CN103785369B - A kind of preparation method of titanium doped silica-based composite aerogel - Google Patents
A kind of preparation method of titanium doped silica-based composite aerogel Download PDFInfo
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- CN103785369B CN103785369B CN201410026654.1A CN201410026654A CN103785369B CN 103785369 B CN103785369 B CN 103785369B CN 201410026654 A CN201410026654 A CN 201410026654A CN 103785369 B CN103785369 B CN 103785369B
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Abstract
The invention belongs to field of new, particularly a kind of preparation method of titanium doped silica-based composite aerogel.The present invention take potassium titanate as titanium source, by the titanium doped silica-based aerogel composite of ion-exchange, sol-gel process and constant pressure and dry production performance excellence, mainly comprises the ion exchange process of (1) titanate and the sol-gel process of tetraethyl orthosilicate; (2) preparation of titanium doped silica-based wet gel; (3) modification of titanium doped silica-based wet gel; (4) constant pressure and dry of titanium doped silica-based aerogel.The method technique is simple, with low cost; be easy to large-scale production; the features such as titanium doped silica-based aerogel photochemical catalyst has nanostructured, specific area is large, hole ratio is high, the sound construction that obtain; and possess hydrophobic performance; can be used for the field such as purification of air, sewage disposal; and be convenient to be separated and reclaim, be applicable to extensive environmental pollution treatment.
Description
Technical field
The invention belongs to technical field of new material preparation, particularly a kind of preparation method of titanium doped silica-based composite aerogel.
Background technology
At present, TiO
2-SiO
2the synthesis of double base aeroge adopts its alkoxide usually, but because Titanium alkoxides is very easily hydrolyzed, makes building-up process comparatively complicated, and course of reaction is difficult to control, and production cost is too high; Application number is 200310109507.2 patent reports with the industrial sulphuric acid oxygen titanium of cheapness and Ludox for raw material, and Bian emulsion reaction method, prepares TiO by the sol-gel process in microemulsion and constant pressure and dry method
2-SiO
2aerogel microball; Application number be 200810011646.4 patent provide a kind of TiO of high pore volume
2-SiO
2composite aerogel, utilizes constant pressure and dry technology to prepare the method for this aeroge; Application number is the patent employing sol-gal process of 200810150216.0, first obtains SiO respectively
2colloidal sol and TiCl
4colloidal sol, then the two is mixed by a certain percentage, obtain the poly-reaction of mixed sols ， Jing Shrink, obtain TiO
2-SiO
2compound alcogel, just obtains TiO after drying
2-SiO
2composite aerogel.
Above patent, usual employing sol-gel processing obtains the single colloidal sol of titanium and silicon respectively, complex sol is obtained again after mixing, finally in counteracting or reduce the capillary condition solvent in except structure that goes down and obtain composite aerogel, but differ widely, as Titanium alkoxides is very easily hydrolyzed because of the hydrolytie polycondensation speed of different component raw material, and the hydrolytie polycondensation speed of silicon alkoxide is relatively stable, incorporation time is selected comparatively complicated, course of reaction is difficult to control, and production cost is too high, be not easy to suitability for industrialized production.
The present invention is easily to control titanium source (potassium titanate) for titanium source, and by the titanium doped silica-based aerogel composite of ion-exchange, sol-gel process and constant pressure and dry production performance excellence, the method technique is simple, with low cost, is easy to large-scale production.
The features such as titanium doped silica-based aerogel photochemical catalyst has nanostructured, specific area is large, hole ratio is high, sound construction that the present invention obtains; and possess hydrophobic performance; can be used for the field such as purification of air, sewage disposal, and be convenient to be separated and reclaim, be applicable to extensive environmental pollution treatment.
The present invention adopts ion-exchange, sol-gel process and constant pressure and dry technology, prepares the titanium doped silica-based aerogel composite that specific surface is controlled.
Summary of the invention
The object of the invention is to openly a kind of take potassium titanate as the method for the titanium doped silica-based composite aerogel in titanium source.
The present invention is realized by following technology, and the preparation method of titanium doped silica-based composite aerogel, in turn includes the following steps:
(1) ion exchange process of titanate and the sol-gel process of tetraethyl orthosilicate; (2) preparation of titanium doped silica-based wet gel; (3) modification of titanium doped silica-based wet gel; (4) constant pressure and dry of titanium doped silica-based aerogel;
Wherein, titanate is generally potassium hexatitanate etc., in acid condition obtained Ti (OH) after ion-exchange
4colloidal sol, with silicon ester hydrolysis and polycondensation process under same system condition, one-step method obtains titanium doped silica-based wet gel.
