CN1142101C - Low temperature sol-gel preparation process of medium pore nanometer titania - Google Patents
Low temperature sol-gel preparation process of medium pore nanometer titania Download PDFInfo
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- CN1142101C CN1142101C CNB011059567A CN01105956A CN1142101C CN 1142101 C CN1142101 C CN 1142101C CN B011059567 A CNB011059567 A CN B011059567A CN 01105956 A CN01105956 A CN 01105956A CN 1142101 C CN1142101 C CN 1142101C
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- gel
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- polyvinylpyrrolidone
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Abstract
The present invention relates to a process for preparing medium pore nanometer titania with a sol-gel method at low temperature. Titanate and polyvinylpyrrolidone (PVP) are used as raw materials and carry out a hydrolysis reaction and a condensation reaction in alcohol solution. TiO2/PVP gel is obtained by controlling the speed of the hydrolysis reaction by taking acid as catalyst, and then the PVP in the gel is removed by heat treatment. In this way, medium pore nanometer TiO2 powder is obtained. The TiO2 as catalyst of the present invention has a mixed crystal effect and has higher photocatalysis activity.
Description
The present invention relates to a kind of preparation method of nano-titanium dioxide powder photocatalyst, relate in particular to a kind of low temperature sol-gel preparation method, belong to catalyzer class new material technology field with nano titanium oxide of middle endoporus (abbreviation mesopore) and mixed crystal effect.
Along with industrial expansion, the environment of human survival is subjected to serious day by day pollution: from the air of relying and breathing, to limited water resource, all can not be polluted by toxic and harmful substance with escaping by luck.For this reason, the pollution problem of solution waste gas waste water becomes an important process in environmental protection field.The conductor oxidate photocatalytic degradation technology that development in recent years is got up is for addressing this problem the approach that provides good.In numerous conductor oxidates, titanium dioxide is because of active high, and good stability is harmless and become a kind of photocatalyst that application prospect is arranged most.Yet the light source that present photocatalyst utilized is mainly UV-light, blackout etc., and the photochemical catalysis time is longer, and institute power consumption source is big, has great economic worth so improve the photocatalytic activity of titanium dioxide.Now the highest titanium dioxide product of photocatalytic activity of generally acknowledging is the P25 that German Degauss company produces, and the mixed crystal effect is its major cause with high light catalytic activity; But just as the tough grade of the Shen Wei of Wuhan University at " TiO
2Light-catalyzed reaction and the application in wastewater treatment thereof " to introduce in (" chemical progress " 1998.12) paper, this being difficult under the laboratory condition at high temperature more than 1000 ℃, by vapor phase process synthetic, nano TiO 2 powder with mixed crystal effect prepares.
The objective of the invention is to propose a kind of sol-gel process for preparing with nano-titanium dioxide powder photocatalyst of central hole structure and mixed crystal effect, this catalyzer not only has mesopore and mixed crystal effect, and the enrichment hydroxyl, effectively improve the photocatalysis efficiency of titanium dioxide.
For realizing such purpose, the present invention is in technical scheme, adopt sol gel process, (less than 600 ℃) prepare the nano titanium oxide novel powder catalyzer with mixed crystal effect at low temperatures, promptly by butyl (tetra) titanate when hydrolysis forms the titanium dioxide network, add polymer poly V-Pyrol RC (PVP), the TiO that makes
2/ PVP colloidal sol obtains titanium dioxide/PVP gel after room temperature leaves standstill, then gel is heat-treated at a certain temperature, after eliminating PVP, in material, form many mesopores, titanium dioxide is anatase octahedrite phase crystalline structure at low temperatures mostly, exist interactional surface then to have rutile to generate mutually with PVP, therefore the mesopore nano-titanium dioxide powder that finally makes has the mixed crystal effect, and higher photocatalytic activity is arranged.
Mesopore nano-titanium dioxide powder of the present invention is to be raw material with butyl (tetra) titanate and PVP, and hydrolysis and condensation reaction take place in the ethanol and the aqueous solution, comes the speed of control hydrolysis reaction with hydrochloric acid as catalyzer, obtains TiO
2/ PVP gel by thermal treatment, is eliminated the PVP in the gel, obtains mesopore TiO
2Nano-powder.
TiO
2The preparation technology of nano-powder mainly comprises the steps:
1, the butyl (tetra) titanate of 1 part of volume is dissolved in 2～5 parts the ethanolic soln, stirred 10～20 minutes;
2, in above-mentioned butyl (tetra) titanate ethanolic soln, add the catalyzer of control hydrolysis speed of response, catalyzer is made up of hydrochloric acid, water and ethanol, hydrochloric acid, water and alcoholic acid proportioning are 1: 3～4: 100, and making pH value is 3～4, behind the adding catalyzer, vigorous stirring 20 minutes obtains the not TiO of complete hydrolysis
2Colloidal sol;
3, PVP is joined in the above-mentioned solution, the consumption of PVP is 0.05-0.25g/ml, continues to stir 2～4 hours, at room temperature leaves standstill, up to forming gel;
4, the gel that will just form is eliminated PVP 450 ℃～550 ℃ thermal treatments, obtains titanium dioxide powder.
