CN102219179B - Silver-doped titanium dioxide film and preparation method thereof - Google Patents
Silver-doped titanium dioxide film and preparation method thereof Download PDFInfo
- Publication number
- CN102219179B CN102219179B CN 201010153504 CN201010153504A CN102219179B CN 102219179 B CN102219179 B CN 102219179B CN 201010153504 CN201010153504 CN 201010153504 CN 201010153504 A CN201010153504 A CN 201010153504A CN 102219179 B CN102219179 B CN 102219179B
- Authority
- CN
- China
- Prior art keywords
- tio
- silver
- colloidal sol
- preparation
- film material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 title abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 239000004332 silver Substances 0.000 claims abstract description 29
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- 239000010409 thin film Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 47
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 3
- 229940096017 silver fluoride Drugs 0.000 claims description 3
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 229960001516 silver nitrate Drugs 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 35
- 239000004408 titanium dioxide Substances 0.000 abstract description 15
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 11
- 239000010408 film Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002135 nanosheet Substances 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000004332 deodorization Methods 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000002055 nanoplate Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 230000000845 anti-microbial effect Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 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 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000012093 association test Methods 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
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the field of noble metal doped oxide semiconductor thin film materials, and particularly relates to Ag/TiO2A film material and a preparation method thereof. The invention is mainly characterized in that a layer of TiO is prepared on the surface of a substrate by a sol-gel method in combination with a sol-gel method and a solvothermal synthesis method preparation technology2Seed layer, then covering with TiO by solvent thermal synthesis method2Ag/TiO grows on the substrate surface of the seed layer2Nanosheets, thereby obtaining Ag/TiO crystals vertically grown on a substrate2Ag/TiO formed by nanosheets2A film material. Ag/TiO compounds of the invention2The film material has the advantages of both titanium dioxide semiconductor material and silver, and has important functions in the aspects of antibacterial material, solar cell, photocatalysis, deodorization, self-cleaning and the like.
Description
Technical field
The invention belongs to the precious metal doping field of oxide semiconductor film materials, particularly a kind of Ag/TiO
2Thin-film material and preparation method thereof.
Background of invention
Titanium dioxide is a kind of semi-conducting material of excellent performance, has nontoxic, environmental protection, advantage such as cheap, is widely used in aspects such as building coating, photocatalysis, solar cell.Nano-TiO wherein
2Photocatalysis antibacterial material has antibiotic and the sterilization double effects; And bactericidal effect is rapid, sterilizing power is strong, to people's safety non-toxic; Yet it is stronger to the dependence of light, generally only under ultra violet lamp, can play a role, and this just makes its range of application receive certain limitation.Silver-series antibacterial agent mainly contains zeolite with carrying silver, silver-loaded zirconium phosphate, carries silver-colored calcium phosphate, solubility is carried silver-colored glass and carry silver-colored silica gel, clay pit, activated carbon etc.; They mainly are the porosity characteristics of utilizing carrier; Ag is combined with carrier with the mode of ion-exchange or physical absorption; Though bactericidal effect is better, the shortcoming that ubiquity silver ion initial stage burst size is big, the later stage discharges deficiency.Therefore, preparation Ag/TiO
2Composite antibacterial material is expected to have concurrently the advantage of two kinds of materials, obtains excellent anti-microbial property.