(1) in proportion ethyl orthosilicate is dissolved in absolute ethyl alcohol, then adds oxalic acid solution and obtain mixed solution; Add in crystal whisker of hexa potassium titanate to above-mentioned mixed solution, 50 ~ 60 DEG C of stirring in water bath 12h after ultrasonic; After stirring terminates, regulate mixed sols pH value to neutral with ammonia spirit, after transfer colloidal sol, leave standstill colloidal sol and become gel, wet gel is formed;
(2) wet gel prepared in step (1) is soaked in absolute ethyl alcohol, hexane solution successively, guarantees that exchange of solvent is thorough and reinforce gel skeleton;
(3) by the wet gel that step (2) processed, be soaked in the mixed and modified solution of trim,ethylchlorosilane that volume ratio is 1:1 and n-hexane and carry out modification;
(4) modified wet gel in step (3) is immersed in hexane solution exchanges unreacted coating material trim,ethylchlorosilane in gel;
(5) step (4) is obtained titanium doped silica-based wet gel carry out constant pressure and dry, namely obtain titanium doped silica-based aerogel.
In described step (1), the volume ratio of ethyl orthosilicate, absolute ethyl alcohol and oxalic acid solution is 5:6:1,
The crystal whisker of hexa potassium titanate quality that every 24ml mixed solution adds is 0.045g ~ 0.36g, and the concentration of oxalic acid solution is 0.008mol/L; Time of repose is 5-10min.
In described step (2), soaking temperature is 40 ~ 50 DEG C, in absolute ethyl alcohol, hexane solution, soak 3 times respectively, and each soak time is 12 ~ 36h.
In described step (3), the volume ratio of wet gel and modified solution is 1:0.3 ~ 1:0.6, and modification temperature is 25 DEG C ~ 30 DEG C, and the time is 6h ~ 12h.
In described step (4), wet gel to be immersed in hexane solution 1 ~ 2 time, each 12 hours.
In described step (5), baking temperature is 60 ~ 80 DEG C, and drying time is 24h.
The present invention has the following advantages:
1. simple, the energy-conserving and environment-protective of present invention process, favorable reproducibility, meet environmental requirement, the titanium doped silica-based composite aerogel of preparation has significant photocatalytic effect.
2. the structure-controllable of the titanium doped silica-based aerogel prepared by the present invention, tested analysis showed that, be that the titanium doped silica-based aerogel specific surface in titanium source is at 103.52m with crystal whisker of hexa potassium titanate
2/ g ~ 628.52m
2between/g.
Accompanying drawing explanation
Nitrogen adsorption-the desorption isotherm of the titanium doped silica-based aerogel of Fig. 1 prepared by the embodiment of the present invention 1 ~ 3.
The transmission electron microscope photo of the 0.5wt% titanium doped silica-based aerogel of Fig. 2 prepared by the invention process 1 example.
The transmission electron microscope photo of the 1wt% titanium doped silica-based aerogel of Fig. 3 prepared by the invention process 2 example.
The transmission electron microscope photo of the 2wt% titanium doped silica-based aerogel of Fig. 4 prepared by the invention process 3 example.
The X-ray energy dispersion spectrogram of the 2wt% titanium doped silica-based aerogel of Fig. 5 prepared by the invention process 3 example.
The efficiency curves of the photocatalytic degradation rhdamine B of the different content titanium doped silica-based aerogel of Fig. 6 prepared by the invention process 1 ~ 3.
Detailed description of the invention
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1
Measure ethyl orthosilicate 10ml, absolute ethyl alcohol 12ml and oxalic acid solution (0.008mol/l) 2ml respectively, after mixing, take 0.045g crystal whisker of hexa potassium titanate (K
2ti
6o
13), join in above mixed solution, after ultrasonic 30 minutes under 55 DEG C of water bath condition, stir 12 hours; Drip ammonia spirit (0.05mol/L) wherein, regulate Phz to neutral, leave standstill colloidal sol and become gel, obtain titanium doped silica-based wet gel; Under the water bath condition of 45 DEG C, in above-mentioned titanium doped silica-based wet gel, add 20ml soaked in absolute ethyl alcohol ageing 12h; Water in exchange gel 3 times, every 12h is once; Exchange ethanol in gel 3 times with the n-hexane of 20ml again, every 12h once; Wet gel is soaked in the hexane solution (volume by volume of trim,ethylchlorosilane and n-hexane is than 1:1) of the trim,ethylchlorosilane of 10ml, after carrying out finishing 6h at 25 DEG C, unreacted coating material is exchanged in gel 2 times with the n-hexane of 20ml, every 12h once, by gained gel at ambient pressure, 60 DEG C of dry 24h, are finally cooled to room temperature, obtain the titanium doped silica-based aerogel of 0.5wt%.
