CN103523829A - Preparation method of lumpy zirconia aerogel having high specific surface area - Google Patents
Preparation method of lumpy zirconia aerogel having high specific surface area Download PDFInfo
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- CN103523829A CN103523829A CN201310459659.9A CN201310459659A CN103523829A CN 103523829 A CN103523829 A CN 103523829A CN 201310459659 A CN201310459659 A CN 201310459659A CN 103523829 A CN103523829 A CN 103523829A
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Abstract
The invention relates to a preparation method of a lumpy zirconia aerogel having a high specific surface area. The technology adopts an originated phenylamine-acetone in-situ generation water method to prepare zirconia gel, and the lumpy zirconia aerogel having the high specific surface area is obtained through aging and solvent replacement and by adopting a high-temperature supercritical drying process. The specific surface area of the prepared zirconia aerogel can reach 318-493 m<2>/g. The synthesis method can effectively suppress the hydrolysis and polycondensation rate of high-reaction-activity zirconium alkoxide without adding a chelator, more easily obtains the lumpy zirconia aerogel having the uniform structure and the high specific surface area, greatly promotes applications of the zirconia aerogel in the fields of catalysis, catalyst carriers, electrodes, piezoelectricity, adsorption, thermal preservation and thermal insulation and the like.
Description
Technical field
The invention belongs to aerogel class technical field of material, relate to the preparation method of the block zirconia aerogels of a kind of high-specific surface area.
Background technology
Zirconia aerogels is the nano-porous materials of a kind of low density, high porosity, high-specific surface area.Its unique nanostructure makes zirconia aerogels have wide practical use in fields such as catalysis, support of the catalyst, electrode, piezoelectric, dielectric medium, absorption, heat insulatings.As support of the catalyst, CuO/ZrO
2with cause hydrogen and CO
2synthesizing methanol; Pt/ZrO
2be used for studying the hydrogenization of first acid.Aspect electrode, zirconia aerogels can be used for the electrode of sensitization solar battery and Solid Oxide Fuel Cell.
The method of preparing zirconia aerogels is mainly sol-gel method.Its presoma is mainly divided into two kinds: inorganic zirconates (is mainly ZrOCl
28H
2o and Zr (NO
3)
45H
2o) and zirconium alkoxide (being mainly tetrabutyl zirconate and zirconium-n-propylate).Compare with inorganic zirconates, the gel that zirconium alkoxide obtains does not contain crystal water, degree of crosslinking is higher, network structure is more perfect.Yet the zirconium alkoxide of take is prepared block zirconia aerogels as source very difficult, reason is that its gelation process is complicated, zirconium alkoxide is active high-leveled and difficult very easily to ftracture in control, drying process.In order to obtain zirconium white gel transparent, even structure, in sol-gel process, conventionally need to add the complexing agents such as methyl ethyl diketone, methyl aceto acetate, acetic acid to control hydrolysis and the polycondensation speed of zirconium alkoxide.Although this method makes to be hydrolyzed and polycondensation speed is controlled, reduce the hydrolytie polycondensation degree of zirconium alkoxide, and then reduced degree of crosslinking and the frame strength of gel, be difficult to obtain the block zirconia aerogels that plasticity is good.Up to the present, take zirconium alkoxide, as source, to prepare the report of the block zirconia aerogels of high-specific surface area fewer.
Summary of the invention
The object of the present invention is to provide the preparation method of the block zirconia aerogels of a kind of high-specific surface area.
For achieving the above object, the present invention adopts take zirconium alkoxide as source, adopts aniline-acetone original position to generate water law, in conjunction with supercritical drying drying process, has prepared the zirconia aerogels block with high-specific surface area.
The preparation method of the block zirconia aerogels of a kind of high-specific surface area that the present invention proposes, concrete steps are as follows:
(1) original position generates water law preparation zirconia sol
Zirconium alkoxide is added in solvent, and stirring at normal temperature 1-10 minute, then adds catalyzer wherein; Products therefrom mixes with the mixing solutions that deionized water, acetone and aniline form, and continues stirring standing after 5-20 minute, can obtain required zirconium white gel in 5h; Wherein: the mol ratio of zirconium alkoxide, solvent, catalyzer, deionized water, acetone, aniline is 1:(0-56): (0.07-0.7): (0-1.0): (3.0-8.0): (3.0-8.0);
(2) aging, replacement is processed
The zirconium white gel that step (1) is obtained covers with alcohol, and then aging 1-5 days replaces 2-4 time with alcohol, and each 12-24 hour, obtains zirconium white wet gel;
(3) supercritical drying
It is drying medium that described supercritical drying is selected ethanol, the zirconium white wet gel that step (2) is obtained is put into supercritical drying equipment, the nitrogen of preliminary filling 0.5-6MPa, then with the speed of 1-3 ℃/min, autoclave temp is risen to 255 ℃, pressure rises to 7-10MPa simultaneously; Keep, after 0-3 hour, with the speed of 20-100KPa/min, alcohol being discharged; Last autoclave is down to normal temperature naturally, takes out sample, obtains zirconia aerogels.
