CN101412517A - Preparation and use of pore diameter controllable mesoporous silicon dioxide microsphere - Google Patents
Preparation and use of pore diameter controllable mesoporous silicon dioxide microsphere Download PDFInfo
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- CN101412517A CN101412517A CNA2008102027728A CN200810202772A CN101412517A CN 101412517 A CN101412517 A CN 101412517A CN A2008102027728 A CNA2008102027728 A CN A2008102027728A CN 200810202772 A CN200810202772 A CN 200810202772A CN 101412517 A CN101412517 A CN 101412517A
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Abstract
The invention discloses a method for preparing a mesoporous silicon dioxide microsphere with controllable aperture. The method takes a novel tetra-quaternary ammonium salt cation surface active agent as a structure-directing agent and synthesizes the mesoporous silicon dioxide microsphere in an ethanol water system under the alkaline condition by a sol-gel method. The method has the advantages that the prepared silicon dioxide is micron spherical particles and has good monodispersion and large specific surface area; the mesoporous microsphere with large aperture can be prepared without an expanding agent; and the silicon dioxide microsphere prepared by the method has stable performance and is suitable for high-efficiency liquid-phase chromatographic separation and analysis.
Description
[technical field]
The present invention relates to the silicon-dioxide technical field, specifically, is a kind of preparation method and application of mesoporous silicon dioxide micro-sphere of controllable aperture.
[background technology]
High performance liquid chromatography is one of contemporary widely used analytical procedure and separation means, is widely used in each department of scientific research and the every field of social production.In liquid chromatographic system, the core of decision analytical results and separation degree quality then is a chromatographic column.Therefore, filler particularly is that the filler of substrate material is the important topic that the chromatogram worker pays close attention to always with silica gel.In modern age liquid chromatography stationary phase, be that the filler of matrix accounts for about 80% in the application of whole high performance liquid chromatography with the silicon dioxide microsphere.This be since silicon dioxide microsphere except having narrower size distribution, big specific surface area, also having an outstanding advantage is exactly to have bigger aperture
Silicon dioxide microsphere early than nineteen sixty-eight by
Take the lead in alcohol-water-ammoniacal liquor-tetraethoxy system, preparing single silicon oxide microsphere that disperses of atresia.1992, the scientist of Mobil company successfully prepared the mesoporous material of M41S series.In recent years, Chinese scholars is right
Method is improved, and has mainly synthesized mesoporous silicon dioxide micro-sphere by adding cats product or other swelling agents.Although it is improved
Method can be synthesized and had different-grain diameter and than the silicon dioxide microsphere of bigger serface, but its aperture is less
Greatly limited its application in biomacromolecule and Separation of Natural Products.Particularly, in the application of chromatographic field bigger challenge has been proposed as stationary phase for silicon dioxide microsphere along with the development of enzyme engineering, proteinology group.In order to address this problem, at present main adopt molecular weight 2000 and more than syllogic polymkeric substance such as Pluronic P123 (EO20-PO70-EO20), Pluronic F127 (EO106PO70EO106) etc. is the directly synthetic wide-aperture mesoporous material of template, though non-ionic syllogic polymkeric substance tool in the wide-aperture mesoporous silicon sphere of preparation plays a very important role, but it is too wide in range to distribute with its microspherulite diameter of preparing, equally also is subjected to certain restriction in the application of chromatographic field.
China Patent No. CN101289190 discloses a kind of functionalized hollow silica microsphere and preparation method thereof, this functionalized hollow silica microsphere is to utilize the polystyrene microsphere that has positive charge to be template, utilize alkali as etching agent and catalyzer, make silane coupling agent in the condensation hydrolysis of polystyrene microsphere surface, polystyrene microsphere itself is etched away back formation simultaneously.
China Patent No. CN101214962 discloses the method that the composite shuttering legal system is equipped with mesoporous silicon dioxide micro-sphere, a kind of composite shuttering legal system is equipped with the method for mesoporous silicon dioxide micro-sphere, preparation process is: compound concentration is the ammonia soln of 1.8～3.0mol/L, calculates the consumption of positive tetraethyl orthosilicate; In ammonia soln, add template and co-template, stirring and dissolving; To go up step gained mixing solutions and be heated to 30～80 ℃,, finish after reacting 5～6h under the constant agitation speed again to the positive tetraethyl orthosilicate of mixed solution and dripping calculated amount; Obtain the former powder of mesoporous silicon oxide after will going up step gained mixture drying; 5～6 hours removed template methods of the former powder roasting of silicon-dioxide with oven dry promptly get pure mesoporous silicon dioxide micro-sphere.
