CN101602507A - A kind of one-dimensional rod-like mesoporous material and its production and application - Google Patents
A kind of one-dimensional rod-like mesoporous material and its production and application Download PDFInfo
- Publication number
- CN101602507A CN101602507A CNA2009100540831A CN200910054083A CN101602507A CN 101602507 A CN101602507 A CN 101602507A CN A2009100540831 A CNA2009100540831 A CN A2009100540831A CN 200910054083 A CN200910054083 A CN 200910054083A CN 101602507 A CN101602507 A CN 101602507A
- Authority
- CN
- China
- Prior art keywords
- mesoporous
- film
- preparation
- organic
- mesoporous material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention discloses a kind of one-dimensional rod-like mesoporous material and its production and application, belongs to mesoporous materials field.The preparation method comprises the preparation of precursor liquid, the suction filtration preparation of compound mesoporous film, the wash-out of film internal surfactants and four steps of dissolving of organic porous films, promptly mainly utilize the suction filtration method that inorganic mesoporous material is assembled in the hole in the polycarbonate membrane and make composite membrane, utilize the extraction type of elution to remove the interior tensio-active agent of this composite membrane again, thereby obtain organic-inorganic compound mesoporous film, again this organic-inorganic compound mesoporous film is immersed in the dichloromethane solvent, promptly gets one-dimensional rod-like mesoporous material after organic porous films dissolves fully.The gained club-shaped material is diameter 200nm, and length 10 μ m have orderly hexagonal mesoporous structure, and the aperture is that 3nm, MCM-41 type or aperture are the one-dimensional mesoporous silica bar of 8nm, SBA-15 type.The gained one-dimensional rod-like mesoporous material is used for fields such as biomacromolecule and catalyzer absorption.
Description
Technical field
The present invention relates to a kind of one-dimensional rod-like mesoporous material and its production and application, belong to mesoporous materials field.
Background technology
Along with the widespread use of mesoporous material in catalytic chemistry and field of petrochemical industry, in recent years, mesoporous material is assembled in the research that forms one-dimensional rod-like mesoporous material in the multiaperture pellumina has caused people's attention.A kind of method that the bar-shaped thing of one-dimensional mesoporous silicon-dioxide prepares one-dimensional rod-like mesoporous material of assembling in multiaperture pellumina is disclosed in " the Self-assembly of a silica surfactantnanocomposite in a porous alumina membrane " literary composition on 2004 the 3rd phases of " Nature Materials " magazine of Britain issuing, the bar-shaped thing length of the prepared one-dimensional mesoporous silicon-dioxide of this method is 40 μ m, and meso-hole structure is not complete ordering.Because this inorganic compound mesoporous film has the defective of following aspect: the cost height of the starting material multiaperture pellumina that is adopted, and this film snappiness is poor, crisp frangible, extremely unstable because of decomposition under weak acid or weakly alkaline environment, particularly prepared inorganic compound mesoporous film is removed after the tensio-active agent through roasting, easier contraction and the more crisp problem of easily splitting of film that mesoporous material in the film occurs.Therefore utilize the method for the one-dimensional rod-like mesoporous material that inorganic compound mesoporous film obtains also to have the deficiency of the following aspects: the raw materials cost height, prepared one-dimensional rod-like mesoporous material oversize (40 μ m) is fracture easily, particularly this method must be removed tensio-active agent in the rod-like mesoporous material by roasting, often cause the duct of rod-like mesoporous material to be shunk, so its hydrothermal stability is relatively poor.
Summary of the invention
The objective of the invention is in order to overcome raw materials cost height of the prior art, one-dimensional rod-like mesoporous material is oversize, especially remove tensio-active agent in the rod-like mesoporous material by roasting, shortcoming such as cause the duct of rod-like mesoporous material to be shunk and its hydrothermal stability is poorer, provide a kind of employing organic porous films as carrier, prepared the method that length is the one-dimensional rod-like ordered mesoporous material of 10 μ m by the mode that extracts wash-out tensio-active agent and organic solvent dissolution organic membrane.
