CN1262476C - Prepn process of monodisperse microporous silica microballoon with great specific surface area - Google Patents
Prepn process of monodisperse microporous silica microballoon with great specific surface area Download PDFInfo
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- CN1262476C CN1262476C CN 200410061041 CN200410061041A CN1262476C CN 1262476 C CN1262476 C CN 1262476C CN 200410061041 CN200410061041 CN 200410061041 CN 200410061041 A CN200410061041 A CN 200410061041A CN 1262476 C CN1262476 C CN 1262476C
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Abstract
The present invention relates to a preparation process of monodisperse microporous silica microballoons with great specific surface areas. The process adopts alkylamine as a template agent and a catalyst for promoting the condensation polymerization of a silicic acid ester compound in a system, which uses alcohol as a solvent and uses water as a dispersed phase, and the self-assembly process of the template agent by hydrolysis of two stages; the granule diameter of a prepared silica microporous microballoon is from 500 to 1500 nm; a nitrogen absorbing specific surface area by a BET process is from 600 to 1500m<2>/g; the porosity is from 40% to 60%; the pore volume is from 0.43 to 0.60cm<3>/g; the pore diameter is from 1.1 to 1.9 nm. The present invention has the advantages of simple operation, low cost and short production periods. Prepared silica granules are in a monodisperse state and are distributed narrowly; each silica granule has the advantages of large specific surface area, high pore volume and regular shape.
Description
Technical field
The invention belongs to monodisperse silica microspheres and preparation method thereof, be specifically related to adopt the template self-assembly to prepare the method for microporous silica microballoon.Belong to chemistry and inorganic materials class technical field.
Background technology
Monodisperse silica sphere particle shape particle has very important application at filler, stdn particle in the fields such as preparation photonic crystal.And the porous silica microballoon is used as sorbing material or solid support material in chromatogram and separation technology field, is the further application of this material.
Since publishing an article on " colloid and interface science magazine " (1968, Vol 62, No.1, pages 62-69), known can obtain monodispersed spherical from people such as W.St ber by polycondensation that tetraalkoxysilane is hydrolyzed.But the specific surface area of the silicon-dioxide that this method is prepared is less, and porosity is lower.
Since finding that zeolite has the good adsorption performance forties in 20th century, the condition of people's natural imitation circle adopts the stay in place form agent to synthesize the unexistent porous material of occurring in nature.Mould plate technique is because of the biomineralization process, and is employed more and more widely.In the biomineralization pattern, the nucleation of inorganic species, growth and morphology control depend on the pre-assembling of organic molecule, and affect its nucleation and process of growth.Prepare porous material with template, not only preparation condition is simple relatively, and seems more flexible at aspects such as the chemical constitution of material and profile controls.
Porous material is according to the definition of International Union of Pure and Applied Chemistry (IUPAC), is divided into the large pore material of pore diameter range greater than 50nm by the size in its aperture, and pore diameter range is the mesoporous material of 2～50nm and the aperture poromerics less than 2nm.Silicon-dioxide is as poromerics because its huge internal surface area and hole dimension uniformly, make its absorption, catalysis, separation and nano wire or bunch fields such as matrix important use is arranged.The study on the synthesis of poromerics is very active always, because its aperture is less, hole wall is thicker comparatively speaking.With it the advantage of himself is arranged as the carrier of catalyzer.Synthetic general employing ion or neutral surface active agent are as template, and resulting mesoporous silica shows as irregular pattern on macroscopic view.
In order to satisfy the needs of using, mesoporous silica also must have suitable profile, for example has the poromerics of film, fiber, hard sphere or the hollow ball-shape of microvoid structure, usually said morphology control that Here it is.The pattern of control mesoporous silica and the application that size can be expanded mesoporous silica are especially in the purposes of exploitation mesoporous silica at aspects such as liquid-phase chromatographic analysis and catalytic materials.But these application requiring silicon-dioxide possess higher specific surface area, bigger pore volume and are monodispersed particle and regular spherical morphology.
