CN109850910B - Preparation method of hierarchical porous silicon oxide - Google Patents
Preparation method of hierarchical porous silicon oxide Download PDFInfo
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Abstract
The invention provides hierarchical porous silicon oxide and a preparation method thereof, belonging to the technical field of porous materials. The hierarchical porous silicon oxide has an obvious hierarchical porous structure, and the aperture of the hierarchical porous silicon oxide is 2-6 nm and 20-80 nm; or the aperture of the graded porous silicon oxide is 1-3 nm and 3-5 nm. The hierarchical porous silica provided by the invention has different levels of pore channels, so that the specific surface area is not reduced while the transmission of various molecules is met, and the active sites are not reduced, thereby showing more excellent performance than single-pore-channel silica in the fields of catalysis, sensing, adsorption and the like.
Description
Technical Field
The invention relates to the technical field of porous material preparation, in particular to hierarchical porous silicon oxide and a preparation method thereof.
Background
The ordered mesoporous molecular sieve material is a novel nano-structure material, has the pore diameter range of 2-50 nm, highly ordered pore diameter and large specific surface area, and is widely applied to high and new technical fields of heterogeneous catalysis, adsorption separation, biology, photoelectricity, sensors and the like.
The mesoporous silicon oxide material can be synthesized under alkaline or strong acid conditions, and the general synthesis procedure is 1) template agents such as surfactant and the like are dissolved in water to obtain uniform solution; 2) adding a silicon source to carry out hydrolytic polycondensation reaction to obtain sol or gel; 3) carrying out hydrothermal treatment reaction and crystallization; 4) cooling to room temperature, filtering, washing and drying; 5) roasting or extracting, removing organic template agents such as surfactant and the like, and obtaining the mesoporous silicon oxide material.
However, the single-pore silicon oxide obtained by the method is generally single-pore silicon oxide, the pore diameter of the single-pore silicon oxide is single, if the pore channel is larger, the specific surface area is reduced, and certain limitations exist in the aspects of stereoselective adsorption, shape selective catalysis and the like of molecules; if the pore channel is small, the specific surface area is high, but the mass transfer resistance inside the pore channel is large, and macromolecules are difficult to enter the inner surface, so that the large-pore-channel adsorption separation method is severely limited in the fields of catalysis, adsorption separation and the like.
Disclosure of Invention
The invention aims to provide the hierarchical porous silicon oxide and the preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides hierarchical porous silicon oxide, which has an obvious hierarchical porous structure, and the pore diameter of the hierarchical porous silicon oxide is 2-6 nm and 20-80 nm; or the aperture of the graded porous silicon oxide is 1-3 nm and 3-5 nm.
The invention also provides a preparation method of the graded porous silicon oxide, which comprises the following steps:
dropwise adding ethyl orthosilicate into a mixed solution containing hexadecyl trimethyl ammonium bromide, a solvent and ammonia water, stirring for a period of time, and filtering to obtain a solid hydrolysate;
carrying out hydrothermal reaction on the ethanol solution of the solid hydrolysate to obtain a hydrothermal reaction product;
calcining the hydrothermal reaction product to obtain hierarchical porous silicon oxide;
the solvent is a water-ethanol mixture or water;
when the solvent is water, the stirring time is (1,120) min; when the solvent is a mixture of water and ethanol, the stirring time is 10min or 120 min.
Preferably, when the solvent is water, the mass ratio of the ethyl orthosilicate to the hexadecyl trimethyl ammonium bromide to the solvent to the ammonia water is 1 (0.33-0.36): (13.5-14.0): 0.23-0.26), and the concentration of the ammonia water is 24-26 wt.%.
Preferably, when the solvent is water, the mixed solution containing cetyltrimethylammonium bromide, the solvent and ammonia water further contains sodium chloride.
Preferably, when the solvent is a water-ethanol mixture, the mass ratio of water to ethanol in the solvent is 1: 1.
Preferably, when the solvent is a water-ethanol mixture, the mass ratio of the ethyl orthosilicate to the hexadecyl trimethyl ammonium bromide to the solvent to the ammonia water is 1 (0.46-0.52) to (18-22) to (2.7-2.9), and the concentration of the ammonia water is 24-26 wt.%.
Preferably, the temperature of the hydrothermal reaction is 100-120 ℃, and the time of the hydrothermal reaction is 20-24 h.
Preferably, the calcining temperature is 550-600 ℃, and the calcining time is 6-12 h.
