CN102476803A - Surface-modified ordered mesoporous silicon dioxide composite material and its preparation method - Google Patents
Surface-modified ordered mesoporous silicon dioxide composite material and its preparation method Download PDFInfo
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Abstract
Belonging to the technical field of porous nano-materials, the invention provides a preparation method of a surface-modified ordered mesoporous silicon dioxide composite material. The method comprises: first conducting degassing treatment on an ordered mesoporous silicon dioxide material, then under an inert gas condition, leaving the degassed ordered mesoporous silicon dioxide material to contact with organosilane in an organic solvent able to dissolve the organosilane, then carrying out filtering, washing and drying so as to obtain the surface-modified ordered mesoporous silicon dioxide composite material. The surface-modified ordered mesoporous silicon dioxide composite material prepared in the invention has a high specific surface area and pore volume, and has columnar regular pore channels, a stable structure, as well as certain hydrophobicity, thus boasting potential application in catalyst carriers, biomolecular carriers, and other aspects.
Description
Technical field
The present invention relates to a kind of surface-treated ordered mesoporous silica dioxide matrix material and preparation method thereof, belong to the porous nanometer material technical field.
Background technology
According to the definition of IUPAC (IUPAC), the aperture is called mesoporous material at the porous material of 2～50nm scope.1992, Mobil company developed novel M41S series Metaporous silicon dioxide material first, has caused researchist's very big concern.Metaporous silicon dioxide material has a wide range of applications in fields such as absorption, catalysis, separation and medicine transmission owing to have higher specific surface area, bigger pore volume, regular adjustable pore size distribution and stable skeleton structure.Afterwards, people have synthesized a series of Metaporous silicon dioxide materials such as HMS, MSU, FDU and SBA successively.These mesoporous materials generally have the adjustable regular pore canal structure of higher specific surface area and aperture.Because the crystalline structure characteristics of silicon-dioxide itself; Easy and the surface adsorption water combination of surface silicon atoms; The tetrahedral coordination that keeps oxygen; Therefore there is a large amount of silicon hydroxyls in inner wall surface in the duct of mesoporous silicon oxide, and these hydroxyls can be used to fixedly reactive group on the one hand, give mesopore molecular sieve new performance; On the other hand, the existence of a large amount of terminal hydroxy group makes mesopore molecular sieve very responsive to ambient moisture, and long-term exposure is unfavorable for keeping its structural stability in air ambient.Surface alkylation modification can potential enhancing SiO 2 mesoporous materials hydrophobicity, improve pore structure stability, help the storage and transport of material in air ambient.Therefore, these ordered mesoporous materials are carried out surface-treated and become one of current research focus.
In the past, people are doing a series of activities aspect the surface-treated of nano silica powder and aerosil, to improve the agglomeration of nano-powder, strengthen the mechanical property and the hydrophobicity of gas gel tissue.As:
(Xie Xiaoling, Guo Liyou are permitted and Du people such as Xie Xiaoling; The research of nano-silica surface modification is used chemical industry, 2007; 36 (7); 703-704) adopt titanic acid ester that nanometer silicon dioxide particle is carried out Research on Surface Modification, make particle become hydrophobicity, improved affinity with polymeric compositions by wetting ability.People such as Feng Junzong (Feng Junzong, Feng Jian, Gao Qingfu; Military latitude, hexamethyldisilazane is to the surface-treated of aerosil, silicate journal; 36 (S1); 89-94) utilize gas phase hexamethyldisilazane and aerosil to react, obtained water contact angle and be about 120 ° hydrophobicity gas gel, and made thermostability and physical strength obtain raising to a certain degree.CN200910039501X discloses a kind of compound method for preparing the high-mechanical property aerosil of organic polymer material that adopts, and has obtained having certain intensity and flexible nano-porous materials.
Summary of the invention
The objective of the invention is to,, improve its surface hydrophobicity, help the stable of pore passage structure through the ordered mesoporous silica dioxide material is carried out surface-treated.
To the foregoing invention purpose, the present invention provides a kind of preparation method of ordered mesoporous silica dioxide matrix material, and this method may further comprise the steps:
(1) to the processing that outgases of ordered mesoporous silica dioxide material;
(2) under inert gas conditions, will pass through the ordered mesoporous silica dioxide material that the degassing handles and in the organic solvent that can dissolve this organosilane, contact with organosilane, filter afterwards, wash, drying, make the ordered mesoporous silica dioxide matrix material.
