CN101323460A - Method for preparing high specific surface area three-dimensional mesoporous active aluminum oxide by hard template - Google Patents
Method for preparing high specific surface area three-dimensional mesoporous active aluminum oxide by hard template Download PDFInfo
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Abstract
The invention relates to a method for utilizing a hard template to prepare three-dimensional mesoporous active aluminium oxide with high specific surface area, belonging to the technical field of the preparation of solid mesoporous material. The existing mesoporous active aluminium oxide has the problems of undeveloped pore canal structure and small specific surface area, etc.; the method provided by the invention adopts tetraethoxysilane as a raw material and uses triblock copolymer (EO106PO70EO106) and hexadecyl trimethyl ammonium bromidec as a soft-template agent; three-dimensional mesoporous SBA-16 with different shapes is synthesized by hydro-thermal reaction; then the three-dimensional mesoporous SBA-16 is used as the hard template and sucrose is used as a carbon source to prepare the three-dimensional mesoporous carbon; finally, the three-dimensional mesoporous carbon is used as the hard template, aluminium nitrate is used as an aluminium source, absolute ethyl alcohol is used as a solvent, the three-dimensional mesoporous active aluminium oxide with high specific surface area is synthesized by the processes of a plurality of times of dipping and ignition in the radiation of ultrasonic wave. The method of the invention has low cost and simple and convenient operation, and the prepared three-dimensional mesoporous active aluminium oxide has the advantages of narrow pore size distribution and large specific surface area, etc.
Description
Technical field
The invention belongs to the solid mesoporous material preparing technical field, being specifically related to a kind of is the method that hard template prepares high specific surface area three-dimensional mesoporous active aluminum oxide with three-dimensional meso-hole carbon.
Background of invention
Activated alumina is widely used as catalyzer, carrier and sorbent material etc., and it is important controlling its specific surface area, pore size and distributed pole thereof.In recent years, along with the foundation of nanometer technology of preparing, make the controlledly synthesis of cellular solid become possibility.Mesoporous active aluminum oxide has advantages such as high-specific surface area, flourishing pore passage structure, help the dispersion of active ingredient and the absorption and the diffusion of reactant molecule, but most of pore structure of mesoporous active aluminum oxide is destroyed under hot conditions, cause specific surface area and active ingredient dispersity to descend significantly, thereby influenced its physico-chemical property widely.Therefore, thermostability is to weigh the important indicator whether mesoporous active aluminum oxide is suitable for doing catalyzer or carrier.Activated alumina (is γ-Al
2O
3) be a kind of in numerous crystal formations of aluminum oxide, normally utilize the aluminium presoma to obtain in 400 ℃ to 600 ℃ calcinations.In in the past 10 years, Chinese scholars has been studied with nonionogenic tenside (Bagshaw S A, et al., Angew.Chem.Int.Ed., 1996,35:1102; Gonz
Et al., Micropor.Mesopor.Mater., 2001,44-45:203; YangP, et al., Chem.Mater., 1999,11:2813), anion surfactant (Yada M, et al., Chem.Commun., 1996:769; Vaudry F, et al., Chem.Mater., 1996,8:1451; Valange S, et al., Micropor.Mesopor.Mater., 2000,35-36:597) and cats product (Cabrera S, et al., Adv.Mater., 1999,11 (5): 379; Deng W, et al., Adv.Funct.Mater., 2003,13:61) be the synthesising mesoporous method of alumina of template, but their prepared most of meso-porous aluminas are amorphous (being non-crystalline state) powder, and thermostability is very poor, thereby have limited its application in catalyzed reaction widely.As of late, people are that template successfully synthesizes the mesoporous γ-Al with certain degree of crystallinity with amine, polyoxyethylene glycol or segmented copolymer
2O
3(Hicks R W, et al., Chem.Mater., 2003,15:78; Zhang Z, et al., J.Am.Chem.Soc., 2002,124:1592; Boissiere C, etal., Chem.Mater., 2006,18:5238).Employings such as Liu " nano-copy " method synthesizes the γ-Al with regular pore passage structure
2O
3Crystal (Liu Q, et al., Chem.Mater., 2006,18:5153), be that template makes mesoporous carbon (CMK-3) with SBA-15 earlier promptly, be template makes mesoporous active aluminum oxide again with CMK-3.Yet the employed hard template of this method (mesoporous silicon and mesoporous carbon) is two-dirnentional structure and specific surface area is lower (less than 1000m
2/ g), make the duct of gained mesoporous active aluminum oxide be two-dirnentional structure and specific surface area is lower (less than 400m
2/ g), limited its application in absorption and catalysis.
