CN104261414A - Synthesis method of bimodal mesoporous silicon dioxide - Google Patents
Synthesis method of bimodal mesoporous silicon dioxide Download PDFInfo
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- CN104261414A CN104261414A CN201410496202.XA CN201410496202A CN104261414A CN 104261414 A CN104261414 A CN 104261414A CN 201410496202 A CN201410496202 A CN 201410496202A CN 104261414 A CN104261414 A CN 104261414A
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Abstract
The invention relates to a synthesis method of bimodal mesoporous silicon dioxide, belonging to the technical field of inorganic porous materials. The method is characterized in that by using a cationic quaternary ammonium salt surfactant as a template, a silicon source is subjected to prehydrolysis treatment in a phosphoric acid system incapable of easily forming ordered mesoporous phase, and a phosphate solid which is weakly alkaline after being dissolved is directly added to induce the synthesis of the bimodal mesoporous silicon dioxide, of which the specific area is 949.7-1181.8 m<2>/g, the pore volume is 0.68-1.05 cm<3>/g and the framework pore sizes are respectively 2.1-2.6nm and 3.3-3.9nm. The synthesis system and preparation conditions used by the method are beneficial to in-situ packaging of various metal ions in different mesoporous pore canals and also beneficial to in-situ coating and immobilization of bioactive guest molecules in different pore canals, so that the method has important application prospects in the field of development of novel commercial catalysts, biocatalysts, multistage porous complex function materials and the like.
Description
Technical field
The synthetic method of a kind of double-mesopore silicon dioxide of the present invention
,belong to inorganic porous material technical field, be specifically related to a kind of under gentle acid and conditions of low ionic strength synthesis there is the method for skeleton pair mesoporous distribution silicon-dioxide.
Background technology
Mesoporous silicon oxide is (J.Am.Chem.Soc. since last century, the early 1990s successfully synthesized; 1992; 114; 10834); wide application prospect (Chem.Rev. is demonstrated in many research fields such as catalysis, absorption, separation, biological medicine, environment protection, host-guest chemistry and new function materials due to features such as its large specific surface area, high pore volume and apertures adjustable flexibly; 1997,97,2373).Particularly in the development field of new catalyst, due to the aperture distribution in monodrome mostly of mesoporous silicon oxide, it can well solve a difficult problem for macromole shape selective catalysis.But actual industrial process feedack shows, the preparation of bulky molecular catalysis cracking catalyst often needs the reasonable disposition of two-stage hole or multi-stage porous, therefore control to synthesize the focus (Pure.Appl.Chem. that the Metaporous silicon dioxide material with two-stage hole or multi-stage porous distribution characteristics has become current porous functional material research field, 2009,81 (12), 2265 etc.).
Existing many scientific and technical literatures are (as J.Mater.Chem. A. at present, 2014,2,5363 and reference etc.) and patented technology (as CN1304871A, CN1304872A, CN1648044A, CN1151065C, CN1380250A, CN101837981A and CN103641122A etc.) disclose the various preparation method with Bu Tong two mesoporous distribution characteristics mesoporous silicon oxide.But, in these published double-mesopore silicon dioxides, its larger mesoporous nano-scale particle that mostly results from piles up the intergranular pore produced, the scope of its pore size distribution depends on size and the accumulation mode thereof of nano particle, and often causes the decline of material meso-hole structure order with the reduction of particle size.Obviously, this accumulation skeleton that is mesoporous and that formed by template action mesoporous between exist essence difference.Because the acquisition of the various functionalization characteristic of mesoporous silicon oxide, as catalytic activity etc., depend on the encapsulation of difference in functionality group in skeleton mesopore orbit and immobilized, the Metaporous silicon dioxide material that therefore preparation has a two mesoporous distribution characteristics of skeleton will have even more important meaning.