China Patent No. CN1032303 discloses the silicon dioxide microsphere that the twin columns legal systems is equipped with homogeneous, a kind of silicon dioxide microsphere technology for preparing homogeneous that provides is provided in the present invention, promptly adopt two notes technology, the method of control concentration of reactants and pH, make the silicon dioxide microsphere that makes distribute very narrow and particle that make is bigger, generally at 1～15 μ.
China Patent No. CN101214965 discloses a kind of macropore-mesoporous silicon dioxide hollow micro-sphere preparation method and application, a kind of macropore-mesoporous silicon dioxide hollow micro-sphere preparation method and application relate to inorganic materials preparation and agricultural chemicals Application Areas, the material preparation process is: add template P123 at aqueous phase, after generating stable oil/water/oily double emulsion, add silicon source tetraethoxy TEOS, issuing unboiled water in the effect of precipitation agent separates, generate the hollow silicon dioxide microballoon, behind its filtration drying, calcining obtained product of the present invention in 6 hours under 550 ℃.
China Patent No. CN1872684 discloses a kind of method of mesoporous silicon dioxide micro-sphere of synthetic high-sequential, the present invention relates to a kind of method of mesoporous silicon dioxide micro-sphere of synthetic high-sequential, belong to the inorganic porous material preparing technical field, in container, template and water-soluble polymers is water-soluble, add acid the pH value of solution value is adjusted between 0.3～4.0; Add silicon ester again and obtain reaction solution, at room temperature stir in the reactor that hydrolysis changed autogenous pressure in 4～20 hours over to, leach in 80～120 ℃ of crystallization 24 hours, washing, drying, at last in retort furnace in 550 ℃ of roastings 6 hours, obtain described mesoporous silicon dioxide micro-sphere product.
The preparation method that China Patent No. CN1124715 discloses a kind of porous silicon dioxide microsphere adopts the cell walls of suitable shape and the biomass cells of size or the cytolemma biological micro-capsule as synthesizing porous property silicon dioxide microsphere, it is in the system of disperse phase that the biological micro-capsule that will contain compound of silicate class and pore-creating agent is dispersed in water, by two stage hydrolytic condensation and gelation reaction, be prepared into particle diameter at 1～200 μ m, the aperture exists
Porosity be 60%～90%, 70% size distribution between 0.8D～1.2D, be applicable to porous silica microballoon as liquid chromatography stationary phase matrix, efficient catalytic agent carrier and high-efficiency adsorbent.
China Patent No. CN1872684 discloses a kind of method of mesoporous silicon dioxide micro-sphere of synthetic high-sequential, and is in container that template and water-soluble polymers is water-soluble, adds acid the pH value of solution value is adjusted between 0.3～4.0; Add silicon ester again and obtain reaction solution, at room temperature stir in the reactor that hydrolysis changed autogenous pressure in 4～20 hours in 80～120 ℃ of crystallization 24 hours, leach, washing, dry, at last in retort furnace in 550 ℃ of roastings 6 hours, obtain described mesoporous silicon dioxide micro-sphere product, the sphericity of mesoporous silicon dioxide micro-sphere that the present invention obtains and good dispersity, pore distribution and size-grade distribution homogeneous, physical strength height, specific surface is big and have the meso-hole structure of high-sequential, can be used as the excellent carrier of efficient liquid phase chromatographic stuffing.
China Patent No. CN101023038 discloses silicon dioxide microsphere, may using of its preparation and accumulative method and silicon dioxide microsphere, the present invention relates to silicon dioxide microsphere (M), it has 50～125 μ m, the external diameter of preferred 60～90 μ m, greater than 1 μ m, the wall thickness of preferred 1～3 μ m and 0.3～0.7g/cm
3Density, and relate to by in induction plasma (P), injecting the production method of silicon dioxide microsphere precursor (MS, PR1, PR1 ', PR2 '), the various possible application of collection approach and silicon dioxide microsphere.
