CN104692399A - Highly-ordered radial spherical crinkled mesoporous silicon dioxide material and preparation method thereof - Google Patents
Highly-ordered radial spherical crinkled mesoporous silicon dioxide material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a highly-ordered radial spherical crinkled mesoporous silicon dioxide material and a preparation method thereof. The preparation method comprises the following steps: hydrolyzing a silicon source TEOS (tetraethyl orthosilicate) at 35 DEG C by using ethanol, cyclohexane and water as solvents, CTAB (cetyltrimethylammonium bromide) as a surfactant and PVP (polyvinyl pyrrolidone) as a coating agent in the solvothermal reaction process, polycondensing, and calcining the formed mixture to obtain the spherical wrinkled mesoporous SiO2 nano material containing radially-highly-ordered radial pore canal structure. The spherical mesoporous SiO2 prepared by the preparation method has the advantages of controllable particle size and ordered and controllable pore canal structure. The particle size is 240-540nm, the specific area is 490-634 m<2>/g, and the pore size is about 7.4-10.1nm. The invention provides a new idea for preparing the highly-ordered radial pore canal spherical wrinkled mesoporous SiO2 nano material which radiates from the center to the sphere surface.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly radial spherical tool wrinkle Metaporous silicon dioxide material of a kind of high-sequential and preparation method thereof.
Background technology
Since MCM-41 series mesoporous silicon oxide has successfully been prepared by Mobile company, mesoporous material has been widely used in carrier, absorption, has been separated and the field such as catalysis because of its unique homogeneous pore passage structure, larger specific surface area and pore volume, controlled aperture and the surface tissue that is easy to modify.But traditional unordered mesoporous silica spheres faces a series of difficulties such as adsorptive capacity is less, catalytic activity is low, therefore, prepare the earth silicon material with ordered mesoporous pore canals structure and have important researching value and potential application prospect.At present, pattern, structure and aperture are controlled becomes one of challenge preparing silica nano material, especially prepares the study hotspot that the earth silicon material containing radial radial ordered mesoporous pore canals structure becomes Many researchers.Such as, Moon etc. for template, have successfully prepared the mesoporous silica spheres (Moon D, Lee J, Langmuir, 2012,28,12341-12347) of orderly radioactivity pore distribution with bicontinuous microemulsions system.Peng etc. utilize CTAB-1,3, the microemulsion system of 5-Three methyl Benzene-alcohol-water composition does template, TEOS is as silicon source, prepare the silica spheres of nucleocapsid structure, there is the worm meso-porous of local Hexagonal array in its core center, shell is distributed with radial ordered mesoporous pore canals, but its aperture less (3-7.3nm).The SiO of this nucleocapsid structure
2ball has higher specific surface area (745-912m
2/ g) and pore volume (0.98-1.34cm
3/ g), result proves that this earth silicon material that there is secondary pore passage structure is expected to be applied to the field such as biocatalysis, absorption (Peng J, Liu J, Liu J, J.Mater.Chem.A, 2014,2,8118-8125).
Chinese patent CN102849750A discloses a kind of radial duct mesopore silicon oxide and preparation method thereof.Its feature is, product S iO
2material is spherical morphology, smooth surface, and particle diameter is 700-1000nm, and duct is the radial duct from center to fringe radiation, there is multistage aperture, and pore size heterogeneity, there is higher specific surface area and pore volume.Concrete preparation method is at room temperature, using water-ethanol-ether as cosolvent, cetyl trimethylammonium bromide (CTAB) or palmityl trimethyl ammonium chloride (CTAC) are template, ammoniacal liquor is catalyzer, promotes silicon source (TEOS) hydrolytie polycondensation and obtains.A certain proportion of silane coupling agent (N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane) must be added in synthetic system of the present invention, strict to the material composition requirement of reaction system.