Up to now, both at home and abroad also not about utilizing three-dimensional meso-hole silicon template SBA-16 and three-dimensional meso-hole carbon document and patent for the three-dimensional mesoporous active aluminum oxide of template synthesizing high specific surface area.
Summary of the invention
The objective of the invention is to solve the problems of the prior art, and provide a kind of pore passage structure prosperity, the synthetic method of the three-dimensional mesoporous active aluminum oxide that specific surface area is high.
Method provided by the present invention is that the three-dimensional meso-hole SBA-16 with high-specific surface area is the three-dimensional meso-hole carbon of hard template synthesizing high specific surface area and flourishing pore structure, be hard template synthesizing high specific surface area three-dimensional mesoporous active aluminum oxide with three-dimensional meso-hole carbon again, concrete steps are as follows:
1) with the tetraethoxy is raw material, triblock copolymer polyethylene glycol-propylene glycol-polyoxyethylene glycol (EO
106PO
70EO
106) and cetyl trimethylammonium bromide be soft template, by the synthetic three-dimensional meso-hole SBA-16 (seeing document " Mesa M, et al., Solid State Sci., 2005,7:990 ") of hydro-thermal reaction;
2) be hard template with the three-dimensional meso-hole SBA-16 for preparing in the step 1), sucrose is carbon source, preparation three-dimensional meso-hole carbon (seeing patent CN101117222);
3) three-dimensional meso-hole carbon black toner end is scattered in Al (NO under agitation condition
3)
3Ethanolic soln in, wherein, mesoporous carbon powder and Al (NO
3)
3Mol ratio be 1: 0.24, after ultrasonic dispersing made in the duct that the aluminum nitrate molecule fully enters three-dimensional meso-hole carbon in 2 hours, heating was evaporated ethanol fully, with the gained solid in nitrogen atmosphere in 300 ℃ of calcinations 2 hours;
4) repeat the step and carry out rapid 3) in dispersion and calcination process 2-3 time after, with the gained pressed powder through absolute ethanol washing, again in air atmosphere in 550 ℃ of calcinations 2 hours, obtain high specific surface area three-dimensional mesoporous active aluminum oxide.
Compared with prior art, the present invention has following beneficial effect:
Method cost provided by the present invention is low, easy and simple to handle, and the target product pore size distribution is narrow, and (pore volume is 0.92-0.99cm
3/ g, mean pore size is 7.0-7.3nm), the big (504-564m of specific surface area
2/ g), and pattern that can be by the modulation mesoporous carbon and meso-hole structure etc. are realized the control to aluminium oxide particles pattern, pore structure and specific surface area.
Description of drawings
Figure 1A, 1B, 1C are respectively Small angle XRD spectra, the N of three-dimensional meso-hole SBA-16
2Adsorption-desorption thermoisopleth and pore size distribution curve, wherein, the mesoporous SBA-16 of polyhedral three-dimensional order of corresponding embodiment 1 preparation of curve (a), the spherical three-dimensional meso-hole SBA-16 of corresponding embodiment 2 preparations of curve (b); Fig. 1 D is the SEM photo of the mesoporous SBA-16 of polyhedral three-dimensional order of embodiment 1 preparation; Fig. 1 E is the SEM photo of the spherical three-dimensional meso-hole SBA-16 of embodiment 2 preparations; Fig. 1 F is the TEM photo of the mesoporous SBA-16 of polyhedral three-dimensional order of embodiment 1 preparation; Fig. 1 G is the TEM photo of the spherical three-dimensional meso-hole SBA-16 of embodiment 2 preparations.
Fig. 2 A, 2B, 2C are respectively Small angle XRD spectra, the N of three-dimensional meso-hole carbon
2Adsorption-desorption thermoisopleth and pore size distribution curve, wherein, the three-dimensional order mesoporous carbon of corresponding embodiment 1 preparation of curve (a), the poroid mesoporous carbon of three-dimensional worm of corresponding embodiment 2 preparations of curve (b); Fig. 2 D is the SEM photo of the three-dimensional order mesoporous carbon of embodiment 1 preparation; Fig. 2 E is the SEM photo of the poroid mesoporous carbon of three-dimensional worm of embodiment 2 preparations; Fig. 2 F is the TEM photo of the three-dimensional order mesoporous carbon of embodiment 1 preparation; Fig. 2 G is the TEM photo of the poroid mesoporous carbon of three-dimensional worm of embodiment 1 preparation.
