CN102774848A - Method for preparing Ti-SBA-15 molecular sieve - Google Patents
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Abstract
The invention provides a method for preparing a Ti-SBA-15 molecular sieve, comprising the following steps: (1) under the condition of preparing glues by hydrolysis, hydrolyzing a template, an inorganic silicon source, an inorganic titanium source and an acidic aqueous solution to obtain a gel mixture; (2) crystallizing the gel mixture under the condition of crystallization, then filtering the crystallized product, drying the solids obtained by filtering, and removing the template to obtain the Ti-SBA-15 molecular sieve. The method disclosed herein is simple and practicable, has the advantages of easy-control conditions, good ability in repeated preparation, and cheap raw materials, and the cost of synthesizing the Ti-SBA-15 molecular sieve is effectively reduced according to the method. Further, the Ti-SBA-15 molecular sieve obtained by the method disclosed herein contains less non-framework titanium than the Ti-SBA-15 molecular sieve obtained by using organic raw materials.
Description
Technical field
The present invention relates to a kind of method of the Ti-SBA-15 of preparation molecular sieve.
Background technology
HTS is one type of new catalytic material (US4410501A) that the eighties of last century the eighties occurs.Because it is structurally ordered, the titanium dispersity high, in catalytic oxidation, shows good activity and selectivity.But the structure of such HTS is generally MFI or MEI structure, the aperture less (＜0.7nm), thereby limited its application in participating in macromolecular oxidizing reaction.1992 is that (Nature, 1992,359 (6397): 710-712) (＞2.0nm) HTS provides new direction for synthetic aperture is big for the appearance of the M41S series mesoporous silica molecular sieve of representative with MCM-41.Siliciumatom in the titanium atom part substituted MCM-41 skeleton can obtain the Ti-MCM-41 mesopore molecular sieve (Chem.Commun., 1994, (2): 147-148), Ti-MCM-41 has shown excellent catalytic activity in the oxidizing reaction that macromole is participated in.But, important meaning is arranged so carry out the development of novel mesoporous material because the synthetic employed quaternary ammonium salt template of MCM-41 class mesoporous material costs an arm and a leg and environmental pollution is serious.
1998, people such as Zhao Dongyuan successfully synthesized mesoporous silica molecular sieve SBA-15 (Science, 1998,279 (5350): 548-552).The SBA-15 mesopore molecular sieve is under acidic conditions, is template with the triblock copolymer, and tetraethoxy is the silicon source, obtains through hydro-thermal is synthetic.Compare with MCM-41, SBA-15 has hydrothermal stability preferably, the aperture adjustment scope (being generally 5-30nm) of bigger aperture and broad.In addition, the employed template of preparation SBA-15 can not cause environmental pollution.
After this, people attempt the framework of molecular sieve of the titanium doped SBA-15 of advancing is prepared the Ti-SBA-15 molecular sieve to be applied to the oxidizing reaction of macromolecule hydrocarbon.So far, the compound method of Ti-SBA-15 molecular sieve mainly contains two types of grafting and copolycondensation methods.When adopting grafting, generally, make titanium be carried on the molecular sieve pore passage surface, but adopt grafting can increase synthesis step the aftertreatment of synthetic pure silicon SBA-15 mesopore molecular sieve process titanium-containing compound.Compare with grafting, the preparation method is simpler for the copolycondensation method, but because in building-up process, the titanium source (organic titanium ester) and silicon source (organo-silicon ester) hydrolysis rate that often use do not match, very easily causes the outer TiO of skeleton
2The generation of species, even when titanium content is higher, can destroy the formation of meso-hole structure.So, adopt very difficulty of traditional hydrothermal synthesis method one step preparation Ti-SBA-15 mesopore molecular sieve.Calendar year 2001, people such as Bharat L.Newalkar adopt microwave heating the method one-step synthesis Ti-SBA-15 molecular sieve (referring to document: Chem.Mater., 2001,13 (2): 552-557).Afterwards, Zhao Dongyuan finds the product after titanic acid ester and the methyl ethyl diketone effect, and its hydrolysis rate reduces greatly, under acidic conditions, can mate with the hydrolysis rate of silicon ester.Their product after with butyl(tetra)titanate and methyl ethyl diketone effect is the silicon source as the presoma of titanium, with the tetraethyl orthosilicate, with tensio-active agent P123 (EO
