CN103785369A - Preparation method of composite silicon-based titanium-doped aerogel - Google Patents
Preparation method of composite silicon-based titanium-doped aerogel Download PDFInfo
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- CN103785369A CN103785369A CN201410026654.1A CN201410026654A CN103785369A CN 103785369 A CN103785369 A CN 103785369A CN 201410026654 A CN201410026654 A CN 201410026654A CN 103785369 A CN103785369 A CN 103785369A
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Abstract
The invention belongs to the field of a novel material, and particularly relates to a preparation method of composite silicon-based titanium-doped aerogel. The composite silicon-based titanium-doped aerogel with excellent properties can be produced from potassium titanate as a titanium source in manners of ion exchange, a sol-gel method and ambient pressure drying. The preparation method mainly comprises the following steps: (1) an ion exchange process of the titanate, and a sol-gel process of tetraethyl orthosilicate; (2) preparation of wet silicon-based titanium-doped gel; (3) modification of the wet silicon-based titanium-doped gel; (4) ambient pressure drying of silicon-based titanium-doped aerogel. The method is simple in process, and low in cost and the large-scale production is easy to achieve, an obtained silicon-based titanium-doped aerogel photocatalyst has a nano structure and the characteristics of being large in specific surface area, high in void ratio, firm in structure and the like, has the hydrophobic performance, can be applied to the fields of air purification, sewage treatment and the like, is convenient to separate and recover, and is applicable to large-scale 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 synthetic of double base aeroge adopts its alkoxide conventionally, but because titanium alkoxide 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 report take cheap industrial sulphuric acid oxygen titanium and Ludox as 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; The patent that application number is 200810011646.4 provides 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 200810150216.0 patent employing sol-gal process, first makes respectively SiO
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 makes TiO after being dried
2-SiO
2composite aerogel.
Above patent, conventionally adopt sol-gel processing to obtain respectively the single colloidal sol of titanium and silicon, after mixing, obtain complex sol again, finally offset or reduce capillary condition go down except structure in solvent obtain composite aerogel, but because the hydrolytie polycondensation speed of different component raw material differs widely, as titanium alkoxide is very easily hydrolyzed, 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) as titanium source, and by the titanium doped silica-based composite aerogel material 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 the titanium doped silica-based aerogels that the present invention obtains has nanostructured, specific area is large, hole ratio is high, sound construction; and possesses hydrophobic performance; can be used for the field such as air cleaning, sewage disposal, and be convenient to separate 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 controlled titanium doped silica-based composite aerogel material of specific surface.
Summary of the invention
The object of the invention is to a kind of openly method take potassium titanate as the titanium doped silica-based composite aerogel in titanium source.
The present invention realizes 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 aeroge;
Wherein, titanate is generally six potassium titanates etc., makes Ti (OH) under acid condition after ion-exchange
4colloidal sol, follows hydrolysis and the polycondensation process of estersil under same system condition, and one-step method makes titanium doped silica-based wet gel.
(1) in proportion ethyl orthosilicate is dissolved in absolute ethyl alcohol, then adds oxalic acid solution to obtain mixed solution; Add crystal whisker of hexa potassium titanate to above-mentioned mixed solution, ultrasonic rear 50 ~ 60 ℃ of stirring in water bath 12h; After stirring finishes,, shift after colloidal sol to neutrality by ammonia spirit adjusting mixed sols pH value, leave standstill colloidal sol and become gel, wet gel forms;
(2) wet gel preparing in step (1) is soaked in absolute ethyl alcohol, hexane solution successively, guarantees exchange of solvent thoroughly and reinforce gel skeleton;
(3) wet gel of step (2) being processed, is soaked in the mixed and modified solution of trim,ethylchlorosilane that volume ratio is 1:1 and n-hexane and carries out modification;
(4) wet gel after modification in step (3) is immersed in and 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, obtain titanium doped silica-based aeroge.
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 0.008 mol/L; Time of repose is 5-10min.
In described step (2), soaking temperature is 40 ~ 50 ℃, soaks respectively 3 times in absolute ethyl alcohol, hexane solution, 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 ℃ ~ 30 ℃, and the time is 6 h ~ 12h.