Preferably, the solid-to-liquid ratio of the solid hydrolysate to ethanol in the ethanol solution of the solid hydrolysate is 1 g: (6-8) mL.
Preferably, before calcining the hydrothermal reaction product, the method further comprises filtering, washing and drying the mixture after the hydrothermal reaction in sequence.
The invention provides hierarchical porous silicon oxide, which has an obvious hierarchical porous structure, and the pore diameter of the hierarchical porous silicon oxide is 2-6 nm and 20-80 nm; or the aperture of the graded porous silicon oxide is 1-3 nm and 3-5 nm. The hierarchical porous silica of the invention has different levels of pore channels, so that the specific surface area can not be reduced while various molecules are transmitted, and the active sites can not be reduced, thereby showing more excellent performance than single-pore-channel silica in the fields of catalysis, sensing, adsorption and the like.
The invention also provides a preparation method of the hierarchical porous silicon oxide, which comprises the following steps: dropwise adding ethyl orthosilicate into a mixed solution containing hexadecyl trimethyl ammonium bromide, a solvent and ammonia water, stirring for a period of time, and filtering to obtain a solid hydrolysate; carrying out hydrothermal reaction on the ethanol solution of the solid hydrolysate to obtain a hydrothermal reaction product; calcining the hydrothermal reaction product to obtain hierarchical porous silicon oxide; the solvent is a water-ethanol mixture or water; when the solvent is water, the stirring time is (1,120) min; when the solvent is a mixture of water and ethanol, the stirring time is 10min or 120 min.
The method comprises the steps of dropwise adding ethyl orthosilicate into a mixed solution containing hexadecyl trimethyl ammonium bromide, a solvent and ammonia water, wherein the solvent is a water-ethanol mixture or water; the mixed solution containing the hexadecyl trimethyl ammonium bromide, the solvent and the ammonia water provides an alkaline environment for the hydrolysis process, and the tetraethoxysilane is hydrolyzed and polycondensed under the alkaline condition; stirring for a period of time after the dropwise adding is finished, and continuously carrying out hydrolytic polycondensation reaction on the tetraethoxysilane to generate silicon dioxide in the stirring process; according to the invention, by controlling the stirring time and carrying out hydrothermal reaction on the ethanol solution of the solid hydrolysate, the ethanol is beneficial to the formation of a hierarchical pore channel, and after the hydrothermal reaction is carried out, the generation of hierarchical porous silica containing hexadecyl trimethyl ammonium bromide can be ensured; then, calcination was carried out to remove cetyltrimethylammonium bromide, and a hierarchical porous silica was obtained.
The porous silicon oxide prepared by the invention is of an obvious hierarchical structure, has a large surface area which can reach 800m2More than g.
In addition, the invention can also regulate and control the pore size of the hierarchical porous silicon oxide by controlling the stirring time and the types of the solvents. When the solvent is water, the aperture range of the obtained hierarchical porous silicon oxide is 2-6 nm and 20-80 nm; when the solvent is a mixture of water and ethanol, the pore diameter of the obtained hierarchical porous silica is in the range of 1-3 nm and 3-5 nm.
According to the invention, sodium chloride is added into the mixed liquid before the ethyl orthosilicate is added, so that the effect of enlarging the aperture of the graded porous silicon oxide can be achieved.
Drawings
FIG. 1 is a graph showing the pore size distribution of silica in examples 1 to 3 and comparative examples 1 to 3;
FIG. 2 is a graph showing the distribution of pore diameters of silica in examples 4 to 5 and comparative examples 4 to 6;
FIG. 3 is a graph showing pore size distributions of silica in examples 4 and comparative examples 7 to 8;
FIG. 4 is an SEM image of silica prepared in example 1;
fig. 5 is a TEM image of the silicon oxide prepared in example 1.
Detailed Description
The invention provides hierarchical porous silicon oxide, which has an obvious hierarchical porous structure, and the pore diameter of the hierarchical porous silicon oxide is 2-6 nm and 20-80 nm; or the aperture of the graded porous silicon oxide is 1-3 nm and 3-5 nm.
When the pore diameter of the hierarchical porous silicon oxide is 1-3 nm and 3-5 nm, the pore diameter of the hierarchical porous silicon oxide is not overlapped, and the hierarchical porous structure is still obvious. Specifically, the pore diameters of the hierarchical porous silica are [1,3] nm and [3,5] nm, or [1,3] nm and (3,5] nm, respectively.