20PO
70EO
20) be template, the Ti-SBA-15 molecular screen material that adopted the hydrothermal method one-step synthesis, and be applied to catalytic oxidation (chemical journal, 2003,61 (2): 202-207) of tetrahydrobenzene.In the same year, CN1428296A discloses under acidic conditions, is template, fluorochemical (NaF or NH with P123
4F), adopt the technology of hydrothermal method one-step synthesis Ti-SBA-15 molecular sieve for catalyzer, silicon ester are that silicon source, titanic acid ester or inorganic titanium-containing compound are the titanium source.2008; The method that people such as Zhao Dongyuan provide a kind of " acid base pair " that utilizes titanate and titanic acid ester to constitute to come the synthesis of titanium silicon mesopore molecular sieve as the mixed with titanium source in CN101274766A specifically comprises: in ethanol or Virahol, prehydrolysis is carried out in the mixed with titanium source and formed titanium source presoma; Mix with silicon ester and template nonionogenic tenside then, in the aqueous solution, carry out self-assembly; Remove tensio-active agent at last and obtain the titanium oxide silicon mesoporous material.2010, they disclosed in CN101746775A again and have used two kinds of silicon sources simultaneously, i.e. silicon ester and 1, and two (triethoxysilicane) ethane of 2-prepare the technology of Ti-SBA-15 mesopore molecular sieve.
This shows that prior art has been done a lot of work for the generation of extra-framework titanium species in the process that reduces preparation Ti-SBA-15 molecular sieve, but in the studies of prior art in order to reduce TiO
2The preparation condition that carries out from reunion is regulated and is all made building-up process become complicated more.And what all use in the process of the synthetic Ti-SBA-15 of prior art is organosilicon source or organic titanium source, and the price in organosilicon source and organic titanium source is extremely expensive, thereby makes that the cost of preparation Ti-SBA-15 molecular sieve is very high.Therefore develop a kind of preparation method who prepares process Ti-SBA-15 molecular sieve simple, with low cost and will become the primary study direction of in the future developing the material of the oxidizing reaction that is suitable for macromolecule hydrocarbon.
Summary of the invention
The method for preparing the Ti-SBA-15 molecular sieve that the objective of the invention is for overcoming prior art is complicated, and the expensive defective of cost provides a kind of method the method for preparing the Ti-SBA-15 molecular sieve simple and with low cost.
Under the instruction of aforementioned background art; Most of investigator all thinks; Adopt organosilicon source, organic titanium source to prepare the better effects if of Ti-SBA-15 molecular sieve; And widely used at present, the oxidation effectiveness preparation of titanium-silicon molecular sieve TS-1 is preferably also used is organosilicon source and organic titanium source, and the studies of titanium-silicon molecular sieve TS-1 all spells out and adopts organosilicon source and replacement inorganic silicon source, organic titanium source and inorganic ti sources can obviously reduce the content of the extra-framework titanium in the titanium-silicon molecular sieve TS-1 in the preparation process.In a very long time; Contriver of the present invention also holds above-mentioned viewpoint; The thinking and contriver of the present invention breaks the normal procedure; In research process, find unexpectedly,, in synthetic Ti-SBA-15 molecular sieve, do not have above-mentioned advantage though use organosilicon source and organic titanium source to have significant advantage in the preparation titanium-silicon molecular sieve TS-1 than inorganic silicon source, inorganic ti sources; And find adopting inorganic silicon source and inorganic ti sources is that raw material not only need not to add dispersion agent and can realize good hydrolysis effect, and the amount of synthesizing extra-framework titanium in the HTS that obtains also seldom.Accomplished the present invention based on above-mentioned discovery.