The ordered mesoporous silica dioxide matrix material that the present invention also provides the method by the invention described above to make.
The present invention utilizes the surface hydroxyl and the organosilane generation condensation reaction of ordered mesoporous silica dioxide material, and hydrocarbyl chain is received on the hole wall of material, has increased the hydrophobicity of material.The invention has the advantages that characteristics such as synthesis device is simple, the easy operation of synthesis technique.The modification Metaporous silicon dioxide material specific surface area of the present invention's preparation is higher, and pore passage structure is stable in order, and can potential application be arranged in a plurality of fields.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the ordered mesoporous silica dioxide material of the embodiment of the invention 1 preparation;
Fig. 2 is the nitrogen adsorption-desorption isotherm and the graph of pore diameter distribution of the ordered mesoporous silica dioxide material of the embodiment of the invention 1 preparation;
Fig. 3 is the transmission electron microscope photo of ordered mesoporous silica dioxide material of the silazane modification of the embodiment of the invention 1 preparation;
Fig. 4 is the nitrogen adsorption-desorption isotherm and the graph of pore diameter distribution of ordered mesoporous silica dioxide material of the silazane modification of the embodiment of the invention 1 preparation.
Embodiment
The invention provides a kind of preparation method of ordered mesoporous silica dioxide matrix material, this preparation method may further comprise the steps:
(1) to the processing that outgases of ordered mesoporous silica dioxide material;
(2) under inert gas conditions, will pass through the ordered mesoporous silica dioxide material that the degassing handles and in the organic solvent that can dissolve this organosilane, contact with organosilane, filter afterwards, wash, drying, make the ordered mesoporous silica dioxide matrix material.
Wherein, the concentration of described organosilane is 0.06～0.15 milliliter/milliliter, and the weight ratio of said organosilane and ordered mesoporous silica dioxide material is 5～24: 1.
Said ordered mesoporous silica dioxide material can be for being selected among SBA-15, MCM-41, SBA-16 and the MCM-48 one or more.
Said organosilane can be selected from chlorosilane, organoalkoxysilane and the disilazane one or more.Wherein, chlorosilane can be selected from one or more in dimethyldichlorosilane(DMCS) and the tri-methyl-chlorosilane; Organoalkoxysilane can be selected from one or more in aminopropyltriethoxywerene werene (APTES), n-octyl Trimethoxy silane (OTMS) and the dodecyl Trimethoxy silane (DTMS); Disilazane can be selected from one or more in hexamethyldisilazane (HMDS), the tetramethyl-disilazane (TMDS).
Said organic solvent can be selected from THF, normal hexane, toluene, the chloroform one or more.
Said step (1) to the ordered mesoporous silica dioxide material treatment condition that outgas is: the process that the said degassing is handled comprises: at 150～250 ℃ of following vacuum outgass 4～12 hours, naturally cooling.
Said step (2) is dissolved in organosilane in the said organic solvent,, add the ordered mesoporous silica dioxide material then, under inert gas atmosphere, 20-30 ℃ condition, stirred 6～24 hours.Rare gas element can be selected from nitrogen, helium, neon, argon gas one or more.
Said ordered mesoporous silica dioxide material preferably makes through the method that may further comprise the steps: tensio-active agent is contacted with the silicon source with inorganic aqueous acid; To contact back gained mixture then leaves standstill respectively the very first time section and second time period under first temperature and second temperature successively; Cool off afterwards, filter, and the solid matter that obtains is dry, roasting, wherein; Said first temperature is lower than second temperature, and said very first time section is less than second time period.
Wherein, the mass concentration of tensio-active agent can be 5-30% in the said aqueous solution, and the concentration of mineral acid can be the 1-3 mol, and the weight ratio of said silicon source and tensio-active agent can be 1-3.0: 1.
Said mineral acid can be in hydrochloric acid, sulfuric acid, nitric acid and the phosphoric acid one or more; Said silicon source can be selected from one or more in methyl silicate, tetraethoxy, the positive silicic acid propyl ester; Said tensio-active agent can be for gathering in oxyethylene ether series triblock copolymer nonionogenic tenside and the T 46155 aliphatic ether series non-ionic surfactants one or more of oxyethylene ether-gather propylene oxide ether-gather.
