CN101117222A - Method for synthesizing high specific surface area meso-porous carbon molecular sieve by using hard mould agent - Google Patents
Method for synthesizing high specific surface area meso-porous carbon molecular sieve by using hard mould agent Download PDFInfo
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Abstract
The invention relates to a preparation method to synthesize a meso-porous carbon molecular sieve with high specific surface area by a hard-template agent, belonging to the solid meso-porous material preparation field. The meso-porous carbon molecular sieve provided with the high specific surface area and developed channel structure is difficult to be synthesized by using the traditional preparation method. The method consisting of two parts is as follows: (1) Tetraethoxysilane is used as silica source, triblock copolymer EO106PO70EO106 and cetyltrimethylammonium bromide are used as the soft-template agent, and then, through controlling the concentration and the dosage of the hydrochloric acid and the dosage of the EO106PO70EO106 and cetyltrimethylammonium bromide and the hydrothermal treatment under the certain temperature in the self-pressure cauldron, the polyhedron ordered meso-porous SBA-16 molecular sieve and the spherical vermicular meso-porous structure SBA-16 molecular sieve are obtained. (2) The two kinds morphology of the SBA-16 are used as the hard-template agent, cane sugar is used as the carbon source, and then the ordered meso-porous carbon molecular sieve and the vermicular meso-porous carbon molecular sieve are synthesized. The invention is adapted to be used as adsorbent, catalyst support, electric double-layer capacitor and hard-template agent for synthesizing the other meso-porous material, etc.
Description
Technical field
The present invention relates to a kind of solid mesoporous material technology of preparing, be specifically related to a kind of method of utilizing mesoporous pure silicon molecular sieve (SBA-16) to come synthesizing high specific surface area meso-porous carbon molecular sieve as hard mould agent.
Background technology
In recent years, nanoparticle and ordered porous materials technology of preparing have obtained developing rapidly, make this type of material of controlledly synthesis become possibility.Because meso-porous carbon material not only has higher specific surface area and pore volume, but also have excellent in chemical inertia and mechanical stability, make its important research object that becomes aspects such as surface tissue and heterogeneous catalyst, be widely used in various fields such as atmosphere and water surrounding purification, gas delivery, heterogeneous catalyst, chromatogram, energy storage.Therefore, the preparation method of the meso-porous carbon molecular sieve of research and development high-specific surface area has great practical value.
The common preparation method of mesoporous carbon be via the raw material of natural or synthetic as presoma reactivate and getting after carbonization, these method major parts are hard template method.The main process of hard template method is to utilize preformed order mesoporous solid duct, desired inorganic salt precursor is impregnated in its duct, the mineralising precursor makes it be transformed into target components at a certain temperature, remove former solid template again, can obtain having the target product of meso-hole structure at last.For example, Ryoo etc. at first utilize Ia3d type MCM-48 molecular sieve to synthesize mesoporous CMK-1 (Ryoo R, et al., J.Phys.Chem.B as hard mould agent, 1999,103:7743) and CMK-4 (Kaneda M, et al., J.Phys.Chem.B, 2002,106:1256).Afterwards, this research group has synthesized CMK-2 (Ryoo R, the et al. of cube pm3n structure respectively with SBA-1 and SBA-15 again as template, Stud.Surf.Sci.Catal., 2001,135:150), CMK-3 (Jun S, et al., the J.Am.Chem.Soc. of two dimension six side p6mm structures, 2000,122:10712) and CMK-5 (Joo SH, et al., Nature, 2001,412:169).Recently, utilize macropore Ia3d type FDU-5 (YangH, et al., Chem.Commun., 2002,2842) and Fm3m type FDU-12 (Fan J, et al., Angew.Chem.Int.Ed., 2003,42:3146) also synthesized cubic-phase mesoporous carbon structure.Yet the space structure of above-mentioned mesoporous silicon material as the synthesising mesoporous carbon of hard template flourishing (for example SBA-15 only is two-dimentional hexagonal structure) and specific surface area inadequately is relatively low (generally at 1000m
2/ g is following), limited its application of synthesizing the highly developed meso-porous carbon molecular sieve of cell size as hard mould agent.The present invention utilizes the mesoporous SBA-16 molecular sieve of three-dimensional Im3m type bigger serface pure silicon (with the California, USA university Santa Barbara branch school name of synthetic SBA-16 first, be numbered 16, Zhao D, et al., J.Am.Soc.Chem., 1998,120:6024) be hard mould agent, opened up a kind of new way of synthetic bigger serface meso-porous carbon molecular sieve material.