The invention provides a kind of method of the Ti-SBA-15 of preparation molecular sieve, this method comprises:
(1) under hydrolysis glue condition, template, inorganic silicon source, inorganic ti sources and acidic aqueous solution are hydrolyzed, obtain gel mixture; (2) above-mentioned gel mixture is carried out crystallization under crystallization condition, then the crystallization products therefrom is filtered, will filter the gained solid drying, the removal template obtains the Ti-SBA-15 molecular sieve.
Method by the invention described above can find out that method of the present invention is simple, and condition is easy to control, and it is good to repeat preparation property.And the cheap cost that effectively reduces synthetic Ti-SBA-15 molecular sieve of raw materials cost of the present invention; Further, method of the present invention Ti-SBA-15 molecular sieve that obtains and the Ti-SBA-15 molecular sieve that uses organic raw material (organosilicon source or organic titanium source) preparation has the analog structure characteristic: higher specific surface area, bigger aperture, even aperture distribution, titanium active sites are evenly distributed; And than the Ti-SBA-15 molecular sieve that uses organic raw material to obtain, the amount of extra-framework titanium is less.
Description of drawings
Fig. 1 is the X-ray diffractogram of the prepared Ti-SBA-15 molecular sieve of embodiment 1-3 and Comparative Examples 1.
Fig. 2 is the N of the prepared Ti-SBA-15 molecular sieve of embodiment 1
2The adsorption isotherm line chart.
Fig. 3 is the pore size distribution curve figure of the prepared Ti-SBA-15 molecular sieve of embodiment 1.
Fig. 4 is the perspective Electronic Speculum figure of the prepared Ti-SBA-15 molecular sieve of embodiment 1.
Fig. 5 is the ultraviolet-visible light spectrogram of the prepared Ti-SBA-15 molecular sieve of embodiment 1-3 and Comparative Examples 1.
Embodiment
The invention provides a kind of method of the Ti-SBA-15 of preparation molecular sieve, this method comprises:
(1) under hydrolysis glue condition, template, inorganic silicon source, inorganic ti sources and acidic aqueous solution are hydrolyzed, obtain gel mixture;
(2) above-mentioned gel mixture is carried out crystallization under crystallization condition, then the crystallization products therefrom is filtered, will filter the gained solid drying, the removal template obtains the Ti-SBA-15 molecular sieve.
Can realize the object of the invention according to aforesaid method of the present invention; Mol ratio to said inorganic ti sources, template and inorganic silicon source does not have particular requirement; Can in the scope of broad, select; Under the preferable case, said inorganic ti sources, template and be 0.0001-0.1: 0.002-0.1 in the mol ratio in the inorganic silicon source of silicon in titanium: 1, be preferably 0.001-0.05: 0.005-0.05: 1.
According to the present invention; As previously mentioned, can realize the object of the invention according to aforesaid method of the present invention, the present invention does not have particular requirement equally to the mass ratio of said template and acidic aqueous solution; Can in the scope of broad, select; Under the preferable case, the mass ratio of said template and acidic aqueous solution is 0.5-20: 100, be preferably 1-12: 100.
Among the present invention, optional a wider range of the volumetric molar concentration of said acidic aqueous solution, under the preferable case, the volumetric molar concentration of solute is 0.01-8mol/L, more preferably 0.1-5mol/L in the said acidic aqueous solution.The present invention does not have particular requirement to the kind of said acidic aqueous solution, can carry out with reference to prior art, but under the preferable case, said acidic aqueous solution is one or more in hydrochloric acid, aqueous sulfuric acid and the aqueous nitric acid.