The hierarchical porous silica provided by the invention has different levels of pore channels, so that the specific surface area is not reduced while various molecular transmissions are met, and the active sites are not reduced, so that the hierarchical porous silica has more excellent performance than single-pore-channel silica in the fields of catalysis, sensing, adsorption and the like.
The invention also provides a preparation method of the graded porous silicon oxide in the technical scheme, which comprises the following steps:
dropwise adding ethyl orthosilicate into a mixed solution containing hexadecyl trimethyl ammonium bromide, a solvent and ammonia water, stirring for a period of time, and filtering to obtain a solid hydrolysate;
carrying out hydrothermal reaction on the ethanol solution of the solid hydrolysate to obtain a hydrothermal reaction product;
calcining the hydrothermal reaction product to obtain hierarchical porous silicon oxide;
the solvent is a water-ethanol mixture or water;
when the solvent is water, the stirring time is (1,120) min; when the solvent is a mixture of water and ethanol, the stirring time is 10min or 120 min.
In the present invention, each raw material is not specifically described, and is a commercially available product known to those skilled in the art.
The method comprises the steps of dropwise adding ethyl orthosilicate into a mixed solution containing hexadecyl trimethyl ammonium bromide, a solvent and ammonia water, stirring for a period of time, and filtering to obtain a solid hydrolysate.
The method comprises the step of firstly dropwise adding ethyl orthosilicate into a mixed solution containing hexadecyl trimethyl ammonium bromide, a solvent and ammonia water to obtain a hydrolysis mixed material.
In the invention, the tetraethoxysilane is used as a silicon source, and the dripping speed is preferably 0.03-0.06 mL/s, and more preferably 0.051-0.06 mL/s; the hexadecyl trimethyl ammonium bromide is used as a template agent and has important influence on the formation of the hierarchical pore structure of the silicon dioxide. The dropwise addition according to the invention is preferably carried out with stirring. The stirring mode of the invention has no special requirement, and the stirring mode known to the skilled person can be adopted. In the present invention, the solvent is a water-ethanol mixture or water; the concentration of the ammonia water is preferably 24-26 wt.%. In the present invention, the temperature of the mixed solution is preferably 35 to 45 ℃, and more preferably 35 to 40 ℃.
In the invention, when the solvent is water, the mass ratio of the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide, the solvent and the ammonia water is preferably 1 (0.33-0.36): (13.5-14.0): 0.23-0.26), and more preferably 1:0.35:13.8: 0.25. When the solvent is water, the mixed solution containing the cetyl trimethyl ammonium bromide, the solvent and the ammonia water further comprises sodium chloride, and the mass ratio of the sodium chloride to the ethyl orthosilicate is preferably 1: 5.2. In the present invention, it is preferable to add sodium chloride to the mixed solution before adding tetraethoxysilane, thereby achieving the effect of enlarging the pore diameter of the graded porous silica.
In the invention, when the solvent is a water-ethanol mixture, the mass ratio of the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide, the solvent and the ammonia water is preferably 1 (0.46-0.52) to (18-22) to (2.7-2.9), and more preferably 1:0.5:21: 2.8. In the present invention, when the solvent is a water-ethanol mixture, the mass ratio of water to ethanol in the solvent is preferably 1: 1.
By controlling the type of the solvent, the invention not only can obtain the graded porous silicon oxide, but also can regulate and control the aperture size of the graded porous silicon oxide. When the solvent is water, the aperture range of the obtained hierarchical porous silicon oxide is 2-6 nm and 20-80 nm; when the solvent is a mixture of water and ethanol, the pore diameter of the obtained hierarchical porous silica is in the range of 1-3 nm and 3-5 nm.
After obtaining the hydrolysis mixture, the invention stirs the hydrolysis mixture for a period of time and filters to obtain the solid hydrolysate.
The stirring mode of the invention has no special requirement, and the stirring mode known to the skilled person can be adopted. In the present invention, when the solvent is water, the stirring time is (1,120) min, preferably 10 to 90min, and more preferably 10 to 60 min. When the solvent is a mixture of water and ethanol, the stirring time is 10min or 120 min. In the stirring process, the tetraethoxysilane is continuously hydrolyzed and condensed to generate silicon dioxide. The invention can ensure the generation of the hierarchical porous silicon oxide by controlling the stirring time and matching with the subsequent hydrothermal reaction and calcination. In the present invention, when the solvent is a water-ethanol mixture, the stirring time is preferably 10min or 120 min.
After stirring, the present invention filters the stirred mixture to obtain a solid hydrolysate. The present invention has no special requirement on the filtering mode, and the filtering mode known to those skilled in the art can be adopted.
