CN102101673B

CN102101673B - Method for preparing silicon dioxide mesoporous hollow sphere material of polyhedral internal morphology

Info

Publication number: CN102101673B
Application number: CN201110080022XA
Authority: CN
Inventors: 车顺爱; 韩璐
Original assignee: Shanghai Jiaotong University
Current assignee: Shanghai Jiaotong University
Priority date: 2011-03-31
Filing date: 2011-03-31
Publication date: 2012-10-31
Anticipated expiration: 2031-03-31
Also published as: CN102101673A

Abstract

The invention discloses a method for preparing a silicon dioxide mesoporous hollow sphere material of a polyhedral internal morphology in the technical field of catalyst adsorption. The method comprises the following steps of: dissolving an anionic surfactant and a nonionic surfactant in deionized water; adding an alkaline silane eutectic structure guiding agent with an amino group and an organic siloxane; and performing filtering separation and high-temperature baking to obtain the silicon dioxide mesoporous hollow sphere material of the polyhedral internal morphology. The method has a wide application prospect in the fields of catalysis, medicament carrying and separation, and preparation of other mesoporous materials such as mesoporous carbon, mesoporous metal oxide and the like by a catalyst carrier method and a hard template method.

Description

Preparation method of polyhedral internal morphology silica mesoporous hollow sphere material

Technical Field

The invention relates to a method in the technical field of catalytic adsorption, in particular to a preparation method of a silicon dioxide mesoporous hollow sphere material with the internal appearance of a polyhedron.

Background

The mesoporous hollow spherical material not only has the advantages of large specific surface area, large pore volume, adjustable pore structure, adjustable pore diameter, surface property capable of being modified by organic groups and the like of the mesoporous material, but also has the characteristics of low density, high stability and good surface permeability, and the hollow part of the mesoporous hollow spherical material can contain a large number of object molecules, so that a microscopic 'packaging' effect and a microscopic 'packaging' effect are generated, and the mesoporous hollow spherical material has extremely wide application prospects in the fields of chemistry, biotechnology and material science, such as drug delivery, molecular recognition and separation, catalysts, gas adsorbents and the like.

Through the search of the prior art, Science 282, 1111 (1998); langmiur 21, 8180 (2005); chem. mater.18, 2733(2006) reports a method for synthesizing mesoporous hollow sphere material by hard template method through other spherical materials; science 271, 1267 (1996); science 282, 1302 (1998); j.am.chem.soc.129, 14576(2007) reports the formation of mesoporous hollow sphere material by a method of forming multilamellar vesicles; science 273, 768 (1996); nano Lett.3, 609(2003) reports a method for synthesizing mesoporous hollow sphere material by an oil-water emulsion method; chem, eur, j, 14, 5346(2008), adv, mater, 14, 1414(2002) report a method of synthesizing mesoporous hollow sphere material using ultrasound generated bubbles as a template. In the methods, the synthesized hollow sphere material has a disordered two-dimensional hexagonal p6mm or bicontinuous cubic Ia-3d structure, the trend of the pore channel and the internal crystal face cannot be effectively controlled, the internal and external appearances are spherical, and the arrangement of the crystal faces plays an important role in the performance of the material. The document chem.mater.21, 612(2009) reports a hollow sphere with hexagonal internal morphology, but its application is limited because its two-dimensional hexagonal p6mm pore structure does not have three-dimensional permeability.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a preparation method of a silicon dioxide mesoporous hollow sphere material with the polyhedral internal morphology, which uses an anionic surfactant as a template and adds a nonionic surfactant as a co-template, so that the organic/inorganic interface curvature of a micelle is adjusted to form a hollow sphere of a multilayer vesicle, and a pore channel with a cubic structure is formed by utilizing the phase transformation of the pore channel structure along with the subsequent recrystallization process, so that the silicon dioxide mesoporous hollow sphere material with the polyhedral morphology is obtained, and the interior of the hollow sphere material is a polyhedron, such as an icosahedron, a decahedron, a truncated octahedron and the like. Compared with the prior art, the method has the advantages that the synthesis steps are simple and convenient, a template for synthesizing the hollow part of the hollow sphere is not needed, such as emulsion or a polymer sphere and the like, mesoporous channels on the spherical shell of the material are highly ordered, the mesoporous channels have huge pore volume and specific surface area, the channel direction, the structural composition and the internal crystal face of the hollow sphere are controlled, and the internal and external permeability of the hollow sphere is improved.