Technical scheme of the present invention
A kind of preparation method of one-dimensional rod-like mesoporous material comprises being prepared as follows step:
(1) preparation of precursor liquid
(a), ionogenic surfactant is cetyl trimethylammonium bromide (CTAB)
With the raw material dehydrated alcohol, tetraethoxy (TEOS) and HCl are according to mol ratio 1.6: 0.56: 2.8 * 10
-5The mixing that feeds intake after slowly stirring, forms solution A, and wherein HCl concentration is that the hydrochloric acid soln of 2.8mmol/L is prepared;
According to dehydrated alcohol, cetyl trimethylammonium bromide (CTAB) and HCl mol ratio are 3.1: 0.042: 2.2 * 10
-3Preparation B mixed solution, wherein HCl concentration is the hydrochloric acid soln preparation of 55mmol/L;
With formed A solution condensing reflux 90min under 60 ℃ water bath condition; Add the B mixed solution then in A solution, behind 25～30 ℃ of following stirring reaction 30min, be cooled to 25 ℃ of precursor liquids that promptly obtain containing CTAB of room temperature, wherein the proportioning of A solution and B mixed solution is 1: 2 by volume;
(b), nonionic surface active agent is EO
20PO
70EO
20(P123)
With the raw material dehydrated alcohol, HCl and deionized water are according to mol ratio 0.31: 1.2 * 10
-3: 0.11 feeds intake mixes and is placed in the three-necked flask, then, is slowly forming mixed solution C under the whipped state, and wherein HCl concentration is that the hydrochloric acid soln of 12mol/L is prepared;
In above-mentioned mixed solution C, add 1.7 * 10
-4Mol nonionic surface active agent tensio-active agent EO
20PO
70EO
20(P123), all dissolve until P123, and the three-necked flask that will fill this mixed solution C places oil bath, under 60 ℃ temperature, slowly behind the stirring reaction 1h, drip the tetraethoxy of 0.10mol more gradually, and under 60 ℃ oil bath temperature, stir aging 12h, be cooled to 25 ℃ of precursor liquids that promptly obtain containing P123 of room temperature then;
Wherein nonionic surface active agent P123 can also select F127 for use;
(2) suction filtration, the assembling of inorganic mesoporous material
The precursor liquid that contains CTAB or P123 that preparation process (1) is obtained is through porous organic porous films suction filtration 3 times, between each suction filtration, under the suction filtration state 5 minutes at interval, promptly gets the organic-inorganic compound mesoporous film that contains Surfactant CTAB or P123;
Wherein organic porous films is polycarbonate membrane or poly-inclined to one side fluorine film; The film diameter 47mm of porous polycarbonate film, bore dia 200 μ m, voidage 10%～15%;
(3) wash-out of film internal surfactants
It is the mixing solutions E that is formed at 1: 5 by volume that the organic-inorganic compound mesoporous film that contains Surfactant CTAB or P123 of step (2) preparation is placed the concentrated hydrochloric acid of mass percent concentration 37.5% and dehydrated alcohol, under 60～80 ℃ of constant temperature oil baths, soak 2～3h with Surfactant CTAB or P123 in the extraction wash-out film, after use deionized water and 95% washing with alcohol respectively 3 times, after at last organic-inorganic compound mesoporous film being placed 60 ℃ of dry 3h of baking oven, promptly get organic/inorganic compound mesoporous film of the present invention;
(4) dissolving of organic porous films
The organic-inorganic compound mesoporous film of preparation process (3) gained is immersed in 2～3min in 1～2ml dichloromethane solvent, treat that the porous polycarbonate film dissolves fully after, through suction filtration can collect one-dimensional rod-like mesoporous material of the present invention.
Show by sem photograph and transmission electron microscope picture:
In the preparation method of one-dimensional rod-like mesoporous material, the one-dimensional rod-like mesoporous material of gained is diameter 200nm when the tensio-active agent in the preparation process (1) adopts cetyl trimethylammonium bromide (CTAB), length 10 μ m, and has orderly hexagonal mesoporous structure, the aperture is 3nm, the one-dimensional mesoporous silica bar of MCM-41 type; Tensio-active agent in preparation process (1) adopts EO
20PO
70EO
20(P123) the diameter 200nm of the one-dimensional rod-like mesoporous material of gained the time, length 10 μ m, and have orderly hexagonal mesoporous structure, the aperture is 8nm, the one-dimensional mesoporous silica bar of SBA-15 type.