The hydrochloric acid of the control hydrolysis speed of response that the present invention adopts can use acid such as hydrofluoric acid, sulfuric acid to substitute.
The present invention has adopted sol gel process, can guarantee that the organic-inorganic component is compound at molecular level, concurrent looks mutual effect.Because the steric hindrance of PVP, make that the titanium dioxide network that forms in the hydrolytic process is very little, make that finally the crystal grain of titanium dioxide is very little after the thermal treatment, and the removal of PVP, can in titanium dioxide, form porous again, so just greatly improve the specific surface area of sample; During thermal treatment, exist interactional titanium dioxide surface can change rutile into mutually with PVP, all the other still are the anatase octahedrite phase, and this two-phase coexistent mode makes titanium dioxide have the mixed crystal effect; Bigger specific surface area, the existence of mesopore and mixed crystal effect make that the photocatalytic activity of sample is more high than P25.
Further describe technical scheme of the present invention below by specific embodiment.
Embodiment:
1, the 5ml butyl (tetra) titanate is dissolved in the ethanolic soln of 15ml, stirred 15 minutes;
2, in butyl (tetra) titanate solution, dropwise add hydrochloric acid, water and alcoholic acid mixed solution (HCl: H that 5ml disposes in advance by volume
2O: CH
3CH
2OH=1: 3: 100), vigorous stirring is 20 minutes;
3,1.2g PVP is joined in the above-mentioned mixed solution and to continue to stir 2 hours;
4, treat that colloidal sol forms gel after, the gel of harsh one-tenth was handled 2 hours at 500 ℃, the acquisition specific surface area is 65m
2/ g, grain-size is about 20nm, intermediate pore size is the nano-titanium dioxide powder of 9nm, wherein anatase octahedrite is respectively 75% and 25% with rutile weight percent mutually mutually.
Claims (1)
1, a kind of low temperature sol-gel preparation method of mesopore nano titanium oxide is characterized in that comprising the steps: that butyl (tetra) titanate with 1 part of volume is dissolved in 2～5 parts the ethanolic soln stirs; In the butyl (tetra) titanate ethanolic soln, add hydrochloric acid, water and alcoholic acid hydrolyst by configuration in 1: 3～4: 100, making it pH value is 3～4, vigorous stirring obtains the not TiO of complete hydrolysis
2Colloidal sol; Polyvinylpyrrolidone is joined in the above-mentioned solution, and the consumption of polyvinylpyrrolidone is 0.05～0.25g/ml, leaves standstill after continuing to stir, and obtains gel; The gel that just formed 450 ℃～550 ℃ thermal treatments, is eliminated polyvinylpyrrolidone, and obtaining intermediate pore size is the nano TiO 2 powder of 9nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011059567A CN1142101C (en) | 2001-04-12 | 2001-04-12 | Low temperature sol-gel preparation process of medium pore nanometer titania |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011059567A CN1142101C (en) | 2001-04-12 | 2001-04-12 | Low temperature sol-gel preparation process of medium pore nanometer titania |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1322676A CN1322676A (en) | 2001-11-21 |
| CN1142101C true CN1142101C (en) | 2004-03-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011059567A Expired - Fee Related CN1142101C (en) | 2001-04-12 | 2001-04-12 | Low temperature sol-gel preparation process of medium pore nanometer titania |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345767C (en) * | 2004-05-14 | 2007-10-31 | 泉耀科技股份有限公司 | Method for synthesizing sol of Nano powder of titanium dioxide in visible light type |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100551522C (en) * | 2007-09-20 | 2009-10-21 | 中国科学院广州地球化学研究所 | The method of producing interpose porus titanium dioxide photocatalyst by hydro-thermal method in weak acid condition |
| CN102343259A (en) * | 2011-04-13 | 2012-02-08 | 浙江大学 | Method for preparing titanium dioxide nanofilm at low temperature |
| CN105214633B (en) * | 2015-09-08 | 2018-05-25 | 北京化工大学 | A kind of preparation method of photocatalytic degradation titanium dioxide integral post |
| CN106238027A (en) * | 2016-07-02 | 2016-12-21 | 北京化工大学 | Nano-TiO2the preparation method of capillary column |
| CN109250752A (en) * | 2018-10-31 | 2019-01-22 | 苏州科技大学 | A kind of nano-TiO2The regulation method of inner void size |
| CN109482241B (en) * | 2018-12-07 | 2021-08-17 | 怀化学院 | TiO2/MOF-5 photocatalyst and preparation method thereof |
| CN110396309A (en) * | 2019-07-15 | 2019-11-01 | 中国科学院合肥物质科学研究院 | TiOx nano porous coating and preparation method thereof |
| CN111957305A (en) * | 2020-08-11 | 2020-11-20 | 上海锐朗光电材料有限公司 | Titanium dioxide microsphere photocatalyst and preparation method thereof |
-
2001
- 2001-04-12 CN CNB011059567A patent/CN1142101C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345767C (en) * | 2004-05-14 | 2007-10-31 | 泉耀科技股份有限公司 | Method for synthesizing sol of Nano powder of titanium dioxide in visible light type |
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| CN1322676A (en) | 2001-11-21 |
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