Fig. 3 A, 3B, 3C are respectively Small angle XRD spectra, extensive angle XRD spectra and the pore size distribution curve of the poroid three-dimensional mesoporous active aluminum oxide of worm, wherein, the poroid three-dimensional mesoporous active aluminum oxide of worm of corresponding embodiment 1 preparation of curve (a), the poroid three-dimensional mesoporous active aluminum oxide of worm of corresponding embodiment 2 preparations of curve (b); Fig. 3 D is the TEM photo of the poroid three-dimensional mesoporous active aluminum oxide of worm of embodiment 1 preparation, and illustration is the SAED pattern; Fig. 3 E is for being the TEM photo of the poroid three-dimensional mesoporous active aluminum oxide of worm of embodiment 2 preparations, and illustration is the SAED pattern.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment
Method in the reference literature among the following embodiment " Mesa M, et al., Solid State Sci., 2005,7:990 " is synthesized three-dimensional meso-hole SAB-16, and concrete steps are as follows:
(a) at room temperature, in hydrochloric acid soln, add triblock copolymer EO
106PO
70EO
106Behind cetyl trimethylammonium bromide, under violent stirring, add tetraethoxy;
(b) mixture of gained in the step (a) is changed over to from pressing in the still and in 95 ℃ of thermostat(t)ed water thermal treatments 5 days, after filtration, behind the deionized water wash in 60 ℃ of dryings 12 hours;
(c) pressed powder with gained in the step (b) places retort furnace, is warming up to 550 ℃ and calcination 3 hours under this temperature with the speed of 1 ℃/min, obtains three-dimensional meso-hole SBA-16.
With reference to the synthetic three-dimensional meso-hole carbon of disclosed method among the patent CN101117222, concrete steps are as follows:
(a) three-dimensional meso-hole SBA-16 being joined sucrose, deionized water and massfraction is in the mixed solution formed of 98% the vitriol oil, after magnetic agitation finishes the moisture evaporation in the mixed solution, with its baking oven of putting into 80 ℃ and 160 ℃ successively respectively constant temperature handled 6 hours;
(b) repeat step (a) 2-3 time;
(c) be to be warming up to 900 ℃ and constant temperature calcination 2 hours with the speed of 1 ℃/min in the stream of nitrogen gas of 100mL/min with the pressed powder of gained in the step (b) in volumetric flow rate;
(d) be that the pressed powder of gained in 10% the HF solution washing step (c) is removed silicon template SBA-16 with massfraction, obtain three-dimensional meso-hole carbon more after drying.
1) the synthetic mesoporous SBA-16 of polyhedral three-dimensional order:
(a) at room temperature, in the hydrochloric acid soln of 0.4mol/L, add EO
106PO
70EO
106Behind cetyl trimethylammonium bromide, under violent stirring, add tetraethoxy, wherein, tetraethoxy, hydrochloric acid, EO
106PO
70EO
106With the mol ratio of cetyl trimethylammonium bromide be 1: 3.5: 0.005: 0.0038;
(b) mixture of gained in the step (a) is transferred to from pressing in the still and in 95 ℃ of thermostat(t)ed water thermal treatments 5 days, after filtration, behind the deionized water wash in 60 ℃ of dryings 12 hours;
(c) pressed powder with gained in the step (b) places retort furnace, is warming up to 550 ℃ and calcination 3 hours under this temperature with the speed of 1 ℃/min, obtains the mesoporous SBA-16 of polyhedral three-dimensional order, and its specific surface area, mean pore size and pore volume see Table 1;
2) synthetic three-dimensional order mesoporous carbon:
(a) the mesoporous SBA-16 of polyhedral three-dimensional order being joined sucrose, deionized water and massfraction is in the mixed solution formed of 98% the vitriol oil, wherein, three-dimensional meso-hole SBA-16, sucrose, deionized water and massfraction are that the mol ratio of 98% the vitriol oil is 1: 0.219: 20: 0.0875, constantly stir, after moisture evaporation in the mixed solution is finished, with its baking oven of putting into 80 ℃ and 160 ℃ successively respectively constant temperature handled 6 hours;
(b) repeat step (a) 3 times;
(c) be to be warming up to 900 ℃ and constant temperature calcination 2 hours with the speed of 1 ℃/mi n in the stream of nitrogen gas of 100mL/min with the pressed powder of gained in the step (b) in volumetric flow rate;
(d) be that the pressed powder of gained in 10% the HF solution washing step (c) is removed silicon template SBA-16 with massfraction, obtain the three-dimensional order mesoporous carbon more after drying, its specific surface area, mean pore size and pore volume see Table 1;
3) the synthetic poroid three-dimensional mesoporous active aluminum oxide of worm: under agitation condition, 0.4g three-dimensional order mesoporous carbon powder is scattered in 16mL Al (NO
3)
3Ethanol solution (0.5mol/L) in, ultrasonic dispersing made Al (NO in 2 hours
3)
3Molecule fully enters in the duct of three-dimensional order mesoporous carbon, after 40 ℃ of heating are evaporated ethanol fully, is to be warming up to 300 ℃ and calcination 2 hours with the speed of 1 ℃/min in the stream of nitrogen gas of 100mL/min with the gained solid in volumetric flow rate;
4) repeating step 3) in dipping and calcination process 3 times after, with gained solid absolute ethanol washing, drying, and in retort furnace, be warming up to 550 ℃ and constant temperature calcination 2 hours with the speed of 1 ℃/min, obtain the poroid three-dimensional mesoporous active aluminum oxide of worm, its specific surface area, mean pore size and pore volume see Table 1.
