CN101559347B - Directional grown mesoporous adsorption material with controllable structure and preparation method thereof - Google Patents
Directional grown mesoporous adsorption material with controllable structure and preparation method thereof Download PDFInfo
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- CN101559347B CN101559347B CN2009100849370A CN200910084937A CN101559347B CN 101559347 B CN101559347 B CN 101559347B CN 2009100849370 A CN2009100849370 A CN 2009100849370A CN 200910084937 A CN200910084937 A CN 200910084937A CN 101559347 B CN101559347 B CN 101559347B
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Abstract
The invention relates to a directional grown mesoporous adsorption material with a controllable structure and a preparation method thereof, and belongs to the technical field of porous adsorption materials. The adsorption material has an alumina-silica composite structure and is assembled by an inorganic-organic interface in an alumina hole, and the mesoporous structure is formed in a directional growing mode along the axial direction of an alumina array hole; and the mesoporous structure of a silica phase can be controlled as a regular and ordered two-dimensional or three-dimensional structure, and the pore canal growing direction and the aperture size of the mesoporous structure are modulated by adjusting and controlling a mixture ratio of a self-assembling system and assembling conditions. The adsorption material has the advantages that the adsorption material has an integral composite structure and is convenient to apply; the pore structure is regular and ordered, the size distribution is even, and the capillary condensation is quick; the porosity is high and the adsorbing capacity is large; and the surface property is adjustable, and the adsorption material is applicable to adsorption substances with different polarities. The adsorption material can be widely applied to quick high-capacity storage of liquid gas or gas solution.
Description
Technical field
The invention belongs to the porous adsorbing material technical field, directional grown mesoporous adsorption material that particularly a kind of structure is controlled and preparation method thereof.This sorbing material is all-in-one-piece aluminium oxide-silicon oxide composite construction, adopts by the inorganic-organic interface assembling in the alumina pore, and meso-hole structure forms along the axial orientation growth pattern of aluminium oxide array hole; This material can be widely used in the quick high-capacity storage of liquid gas or gas solution.
Background technology
Sorbing material is the focus of current scientific research, and its range of application is very extensive, as is used for energy storage adsorbent, water body and atmospheric cleaning adsorbent, large biological molecule absorption carrier etc.Material as adsorbent mainly contains silicate material, molecular screen material, metal material and other cavernous structure metal oxide materials etc. at present.The characteristic that superior adsorbent should have mainly is that adsorbate is had bigger adsorption capacity, and has good selectivity.Reach target call, must know adsorption mechanism, the structure of grasping sorbing material is related with performance.
The reinforcement storage of gas is the important content that sorbing material is used, and the reinforcement storage of learning gas is extremely important for development clean energy resource and protection environment.Strengthening mechanism is divided into chemical action and physical action two classes substantially.The former requires the specific area of material high as far as possible, because chemisorbed must be monolayer absorption, but specific area influences not quite the latter, because gas will enter the inside of material, perhaps in the micro-space that material provides chemical change takes place.Because chemical bond has saturability, therefore monolayer absorption can only take place.The unique channel of strengthening absorption is the specific area that increases adsorbent.Forming chemical bond needs the uniform temperature condition, and destroying chemical bond also needs the uniform temperature condition, thus with the gas storage of chemisorbed principle, be cost with extra energy consumption, and charge and discharge the gas inconvenience.Can be used for strengthening the physical action mechanism of atmosphere storage, mainly is compression, liquefaction and physical absorption.If gas molecule is to be fixed on solid material surface by model ylid bloom action power, then be physical absorption.The key condition of decision physical absorption mechanism is an adsorption temp.If adsorption temp is higher than the critical-temperature of gas, though it is not chemical action power that the interface interaction power of absorption takes place, but remain and can only be monolayer absorption, irrelevant with the geometric properties of sorbing material, its basic reason be that the above gas of critical-temperature can not condense.If adsorption temp is below the critical-temperature of gas, then adsorption mechanism depends on the architectural feature of sorbing material.Because gas all has coherency, thus can be in the absorption of open surface generation polymolecular layer, and (aperture＜2nm) volume takes place to fill, (2～50nm) capillary condensation takes place at mesopore at micropore.Therefore, if utilize physical absorption to strengthen storage, more than critical-temperature, can only be by increasing adsorbent specific area and the method that reduces adsorption temp; Below critical-temperature, adjust the aperture and increase pore volume and can receive remarkable result.