Technique effect of the present invention
The present invention is on existing preparation method's basis, adopt the more cheap organic porous films of material cost---polycarbonate membrane, for avoiding removing in the process of tensio-active agent the destruction of material structure and the change of performance because of roasting, adopt the method for extraction wash-out to remove tensio-active agent simultaneously, thereby prepare one-dimensional rod-like mesoporous material.For former reported method, this method cost is lower, processing step is simpler, particularly prepared one-dimensional rod-like mesoporous material has orderly meso-hole structure and shorter length, so these mesoporous materials can be applicable to the field such as fixing of the absorption of biomacromolecule or catalyzer.
Description of drawings
The sem photograph of Fig. 1 MCM-41 type one-dimensional rod-like material
The EDS energy ultimate analysis of Fig. 2 MCM-41 type one-dimensional rod-like material
The transmission electron microscope picture of Fig. 3 MCM-41 type one-dimensional rod-like material
The sem photograph of Fig. 4 SBA-15 type one-dimensional rod-like material
The EDS energy ultimate analysis of Fig. 5 SBA-15 type one-dimensional rod-like material
The transmission electron microscope picture of Fig. 6 SBA-15 type one-dimensional rod-like material
The absorption of Fig. 7 horseradish peroxidase in SBA-15 type one-dimensional rod-like mesoporous material
Embodiment
Below in conjunction with embodiment the present invention is further set forth, but do not limit the present invention.
Embodiment 1
The preparation of MCM-41 type one-dimensional rod-like mesoporous material
With the 7.68g dehydrated alcohol, 11.57g tetraethoxy and 1ml hydrochloric acid (2.8mmol/L) mix, after slowly stirring, and condensing reflux 90min under 60 ℃ water bath condition; Add the 15g dehydrated alcohol then, 1.52g cetyl trimethylammonium bromide (CTAB) after the mixed solution that 4ml hydrochloric acid (55mmol/L) is formed, behind 25 ℃ of following stirring reaction 30min of normal temperature, is cooled to 25 ℃ of precursor liquids that promptly obtain containing CTAB of room temperature.(the Shanghai fast science equipment company limited that rubs produces to utilize suction filter pump, the HPD-25 type does not have oily suction filter pump) and the standing suction filtration device in laboratory (1000ml filter flask), divide three times (each 2ml) to filter (the Britain Whatman company production of porous polycarbonate film the precursor liquid of 6ml (containing CTAB), film diameter 47mm, bore dia 200 μ m, voidage 15%), between each suction filtration, interval 5min under the suction filtration state.
The mixing solutions that places 5ml concentrated hydrochloric acid (mass percent concentration 37.5%) and 25ml dehydrated alcohol to be formed the compound mesoporous film that contains Surfactant CTAB of above-mentioned preparation, under 60 ℃ of constant temperature oil baths, soak 2h with the tensio-active agent in the extraction wash-out film, and then divide three times with deionized water wash and 95% ethanol respectively, each 2ml washing, get final product wash-out film internal surfactants, eluting rate (being about 65%), after this film being placed 60 ℃ of dry 3h of baking oven at last, thereby make the organic-inorganic compound mesoporous film of MCM-41.
Above-mentioned MCM-41 type organic/inorganic compound mesoporous film is immersed in the 1ml dichloromethane solvent behind the 2min, and the porous polycarbonate film dissolves fully, can collect the rod-like mesoporous material that obtains one dimension MCM-41 type through suction filtration.
Through scanning electron microscope, the analysis and characterization of EDS power spectrum and transmission electron microscope (seeing accompanying drawing 1～3) can be found, the constitutional features of preparation method's material of one-dimensional rod-like mesoporous material is as follows:
Can observe this club-shaped material by accompanying drawing 1 is that diameter is 200nm, and length is the one-dimensional rod-like material of 10 μ m;
Can observe this club-shaped material by accompanying drawing 2 is made up of silicon and oxygen element;
By accompanying drawing 3 as can be known, above-mentioned one dimension silica bar has orderly hexagonal mesoporous structure, and the aperture is 3nm, and this constructional feature is corresponding to the mesoporous material of MCM-41 type.