In the present invention, zirconium alkoxide described in step (1) is any in tetrabutyl zirconate or zirconium-n-propylate.The preferential tetrabutyl zirconate of selecting.
In the present invention, solvent described in step (1) is any in ethanol, methyl alcohol, Virahol or propyl carbinol.The preferential ethanol of selecting.
In the present invention, catalyzer described in step (1) is any in hydrochloric acid, nitric acid, acetic acid or oxalic acid.
Beneficial effect of the present invention: in sol-gel process, under sour catalysis, acetone and aniline can deferred reaction original position generate water, have effectively controlled hydrolysis and the polycondensation speed of high reaction activity zirconium alkoxide, without adding any complexing agent, just can obtain zirconium white gel transparent, even structure.After supercritical drying, obtain the block zirconia aerogels with high-specific surface area.
Accompanying drawing explanation
Fig. 1 is embodiment 1 aerogel pictorial diagram.
Fig. 2 is embodiment 2 aerogel TEM photos.
Fig. 3 is embodiment 3 aerogel infared spectrums.
Fig. 4 is embodiment 4 aerogel electron diffraction collection of illustrative plates.
Fig. 5 is embodiment 5 aerogel XRD figure spectrums.
Embodiment
The invention will be further described by the following examples, but these embodiment must not be for explaining limiting the scope of the invention.
embodiment 1: tetrabutyl zirconate is added in ethanol, and stirring at normal temperature 1 minute, then adds hydrochloric acid wherein; Products therefrom mixes with the solution of deionized water, acetone and aniline, continue to stir after 5 minutes standingly, in 3 (uncertain concepts) hour, can obtain required zirconium white gel; Wherein: the mol ratio of tetrabutyl zirconate, ethanol, hydrochloric acid, deionized water, acetone, aniline is 1:30:0.07:0.5:3:3.The zirconium white gel obtaining covers with alcohol, and aging 1 day, then with alcohol, replace 4 times, each 12 hours, obtain zirconium white wet gel.
Zirconium white wet gel is put into supercritical drying equipment, the nitrogen of preliminary filling 0.5MPa, then with the speed of 1 ℃/min, autoclave temp is risen to 255 ℃, pressure rises to 7MPa simultaneously; Keep, after 3 hours, with the speed of 20KPa/min, alcohol being discharged; Last autoclave is down to normal temperature naturally, takes out sample, obtains zirconia aerogels.
The density that obtains bulk sample is 91mg/cm
3.Its specific surface area is 384m
2/ g.Sample appearance after supercritical drying as shown in Figure 1.
embodiment 2: zirconium-n-propylate is added in Virahol, and stirring at normal temperature 10 minutes, then adds nitric acid wherein; Products therefrom mixes with the solution of deionized water, acetone and aniline, continues stirring standing after 20 minutes, in 3 hours, can obtain required zirconium white gel; Wherein: the mol ratio of zirconium-n-propylate, Virahol, nitric acid, deionized water, acetone, aniline is 1:40:0.2:1:3:8.The zirconium white gel obtaining covers with alcohol, and aging 5 days, then with alcohol, replace 2 times, each 24 hours, obtain zirconium white wet gel.
Zirconium white wet gel is put into supercritical drying equipment, the nitrogen of preliminary filling 6MPa, then with the speed of 3 ℃/min, autoclave temp is risen to 255 ℃, pressure rises to 10MPa simultaneously; Then with the speed of 100KPa/min, alcohol is discharged immediately; Last autoclave is down to normal temperature naturally, takes out sample, obtains zirconia aerogels.