At present, gas storage research research course from the exploitation of super-activated carbon to CNT, the organic framework thing of metal, organic synthetic to grid type, but do not form available industrial gas storage technology so far.More new material new technologies are demanded exploitation urgently, especially will strengthen effective utilization of the structure or the surface nature of sorbing material.
The preparation of sorbing material mainly faces two huge challenges.On the one hand, the material shortage monolithic construction, how implementation structure preparation or effective integration are very important; On the other hand, the pore structure degree of order of material is poor, and pore-size distribution is inhomogeneous, causes adsorbance and adsorptive selectivity not high.At above two science difficult points, we have proposed a kind of preparation method of monoblock type sorbing material, and by the inorganic-organic interface assembling in the alumina pore, meso-hole structure forms along the axial orientation growth pattern of aluminium oxide array hole; Gained sorbing material pore structure degree of order height, two dimension or 3 D pore canal are controlled, even aperture distribution, size adjustable, and its all-in-one-piece membrane structure is convenient to use.This material can be widely used in the quick high-capacity storage of liquid gas or gas solution.
Summary of the invention
The object of the present invention is to provide controlled directional grown mesoporous adsorption material of a kind of structure and preparation method thereof, solved the material shortage monolithic construction, the problem of the pore structure degree of order difference of material.
Sorbing material of the present invention is the aluminium oxide-silicon oxide composite construction, adopts by the inorganic-organic interface assembling in the alumina pore, and meso-hole structure forms along the axial orientation growth pattern of aluminium oxide array hole; The meso-hole structure of silica phase may be controlled to regular orderly two dimension or three-dimensional structure, also can by regulation and control self-assembly system batching when assembling condition its duct direction of growth and aperture size are carried out modulation.
The preparation method of mesoporous adsorption material of the present invention is as follows:
(1) preparation of silica precursors solution
With polyvinylether-polypropylene ether-polyvinylether block copolymer (P123), concentrated hydrochloric acid, ethanol (EtOH) and water stir down at 15～60 ℃, form the solution of transparent homogeneous.Add hydrophobic small molecules additive (additive), stirred 1～3 hour, again ethyl orthosilicate (TEOS) is dropwise added in the P123 solution, continue to stir 0.5～3 hour.Each material molar ratio of solution is 1 TEOS:0.006～0.06 P123:4～12 H
2O:3～103～10 EtOH:0.001～0.05 HCl:0.01～0.5 additive.
(2) silica and aluminium oxide is compound
With anodic alumina films, impregnated in the silica precursors solution in the step (1), vacuum condition volatilized 0.5～2 hour down, and solution forms sticking shape colloidal sol; Take out pellumina, room temperature nature crystallization.
(3) post processing of silica-alumina composite construction
Block copolymer P123 in the alcohol reflux spe membrane, drying at room temperature; The mesoporous aperture of the homogeneous that obtains having, the adjustable sorbing material of its size 5～12nm.
Additive in the step (1) comprises benzene, toluene, the aromatic series micromolecular material of dimethylbenzene, trimethylbenzene one class or with in the organoalkoxysilane at hydrophobic position any one; Fragrance same clan additive can form orderly two-dimentional hexagonal hole structure, and the organosilan additive can form the three-dimensional cubic pore structure; The intact uniform monoblock type composite construction that sorbing material after step (3) is handled has, mesoporous aperture homogeneous, 5～12nm is adjustable for its size.
Remarkable advantage of the present invention is the axial orientation growth of meso-hole structure along the aluminium oxide array hole, and pore structure is regular in order, the Size Distribution homogeneous; The hole prosperity, capillary condensation is fast, and adsorbance is big; Surface nature is adjustable, is applicable to the adsorbate of opposed polarity; The quick high-capacity storage that can be widely used in liquid gas or gas solution.In addition, the present invention is the monoblock type composite construction, is convenient to use.
