CN1657186A - Preparation method of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide - Google Patents
Preparation method of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide Download PDFInfo
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- CN1657186A CN1657186A CN 200510017433 CN200510017433A CN1657186A CN 1657186 A CN1657186 A CN 1657186A CN 200510017433 CN200510017433 CN 200510017433 CN 200510017433 A CN200510017433 A CN 200510017433A CN 1657186 A CN1657186 A CN 1657186A
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Abstract
A process for preparing the film modified by nano-TiO2 doped of noble metal-RE oxide features the combination of the RE doped and modified TiO2 sol-gel method with the ultrasonic spray-thermodecomposing method of silver nitrate solution. Said sol is prepared from methanol-ethanol mixture, Ti precursor, ammonium fluoride, soluble RE salt, surfactant, catalyst and stabilizer. Its resultant film has high catalytic activity for decomposing harmful gas in room.
Description
Technical field
The invention belongs to the nanometer new material technology field, relate in particular to a kind of under ultraviolet and visible light, have catalytic activity the preparation method of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide.
Background technology
Current nano titanium oxide is nontoxic owing to having, raw material is easy to get, has stronger photocatalysis performance, thereby be used in photocatalysis to degrade organic matter, degerming and obtained application from the preparation aspect of clean film, but because its above performance just shows the zone less than the UV-irradiation of 387nm, and sunshine middle-ultraviolet lamp proportion very little (about some thousandths of) makes the application of this class film be subjected to very big restriction.Thereby prepare the modified photocatalyst material that under ultraviolet and visible light, has catalytic activity and film has become the focus of field scientific worker research for this reason.
Summary of the invention
The object of the present invention is to provide a kind of under ultraviolet and visible light, all the have noble metal of catalytic activity, the preparation method of doped with rare-earth oxide modified film by nanometer titanium dioxide.
The object of the present invention is achieved like this: adopt rear-earth-doped modifying titanium dioxide sol-gel process and liquor argenti nitratis ophthalmicus ultrasonic spray pyrolysis to combine and prepare, wherein consisting of of colloidal sol contained the titanium precursor body that concentration expressed in percentage by weight is 10-20%, the ammonium fluoride of 0.5-10%, the rare earth soluble-salt of 0.5-12%, the surfactant of 0.001-0.01%, catalyst and the 2-5% stabilizing agent of 0.5-1% in 1: 1 first, alcohol mixed solution.
The preparation method of film carries out as follows:
(1), at first use chromic acid lotion and liquid detergent, deionized water that glass or ceramic substrate are cleaned, 120 ℃ of dry for standby,
(2), glass substrate is adopted the silester ethanolic solution of 10-20%, with the pull rate of 10-20 centimeters/minute, 150 ℃ of heating 30 minutes make the silica separation layer,
(3), the catalyst that adds 0.5-1% in 1: 1 mixed liquor of first and second alcohol earlier, the stabilizing agent that adds 0.001-0.01% surfactant, 2-5% after stirring, the ammonium fluoride of 0.5-10%, add the titanium precursor body after stirring again, the rare earth soluble-salt that adds 0.5-12% at last is one of cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm, after stirring, and ageing 24 hours, get Sol A
(4), silver nitrate is made 1% aqueous solution that contains 1% nitric acid, lucifuge is standby, solution B,
(5), the glass substrate or the ceramic wafer that will make the silica separation layer be positioned in the solution A, soaks after 2 minutes, after lifting from Sol A with the pull rate of 10-20 cm per minute, 120 ℃ boil off solvent,
(6), to the above-mentioned substrate that boils off solvent, be heated to 150 ℃ after, with the ultrasonic spray apparatus of 1700KHz, the translational speed of solution B with 50 centimeters/minute is sprayed on the substrate,
(7), will be positioned in the baking oven through the substrate that the last step handles, in nitrogen atmosphere with 2-10 ℃/minute programming rate, be heated to 500 ℃ after insulation 1-2 hour, promptly make final products of the present invention.
Described titanium precursor body is butyl titanate, isopropyl titanate or tetraethyl titanate.Described surfactant adopts Tween-40 or Henkel LS-45.Described stabilizing agent adopts acetylacetone,2,4-pentanedione or ethylene glycol.Described catalyst adopts analytically pure hydrochloric acid, glacial acetic acid or nitric acid, and its usage ratio is 0.5-1% with pure acid content.The rare earth soluble-salt that described film production adopts is cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm.