embodiment 2
Measure ethyl orthosilicate 20ml, absolute ethyl alcohol 24ml and oxalic acid solution (0.008mol/l) 4ml respectively, after mixing, take 0.18g crystal whisker of hexa potassium titanate (K
2ti
6o
13), join in above mixed solution, after ultrasonic 30 minutes under 60 DEG C of water bath condition, stir 12 hours; Drip ammonia spirit (0.05mol/L) wherein, regulate pH to neutral, leave standstill colloidal sol and become gel, obtain titanium doped silica-based wet gel; Under the water bath condition of 50 DEG C, in above-mentioned titanium doped silica-based wet gel, add 40ml soaked in absolute ethyl alcohol ageing 12h; Water in exchange gel 3 times, every 12h is once; Exchange ethanol in gel 3 times with the n-hexane of 40ml again, every 12h once; Wet gel is soaked in the hexane solution (volume by volume of trim,ethylchlorosilane and n-hexane is than 1:1) of the trim,ethylchlorosilane of 20ml, after carrying out finishing 8h at 30 DEG C, to exchange in gel unreacted coating material 2 times with the n-hexane of 20ml, every 12h once; By gained gel at ambient pressure, 70 DEG C of dry 24h, are finally cooled to room temperature, obtain the titanium doped silica-based aerogel of 1wt%.
embodiment 3
Measure ethyl orthosilicate 10ml, absolute ethyl alcohol 12ml and oxalic acid solution (0.008mol/l) 2ml respectively, after mixing, take 0.18g crystal whisker of hexa potassium titanate (K
2ti
6o
13), join in above mixed solution, after ultrasonic 30 minutes under 50 DEG C of water bath condition, stir 12 hours; Drip ammonia spirit (0.05mol/L) wherein, regulate pH to neutral, leave standstill colloidal sol and become gel, obtain titanium doped silica-based wet gel; Under the water bath condition of 40 DEG C, in above-mentioned titanium doped silica-based wet gel, add 20ml soaked in absolute ethyl alcohol ageing 12h; Water in exchange gel 3 times, every 12h is once; Exchange ethanol in gel 3 times with the n-hexane of 20ml again, every 12h once; Wet gel is soaked in the hexane solution (volume by volume of trim,ethylchlorosilane and n-hexane is than 1:1) of the trim,ethylchlorosilane of 10ml, after carrying out finishing 12h at 30 DEG C, to exchange in gel unreacted coating material 2 times with the n-hexane of 20ml, every 12h once; By gained gel at ambient pressure, 80 DEG C of dry 24h, are finally cooled to room temperature, obtain the titanium doped silica-based aerogel of 2wt%.
Nitrogen adsorption-the desorption isotherm of titanium doped silica-based aerogel material, transmission electron microscope photo and X-ray energy dispersion spectrogram are shown in Fig. 1, Fig. 2 ~ 4, Fig. 5 respectively.
Fig. 1 is that the specific surface of the silica-based aerogel material of different titanium doped content in embodiment 1 ~ 3 characterizes.
Fig. 1 illustrates: the specific surface of the silica-based aerogel material of different titanium doped content is at 103.52 ~ 628.52m
2between/g.
Fig. 2 ~ 4: in embodiment, the appearance structure of the silica-based aerogel material of different titanium doped content characterizes.
Fig. 2 ~ 4 illustrate: the synthetic product that the silica-based aerogel material of different titanium doped content is corresponding is typical aerogel structure, and with the rising of titanium doped amount, the aeroge cluster in unit volume increases to hundreds of nanometer from tens nanometers.This illustrates that the pattern of different content to silica-based composite aerogel of titanium has control structure effect.
Fig. 5: in embodiment, the composition of the titanium doped silica-based aerogel material of 2wt% characterizes.
Fig. 5 illustrates: being made up of elements such as silicon, titanium, oxygen of the silica-based aerogel material of titanium doped content.
Fig. 6: the photocatalytic effect of the silica-based aerogel material of different titanium doped content in embodiment, as can be seen from Figure 6: when the silica-based aerogel material of titanium doped content is to rhodamine B, has excellent photocatalytic degradation effect.
Each raw material cited by the present invention, and the bound of each raw material of the present invention, interval value, and the bound of technological parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.