The method for preparing the Ag/TiO2 composite is related to by a lot of articles and patent, comprises infusion process, sol-gal process, hydro-thermal method etc., prepares the Ag/TiO of different compositions and pattern
2Composite wherein also has raising Ag/TiO
2Composite dark place anti-microbial property report.(Adv.Funct.Mater.2008,18,3179) such as Martha Ec-Souni utilize infusion process on metallic substrates, to prepare Ag/TiO
2Nano compound film, the doping of silver is 50.00wt%, is not having film under the situation of ultra violet lamp to have excellent antibacterial effect and low cell adhesion rate.(J.Mater.Chem.2007,17,2367) such as Boris Mahltig are raw material with tetraisopropyl titanate, silver nitrate and absolute ethyl alcohol, adopt solvent-thermal method to prepare Ag/TiO
2Nano combined colloidal sol, the doping of silver is 4.80atom%, under dark condition, Escherichia coli is also had certain antibacterial effect.(" fine chemistry industry ", 2005,22 (1): the nanometer Ag/TiO of doping different quality mark silver that 59) adopted Prepared by Sol Gel Method such as Ju Jianfeng
2Composite, anti-bacteria test result show, the composite after silver mixes does not need UV-irradiation just to have stronger anti-microbial property with the textile of using its arrangement, and the transparent inhibition zone of Escherichia coli and Staphylococcus aureus is reached 13～17mm.Yang Hui etc. (CN200610104711.9) are raw material with silver nitrate, ammoniacal liquor and titanium sulfate, adopt collosol and gel and calcining post processing to prepare nanometer Ag/TiO
2Composite, particle size 4～5nm, main crystal consists of Detitanium-ore-type TiO
2, do not having still have stronger bactericidal action under the ultraviolet ray excited situation.Lin Changjian etc. (CN200510126613.0) are raw material with absolute ethyl alcohol, positive four butyl esters of metatitanic acid, ethyl acetoacetate and silver nitrate ethanolic solution; Adopt sol-gal process and calcining post processing to obtain the titania nanoparticles of silver-doped nano particle; Add sodium hydroxide solution then and carry out titania nanotube and the nano belt that hydro-thermal reaction has prepared the silver-doped nano particle, the diameter of Nano silver grain is 2～10nm.Liu Hezhou etc. (CN200510029892.9) utilize liquid-phase coprecipitation and subsequent heat treatment to prepare argentum-carried hydroxylapatite/nano titanium oxide composite granule.Shen Qianhong etc. (CN200910100623.5) adopt low temperature wet local reduction way to prepare Ag-carried nanometer titanium dioxide antimildew and antibacterial agent.
The inventor utilizes sol-gal process to go up preparation one deck TiO at substrate surface (like glass, silicon chip, potsherd etc.)
2Seed Layer utilizes the solvent thermal synthetic method being coated with TiO then
2The substrate surface of Seed Layer grows Ag/TiO
2Nanometer sheet is because TiO
2The high anisotropy of crystal grain, in organic acid soln, TiO
2Obviously greater than the growth rate along the c-axle, the nanometer sheet that finally causes obtaining obtains the Ag/TiO of vertical substrate grown perpendicular to substrate grown to crystal grain along the growth rate of ab-axle
2The Ag/TiO that nanometer sheet is formed
2Thin-film material, the doping of silver is 0.16～5atom%, material of the present invention all has excellent antibacterial action under illumination and dark condition.Preparation method that the inventor uses and the Ag/TiO for preparing according to this preparation method
2Nano sheet film materials does not appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide a kind of Ag/TiO
2Thin-film material.
A purpose more of the present invention provides Ag/TiO
2The preparation method of thin-film material.
The titania-doped thin-film material of silver of the present invention is at suprabasil Ag/TiO by vertical-growth
2Nanometer sheet constitutes, described Ag/TiO
2The height of nanometer sheet is 0.4～2 μ m, and thickness is 5～15nm, and silver-colored doping is 0.16～5atom%.
The preparation of the titania-doped thin-film material of silver of the present invention is to combine sol-gal process and two steps of solvent thermal synthetic method to make.
Described sol-gal process is meant that metallo-organic compound or metal inorganic compound form the method for oxide or other solid chemical compound through the sol-gel processing; Its principle and technology can be opened the will Kun with reference to " nanometer technology and nanosecond science and technology ", the Cui Zuolin work; National Defense Industry Press, 2000, p131).
Described solvent thermal synthetic method is meant in closed reactor; To be heated in the reaction system in the presence of the organic solvent near critical-temperature; Under the hyperbaric environment that reaction system self produces, carry out the preparation of inorganic nano material, its principle and technology can be with reference to " nanometer medicine " (Xu Huibi works; Publishing house of Tsing-Hua University, 2004, p317).
