CN102295310A - Preparation method of metal ion doped titanium dioxide transparent water sol - Google Patents
Preparation method of metal ion doped titanium dioxide transparent water sol Download PDFInfo
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- CN102295310A CN102295310A CN2010102206937A CN201010220693A CN102295310A CN 102295310 A CN102295310 A CN 102295310A CN 2010102206937 A CN2010102206937 A CN 2010102206937A CN 201010220693 A CN201010220693 A CN 201010220693A CN 102295310 A CN102295310 A CN 102295310A
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- inorganic salt
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 24
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002019 doping agent Substances 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- -1 titanium ions Chemical class 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 238000002156 mixing Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 17
- 238000003916 acid precipitation Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical class [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229940037003 alum Drugs 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 239000010936 titanium Substances 0.000 abstract description 7
- 229910052719 titanium Inorganic materials 0.000 abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 230000004298 light response Effects 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 230000001376 precipitating effect Effects 0.000 description 8
- 241000370738 Chlorion Species 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000010748 Photoabsorption Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 2
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 description 2
- 229910001000 nickel titanium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 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 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 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
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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Abstract
The invention relates to a titanium dioxide photocatalyst, in particular to a low-temperature preparation method of a visible light response type titanium dioxide transparent water sol doped with metal ions. Dissolving titanium inorganic salt and metal inorganic salt as a doping agent into water together to form a mixed solution; wherein the molar ratio of metal ions in the metal inorganic salt serving as the doping agent to titanium ions in the titanium inorganic salt is 0.001-0.2; and then dropwise adding an inorganic alkali liquor until the pH value of the mixed solution is about 7-11 to obtain a composite titanic acid precipitate, washing the composite titanic acid precipitate with water, filtering, dispersing with a hydrogen peroxide aqueous solution, and heating at 50-100 ℃ for 1-24 hours to obtain the metal ion doped titanium dioxide transparent aqueous sol. The low-temperature preparation method of the metal ion doped titanium dioxide transparent water-based sol avoids the problem of environmental pollution, and the obtained sol is transparent, neutral and water-based and has good photocatalytic effect under visible light.
Description
Technical field
The present invention relates to a class titanium dioxide optical catalyst, the clear aqueous Sol at Low Temperature preparation method of visible-light response type titanium dioxide of particularly a series of metal ion dopings.
Background technology
Titanium dioxide is a kind of metal oxide semiconductor material that has photocatalytic activity under UV-irradiation, because characteristics such as simple, with low cost, the safety non-toxic of its photochemical catalysis Technology, nonirritant, non-secondary pollution, chemical stability and Heat stability is good all are widely used at aspects such as solar energy converting, environmental purification, chemical sensors.But there are some defectives in titanium dioxide in actual applications as semiconductor material with wide forbidden band.Titanium dioxide can only be subjected to the ultraviolet excitation of wavelength less than 385nm, and this part UV-light less than 5% in solar spectrum has limited the utilization to sunlight.Therefore, how titanium dioxide is carried out modification, improve its utilization sunlight, the particularly utilization of visible light part, thus improve photocatalysis efficiency, become the focus and the difficult point problem of research.
Existing studies show that, method such as noble metal decorated, ion doping, composite semiconductor, dye sensitization all is effective means.Simple various the receiving much concern of metal ion mixing, adulterating method various wherein because of its doping ionic species.The research of traditional metal ion doped titanium dioxide mainly concentrates on preparation and has paramagnetic dilute magnetic semiconductor (Diluted magnetic semiconductors, DMS) aspect, just progressively turned to photocatalysis field in recent years, metal ion mixing has following two big advantages:
(1) can reduce the product energy gap, make photo-absorption region move to visible region, thereby improve the utilising efficiency of titanium dioxide sunlight;
(2) an amount of metal ion mixing can improve the interfacial charge transfer rate, reduces electronics-hole-recombination speed, thereby improves the photocatalysis performance of titanium dioxide.
Choi etc. [Angew.Chem.Int.Ed., 1994,33:1091-1092.] have studied metal ion mixing to TiO
2Photochemical catalytic oxidation chloroform and photo catalytic reduction CCl
4Influence, find that doping is the Fe of massfraction 0.5%
3+, Ru
3+, Os
3+Re
3+, V
5+Or Rh
3+Can increase photocatalytic activity.At present, the photocatalyst material that obtains by metal ion mixing mostly is powder greatly, needs high-temperature calcination to make the titanium dioxide crystallization, far lags behind the colloidal sol series products aspect practicality.TiO 2 sol is as uniform and stable dispersion system, having can be low temperature crystallized, particle is difficult for reuniting, colloidal sol uses advantages such as not being subjected to the substrate shape limitation, can be used for the synthetic or automatically cleaning high grade paint of photocatalysis thin film coating etc., and especially aqueous sol has more environment protection requirement.The method for preparing at present metal ion doped titanium dioxide colloidal sol generally is to adopt the method for titanium organic compound or the acidolysis of Ti-inorganic compound, titanium organic compound reaction by product pollutes environment, and the colloidal sol that obtains generally contains a large amount of mineral acids, has limited and has produced and use.As the patent of codoping titanium dioxide nano sol of CN200710068437.9 and preparation method thereof, it discloses the method for using butyl (tetra) titanate to obtain ions doped titanium dioxide colloidal sol as raw material under the hydrochloric acid effect.At present, the preparation of non-acid metal ion doped titanium dioxide aqueous sol does not still have report.