The density that obtains bulk sample is 83mg/cm
3.Its specific surface area is 318m
2/ g.Fig. 2 is its TEM photo, as seen from the figure, is uniform nanoporous network structure after aerogel supercritical drying, irregular spherical particle, consists of, and particle size is between 5-10nm.
embodiment 3: tetrabutyl zirconate is added in methyl alcohol, and stirring at normal temperature 5 minutes, then adds nitric acid wherein; Products therefrom mixes with the solution of acetone and aniline, continues stirring standing after 10 minutes, in 3 hours, can obtain required zirconium white gel; Wherein: the mol ratio of tetrabutyl zirconate, methyl alcohol, nitric acid, acetone, aniline is 1:56:0.7:4:4.The zirconium white gel obtaining covers with alcohol, and aging 4 days, then with alcohol, replace 4 times, each 12 hours, obtain zirconium white wet gel.
Zirconium white wet gel is put into supercritical drying equipment, the nitrogen of preliminary filling 2MPa, then with the speed of 1 ℃/min, autoclave temp is risen to 255 ℃, pressure rises to 7MPa simultaneously; Keep, after 1 hour, with the speed of 30KPa/min, alcohol being discharged; Last autoclave is down to normal temperature naturally, takes out sample, obtains zirconia aerogels.
The density that obtains bulk sample is 57mg/cm
3.Fig. 3 is the infared spectrum of this zirconia aerogels, 3423 cm
-1for-OH; 2962cm
-1, 2920cm
-1, 2875cm
-1representative-CH
3; 1049 cm
-1be derived from the vibration of the end of n-butoxy group; 1411 cm
-1with 1456 cm
-1represent respectively CH
2and CH
3the stretching vibration of group and flexural vibration, 497 cm
-1, 605 cm
-1, 736 cm
-1be derived from the vibration of Zr-O-Zr.
embodiment 4: zirconium-n-propylate is added in propyl carbinol, and stirring at normal temperature 5 minutes, then adds oxalic acid wherein; Products therefrom mixes with the solution of deionized water, acetone and aniline, continues stirring standing after 10 minutes, in three hours, can obtain required zirconium white gel; Wherein: the mol ratio of zirconium-n-propylate, propyl carbinol, oxalic acid, deionized water, acetone, aniline is 1:30:0.2:0.5:8:4.The zirconium white gel obtaining covers with alcohol, and aging 3 days, then with alcohol, replace 3 times, each 12 hours, obtain zirconium white wet gel.
Zirconium white wet gel is put into supercritical drying equipment, the nitrogen of preliminary filling 6MPa, then with the speed of 3 ℃/min, autoclave temp is risen to 255 ℃, pressure rises to 10MPa simultaneously; Keep, after 1 hour, with the speed of 50KPa/min, alcohol being discharged; Last autoclave is down to normal temperature naturally, takes out sample, obtains zirconia aerogels.
The density that obtains bulk sample is 87mg/cm
3.Its specific surface area is 431m
2/ g.Fig. 4 is its electron diffraction collection of illustrative plates, and its multistage concentric diffraction annulus explanation gained zirconia aerogels is polycrystalline structure.
embodiment 5: tetrabutyl zirconate is directly added in acetic acid to stirring at normal temperature 5 minutes; Products therefrom mixes with the solution of acetone and aniline, continues stirring standing after 10 minutes, in 3 hours, can obtain required zirconium white gel; Wherein: the mol ratio of tetrabutyl zirconate, acetic acid, acetone, aniline is 1:0.1:4:4.The zirconium white gel obtaining covers with alcohol, and aging 3 days, then with alcohol, replace 4 times, each 12 hours, obtain zirconium white wet gel.
Zirconium white wet gel is put into supercritical drying equipment, the nitrogen of preliminary filling 3MPa, then with the speed of 2 ℃/min, autoclave temp is risen to 255 ℃, pressure rises to 8MPa simultaneously; Keep, after 1 hour, with the speed of 50KPa/min, alcohol being discharged; Last autoclave is down to normal temperature naturally, takes out sample, obtains zirconia aerogels.
The density that obtains bulk sample is 159mg/cm
3.Its specific surface area is 493m
2/ g.Fig. 5 is its XRD figure spectrum, and in figure, the diffraction peak at 30,35,50,60,74 places represents tetragonal phase zirconium oxide, its crystalline phase of the wider explanation of diffraction peak a little less than.