1) synthetic spherical three-dimensional meso-hole SBA-16:
(a) at room temperature, in the hydrochloric acid soln of 0.8mol/L, add EO
106PO
70EO
106Behind cetyl trimethylammonium bromide, under violent stirring, add tetraethoxy, wherein, tetraethoxy, hydrochloric acid, EO
106PO
70EO
106With the mol ratio of cetyl trimethylammonium bromide be 1: 6.9: 0.002: 0.0038;
(b) with the step 1) among the embodiment 1-(a);
(c) pressed powder with gained in the step (b) places retort furnace, is warming up to 550 ℃ and calcination 3 hours under this temperature with the speed of 1 ℃/min, obtains spherical three-dimensional meso-hole SBA-16, and its specific surface area, mean pore size and pore volume see Table 1;
2) the synthetic poroid mesoporous carbon of three-dimensional worm:
(a) with the step 2 among the embodiment 1)-(a);
(b) repeat step (a) 3 times;
(c) with the step 2 among the embodiment 1)-(c);
(d) be that the pressed powder of gained in 10% the HF solution washing step (c) is removed silicon template SBA-16 with massfraction, obtain the poroid mesoporous carbon of three-dimensional worm more after drying, its specific surface area, mean pore size and pore volume see Table 1;
3) the three-dimensional shape mesoporous active aluminum oxide in synthetic worm hole: under agitation condition, the poroid mesoporous carbon powder of the three-dimensional worm of 0.4g is scattered in 16mL Al (NO
3)
3Ethanol solution (0.5mol/L) in, ultrasonic dispersing made Al (NO in 2 hours
3)
3Molecule fully enters in the duct of three-dimensional order mesoporous carbon, after 40 ℃ of heating are evaporated ethanol fully, is to be warming up to 300 ℃ and calcination 2 hours with the speed of 1 ℃/min in the stream of nitrogen gas of 100mL/min with the gained solid in volumetric flow rate;
4) repeating step 3) in dipping and calcination process 3 times after, with gained solid absolute ethanol washing, drying, and in retort furnace, be warming up to 550 ℃ and constant temperature calcination 2 hours with the speed of 1 ℃/min, obtain the poroid three-dimensional mesoporous active aluminum oxide of high-specific surface area worm, its specific surface area, mean pore size and pore volume see Table 1.
With products therefrom X-ray diffractometer (XRD), N
2Adsorption-desorption, scanning electronic microscope (SEM), transmission electron microscope (TEM), selected area electron diffraction technology such as (SAED) characterize, and the result is shown in Fig. 1,2 and 3.
| Sample | Mean pore size (nm) | Specific surface area (m 2/g) | Pore volume (cm 3/g) |
| The mesoporous SBA-16 of polyhedral three-dimensional order | 3.6 | 1011 | 1.00 |
| Spherical three-dimensional meso-hole SBA-16 | 3.5 | 809 | 0.67 |
| The three-dimensional order mesoporous carbon | 3.1 | 1600 | 1.42 |
| The poroid mesoporous carbon of three-dimensional worm | 3.5 | 966 | 0.91 |
| The poroid three-dimensional mesoporous active aluminum oxide of worm | 7.0 | 564 | 0.99 |
| The poroid three-dimensional mesoporous active aluminum oxide of worm | 7.3 | 504 | 0.92 |
Specific surface area, mean pore size and the pore volume of three-dimensional meso-hole SBA-16, three-dimensional meso-hole carbon and three-dimensional mesoporous active aluminum oxide that table 1, the present invention are prepared.