The present invention does not have particular requirement to the kind in said inorganic silicon source, can be the various water-soluble inorganic silicon-containing compounds that can be used in the preparation molecular sieve, and under the preferable case, said inorganic silicon source is one or more in water glass, Starso and the silicon sol.
The present invention does not have particular requirement to the kind of said inorganic ti sources, can be the various water-soluble inorganic titanium-containing compounds that can be used in the preparation molecular sieve, and under the preferable case, said inorganic ti sources is TiCl
3, TiCl
4, TiOCl
2, Ti (NO
3)
4, TiOSO
4And Ti (SO
4)
2In one or more, TiCl more preferably
3, TiCl
4, TiOSO
4In one or more.
The present invention does not have particular requirement to the kind of said template, can adopt the conventional used template of synthetic SBA-15 molecular sieve, for example can be nonionogenic tenside; More preferably said template is EO for having general formula
aPO
bEO
aThe polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer; More preferably, wherein the numerical value of a is 5-140, and b is 30-100; Be preferably P123 (EO especially
20PO
70EO
20), F108 (EO
132PO
50EO
132), P103 (EO
17PO
55EO
17) and F127 (EO
106PO
70EO
106) in one or more.
According to the present invention, the present invention does not have particular requirement to said hydrolysis glue condition, and under the preferable case, said hydrolysis glue condition comprises that the temperature of hydrolysis is 20-60 ℃, more preferably 30-50 ℃; Time is 5-50 hour, more preferably 10-40 hour.
According to the present invention, the present invention does not have particular requirement to said crystallization condition, and under the preferable case, said crystallization condition comprises: the temperature of crystallization is 70-150 ℃ in confined conditions, more preferably 80-120 ℃; Time is 8-72 hour, more preferably 20-30 hour.
The present invention does not have particular requirement to said exsiccant condition, and under the preferable case, said exsiccant temperature is 70-120 ℃, and the time is 3-10 hour.
The present invention does not have particular requirement to the method for said removal template, can carry out with reference to prior art, for example can be roasting or extraction.
The present invention does not have particular requirement to the condition of said roasting, and under the preferable case, the temperature of said roasting is 300-650 ℃, and the time is 2-16 hour.
The present invention does not have particular requirement to the condition of said extraction, and under the preferable case, the solvent of said extraction is acidifying methyl alcohol, acidifying ethanol or THF, and the extraction time is 12-36 hour, and extraction temperature is 60-90 ℃.Among the present invention, said acidifying methyl alcohol refers to hydrochloric acid and methanol mixture, and acidifying ethanol refers to hydrochloric acid and alcoholic acid mixture, and those skilled in the art all can know this, repeat no more at this.
Can realize the object of the invention according to method of the present invention, practical implementation can be carried out with reference to prior art, under the preferable case, can carry out according to following steps:
(1) under 30-50 ℃ temperature condition, template is dissolved in the hydrochloric acid soln that concentration is 0.1-5mol/L, stirred 0.5-4 hour.The preferred 1-12% of the mass percent concentration of template in said hydrochloric acid soln wherein.
(2) under 30-50 ℃ temperature condition, in the above-mentioned hydrochloric acid soln that contains template, add inorganic silicon source and inorganic ti sources, stir and obtained gel mixture in 12-30 hour.Wherein, be 0.001-0.1: 0.005-0.05 preferably: 1 in the said inorganic ti sources of titanium, template and in the mol ratio in the inorganic silicon source of silicon.
(3) above-mentioned gel mixture is transferred to airtight water heating kettle, 80-120 ℃ of hydrothermal treatment consists (also claiming crystallization) 20-30 hour.
(4) be cooled to room temperature after, open airtight still, solid product is separated with mother liquor, to neutral, obtained the Ti-SBA-15 molecular screen primary powder with deionized water wash at 70-120 ℃ air drying 3-10 hour.