The preparation of SBA-15 type one-dimensional rod-like mesoporous material
With the 15g dehydrated alcohol, 0.10g hydrochloric acid (12mol/L) and 2.0g deionized water mix and place three-necked flask, then, under slow whipped state, adding 1.0g tensio-active agent P123 in this mixed solution all dissolves until P123, and the three-necked flask that this mixing solutions will be housed places oil bath, under 60 ℃ temperature, slowly behind the stirring reaction 1h, drip the tetraethoxy of 2.13g more gradually, and under 60 ℃ oil bath temperature, stir aging 12h, be cooled to the precursor liquid that room temperature promptly obtains containing P123 then.(the Shanghai fast science equipment company limited that rubs produces to utilize suction filter pump, the HPD-25 type does not have oily suction filter pump) and the standing suction filtration device in laboratory (1000ml filter flask), divide three times (each 2ml) to filter (the Britain Whatman company production of porous polycarbonate film the precursor liquid of 6ml (containing P123), film diameter 47mm, bore dia 200 μ m, voidage 15%), between each suction filtration, interval 5min under the suction filtration state.
The mixing solutions that places 5ml concentrated hydrochloric acid (mass percent concentration 37.5%) and 25ml dehydrated alcohol to be formed the compound mesoporous film that contains tensio-active agent P123 of above-mentioned preparation, under 80 ℃ of constant temperature oil baths, soak 3 hours with the tensio-active agent in the extraction wash-out film, and then divide three times with deionized water wash and 95% ethanol respectively, each 2ml washing, get final product wash-out film internal surfactants, eluting rate (being about 65%), after this film being placed 60 ℃ of dry 3h of baking oven at last, thereby make the organic/inorganic compound mesoporous film of SBA-15 type.
Above-mentioned SBA-15 type organic/inorganic compound mesoporous film is immersed in the 2ml dichloromethane solvent behind the 3min, and the porous polycarbonate film dissolves fully, can collect the rod-like mesoporous material that obtains one dimension SBA-15 type through suction filtration.
Through scanning electron microscope, the analysis and characterization of EDS power spectrum and transmission electron microscope (seeing accompanying drawing 4～6) can be found, the constitutional features of above-mentioned synthetic organic/inorganic compound mesoporous film is as follows:
Can observe this club-shaped material by accompanying drawing 4 is that diameter is 200nm, and length is 10 μ m;
Can observe this club-shaped material by accompanying drawing 5 is made up of silicon and oxygen element;
By accompanying drawing 6 as can be known, above-mentioned one dimension silica bar has orderly hexagonal mesoporous structure, and the aperture is 8nm, and this constructional feature is corresponding to the mesoporous material of SBA-15 type.
Six SBA-15 type one-dimensional rod-like Metaporous silicon dioxide materials that organic-inorganic compound mesoporous film generated are placed 5ml, 0.04mg/ml the aqueous solution of horseradish peroxidase in, detect to soak horseradish peroxidase solution absorbancy variation of (the visible maximum absorption band of horseradish peroxidase) at 402nm place that this mesoporous material is arranged by ultraviolet-visible spectrophotometry, the variation of this absorbancy is directly related in the absorption of this mesoporous material with horseradish peroxidase.
The absorbancy of (the visible maximum absorption band of horseradish peroxidase) reduces gradually along with the increase of SBA-15 type one-dimensional rod-like Metaporous silicon dioxide material soak time in horseradish peroxidase solution at the 402nm place can to observe horseradish peroxidase solution by accompanying drawing 7, substantially reach stable behind the 4h, show this mesoporous material can the adsorbed molecules size less than the biomacromolecule in its mesoporous aperture, as horseradish peroxidase, calculate adsorptive capacity and be about 0.06mg (horseradish peroxidase)/0.1mg (SBA-15 type one-dimensional rod-like Metaporous silicon dioxide material).