The method is realized by the following technical scheme that firstly, an anionic surfactant and a nonionic surfactant are dissolved in deionized water, an amino-bearing alkaline silane co-structure directing agent and organosiloxane are added, and the mixture is filtered, separated and then roasted at high temperature to obtain the silicon dioxide mesoporous hollow sphere material with the internal appearance of a polyhedron.

The mol ratio of the anionic surfactant, the nonionic surfactant, the alkaline silane with amino, the organosilane and the deionized water is 1: 1.4-1.5: 2: 15: 2330.

The dissolving in deionized water refers to that: stirring and dissolving in deionized water at 50-60 deg.C.

The structural formula of the anionic surfactant is as follows:

wherein: r₁Is C_nH_2n+1，n＝8-22；R₂Is CH₃，COOH，C(CH₃)₂，C(CH₃)CH₂CH₃，CHC₆H₅，CH₂CH₂SCH₃Or (CH)₂)₆C₆H₅；R₃Is H or CH₃(ii) a A is COO, CH₂COO，CH₂CH₂COO，OSO₃，OSO₂Or OPO₃(ii) a Among them, 12-D-hydroxy-N-octadecylcarboxylic acid, 12-L-hydroxy-N-octadecylcarboxylic acid, N-octanoic acid, N-decanoic acid, dodecylcarboxylic acid, tetradecylcarboxylic acid, hexadecylcarboxylic acid, octadecylcarboxylic acid, eicosylcarboxylic acid, docosylcarboxylic acid. N-N-octanoyl-L-alanine, N-N-decanoyl-L-alanine, N-dodecanoyl-L-alanine, N-tetradecyl-L-alanine, N-hexadecyl-L-alanine, N-octadecyl-L-alanine, N-eicosyl-L-alanine, N-docosyl-L-alanine. N-N-octanoyl-D-alanine, N-N-decanoyl-D-alanine, N-dodecanoyl-D-alanine, N-tetradecyl-D-alanine, N-hexadecyl-D-alanine, N-octadecyl-D-alanine, N-eicosyl-D-alanine, N-docosyl-D-alanine. N-N-octanoyl-L-glutamic acid, N-N-decanoyl-L-glutamic acid, N-dodecanoyl-L-glutamic acid, N-tetradecyl-L-glutamic acid, N-Cetyl acyl-L-glutamic acid, N-octadecyl acyl-L-glutamic acid, N-eicosyl acyl-L-glutamic acid, N-docosyl acyl-L-glutamic acid. N-N-octanoyl-D-glutamic acid, N-N-decanoyl-D-glutamic acid, N-dodecanoyl-D-glutamic acid, N-tetradecyl-D-glutamic acid, N-hexadecyl-D-glutamic acid, N-octadecyl-D-glutamic acid, N-eicosyl-D-glutamic acid, and N-docosyl-D-glutamic acid. N-N-octanoyl-L-propylamino sulfuric acid, N-N-decanoyl-L-propylamino sulfuric acid, N-dodecanoyl-L-propylamino sulfuric acid, N-tetradecyl-L-propylamino sulfuric acid, N-hexadecyl-L-propylamino sulfuric acid, N-octadecyl-L-propylamino sulfuric acid, N-eicosyl-L-propylamino sulfuric acid, and N-docosyl-L-propylamino sulfuric