(5) adopt any one removal template in following two kinds of methods to obtain the Ti-SBA-15 molecular sieve:
(a) with the Ti-SBA-15 molecular screen primary powder at 300-650 ℃ of roasting 2-16 hour;
(b) with the reflux extraction in the solvent of extraction of Ti-SBA-15 molecular screen primary powder, extraction temperature is 60-90 ℃, and the extraction time is 12-36 hour.
16.0g nonionogenic tenside P123 is joined in the aqueous hydrochloric acid of 400g 2mol/L, stirred 1 hour down, add 34.9g water glass (SiO then at 35 ℃
2Content is 28.26 weight %) and 4.8g 17.0 weight %TiCl
3The aqueous solution, stir down at 35 ℃ and to obtain gel mixture in 24 hours; Above-mentioned gel mixture is transferred to water heating kettle, airtight, 100 ℃ of hydrothermal crystallizings 24 hours, filter then and obtain solid product, use the deionized water wash solid to neutral again, 110 ℃ air dryings 5 hours; 450 ℃ of following roastings 4 hours, obtain Ti-SBA-15 sieve sample 1 then.
The BET specific surface area of this sample is 1018m
2/ g; Its X-ray diffraction spectrogram (XRD) is as shown in Figure 1, can find out that by Fig. 1 this sample has the hexagonal mesoporous structure of typical two dimension, with document (Science, 1998,279 (5350): the SBA-15 molecular sieve 548-552) has identical constitutional features; Its N
2The adsorption-desorption isothermal map is as shown in Figure 2; Be the typical IV type of mesopore molecular sieve adsorption-desorption thermo-isopleth; Its hysteresis loop is the H1 type, this sample meso-hole structure of surface in order and the duct be the round shape of standard, with document (Science; 1998,279 (5350): the SBA-15 molecular sieve 548-552) has identical characteristic; Figure is as shown in Figure 3 for its pore size distribution curve, can be found out by Fig. 3, and the pore size distribution range of this sample is narrower, and mean pore size is 7.5nm, and pore volume is 1.4cm
3/ g; Its transmission electron microscope picture is as shown in Figure 4, can be found out the duct marshalling rule of sample, aperture homogeneous by Fig. 4; Its ultraviolet-visible light spectrogram is as shown in Figure 5; Can find out that by Fig. 5 in the sample, wavelength has very strong absorption band (these bands of a spectrum are corresponding to the skeleton titanium species of four-coordination) between 200-220nm; Proof Ti species have entered into framework of molecular sieve; And wavelength does not almost absorb more than 230nm, proves on this sample, has non-skeleton TiO hardly
2Species.
24.0g nonionogenic tenside P123 is joined in the aqueous hydrochloric acid of 600g 2mol/L, stirred 1 hour down at 40 ℃; The Na that adds 123.3g 20.0 weight % then
2SiO
3The TiCl of the aqueous solution and 8.6g17.0 weight %
4The aqueous solution stirs under 40 ℃ and obtained gel mixture in 24 hours; Said mixture is transferred to water heating kettle, and airtight, 100 ℃ of hydrothermal crystallizings 24 hours, after-filtration obtained solid product, with deionized water with solids wash to neutral, obtained the Ti-SBA-15 molecular screen primary powder in 5 hours at 110 ℃ air dryings.10.0g Ti-SBA-15 molecular screen primary powder is mixed with the 100g THF, 70 ℃ of reflux extractions 24 hours, then through filtering, wash, obtaining Ti-SBA-15 sieve sample 2 in 5 hours 60 ℃ of vacuum-dryings.
The BET specific surface area of this sample is 994m
2/ g, mean pore size is 7.7nm, pore volume is 1.1cm
3/ g; Its X-ray diffraction spectrogram is as shown in Figure 1, can find out that by figure sample 2 has identical constitutional features with sample 1; The ultraviolet-visible light spectrogram is as shown in Figure 5, can be found out by figure, does not have non-skeleton TiO in the sample 2 equally
2Species; N
2Adsorption isotherm line chart, pore size distribution curve figure and transmission electron microscope picture all with embodiment 1 in sample characteristic consistent.