Summary of the invention
The objective of the invention is to overcome other shortcoming that hard template method gained sample well compound with regular structure degree is relatively poor, specific surface area is lower in the past, the meso-porous carbon molecular sieve synthetic method of a kind of easy and simple to handle, target product specific surface area height and pore structure prosperity is provided.
The present invention is raw material with the tetraethoxy, with triblock copolymer EO
106PO
70EO
106With cetyl trimethylammonium bromide be soft template, the mesoporous SBA-16 molecular sieve that synthesizes different-shape by hydro-thermal reaction, afterwards with it as hard mould agent, be carbon source with sucrose, obtain having the meso-porous carbon molecular sieve of highly developed pore structure and high-specific surface area.
A kind of method of utilizing the hard mould agent synthesizing high specific surface area meso-porous carbon molecular sieve is characterized in that, may further comprise the steps:
(1) at room temperature, in hydrochloric acid soln, add triblock copolymer EO
106PO
70EO
106With the cetyl trimethylammonium bromide soft template, under violent stirring, add tetraethoxy and stirring;
When concentration of hydrochloric acid is 0.4mol/L and tetraethoxy: hydrochloric acid: EO
106PO
70EO
106: the mol ratio of cetyl trimethylammonium bromide is 1: 3.5: 0.005: 0.02 o'clock, the surface topography of gained SBA-16 was a polyhedral;
When concentration of hydrochloric acid is 0.8mol/L and tetraethoxy: hydrochloric acid: EO
106PO
70EO
106: the mol ratio of cetyl trimethylammonium bromide is 1: 6.9: 0.002: 0.02 o'clock, the surface topography of gained SBA-16 was spherical;
(2) the gained mixture is changed over to from pressing still 95 ℃ of thermostat(t)ed water thermal treatments 5 days, after filtration, behind the deionized water wash in 60 ℃ of dryings 12 hours;
(3) in retort furnace with the speed temperature programming to 550 of 1 ℃/min ℃ and 550 ℃ of following constant temperature calcinations 3 hours, obtain the SBA-16 white powder;
(4) SBA-16 is joined by sucrose: deionized water: massfraction is that 98% vitriol oil mol ratio is 1: 0.219: 20: in 0.0875 mixed solution of forming, magnetic agitation finishes the moisture evaporation in this mixed solution, and the baking oven of then it being put into 80 ℃ and 160 ℃ successively constant temperature was handled 6 hours;
(5) add in the gained powder by sucrose: deionized water: vitriol oil mol ratio is 0.132: 20: 0.05 mixed solution of forming, and magnetic agitation in the repeating step (4) and drying operation are once again;
(6) solid that obtains in nitrogen atmosphere with the speed temperature programming to 900 of 1 ℃/min ℃ and constant temperature calcination 2 hours under this temperature, with massfraction be 10%HF solution washing gained pressed powder to remove the silicon template, after seasoning, promptly obtain meso-porous carbon molecular sieve again.
With products therefrom X-ray diffractometer (XRD), N
2Adsorption-desorption, scanning electronic microscope (SEM), transmission electron microscope technology such as (TEM) characterize.The result shows, the meso-porous carbon molecular sieve that adopting the obtained sample of present method is the pore structure prosperity, specific surface area is high, and specific surface area is 966～1600m
2/ g, mean pore size is 3.1～3.5nm.
The present invention has adopted a kind of simple hard template method to prepare the meso-porous carbon molecular sieve of multiple regular pattern.Present method preparation cost is low, operating process is easy, and the target product pore size distribution is narrow, and specific surface area is big, particle morphology is regular, and adjustable deliquescing template kind and consumption, hydro-thermal time and hydrothermal temperature etc. are realized the control to particle morphology, pore structure and specific surface area.