Wherein, the condition of contact comprises that temperature is 25-60 ℃, and the time is 5-30 minute; Said contact is under agitation carried out, and stirring velocity is 400-1500 rev/min.
Said first temperature is 25-60 ℃, and very first time section is 10-30 hour; Said second temperature is 60-100 ℃, and second time period was 36-60 hour; Said refrigerative temperature is 20-30 ℃; Said exsiccant temperature is 100-150 ℃; The temperature of said roasting is that 500-600 ℃, time are 4-12 hour.
According to a kind of ordered mesoporous silica dioxide matrix material provided by the invention; Wherein, The characteristic of matrix material: the ordered mesoporous silica dioxide matrix material has not only kept higher specific surface area and regular pore passage structure, has improved the stability of vesicular structure, also has certain hydrophobic performance; Give material new performance, expanded its Application Areas.
The transmission electron microscope photo of sample is by Tecnai G
2The 20ST transmission electron microscope records, and acceleration voltage is 200KV; Nitrogen adsorption isotherm is recorded under 77K by Tristar II 3020 instruments of Merck & Co., Inc; Sample was handled 6 hours 250 ℃ of vacuum hydro-extractions before test; The specific surface area of sample is calculated by the adsorpting data of relative pressure between 0.06-0.20 according to BET (Brunauer-Emmett-Teller) formula, and the pore size distribution result of material adopts BJH (Barrett-Joyner-Halenda) model to be obtained by the desorption curve calculation; Water contact angle adopts the full-automatic contact angle measurement of DSA100 of Kr ü ss company that the sample compressing tablet is tested and obtains.
Below in conjunction with embodiment the present invention is further set forth.
Embodiment 1
Get 20.0 gram polyethers block polymer EO
20PO
70EO
20(P123, Sigma-Aldrich company) joins in 150.0 gram deionized waters and the 600.0 gram 2M hydrochloric acid; Stir to clarify, add 42.5 gram tetraethoxys (TEOS, Sigma-Aldrich company); Stirred 5～10 minutes, under 35 ℃ and 90 ℃, placed respectively then 20 hours and 48 hours, obtain white product through overcooling, filtration, washing; After the white product drying in 550 ℃ of following roastings 5 hours; Obtain ordered mesoporous silica dioxide material SBA-15, can know that by Fig. 1 its microtexture is orderly two-dimentional hexagonal mesoporous structure (p6mm), can know that by Fig. 2 its specific surface area is 900m
2/ g, pore volume are 0.99cm
3/ g, BJH most probable aperture is 7.60nm.Water droplet tiles on the sample compressing tablet fully, and sample has fabulous wetting ability.
Get 5.0 gram SBA-15,200 ℃ of following vacuum outgass 6 hours, naturally cooling; The hexane solution (1 milliliter/15 milliliters of strength of solution) that adds 80 milliliters of hexamethyldisilazanes (HMDS, Sigma-Aldrich company), nitrogen atmosphere, 25 ℃ of following stirrings 24 hours; Suction filtration; Normal hexane cleans, and 100 ℃ of following vacuum-dryings 10 hours, obtains the SBA-15 that silazane is modified.Fig. 3 is the transmission electron microscope photo of the SBA-15 material of above-mentioned silazane modification, and as can be seen from the figure microtexture is orderly two-dimentional hexagonal mesoporous structure (p6mm).Fig. 4 is the nitrogen adsorption-desorption isotherm and the graph of pore diameter distribution of above-mentioned Metaporous silicon dioxide material, and the specific surface area that from figure, can calculate this material is 550m
2/ g, pore volume are 0.66cm
3/ g, BJH most probable aperture is 5.60nm.Water contact angle is 125.5 °, and sample has good hydrophobicity.
Embodiment 2
Get 20.0 gram P123, join in 100.0 gram deionized waters and the 400.0 gram 1M hydrochloric acid, stir to clarify; Add 42.5 gram TEOS, stirred 5～10 minutes, under 25 ℃ and 80 ℃, placed respectively then 20 hours and 48 hours; Obtain white product through overcooling, filtration, washing, in 550 ℃ of following roastings 5 hours, obtain ordered mesoporous silica dioxide material SBA-15 after the white product drying; Its microtexture is orderly two-dimentional hexagonal mesoporous structure (p6mm), and specific surface area is 900m
2/ g, pore volume are 0.99cm
3/ g, BJH most probable aperture is 7.60nm.Water droplet tiles on the sample compressing tablet fully, and sample has fabulous wetting ability.