The preparation method of the titania-doped thin-film material of silver of the present invention may further comprise the steps:
1) preparation TiO
2Colloidal sol, described TiO
2Colloidal sol is to be 1～20% titanate esters or titanate by mass fraction, and mass fraction is that 2～8% inorganic acid and surplus ethanol are formed;
2) TiO that step 1) is obtained
2Colloidal sol is coated in clean substrate surface, and coated weight is 2～20mL/m
2, will apply TiO then
2The substrate of colloidal sol was calcined 1～3 hour under 450～550 ℃ in Muffle furnace, obtained the TiO that diameter is 10～50nm at substrate surface
2Nano particle;
3) Ag/TiO of the synthetic usefulness of preparation solvent thermal
2Precursor colloidal sol, described Ag/TiO
2Precursor colloidal sol is to be 0.25～2.5% titanate esters by mass fraction, and mass fraction is that 0.05～2% silver salt and surplus glacial acetic acid are formed;
4) with step 2) obtain be coated with TiO
2The substrate of nano particle is immersed in the Ag/TiO that the step 3) in the container obtains
2In the precursor colloidal sol,, be 50～160 ℃ in temperature and heated 1～48 hour down putting into baking oven after the seal of vessel; In baking oven, take out container, be cooled to room temperature, openable container; From colloidal sol, take out substrate; After rinsing well with deionized water, oven dry obtains the titania-doped thin-film material of silver of the present invention.
Described titanate esters can be butyl titanate, tetraethyl titanate or metatitanic acid orthocarbonate etc.; Described titanate is a titanium tetrachloride etc.
Described inorganic acid can be hydrochloric acid or nitric acid etc.
Described silver salt can be silver nitrate, silver fluoride, silver acetate or silver chlorate etc.
Principal character of the present invention is to combine sol-gal process and solvent thermal synthetic method technology of preparing, utilizes sol-gal process on substrate surface, to prepare one deck TiO
2Seed Layer utilizes the solvent thermal synthetic method being coated with TiO then
2The substrate surface of Seed Layer grows Ag/TiO
2Nanometer sheet, obtain thus vertical-growth suprabasil by Ag/TiO
2The Ag/TiO that nanometer sheet is formed
2Thin-film material.Ag/TiO of the present invention
2Thin-film material has titanium dioxide semiconductor material and silver-colored advantage concurrently, at aspects such as anti-biotic material, solar cell, photocatalysis, deodorizing, automatically cleanings important effect is arranged.
Description of drawings
Fig. 1 is the Ag/TiO of the embodiment of the invention 1 preparation
2The sem photograph of thin-film material.
Fig. 2 is the Ag/TiO of the embodiment of the invention 1 preparation
2The profile scanning Electronic Speculum figure of thin-film material.
Fig. 3 is the Ag/TiO of the embodiment of the invention 2 preparations
2The sem photograph of thin-film material.
Fig. 4 is the Ag/TiO of the embodiment of the invention 3 preparations
2The sem photograph of thin-film material.
Fig. 5 is the Ag/TiO of the embodiment of the invention 4 preparations
2The sem photograph of thin-film material.
The specific embodiment
Embodiment 1
1) preparation TiO
2Colloidal sol, described TiO
2Colloidal sol is 20.00% butyl titanate by mass fraction, and mass fraction is that 8.00% the hydrochloric acid and the ethanol of surplus are formed;
2) TiO that step 1) is obtained
2Colloidal sol is coated in clean glass basic surface, and coated weight is 12mL/m
2, will apply TiO then
2The substrate of glass of colloidal sol was calcined 2 hours under 500 ℃ in Muffle furnace; Obtain the TiO that diameter is 20～50nm at glass basic surface
2Nano particle;
3) Ag/TiO of the synthetic usefulness of preparation solvent thermal
2Precursor colloidal sol, described Ag/TiO
2Precursor colloidal sol is to be 2.00% butyl titanate by mass fraction, and mass fraction is that 1.00% silver nitrate and surplus glacial acetic acid are formed;
4) with step 2) obtain be coated with TiO
2The substrate of glass of nano particle is immersed in the Ag/TiO that the step 3) in the container obtains
2In the precursor colloidal sol,, be 150 ℃ in temperature and heated 48 hours down putting into baking oven after the seal of vessel; In baking oven, take out container, be cooled to room temperature, openable container; From colloidal sol, take out substrate of glass; After rinsing well with deionized water, oven dry obtains the titania-doped thin-film material of described silver.ESEM is seen Fig. 1,2, can find out: Ag/TiO
2Thin-film material be by titanium dioxide nanoplate array vertical-growth at glass basic surface, silver is entrained in the titanium dioxide nanoplate, the thickness of titanium dioxide nanoplate is 15nm, highly is 2 μ m, silver-colored doping is 3.00atom%.