acid. N-N-octanoyl-D-propylaminosulfuric acid, N-N-decanoyl-D-propylaminosulfuric acid, N-dodecanoyl-D-propylaminosulfuric acid, N-tetradecyl-D-propylaminosulfuric acid, N-hexadecyl-D-propylaminosulfuric acid, N-octadecyl-D-propylaminosulfuric acid, N-eicosyl-D-propylaminosulfuric acid and N-docosyl-D-propylaminosulfuric acid. N-N-octanoyl-L-valine, N-N-decanoyl-L-valine, N-dodecanoyl-L-valine, N-tetradecyl-L-valine, N-hexadecyl-L-valine, N-octadecanoyl-L-valine, N-eicosyl-L-valine, N-docosanoyl-L-valine. N-N-octanoyl-D-valine, N-N-decanoyl-D-valine, N-dodecanoyl-D-valine, N-tetradecyl-D-valine, N-hexadecyl-D-valine, N-octadecanoyl-D-valine, N-eicosyl-D-valine, N-docosanoyl-D-valine. N-N-octanoyl-L-isoleucine, N-N-decanoyl-L-isoleucine, N-dodecanoyl-L-isoleucine, N-tetradecanoyl-L-isoleucine, N-hexadecanoyl-L-isoleucine, N-octadecanoyl-L-isoleucine, N-eicosanoyl-L-isoleucine, N-docosanoyl-L-isoleucine, N-N-octanoyl-L-phenylalanine, N-N-decananoyl-L-phenylalanineAcid, N-dodecyl-L-phenylalanine, N-tetradecyl-L-phenylalanine, N-hexadecyl-L-phenylalanine, N-octadecyl-L-phenylalanine, N-eicosyl-L-phenylalanine, and N-docosyl-L-phenylalanine. N-N-octanoyl-D-phenylalanine, N-N-decanoyl-D-phenylalanine, N-dodecanoyl-D-phenylalanine, N-tetradecyl-D-phenylalanine, N-hexadecyl-D-phenylalanine, N-octadecyl-D-phenylalanine, N-eicosyl-D-phenylalanine, N-docosyl-D-phenylalanine. N-N-octanoyl-DL-phenylalanine, N-N-decanoyl-DL-phenylalanine, N-dodecanoyl-DL-phenylalanine, N-tetradecyl-DL-phenylalanine, N-hexadecyl-DL-phenylalanine, N-octadecyl-DL-phenylalanine, N-eicosyl-DL-phenylalanine, N-docosyl-DL-phenylalanine. N-N-octanoyl-L-methionine, N-N-decanoyl-L-methionine, N-dodecanoyl-L-methionine, N-tetradecyl-L-methionine, N-hexadecyl-L-methionine, N-octadecyl-L-methionine, N-eicosyl-L-methionine, N-docosyl-L-methionine. N-N-octanoyl-D-methionine, N-N-decanoyl-D-methionine, N-dodecanoyl-D-methionine, N-tetradecyl-D-methionine, N-hexadecyl-D-methionine, N-octadecyl-D-methionine, N-eicosyl-D-methionine, N-docosyl-D-methionine. N-N-octanoyl-L-proline, N-N-decanoyl-L-proline, N-dodecanoyl-L-proline, N-tetradecyl-L-proline, N-hexadecyl-L-proline, N-octadecyl-L-proline, N-eicosyl-L-proline and N-docosyl-L-proline. N-N-octanoyl-D-proline, N-N-decanoyl-D-proline, N-dodecanoyl-D-proline, N-tetradecyl-D-proline, N-hexadecyl-D-proline, N-octadecyl-D-proline, N-eicosyl-D-proline or N-docosyl-D-proline(ii) an amino acid.