Chinese patent CN104129791A discloses a kind of containing radial mesopore orbit structure spherical silicon dioxide material and preparation method thereof.It is characterized in that, this invention utilizes CTAB, and the oil-in-water microemulsion system that PVP-ethanol-hexanaphthene-water is formed does template, and silicon source TEOS is in micro emulsion drop ball surface hydrolysis, polycondensation, and self assembly is containing the spherical mesoporous SiO of radial mesopore orbit structure
2nano material.Described mesoporous silicon oxide is monodisperse spherical, and particle size range is 350-650nm, and specific surface area is 975-1114m
2/ g, aperture is 3.9-4.1nm, the edge of mesopore orbit from the center radiation of ball to ball.But mesoscopic structure is stablized, particle diameter is less than 300nm, aperture is greater than 7nm and preparation method containing the tool wrinkle silica nanosphere of the radial radial radiation mesopore orbit of high-sequential did not also report.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of high-sequential radial tool wrinkle mesoporous silica nanospheres.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for the radial spherical tool wrinkle mesopore silicon dioxide nano material of high-sequential, comprises the following steps:
(1) tetraethoxy (TEOS) is dispersed in cyclohexane solution, TEOS: hexanaphthene=(0.2-1.0) g:(2-5) mL;
(2) cetyl trimethylammonium bromide (CTAB) and polyvinylpyrrolidone (PVP) being joined volume fraction is in the ethanolic soln of 37.5%, described mass ratio CTAB:PVP=(0.05-1.20) g:(0-1.20) g, CTAB: ethanolic soln=(0.05-1.20) g:40mL, stirring and dissolving;
(3) under the condition constantly stirred, joined by the solution that step (1) obtains in the solution of step (2) gained, Keep agitation forms mixing solutions;
(4) mixing solutions obtained to step (3) adds the ammoniacal liquor that mass concentration is 25%-28%, make the volume ratio of described mixing solutions and ammoniacal liquor for (42-46): 0.5, continue stirring reaction, solution environmental is made to become weakly alkaline, accelerate the hydrolysis rate of silicon source TEOS, Reaction time shorten;
(5) mixing solutions that step (4) obtains is transferred in the teflon-lined autoclave of 100ml;
(6) autoclave in step (5) is tightened put into baking oven, after solvent heat treatment, autoclave is naturally cooled to room temperature;
(7) by the throw out centrifugation in step (6), cleaning-drying;
(8) throw out calcining step (7) obtained obtains containing the orderly radial duct of radial height spherical tool wrinkle mesopore silicon dioxide nano material.
Described step (1), (2) are carried out under room temperature (25 DEG C).
Described step (3) Keep agitation 1.5-2.5h (preferred 2h) forms mixing solutions.
Described step (4) continues stirring reaction (4-24) h at (25-100) DEG C, and preferably 35 DEG C are continued stirring reaction 4h.
Described step (6) at (80-140) DEG C solvent thermal reaction (12-18) h, preferably 100 DEG C of solvent thermal reaction 12h.
Described step (7) uses distilled water cleaning 2-5 time (preferably 3 times), and 55-65 DEG C (preferably 60 DEG C) dry 20-30h (preferred 24h).
Described step (8) is calcining (4-6) h at (450-600) DEG C, preferably calcines 6h under 550 DEG C of conditions.
Earth silicon material prepared by aforesaid method, its sight order that is situated between is extended to whole particle, and overall pattern is monodisperse spherical granule-morphology, and spherome surface is pleated structure, and is distributed with radioactivity duct.Particle size range is 240-540nm, and specific surface area is 490-634m
2/ g, mean pore size is 7.4-10.1nm.Mesoporous arrangement mode is the radiate from center perpendicular to surface, and mesopore orbit is from the marginal surface being radially aligned to ball of ball.
Beneficial effect of the present invention:
The preparation method of high-sequential provided by the invention radial spherical tool wrinkle mesopore silicon dioxide nano material, obtains required containing the orderly radial duct of radial height spherical tool wrinkle mesopore silicon dioxide nano material.Adopt the SiO that method of the present invention is obtained
2nano material is that size is controlled, pore passage structure long-range order, the surperficial spherical mesoporous SiO for different pleated structure
2, particle size range is 240-540nm, and specific surface area is 490-634m
2/ g, mean pore size is 7.4-10.1nm.Wherein high molecular polymer PVP is as coating agent, and its space steric effect stops the growth of Nucleating particles, reduces the probability of particle growth, thus reaches the effect of grain-size size, prevent the reunion of nanoparticle.