Description of drawings
Fig. 1 is the sem photograph of silica-alumina composite construction, and interior illustration is the transmission electron microscope picture of the silica phase of two-dimentional hexagonal ring shape pore structure.
The specific embodiment
Embodiment 1
(1) preparation of silica precursors solution
With being dissolved in the mixed liquor of 4.8g ethanol and 1.2g 0.2M HCl under 0.687g polyvinylether-polypropylene ether-polyvinylether block copolymer (P123) room temperature, form the P123 solution of transparent homogeneous.Add 0.05g toluene, stirred 2 hours.2.08g ethyl orthosilicate dropwise adds in the solution, stirs 1 hour.
(2) silica and aluminium oxide is compound
With the 47mm diameter, the anodic alumina films in 200nm aperture impregnated in the silica precursors solution in the step (1), and vacuum condition volatilized 1 hour down.Take out pellumina, natural crystallization 1 day.
(3) post processing of silica-alumina composite construction
60mL alcohol reflux extraction in 12 hours block copolymer P123, the ethanol that more renews extracted 12 hours again.Drying at room temperature.
Promptly prepare the sorbing material of two-dimentional hexagonal ring shape pore structure.
Embodiment 2
(1) preparation of silica precursors solution
With being dissolved in the mixed liquor of 5g ethanol and 1g0.2M HCl under 1g polyvinylether-polypropylene ether-polyvinylether block copolymer (P123) room temperature, form the P123 solution of transparent homogeneous.Add the 0.15g mercaptopropyl trimethoxysilane, stirred 2 hours.2.08g ethyl orthosilicate dropwise adds in the solution, stirs 1 hour.
(2) silica and aluminium oxide is compound
With the 47mm diameter, the anodic alumina films in 200nm aperture impregnated in the silica precursors solution in the step (1), and vacuum condition volatilized 1 hour down.Take out pellumina, natural crystallization 1 day.
(3) post processing of silica-alumina composite construction
60mL alcohol reflux extraction in 12 hours block copolymer P123, the ethanol that more renews extracted 12 hours again.Drying at room temperature.
Promptly prepare the sorbing material of three-dimensional cubic pore structure.
Embodiment 3
(1) preparation of silica precursors solution
Be dissolved in the mixed liquor of 5g ethanol and 1g0.2M HCl under 35 ℃ of 1g polyvinylether-polypropylene ethers-polyvinylether block copolymer (P123), form the P123 solution of transparent homogeneous.Add the 0.05g trimethylbenzene, stirred 2 hours.2.08g ethyl orthosilicate dropwise adds in the solution, stirs 1 hour.
(2) silica and aluminium oxide is compound
With the 47mm diameter, the anodic alumina films in 200nm aperture impregnated in the silica precursors solution in the step (1), and vacuum condition volatilized 1 hour down.Take out pellumina, natural crystallization 1 day.
(3) post processing of silica-alumina composite construction
60mL alcohol reflux extraction in 12 hours block copolymer P123, the ethanol that more renews extracted 12 hours again.Drying at room temperature.
Promptly prepare the sorbing material of the straight shape pore structure of two dimension six sides.
Embodiment 4
With embodiment 1 gained two dimension hexagonal ring shape pore structure sorbing material, with embodiment 2 gained three-dimensional cubic pore structure sorbing materials, remove the aluminium oxide phase fully with 5M HCl solution, its silica is carried out transmission electron microscope, little angle XRD sign and the test of gas adsorption desorption mutually, and pore structure parameter and absorption property are listed in table 1.