Description of drawings
For further understanding the present invention, elaborate with embodiment below, and provide accompanying drawing and describe the high specific surface area meso-porous carbon molecular sieve that the present invention obtains, wherein:
Figure 1A, 1B are respectively the mesoporous SBA-16 of institute's synthetic and as the Small angle XRD spectra of hard mould agent institute synthetic meso-porous carbon molecular sieve, wherein curve (a) is the Small angle XRD spectra of polyhedron SBA-16 among Figure 1A, and curve (b) is the Small angle XRD spectra of spherical SBA-16; Curve among Figure 1B (a) is the Small angle XRD spectra of embodiment 1 sample, and curve (b) is the Small angle XRD spectra of embodiment 2 samples.
Fig. 2 A, 2B are respectively the N of the mesoporous SBA-16 of institute's synthetic
2Adsorption-desorption thermoisopleth and its pore size distribution curve, wherein curve (a) and (b) be respectively the N of polyhedron SBA-16 and spherical SBA-16 among Fig. 2 A
2The adsorption-desorption thermoisopleth; Curve among Fig. 2 B (a) and (b) be respectively the pore size distribution curve of polyhedron SBA-16 and spherical SBA-16.
Fig. 3 A, 3B are respectively the N of embodiment 1～2 sample
2Adsorption-desorption thermoisopleth and its pore size distribution curve, wherein curve (a) and (b) be respectively the N of embodiment 1 and embodiment 2 samples among Fig. 3 A
2The adsorption-desorption thermoisopleth; Curve among Fig. 3 B (a) and (b) be respectively the pore size distribution curve of embodiment 1 and embodiment 2 samples.
Fig. 4 A, 4B are respectively the SEM photo of synthetic polyhedron SBA-16 of institute and spherical SBA-16.
Fig. 5 A, 5B are respectively the TEM photo of synthetic polyhedron SBA-16 of institute and spherical SBA-16.
Fig. 6 A, 6B are respectively the TEM photo of embodiment 1 and embodiment 2 samples.
Table 1 is for the synthetic SBA-16 of institute and as specific surface area, mean pore size and the pore volume of hard mould agent synthetic meso-porous carbon molecular sieve.
Embodiment
Embodiment 1: at room temperature, add EO in the 0.4mol/L hydrochloric acid soln
106PO
70EO
106And cetyl trimethylammonium bromide, under violent stirring, add in the above-mentioned solution tetraethoxy and stirring, wherein tetraethoxy: hydrochloric acid: EO
106PO
70EO
106: the mol ratio of cetyl trimethylammonium bromide is 1: 3.5: 0.005: 0.02, change over to from pressing still 95 ℃ of hydro-thermals 5 days, after filtration, following dry 12 hours behind the deionized water wash at 60 ℃, then in retort furnace with the speed temperature programming to 550 of 1 ℃/min ℃ and 550 ℃ of following calcinations 3 hours, obtain polyhedron SBA-16 white powder.It is in 98% the vitriol oil that sucrose is added to deionized water and massfraction, after polyhedron SBA-16 is added in the above-mentioned solution, SBA-16 wherein, sucrose, deionized water and massfraction are that 98% vitriol oil mole consisted of 1: 0.219: 20: 0.0875, mixture almost evaporates down to moisture in magnetic agitation, change in 80 ℃ of baking ovens and heated 6 hours, 160 ℃ were heated 6 hours, in the powder that obtains, add mol ratio again and be 0.132: 20: 0.05 sucrose, deionized water and massfraction are in the mixed solution of 98% the vitriol oil, and be transferred in 80 ℃ of baking ovens heating 6 hours, 160 ℃ were heated 6 hours, the solid that obtains is in 900 ℃ of calcinations 2 hours in the nitrogen atmosphere of 100ml/min with the speed temperature programming to 900 of 1 ℃/min ℃ and at flow velocity in nitrogen atmosphere, remove the silicon template with massfraction for the 10%HF solution washing at last, promptly get order mesoporous carbonaceous molecular sieve again after seasoning, its specific surface area is 1600m
2/ g, mean pore size is 3.1nm, pore volume is 1.42cm
3/ g.