In described step (4), wet gel is immersed in hexane solution 1 ~ 2 time, each 12 hours.
In described step (5), baking temperature is 60 ~ 80 ℃, and be 24 h drying time.
The present invention has the following advantages:
1. simple, the energy-conserving and environment-protective of technique of the present invention, favorable reproducibility, meet environmental requirement, and the titanium doped silica-based composite aerogel of preparation has significant photocatalytic effect.
2. the structure of the titanium doped silica-based aeroge of preparing by the present invention is controlled, tested analysis showed that, the titanium doped silica-based aeroge specific surface take crystal whisker of hexa potassium titanate as titanium source is at 103.52 m
2/ g ~ 628.52 m
2between/g.
Accompanying drawing explanation
Fig. 1 is the nitrogen adsorption-desorption isotherm of the prepared titanium doped silica-based aeroge of the embodiment of the present invention 1 ~ 3.
Fig. 2 is the transmission electron microscope photo of the prepared titanium doped silica-based aeroge of 0.5wt% of the invention process 1 example.
Fig. 3 is the transmission electron microscope photo of the prepared titanium doped silica-based aeroge of 1wt% of the invention process 2 examples.
Fig. 4 is the transmission electron microscope photo of the prepared titanium doped silica-based aeroge of 2wt% of the invention process 3 examples.
Fig. 5 is the X ray energy dispersion spectrogram of the prepared titanium doped silica-based aeroge of 2wt% of the invention process 3 examples.
Fig. 6 is the efficiency curves of the photocatalytic degradation rhdamine B of the prepared titanium doped silica-based aeroge of different content of the invention process 1 ~ 3.
The specific embodiment
Below in conjunction with concrete embodiment, the present invention will be further described.
Measure respectively ethyl orthosilicate 10 ml, absolute ethyl alcohol 12 ml and oxalic acid solution (0.008 mol/l) 2ml, after mixing, take 0.045 g crystal whisker of hexa potassium titanate (K
2ti
6o
13), join in above mixed solution, after ultrasonic 30 minutes, under 55 ℃ of water bath condition, stir 12 hours; Drip wherein ammonia spirit (0.05 mol/L), 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 ℃, in above-mentioned titanium doped silica-based wet gel, add 20 ml soaked in absolute ethyl alcohol ageing 12 h; Water in exchange gel 3 times, every 12 h are once; With the ethanol in the n-hexane exchange gel of 20 ml 3 times, every 12 h once again; Wet gel is soaked in to the hexane solution (trim,ethylchlorosilane with the volume by volume of n-hexane than 1:1) of the trim,ethylchlorosilane of 10 ml, at 25 ℃, carry out after finishing 6 h, with unreacted coating material in the n-hexane exchange gel of 20 ml 2 times, every 12 h once, by gained gel under normal pressure, 60 ℃ of dry 24 h, are finally cooled to room temperature, obtain the titanium doped silica-based aeroge of 0.5wt%.
embodiment 2
Measure respectively ethyl orthosilicate 20 ml, absolute ethyl alcohol 24 ml and oxalic acid solution (0.008 mol/l) 4ml, after mixing, take 0.18 g crystal whisker of hexa potassium titanate (K
2ti
6o
13), join in above mixed solution, after ultrasonic 30 minutes, under 60 ℃ of water bath condition, stir 12 hours; Drip wherein ammonia spirit (0.05 mol/L), 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 ℃, in above-mentioned titanium doped silica-based wet gel, add 40 ml soaked in absolute ethyl alcohol ageing 12 h; Water in exchange gel 3 times, every 12 h are once; With the ethanol in the n-hexane exchange gel of 40 ml 3 times, every 12 h once again; Wet gel is soaked in to the hexane solution (trim,ethylchlorosilane with the volume by volume of n-hexane than 1:1) of the trim,ethylchlorosilane of 20 ml, at 30 ℃, carry out after finishing 8 h, with unreacted coating material in the n-hexane exchange gel of 20 ml 2 times, every 12 h once; By gained gel, under normal pressure, 70 ℃ of dry 24 h, are finally cooled to room temperature, obtain the titanium doped silica-based aeroge of 1wt%.