Traditional small-bore SiO
2there is guest molecule and cannot enter or the restriction that blocks easily occurs in duct in nano material, thus greatly limit its application at catalytic field.This spherical mesoporous SiO prepared by the present invention
2the radioactivity mesopore orbit of the wide aperture that material has and long-range order makes mesoporous SiO
2material shows the unrivaled superiority of other porous materials and application potential in fields such as absorption, separation, has that selectivity is high, adsorptive capacity is large, adsorb the features such as fast.Secondly, have broad application prospects in catalyst research field, show as advantageously in the abundant contact catalysis avtive spot of catalyzer, improve reaction yield, also can realize the recovery of avtive spot, thus reach the object of recycle.In addition, this high-sequential radioactivity duct can better controlled modification functional group to mesoporous SiO
2the modification of material, ensure that modification group being more evenly distributed in whole material.
Accompanying drawing explanation
The SiO of Fig. 1 prepared by different PVP consumption
2the field emission scanning electron microscope (FESEM) of nano material, wherein Fig. 1 a is the FESEM figure of embodiment 1, Fig. 1 b is that the FESEM of embodiment 2 schemes, and Fig. 1 c is the FESEM figure of embodiment 3, Fig. 1 d is that the FESEM of embodiment 4 schemes;
The SiO of Fig. 2 prepared by embodiment 2 and embodiment 3
2high-resolution-ration transmission electric-lens (HRTEM) figure of nano material, wherein Fig. 2 a is the HRTEM figure of embodiment 2, Fig. 2 b is that the HRTEM of embodiment 3 schemes;
The SiO of Fig. 3 prepared by embodiment 2 and embodiment 4
2little angle x-ray diffraction pattern (SAXRD) of nano material, wherein Fig. 3 a is the SAXRD figure of embodiment 2, Fig. 3 b is that the SAXRD of embodiment 4 schemes;
The SiO of Fig. 4 prepared by embodiment 1 and embodiment 3
2the N of nano material
2adsorption-desorption isothermal curve, Fig. 4 a is the N of embodiment 1
2adsorption-desorption isothermal curve, Fig. 4 b is the N of embodiment 3
2adsorption-desorption isothermal curve.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described.
Embodiment 1
(1), under room temperature, the TEOS of 0.5g is dispersed in 4mL cyclohexane solution;
(2) under room temperature, the CTAB of 0.08g is joined in 25mL distilled water and 15mL alcohol mixed solution, constantly stir until form clear solution;
(3) under the condition constantly stirred, the solution that step (1) obtains is joined rapidly by the clear solution of step (2) gained, carry out stirring 2h and form mixing solutions;
(4) mixing solutions obtained to step (3) adds 0.5mL ammoniacal liquor, continues stirring reaction 4h at 35 DEG C;
(5) mixing solutions that step (4) obtains is transferred in the teflon-lined autoclave of 100mL;
(6) autoclave in step (5) is tightened put into baking oven, after 100 DEG C of solvent thermal reaction 12h, autoclave is naturally cooled to room temperature;
(7) by the throw out centrifugation in step (6), use distilled water to clean 3 times, in air dry oven, dry 24h for 60 DEG C and obtain product;
(8) product that step (7) obtains is placed in box-type calcining oven, calcines 6h at 550 DEG C, obtain SiO
2powder.
The scanning electron microscope of product as shown in Figure 1a, product S iO
2pattern spherical in shape, median size is 540nm, and spherome surface is pleated structure, can see that radioactivity is mesoporous, but radioactivity mesoporous pore size is not of uniform size.The N of product
2adsorption-desorption isothermal curve 4a shows, and the specific surface area of Mesoporous Spheres is 490m
2/ g.