Summary of the invention
The objective of the invention is on the preparation method basis of titanium oxide water sol, provide a kind of clear aqueous Sol at Low Temperature preparation method of visible-light response type titanium dioxide of metal ion mixing of environmental protection, to overcome the shortcoming that prior art exists.
The preparation method of the clear aqueous colloidal sol of titanium dioxide of metal ion mixing of the present invention may further comprise the steps:
1), forms mixing solutions with Ti-inorganic salt and soluble in water jointly as the metal inorganic salt of doping agent; Wherein, the molar ratio as the titanium ion in metal ion in the metal inorganic salt of doping agent and the Ti-inorganic salt is 0.001～0.2;
2) the inorganic alkali lye of mixed solution and dripping that obtains to step 1) is about 7～11 to the pH of mixing solutions, obtains the composite titanic acid precipitation, washes and remove by filter the composite titanic acid precipitation with water used Ti-inorganic salt and as the negatively charged ion in the metal inorganic salt of doping agent;
3) with step 2) composite titanic acid precipitation behind the washing and filtering disperses with aqueous hydrogen peroxide solution that (molar ratio of the titanium ion of the hydrogen peroxide in the preferred aqueous hydrogen peroxide solution in precipitating with composite titanic acid is 1～25; The massfraction of preferred aqueous hydrogen peroxide solution is 5～30%), be 50～100 ℃ in temperature and heated 1～24 hour down, obtain the clear aqueous colloidal sol of titanium dioxide of metal ion mixing.
The clear aqueous colloidal sol of the titanium dioxide of the metal ion mixing of gained is neutral, and the pH value is between 5.5～8.
Described Ti-inorganic salt is selected from one or more in titanium tetrachloride, titanium sulfate, titanyl sulfate, four Titanium Nitrates, the titanium tetrafluoride etc.
Described metal inorganic salt as doping agent is the commercially available prod, is selected from not to be in the soluble salt in the villiaumite of one or more metallic elements in the thorium, villaumite, bromine salt, vitriol, sulphite, hydrosulfate, hydrosulphite, nitrate, nitrite, phosphoric acid salt, monohydric phosphate, dihydrogen phosphate, oxymuriate, the acetate one or more in IIA～VA, IB～VIIB in the periodic table of elements and the VIII family; Preferred is alum, chromium, manganese, iron, cobalt, nickel, copper, zirconium, silver, barium, tungsten, erbium, aluminium or tin as the metallic element in the metal inorganic salt of doping agent.
Described inorganic alkali lye is selected from one or more in ammoniacal liquor, sodium hydroxide solution, potassium hydroxide solution, the lithium hydroxide solution etc.
Describedly remove by filter used Ti-inorganic salt and be in fluorion, chlorion, bromide anion, sulfate ion, sulfite ion, nitrate ion, nitrite ion, phosphate anion, chloranion, the acetate ion one or more as the negatively charged ion in the metal inorganic salt of doping agent.
The clear aqueous Sol at Low Temperature preparation method of visible-light response type titanium dioxide of metal ion mixing of the present invention has avoided the pollution problem to environment, and gained colloidal sol is transparent, neutral, water-based, has good photochemical catalysis effect under visible light.The photocatalysis efficiency of gained aqueous sol under the visible light more not pure titinium dioxide of doped metal ion is improved, and improved 100%～400%.
Description of drawings
Fig. 1. the digital photograph in kind of the clear aqueous colloidal sol of titanium dioxide of the metal ion mixing of embodiment 1～5.
Fig. 2. the XRD spectra of the titanium dioxide of the metal ion mixing that the embodiment of the invention 1～3 obtains.
Fig. 3. the ultraviolet-visible diffuse-reflectance spectrogram of the titanium dioxide of the metal ion mixing that the embodiment of the invention 1～3 obtains.
Fig. 4. the degradation of methylene blue efficiency diagram after the TiO 2 sol film forming of the metal ion mixing that the embodiment of the invention 1～5 obtains.