China Patent No. CN101289190 discloses a kind of functionalized hollow silica microsphere and preparation method thereof, the invention belongs to matrix material and technical field of function materials, is specially a kind of functionalized hollow silica microsphere and preparation method thereof; This functionalized hollow silica microsphere is to utilize the polystyrene microsphere that has positive charge to be template, utilize alkali as etching agent and catalyzer, make silane coupling agent in the condensation hydrolysis of polystyrene microsphere surface, polystyrene microsphere itself is etched away back formation simultaneously.
For this reason, we develop a kind of novel four-head quaternary cationics is structure directing agent, passes through the method for sol-gel method synthesizing mesoporous silicon dioxide microsphere under alkaline condition; By the simple adjustment aging temperature, need not to add any swelling agent and altogether template can prepare controllable aperture, specific surface area is big, the uniform mesoporous silicon dioxide micro-sphere of particle diameter, and its performance on high performance liquid chromatography studied.
[summary of the invention]
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method and application of mesoporous silicon dioxide micro-sphere of controllable aperture are provided.
The objective of the invention is to be achieved through the following technical solutions:
A kind of preparation method of mesoporous silicon dioxide micro-sphere of controllable aperture comprises step and is,
(1) three sections copolymerization tensio-active agents of novel four-head quaternary ammonium salt cationic is synthetic:
(1) successively be dissolved in the dehydrated alcohol by polyetheramine, epoxy chloropropane, at room temperature stirred 12～24 hours, decompression steams solvent and unnecessary reactant; Wherein, the mol ratio of polyetheramine and epoxy chloropropane is 1:4～1:8;
The molecular-weight average 2000～4000 of described polyetheramine;
(2) product that step (1) is obtained is dissolved in the dehydrated alcohol, adds the Trimethylamine 99 alcoholic solution, 80～85 ℃ of reactions 6～24 hours, removes solvent under reduced pressure, and obtaining colourless or faint yellow dope is novel four-head quaternary cationics; Wherein, the mol ratio of polyetheramine and Trimethylamine 99 is 1:4～1:8;
(2) preparation of single dispersed silicon gel micro-ball
Novel four-head quaternary cationics and estersil are dissolved in the mixed system of alcohol, deionized water and alkali source, and the pH value scope of solution is controlled at 8～10, stirs 15～30 minutes down at 25～45 ℃, treats to stop to stir after the solution becomes muddiness; Leave standstill maintenance after 180～240 minutes, filter to isolate throw out, get uniform silicon gel micro-ball after the drying at room temperature;
Wherein, the mol ratio of novel four-head quaternary cationics, alcohol, deionized water, alkali source and estersil is 1:10000:26000:9:128～3:4000:4000:11:58;
Described estersil is selected from the mixture of one or both estersil in methyl silicate or the tetraethoxy;
Described alcohol is selected from a kind of in anhydrous methanol or the dehydrated alcohol, and what adopted is alcohol-water system;
Described alkali source is organic bases or mineral alkali; Organic bases is dimethylamine, diethylamine, Trimethylamine 99, triethylamine, n-Butyl Amine 99 etc.; Mineral alkali is NaOH, KOH, Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3, ammoniacal liquor etc., wherein, mineral alkali is preferably ammoniacal liquor;
(3) preparation of monodisperse mesoporous silica microballoon
The silicon gel micro-ball that step (two) is obtained is aging under hydrothermal condition, and concrete steps are to change silicon gel micro-ball, deionized water in band teflon-lined autoclave hydrothermal aging processing behind the homodisperse.Through filtering, air is dry down, can obtain the white solid powder, 30～450 ℃ of temperature programmings 1.5～2.5 hours, is preferably 2 hours; Under 450 ℃～600 ℃ temperature, temperature is preferably 500 ℃, continues roasting time 3.5～4.5 hours, and the time is preferably 4 hours, obtains mesoporous silicon dioxide micro-sphere; Wherein: aged silicon gel micro-ball is 1:5～10 with the quality ratio; Aging temperature is 55～135 ℃; Digestion time is 12～48 hours.
The preparation method of the mesoporous silicon dioxide micro-sphere of a kind of controllable aperture of the present invention and the positively effect of application are:
(1) preparation method of the present invention prepares simple and easy to do;
(2) by the differing temps hydrothermal treatment consists, the silicon dioxide microsphere controllable aperture (68 of gained
～195
);
(3) other common template or swelling agent need not be added and wide-aperture mesoporous material (195 can be obtained
);
(4) the silicon dioxide microsphere particle diameter is even, has monodispersity;
(5) silicon dioxide microsphere has pore structure and surface tissue (aperture, pore volume, specific surface area etc.) and all meets the requirement of high performance liquid chromatography with substrate material.