At present, the mesoporous silica microballoon of these patterns all adopts three-phase system (as surperficial template, cosurfactant, cosolvent, acid or alkaline catalysts etc.) synthetic, the condition more complicated of synthetic microporous silica spheres, generated time is longer, perhaps also need high temperature, condition of high voltage, and the pattern of the silicon-dioxide of preparation is also irregular, and the particle size range of spheroidal particle is very wide, thereby has limited the practical application and the scale operation of silicon-dioxide.
Summary of the invention
The objective of the invention is at the problems referred to above, a kind of single method of disperseing the high-specific surface area microporous silica microballoon for preparing is provided.The microporous silica microballoon of this method preparation not only has higher specific surface area and bigger pore volume, and spheroidal particle presents monodispersed state, and size distribution is narrower.
The object of the invention adopts following technical proposals to realize: a kind of single preparation method who disperses the high-specific surface area microporous silica microballoon, and this method is used alkylamine and is made organic formwork agent and catalyzer, and its preparation process is:
1st, alkylamine under agitation is dissolved in the mixed solution of alcoholic solvent and distilled water, treat that alkylamine dissolves fully after, compound of silicate class dropwise is added in the above-mentioned solution, after reacting 1～10 hour under 5～35 ℃ of temperature, obtain white precipitation;
2nd, the prepared white precipitate filtration of step 1, washing, alcohol are washed, in vacuum chamber under 20～100 ℃ of temperature dry 2～10 hours, in stove, heat-treated 2～10 hours in 200～800 ℃ then, can obtain the high-specific surface area microporous silica microballoon;
Wherein said alkylamine is RNH
2Its R represents that carbon number is the alkyl of 12-18, described solvent is any in methyl alcohol, ethanol, propyl alcohol and the butanols, described compound of silicate class is selected any of methyl silicate, tetraethoxy, positive silicic acid propyl ester and butyl silicate for use, the volumetric molar concentration of alkylamine is 0.01～0.04M in the described solution, the volumetric molar concentration of described silicon ester is 0.05～0.4M, and the volume ratio of alcoholic solvent and distilled water is 0.5～5: 1.
Described alkylamine is selected any in amino dodecane, tetradecy lamine, cetylamine and the stearylamine for use.
The volumetric molar concentration of alkylamine is 0.016～0.03M in the described solution.
The volumetric molar concentration of described compound of silicate class is 0.1～0.25M.
The volume ratio of solvent and distilled water is 2.5～4: 1 in the described solution.
Described temperature of reaction is 10～20 ℃.
The described reaction times is 3～5 hours.
Described washing is with the distillation washing.
It is to wash with ethanol that described alcohol is washed.
Described vacuum-drying temperature is 20～100 ℃, and be 2～10 hours time of drying.
Described vacuum-drying temperature is preferably 50～80 ℃.
Described thermal treatment temp is 400～600 ℃.
Disperseing the particle diameter of high-specific surface area microporous silica microballoon with method of the present invention preparation single is 500～1500nm, and specific surface area is 600～1500m
2/ g, porosity is 40～60%, pore volume is 0.43～0.60cm
3/ g, the aperture is 1.1～1.9nm.
The synthetic method of microporous silica microballoon of the present invention is organic formwork agent and catalyzer with the alkylamine, under neutrallty condition the hydrolysis of silicon source is obtained.Amine groups possess hydrophilic property in the alkylamine forms NH in the aqueous solution
4 +Promote the hydrolysis of tetraethoxy, form the primary particle of silicic acid monomer, primary particle condenses the formation offspring then, offspring is piled up and is state of aggregation, terminal at the Si-O-Si chain is Si-OH, so on the surface of a micelle a large amount of hydroxyls is arranged, the carbochain in the alkylamine then is adsorbed on the primary particle with hydrogen bond action.Owing to during the primary particle cohesion, be not according to the close-packed mode but arrangement mussily, so in offspring, form various irregular holes.When template during not by burning-off, it has clogged the hole, and the specific surface area that records is smaller.
The particle size range of the microporous silica microballoon that the present invention synthesizes can reach 500～1500nm, is the monodisperse status of height, referring to Fig. 1.The particle diameter of microporous silica microballoon can be selected as required.
The specific surface area of synthetic mesoporous silica microballoon of the present invention reaches 600～1500m
2/ g, pore volume are 0.43～0.60cm
3/ g, porosity is 40～60%, the aperture is 1.1～1.9nm.