Claims (1)
1, a kind of method of utilizing hard template to prepare high specific surface area three-dimensional mesoporous active aluminum oxide is characterized in that, may further comprise the steps:
1) with the tetraethoxy is raw material, triblock copolymer polyethylene glycol-propylene glycol-polyoxyethylene glycol EO
106PO
70EO
106With cetyl trimethylammonium bromide be soft template, by the synthetic three-dimensional meso-hole SBA-16 of hydro-thermal reaction;
2) be hard template with the three-dimensional meso-hole SBA-16 for preparing in the step 1), sucrose is carbon source, preparation three-dimensional meso-hole carbon;
3) with step 2) in the preparation the three-dimensional meso-hole carbon dust under agitation condition, be scattered in Al (NO
3)
3Ethanolic soln in, wherein, mesoporous carbon powder and Al (NO
3)
3Mol ratio be 1: 0.24, ultrasonic dispersing is after 2 hours, heating is evaporated ethanol fully, with the gained solid in nitrogen atmosphere in 300 ℃ of calcinations 2 hours;
4) repeat the step and carry out rapid 3) after 2-3 time, with gained pressed powder absolute ethanol washing, again in air atmosphere in 550 ℃ of calcinations 2 hours, obtain high specific surface area three-dimensional mesoporous active aluminum oxide.
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Cited By (6)
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|---|---|---|---|---|
| CN103638896A (en) * | 2013-12-23 | 2014-03-19 | 重庆出入境检验检疫局检验检疫技术中心 | Mesoporous nanometer aluminium oxide solid phase adsorbing agent and preparation method and application thereof |
| CN104445296A (en) * | 2014-11-25 | 2015-03-25 | 重庆文理学院 | Synthesis method of spherical MgO nano particle |
| CN104549156A (en) * | 2015-01-28 | 2015-04-29 | 中南大学 | Aluminum oxide loaded mesoporous carbon material and application method thereof |
| CN105621462A (en) * | 2014-10-30 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparing aluminium oxide material |
| CN108190906A (en) * | 2018-01-23 | 2018-06-22 | 浙江睿升环保科技有限公司 | A kind of method that ordered mesoporous material SBA-16 is prepared using attapulgite |
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| DE19730126A1 (en) * | 1997-07-14 | 1999-01-21 | Basf Ag | Solid surface containing alumina |
| CN100390062C (en) * | 2005-04-13 | 2008-05-28 | 中国科学院大连化学物理研究所 | Ordered mesopore alumina preparation method |
| CN100494066C (en) * | 2007-02-08 | 2009-06-03 | 北京化工大学 | Method for preparing ordered mesoporous aluminium oxide |
| CN100564258C (en) * | 2007-07-13 | 2009-12-02 | 北京工业大学 | A kind of method of utilizing the hard mould agent synthesizing high specific surface area meso-porous carbon molecular sieve |
| CN101134586B (en) * | 2007-07-20 | 2010-06-02 | 北京化工大学 | Method for preparing nano alumina hollow ball |
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| CN103638896A (en) * | 2013-12-23 | 2014-03-19 | 重庆出入境检验检疫局检验检疫技术中心 | Mesoporous nanometer aluminium oxide solid phase adsorbing agent and preparation method and application thereof |
| CN105621462A (en) * | 2014-10-30 | 2016-06-01 | 中国石油化工股份有限公司 | Method for preparing aluminium oxide material |
| CN104445296A (en) * | 2014-11-25 | 2015-03-25 | 重庆文理学院 | Synthesis method of spherical MgO nano particle |
| CN104445296B (en) * | 2014-11-25 | 2016-02-10 | 重庆文理学院 | A kind of synthetic method of spherical MgO nano particle |
| CN104549156A (en) * | 2015-01-28 | 2015-04-29 | 中南大学 | Aluminum oxide loaded mesoporous carbon material and application method thereof |
| CN108190906A (en) * | 2018-01-23 | 2018-06-22 | 浙江睿升环保科技有限公司 | A kind of method that ordered mesoporous material SBA-16 is prepared using attapulgite |
| CN115231597A (en) * | 2022-07-08 | 2022-10-25 | 太原理工大学 | Fly ash-based mesoporous silicon-aluminum composite oxide material and preparation method thereof |
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