CN102101673A - Method for preparing silicon dioxide mesoporous hollow sphere material of polyhedral internal morphology - Google Patents

Abstract

A method for preparing a polyhedral internal morphology silica mesoporous hollow sphere material in the field of catalyst adsorption technology. First, anionic surfactants and nonionic surfactants are dissolved in deionized water, and alkaline silanes with amine groups are added. The structure directing agent and organosiloxane are separated by filtration and then calcined at a high temperature to obtain a hollow silica mesoporous sphere material with polyhedral internal morphology. The invention has wide application prospects in the fields of catalysis, drug loading and separation, catalyst carrier and preparation of other mesoporous materials such as mesoporous carbon and mesoporous metal oxide by 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 method for preparing a polyhedral internal shape silica mesoporous hollow sphere material.

Background technique

Mesoporous hollow spherical materials not only have the advantages of large specific surface area, large pore volume, adjustable pore structure, adjustable pore size, and surface properties that can be modified by organic groups, but also have low density and high stability. Its hollow part can accommodate a large number of guest molecules, resulting in microscopic "encapsulation" and "wrapping" effects, making it have extremely wide application prospects in the fields of chemistry, biotechnology, and material science, such as Used as drug delivery, molecular recognition and separation, catalyst, gas adsorbent, etc.

After searching the prior art, it was found that Science 282, 1111 (1998); Langmiur 21, 8180 (2005); Chem.Mater.18, 2733 (2006) reported the synthesis of mesoporous hollow spheres by other spherical materials as hard templates Methods of materials; Science 271, 1267 (1996); Science 282, 1302 (1998); J.Am.Chem.Soc. 129, 14576 (2007) reported the formation of mesoporous hollow spheres by forming multilamellar vesicles Materials; Science 273,768(1996); Nano Lett.3,609(2003) has reported the method for synthesizing mesoporous hollow sphere material with oil-water emulsion method; Chem.Eur.J.14,5346(2008), Adv .Mater.14, 1414 (2002) reported a method for synthesizing mesoporous hollow spheres using ultrasonically generated bubbles as a template. In these methods, the synthesized hollow sphere material structure is disordered, two-dimensional hexagonal p6mm or bicontinuous cubic Ia-3d structure, which cannot effectively control the direction of the channel and the internal crystal plane, and the internal and external morphology is spherical, while The arrangement of crystal planes plays an important role in the properties of materials. Literature Chem.Mater.21, 612 (2009) reported a hollow sphere with a hexagonal internal morphology, but its application was limited due to its two-dimensional hexagonal p6mm channel structure without three-dimensional permeability.

Contents of the invention

The present invention aims at the above-mentioned deficiencies existing in the prior art, and provides a method for preparing a polyhedral internal shape silica mesoporous hollow sphere material, by using anionic surfactant as a template and adding a nonionic surfactant as a co-template, In this way, the curvature of the organic/inorganic interface of micelles is adjusted to form a hollow sphere of multilayered vesicles, and with the subsequent recrystallization process, the phase transition of the channel structure is used to form pores with a cubic structure, thereby obtaining a polyhedron The shape of the silica mesoporous hollow sphere material has a polyhedron inside, such as an icosahedron, a decahedron, and a regular octahedron with its vertices cut off. Compared with the previous technology, the present invention not only has simple synthesis steps, but also does not require templates such as emulsions or polymer spheres for the synthesis of hollow parts of hollow spheres, and the mesoporous channels on the spherical shell of the material are highly ordered and have a huge pore volume and specific surface area, control the direction and structure composition of the hollow sphere and the internal crystal plane, and improve the internal and external permeability of the hollow sphere.

The present invention is achieved through the following technical proposals. In the present invention, the anionic surfactant and the nonionic surfactant are dissolved in deionized water, and an alkaline silane co-structure directing agent with an amine group and an organosiloxane are added, and filtered After the separation, high-temperature roasting is carried out to obtain a polyhedral inner shape silica mesoporous hollow sphere material.

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

Said dissolving in deionized water means: stirring and dissolving in deionized water under the environment of 50-60°C.