Embodiment 2
(1), under room temperature, the TEOS of 0.5g is dispersed in 4mL cyclohexane solution;
(2) PVP of CTAB and 0.2g of 0.08g is joined in 25mL distilled water and 15mL alcohol mixed solution, constantly stir until form clear solution;
(3) under the condition constantly stirred, the solution that step (1) obtains is joined rapidly by the clear solution of step (2) gained, carry out stirring 2h and form mixing solutions;
(4) mixing solutions obtained to step (3) adds 0.5mL ammoniacal liquor, continues stirring reaction 4h at 35 DEG C;
(5) mixing solutions that step (4) obtains is transferred in the teflon-lined autoclave of 100mL;
(6) autoclave in step (5) is tightened put into baking oven, after 100 DEG C of solvent thermal reaction 12h, autoclave is naturally cooled to room temperature;
(7) by the throw out centrifugation in step (6), use distilled water to clean 3 times, in air dry oven, dry 24h for 60 DEG C and obtain product;
(8) product that step (7) obtains is placed in box-type calcining oven, calcines 6h at 550 DEG C, obtain SiO
2powder.
As shown in Figure 1 b, the particle diameter of Mesoporous Spheres is about 480nm to the scanning electron microscope analysis of product, favorable dispersity.Spherome surface is sparse pleated structure, still there is radioactivity mesoporous.Transmission electron microscope 2a can find out the radioactivity pore passage structure of long-range order.The mesopore orbit that the little angle x-ray diffraction pattern 3a of product proves this mesoporous material in order and radially arranged evenly.
Embodiment 3
(1), under room temperature, the TEOS of 0.5g is dispersed in 4mL cyclohexane solution;
(2) PVP of CTAB and 0.4g of 0.08g is joined in 25mL distilled water and 15mL alcohol mixed solution, constantly stir until form clear solution;
(3) under the condition constantly stirred, the solution that step (1) obtains is joined rapidly by the clear solution of step (2) gained, carry out stirring 2h and form mixing solutions;
(4) mixing solutions obtained to step (3) adds 0.5mL ammoniacal liquor, continues stirring reaction 4h at 35 DEG C;
(5) mixing solutions that step (4) obtains is transferred in the teflon-lined autoclave of 100mL;
(6) autoclave in step (5) is tightened put into baking oven, after 100 DEG C of solvent thermal reaction 12h, autoclave is naturally cooled to room temperature;
(7) by the throw out centrifugation in step (6), use distilled water to clean 3 times, in air dry oven, dry 24h for 60 DEG C and obtain product;
(8) product that step (7) obtains is placed in box-type calcining oven, calcines 6h at 550 DEG C, obtain SiO
2powder.
Scanning electron microscopic observation result as illustrated in figure 1 c, spherical mesoporous SiO
2the diameter of powder is about 360nm, and ball surface portions exists the rough pleats structure containing radioactivity hole, part sphere smooth surface, favorable dispersity.The radioactivity mesopore orbit of the high-sequential extending to spherome surface from center obviously can be seen from transmission electron microscope 2b.The specific surface area of Mesoporous Spheres is 629m
2/ g, its N
2adsorption-desorption isothermal curve is as Fig. 4 b.
Embodiment 4
(1), under room temperature, the TEOS of 0.5g is dispersed in 4mL cyclohexane solution;
(2) PVP of CTAB and 0.8g of 0.08g is joined in 25mL distilled water and 15mL alcohol mixed solution, constantly stir until form clear solution;
(3) under the condition constantly stirred, the solution that step (1) obtains is joined rapidly by the clear solution of step (2) gained, carry out stirring 2h and form mixing solutions;
(4) mixing solutions obtained to step (3) adds 0.5mL ammoniacal liquor, continues stirring reaction 4h at 35 DEG C;
(5) mixing solutions that step (4) obtains is transferred in the teflon-lined autoclave of 100mL;
(6) autoclave in step (5) is tightened put into baking oven, after 100 DEG C of solvent thermal reaction 12h, autoclave is naturally cooled to room temperature;
(7) by the throw out centrifugation in step (6), use distilled water to clean 3 times, in air dry oven, dry 24h for 60 DEG C and obtain product;
(8) product that step (7) obtains is placed in box-type calcining oven, calcines 6h at 550 DEG C, obtain SiO
2powder.