The nonionic surfactant is Brij series surfactant, and comprises C₁₆H₃₃(OCH₂CH₂)₂OH(Brij52)，C₁₆H₃₃(OCH₂CH₂)₁₀OH(Brij56)，C₁₆H₃₃(OCH₂CH₂)₂₀OH(Brij58)，C₁₈H₃₇(OCH₂CH₂)₂OH(Brij72)，C₁₈H₃₇(OCH₂CH₂)₁₀OH(Brij76)，C₁₈H₃₇(OCH₂CH₂)₂₀OH(Brij78)。

The co-structure directing agent is alkaline silane with amino, and the structural formula is as follows: (R)₁O)₃Si-R-NH₂Wherein: r₁Is C₁-C₄Straight-chain, branched-chain alkyl radicals or hydrogen atoms, R being C₁-C₄Such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or 4-aminobutyltrimethoxysilane, etc.

The structural formula of the organosilane is as follows: (R)₁O)_m-Si-R, wherein: m is an integer of 2 to 4, R₁Is C₁-C₄A straight-chain, branched-chain alkyl group of (A) or a hydrogen atom, R is C₁-C₄Such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydimethylsilane, trimethoxymethylsilane or dimethoxydiisopropylsilane.

The high-temperature roasting refers to: the prepared material was charged into a crucible, heated to 550 ℃ over 6 hours in a muffle furnace and held for 6 hours to remove surfactant molecules for forming mesoporous channels.

The polyhedron is a closed space formed by n planes, wherein n is more than or equal to 4, such as a regular icosahedron, a regular decahedron or a regular octahedron with vertexes removed.

The invention uses a mixed template of anionic surfactant and nonionic surfactant and a co-structure directing agent to synthesize a silicon dioxide mesoporous hollow sphere material with polyhedral morphology for the first time, wherein the interior of the material is a polyhedron such as an icosahedron, a decahedron, a regular octahedron with a cut-off vertex and the like, the size of the material is 600 nm-2 mu m, the material has a cubic system bicontinuous diamond Pn-3m structure, and the inner surface is a {111} or {100} crystal face; the mesoporous material has a pore diameter of 4-7 nm and a pore volume of about 1.0-1.3 cm³g^-1The specific surface area is about 500 to 800m²g^-1(ii) a The invention has wide application prospect in the fields of catalysis, drug loading and separation, catalyst carrier and hard template method for preparing other mesoporous materials such as mesoporous carbon, mesoporous metal oxide and the like.

Drawings

Fig. 1 is a scanning electron microscope photograph of the hollow mesoporous silica sphere material having the polyhedral internal morphology obtained in example 1.

Fig. 2 is a scanning electron microscope photograph of a section of the hollow mesoporous silica sphere material with polyhedral internal morphology cut by an argon ion beam obtained in example 1.

Fig. 3 is a transmission electron microscope photograph of the hollow mesoporous silica sphere material with polyhedral internal morphology obtained in example 2.

Fig. 4 is a transmission electron microscope photograph of the hollow mesoporous silica sphere material with polyhedral internal morphology obtained in example 4.

Detailed Description

The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.

Example 1

0.207g (0.5mmol) of C was weighed₁₈GluA and 0.5g (0.72mmol) Brij-56 were dispersed in 21g (1.167mol) deionized water, stirred at 50C, and to this solution 0.179g (1mmol) APS and 1.56g (7.5mmol) TEOS were added simultaneously. After 20min, stirring was stopped and the aging in the water bath was continued for 2 days at this temperature. The resulting white powder was isolated by filtration, dried overnight at 60 ℃ and calcined at 550 ℃ for 6h to remove the surfactant. The diamond has the size of 600 nm-2 mu m, has a cubic crystal system bicontinuous diamond Pn-3m structure, and has an inner surface of a {111} or a {100} crystal face; the mesoporous material has a pore diameter of 5.3nm and a pore volume of about 1.2cm³g^-1A specific surface area of about 689m²g^-1. FIG. 1 is a scanning electron microscope photograph of the material, which shows that the material is spherical and has the internal shape of polyhedron; FIG. 2 is a transmission electron micrograph of the mesoporous material, which shows that the material has regular internal morphology and uniformly distributed mesopores on the wall.

Example 2

0.207g (0.5mmol) of C was weighed₁₈GluA and 0.5g (0.69mmol) Brij-76 were dispersed in 21g (1.167mol) deionized water, stirred at 50 deg.C, and to this solution 0.179g (1mmol) APS and 1.56g (7.5mmol) TEOS were added simultaneously. After 20min, stirring was stopped and the aging in the water bath was continued for 2 days at this temperature. The resulting white powder was isolated by filtration, dried overnight at 60 ℃ and calcined at 550 ℃ for 6h to remove the surfactant. The diamond has the size of 600 nm-2 mu m, has a cubic crystal system bicontinuous diamond Pn-3m structure, and has an inner surface of a {111} or a {100} crystal face; the mesoporous material has a pore diameter of 5.9nm and a pore volume of about 1.3cm³g^-1The specific surface area is about 714m²g^-1. FIG. 3 is a transmission electron microscope photograph of the material, from which it can be seen that the material has a polyhedral internal morphology and mesopores are uniformly distributed on the wall.