Summary of the invention
The synthetic method of a kind of double-mesopore silicon dioxide of the present invention, its object is to provide a kind of and adopt the agent of cationic quaternary ammonium salt surfactants as template, be difficult to be formed in the gentle acid system of order mesoporous thing phase, by to after the room temperature prehydrolysis process in silicon source used, directly add after dissolving in weakly alkaline phosphoric acid salt solid, Induced synthesis has the method for the ordered mesoporous silica dioxide of the two mesoporous distribution characteristics of skeleton, the synthetic system that present method uses and preparation condition are not only conducive to the original position encapsulation of each metal ion species in different mesopore orbit, also the various situ coating of biological activity guest molecule in different mesopore orbit and immobilized of having is conducive to, at infant industry catalyzer, the development field of biological catalyst and multi-stage porous composite functional material etc. has important application prospect.
The synthetic method of a kind of double-mesopore silicon dioxide of the present invention, it is characterized in that a kind ofly being difficult to be formed in the Phosphoric Acid of order mesoporous thing phase, by to after the prehydrolysis process at room temperature of silicon source used, directly add after dissolving in weakly alkaline phosphoric acid salt solid, Induced synthesis has the method for the ordered mesoporous silica dioxide of the two mesoporous distribution characteristics of skeleton, the method adopts the agent of cationic quaternary ammonium salt surfactants as template, do silicon source with methyl silicate (TMOS) or tetraethoxy (TEOS), the concentration relatively gentle by acidity is the H of 85%
3pO
4make silicon source hydrolyst, with water as solvent, by after the prehydrolysis process at room temperature of silicon source used, directly add in weakly alkaline phosphoric acid salt solid after dissolving, Induced synthesis specific surface area is 949.7-1181.8m
2/ g, pore volume is 0.68-1.05cm
3/ g, skeleton aperture is respectively the double-mesopore silicon dioxide of 2.1-2.6nm and 3.3-3.9nm, and its concrete technology step is as follows:
1) first template, phosphoric acid, silicon source and water are at room temperature uniformly mixed successively, the mol ratio of its initial reactant is silicon source: template: phosphoric acid: water=1:(0.184-0.369): 0.654:100;
2) after the complete homogeneous phase of system, continue stir process 4-6 hour in room temperature, then the direct phosphoric acid salt solid by phosphoric acid salt/TEOS mol ratio=0.5-2.2 under agitation adds in above-mentioned reaction system;
3) stir process is continued under room temperature after 10 minutes-24 hours, by the precipitation and centrifugal separation separated out, with deionized water wash, in 60-100 DEG C of oven dry, again with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550-600 DEG C of roasting 6 hours with removed template method, obtain the ordered mesoporous silica dioxide with the two mesoporous distribution of skeleton.
The synthetic method of above-mentioned a kind of double-mesopore silicon dioxide, is characterized in that described cationic quaternary ammonium salt tensio-active agent is: Trimethyllaurylammonium bromide (DTAB), Tetradecyl Trimethyl Ammonium Bromide (MTAB), cetyl trimethylammonium bromide (CTAB) or Cetyltrimethylammonium bromide (STAB).
The synthetic method of above-mentioned a kind of double-mesopore silicon dioxide, is characterized in that described phosphoric acid salt is weakly acidic ammonium phosphate ((NH after dissolving
4)
3pO
43H
2o), sodium phosphate ((Na
3pO
412H
2and Sodium phosphate dibasic ((Na O)
2hPO
412H
2o).
The synthetic method of above-mentioned a kind of double-mesopore silicon dioxide, is characterized in that described ambient temperature scope is 5-28 DEG C.
The synthetic method of a kind of double-mesopore silicon dioxide of the present invention, its advantage is:
1, be difficult to be formed in the Phosphoric Acid of order mesoporous thing phase at one, by to after the prehydrolysis process at room temperature of silicon source used, directly add after dissolving in weakly alkaline phosphoric acid salt solid, namely the ordered mesoporous silica dioxide with the two mesoporous distribution characteristics of skeleton is formed after 10 minutes at stirring reaction, shorten the preparation cycle of material, improve the preparation efficiency of material.