Embodiment 2
1) preparation TiO
2Colloidal sol, described TiO
2Colloidal sol is 12.50% tetraethyl titanate by mass fraction, and mass fraction is that 6.00% the hydrochloric acid and the ethanol of surplus are formed;
2) TiO that step 1) is obtained
2Colloidal sol is coated in clean silicon wafer-based basal surface, and coated weight is 20mL/m
2, will apply TiO then
2In Muffle furnace, calcined 3 hours under 550 ℃ at the bottom of the silicon wafer-based of colloidal sol; Obtain the TiO that diameter is 10～50nm at the silicon wafer-based basal surface
2Nano particle;
3) Ag/TiO of the synthetic usefulness of preparation solvent thermal
2Precursor colloidal sol, described Ag/TiO
2Precursor colloidal sol is to be 1.50% metatitanic acid orthocarbonate by mass fraction, and mass fraction is that 0.50% silver fluoride and surplus glacial acetic acid are formed;
4) with step 2) obtain be coated with TiO
2Be immersed in the Ag/TiO that the step 3) in the container obtains at the bottom of the silicon wafer-based of nano particle
2In the precursor colloidal sol,, be 120 ℃ in temperature and heated 6 hours down, in baking oven, take out container putting into baking oven after the seal of vessel; Be cooled to room temperature, openable container takes out at the bottom of the silicon wafer-based from colloidal sol; After rinsing well with deionized water, oven dry obtains the titania-doped thin-film material of described silver.ESEM is seen Fig. 3, can find out: Ag/TiO
2Thin-film material be by titanium dioxide nanoplate array vertical-growth at the silicon wafer-based basal surface, silver is entrained in the titanium dioxide nanoplate, the thickness of titanium dioxide nanoplate is 8nm, highly is 1 μ m, silver doping be 1.50atom%.
Embodiment 3
1) preparation TiO
2Colloidal sol, described TiO
2Colloidal sol is 8.60% metatitanic acid orthocarbonate by mass fraction, and mass fraction is that 2.00% the hydrochloric acid and the ethanol of surplus are formed;
2) TiO that step 1) is obtained
2Colloidal sol is coated in clean silicon wafer-based basal surface, and coated weight is 2mL/m
2, will apply TiO then
2In Muffle furnace, calcined 1 hour under 450 ℃ at the bottom of the silicon wafer-based of colloidal sol; Obtain the TiO that diameter is 10～20nm at the silicon wafer-based basal surface
2Nano particle;
3) Ag/TiO of the synthetic usefulness of preparation solvent thermal
2Precursor colloidal sol, described Ag/TiO
2Precursor colloidal sol is to be 0.25% tetraethyl titanate by mass fraction, and mass fraction is that 0.05% silver acetate and surplus glacial acetic acid are formed;
4) with step 2) obtain be coated with TiO
2Be immersed in the Ag/TiO that the step 3) in the container obtains at the bottom of the silicon wafer-based of nano particle
2In the precursor colloidal sol,, be 80 ℃ in temperature and heated 6 hours down, in baking oven, take out container putting into baking oven after the seal of vessel; Be cooled to room temperature, openable container takes out at the bottom of the silicon wafer-based from colloidal sol; After rinsing well with deionized water, oven dry obtains the titania-doped thin-film material of described silver.ESEM is seen Fig. 4, can find out: Ag/TiO
2Thin-film material be by titanium dioxide nanoplate array vertical-growth at the silicon wafer-based basal surface, silver is entrained in the titanium dioxide nanoplate, the thickness of titanium dioxide nanoplate is 8nm, highly is 0.4 μ m, silver doping be 0.20atom%.