The present invention has following good effect:
The made film of the present invention has very strong catalytic activity under visible light, can make full use of sunshine and indoor fluorescent lamp etc. is light source, this class film is on glass as being supported on, can be made into building glass with visible light catalysis activity, be used for the harmful gas pollution that the decomposition chamber interior decoration causes, but be supported on deodorizing on the ceramic, be used on the cleaners and polishes, can suppress to urinate the generation of dirt, can be used for many aspects such as wastewater treatment in addition.Solved the separation regeneration problem after Powdered photochemical catalyst uses, and, had very big promotional value because its low cost of manufacture, technology are simple.
The specific embodiment
Embodiment 1:
The glass substrate that makes the silica separation layer in (2) step placed to contain by what (3) program made contain 15% butyl titanate, 1% analyzes pure nitric acid 2% acetylacetone,2,4-pentanedione, 1.0% cerous nitrate, 0.001% Henkel LS-45, soaked in the colloidal sol of 0.5% ammonium fluoride 2 minutes, and after with the speed of 10 cm per minute substrate being lifted out, be positioned in 120 ℃ of baking ovens and boil off solvent, use the ultrasonic spray apparatus of 1700KHz then, the translational speed of solution B with 50 centimeters/minute is sprayed on the substrate.In nitrogen atmosphere with 2-10 ℃/minute programming rate, be heated to 500 ℃ after the insulation 1-2 hour.Make sample one.
Embodiment 2:
The glass substrate that makes the silica separation layer in (2) step placed to contain by what (3) program made contain 18% butyl titanate, 1% nitric acid, 3% acetylacetone,2,4-pentanedione, 1.2% cerous nitrate, 0.001% Henkel LS-45 soaked 2 minutes in the colloidal sol of 1% ammonium fluoride, after with the speed of 10 cm per minute substrate being lifted out, be positioned in 120 ℃ of baking ovens and boil off solvent, use the ultrasonic spray apparatus of 1700KHz then, the translational speed of solution B with 50 centimeters/minute is sprayed on the substrate.In nitrogen atmosphere with 2-10 ℃/minute programming rate, be heated to 500 ℃ after the insulation 1-2 hour.Make sample two.
Embodiment 3:
The glass substrate that makes the silica separation layer in (2) step placed to contain by what (3) program made contain 20% butyl titanate, 1% analyzes pure nitric acid, 3% acetylacetone,2,4-pentanedione, 1.5% cerous nitrate, 0.001% Henkel LS-45 soaked 2 minutes in the colloidal sol of 5% ammonium fluoride, after with the speed of 10 cm per minute substrate being lifted out, be positioned in 120 ℃ of baking ovens and boil off solvent, use the ultrasonic spray apparatus of 1700KHz then, the translational speed of solution B with 50 centimeters/minute is sprayed on the substrate.In nitrogen atmosphere with 2-10 ℃/minute programming rate, be heated to 500 ℃ after the insulation 1-2 hour.Make sample three.
Embodiment 4:
The glass substrate that makes the silica separation layer in (2) step placed to contain by what (3) program made contain 25% butyl titanate, 1% analyzes pure nitric acid, 3% acetylacetone,2,4-pentanedione, 2.0% cerous nitrate, 0.001% Henkel LS-45 soaked 2 minutes in the colloidal sol of 10% ammonium fluoride, after with the speed of 10 cm per minute substrate being lifted out, be positioned in 120 ℃ of baking ovens and boil off solvent, use the ultrasonic spray apparatus of 1700KHz then, the translational speed of solution B with 50 centimeters/minute is sprayed on the substrate.In nitrogen atmosphere with 2-10 ℃/minute programming rate, be heated to 500 ℃ after the insulation 1-2 hour.Make sample four.
Embodiment 5:
The glass substrate that makes the silica separation layer in (2) step placed to contain by what (3) program made contain 15% butyl titanate, 1% analyzes pure nitric acid, 3% acetylacetone,2,4-pentanedione, 0.001% Henkel LS-45, soaked in the colloidal sol 2 minutes, and after with the speed of 12 cm per minute substrate being lifted out, be positioned in 120 ℃ of baking ovens and boil off solvent, in nitrogen atmosphere with 2-10 ℃/minute programming rate, be heated to 500 ℃ after the insulation 1-2 hour.