After the solid hydrolysate is obtained, the ethanol solution of the solid hydrolysate is subjected to hydrothermal reaction to obtain a hydrothermal reaction product.
In the present invention, the solid-to-liquid ratio of the solid hydrolysate to ethanol is preferably 1 g: (6-8) mL. The ethanol is beneficial to the formation of the silica grading pore canal. In the invention, the temperature of the hydrothermal reaction is preferably 100-120 ℃; the time of the hydrothermal reaction is preferably 20-24 hours, and more preferably 22-24 hours.
After a hydrothermal reaction product is obtained, the invention calcines the hydrothermal reaction product to obtain the graded porous silicon oxide.
Before the hydrothermal reaction product is calcined, the invention preferably further comprises filtering, washing and drying the mixture after the hydrothermal reaction in sequence. The present invention does not require any particular filtering or washing operation, and may be performed by any filtering or washing operation known to those skilled in the art. In the present invention, the drying is preferably performed at 120 ℃ for 12 hours.
The invention calcines the hydrothermal reaction product to obtain the hierarchical porous silicon oxide. In the invention, the calcination temperature is preferably 550-600 ℃, and more preferably 550 ℃; the calcination time is preferably 6-12 h, and more preferably 6 h. In the present invention, the atmosphere of the calcination is preferably an air atmosphere. The calcination of the invention can remove hexadecyl trimethyl ammonium bromide to obtain the hierarchical porous silicon oxide.
The present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
At 35 ℃, 2.53g of hexadecyl trimethyl ammonium bromide (CTAB) is dissolved in 100g of deionized water, 1.825g of ammonia water (weight percent, 24-26) is added, 7.233g of tetraethoxysilane is dropwise added, stirring is continuously carried out for 10min after the dropwise addition is finished, a primary product is obtained by filtration and added into 70mL of absolute ethyl alcohol, and finally the mixture is transferred to a reaction kettle. Aging the mixture in a reaction kettle at 100 ℃ for 24 hours; cooling the reaction kettle to room temperature, filtering and washing to obtain a product, drying at 120 ℃ for 12h, and finally calcining at 550 ℃ for 6 h; obtaining the porous silicon oxide which is named as HPS-1-10 min.
Examples 2 to 3
Hierarchical porous silica was prepared according to the procedure of example 1 except that the stirring time was 30min and 60min, respectively, to obtain porous silica, which were designated as HPS-1-30min (example 2) and HPS-1-1h (example 3), respectively.
Example 4
Dissolving 2.5g of hexadecyl trimethyl ammonium bromide in 50g of deionized water at 35 ℃, adding 13.2g of ammonia water (weight percent is 24-26), then adding 50g of absolute ethyl alcohol, and dropwise adding 4.7g of TEOS; continuously stirring for 2h, filtering, adding the obtained primary product into 70mL of absolute ethyl alcohol, finally transferring to a reaction kettle, and aging the mixture in the reaction kettle at 100 ℃ for 24 h; cooling the reaction kettle to room temperature, filtering and washing to obtain a product, and drying at 120 ℃ for 72 hours; and finally calcining for 6h at 550 ℃ to obtain the porous silicon oxide which is named as HPS-2-2 h.
Example 5
Hierarchical porous silica was prepared according to the procedure of example 4 except that the stirring time was 10min to obtain porous silica, HPS-2-10 min.
Comparative example 1
Porous silica was prepared by following the procedure of example 1 except that the stirring time was 1min, and the obtained product was named HPS-1-1 min.
Comparative example 2
Porous silica was prepared according to the procedure of example 1 except that the stirring time was 120min, and the obtained product was named HPS-1-2 h.
Comparative example 3
Porous silica was prepared according to the procedure of example 1, except that 1.39g of sodium chloride was further added during the reaction, and the obtained product was named HPS-1-10 min-NaCl.
Comparative examples 4 to 6
Porous silica was prepared by following the procedure of example 4 except that the stirring time was 1min, 30min and 60min, respectively, to obtain porous silica, which were designated HPS-2-1min (comparative example 4), HPS-2-30min (comparative example 5) and HPS-2-1h (comparative example 6), respectively.
Comparative examples 7 to 8
A porous silica was prepared by following the procedure of example 5 except that the surfactants were CTAB-F127 (comparative example 7, 2.5g of CTAB, 2g of F127 polyoxyethylene polyoxypropylene ether block copolymer) and CTAB-P123 (comparative example 8, 2.5g of CTAB, 2g of P123 polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer), respectively, to give a porous silica.