Get 2.5 gram SBA-15,150 ℃ of following vacuum outgass 4 hours, naturally cooling; The tetrahydrofuran solution (1 milliliter/25 milliliters of strength of solution) that adds 60 milliliters of tetramethyl-disilazanes (TMDS, Sigma-Aldrich company), nitrogen atmosphere, 25 ℃ of following stirring at room 6 hours; Suction filtration; THF cleans, and 50 ℃ of following vacuum-dryings 10 hours, obtains the SBA-15 that silazane is modified.Water contact angle is 125.4 °.
The transmission electron microscope photo of embodiment 2, nitrogen adsorption-desorption isotherm and graph of pore diameter distribution are similar with embodiment 1.
Embodiment 3
Get 20.0 gram P123, join in 200.0 gram deionized waters and the 600.0 gram 3M nitric acid, stir to clarify; Add 42.5 gram positive silicic acid propyl ester (TPOS, Sigma-Aldrich company), stirred 5～10 minutes; Then under 50 ℃ and 100 ℃, placed respectively 20 hours and 48 hours; Obtain white product through overcooling, filtration, washing, in 550 ℃ of following roastings 5 hours, obtain ordered mesoporous silica dioxide material SBA-15 after the white product drying.
Get 10.0 gram SBA-15,250 ℃ of following vacuum outgass 12 hours, naturally cooling; The toluene solution (strength of solution is 1 milliliter/10 milliliters) that adds 80 milliliters of hexamethyldisilazanes (HMDS, Sigma-Aldrich company), nitrogen atmosphere, 25 ℃ of following stirrings 24 hours; Suction filtration; Toluene cleans, and 100 ℃ of following vacuum-dryings 15 hours, obtains the SBA-15 that silazane is modified.Water contact angle is 125.4 °.
The transmission electron microscope photo of embodiment 3, nitrogen adsorption-desorption isotherm and graph of pore diameter distribution are similar with embodiment 1.
Embodiment 4
Get the ordered mesoporous silica dioxide material SBA-15 of embodiment 2.
Get 15.0 gram SBA-15,200 ℃ of following vacuum outgass 6 hours, naturally cooling; The chloroformic solution (strength of solution is 1 milliliter/10 milliliters) that adds 80 milliliters of aminopropyltriethoxywerene werene (APTES, Sigma-Aldrich company), nitrogen atmosphere, 25 ℃ of following stirrings 24 hours; Suction filtration; Chloroform cleans, and 100 ℃ of following drying under vacuum overnight, obtains the SBA-15 that the aminopropyl triethoxy is modified.Water contact angle is 118.8 °.
The transmission electron microscope photo of embodiment 4, nitrogen adsorption-desorption isotherm and graph of pore diameter distribution are similar with embodiment 1.
Embodiment 5
TEOS, cetyl trimethylammonium bromide (CTAB, Beijing chemical reagents corporation), NaOH and deionized water are at room temperature according to mol ratio: TEOS: CTAB: NaOH: H
2O=1.0: 0.12: 0.5: 130, stirred 24 hours, through filtering, washing; 100 ℃ of following vacuum-dryings 10 hours, use 1M HCl/ ethanolic soln extraction surface promoting agent then, use absolute ethanol washing again; In vacuum-drying 10 hours, obtain ordered mesoporous silica dioxide material MCM-41 at last.
Get 5.0 gram MCM-41,200 ℃ of following vacuum outgass 6 hours, naturally cooling; The chloroformic solution (strength of solution is 1 milliliter/25 milliliters) that adds 100 milliliters of aminopropyltriethoxywerene werene; Nitrogen atmosphere, 25 ℃ of following stirrings 24 hours, suction filtration, chloroform cleans; 30 ℃ of following vacuum-dryings 10 hours, obtain the MCM-41 that aminopropyl is modified.Water contact angle is 120.0 °.
Embodiment 6
20.0 gram EO
132PO
70EO
132(F 108, Sigma-Aldrich company) and 52.4 gram K
2SO
4Be dissolved in the hydrochloric acid of 600 milliliters of 2M, hierarchy of control temperature is 38 ℃.Add 42.0 gram TEOS under the vigorous stirring, stirred 15 minutes, 38 ℃ static 1 day.White powder is washed with a large amount of de-ionizeds, and drying at room temperature obtains ordered mesoporous silica dioxide material SBA-16.
