-PEG]
CuBr, PMDETA, β-CD-g-PtBA-N are added in ampoule bottle3, mPEG-propargyl, their molar ratio is
CuBr：PMDETA：β-CD-g-PtBA-N3：MPEG-propargyl=10：10：1：1.2, and add DMF as solvent, make β-
CD-g-PtBA-N3Concentration be 1g/10mL；It is subsequently placed in liquid nitrogen and is de-gassed by freezing-vacuumizing degassing-defrosting,
Circulation three times, is put into ampoule bottle in 90 DEG C of oil baths, magnetic agitation 24h after closed；Room temperature is cooled to, it is dilute to add dichloromethane
Release, be splined on neutral alumina column, collect efflux, precipitated in -20 DEG C of methanol, gained white powder product is placed at 60
12h is dried in vacuo at DEG C, to obtain the final product.
5. the preparation method of water-soluble titanium dioxide nano particle according to claim 1, it is characterised in that step (4)
Specific method be：0.3g β-CD-g- [PtBA-b-PEG] are dissolved in 30mL dichloromethane, three are added under 0 DEG C of stirring
Fluoroacetic acid, trifluoroacetic acid addition is 5 times of tert-butyl acrylate monomer molar amount in β-CD-g- [PtBA-b-PEG], at 0 DEG C
Continue after keeping 3h, continue stirring reaction 21h at room temperature, produce white depositions, filtering, precipitation is washed with dichloromethane
Thing, and vacuum freeze drying, to obtain the final product.
6. the preparation method of water-soluble titanium dioxide nano particle according to claim 1, it is characterised in that step (5)
Specific method be：β-CD-g- [PAA-b-PEG] are dissolved in DMF, unimolecular micelle template solution is made；Before adding
Body isopropyl titanate is driven, back flow reaction, is made water-soluble titanium dioxide nano particle.
7. the preparation method of water-soluble titanium dioxide nano particle according to claim 6, it is characterised in that before described
Drive body isopropyl titanate and the molar ratio of acrylic acid repetitive unit in β-CD-g- [PAA-b-PEG] is not less than 5：1.
8. the preparation method of water-soluble titanium dioxide nano particle according to claim 7, it is characterised in that described returns
It is 150-200 DEG C to flow reaction temperature, time 2-4h.
9. sodium dioxide nano particle prepared by a kind of claim 1-8 any one of them method is preparing organic pollution
Application in photocatalytic degradation and synthesis photo-catalytic coating.
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| CN108707212A (en) * | 2018-05-02 | 2018-10-26 | 上海交通大学 | A kind of controllable method for preparing of soluble conjugated polymer nano-particle |
| CN109231255A (en) * | 2018-09-27 | 2019-01-18 | 安徽大学 | Preparation method of multi-metal oxide nanoparticles |
| CN111554913A (en) * | 2020-05-20 | 2020-08-18 | 佛山科学技术学院 | Multilayer titanium dioxide mesoporous film electrode material and preparation method and application thereof |
| CN113072897A (en) * | 2021-03-09 | 2021-07-06 | 宁波恩派新材料科技有限公司 | High-temperature vulcanized natural latex adhesive and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108707212A (en) * | 2018-05-02 | 2018-10-26 | 上海交通大学 | A kind of controllable method for preparing of soluble conjugated polymer nano-particle |
| CN108707212B (en) * | 2018-05-02 | 2020-01-07 | 上海交通大学 | Controllable preparation method of water-soluble conjugated polymer nanoparticles |
| CN109231255A (en) * | 2018-09-27 | 2019-01-18 | 安徽大学 | Preparation method of multi-metal oxide nanoparticles |
| CN111554913A (en) * | 2020-05-20 | 2020-08-18 | 佛山科学技术学院 | Multilayer titanium dioxide mesoporous film electrode material and preparation method and application thereof |
| CN111554913B (en) * | 2020-05-20 | 2021-06-15 | 佛山科学技术学院 | Multilayer titanium dioxide mesoporous film electrode material and preparation method and application thereof |
| CN113072897A (en) * | 2021-03-09 | 2021-07-06 | 宁波恩派新材料科技有限公司 | High-temperature vulcanized natural latex adhesive and preparation method thereof |
| CN113072897B (en) * | 2021-03-09 | 2022-08-05 | 宁波恩派新材料科技有限公司 | High-temperature vulcanized natural latex adhesive and preparation method thereof |
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