[description of drawings]
The structural formula of the novel four-head quaternary cationics of Fig. 1;
The sem photograph of Fig. 2 a mesoporous silicon dioxide micro-sphere particle diameter 1 μ m;
The sem photograph of Fig. 2 b mesoporous silicon dioxide micro-sphere particle diameter 1.7 μ m;
Fig. 3 mesoporous silicon dioxide micro-sphere N
2(Fig. 3 a) and graph of pore diameter distribution (Fig. 3 b) for absorption-desorption isotherm;
Fig. 4 is isolating color atlas under hydrophilic pattern to polar material and nucleosides material: 1 is uridylic, and 2 is uridine, and 3 is five flucytosines, and 4 is cytosine(Cyt); With chromatographic condition be: the formic acid of moving phase: acetonitrile/100mMpH 3.0/ammonium formiate buffered soln=95:5 (v/v), flow velocity 0.2-1ml/min detects wavelength: 254nm.
[embodiment]
The preparation method of mesoporous silicon dioxide micro-sphere of a kind of controllable aperture of the present invention and the embodiment of application below are provided.
(1) novel four-head quaternary cationics is synthetic
Step (1) adds the 10g polyetheramine in the 50ml round-bottomed flask, its molecular-weight average is 4000, and 1.1g epoxy chloropropane, 25g dehydrated alcohol stirred under room temperature 12～24 hours, and decompression steams solvent and unnecessary reactant.
The product that step (2) obtains step 1 is dissolved in the 25g dehydrated alcohol, add 0.70g Trimethylamine 99 alcoholic solution, 80～85 ℃ of reactions 12～24 hours, remove solvent under reduced pressure, obtain colourless or faint yellow dope and be novel four-head quaternary cationics 1.
In embodiment 1 step (1), with the 10g molecular-weight average is that to replace with molecular-weight average be 2000 polyetheramine for 4000 polyetheramine, 1.1g epoxy chloropropane replaces with the 0.55g epoxy chloropropane, in embodiment 1 step (2), 0.70g Trimethylamine 99 alcoholic solution is replaced with 0.35g Trimethylamine 99 alcoholic solution, other step all by embodiment 1 operation, obtains colourless or faint yellow dope and is novel four-head quaternary cationics 2.
Fig. 1 is the chemical structure synoptic diagram of novel four-head quaternary cationics 1 and 2.
(2) preparation of mesoporous silicon dioxide micro-sphere
Embodiment 3
Step (1) adds 0.50g tensio-active agent 1 in the 100ml round-bottomed flask, the 32g anhydrous methanol, the 40g deionized water stirred 20 minutes in 35 ℃, treat that solution is vitreous state, drip 0.05ml ammoniacal liquor and 2.5g methyl silicate then, stop after the solution muddiness stirring, leave standstill 3 hours after-filtration, after the anhydrous methanol washing 2～4 times, drying at room temperature.
Step (2) is with the solid 1g of gained, add the 50ml deionized water, place in the autoclave of the poly-tetrafluoro of liner, left standstill under 55 ℃ 24 hours, cooled and filtered is behind deionized water wash 2～3 times, dry under the room temperature, place 30～500 ℃ of temperature programmings of retort furnace 2 hours then, 500 ℃ of lasting roastings 4 hours obtain white powder.
Through scanning electron microscope analysis, recording size is 1 μ m.Utilize N
2The adsorption/desorption instrument is analyzed, and recording mean pore size is 6.753nm, and specific surface area is 478m
2/ g.
Fig. 2 a is the sem photograph of mesoporous silicon dioxide micro-sphere particle diameter 1 μ m.
Embodiment 4
Left standstill under 75 ℃ 24 hours leaving standstill to replace with in 24 hours under 55 ℃ (2) in embodiment 3 steps (two), and other step all by embodiment 3 operations, also can obtain monodisperse silica microspheres.
Utilize N
2The adsorption/desorption instrument is analyzed, and recording mean pore size is 9.66nm, specific surface area 399.25m
2/ g.
