CN1182030C - Prepn of silica with great specific surface area - Google Patents
Prepn of silica with great specific surface area Download PDFInfo
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- CN1182030C CN1182030C CNB01126876XA CN01126876A CN1182030C CN 1182030 C CN1182030 C CN 1182030C CN B01126876X A CNB01126876X A CN B01126876XA CN 01126876 A CN01126876 A CN 01126876A CN 1182030 C CN1182030 C CN 1182030C
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- polystyrene spheres
- polystyrene
- macropore
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Abstract
The present invention relates to a method for preparing a silicon oxide material having a high order degree macropore-meson pore and a high specific surface area, which belongs to the technical field of a molecular sieve inorganic material. A surface active agent is used as a structure directing agent, and is combined with an inorganic silicon material to assemble into an ordered mesostructure; the ordered mesostructure is molded with a sol-gel process by the guiding of the polystyrene ball as a new macropore template agent; at the same time, the surface active agent and the polystyrene ball respectively used as the templates of a meson pore and a macropore are removed at high temperature to prepare a multistage silicon oxide material with a high order degree macropore-meson pore. The multistage porous material has wide application prospects in the aspects of adsorption, separation, sensors, optical materials, etc.
Description
Technical field
The invention belongs to material field, inorganic hole, relate to a kind of preparation high degree of order macropore--method of mesoporous diplopore, silica with great specific surface area material.
Technical background
At present, people adopt a kind of artificial opals of being piled into by the polystyrene sphere of size homogeneous as template, infiltrate silica sol therein, treat that colloidal sol condenses after, remove polystyrene sphere as template, made the macropore silicon oxide material.Because the macropore of this material has the face-centred cubic structure of three-dimensional order, makes it have special optical property.And the hole of this material is more than 50nm, can be used for separation, catalyzed reaction of large protein etc.But the specific surface area of this material is compared less with general support of the catalyst, has limited its application aspect catalysis; And the hole wall of this material is made up of silicon oxide fully, limited its application aspect optics.If mesoporous material and large pore material that can specific surface area is big combine, just can address these problems preferably.
Summary of the invention
The objective of the invention is to propose preparation high degree of order macropore a--method of mesoporous diplopore, silica with great specific surface area material.
The method for preparing the silica with great specific surface area material that the present invention proposes, be to be structure directing agent with the tensio-active agent, be assembled into the sight ordered structure that is situated between altogether with the inorganic silicon material, and under the guiding of new macropore template polystyrene spheres by colloidal sol-gelation process moulding, slough simultaneously under the high temperature respectively as tensio-active agent and polystyrene spheres mesoporous, the macropore template, obtain the method for a kind of high degree of order macropore-mesoporous multi-stage oxidizing silicon materials.Concrete steps are as follows:
(1) in the alcohol solvent, under the hydrochloric acid effect, with teos hydrolysis, and self-assembly under the surfactant structure guide effect, the mass ratio of each component is an ethanol: the hydrochloric acid of tensio-active agent: tetraethoxy: 0.02M: water=15: (0.7-1.2): (1.80-2.28): (0.4-0.6): (0.4-0.6);
(2) drips of solution that at room temperature will be dispersed with polystyrene sphere is added on the smooth substrate, and the polystyrene sphere diameter is 50-400nm, and the weight concentration of its solution is 5-30%;
(3) under the condition that vacuumizes, allow the solution evaporation that is dispersed with polystyrene sphere, to doing;
(4) under the condition of suction filtration, the drips of solution that makes in the step (1) is added on the block of polystyrene spheres accumulation, treat solvent evaporates under the room temperature, this moment, silicon-dioxide, tensio-active agent formed orderly organic in the accumulation gap of polystyrene spheres--inorganic mesoscopic structure, repeat 2-5 time, be filled until the gap of polystyrene spheres;
(5) with the material of moulding in the step (4) 500-600 ℃ of roasting, slough polystyrene spheres and tensio-active agent as template, obtain macropore--mesoporous multilevel hole material.