16.0g nonionogenic tenside P123 is joined in the aqueous hydrochloric acid of 400g 2mol/L, stirred 1 hour down, add 39.5g silicon sol (SiO then at 35 ℃
2Mass content is 25.0%) and the TiOSO of 4.2g mass content 20.0%
4The aqueous solution, stir down at 35 ℃ and to obtain gel mixture in 24 hours; Above-mentioned gel mixture is transferred to water heating kettle, airtight, 100 ℃ of hydrothermal crystallizings 24 hours, filter then and obtain solid product, use the deionized water wash solid to neutral again, 110 ℃ air dryings 5 hours; 450 ℃ of following roastings 4 hours, obtain Ti-SBA-15 sieve sample 3 then.
The BET specific surface area of this sample is 1007m
2/ g, mean pore size is 7.6nm, pore volume is 1.4cm
3/ g; Its X-ray diffraction spectrogram is as shown in Figure 1, can find out that by figure sample 3 has identical constitutional features with sample 1; The ultraviolet-visible light spectrogram is as shown in Figure 5, can be found out by figure, does not have non-skeleton TiO in the sample 3 equally
2Species; N
2Adsorption isotherm line chart, pore size distribution curve figure and transmission electron microscope picture all with embodiment 1 in sample characteristic consistent.
Comparative Examples 1
16.0g nonionogenic tenside P123 is joined in the aqueous hydrochloric acid of 400g 2mol/L, stirred 1 hour down, add 34.2g tetraethyl orthosilicate and 1.8g tetrabutyl titanate then, stir down at 35 ℃ and obtained gel mixture in 24 hours at 35 ℃; Above-mentioned gel mixture is transferred to water heating kettle, airtight, 100 ℃ of hydrothermal crystallizings 24 hours, filter then and obtain solid product, use the deionized water wash solid to neutral again, 110 ℃ air dryings 5 hours; 450 ℃ of following roastings 4 hours, obtain Ti-SBA-15 molecular sieve comparative sample 1 then.
The BET specific surface area of this sample is 864m
2/ g is starkly lower than embodiment sample 1-3; This sample average aperture is 7.0nm, and pore volume is 1.0cm
3/ g; Its X-ray diffraction spectrogram is as shown in Figure 1, has identical constitutional features, N with sample 1
2The characteristic of the sample 1 that adsorption isotherm line chart, pore size distribution curve figure and transmission electron microscope picture all obtain with embodiment 1 is consistent; The ultraviolet-visible light spectrogram of this sample is as shown in Figure 5.Can find out that by Fig. 5 the main absorption band of this sample is between 200-230nm, corresponding to the skeleton titanium species of four-coordination; Obvious absorption is also arranged between 250-360nm in addition, and near the absorption the 270nm is corresponding to the titanium species of distortion pentacoordinate, near the absorption the 330nm is explained to have the outer titanium species of skeleton on this sample corresponding to the crystalline anatase octahedrite.
Claims (10)
1. method for preparing the Ti-SBA-15 molecular sieve, this method comprises:
(1) under hydrolysis glue condition, template, inorganic silicon source, inorganic ti sources and acidic aqueous solution are hydrolyzed, obtain gel mixture;
(2) above-mentioned gel mixture is carried out crystallization under crystallization condition, then the crystallization products therefrom is filtered, will filter the gained solid drying, the removal template obtains the Ti-SBA-15 molecular sieve.
2. method according to claim 1 wherein, is 0.0001-0.1: 0.002-0.1 in the said inorganic ti sources of titanium, template and in the mol ratio in the inorganic silicon source of silicon: 1, be preferably 0.001-0.05: 0.005-0.05: 1.