Described anionic surfactant, its structural formula is as follows:

Among them: R ₁ is C _n H _2n+1 , n=8-22; R ₂ is CH ₃ , COOH, C(CH ₃ ) ₂ , C(CH ₃ )CH ₂ CH ₃ , CHC ₆ H ₅ , CH ₂ CH ₂ SCH ₃ or (CH ₂ ) ₆ C ₆ H ₅ ; R ₃ is H or CH ₃ ; A is COO, CH ₂ COO, CH ₂ CH ₂ COO, OSO ₃ , OSO ₂ or OPO ₃ ; where there are 12- D-Hydroxy-N-octadecylcarboxylic acid, 12-L-hydroxy-N-octadecylcarboxylic acid, n-octanoic acid, n-decanoic acid, dodecylcarboxylic acid, tetradecylcarboxylic acid, Hexaalkyl carboxylic acid, octadecyl carboxylic acid, eicosyl carboxylic acid, behenyl carboxylic acid. N-octyl acyl-L-alanine, N-decyl acyl-L-alanine, N-dodecyl acyl-L-alanine, N-tetradecyl Alkyl-L-alanine, N-hexadecyl-L-alanine, N-octadecyl-L-alanine, N-eicosyl- L-alanine, N-behenyl-L-alanine. N-octyl acyl-D-alanine, N-decyl acyl-D-alanine, N-dodecyl acyl-D-alanine, N-tetradecyl Alkyl acyl-D-alanine, N-hexadecyl-D-alanine, N-octadecyl-D-alanine, N-eicosyl- D-alanine, N-docosyl-D-alanine. N-octyl acyl-L-glutamic acid, N-decyl acyl-L-glutamic acid, N-dodecyl acyl-L-glutamic acid, N-tetradecyl Alkyl acyl-L-glutamic acid, N-hexadecyl acyl-L-glutamic acid, N-octadecyl acyl-L-glutamic acid, N-eicosyl acyl- L-glutamic acid, N-behenyl-L-glutamic acid. N-octyl acyl-D-glutamic acid, N-decyl acyl-D-glutamic acid, N-dodecyl acyl-D-glutamic acid, N-tetradecyl Alkyl acyl-D-glutamic acid, N-hexadecyl acyl-D-glutamic acid, N-octadecyl acyl-D-glutamic acid, N-eicosyl acyl- D-glutamic acid, N-docosyl-D-glutamic acid. N-octyl acyl-L-propylaminosulfuric acid, N-decanealkylyl-L-propylaminosulfuric acid, N-dodecylaminoyl-L-propylaminosulfuric acid, N-tetradecylaminosulfuric acid Alkyl acyl-L-propyl aminosulfuric acid, N-hexadecyl-L-propyl aminosulfuric acid, N-octadecyl-L-propyl aminosulfuric acid, N-eicosyl acyl amino-sulfuric acid- L-Alanine Sulfuric Acid, N-Docosyl-L-Alanine Sulfuric Acid. N-octyl acyl-D-propylaminosulfuric acid, N-decylalkylamino-D-propylaminosulfuric acid, N-dodecylaminoyl-D-propylaminosulfuric acid, N-tetradecylaminosulfuric acid Alkyl acyl-D-propylaminosulfuric acid, N-hexadecyl-D-propylaminosulfuric acid, N-octadecylamino-D-propylaminosulfuric acid, N-eicosylaminoyl- D-Alanine Sulfuric Acid, N-Docosyl-D-Alanine Sulfuric Acid. N-octyl acyl-L-valine, N-decyl acyl-L-valine, N-dodecyl acyl-L-valine, N-tetradecyl Alkyl acyl-L-valine, N-hexadecyl-L-valine, N-octadecyl-L-valine, N-eicosyl- L-valine, N-behenyl-L-valine. N-octyl acyl-D-valine, N-decyl acyl-D-valine, N-dodecyl acyl-D-valine, N-tetradecyl Alkyl acyl-D-valine, N-hexadecyl-D-valine, N-octadecyl-D-valine, N-eicosyl- D-valine, N-behenyl-D-valine. N-octyl acyl-L-isoleucine, N-decyl acyl-L-isoleucine, N-dodecyl acyl-L-isoleucine, N -tetradecyl-L-isoleucine, N-hexadecyl-L-isoleucine, N-octadecyl-L-isoleucine, N-di Decyl acyl-L-isoleucine, N-dodecyl acyl-L-isoleucine, N-octyl acyl-L-phenylalanine, N-decyl Alkanoyl-L-phenylalanine, N-dodecyl-L-phenylalanine, N-tetradecyl-L-phenylalanine, N-hexadecane Acyl-L-phenylalanine, N-octadecyl-L-phenylalanine, N-eicosyl-L-phenylalanine, N-docosyl Acyl-L-phenylalanine. N-octyl acyl-D-phenylalanine, N-decyl acyl-D-phenylalanine, N-dodecyl acyl-D-phenylalanine, N -tetradecyl-D-phenylalanine, N-hexadecyl-D-phenylalanine, N-octadecyl-D-phenylalanine, N-di Decyl acyl-D-phenylalanine, N-behenyl acyl-D-phenylalanine. N-octyl acyl-DL-phenylalanine, N-decyl acyl-DL-phenylalanine, N-dodecyl acyl-DL-phenylalanine, N -tetradecyl-DL-phenylalanine, N-hexadecyl-DL-phenylalanine, N-octadecyl-DL-phenylalanine, N-di Decanoyl-DL-phenylalanine, N-behenyl-DL-phenylalanine. N-octyl acyl-L-methionine, N-decyl acyl-L-methionine, N-dodecyl acyl-L-methionine, N -tetradecyl-L-methionine, N-hexadecyl-L-methionine, N-octadecyl-L-methionine, N-di Decyl acyl-L-methionine, N-dodecyl acyl-L-methionine. N-octyl acyl-D-methionine, N-decyl acyl-D-methionine, N-dodecyl acyl-D-methionine, N -tetradecyl-D-methionine, N-hexadecyl-D-methionine, N-octadecyl-D-methionine, N-di Decyl acyl-D-methionine, N-dodecyl acyl-D-methionine. N-octyl acyl-L-proline, N-decyl acyl-L-proline, N-dodecyl acyl-L-proline, N-tetradecyl Alkyl acyl-L-proline, N-hexadecyl-L-proline, N-octadecyl-L-proline, N-eicosyl- L-proline, N-behenyl-L-proline. N-octyl acyl-D-proline, N-decyl acyl-D-proline, N-dodecyl acyl-D-proline, N-tetradecyl Alkyl acyl-D-proline, N-hexadecyl acyl-D-proline, N-octadecyl acyl-D-proline, N-eicosyl acyl- D-proline or N-behenyl-D-proline.