In the present invention, can adopt the ball of diameter homogeneous, specifically can select the different size of diameter from 50nm to 400nm as the polystyrene spheres of macropore template.By polystyrene spheres natural subsidence in solution, the polystyrene spheres of homogeneous diameter can be arranged in three-dimensional face-centred cubic structure.Among the present invention, polystyrene sphere also can be selected two kinds of different diameters.For example, selecting diameter is that the polystyrene sphere of 210nm and polystyrene sphere that diameter is 130nm are piled up by 1: 13 mol ratio, AB
13Structure.(SEM) can confirm by scanning electronic microscope, by the present invention obtain macropore--the macropore diameter of mesoporous multilevel hole material is approximately 70% of polystyrene sphere diameter, can adjust macropore diameter by the diameter that changes polystyrene sphere.Orderly block materials can reach several square millimeters size continuously.
In the present invention, the also mode of available mechanical compressing tablet of step (3).Be about to polystyrene spheres dry powder is pressed into the 1---2 millimeter on infrared tabletting machine sheet.The mechanical pressure of compressing tablet is the 5-10 kg/cm.Polystyrene spheres can be arranged in approximate closely packed mode.Also can obtain macropore at last--mesoporous diplopore silica material.
In the methods of the invention, can adopt different tensio-active agents in the step (1).(polyoxyethylene-polyoxypropylene-polyoxyethylene blocks formula multipolymer, molecular formula is EO for example can to adopt three block tensio-active agent Pluronic P123
20PO
70EO
20, molecular-weight average=5800) and do that structure directing agent, resulting macropore--the mesoporous aperture in the mesoporous diplopore silica material can reach 7-9nm; In the time of also can adopting hexadecyl trimethyl ammonium bromide to make structure directing agent, the macropore that obtains--the mesoporous aperture in the mesoporous diplopore silica material is 2---4nm.Mesoporous diameter can be measured by low temperature nitrogen adsorption experiment (BET).Low temperature nitrogen adsorption experiment (BET) result has shown that also mesoporous in the material has the pore distribution of homogeneous and big specific surface area.Also can be clearly seen that the mesopore orbit that sequential 2 D is arranged from transmission electron microscope (TEM) photo.Change is as the kind of the tensio-active agent of meso-hole structure directed agents, can change last resulting macropore--mesoporous aperture even structure in the mesoporous diplopore silica material, thereby can prepare suitable macropore as required--mesoporous diplopore silica material.Macropore--the high specific surface area that mesoporous diplopore silica material is had, the macroporous structure of three-dimensional order, orderly 2 D mesopore duct make that macropore--mesoporous diplopore silica material is at optics, and aspects such as catalysis have wide practical use.
In the present invention, step (3) and step (4) can be reduced to a step, the polystyrene spheres dry powder of the certain size that is about to choose or be dispersed with the solution of polystyrene spheres and step (1) in the solution that makes mix, in polystyrene spheres: the ratio of silicon oxide is 1: 1-1: 2 (weight ratios), fierce concussion is evenly dispersed in the polystyrene spheres powder in the solution as far as possible in ultrasonic wave.After the dispersion, mixing solutions is poured in the watch-glass, allows solvent volatilize naturally.In the process of solvent evaporates, polystyrene spheres settles down at leisure and is piled into the face-centred cubic structure or the AB of three-dimensional order
13Ordered structure.Simultaneous oxidation silicon and tensio-active agent are assembled into Jie's sight ordered structure and are filled in the gap of piling up good polystyrene spheres.The gap between the filled polystyrene ball more fully in this way.The macropore that obtains--mesoporous diplopore silicon oxide film mechanical stability is better.
Embodiment
The invention will be further elaborated for following Application Example:
Embodiment 1, at first, in 10 gram alcohol solvents, adds 0.4 gram (0.1M) hydrochloric acid, and 0.5 gram water and 2.08 restrains tetraethoxys, stirs under the room temperature to be hydrolyzed; In other 5 gram alcohol solvents, add 0.9 gram three block tensio-active agents (Pluronic P123, molecular-weight average=5800), stirring and dissolving under the room temperature.After 30 minutes, two solution are mixed, continue to stir 2 hours.
At room temperature will be dispersed with size evenly the solution (weight concentration 10%) of the polystyrene sphere of (210nm) drip on silicon substrate or be poured in the culture dish.Allow the solution evaporation that is dispersed with polystyrene sphere under the condition that vacuumizes, after volatilization was done, polystyrene sphere was piled up with face-centred cubic accumulation mode.