Claims (4)
1, a kind of preparation method of one-dimensional rod-like mesoporous material comprises being prepared as follows step:
(1) preparation of precursor liquid
(a), ionogenic surfactant is cetyl trimethylammonium bromide (CTAB)
With the raw material dehydrated alcohol, tetraethoxy (TEOS) and HCl are according to mol ratio 1.6: 0.56: 2.8 * 10
-5The mixing that feeds intake after slowly stirring, forms solution A, and wherein HCl concentration is that the hydrochloric acid soln of 2.8mmol/L is prepared;
According to dehydrated alcohol, cetyl trimethylammonium bromide (CTAB) and HCl mol ratio are 3.1: 0.042: 2.2 * 10
-3Preparation B mixed solution, wherein HCl concentration is the hydrochloric acid soln preparation of 55mmol/L;
With formed A solution condensing reflux 90min under 60 ℃ water bath condition; Add the B mixed solution then in A solution, behind 25～30 ℃ of following stirring reaction 30min, be cooled to 25 ℃ of precursor liquids that promptly obtain containing CTAB of room temperature, wherein the proportioning of A solution and B mixed solution is 1: 2 by volume;
(b), nonionic surface active agent is EO
20PO
70EO
20(P123)
With the raw material dehydrated alcohol, HCl and deionized water are according to mol ratio 0.31: 1.2 * 10
-3: 0.11 feeds intake mixes and is placed in the three-necked flask, then, is slowly forming mixed solution C under the whipped state, and wherein HCl concentration is that the hydrochloric acid soln of 12mol/L is prepared;
In above-mentioned mixed solution C, add 1.7 * 10
-4Mol nonionic surface active agent tensio-active agent EO
20PO
70EO
20(P123), all dissolve until P123, and the three-necked flask that will fill this mixed solution C places oil bath, under 60 ℃ temperature, slowly behind the stirring reaction 1h, drip the tetraethoxy of 0.10mol more gradually, and under 60 ℃ oil bath temperature, stir aging 12h, be cooled to 25 ℃ of precursor liquids that promptly obtain containing P123 of room temperature then;
Wherein nonionic surface active agent P123 can also select F127 for use;
(2) suction filtration, the assembling of inorganic mesoporous material
The precursor liquid that contains CTAB or P123 that preparation process (1) is obtained is through porous organic porous films suction filtration 3 times, between each suction filtration, under the suction filtration state 5 minutes at interval, promptly gets the organic-inorganic compound mesoporous film that contains Surfactant CTAB or P123;
Wherein organic porous films is polycarbonate membrane or poly-inclined to one side fluorine film; The film diameter 47mm of porous polycarbonate film, bore dia 200 μ m, voidage 10%～15%;
(3) wash-out of film internal surfactants
It is the mixing solutions E that is formed at 1: 5 by volume that the organic-inorganic compound mesoporous film that contains Surfactant CTAB or P123 of step (2) preparation is placed the concentrated hydrochloric acid of mass percent concentration 37.5% and dehydrated alcohol, under 60～80 ℃ of constant temperature oil baths, soak 2～3h with Surfactant CTAB or P123 in the extraction wash-out film, after use deionized water and 95% washing with alcohol respectively 3 times, after at last organic-inorganic compound mesoporous film being placed 60 ℃ of dry 3h of baking oven, promptly get organic/inorganic compound mesoporous film of the present invention;
(4) dissolving of organic porous films
The organic-inorganic compound mesoporous film of preparation process (3) gained is immersed in 2～3min in 1～2ml dichloromethane solvent, treat that the porous polycarbonate film dissolves fully after, through suction filtration can collect one-dimensional rod-like mesoporous material of the present invention.
2, the preparation method of a kind of one-dimensional rod-like mesoporous material as claimed in claim 1, the one-dimensional rod-like mesoporous material of gained is diameter 200nm when it is characterized in that the tensio-active agent employing cetyl trimethylammonium bromide (CTAB) in the preparation process (1), length 10 μ m, and has orderly hexagonal mesoporous structure, the aperture is 3nm, the one-dimensional mesoporous silica bar of MCM-41 type.
3, the preparation method of a kind of one-dimensional rod-like mesoporous material as claimed in claim 1 is characterized in that the tensio-active agent in the preparation process (1) adopts EO
20PO
70EO
20(P123) the diameter 200nm of the one-dimensional rod-like mesoporous material of gained the time, length 10 μ m, and have orderly hexagonal mesoporous structure, the aperture is 8nm, the one-dimensional mesoporous silica bar of SBA-15 type.