The pore diameters of the porous silicas of examples 1 to 3 and comparative examples 1 to 3 were measured by a TriStarII3020 type nitrogen adsorption/desorption analyzer from Michkoku corporation, and the results are shown in FIG. 1. As shown, when the stirring time was 1min, a single hole was shown; when the stirring time is 10-110 min, a large-small graded porous structure is presented, the small aperture is 3nm, the large aperture is 30-60 nm, and the large pore channel is gradually weakened. When the reaction time was 120min, a single pore of about 2.5nm was exhibited, indicating that a graded porous silica could be obtained when the stirring time was (1,120) min. When the stirring time is 10min, NaCl is added in the reaction process, and the figure shows that the pore diameter of the macropore is expanded from 30nm to about 50nm, which shows that NaCl has the effect of reaming.
The pore diameter test was performed on the silica of examples 4 to 5 and comparative examples 4 to 6, and the test results are shown in FIG. 2. The results in FIG. 2 show that when the stirring time is 10min or 120min, two different pores are present, the first pore size is 2-3 nm, and the second pore size is 3-5 nm (note: the two pore sizes are not 3nm at the same time). And when the stirring time is other, all obtained materials are single-hole.
Pore diameter tests were performed on the porous silicas of example 4 and comparative examples 7-8, and the results are shown in FIG. 3. The results in fig. 3 show that under the influence of F127 and P123, the hierarchical porosity becomes single-pore.
In addition, the present inventors also performed SEM test (fig. 4) and TEM (fig. 5) tests on the graded porous silica prepared in example 1, and as can be seen from fig. 4 and 5, the graded porous silica prepared in the present invention has uniform size, uniform distribution, and no agglomeration.
From the above examples, it can be seen that the present invention provides a hierarchical porous silica and a method for preparing the same, wherein the silica having an apparent hierarchical porous structure is obtained by controlling the type of solvent, the stirring time and the type of surfactant, and the hierarchical porous silica of the present invention has excellent performance in the fields of catalysis, adsorption separation.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A preparation method of hierarchical porous silicon oxide comprises the following steps:
dropwise adding ethyl orthosilicate into a mixed solution containing hexadecyl trimethyl ammonium bromide, a solvent and ammonia water, stirring for a period of time, and filtering to obtain a solid hydrolysate;
carrying out hydrothermal reaction on the ethanol solution of the solid hydrolysate to obtain a hydrothermal reaction product;
calcining the hydrothermal reaction product to obtain hierarchical porous silicon oxide;
the solvent is a water-ethanol mixture or water;
when the solvent is water, the stirring time is (1,120) min; when the solvent is a mixture of water and ethanol, the stirring time is 10min or 120 min;
the concentration of the ammonia water is 24-26 wt.%;
when the solvent is water, the mass ratio of the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide, the solvent and the ammonia water is 1 (0.33-0.36) to (13.5-14.0) to (0.23-0.26);
when the solvent is a water-ethanol mixture, the mass ratio of water to ethanol in the solvent is 1: 1; the mass ratio of the ethyl orthosilicate, the hexadecyl trimethyl ammonium bromide, the solvent and the ammonia water is 1 (0.46-0.52) to (18-22) to (2.7-2.9);
the hierarchical porous silicon oxide has an obvious hierarchical porous structure, and the aperture of the hierarchical porous silicon oxide is 2-6 nm and 20-80 nm; or the aperture of the graded porous silicon oxide is 1-3 nm and 3-5 nm;
when the pore diameter of the hierarchical porous silicon oxide is 1-3 nm and 3-5 nm, the pore diameter of the hierarchical porous silicon oxide is not overlapped, and the hierarchical porous structure is still obvious.
2. The method according to claim 1, wherein when the solvent is water, a mixed solution containing cetyltrimethylammonium bromide, the solvent and ammonia water further contains sodium chloride.
3. The preparation method according to claim 1, wherein the temperature of the hydrothermal reaction is 100 to 120 ℃ and the time of the hydrothermal reaction is 20 to 24 hours.
4. The preparation method of claim 1, wherein the calcination temperature is 550 ℃ to 600 ℃, and the calcination time is 6 to 12 hours.
5. The method according to claim 1, wherein the solid-to-liquid ratio of the solid hydrolysate to ethanol in the ethanol solution of the solid hydrolysate is 1 g: (6-8) mL.
6. The preparation method according to claim 1, further comprising filtering, washing and drying the mixture after the hydrothermal reaction in sequence before calcining the hydrothermal reaction product.
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