Embodiment 2: at room temperature, add EO in the 0.8mol/L hydrochloric acid soln
106PO
70EO
106And cetyl trimethylammonium bromide, under violent stirring, add in the above-mentioned solution tetraethoxy and stirring, tetraethoxy, hydrochloric acid, EO
106PO
70EO
106With the mol ratio of cetyl trimethylammonium bromide be 1: 6.9: 0.002: 0.02, change over to from pressing still 95 ℃ of hydro-thermals 5 days, after filtration, dry down behind the deionized water wash at 60 ℃, then in retort furnace with the speed temperature programming to 550 of 1 ℃/min ℃ and 550 ℃ of following calcinations 3 hours, obtain spherical SBA-16 white powder.It is 98% the vitriol oil that sucrose is added to deionized water and massfraction, after spherical SBA-16 is added in the above-mentioned solution, SBA-16 wherein, sucrose, deionized water and massfraction are that 98% vitriol oil mole consisted of 1: 0.219: 20: 0.0875, mixture almost evaporates down to moisture in magnetic agitation, and placed 80 ℃ of baking oven constant temperature 6 hours, 160 ℃ were heated 6 hours, in the powder that obtains, add mol ratio again and be 0.132: 20: 0.05 sucrose, in deionized water and the vitriol oil mixed solution, and put into 80 ℃ of baking oven constant temperature and handled 6 hours, 160 ℃ were heated 6 hours, the solid that obtains is in 900 ℃ of calcinations 2 hours in the nitrogen atmosphere of 100ml/min with the speed temperature programming to 900 of 1 ℃/min ℃ and at flow velocity in nitrogen atmosphere, remove the silicon template with massfraction for the 10%HF solution washing at last, promptly get the carbonaceous molecular sieve of worm meso-porous structure again after seasoning, its specific surface area is 966m
2/ g, mean pore size is 3.5nm, pore volume is 0.91cm
3/ g.
| Sample | Mean pore size (nm) | Specific surface area (m 2/g) | Pore volume 10 (cm 3/g) |
| The mesoporous SBA-16 of polyhedron | 3.6 | 1011 | 1.00 |
| Spherical mesoporous SBA-16 | 3.5 | 809 | 0.67 |
| By the order mesoporous carbonaceous molecular sieve of the mesoporous SBA-16 synthetic of polyhedron | 3.1 | 1600 | 1.42 |
| Carbonaceous molecular sieve by the worm meso-porous structure of spherical mesoporous SBA-16 synthetic | 3.5 | 966 | 0.91 |
Claims (1)
1. a method of utilizing the hard mould agent synthesizing high specific surface area meso-porous carbon molecular sieve is characterized in that, may further comprise the steps:
(1) at room temperature, in hydrochloric acid soln, add triblock copolymer EO
106PO
70EO
106With the cetyl trimethylammonium bromide soft template, under violent stirring, add tetraethoxy and stirring;
When concentration of hydrochloric acid is 0.4mol/L and tetraethoxy: hydrochloric acid: EO
106PO
70EO
106: the mol ratio of cetyl trimethylammonium bromide is 1: 3.5: 0.005: 0.02 o'clock, the surface topography of gained SBA-16 was a polyhedral;
When concentration of hydrochloric acid is 0.8mol/L and tetraethoxy: hydrochloric acid: EO
106PO
70EO
106: the mol ratio of cetyl trimethylammonium bromide is 1: 6.9: 0.002: 0.02 o'clock, the surface topography of gained SBA-16 was spherical;
(2) the gained mixture is changed over to from pressing still 95 ℃ of thermostat(t)ed water thermal treatments 5 days, after filtration, behind the deionized water wash in 60 ℃ of dryings 12 hours;
(3) in retort furnace with the speed temperature programming to 550 of 1 ℃/min ℃ and 550 ℃ of following constant temperature calcinations 3 hours, obtain the SBA-16 white powder;
(4) SBA-16 is joined by sucrose: deionized water: massfraction is that 98% vitriol oil mol ratio is 1: 0.219: 20: in 0.0875 mixed solution of forming, magnetic agitation finishes the moisture evaporation in this mixed solution, and the baking oven of then it being put into 80 ℃ and 160 ℃ successively constant temperature was handled 6 hours;
(5) add in the gained powder by sucrose: deionized water: vitriol oil mol ratio is 0.132: 20: 0.05 mixed solution of forming, and magnetic agitation in the repeating step (4) and drying operation are once again;
(6) solid that obtains in nitrogen atmosphere with the speed temperature programming to 900 of 1 ℃/min ℃ and constant temperature calcination 2 hours under this temperature, with massfraction be 10%HF solution washing gained pressed powder to remove the silicon template, after seasoning, promptly obtain meso-porous carbon molecular sieve again.
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