Specific surface area and mean pore size are all tested at 77K by nitrogen adsorption method among the present invention, and pore volume is at relative pressure P/P
0Test under=0.975 the condition, pore size distribution curve adopts the HK method to be measured by the isothermal desorption branch curved portion of nitrogen adsorption-desorption.Here, specific surface area, pore volume and mean pore size are tested with 600 ℃ of baked silicon-dioxide.
Have I type thermoisopleth on the adsorption-desorption thermoisopleth of the silicon dioxide microparticle of the inventive method preparation, this is the feature of typical poromerics, referring to Fig. 2.Simultaneously, absorption and desorption branch do not have hysteresis loop, have connective preferably between this explanation Kong Yukong.Fig. 3 is the pore size distribution curve of gained microporous silica microballoon of the present invention after 600 ℃ of roastings.
Resulting product carries out the small angle X-ray diffraction analysis, referring to Fig. 4.Have only the diffraction peak of a broad in the low angle zone, the distribution that micropore is described is random, does not have the lattice of formation rule, and particulate has unordered nanostructure, and as calculated, the pitch of holes of this nanostructure is 3.1nm.The particle diameter of silicon-dioxide, specific surface area, pore volume can be adjusted by changing concentration of reactants.The silicon-dioxide of the present invention preparation is in catalysis, absorption and separate, be widely used in the preparation of functional materialss such as transmitter, micro element and light, electricity, magnetic.
Description of drawings
Fig. 1 is the electron scanning micrograph of the embodiment of the invention 1 gained microporous silica microballoon after 600 ℃ of roastings.
Fig. 2 is the nitrogen adsorption-desorption isothermal curve of the embodiment of the invention 1 gained microporous silica microballoon after 600 ℃ of roastings.
Fig. 3 is the pore size distribution curve of the embodiment of the invention 1 gained microporous silica microballoon after 600 ℃ of roastings.
Fig. 4 is the little angle x-ray diffraction pattern of the embodiment of the invention 1 gained microporous silica microballoon after 600 ℃ of roastings.
Fig. 5 is the electron scanning micrographs of the embodiment of the invention 3 gained microporous silica microballoon after 600 ℃ of roastings.The concentration of tetraethoxy is respectively (01) 0.11M, (02) 0.14M, (03) 0.22M, (04) 0.25M.
Fig. 6 is the electron scanning micrographs of the embodiment of the invention 4 gained microporous silica microballoon after 600 ℃ of roastings.The concentration of amino dodecane is respectively (05) 0.016M, (06) 0.024M, (07) 0.03M.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
The scanning electron photomicrograph of silica dioxide granule is to adopt the JSM-5610LV type scanning electron microscope of Jeol Ltd. to measure among the embodiment.
The specific surface area of silicon-dioxide, pore volume, pore size and distribution are measured with Quantachrome ASIC-4 nitrogen adsorption device among the embodiment.
The XRD of silicon-dioxide test is to measure at the HZG41B-PC of East Germany type X-ray diffractometer among the embodiment.
In the beaker of a 300ml, the amino dodecane of 1.0 grams is dissolved under magnetic agitation in 160ml ethanol and the 100ml water blended solution, after treating that amino dodecane dissolves fully, the tetraethoxy of 10ml is dropwise joined in the above-mentioned mixing solutions, temperature of reaction is approximately 15 ℃.Stir after 4 hours,, successively clean 4 times with distilled water, ethanol with the sedimentation and filtration that obtains.The organic/inorganic complex body that obtains 80 ℃ of vacuum-drying 4 hours in vacuum drying oven, 600 ℃ of roastings 4 hours in muffle furnace then, electron scanning micrograph, nitrogen adsorption-desorption isothermal curve, pore size distribution curve and the little angle x-ray diffraction pattern of gained microporous silica microballoon after 600 ℃ of roastings seen Fig. 1, Fig. 2, Fig. 3 and Fig. 4 respectively.