Example 3

0.207g (0.5mmol) of C was weighed₁₈GluA and 0.5g (0.72mmol) Brij-56 were dispersed in 21g (1.167mol) deionized water, stirred at 60 ℃ and to this solution were added 0.179g (1mmol) APS and 1.56g (7.5mmol) TEOS simultaneously. After 20min, stirring was stopped and the aging in the water bath was continued for 2 days at this temperature. The resulting white powder was isolated by filtration, dried overnight at 60 ℃ and calcined at 550 ℃ for 6h to remove the surfactant. The diamond has a size of 1-2 μm, has a cubic bicontinuous diamond Pn-3m structure, and has {111} or {100} crystal face as an inner surface; the mesoporous material has a pore diameter of 5.5nm and a pore volume of about 1.3cm³g^-1A specific surface area of about 694m²g^-1. FIG. 4 is a transmission electron micrograph of the material, from which it can be seen that the material has a thinner spherical shell and a polyhedral internal morphology, and mesopores are uniformly distributed on the wall.

Claims

1. A preparation method of a polyhedral internal morphology silica mesoporous hollow sphere material is characterized in that an anionic surfactant and a nonionic surfactant are dissolved in deionized water, an amino-containing alkaline silane co-structure directing agent and organosiloxane are added, and the mixture is filtered, separated and then roasted at a high temperature to obtain the polyhedral internal morphology silica mesoporous hollow sphere material; wherein,

the mol ratio of the anionic surfactant, the nonionic surfactant, the alkaline silane with amino, the organosilane and the deionized water is 1: 1.4-1.5: 2: 15: 2330;

2. The method for preparing the polyhedral internal morphology silica mesoporous hollow sphere material according to claim 1 or 2, wherein the structural formula of the anionic surfactant is as follows:

R₁-AH or

Wherein: r₁Is C_nH_2n+1N = natural constants of 8-22; r₂Is CH₃、COOH、C(CH₃)₂、C(CH₃)CH₂CH₃、CHC₆H₅、CH₂ CH₂S CH₃Or (CH)₂)₆C₆H₅，R₃Is H or CH₃A is COO or CH₂COO、CH₂CH₂COO、OSO₃、OSO₂Or OPO₃。

3. The method for preparing the polyhedral internal morphology silica mesoporous hollow sphere material according to claim 1, wherein the nonionic surfactant is C₁₆H₃₃(OCH₂CH₂)₂OH、C₁₆H₃₃(OCH₂CH₂)₁₀OH，C₁₆H₃₃(OCH₂CH₂)₂₀OH、C₁₈H₃₇(OCH₂CH₂)₂OH、C₁₈H₃₇(OCH₂CH₂)₁₀OH or C₁₈H₃₇(OCH₂CH₂)₂₀OH。

4. The method for preparing the polyhedral internal morphology silica mesoporous hollow sphere material according to claim 1, wherein the co-structure directing agent is basic silane with amino groups, and the structural formula of the co-structure directing agent is as follows: (R)₁O)₃Si——R-NH₂Wherein: r₁Is C₁-C₄Straight-chain, branched-chain alkyl radicals or hydrogen atoms, R being C₁-C₄Straight-chain or branched chain alkyl of (1).

5. The method for preparing the polyhedral internal morphology silica mesoporous hollow sphere material according to claim 1 or 4, wherein the co-structure directing agent is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or 4-aminobutyltrimethoxysilane.

6. The preparation method of the polyhedral internal morphology silica mesoporous hollow sphere material according to claim 1, wherein the structural formula of the organosilane is as follows: (R)₁O)_m-Si-R, wherein: integer m =2-4, R₁Is C₁-C₄A chain, branched chain alkyl group or a hydrogen atom of (A), R is C₁-C₄Straight-chain or branched chain alkyl of (1).

7. The method for preparing the polyhedral internal morphology silica mesoporous hollow sphere material according to claim 1 or 4, wherein the organosilane is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydimethylsilane, trimethoxymethylsilane, or dimethoxydiisopropylsilane.

8. The preparation method of the polyhedral internal morphology silica mesoporous hollow sphere material according to claim 1, wherein the high temperature roasting is: the prepared material was charged into a crucible, heated to 550 ℃ over 6 hours in a muffle furnace and held for 6 hours to remove surfactant molecules for forming mesoporous channels.