Make sample five and compare reference:
The properties of sample test
Using marine products Unico ultraviolet-visible spectrophotometer, is that blank is tested the sample catalytic activity with the deionized water at 520nm:
Sample one to five usefulness glass cutter is divided into the slide of 2 * 4cm, places culture dish to add the methyl orange solution of 10 milliliter of 10 mg/litre respectively, irradiation is after 2 hours under sunshine, and recording the methyl orange degradation rate at 520nm is shown in the following table:
| Sample number into spectrum | One | Two | Three | Four | Five |
| 2 hours methyl orange degradation rates | ????85％ | ????86％ | ????95％ | ????96％ | ????8％ |
Claims (7)
1, a kind of preparation method of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide, it is characterized in that: adopt rear-earth-doped modifying titanium dioxide sol-gel process and liquor argenti nitratis ophthalmicus ultrasonic spray pyrolysis to combine and prepare, wherein consisting of of colloidal sol contained the titanium precursor body that concentration expressed in percentage by weight is 10-20%, the ammonium fluoride of 0.5-10%, the rare earth soluble-salt of 0.5-12%, the surfactant of 0.001-0.01%, catalyst and the 2-5% stabilizing agent of 0.5-1% in 1: 1 first, alcohol mixed solution.
2, the preparation method of a kind of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide according to claim 1 is characterized in that: the preparation method of film carries out as follows:
(1), at first use chromic acid lotion and liquid detergent, deionized water that glass or ceramic substrate are cleaned, 120 ℃ of dry for standby,
(2), glass substrate is adopted the silester ethanolic solution of 10-20%, with the pull rate of 10-20 centimeters/minute, 150 ℃ of heating 30 minutes make the silica separation layer,
(3), the catalyst that adds 0.5-1% in 1: 1 mixed liquor of first and second alcohol earlier, the stabilizing agent that adds 0.001-0.01% surfactant, 2-5% after stirring, the ammonium fluoride of 0.5-10%, add the titanium precursor body after stirring again, the rare earth soluble-salt that adds 0.5-12% at last is one of cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm, after stirring, and ageing 24 hours, get Sol A
(4), silver nitrate is made 1% aqueous solution that contains 1% nitric acid, lucifuge is standby, solution B,
(5), the glass substrate or the ceramic wafer that will make the silica separation layer be positioned in the solution A, soaks after 2 minutes, after lifting from Sol A with the pull rate of 10-20 cm per minute, 120 ℃ boil off solvent,
(6), to the above-mentioned substrate that boils off solvent, be heated to 150 ℃ after, with the ultrasonic spray apparatus of 1700KHz, the translational speed of solution B with 50 centimeters/minute is sprayed on the substrate,
(7), will be positioned in the baking oven through the substrate that the last step handles, in nitrogen atmosphere with 2-10 ℃/minute programming rate, be heated to 500 ℃ after insulation 1-2 hour, promptly make final products of the present invention.
3, the preparation method of a kind of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide according to claim 1 and 2 is characterized in that: described titanium precursor body is butyl titanate, isopropyl titanate or tetraethyl titanate.
4, the preparation method of a kind of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide according to claim 1 and 2 is characterized in that: described surfactant adopts Tween-40 or Henkel LS-45.
5, the preparation method of a kind of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide according to claim 1 and 2 is characterized in that: described stabilizing agent adopts acetylacetone,2,4-pentanedione or ethylene glycol.
6, the preparation method of a kind of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide according to claim 1 and 2, it is characterized in that: described catalyst adopts analytically pure hydrochloric acid, glacial acetic acid or nitric acid, and its usage ratio is 0.5-1% with pure acid content.
7, the preparation method of a kind of modified film by nanometer titanium dioxide doped of noble metal rare earth oxide according to claim 1 and 2 is characterized in that: the rare earth soluble-salt that described film production adopts is cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm.