In the beaker of a 300ml, the stearylamine of 1.0 grams is dissolved under magnetic agitation in 160ml ethanol and the 100ml water blended solution, after treating that stearylamine dissolves fully, the tetraethoxy of 10ml is dropwise joined in the above-mentioned mixing solutions, temperature of reaction is approximately 15 ℃.Stir after 4 hours,, successively clean 4 times with distilled water, ethanol with the sedimentation and filtration that obtains.The organic/inorganic complex body that obtains 80 ℃ of vacuum-drying 4 hours in vacuum drying oven, 400 ℃ and 600 ℃ roasting 4 hours respectively in muffle furnace then can obtain monodispersed silicon dioxide microsphere.
Checking tetraethoxy concentration is to the influence of mesoporous silica pattern, and except that tetraethoxy concentration, other condition such as amino dodecane concentration, ethanol content, temperature of reaction, thermal treatment temp and time are all identical with embodiment 1.Tetraethoxy concentration is respectively 0.11,0.14,0.22 and 0.25M.Found through experiments, when tetraethoxy concentration is 0.22 and during 0.25M, the microballoon of preparing has a spot of agglomeration, and tetraethoxy concentration is 0.11 and during 0.14M, the microballoon of preparation presents monodisperse status and the particle grain size distribution curve is narrower, sees Fig. 5.
In order to verify the influence of amino dodecane concentration to the mesoporous silica pattern, except that amino dodecane concentration, other condition such as tetraethoxy concentration, ethanol content, temperature of reaction, thermal treatment temp and time are all identical with embodiment 1.Amino dodecane concentration is respectively 0.016M, 0.024M, 0.03M.Found through experiments, when amino dodecane concentration was 0.03M, the microballoon of preparing had aggregation phenomenon, and tetraethoxy concentration is 0.016 and during 0.024M, and the microballoon of preparing presents highly monodispersed state, and the particle grain size distribution curve is narrower, sees Fig. 6.
For the influence of confirmatory reaction temperature to the silicon-dioxide pattern, except that the temperature of reaction difference, other experiment condition such as tetraethoxy concentration and amino dodecane concentration are all identical with embodiment 1.When temperature of reaction is low when being 5 ℃, it is very little to generate particle grain size, be embedded among the colloidal sol network of silicon-dioxide, and it is longer to generate the required time of precipitation, and this is because low temperature causes the speed of teos hydrolysis polycondensation too slowly.When the temperature of reaction height is 35 ℃, generate particle grain size and increase, but agglomeration is obvious, the size distribution broad, it is shorter to produce the sedimentary time, and this is because higher temperature has promoted the hydrolytie polycondensation of tetraethoxy.When temperature between 10～20 ℃, the silicon-dioxide prepared is better dispersed.
Embodiment 6
In order to verify the influence of solvent to the silicon-dioxide pattern, except that the reaction solvent difference, other experiment condition such as tetraethoxy concentration and amino dodecane concentration, temperature of reaction and time, thermal treatment temp and time are all identical with embodiment 1.Solvent is selected methyl alcohol, ethanol, propyl alcohol, butanols respectively for use, found that selecting methyl alcohol for use is that the silica granules that makes of solvent is bigger, is that the prepared particle of solvent is less and be embedded among the colloidal sol network of silicon-dioxide and select butanols for use.
Embodiment 7
In order to verify the influence of amino dodecane concentration to microporous silica microballoon specific surface area, pore volume, porosity and mean pore size, other experiment condition such as tetraethoxy concentration and ethanol content, temperature of reaction and time, thermal treatment temp and time are all identical with embodiment 1.The concentration of amino dodecane is respectively 0.016,0.024,0.030M.Adopt the structural parameter of nitrogen physisorption method measurement the specific area and micropore, gained the results are shown in following table and compares.As can be seen, increase along with amino dodecane concentration, silicon dioxide microsphere specific surface area, pore volume, porosity and mean pore size increase gradually, this be because amino dodecane as template, in the forming process of spherical, the growth that participates in microballoon forms organic/inorganic compounding ball, the concentration of amino dodecane is big more, the organic content of compound ball is just big more, and the micropore that forms after the thermal treatment is just many more, and this illustrates that also micropore derives from the space that is occupied by amino dodecane in the compound ball.