Embodiment
Embodiment 1
With 0.01mol manganous sulfate (MnSO
4) be dissolved in jointly and form manganese-titanium mixing solutions in the 500mL water with the 0.1mol titanium tetrachloride, to the mixed solution and dripping ammonia soln to pH be 10, obtain manganese-titanium composite titanic acid precipitation, wash and remove by filter wherein sulfate radical and chlorion with water; To be scattered in the 50mL mass concentration through washing and filtering precipitation is (molar ratio of the titanium ion of hydrogen peroxide in precipitating with composite titanic acid is 5) in 30% the superoxol, 90 ℃ of reflux 4 hours, obtain the TiO 2 sol (material object is seen Fig. 1) of manganese ion doping, the pH value is between 7.5～8.0.
Embodiment 2:
With 0.0001mol neutralized verdigris (Cu (CH
3COO)
2) be dissolved in jointly and form copper-titanium mixing solutions in the 500mL water with the 0.1mol titanium tetrachloride, to the mixed solution and dripping ammonia soln to pH be 10, obtain copper-titanium composite titanic acid precipitation, wash and remove by filter wherein acetate and chlorion with water; To be scattered in the 60mL mass concentration through washing and filtering precipitation is (molar ratio of the titanium ion of hydrogen peroxide in precipitating with composite titanic acid is 1) in 5% the superoxol, 90 ℃ of reflux 1 hour, obtain copper ion doped TiO 2 sol (material object is seen Fig. 1), the pH value is between 6.0～6.5.
Embodiment 3:
With 0.005mol Xiao Suangu (Co (NO
3)
2) be dissolved in jointly and form cobalt-titanium mixing solutions in the 500mL water with the 0.1mol titanyl sulfate, to dropping aqueous solution of sodium to pH be 8, obtain cobalt-titanium composite titanic acid precipitation, wash and remove by filter wherein sulfate radical and nitrate ion with water; To be scattered in the 200mL mass concentration through washing and filtering precipitation is (molar ratio of the titanium ion of hydrogen peroxide in precipitating with composite titanic acid is 10) in 15% the superoxol, 100 ℃ of reflux 2 hours, obtain the adulterated TiO 2 sol of cobalt ion (material object is seen Fig. 1), the pH value is between 6.5～6.5.
Embodiment 4:
With 0.001mol nickelous chloride (NiCl
2) be dissolved in jointly in the 500mL water with 0.1mol four Titanium Nitrates and form the Ni-Ti mixing solutions, to the mixed solution and dripping potassium hydroxide aqueous solution to pH be 7, obtain Ni-Ti composite titanic acid precipitation, wash and remove by filter wherein nitrate radical and chlorion with water; To be scattered in the 250mL mass concentration through washing and filtering precipitation is (molar ratio of the titanium ion of hydrogen peroxide in precipitating with composite titanic acid is 25) in 30% the superoxol, 100 ℃ of reflux 8 hours, obtain the adulterated TiO 2 sol of nickel ion (material object is seen Fig. 1), the pH value is between 7.0～7.5.
Embodiment 5:
With 0.02mol iron trichloride (FeCl
3) be dissolved in jointly and form iron-titanium mixing solutions in the 500mL water with the 0.1mol titanium sulfate, to the mixed solution and dripping ammonia soln to pH be 11, obtain iron-titanium composite titanic acid precipitation, wash and remove by filter wherein sulfate radical and chlorion with water; To be scattered in the 150mL mass concentration through washing and filtering precipitation is (molar ratio of the titanium ion of hydrogen peroxide in precipitating with composite titanic acid is 5) in 10% the superoxol, 50 ℃ of reflux 24 hours, obtain the adulterated TiO 2 sol of iron ion (material object is seen Fig. 1), the pH value is between 5.5～6.0.
Embodiment 6:
With 0.003mol cupric nitrate (Cu (NO
3)
2), 0.001mol copper sulfate (CuSO
4) be dissolved in jointly and form copper-titanium mixing solutions in the 500mL water with the 0.1mol titanium tetrachloride, to the mixed solution and dripping ammonia soln to pH be 10, obtain copper-titanium composite titanic acid precipitation, wash and remove by filter wherein nitrate radical, sulfate radical and chlorion with water; To be scattered in the 100mL mass concentration through washing and filtering precipitation is (molar ratio of the titanium ion of hydrogen peroxide in precipitating with composite titanic acid is 10) in 30% the superoxol, 90 ℃ of reflux 8 hours, obtain copper ion doped TiO 2 sol, the pH value is between 6.0～6.5.