2, the gentle acidic medium that uses of present method and the follow-up of phosphoric acid salt solid directly add, reduce the ionic strength of synthetic system to the full extent, and then decrease in system cross high ionic strength to having bioactive molecules structural damage effect, contribute to variously there is bioactive guest molecule by the mode of the directly synthesis in-stiu coating in two mesopore orbit different zones, for the preparation of New biocatalyst and new multistage hole composite functional material provides new chance.
3, the gentle acidic medium that present method uses and follow-up phosphoric acid salt solid directly add the operating method that rapid induction synthesizes double-mesopore silicon dioxide, contribute to various there is different catalytically active metal ion being uniformly distributed in two mesopore orbit different zones, because weak acidic medium contributes to dispersed in surfactant micelle template different zones of metal ion, while adding phosphoric acid salt dissolution of solid, the rapid formation of two meso-hole structure synchronously can realize metal ion fixing in different mesopore orbit, present method is that the preparation of new multistage pore catalyst provides new chance.
4, the double-mesopore silicon dioxide of present method synthesis is adopted to have the XRD diffracting spectrum feature (as Figure of description 1,3 and 5) of six side's ordered mesoporous silica dioxides, but its N
2the desorption branch of adsorption-desorption isothermal shows one and significantly adsorbs step in the scope that relative pressure is 0.2-0.5, and interval at same relative pressure, and desorption branch then shows 2 obvious desorption steps (as Figure of description 2 and 4).
5, in the silicon source-template-aqueous systems used in present method, phosphoric acid is individually added or phosphoric acid salt all cannot obtain the mesoporous silicon oxide with two mesoporous distribution characteristicss.
6, adopting two kinds in double-mesopore silicon dioxide synthesized by present method, mesoporous to be skeleton mesoporous, and its aperture regulates respectively by the size and concentration changing template in the scope of 2.1-2.6nm and 3.3-3.9nm.
7, the silicon source hydrolyst used in present method can also be that other Individual existence is difficult to be formed the non-strong acid of order mesoporous thing phase as boric acid, formic acid, acetic acid or citric acid etc.
Accompanying drawing explanation
Fig. 1 is the x-ray diffractogram of powder (XRD) of roasting sample in embodiment 1.
Fig. 2 is nitrogen adsorption isotherm and the pore size distribution thereof of roasting sample in embodiment 1.
Fig. 3 is the x-ray diffractogram of powder (XRD) of roasting sample in embodiment 2.
Fig. 4 is nitrogen adsorption isotherm and the pore size distribution thereof of roasting sample in embodiment 2.
Fig. 5 is the x-ray diffractogram of powder (XRD) of roasting sample in embodiment 3.
Embodiment
Embodiment 1:
By 0.404 gram of STAB, the phosphoric acid solution of 0.25 milliliter 85%, 1.25 milliliters of TEOS and 10 milliliter H
2o is uniformly mixed successively at 25 DEG C, after the complete homogeneous phase of system, continue stir process 6 hours in 25 DEG C, then direct 1.22 grams of ammonium phosphate solids are under agitation added in above-mentioned reaction system, at 25 DEG C, continue stir process after 24 hours, by the precipitation and centrifugal separation separated out, with deionized water wash, in 60 DEG C of oven dry, then with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550 DEG C of roastings 6 hours with removed template method, obtain double-mesopore silicon dioxide, its XRD figure is shown in Fig. 1, its N
2adsorption isothermal line and corresponding pore size distribution curve are shown in Fig. 2, and its specific surface area is 1038.3m
2/ g, pore volume is 0.96cm
3/ g, skeleton mesoporous pore size is respectively 2.6nm and 3.3nm.