4, the preparation method of a kind of one-dimensional rod-like mesoporous material as claimed in claim 1 is characterized in that the gained one-dimensional rod-like mesoporous material is used for the absorption of biomacromolecule or the fixed network of catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100540831A CN101602507B (en) | 2009-06-29 | 2009-06-29 | One-dimensional rod-like mesoporous material and preparation method thereof and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100540831A CN101602507B (en) | 2009-06-29 | 2009-06-29 | One-dimensional rod-like mesoporous material and preparation method thereof and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101602507A true CN101602507A (en) | 2009-12-16 |
| CN101602507B CN101602507B (en) | 2011-08-03 |
Family
ID=41468425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100540831A Expired - Fee Related CN101602507B (en) | 2009-06-29 | 2009-06-29 | One-dimensional rod-like mesoporous material and preparation method thereof and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101602507B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101961641A (en) * | 2010-10-21 | 2011-02-02 | 上海烟草（集团）公司 | Porous oxide xerogel absorbing material and preparation method thereof |
| CN103285904A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Hydrogenation catalyst, and preparation method and application thereof |
| CN103482704A (en) * | 2013-09-04 | 2014-01-01 | 重庆大学 | MnO2 nanosheet self-assembled nanotube and preparation method thereof |
| CN103877950A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Composite porous material of graphite oxide and chromium-containing coordination polymer and preparation thereof |
| CN103949219A (en) * | 2014-05-13 | 2014-07-30 | 东南大学 | Preparation method of porous composite material capable of selectively absorbing aromatic hydrocarbon |
| CN105435850A (en) * | 2014-06-09 | 2016-03-30 | 中国石油化工股份有限公司 | Illite mesoporous composite material, supported catalyst and preparation method and application thereof and preparation method of cyclohexanone glyceryl ketal |
| CN107414071A (en) * | 2017-09-04 | 2017-12-01 | 哈尔滨工业大学 | A kind of preparation method of the controllable bar-shaped gallium particle of size |
| CN110755690A (en) * | 2019-11-21 | 2020-02-07 | 南京鼓楼医院 | Preparation method of mesoporous silica in-situ doped acrylic resin bone cement composite material for enhancing sustained release capacity of drugs |
| CN111135852A (en) * | 2018-11-06 | 2020-05-12 | 中国石油化工股份有限公司 | Non-noble metal isobutane dehydrogenation catalyst with rodlike mesoporous molecular sieve as carrier and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103464093B (en) * | 2013-09-22 | 2015-03-11 | 南京理工大学 | CoFe2O4@MCM-41 composite material, preparation method thereof and method for adsorbing radioactive wastewater by using CoFe2O4@MCM-41 composite material |
-
2009
- 2009-06-29 CN CN2009100540831A patent/CN101602507B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101961641B (en) * | 2010-10-21 | 2012-12-19 | 上海烟草集团有限责任公司 | Porous oxide xerogel absorbing material and preparation method thereof |
| CN101961641A (en) * | 2010-10-21 | 2011-02-02 | 上海烟草（集团）公司 | Porous oxide xerogel absorbing material and preparation method thereof |
| CN103285904B (en) * | 2012-02-29 | 2015-03-04 | 北京安耐吉能源工程技术有限公司 | Hydrogenation catalyst, and preparation method and application thereof |
| CN103285904A (en) * | 2012-02-29 | 2013-09-11 | 北京安耐吉能源工程技术有限公司 | Hydrogenation catalyst, and preparation method and application thereof |
| CN103877950A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Composite porous material of graphite oxide and chromium-containing coordination polymer and preparation thereof |
| CN103482704A (en) * | 2013-09-04 | 2014-01-01 | 重庆大学 | MnO2 nanosheet self-assembled nanotube and preparation method thereof |
| CN103482704B (en) * | 2013-09-04 | 2015-03-18 | 重庆大学 | MnO2 nanosheet self-assembled nanotube and preparation method thereof |
| CN103949219A (en) * | 2014-05-13 | 2014-07-30 | 东南大学 | Preparation method of porous composite material capable of selectively absorbing aromatic hydrocarbon |