Table 1: the sorbing material silica of two-dimentional hexagonal hole structure and three-dimensional cubic pore structure pore structure parameter and gas absorption property mutually
| Sorbing material silica phase pore structure | XRD records cell parameter (nm) | TEM records aperture (nm) | Specific surface (m 2/g) | Nitrogen saturated extent of adsorption (molecule/nm 2) | Steam-laden adsorbance (molecule/nm 2) |
| The two dimension hexagonal structure | 11 | 7.4 | 425 | 7 | 11 |
| Three-dimensional cubic structure | 24 | 7.0 | 450 | 8 | 13 |
Claims (2)
1. directional grown mesoporous adsorption material that structure is controlled, it is characterized in that: this sorbing material is the aluminium oxide-silicon oxide composite construction, adopt by the inorganic-organic interface assembling in the alumina pore, meso-hole structure forms along the axial orientation growth pattern of aluminium oxide array hole; The meso-hole structure of silica phase is controlled to be regular orderly two dimension or three-dimensional structure, or by regulation and control self-assembly system batching when assembling condition its duct direction of growth and aperture size are carried out modulation;
This sorbing material is prepared by the following step:
(1) preparation of silica precursors solution
With polyvinylether-polypropylene ether-polyvinylether block copolymer P123, concentrated hydrochloric acid, the second alcohol and water stirs down at 15～60 ℃, forms the solution of transparent homogeneous; Add the hydrophobic small molecules additive, stirred 1～3 hour, again ethyl orthosilicate is dropwise added in the P123 solution, continue to stir 0.5～3 hour; Each material molar ratio of solution is 1 ethyl orthosilicate: 0.006～0.06P123: 4～12H
2O: 3～10 ethanol: 0.001～0.05HCl: 0.01～0.5 hydrophobic small molecules additive; Additive is benzene, toluene, the aromatic series micromolecular material of dimethylbenzene, trimethylbenzene or with in the organoalkoxysilane at hydrophobic position any one; Fragrance same clan additive forms orderly two-dimentional hexagonal hole structure, and the organoalkoxysilane additive forms the three-dimensional cubic pore structure;
(2) silica and aluminium oxide is compound
With anodic alumina films, impregnated in the silica precursors solution in the step (1), vacuum condition volatilized 0.5～2 hour down, and solution forms sticking shape colloidal sol; Take out pellumina, room temperature nature crystallization;
(3) post processing of silica-alumina composite construction
Block copolymer P123 in the alcohol reflux spe membrane, drying at room temperature; The mesoporous aperture of the homogeneous that obtains having, the adjustable sorbing material of its size 5～12nm.
2. method for preparing the described sorbing material of claim 1, it is characterized in that: processing step is
(1) preparation of silica precursors solution
With polyvinylether-polypropylene ether-polyvinylether block copolymer P123, concentrated hydrochloric acid, the second alcohol and water stirs down at 15～60 ℃, forms the solution of transparent homogeneous; Add the hydrophobic small molecules additive, stirred 1～3 hour, again ethyl orthosilicate is dropwise added in the P123 solution, continue to stir 0.5～3 hour; Each material molar ratio of solution is 1 ethyl orthosilicate: 0.006～0.06P123: 4～12H
2O: 3～10 ethanol: 0.001～0.05HCl: 0.01～0.5 hydrophobic small molecules additive;
(2) silica and aluminium oxide is compound
With anodic alumina films, impregnated in the silica precursors solution in the step (1), vacuum condition volatilized 0.5～2 hour down, and solution forms sticking shape colloidal sol; Take out pellumina, room temperature nature crystallization;
(3) post processing of silica-alumina composite construction
Block copolymer P123 in the alcohol reflux spe membrane, drying at room temperature; The mesoporous aperture of the homogeneous that obtains having, the adjustable sorbing material of its size 5～12nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1037940B1 (en) * | 1997-12-09 | 2004-09-08 | SBA Materials, Inc. | Block polymer processing for mesostructured inorganic oxide materials |
| CN101049937A (en) * | 2007-05-17 | 2007-10-10 | 上海交通大学 | Method for preparing mesoporous silicon dioxide film with macroscopical ordered orientation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1037940B1 (en) * | 1997-12-09 | 2004-09-08 | SBA Materials, Inc. | Block polymer processing for mesostructured inorganic oxide materials |
| CN101049937A (en) * | 2007-05-17 | 2007-10-10 | 上海交通大学 | Method for preparing mesoporous silicon dioxide film with macroscopical ordered orientation |
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