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Cited By (11)
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| CN1318133C (en) * | 2005-12-02 | 2007-05-30 | 厦门大学 | Method for loading silver nanometer particles onto nanometer titanium dioxide |
| CN101190801B (en) * | 2006-11-22 | 2010-05-12 | 北京航空航天大学 | Preparation of metal ion doping titanium dioxide line pipe by ion exchange method |
| CN101947447A (en) * | 2010-09-10 | 2011-01-19 | 山东大学 | Patternable environmental catalysis materials and size preparation method thereof |
| CN104403476A (en) * | 2014-11-28 | 2015-03-11 | 安徽省金盾涂料有限责任公司 | Self-cleaning antibacterial fluorocarbon coating |
| CN104624212A (en) * | 2015-02-11 | 2015-05-20 | 合肥工业大学 | Method for enhancing photocatalytic performance of nano-silver/titanium dioxide composite film |
| CN104785791A (en) * | 2015-04-16 | 2015-07-22 | 柳州豪祥特科技有限公司 | Technology for preparing tungsten powder mixing with titanium |
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| CN108997029A (en) * | 2018-08-31 | 2018-12-14 | 东北大学 | A kind of preparation method for the anti-bacteria ceramic having excellent anti-bacterium capability |
| CN109279916A (en) * | 2018-10-17 | 2019-01-29 | 东北大学 | A kind of preparation method and plated film anti-bacteria ceramic of plated film anti-bacteria ceramic |
| CN110573656A (en) * | 2016-12-22 | 2019-12-13 | 法国电力公司 | Sol-gel process for producing corrosion-resistant coatings on metal substrates |
| CN111013409A (en) * | 2019-12-27 | 2020-04-17 | 天津工业大学 | Mixed matrix membrane filled with lanthanide fluoride porous nanosheets and preparation method and application thereof |
Family Cites Families (3)
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| DE19845291A1 (en) * | 1998-10-01 | 2000-04-13 | Fraunhofer Ges Forschung | Process for the deposition of titanium oxide layers using soluble powders |
| CN1197662C (en) * | 2001-09-24 | 2005-04-20 | 中国科学院理化技术研究所 | Method for forming metal composite titanium dioxide nano particle film on ceramic surface |
| CN1424282A (en) * | 2003-01-06 | 2003-06-18 | 华东理工大学 | Titania nano film containing rare earth and silica and production thereof |
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2005
- 2005-03-21 CN CNB2005100174339A patent/CN1305588C/en not_active Expired - Fee Related
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| CN1318133C (en) * | 2005-12-02 | 2007-05-30 | 厦门大学 | Method for loading silver nanometer particles onto nanometer titanium dioxide |
| CN101190801B (en) * | 2006-11-22 | 2010-05-12 | 北京航空航天大学 | Preparation of metal ion doping titanium dioxide line pipe by ion exchange method |
| CN101947447A (en) * | 2010-09-10 | 2011-01-19 | 山东大学 | Patternable environmental catalysis materials and size preparation method thereof |
| CN104403476A (en) * | 2014-11-28 | 2015-03-11 | 安徽省金盾涂料有限责任公司 | Self-cleaning antibacterial fluorocarbon coating |
| CN104624212B (en) * | 2015-02-11 | 2017-06-13 | 合肥工业大学 | A kind of method for strengthening Nano Silver/titania coextruded film photocatalysis performance |
| CN104624212A (en) * | 2015-02-11 | 2015-05-20 | 合肥工业大学 | Method for enhancing photocatalytic performance of nano-silver/titanium dioxide composite film |
| CN104785791A (en) * | 2015-04-16 | 2015-07-22 | 柳州豪祥特科技有限公司 | Technology for preparing tungsten powder mixing with titanium |
| CN110573656A (en) * | 2016-12-22 | 2019-12-13 | 法国电力公司 | Sol-gel process for producing corrosion-resistant coatings on metal substrates |
| CN110573656B (en) * | 2016-12-22 | 2022-05-24 | 法国电力公司 | Sol-gel process for producing corrosion-resistant coatings on metal substrates |
| CN107892488A (en) * | 2017-11-30 | 2018-04-10 | 海南中航特玻科技有限公司 | A kind of film-coating type anti-blue light eyeshield glass |
| CN107892488B (en) * | 2017-11-30 | 2020-08-25 | 海南中航特玻科技有限公司 | Blue light eye-protecting glass is prevented to coating film type |
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