Left standstill under 95 ℃ 24 hours leaving standstill to replace with in 24 hours under 55 ℃ (2) in embodiment 3 steps (two), and other step all by embodiment 3 operations, also can obtain monodisperse silica microspheres.
Utilize N
2The adsorption/desorption instrument is analyzed, and recording mean pore size is 13.16nm, specific surface area 217.23m
2/ g.
Embodiment 6
Left standstill under 115 ℃ 24 hours leaving standstill to replace with in 24 hours under 55 ℃ (2) in embodiment 3 steps (two), and other step all by embodiment 3 operations, also can obtain monodisperse silica microspheres.
Utilize N
2The adsorption/desorption instrument is analyzed, and recording mean pore size is 19.54nm, specific surface area 154.27m
2/ g.
Left standstill under 115 ℃ 48 hours leaving standstill to replace with in 24 hours under 55 ℃ (2) in embodiment 3 steps (two), and other step all by embodiment 3 operations, also can obtain monodisperse silica microspheres.
Utilize N
2The adsorption/desorption instrument is analyzed, and recording mean pore size is 19.03nm, specific surface area 161.52m
2/ g.
Fig. 3 a and Fig. 3 b are embodiment 1～5 mesoporous silicon dioxide micro-sphere N
2Absorption-desorption isotherm and be graph of pore diameter distribution.
(1) in embodiment 3 steps (), it is 36% Trimethylamine 99 alcoholic solution that 0.05ml ammoniacal liquor is replaced with the 0.02ml massfraction; Left standstill under 135 ℃ 48 hours leaving standstill to replace with in 24 hours under 55 ℃ (2) in embodiment 3 steps (two), and other step all by embodiment 3 operations, also can obtain monodisperse silica microspheres.
Utilize N
2The adsorption/desorption instrument is analyzed, and recording mean pore size is 21.69nm, specific surface area 213.48m
2/ g.
Embodiment 9
(2) in embodiment 3 steps (two) replace with the 2.5g tetraethoxy with the 2.5g methyl silicate, and the 35g deionized water replaces with the 38g deionized water; In (2) in embodiment 3 steps (two), left standstill under 95 ℃ 24 hours leaving standstill to replace with in 24 hours under 55 ℃, other step all by embodiment 3 operations, also can obtain monodisperse silica microspheres.
Through scanning electron microscope analysis, recording size is 1.7 μ m.Utilize N
2The adsorption/desorption instrument is analyzed, and recording mean pore size is 13.30nm, specific surface area 301.40m
2/ g.
Fig. 2 b is the sem photograph of mesoporous silicon dioxide micro-sphere particle diameter 1.7 μ m.
In (1) in embodiment 3 steps (), 0.50g tensio-active agent 1 is replaced to 0.42g tensio-active agent 2, the 32g anhydrous methanol replaces with the 42g anhydrous methanol, and the 35g deionized water replaces with the 40g deionized water; In (2) in embodiment 3 steps (two), left standstill under 95 ℃ 24 hours leaving standstill to replace with in 24 hours under 55 ℃, other step all by embodiment 3 operations, also can obtain monodisperse silica microspheres.
Utilize N
2The adsorption/desorption instrument is analyzed, and recording mean pore size is 10.35nm, specific surface area 471.45m
2/ g.