Embodiment 4
1) preparation TiO
2Colloidal sol, described TiO
2Colloidal sol is 5.30% TiCl by mass fraction
4, mass fraction is that the ethanol of 3.00% nitric acid and surplus is formed;
2) TiO that step 1) is obtained
2Colloidal sol is coated in clean potsherd substrate surface, and coated weight is 6mL/m
2, will apply TiO then
2The potsherd substrate of colloidal sol was calcined 2 hours under 450 ℃ in Muffle furnace; Obtain the TiO that diameter is 10～20nm at the potsherd substrate surface
2Nano particle;
3) Ag/TiO of the synthetic usefulness of preparation solvent thermal
2Precursor colloidal sol, described Ag/TiO
2Precursor colloidal sol is to be 2.50% butyl titanate by mass fraction, and mass fraction is that 2.00% silver chlorate and surplus glacial acetic acid are formed;
4) with step 2) obtain be coated with TiO
2The potsherd substrate of nano particle is immersed in the Ag/TiO that the step 3) in the container obtains
2In the precursor colloidal sol,, be 100 ℃ in temperature and heated 36 hours down putting into baking oven after the seal of vessel; In baking oven, take out container, be cooled to room temperature, openable container; From colloidal sol, take out the potsherd substrate; After rinsing well with deionized water, oven dry obtains the titania-doped thin-film material of described silver.ESEM is seen Fig. 5, can find out: Ag/TiO
2Thin-film material be by titanium dioxide nanoplate array vertical-growth at the potsherd substrate surface, silver is entrained in TiO
2In the nanometer sheet, the thickness of titanium dioxide nanoplate is 12nm, highly is 1.8 μ m, and the doping of silver is 5.00atom%.
The anti-microbial property test:
The anti-microbial property test is to entrust Chinese antibiotic association test experience chamber to carry out, and is experimental strain with Escherichia coli and Staphylococcus aureus, has detected sample at illumination (optical wavelength 365nm, 0.1mW/cm
2Ultra violet lamp, irradiation time is 24 hours) and dark (be 24 hours standing time) condition under anti-microbial property, the result sees table 1.
Table 1 Ag-TiO
2The anti-bacteria test result of nanometer sheet film
Claims (6)
1. titania-doped thin-film material of silver, it is characterized in that: the titania-doped thin-film material of described silver is at suprabasil Ag/TiO by vertical-growth
2Nanometer sheet constitutes, described Ag/TiO
2The height of nanometer sheet is 0.4～2 μ m, and thickness is 5～15nm, and silver-colored doping is 0.16～5atom%.
2. the titania-doped thin-film material of silver according to claim 1 is characterized in that: described substrate is glass, silicon chip or potsherd.
3. the preparation method of the titania-doped thin-film material of silver according to claim 1 and 2 is characterized in that, this method may further comprise the steps:
1) preparation TiO
2Colloidal sol, described TiO
2Colloidal sol is to be 1～20% titanate esters or titanate by mass fraction, and mass fraction is that 2～8% inorganic acid and surplus ethanol are formed;
2) TiO that step 1) is obtained
2Colloidal sol is coated in clean substrate surface, and coated weight is 2～20mL/m
2, will apply TiO then
2The substrate of colloidal sol was calcined 1～3 hour under 450～550 ℃ in Muffle furnace, obtained the TiO that particle diameter is 10～50nm at substrate surface
2Nano particle;
3) Ag/TiO of the synthetic usefulness of preparation solvent thermal
2Precursor colloidal sol, described Ag/TiO
2Precursor colloidal sol is to be 0.25～2.5% titanate esters by mass fraction, and mass fraction is that 0.05～2% silver salt and surplus glacial acetic acid are formed;
4) with step 2) obtain be coated with TiO
2The substrate of nano particle is immersed in the Ag/TiO that the step 3) in the container obtains
2In the precursor colloidal sol,, be 50～160 ℃ in temperature and heated 1～48 hour down putting into baking oven after the seal of vessel; In baking oven, take out container, be cooled to room temperature, openable container; From colloidal sol, take out substrate; After rinsing well with deionized water, oven dry obtains the titania-doped thin-film material of described silver.
4. preparation method according to claim 3 is characterized in that: described titanate esters is butyl titanate, tetraethyl titanate or metatitanic acid orthocarbonate; Described titanate is a titanium tetrachloride.
5. preparation method according to claim 3 is characterized in that: described inorganic acid is hydrochloric acid or nitric acid.