Embodiment 2:
By 0.375 gram of CTAB, the phosphoric acid solution of 0.25 milliliter 85%, 1.25 milliliters of TEOS and 10 milliliter H
2o is uniformly mixed successively at 25 DEG C, after the complete homogeneous phase of system, continue stir process 6 hours in 25 DEG C, then direct 1.22 grams of ammonium phosphate solids are under agitation added in above-mentioned reaction system, at 25 DEG C, continue stir process after 24 hours, by the precipitation and centrifugal separation separated out, with deionized water wash, in 60 DEG C of oven dry, then with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550 DEG C of roastings 6 hours with removed template method, obtain double-mesopore silicon dioxide, its XRD figure is shown in Fig. 3, its N
2adsorption isothermal line and corresponding pore size distribution curve are shown in Fig. 4, and its specific surface area is 1131.6m
2/ g, pore volume is 0.82cm
3/ g, skeleton mesoporous pore size is respectively 2.3nm and 3.4nm.
Embodiment 3:
By 0.404 gram of STAB, the phosphoric acid solution of 0.25 milliliter 85%, 1.25 milliliters of TEOS and 10 milliliter H
2o is uniformly mixed successively at 25 DEG C, stir process is continued 6 hours in 25 DEG C after the complete homogeneous phase of system, then direct 1.83 grams of ammonium phosphate solids are under agitation added in above-mentioned reaction system, at 25 DEG C, continue stir process after 10 minutes, by the precipitation and centrifugal separation separated out, with deionized water wash, in 60 DEG C of oven dry, then with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550 DEG C of roastings 6 hours with removed template method, obtain double-mesopore silicon dioxide, its XRD figure is shown in Fig. 5.
Embodiment 4:
By 0.375 gram of CTAB, the phosphoric acid solution of 0.25 milliliter 85%, 1.25 milliliters of TEOS and 10 milliliter H
2o is uniformly mixed successively at 25 DEG C, stir process is continued 4 hours in 25 DEG C after the complete homogeneous phase of system, then direct 2.066 grams of Sodium phosphate dibasic solids are under agitation added in above-mentioned reaction system, stir process is continued after 24 hours at 25 DEG C, by the precipitation and centrifugal separation separated out, with deionized water wash, in 60 DEG C of oven dry, again with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550 DEG C of roastings 6 hours with removed template method, obtain double-mesopore silicon dioxide, its specific surface area is 1181.8m
2/ g, pore volume is 0.8cm
3/ g, skeleton mesoporous pore size is respectively 2.4nm and 3.5nm.
Embodiment 5:
By 0.346 gram of MTAB, the phosphoric acid solution of 0.25 milliliter 85%, 1.25 milliliters of TEOS and 10 milliliter H
2o is uniformly mixed successively at 25 DEG C, stir process is continued 6 hours in 25 DEG C after the complete homogeneous phase of system, then direct 1.22 grams of ammonium phosphate solids are under agitation added in above-mentioned reaction system, at 25 DEG C, continue stir process after 24 hours, by the precipitation and centrifugal separation separated out, with deionized water wash, in 60 DEG C of oven dry, then with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550 DEG C of roastings 6 hours with removed template method, obtain double-mesopore silicon dioxide, its specific surface area is 1030.9m
2/ g, pore volume is 0.83cm
3/ g, skeleton mesoporous pore size is respectively 2.1nm and 3.9nm.
Embodiment 6:
By 0.317 gram of DTAB, the phosphoric acid solution of 0.25 milliliter 85%, 1.25 milliliters of TEOS and 10 milliliter H
2o is uniformly mixed successively at 25 DEG C, stir process is continued 6 hours in 25 DEG C after the complete homogeneous phase of system, then direct 1.22 grams of ammonium phosphate solids are under agitation added in above-mentioned reaction system, at 25 DEG C, continue stir process after 24 hours, by the precipitation and centrifugal separation separated out, with deionized water wash, in 60 DEG C of oven dry, then with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550 DEG C of roastings 6 hours with removed template method, obtain double-mesopore silicon dioxide, its specific surface area is 949.7m
2/ g, pore volume is 0.68cm
3/ g, skeleton mesoporous pore size is respectively 2.1nm and 3.5nm.