embodiment 3
Measure respectively ethyl orthosilicate 10 ml, absolute ethyl alcohol 12 ml and oxalic acid solution (0.008 mol/l) 2ml, after mixing, take 0.18 g crystal whisker of hexa potassium titanate (K
2ti
6o
13), join in above mixed solution, after ultrasonic 30 minutes, under 50 ℃ of water bath condition, stir 12 hours; Drip wherein ammonia spirit (0.05 mol/L), 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 ℃, in above-mentioned titanium doped silica-based wet gel, add 20 ml soaked in absolute ethyl alcohol ageing 12 h; Water in exchange gel 3 times, every 12 h are once; With the ethanol in the n-hexane exchange gel of 20 ml 3 times, every 12 h once again; Wet gel is soaked in to the hexane solution (trim,ethylchlorosilane with the volume by volume of n-hexane than 1:1) of the trim,ethylchlorosilane of 10 ml, at 30 ℃, carry out after finishing 12 h, with unreacted coating material in the n-hexane exchange gel of 20 ml 2 times, every 12 h once; By gained gel, under normal pressure, 80 ℃ of dry 24 h, are finally cooled to room temperature, obtain the titanium doped silica-based aeroge of 2wt%.
Nitrogen adsorption-desorption isotherm, transmission electron microscope photo and the X ray energy dispersion spectrogram of titanium doped silica-based aerogel material are shown in respectively Fig. 1, Fig. 2 ~ 4, Fig. 5.
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 explanation: the specific surface of the silica-based aerogel material of different titanium doped content is at 103.52 ~ 628.52 m
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 explanation: the synthetic product corresponding to silica-based aerogel material of different titanium doped content is typical aeroge structure, follows the rising of titanium doped amount, and the aeroge cluster in unit volume increases to hundreds of nanometer from tens nanometers.The different content of this explanation titanium has control structure effect to the pattern of silica-based composite aerogel.
Fig. 5: in embodiment, the composition of the titanium doped silica-based aerogel material of 2wt% characterizes.
Fig. 5 explanation: being formed by 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, have excellent photocatalytic degradation effect.
Each raw material that the present invention is cited, and the bound of the 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 to obtain mixed solution; Add crystal whisker of hexa potassium titanate to above-mentioned mixed solution, ultrasonic rear 50 ~ 60 ℃ of stirring in water bath 12h; After stirring finishes,, shift after colloidal sol to neutrality by ammonia spirit adjusting mixed sols pH value, leave standstill colloidal sol and become gel, wet gel forms;
(2) wet gel preparing in step (1) is soaked in absolute ethyl alcohol, hexane solution successively, guarantees exchange of solvent thoroughly and reinforce gel skeleton;
(3) wet gel of step (2) being processed, is soaked in the mixed and modified solution of trim,ethylchlorosilane that volume ratio is 1:1 and n-hexane and carries out modification;
(4) wet gel after modification in step (3) is immersed in and 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, obtain titanium doped silica-based aeroge.
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 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, and the concentration of oxalic acid solution is 0.008 mol/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 ℃, soaks respectively 3 times in absolute ethyl alcohol, hexane solution, 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 ℃ ~ 30 ℃, and the time is 6 h ~ 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 is 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 ℃, and be 24 h drying time.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106145881A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrophobic type fiber felt strengthens 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 |
| 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 |
| CN108342081A (en) * | 2018-02-09 | 2018-07-31 | 中国人民解放军陆军军医大学 | A kind of carbon fibre resin liquid-oxygen container and preparation method thereof |
| WO2019075793A1 (en) * | 2017-10-19 | 2019-04-25 | 加新科技(深圳)有限公司 | Method for continuously preparing boron-doped sio2 aerogel |
| 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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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106145881A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrophobic type fiber felt strengthens titanium silicon compound aerogel and preparation method |
| 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 |
| WO2019075793A1 (en) * | 2017-10-19 | 2019-04-25 | 加新科技(深圳)有限公司 | Method for continuously preparing boron-doped sio2 aerogel |
| 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 |
| CN108342081A (en) * | 2018-02-09 | 2018-07-31 | 中国人民解放军陆军军医大学 | A kind of carbon fibre resin liquid-oxygen container 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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