| CN105435850A (en) * | 2014-06-09 | 2016-03-30 | 中国石油化工股份有限公司 | Illite mesoporous composite material, supported catalyst and preparation method and application thereof and preparation method of cyclohexanone glyceryl ketal |
| CN105435850B (en) * | 2014-06-09 | 2017-09-29 | 中国石油化工股份有限公司 | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals |
| CN107414071A (en) * | 2017-09-04 | 2017-12-01 | 哈尔滨工业大学 | A kind of preparation method of the controllable bar-shaped gallium particle of size |
| CN111135852A (en) * | 2018-11-06 | 2020-05-12 | 中国石油化工股份有限公司 | Non-noble metal isobutane dehydrogenation catalyst with rodlike mesoporous molecular sieve as carrier and preparation method and application thereof |
| CN110755690A (en) * | 2019-11-21 | 2020-02-07 | 南京鼓楼医院 | Preparation method of mesoporous silica in-situ doped acrylic resin bone cement composite material for enhancing sustained release capacity of drugs |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101602507B (en) | 2011-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101602507B (en) | One-dimensional rod-like mesoporous material and preparation method thereof and application thereof | |
| CN101628204B (en) | Organic-inorganic compound mesoporous membrane and preparation method and application thereof | |
| DE19648798C2 (en) | Process for the production of organically modified aerogels by surface modification of the aqueous gel (without prior solvent exchange) and subsequent drying | |
| Wang et al. | Direct synthesis and catalytic applications of ordered large pore aminopropyl-functionalized SBA-15 mesoporous materials | |
| CN101985358B (en) | Method for quickly preparing carbon-silicon dioxide composite aerogel | |
| CN101274766A (en) | Method for synthesizing ordered mesoporous titanium oxide molecular sieve | |
| CN101875016A (en) | Catalyst for preparing methane by low-temperature oxidization of methane and preparation method and application thereof | |
| CN105603584A (en) | Polyacrylonitrile mesoporous activated carbon fiber for super capacitor electrode and preparation method of fiber | |
| CN101264892A (en) | Method for preparing double-channel mesoporous silicon oxide hollow sphere | |
| CN107051339B (en) | Fiber composite toughened SiO2Aerogel and preparation method thereof | |
| CN103936660B (en) | The preparation method and application of N-methyl-2-phenyl-3, the 4-soccerballene base tetramethyleneimine of a kind of micron of acicular structure | |
| WO2019227872A1 (en) | Formaldehyde purification fiber and preparation method therefor | |
| CN101259964A (en) | Constant pressure and dry preparation method for high-performance silicon dioxide aerogel by using rice husk ash as raw material | |
| CN101148259A (en) | Method for fast eliminating organic template agent in porous material under low temperature | |
| CN101863480A (en) | Preparation method for silicon dioxide aerogel | |
| CN103922308B (en) | The preparation method of the ordered porous carbon material of N doping honeycomb | |
| FR2796312A1 (en) | SUPPORTED METAL CATALYST, ITS PREPARATION AND ITS APPLICATIONS IN THE DIRECT MANUFACTURE OF HYDROGEN PEROXIDE | |
| CN103408028B (en) | Production technique of super-heat-insulation material silica gel | |
| CN105214734A (en) | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals | |
| CN104528743A (en) | Preparation method of mesoporous one-dimensional silicon dioxide nanofiber with high specific surface area | |
| CN103073036A (en) | Super-microporous high-specific surface area aluminium oxide material and preparation method thereof | |
| CN102228808B (en) | Composite mesoporous film of PETP (polyethylene glycol terephthalate) as well as preparation method and application thereof | |
| CN104437474A (en) | Ordered mesoporous carbon material loaded platinum catalyst and application thereof to catalytic hydrogenation of aromatic nitro compound | |
| CN1120801C (en) | Dual-pore molecular sieve and its preparing process | |
| CN101822949A (en) | High-hydrophilicity composite PVDF meso-porous film, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110803 Termination date: 20140629 |
|
| EXPY | Termination of patent right or utility model |