Embodiment 7:
With 0.005mol zirconium nitrate (Zr (NO
3)
4), 0.005mol tin chloride (SnCl
4) be dissolved in jointly and form zirconium/tin-titanium mixing solutions in the 500mL water with the 0.1mol titanium tetrachloride, to the mixed solution and dripping ammonia soln to pH be 11, obtain zirconium/tin-titanium composite titanic acid precipitation, wash and remove by filter wherein nitrate radical and chlorion with water; To be scattered in the 50mL mass concentration through washing and filtering precipitation is (molar ratio of the titanium ion of hydrogen peroxide in precipitating with composite titanic acid is 5) in 30% the superoxol, 100 ℃ of reflux 4 hours, obtain the TiO 2 sol of zirconium/stannum ion codope, the pH value is between 5.5～6.0.
Embodiment 8:
With the metal ion doped titanium dioxide colloidal sol of gained among the embodiment 1～3, the metal ion doped titanium dioxide powder that obtains after 100 ℃ of dryings, XRD spectra proves that it is the anatase titanium dioxide (see figure 2).Simultaneously, characterize its photoabsorption situation with ultraviolet-visible pectrophotometer diffuse-reflectance pattern, the ABSORPTION EDGE of the clear aqueous colloidal sol of metal ion doped titanium dioxide all red shift to visible region (greater than 550nm), and in the absorbancy of 400～800nm visible region apparently higher than the pure titinium dioxide (see figure 3).
Embodiment 9:
The colloidal sol that makes with embodiment 1～5, by the glass surface film forming of crystal pulling method in the supersound washing cleaning, intercepting 1 * 2cm width sheet glass was immersed in the 2mmol/L methylene blue solution after 24 hours, taking-up washes down with pure water, immerse again in the 20mL 1mmol/L methylene blue solution, after the 18W fluorescent light was according to 2 hours, measure it to the methylene blue degradation efficiency, use spectral filter to filter out the following UV-light of 400nm.By calculating the photocatalysis efficiency of five kinds of colloidal sols, confirm that it has good photochemical catalysis effect under visible light, compare with pure titinium dioxide, the prepared colloidal sol of embodiment 1～5 has improved about 150%, 200%, 100%, 250% and 400% respectively to the degradation efficiency of methylene blue, see Fig. 4.
Claims (8)
1. the preparation method of the clear aqueous colloidal sol of titanium dioxide of a metal ion mixing is characterized in that, this method may further comprise the steps:
1), forms mixing solutions with Ti-inorganic salt and soluble in water jointly as the metal inorganic salt of doping agent; Wherein, the molar ratio as the titanium ion in metal ion in the metal inorganic salt of doping agent and the Ti-inorganic salt is 0.001～0.2;
2) the inorganic alkali lye of mixed solution and dripping that obtains to step 1) to the pH of mixing solutions be 7～11, obtain the composite titanic acid precipitation, wash and remove by filter the composite titanic acid precipitation with water used Ti-inorganic salt and as the negatively charged ion in the metal inorganic salt of doping agent;
3) with step 2) composite titanic acid precipitation behind the washing and filtering disperses with aqueous hydrogen peroxide solution, is 50～100 ℃ of heating 1～24 hour down in temperature, obtains the clear aqueous colloidal sol of titanium dioxide of metal ion mixing.
2. preparation method according to claim 1 is characterized in that: the clear aqueous colloidal sol of the titanium dioxide of the metal ion mixing that obtains is for neutral, and the pH value is between 5.5～8.
3. preparation method according to claim 1 is characterized in that: the molar ratio of the titanium ion in hydrogen peroxide in the aqueous hydrogen peroxide solution in the step 3) and the composite titanic acid precipitation is 1～25.
4. according to claim 1 or 3 described preparation methods, it is characterized in that: the massfraction of described aqueous hydrogen peroxide solution is 5～30%.
5. preparation method according to claim 1 is characterized in that: described Ti-inorganic salt is selected from one or more in titanium tetrachloride, titanium sulfate, titanyl sulfate, four Titanium Nitrates, the titanium tetrafluoride.
6. preparation method according to claim 1 is characterized in that: described metal inorganic salt as doping agent is selected from and is not in the soluble salt in the villiaumite of one or more metallic elements in the thorium, villaumite, bromine salt, vitriol, sulphite, hydrosulfate, hydrosulphite, nitrate, nitrite, phosphoric acid salt, monohydric phosphate, dihydrogen phosphate, oxymuriate, the acetate one or more in IIA～VA, IB～VIIB in the periodic table of elements and the VIII family.
7. preparation method according to claim 6 is characterized in that: described is alum, chromium, manganese, iron, cobalt, nickel, copper, zirconium, silver, barium, tungsten, erbium, aluminium or tin as the metallic element in the metal inorganic salt of doping agent.
8. preparation method according to claim 1 is characterized in that: described inorganic alkali lye is selected from one or more in ammoniacal liquor, sodium hydroxide solution, potassium hydroxide solution, the lithium hydroxide solution.
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