| Amino dodecane concentration (M) | BET specific surface area (m 2/g) | Porosity (%) | Pore volume (cm 3/g) | Mean pore size (nm) |
| 0.016 0.024 | 828 965 | 54.2 59.0 | 0.4377 0.5414 | 1.43 1.54 |
| 0.030 | 1223 | 61.4 | 0.5895 | 1.93 |
Embodiment 8
In order to check the influence of thermal treatment temp to microporous silica microballoon specific surface area, pore volume, porosity and mean pore size, other experiment condition such as tetraethoxy concentration and amino dodecane concentration, temperature of reaction and time are all identical with embodiment 1.The sample of preparation was handled respectively 4 hours at 80 ℃, 200 ℃, 400 ℃ and 600 ℃.Adopt the structural parameter of nitrogen physisorption method measurement the specific area and micropore, gained the results are shown in following table and compares.As can be seen, along with the raising of thermal treatment temp, specific surface area, pore volume, porosity increase gradually, and mean pore size reduces a little, this is because along with the rising of temperature, and the organic formwork agent that silicon dioxide microsphere contains is caused by the polycondensation of gradually carbonization decomposition and silicon dioxide structure.
| Maturing temperature (℃) | BET specific surface area (m 2/g) | Porosity (%) | Pore volume (cm 3/g) | Mean pore size (nm) |
| 80 200 400 600 | 513 617 986 1121 | 42.2 47.0 57.5 59.4 | 0.2702 0.3281 0.5012 0.5418 | 2.11 2.13 2.02 1.93 |
Claims (12)
1, a kind of monodisperse silica micropore microballoon, the particle diameter that it is characterized in that this microporous silica microballoon is 500～1500nm, specific surface area is 600～1500m
2/ g, voidage is 40～60%, pore volume is 0.43～0.60cm
3/ g, the aperture is 1.1～1.9nm.
2, the preparation method of the described monodisperse silica micropore of claim 1 microballoon is characterized in that this method uses alkylamine and make organic formwork agent and catalyzer, and its preparation process is:
1st, alkylamine under agitation is dissolved in the mixed solution of alcoholic solvent and distilled water, treat that alkylamine dissolves fully after, compound of silicate class dropwise is added in the above-mentioned solution, after reacting 1～10 hour under 5～35 ℃ of temperature, obtain white precipitation;
2nd, the prepared white precipitate filtration of step 1, washing, alcohol are washed, in vacuum chamber under 20～100 ℃ of temperature dry 2～10 hours, heat-treated 2～10 hours in 200～800 ℃ in stove then, can obtain particle diameter is 500～1500nm, and specific surface area is 600～1500m
2/ g, voidage is 40～60%, pore volume is 0.43～0.60cm
3/ g, the aperture is the microporous silica microballoon of 1.1～1.9nm;
Wherein said alkylamine is RNH
2Its R represents that carbon number is the alkyl of 12-18, described alcoholic solvent is any in methyl alcohol, ethanol, propyl alcohol and the butanols, described compound of silicate class is selected any of methyl silicate, tetraethoxy, positive silicic acid propyl ester and butyl silicate for use, the volumetric molar concentration of alkylamine is 0.01～0.04M in the described solution, the volumetric molar concentration of described compound of silicate class is 0.05～0.4M, and the volume ratio of alcoholic solvent and distilled water is 0.5～5: 1.
3, method as claimed in claim 2 is characterized in that described alkylamine selects any in amino dodecane, tetradecy lamine, cetylamine and the stearylamine for use.
4, method as claimed in claim 2, the volumetric molar concentration that it is characterized in that alkylamine in the described solution is 0.016～0.03M.
5, method as claimed in claim 2, the volumetric molar concentration that it is characterized in that described compound of silicate class is 0.1～0.25M.
6, method as claimed in claim 2 is characterized in that the volume ratio of alcoholic solvent and distilled water is 2.5～4: 1 in the described solution.
7, method as claimed in claim 2 is characterized in that described temperature of reaction is 10～20 ℃.
8, method as claimed in claim 2 is characterized in that the described reaction times is 3～5 hours.
9, method as claimed in claim 2 is characterized in that described washing is with the distillation washing.
10, method as claimed in claim 2 is characterized in that it is to wash with ethanol that described alcohol is washed.
11, method as claimed in claim 2 is characterized in that described vacuum-drying temperature is 50～80 ℃.
12, method as claimed in claim 2 is characterized in that described thermal treatment temp is 400～600 ℃.
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