3. method according to claim 1, wherein, the mass ratio of said template and acidic aqueous solution is 0.5-20: 100, be preferably 1-12: 100, the volumetric molar concentration of solute is 0.01-8mol/L in the acidic aqueous solution, is preferably 0.1-5mol/L; More preferably, said acidic aqueous solution is one or more in hydrochloric acid, aqueous sulfuric acid and the aqueous nitric acid.
4. according to any described method among the claim 1-3, wherein, said inorganic silicon source is one or more in water glass, Starso and the silicon sol.
5. according to any described method among the claim 1-3, wherein, said inorganic ti sources is TiCl
3, TiCl
4, TiOCl
2, Ti (NO
3)
4, TiOSO
4And Ti (SO
4)
2In one or more, be preferably TiCl
3, TiCl
4, TiOSO
4In one or more.
6. according to any described method among the claim 1-3, wherein, said template is a nonionogenic tenside; Be preferably that to have general formula be EO
aPO
bEO
aThe polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer; More preferably, wherein the numerical value of a is 5-140, and b is 30-100; Be preferably EO especially
20PO
70EO
20, EO
132PO
50EO
132, EO
17PO
55EO
17And EO
106PO
70EO
106In one or more.
7. according to any described method among the claim 1-3, wherein, said hydrolysis glue condition comprises that the temperature of hydrolysis is 20-60 ℃, is preferably 30-50 ℃; Time is 5-50 hour, is preferably 10-40 hour.
8. according to any described method among the claim 1-3, wherein, the condition of said crystallization comprises: the temperature of crystallization is 70-150 ℃ in confined conditions, is preferably 80-120 ℃; Time is 8-72 hour, is preferably 20-30 hour.
9. according to any described method among the claim 1-3, wherein, said exsiccant temperature is 70-120 ℃, and the time is 3-10 hour.
10. according to any described method among the claim 1-3, wherein, the method for said removal template is roasting or extraction; The temperature of preferred said roasting is 300-650 ℃, and the time is 2-16 hour; The solvent of preferred said extraction is acidifying methyl alcohol, acidifying ethanol or THF, and the extraction time is 12-36 hour, and extraction temperature is 60-90 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084382A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Mesoporous titanosilicate material and synthesizing method thereof |
| CN111204770A (en) * | 2020-01-19 | 2020-05-29 | 上海交通大学 | Sound-absorbing material for improving low-frequency responsiveness of loudspeaker and preparation method thereof |
| CN114832800A (en) * | 2022-06-06 | 2022-08-02 | 宁波大学 | Solid phase micro-extraction probe, preparation method and application thereof in biogenic amine detection |
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| CN1428296A (en) * | 2001-12-28 | 2003-07-09 | 中国科学院大连化学物理研究所 | Method for synthesizing new titanium-silicone metapore molecular sieve |
| CN101746775A (en) * | 2009-12-15 | 2010-06-23 | 上海师范大学 | Preparation method for organic functional ordered mesoporous titanium oxide silicon molecular sieve |
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2011
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| CN1428296A (en) * | 2001-12-28 | 2003-07-09 | 中国科学院大连化学物理研究所 | Method for synthesizing new titanium-silicone metapore molecular sieve |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084382A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Mesoporous titanosilicate material and synthesizing method thereof |
| CN111204770A (en) * | 2020-01-19 | 2020-05-29 | 上海交通大学 | Sound-absorbing material for improving low-frequency responsiveness of loudspeaker and preparation method thereof |
| CN111204770B (en) * | 2020-01-19 | 2023-03-14 | 上海交通大学 | Sound-absorbing material for improving low-frequency responsiveness of loudspeaker and preparation method thereof |
| CN114832800A (en) * | 2022-06-06 | 2022-08-02 | 宁波大学 | Solid phase micro-extraction probe, preparation method and application thereof in biogenic amine detection |
| CN114832800B (en) * | 2022-06-06 | 2023-08-01 | 宁波大学 | Solid-phase microextraction probe, preparation method and application thereof in biogenic amine detection |
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