Scanning electron microscope 1d shows, and spherical mesoporous ball size is homogeneous, and particle diameter is about 240nm, favorable dispersity, and spherome surface ubiquity radioactivity duct, closely knit pleated structure forms cellular spheroid.The little angle x-ray diffraction pattern 3b of product proves that this Mesoporous Spheres exists orderly mesopore orbit and radially arranged evenly.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (6)
1. a preparation method for the radial spherical tool wrinkle Metaporous silicon dioxide material of high-sequential, is characterized in that, comprise the following steps:
(1) tetraethoxy is dispersed in cyclohexane solution, in every 2-5mL hexanaphthene, adds 0.2-1.0g TEOS;
(2) cetyl trimethylammonium bromide and polyvinylpyrrolidone being joined volume fraction is in the ethanolic soln of 37.5%, the mass ratio of described CTAB and PVP is 0.05-1.20:0-1.20, described in every 40mL 37.5% ethanolic soln in add 0.05-1.20g CTAB, stirring and dissolving;
(3) under the condition constantly stirred, joined by the solution that step (1) obtains in the solution of step (2) gained, Keep agitation 1.5-2.5h forms mixing solutions;
(4) mixing solutions obtained to step (3) adds the ammoniacal liquor that mass concentration is 25%-28%, makes the volume ratio of described mixing solutions and ammoniacal liquor be 42-46:0.5, continues stirring reaction 4-24h at 25-100 DEG C;
(5) mixing solutions that step (4) obtains is transferred in teflon-lined autoclave;
(6) autoclave in step (5) is tightened put into baking oven, after the temperature range internal solvent thermal response 12-18h of 80-140 DEG C, autoclave is naturally cooled to room temperature;
(7) by the throw out centrifugation in step (6), washing, drying, calcining obtain containing the orderly radial duct of radial height spherical tool wrinkle mesopore silicon dioxide nano material.
2. preparation method according to claim 1, is characterized in that: described step (6) is at 100 DEG C of solvent thermal reaction 12h.
3. preparation method according to claim 2, is characterized in that: described step (1) and step (2) are at room temperature carried out.
4. preparation method according to claim 3, is characterized in that: described step (3) Keep agitation 2h forms mixing solutions; Described step (4), continues stirring reaction 4h at 35 DEG C.
5. preparation method according to claim 4, is characterized in that: in described step (7), uses distilled water to clean 3 times, dries 24h, under 550 DEG C of conditions, calcine 6h at 60 DEG C.
6., according to earth silicon material prepared by the arbitrary described preparation method of claim 1-5, it is characterized in that: the particle size range of described earth silicon material is 240-540nm, and specific surface area is 490-634m
2/ g, mean pore size is 7.4-10.1nm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030095908A1 (en) * | 1999-11-09 | 2003-05-22 | Board Of Trustees Operating Michigan State University | Ultra-stable lamellar mesoporous silica compositions and process for the preparation thereof |
| KR101308764B1 (en) * | 2011-08-24 | 2013-09-17 | 서울대학교산학협력단 | Silica nano particle, method for producing the same, complex and method for producing the same |
| CN103771427A (en) * | 2014-01-28 | 2014-05-07 | 齐鲁工业大学 | Method for preparing sphere-like mesoporous silica |
| CN104129791A (en) * | 2014-08-20 | 2014-11-05 | 齐鲁工业大学 | Spherical SiO2 material with radial mesoporous structure and preparation method of spherical SiO2 material |
-
2015
- 2015-02-09 CN CN201510067638.1A patent/CN104692399B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030095908A1 (en) * | 1999-11-09 | 2003-05-22 | Board Of Trustees Operating Michigan State University | Ultra-stable lamellar mesoporous silica compositions and process for the preparation thereof |
| KR101308764B1 (en) * | 2011-08-24 | 2013-09-17 | 서울대학교산학협력단 | Silica nano particle, method for producing the same, complex and method for producing the same |
| CN103771427A (en) * | 2014-01-28 | 2014-05-07 | 齐鲁工业大学 | Method for preparing sphere-like mesoporous silica |
| CN104129791A (en) * | 2014-08-20 | 2014-11-05 | 齐鲁工业大学 | Spherical SiO2 material with radial mesoporous structure and preparation method of spherical SiO2 material |
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