Claims (4)
1. a preparation method for the block zirconia aerogels of high-specific surface area, is characterized in that concrete steps are as follows:
(1) original position generates water law preparation zirconia sol
Zirconium alkoxide is added in solvent, and stirring at normal temperature 1-10 minute, then adds catalyzer wherein; Products therefrom mixes with the mixing solutions that deionized water, acetone and aniline form, and continues stirring standing after 5-20 minute, can obtain required zirconium white gel in 5h; Wherein: the mol ratio of zirconium alkoxide, solvent, catalyzer, deionized water, acetone, aniline is 1:(0-56): (0.07-0.7): (0-1.0): (3.0-8.0): (3.0-8.0);
(2) aging, replacement is processed
The zirconium white gel that step (1) is obtained covers with alcohol, and then aging 1-5 days replaces 2-4 time with alcohol, and each 12-24 hour, obtains zirconium white wet gel;
(3) supercritical drying
It is drying medium that described supercritical drying is selected ethanol, the zirconium white wet gel that step (2) is obtained is put into supercritical drying equipment, the nitrogen of preliminary filling 0.5-6MPa, then with the speed of 1-3 ℃/min, autoclave temp is risen to 255 ℃, pressure rises to 7-10MPa simultaneously; Keep, after 0-3 hour, with the speed of 20-100KPa/min, alcohol being discharged; Last autoclave is down to normal temperature naturally, takes out sample, obtains zirconia aerogels.
2. method according to claim 1, is characterized in that zirconium alkoxide described in step (1) is any in tetrabutyl zirconate or zirconium-n-propylate.
3. method according to claim 1, is characterized in that solvent described in step (1) is any in ethanol, methyl alcohol, Virahol or propyl carbinol.
4. method according to claim 1, is characterized in that catalyzer described in step (1) is any in hydrochloric acid, nitric acid, acetic acid or oxalic acid.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817108A (en) * | 2015-04-24 | 2015-08-05 | 大连医科大学 | Preparation method of hydrophilic mesoporous zirconium dioxide aerogel materials |
| TWI550024B (en) * | 2015-01-09 | 2016-09-21 | 中原大學 | Method of producing polyaniline zorcornia nanocomposite and uses thereof |
| CN107162050A (en) * | 2017-06-06 | 2017-09-15 | 浙江大学 | A kind of method that block zirconia aerogels are prepared by gel accelerator of acidic amino acid |
| CN107215893A (en) * | 2017-06-15 | 2017-09-29 | 浙江大学 | A kind of method that block zirconia aerogels are prepared by gel accelerator of L malic acid |
| CN108484095A (en) * | 2018-04-09 | 2018-09-04 | 翟琳 | A kind of preparation method of high-strength heat-insulating type aerogel material |
| CN108483492A (en) * | 2018-04-18 | 2018-09-04 | 南京工业大学 | Preparation method of zirconia aerogel |
| CN112341224A (en) * | 2020-11-25 | 2021-02-09 | 辽宁科技大学 | Preparation method of zirconia-mullite complex-phase porous high-strength refractory block |
| CN112409010A (en) * | 2020-11-25 | 2021-02-26 | 辽宁科技大学 | Preparation method of magnesia-zirconia complex phase porous high thermal shock refractory block |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI550024B (en) * | 2015-01-09 | 2016-09-21 | 中原大學 | Method of producing polyaniline zorcornia nanocomposite and uses thereof |
| CN104817108A (en) * | 2015-04-24 | 2015-08-05 | 大连医科大学 | Preparation method of hydrophilic mesoporous zirconium dioxide aerogel materials |
| CN107162050A (en) * | 2017-06-06 | 2017-09-15 | 浙江大学 | A kind of method that block zirconia aerogels are prepared by gel accelerator of acidic amino acid |
| CN107162050B (en) * | 2017-06-06 | 2019-04-16 | 浙江大学 | A method of blocky zirconia aerogels are prepared by gel promotor of acidic amino acid |
| CN107215893A (en) * | 2017-06-15 | 2017-09-29 | 浙江大学 | A kind of method that block zirconia aerogels are prepared by gel accelerator of L malic acid |
| CN108484095A (en) * | 2018-04-09 | 2018-09-04 | 翟琳 | A kind of preparation method of high-strength heat-insulating type aerogel material |
| CN108483492A (en) * | 2018-04-18 | 2018-09-04 | 南京工业大学 | Preparation method of zirconia aerogel |
| CN112341224A (en) * | 2020-11-25 | 2021-02-09 | 辽宁科技大学 | Preparation method of zirconia-mullite complex-phase porous high-strength refractory block |
| CN112409010A (en) * | 2020-11-25 | 2021-02-26 | 辽宁科技大学 | Preparation method of magnesia-zirconia complex phase porous high thermal shock refractory block |
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Effective date of registration: 20151120 Address after: 061000 Lingang chemical industry park, Hebei, Cangzhou, south of route four, south of Chemical Road Patentee after: Epee and new materials Co., Ltd. Address before: 200092 Shanghai City, Yangpu District Siping Road No. 1239 Patentee before: Tongji University |