Get 5.0 gram SBA-16,200 ℃ of following vacuum outgass 6 hours, naturally cooling; Add the chloroformic solution (strength of solution is 15 milliliters/100 milliliters) of 100 milliliters of n-octyl Trimethoxy silanes (OTMS, Sigma-Aldrich company), add 75 milligrams of p-methyl benzenesulfonic acids as catalyzer; Nitrogen atmosphere, 25 ℃ of following stirrings 24 hours, suction filtration, chloroform cleans; 30 ℃ of following vacuum-dryings 10 hours, obtain the SBA-16 that n-octyl is modified.Water contact angle is 123.2 °.
Embodiment 7
37.0 gram CTAB, 2.5 gram NaOH and 150.0 gram deionized waters are heated to 70 ℃ and stirred 10 minutes, dropwise add 42.0 gram TEOS; Continued heated and stirred 2 hours; Obtain even colloidal sol, colloidal sol is sealed in the teflon-lined stainless steel cauldron, in 100 ℃ of following crystallization 3 days (filling ratio is 80%); Complete after-filtration to be aging, washing, drying at room temperature obtain ordered mesoporous silica dioxide material MCM-48.
Get 5.0 gram MCM-48,200 ℃ of following vacuum outgass 6 hours, naturally cooling; Add the chloroformic solution (strength of solution is 15 milliliters/100 milliliters) of 100 milliliters of dodecyl Trimethoxy silanes (DTMS, Sigma-Aldrich company), add 75 milligrams of p-methyl benzenesulfonic acids as catalyzer; Nitrogen atmosphere, 25 ℃ of following stirrings 24 hours, suction filtration, chloroform cleans; 30 ℃ of following vacuum-dryings 10 hours, obtain the MCM-48 that dodecyl is modified.Water contact angle is 122.2 °.
Embodiment 8
Get 5.0 SBA-15s of gram among the embodiment 1,200 ℃ of following vacuum outgass 6 hours, naturally cooling; The cyclohexane solution (strength of solution is 15 milliliters/100 milliliters) that adds 100 milliliters of tri-methyl-chlorosilanes (TMCS, Sigma-Aldrich company), nitrogen atmosphere, 25 ℃ of following stirrings 24 hours; Suction filtration; Cyclohexane 30 ℃ of following vacuum-dryings 10 hours, obtains the SBA-15 that the front three alkyl is modified.Water contact angle is 117.0 °.
Embodiment 9
This embodiment is used to explain the purposes of modification ordered mesoporous silica dioxide material provided by the invention.
Get the SBA-15 of the prepared silazane modification of 10 milligrams of embodiment 2; The butyl rhodamine b aqueous solution that to be distributed to 100 milliliters of mass concentrations be 0.01 mg/ml; Left standstill 8 hours; High speed centrifugation separates, and detects the absorption (maximum absorption wavelength of butyl rhodamine b) of the butyl rhodamine b aqueous solution of Metaporous silicon dioxide material in 558 nanometers with ultraviolet-visible pectrophotometer, and the variation of this absorbancy is directly related to the absorption of butyl rhodamine b with mesoporous silicon oxide.Experimental result finds that modification ordered mesoporous silica dioxide material reaches 70% to the percent of decolourization of butyl rhodamine b, and promptly 10 milligrams of Metaporous silicon dioxide materials have adsorbed 0.70 milligram of butyl rhodamine b.
Claims (10)
1. the preparation method of an ordered mesoporous silica dioxide matrix material, this preparation method may further comprise the steps:
(1) to the processing that outgases of ordered mesoporous silica dioxide material;
(2) under inert gas conditions, will pass through the ordered mesoporous silica dioxide material that the degassing handles and in the organic solvent that can dissolve this organosilane, contact with organosilane, filter afterwards, wash, drying, make the ordered mesoporous silica dioxide matrix material.
2. method according to claim 1, wherein, the concentration of said organosilane is 0.04～0.15 milliliter/milliliter, the weight ratio of said organosilane and ordered mesoporous silica dioxide material is 5～24: 1.
3. method according to claim 1 and 2, wherein, the ordered mesoporous silica dioxide material is selected from one or more among SBA-15, MCM-41, SBA-16 and the MCM-48; Said organosilane is selected from one or more in chlorosilane, organoalkoxysilane and the disilazane; Said organic solvent is selected from one or more in THF, normal hexane, toluene, the chloroform.