The bulk material that the polystyrene spheres that previous step is obtained in rapid is piled into is transferred to filter flask, under the condition of slight suction filtration, the drips of solution that makes in the first step is added on the block that polystyrene spheres piles up, allows the gap of solution infiltration by polystyrene spheres, treat under the room temperature that solvent volatilizees gradually.This moment, silicon-dioxide, tensio-active agent formed orderly organic in the accumulation gap of polystyrene spheres--inorganic mesoscopic structure.Repeat for several times, till solution infiltrated no longer easily, this moment, the gap of polystyrene spheres almost was filled.
Good material to be infiltrated at 550 ℃ of roasting 5---7 hours, is sloughed polystyrene spheres and tensio-active agent as template with it after doing simultaneously, promptly obtains macropore--mesoporous diplopore silica material.By scanning electronic microscope (SEM) as can be known, resulting macropore--the macropore diameter of mesoporous diplopore silica material is about 140nm, compares with initial polystyrene spheres and has dwindled about 30%.Macropore has the three-dimensional face-centred cubic structure the same with polystyrene spheres.Mesoporous can the sign in the material by low temperature nitrogen adsorption experiment (BET) and transmission electron microscope (TEM).Mesoporous diplopore silica material has the mesoporous of size homogeneous, and the aperture is about 8nm in low temperature nitrogen absorption--desorption curve (BET) shows resulting macropore--.Specific surface area is 915 meters squared per gram.The test result of transmission electron microscope (TEM) and X-ray diffraction all shows the mesoporous duct that sequential 2 D is arranged that has.
Embodiment 2, and in the first step of embodiment 1, except 0.9 gram three block tensio-active agents (Pluronic P123, molecular-weight average=5800) being changed into 0.8 gram hexadecyl trimethyl ammonium bromide (CTAB), other each steps are all identical.
By scanning electronic microscope (SEM) as can be known, the macropore diameter of resulting macropore--mesoporous diplopore silica material still is about 140nm, has the three-dimensional face-centred cubic structure the same with polystyrene spheres.And low temperature nitrogen absorption--desorption curve (BET) shows that the mesoporous aperture in the material is 4nm at this moment.On transmission electron microscope (TEM) photo, the mesoporous hexagonal that still is sequential 2 D is arranged.
Embodiment 3, and in second step of embodiment 1, the polystyrene sphere that adopts 300nm is as template.Other each steps and reagent are all identical.
By scanning electronic microscope (SEM) as can be known, resulting macropore--the macropore diameter of mesoporous diplopore silica material is about 210nm, has the three-dimensional face-centred cubic structure the same with polystyrene spheres.Mesoporous size and structure are with embodiment 1.As seen by changing the size of polystyrene spheres, can change macropore--the macropore diameter in the mesoporous diplopore silica material.
Embodiment 4, step (3) among the embodiment 1 and step (4) are reduced to a step, other each step and reagent are all identical: the solution that makes in 1 gram polystyrene spheres dry powder and the 25 gram steps (1) is mixed, this moment polystyrene spheres: the ratio of silicon oxide is 1: 1 (weight ratio).
With mixture fierce concussion and fully stirring in ultrasonic wave, the polystyrene spheres powder is evenly dispersed in the solution as far as possible.After the dispersion, mixing solutions is poured in the watch-glass, allows solvent volatilize naturally.In the process of solvent evaporates, polystyrene spheres settles down at leisure and piles up.Simultaneous oxidation silicon and tensio-active agent are assembled into Jie's sight ordered structure and are filled in the gap of piling up good polystyrene spheres.
After treating that material is done, it at 550 ℃ of roasting 5---7 hours, is sloughed polystyrene spheres and tensio-active agent as template simultaneously.
Resulting macropore--mesoporous diplopore silica material has and the identical structure of embodiment 1 product.The gap between the filled polystyrene ball more fully in this way.Resulting macropore--mesoporous diplopore silicon oxide film mechanical stability is better.
Embodiment 5, and in second step of embodiment 1, the polystyrene sphere that adopts 1: 13 210nm of mol ratio and 130nm is as template.Other each steps and reagent are all identical.
By various signs as can be known, the mesoporous size of resulting macropore--mesoporous diplopore silica material and structure are with embodiment 1, and macropore has AB
13Three-dimensional structure.This shows, use the polystyrene sphere of different size and preparation by a certain percentage, can change macropore--the macroporous structure in the mesoporous diplopore silica material.
Embodiment 6, in second step of embodiment 1, and the natural subsidence polystyrene spheres close packed array process mode that can use mechanical compressing tablet instead lentamente.Polystyrene spheres dry powder is pressed into the sheet of 1---2 millimeter on infrared tabletting machine.The mechanical pressure of compressing tablet is 5 kg/cm.Polystyrene spheres can be arranged in approximate closely packed mode.Other each steps and reagent are all identical.