6. preparation method according to claim 3 is characterized in that: described silver salt is silver nitrate, silver fluoride, silver acetate or silver chlorate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010153504 CN102219179B (en) | 2010-04-19 | 2010-04-19 | Silver-doped titanium dioxide film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010153504 CN102219179B (en) | 2010-04-19 | 2010-04-19 | Silver-doped titanium dioxide film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102219179A CN102219179A (en) | 2011-10-19 |
| CN102219179B true CN102219179B (en) | 2012-12-26 |
Family
ID=44775935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010153504 Expired - Fee Related CN102219179B (en) | 2010-04-19 | 2010-04-19 | Silver-doped titanium dioxide film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102219179B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102784635A (en) * | 2012-05-25 | 2012-11-21 | 北京工业大学 | Yttrium doped titanium dioxide nano film synthesized from rare earth tri-phosphor fluorescent powder waste and technology |
| CN103013196A (en) * | 2012-12-18 | 2013-04-03 | 上海迪道科技有限公司 | Method for manufacturing ultrathin nano-coating used for surface modification of inorganic nonmetallic material |
| CN103345977B (en) * | 2013-06-07 | 2016-11-23 | 徐东 | A kind of preparation method of Ag doping ito thin film |
| CN103408166B (en) * | 2013-07-17 | 2014-11-26 | 浙江理工大学 | Composite type portable energy saving water purifier |
| CN103990472A (en) * | 2014-06-09 | 2014-08-20 | 中国科学技术大学 | Stable and efficient hydrogen production co-catalyst and preparation method thereof |
| CN104258850A (en) * | 2014-09-26 | 2015-01-07 | 苏州纽艾之光净化设备有限公司 | Ag-doped TiO2 nano thin film and composite material containing thin film |
| CN104311142B (en) * | 2014-09-30 | 2016-10-12 | 东南大学 | A kind of vertical-growth TiO2nanometer sheet and preparation method thereof |
| US9650265B2 (en) * | 2015-03-04 | 2017-05-16 | Claire Technologies, Llc | Disinfection compositions and methods |
| CN105060735B (en) * | 2015-08-26 | 2018-01-16 | 河南科技大学 | A kind of preparation method of the antifogging self-cleaning glass with composite coating |
| DE102016108198A1 (en) * | 2016-05-03 | 2017-11-09 | B. Braun Avitum Ag | Medical device with antimicrobial surface coating and method for controlling microorganisms on the surface of such a device |
| CN106298246B (en) * | 2016-08-05 | 2018-06-12 | 宜兴锦尚太阳能科技有限公司 | A kind of preparation method of solar cell surface influx and translocation layer |
| CN107981701A (en) * | 2016-10-26 | 2018-05-04 | 佛山市顺德区美的电热电器制造有限公司 | Titanium-based carries silver-colored titanium dioxide composite antibacterial base material and preparation method thereof and titanium-based cookware and preparation method thereof |
| CN110698079A (en) * | 2019-12-04 | 2020-01-17 | 新沂市复兴玻璃制品有限公司 | Water-stain-proof glassware and manufacturing process thereof |
| CN114005603A (en) * | 2021-11-02 | 2022-02-01 | 合肥工业大学智能制造技术研究院 | Method for improving conductivity of nano-silver film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101281932A (en) * | 2008-05-21 | 2008-10-08 | 北京化工大学 | Photoelectricity conversion thin film based on inorganic nano sheet and preparation method thereof |
| CN101580244A (en) * | 2008-05-15 | 2009-11-18 | 中国科学院化学研究所 | Method for preparing mesoscopic material with controllable appearance |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009065180A1 (en) * | 2007-11-23 | 2009-05-28 | The University Of Queensland | Non-metal doped metal oxide nanosheets and method of production thereof |
-
2010
- 2010-04-19 CN CN 201010153504 patent/CN102219179B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580244A (en) * | 2008-05-15 | 2009-11-18 | 中国科学院化学研究所 | Method for preparing mesoscopic material with controllable appearance |