Claims (4)
1. the synthetic method of a double-mesopore silicon dioxide, it is characterized in that a kind ofly being difficult to be formed in the Phosphoric Acid of order mesoporous thing phase, by to after the prehydrolysis process at room temperature of silicon source used, directly add after dissolving in weakly alkaline phosphoric acid salt solid, Induced synthesis has the method for the ordered mesoporous silica dioxide of the two mesoporous distribution characteristics of skeleton, the method adopts the agent of cationic quaternary ammonium salt surfactants as template, do silicon source with methyl silicate (TMOS) or tetraethoxy (TEOS), the concentration relatively gentle by acidity is the H of 85%
3pO
4make silicon source hydrolyst, with water as solvent, by after the prehydrolysis process at room temperature of silicon source used, directly add in weakly alkaline phosphoric acid salt solid after dissolving, Induced synthesis specific surface area is 949.7-1181.8m
2/ g, pore volume is 0.68-1.05cm
3/ g, skeleton aperture is respectively the double-mesopore silicon dioxide of 2.1-2.6nm and 3.3-3.9nm, and its concrete technology step is as follows:
1) first template, phosphoric acid, silicon source and water are at room temperature uniformly mixed successively, the mol ratio of its initial reactant is silicon source: template: phosphoric acid: water=1:(0.184-0.369): 0.654:100;
2) after the complete homogeneous phase of system, continue stir process 4-6 hour in room temperature, then the direct phosphoric acid salt solid by phosphoric acid salt/TEOS mol ratio=0.5-2.2 under agitation adds in above-mentioned reaction system;
3) stir process is continued under room temperature after 10 minutes-24 hours, by the precipitation and centrifugal separation separated out, with deionized water wash, in 60-100 DEG C of oven dry, again with the temperature rise rate of 2.5 DEG C/min, by the sample after drying in 550-600 DEG C of roasting 6 hours with removed template method, obtain the ordered mesoporous silica dioxide with the two mesoporous distribution of skeleton.
2., according to a kind of described in claim 1 synthetic method of double-mesopore silicon dioxide, it is characterized in that described cationic quaternary ammonium salt tensio-active agent is: Trimethyllaurylammonium bromide (DTAB), Tetradecyl Trimethyl Ammonium Bromide (MTAB), cetyl trimethylammonium bromide (CTAB) or Cetyltrimethylammonium bromide (STAB).
3., according to a kind of described in claim 1 synthetic method of double-mesopore silicon dioxide, it is characterized in that described phosphoric acid salt is weakly acidic ammonium phosphate ((NH after dissolving
4)
3pO
43H
2o), sodium phosphate ((Na
3pO
412H
2and Sodium phosphate dibasic ((Na O)
2hPO
412H
2o).
4., according to a kind of described in claim 1 synthetic method of double-mesopore silicon dioxide, it is characterized in that described ambient temperature scope is 5-28 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105879840A (en) * | 2016-04-21 | 2016-08-24 | 苏州云舒新材料科技有限公司 | Organic-inorganic compound and application thereof in water treatment |
| CN110028072A (en) * | 2019-05-06 | 2019-07-19 | 浙江大学 | A kind of preparation method of additive Mn mesoporous silicon dioxide nano particle |
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2014
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| CN105879840A (en) * | 2016-04-21 | 2016-08-24 | 苏州云舒新材料科技有限公司 | Organic-inorganic compound and application thereof in water treatment |
| CN110028072A (en) * | 2019-05-06 | 2019-07-19 | 浙江大学 | A kind of preparation method of additive Mn mesoporous silicon dioxide nano particle |
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