The macropore that obtains at last--mesoporous diplopore silica material has meso-hole structure identical with embodiment 1 product and big specific surface, and big hole dimension is also identical.
Claims (7)
1, a kind of method for preparing silica material is characterized in that concrete steps are as follows:
(1) in the alcohol solvent, under the hydrochloric acid effect, with teos hydrolysis, and self-assembly under the surfactant structure guide effect, the mass ratio of each component is an ethanol: the hydrochloric acid of tensio-active agent: tetraethoxy: 0.02M: water=15: (0.7-1.2): (1.80-2.28): (0.4-0.6): (0.4-0.6);
(2) drips of solution that at room temperature will be dispersed with polystyrene sphere is added on the smooth substrate, and the polystyrene sphere diameter is 50-400nm, and the weight concentration of its solution is 5-30%;
(3) under the condition that vacuumizes, allow the solution evaporation that is dispersed with polystyrene sphere, to doing;
(4) under the condition of suction filtration, the drips of solution that makes in the step (1) is added on the block of polystyrene spheres accumulation, treat solvent evaporates under the room temperature, this moment, silicon-dioxide, tensio-active agent formed orderly organic in the accumulation gap of polystyrene spheres--inorganic mesoscopic structure, repeat 2-5 time, be filled until the gap of polystyrene spheres;
(5) with the material of moulding in the step (4) 500-600 ℃ of roasting, slough polystyrene spheres and tensio-active agent as template, obtain required silica material.
2, preparation method according to claim 1 is characterized in that used polystyrene spheres size homogeneous, and obtains the face-centered cubic arrangement by the method for natural subsidence.
3, preparation method according to claim 1 is characterized in that used polystyrene spheres is two kinds of different diameters, and the polystyrene spheres that is respectively 210nm and 130nm with diameter is mixed by 1: 13 molar ratio, is piled into AB
13Structure.
4, preparation method according to claim 1 is characterized in that the tensio-active agent that adopts is polyoxyethylene-poly-oxypropylene polyoxyethylene blocked multipolymer EO in step (1)
20PO
70EO
20, molecular-weight average is 5800.
5, preparation method according to claim 1 is characterized in that the tensio-active agent that adopts is a hexadecyl trimethyl ammonium bromide in step (1).
6, preparation method according to claim 1 is characterized in that adopting mechanical mode that the polystyrene spheres powder is pressed into sheet in step (3), and mechanical pressure is the 5-10 kg/cm.
7, preparation method according to claim 1, it is characterized in that step (3), (4) are replaced by another step: with the solution in polystyrene spheres dry powder and the step (1) according to polystyrene spheres: silicon oxide 1: 1--1: 2 is mixed, and teos hydrolysis and ethanol are volatilized.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB01126876XA CN1182030C (en) | 2001-09-26 | 2001-09-26 | Prepn of silica with great specific surface area |
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| CNB01126876XA CN1182030C (en) | 2001-09-26 | 2001-09-26 | Prepn of silica with great specific surface area |
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| CN1182030C true CN1182030C (en) | 2004-12-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1313207C (en) * | 2004-02-13 | 2007-05-02 | 中国石油天然气集团公司 | Method for preparing uniform nanometer molecular sieve material with high catalytic activity |
| US7589041B2 (en) * | 2004-04-23 | 2009-09-15 | Massachusetts Institute Of Technology | Mesostructured zeolitic materials, and methods of making and using the same |
| CN102646764B (en) * | 2012-04-25 | 2014-07-16 | 清华大学 | Overall wet chemical preparation method for nanoscale patterning sapphire substrate |
| CN102849749B (en) * | 2012-09-19 | 2014-12-03 | 复旦大学 | Mesoporous-macroporous multilevel ordered monodisperse micron sphere and preparation method thereof |
| CN104174425B (en) * | 2014-07-11 | 2017-08-11 | 中国科学院生态环境研究中心 | It is a kind of for catalyst of volatile organic matter catalysis oxidation and preparation method thereof |
| CN108508155B (en) * | 2018-04-03 | 2021-04-06 | 宁夏大学 | High-specific-surface-area ordered large-mesoporous nickel oxide acetone gas-sensitive material and preparation method thereof |
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