| CN101281932A (en) * | 2008-05-21 | 2008-10-08 | 北京化工大学 | Photoelectricity conversion thin film based on inorganic nano sheet and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| Fabrication of three-dimensional ZnO/TiO2 heteroarchitectures via a solution process;Nuanxia Wang et al.;《Journal of Materials Chemistry》;20080718;第18卷;第3909-3911页 * |
| Layer-by-layer assembly of gold nanoparticles with titania nanosheets:control of plasmon resonance and photovoltaic properties;Nobuyuki Sakai et al.;《Journal of Materials Chemistry》;20100412;第20卷;第4371-4378页 * |
| Nobuyuki Sakai et al..Layer-by-layer assembly of gold nanoparticles with titania nanosheets:control of plasmon resonance and photovoltaic properties.《Journal of Materials Chemistry》.2010,第20卷第4371-4378页. |
| Nuanxia Wang et al..Fabrication of three-dimensional ZnO/TiO2 heteroarchitectures via a solution process.《Journal of Materials Chemistry》.2008,第18卷第3909-3911页. |
| TiO2 纳米片的合成、表征及其光催化性能;顾玉芬等;《兰州理工大学学报》;20090430;第35卷(第2期);第21-24页 * |
| 顾玉芬等.TiO2 纳米片的合成、表征及其光催化性能.《兰州理工大学学报》.2009,第35卷(第2期),第21-24页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102219179A (en) | 2011-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102219179B (en) | Silver-doped titanium dioxide film and preparation method thereof | |
| Trapalis et al. | TiO2 (Fe3+) nanostructured thin films with antibacterial properties | |
| Ubonchonlakate et al. | Photocatalytic disinfection of P. aeruginosa bacterial Ag-doped TiO2 film | |
| KR101414899B1 (en) | Photocatalyst titanium oxide sol, and coating composition and member utilizing the same | |
| RU2647086C2 (en) | Surface coating | |
| Poongodi et al. | Structural, optical and visible light photocatalytic properties of nanocrystalline Nd doped ZnO thin films prepared by spin coating method | |
| CN107935039B (en) | Preparation method of titanium dioxide water-based sol | |
| CN1176743C (en) | Nano titanium dioxide photocatalyst,prep. and use thereof | |
| US20120168666A1 (en) | Coating composition and uses thereof | |
| US10000841B2 (en) | Hydrophilic-hydrophobic transformable composite film and the method of fabricating the same | |
| JP6283922B1 (en) | Photocatalyst material and photocatalyst coating composition | |
| KR101028797B1 (en) | The functional coating agent and manufacturing mtehod the same | |
| KR100941738B1 (en) | Photoactive composition comprising scoria and preparation method thereof | |
| Hossein Habibi et al. | Nanostructure thin films of titanium dioxide coated on glass and its anti UV effect for living organisms | |
| Lee et al. | Preparation of photocatalytic TiO 2− SiO 2 thin film by sol-gel coating | |
| CN106745227B (en) | Visible-light response nano TiO2And the preparation method of the self-cleaning ceramic film containing it | |
| CN101580617B (en) | Antimicrobial polyvinyl chloride plastic and preparation method thereof | |
| CN108529892A (en) | A kind of glass with clean and preparation method with efficient visible light catalysis and Superhydrophilic function | |
| Zhou et al. | Expanding the spectral tunability of TiO2 nanocrystals by codoping with fluorine and tungsten for energy-efficient windows | |
| JP7416427B2 (en) | self-cleaning coating | |
| Kazemi Hakki et al. | Preparation and Study of Photocatalytic Hydrophobic Surface-Modified TiO2 Coatings in Degradation of E. coli and Various Azo Dyes | |
| Nurhamizah et al. | Effect of Dipping Numbers on the Crystalline Phase and Microstructure of Ag-TiO2 Coating | |
| Zaharuddin et al. | Effect of Silver Doping on the Microstructure and Photocatalytic Performance of Ag-TiO2 Coatings on Unglazed Ceramic | |
| Liu et al. | Ag/TiO2 nano-membrane formed on the surface of domestic ceramic for the enhancement of photocatalytic property | |
| Di et al. | Photo-Catalytic Activity of Fe3+/Sn4+ Co-Doped Titanium Dioxide Nano-Crystalline Thin Films for Methyl Orange Degradation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121226 Termination date: 20140419 |