Claims (6)
1. a preparation method for titanium doped silica-based composite aerogel, is characterized in that carrying out in accordance with the following steps:
(1) in proportion ethyl orthosilicate is dissolved in absolute ethyl alcohol, then adds oxalic acid solution and obtain mixed solution; Add in crystal whisker of hexa potassium titanate to above-mentioned mixed solution, 50 ~ 60 DEG C of stirring in water bath 12h after ultrasonic; After stirring terminates, regulate mixed sols pH value to neutral with ammonia spirit, after transfer colloidal sol, leave standstill colloidal sol and become gel, wet gel is formed;
(2) wet gel prepared in step (1) is soaked in absolute ethyl alcohol, hexane solution successively, guarantees that exchange of solvent is thorough and reinforce gel skeleton;
(3) by the wet gel that step (2) processed, be soaked in the mixed and modified solution of trim,ethylchlorosilane that volume ratio is 1:1 and n-hexane and carry out modification;
(4) modified wet gel in step (3) is immersed in hexane solution exchanges unreacted coating material trim,ethylchlorosilane in gel;
(5) step (4) is obtained titanium doped silica-based wet gel carry out constant pressure and dry, namely obtain titanium doped silica-based aerogel;
In described step (1), the volume ratio of ethyl orthosilicate, absolute ethyl alcohol and oxalic acid solution is 5:6:1, and the crystal whisker of hexa potassium titanate quality that every 24ml mixed solution adds is 0.045g ~ 0.36g.
2. the preparation method of a kind of titanium doped silica-based composite aerogel as claimed in claim 1, is characterized in that:
In described step (1), the concentration of oxalic acid solution is 0.008mol/L; Time of repose is 5-10min.
3. the preparation method of a kind of titanium doped silica-based composite aerogel as claimed in claim 1, is characterized in that:
In described step (2), soaking temperature is 40 ~ 50 DEG C, in absolute ethyl alcohol, hexane solution, soak 3 times respectively, and each soak time is 12 ~ 36h.
4. the preparation method of a kind of titanium doped silica-based composite aerogel as claimed in claim 1, is characterized in that:
In described step (3), the volume ratio of wet gel and modified solution is 1:0.3 ~ 1:0.6, and modification temperature is 25 DEG C ~ 30 DEG C, and the time is 6h ~ 12h.
5. the preparation method of a kind of titanium doped silica-based composite aerogel as claimed in claim 1, is characterized in that:
In described step (4), wet gel to be immersed in hexane solution 1 ~ 2 time, each 12 hours.
6. the preparation method of a kind of titanium doped silica-based composite aerogel as claimed in claim 1, is characterized in that:
In described step (5), baking temperature is 60 ~ 80 DEG C, and drying time is 24h.
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| CN104525062A (en) * | 2014-11-18 | 2015-04-22 | 安徽瑞研新材料技术研究院有限公司 | Processing technology of titanium doped silicon-based composite aerogel |
| CN106145881B (en) * | 2015-03-27 | 2018-06-29 | 中国石油化工股份有限公司 | A kind of hydrophobic type fibrofelt enhancing titanium silicon compound aerogel and preparation method |
| CN107226710A (en) * | 2017-06-28 | 2017-10-03 | 常州麒通国际贸易有限公司 | A kind of preparation method of silica nanometer hole super insulating material |
| CN107662923B (en) * | 2017-10-19 | 2020-12-18 | 加新科技(深圳)有限公司 | Continuous preparation of boron-doped SiO2Method for producing aerogels |
| CN107732259A (en) * | 2017-10-31 | 2018-02-23 | 绍兴文理学院 | A kind of preparation method of the titanium doped platinum catalyst of titanium dioxide |
| CN108342081B (en) * | 2018-02-09 | 2020-11-10 | 中国人民解放军陆军军医大学 | Carbon fiber resin liquid oxygen bottle and preparation method thereof |
| CN111495403A (en) * | 2020-04-23 | 2020-08-07 | 厦门理工学院 | Preparation method of photocatalyst, photocatalyst and application thereof |
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| CN101503195A (en) * | 2009-02-05 | 2009-08-12 | 扬州天辰精细化工有限公司 | Method for preparing hydrophobic SiO2 aerogel |
| CN102671586A (en) * | 2012-04-20 | 2012-09-19 | 大连工业大学 | Method for preparing TiO2-SiO2 composite aerogel |
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| CN101288835A (en) * | 2008-06-02 | 2008-10-22 | 大连工业大学 | TiO2-SiO2 compound aerogel and its preparation method |
| CN101503195A (en) * | 2009-02-05 | 2009-08-12 | 扬州天辰精细化工有限公司 | Method for preparing hydrophobic SiO2 aerogel |
| CN102671586A (en) * | 2012-04-20 | 2012-09-19 | 大连工业大学 | Method for preparing TiO2-SiO2 composite aerogel |
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