4. method according to claim 3, wherein, said chlorosilane is selected from one or more in dimethyldichlorosilane(DMCS) and the tri-methyl-chlorosilane; Organoalkoxysilane is selected from one or more in aminopropyltriethoxywerene werene, n-octyl Trimethoxy silane and the dodecyl Trimethoxy silane; Disilazane is selected from one or more in hexamethyldisilazane, the tetramethyl-disilazane.
5. method according to claim 1, wherein, in step (1), the process that the said degassing is handled comprises: at 150～250 ℃ of following vacuum outgass 4～12 hours, naturally cooling.
6. method according to claim 1, wherein, in step (2), the process of said contact comprises: organosilane is dissolved in the said organic solvent, adds the ordered mesoporous silica dioxide material then, nitrogen atmosphere, 20-30 ℃ following the stirring 6～24 hours.
7. method according to claim 1; The preparation process of said ordered mesoporous silica dioxide material comprises: tensio-active agent is contacted with the silicon source with inorganic aqueous acid, will contact back gained mixture then and under first temperature and second temperature, leave standstill respectively the very first time section and second time period successively, cool off afterwards, filter; And the solid matter that obtains is dry, roasting; Wherein, said first temperature is lower than second temperature, and said very first time section is less than second time period.
8. method according to claim 7, wherein, the mass concentration of tensio-active agent is 5-30% in the said aqueous solution, and the concentration of mineral acid is the 1-3 mol, and the weight ratio of said silicon source and tensio-active agent is 1-3.0: 1; Said mineral acid is one or more in hydrochloric acid, sulfuric acid, nitric acid and the phosphoric acid; Said silicon source is selected from one or more in methyl silicate, tetraethoxy, the positive silicic acid propyl ester; Said tensio-active agent is to gather in oxyethylene ether series triblock copolymer nonionogenic tenside and the T 46155 aliphatic ether series non-ionic surfactants one or more of oxyethylene ether-gather propylene oxide ether-gather.
9. method according to claim 7, wherein, the condition of contact comprises that temperature is 25-60 ℃, the time is 5-30 minute; Said first temperature is 25-60 ℃, and very first time section is 10-30 hour; Said second temperature is 60-100 ℃, and second time period was 36-60 hour; Said refrigerative temperature is 20-30 ℃; Said exsiccant temperature is 100-150 ℃; The temperature of said roasting is that 500-600 ℃, time are 4-12 hour.
10. an ordered mesoporous silica dioxide matrix material is characterized in that, this matrix material is prepared by any described method among the right 1-9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088597A (en) * | 2006-06-13 | 2007-12-19 | 中国科学院过程工程研究所 | Adsorbent for adsorbing six-valent chromium ion and its prepn process |
| CN101219792A (en) * | 2008-01-24 | 2008-07-16 | 同济大学 | Process for producing modified silicon based mesoporous material RA-SBA-15 |
| CN101792147A (en) * | 2010-01-12 | 2010-08-04 | 清华大学深圳研究生院 | Surface modification method of silica particles and method for displaying latent fingerprints |
| CN101811050A (en) * | 2010-05-05 | 2010-08-25 | 中国科学院山西煤炭化学研究所 | Organic hydrophobic modified cobalt-based fischer-tropsch synthesis catalyst, preparation thereof and application thereof |
-
2010
- 2010-11-29 CN CN201010572179XA patent/CN102476803A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088597A (en) * | 2006-06-13 | 2007-12-19 | 中国科学院过程工程研究所 | Adsorbent for adsorbing six-valent chromium ion and its prepn process |
| CN101219792A (en) * | 2008-01-24 | 2008-07-16 | 同济大学 | Process for producing modified silicon based mesoporous material RA-SBA-15 |
| CN101792147A (en) * | 2010-01-12 | 2010-08-04 | 清华大学深圳研究生院 | Surface modification method of silica particles and method for displaying latent fingerprints |
| CN101811050A (en) * | 2010-05-05 | 2010-08-25 | 中国科学院山西煤炭化学研究所 | Organic hydrophobic modified cobalt-based fischer-tropsch synthesis catalyst, preparation thereof and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| XINGDONG YUAN ET AL.: "Periodic Mesoporous Organosilicas Functionalized with Sulfonic Acid Group. Synthesis and Alkylation of Phenol", 《CHEMISTRY LETTERS》 * |
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