(3) application of mesoporous silicon dioxide micro-sphere in high performance liquid chromatography separates
Embodiment 11
With the monodisperse silica microspheres of gained among the embodiment 9, load 2.1 * 50mm stainless steel chromatogram post with the homogenate method, under hydrophilic pattern, analyze with polar material and nucleosides material.Formic acid/ammonium formiate buffered soln with acetonitrile-100mMpH3.0 is moving phase, and the chromatographic behavior of 4 kinds of compounds as shown in Figure 4.Used chromatographic condition is: moving phase: the formic acid of acetonitrile/100mM pH 3.0/ammonium formiate buffered soln=95:5 (v/v), flow velocity 0.2～1ml/min detects wavelength: 254nm.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (10)
1. the preparation method of the mesoporous silicon dioxide micro-sphere of a controllable aperture is characterized in that, comprise concrete steps to be,
(1) three sections copolymerization tensio-active agents of novel four-head quaternary ammonium salt cationic is synthetic:
(1) successively be dissolved in the dehydrated alcohol by polyetheramine, epoxy chloropropane, at room temperature stirred 12～24 hours, decompression steams solvent and unnecessary reactant; Wherein, the mol ratio of polyetheramine and epoxy chloropropane is 1:4～1:8;
(2) product that step (1) is obtained is dissolved in the dehydrated alcohol, adds the Trimethylamine 99 alcoholic solution, 80～85 ℃ of reactions 6～24 hours, removes solvent under reduced pressure, and obtaining colourless or faint yellow dope is novel four-head quaternary cationics; Wherein, the mol ratio of polyetheramine and Trimethylamine 99 is 1:4～1:8;
(2) preparation of single dispersed silicon gel micro-ball
Novel four-head quaternary cationics and estersil are dissolved in the mixed system of alcohol, deionized water and alkali source, and the pH value scope of solution stirred 15～30 minutes down at 25～45 ℃ 8～10, treated to stop to stir after the solution becomes muddiness; Leave standstill maintenance after 180～240 minutes, filter to isolate throw out, get uniform silicon gel micro-ball after the drying at room temperature;
Wherein, the mol ratio of novel four-head quaternary cationics, alcohol, deionized water, alkali source and estersil is 1:10000:26000:9:128～3:4000:4000:11:58;
(3) preparation of monodisperse mesoporous silica microballoon
The silicon gel micro-ball that step (two) is obtained is aging under hydrothermal condition, and concrete steps are to change silicon gel micro-ball, deionized water in band teflon-lined autoclave hydrothermal aging processing behind the homodisperse.Through filtering, air is dry down, can obtain the white solid powder, 30～450 ℃ of temperature programmings 1.5～2.5 hours; Under 450 ℃～600 ℃ temperature, continue roasting time 3.5～4.5 hours, obtain mesoporous silicon dioxide micro-sphere; Wherein: aged silicon gel micro-ball is 1:5～10 with the quality ratio; Aging temperature is 55～135 ℃; Digestion time is 12～48 hours.
2. the preparation method of the mesoporous silicon dioxide micro-sphere of a kind of controllable aperture according to claim 1 is characterized in that, in described step (), and the molecular-weight average 2000～4000 of described polyetheramine.
3. the preparation method of the mesoporous silicon dioxide micro-sphere of a kind of controllable aperture according to claim 1 is characterized in that, in described step (two), described estersil is selected from the mixture of one or both estersil in methyl silicate or the tetraethoxy.
4. the preparation method of the mesoporous silicon dioxide micro-sphere of a kind of controllable aperture according to claim 1 is characterized in that, in described step (two), what adopted is alcohol-water system, and described alcohol is selected from a kind of in anhydrous methanol or the dehydrated alcohol.
5. the preparation method of the mesoporous silicon dioxide micro-sphere of a kind of controllable aperture according to claim 1 is characterized in that, in described step (two), described alkali source is selected from organic bases or mineral alkali.
6. the preparation method of the mesoporous silicon dioxide micro-sphere of a kind of controllable aperture according to claim 5 is characterized in that, described organic bases is selected from dimethylamine, diethylamine, Trimethylamine 99, triethylamine, n-Butyl Amine 99.
7. the preparation method of the mesoporous silicon dioxide micro-sphere of a kind of controllable aperture according to claim 5 is characterized in that, described mineral alkali is selected from NaOH, KOH, Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3, a kind of in the ammoniacal liquor.
8. the preparation method of the mesoporous silicon dioxide micro-sphere of a kind of controllable aperture according to claim 7 is characterized in that, described mineral alkali is preferably ammoniacal liquor.
9. the preparation method of the mesoporous silicon dioxide micro-sphere of a kind of controllable aperture according to claim 1 is characterized in that, in described step (three), 30～450 ℃ of temperature programmings 2 hours; Under 500 ℃ of temperature, continue roasting time 4 hours.
10. the application of mesoporous silicon dioxide micro-sphere in the high performance liquid chromatography compartment analysis of the preparation method of the mesoporous silicon dioxide micro-sphere of a kind of controllable aperture according to claim 1 preparation.
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| CN117263193B (en) * | 2023-09-04 | 2024-04-30 | 金三江(肇庆)硅材料股份有限公司 | Porous silicon dioxide and preparation method and application thereof |
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2008
- 2008-11-14 CN CNA2008102027728A patent/CN101412517A/en active Pending
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