The nonionic surfactants are Brij series surfactants, including C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₂ OH (Brij52), C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₁₀ OH (Brij56), C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₂₀ OH (Brij58), C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₂ OH (Brij72), C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH (Brij76), C ₁₈ H ₃₇ ( _OCH2CH2 ) _20OH ( _Brij78 ).

The co-structure directing agent is a basic silane with an amino group, and its structural formula is: (R ₁ O) ₃ Si-R-NH ₂ , wherein: R ₁ is a C ₁ -C ₄ straight chain, branched chain alkyl Or hydrogen atom, R is C ₁ -C ₄ linear or branched chain alkyl, such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or 4-aminobutyltrimethoxy Silane etc.

The structural formula of the organosilane is: (R ₁ O) _m ——Si——R, wherein: m=2-4 integer, R ₁ is C ₁ -C ₄ straight chain, branched chain alkyl or hydrogen atom, R is C ₁ -C ₄ linear or branched chain alkyl, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, Dimethoxydimethylsilane, trimethoxymethylsilane or dimethoxydiisopropylsilane.

The high-temperature calcination refers to: put the prepared material into a crucible, raise the temperature to 550° C. in a muffle furnace for 6 hours and keep it for 6 hours to remove the surfactant molecules used to form mesoporous channels.

The polyhedron is a closed space composed of n planes, where n is greater than or equal to 4, such as a regular icosahedron, a regular decahedron, or a regular octahedron with vertices removed.

The present invention uses a mixed template of anionic surfactant and nonionic surfactant and a co-structure directing agent to synthesize a silica mesoporous hollow sphere material with polyhedral morphology for the first time, and the interior is polyhedron, such as icosahedron and decahedron , the regular octahedron whose apex is cut off, etc., its size is 600nm～2μm, with cubic bicontinuous diamond Pn-3m structure, the inner surface is {111} or {100} crystal plane; the pore diameter of mesoporous material is 4～7nm , the pore volume is about 1.0-1.3 cm ³ g ^-1 , and the specific surface area is about 500-800 m ² g ^-1 ; the present invention will prepare other mesoporous materials such as Mesoporous carbon and mesoporous metal oxides have broad application prospects.

Description of drawings

Fig. 1 is a scanning electron micrograph of the silica mesoporous hollow sphere material with polyhedral internal morphology obtained in Example 1.

Fig. 2 is a cross-sectional scanning electron micrograph of the silicon dioxide mesoporous hollow sphere material with polyhedral internal morphology obtained in Example 1 cut by an argon ion beam.

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

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

Detailed ways

The embodiments of the present invention are described in detail below. This embodiment is implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operating procedures are provided, but the protection scope of the present invention is not limited to the following implementation example.

Example 1

Weigh 0.207g (0.5mmol) C ₁₈ GluA and 0.5g (0.72mmol) Brij-56 and disperse them into 21g (1.167mol) deionized water, stir at 50C, add 0.179g (1mmol) APS and 1.56 g (7.5 mmol) TEOS. Stirring was stopped after 20 min, and aging was continued in a water bath at this temperature for 2 days. The resulting white powder was separated by filtration, dried overnight at 60°C, and calcined at 550°C for 6h to remove the surfactant. Its size is 600nm～2μm, it has a cubic bicontinuous diamond Pn-3m structure, and the inner surface is a {111} or {100} crystal plane; the pore diameter of the mesoporous material is 5.3nm, and the pore volume is about 1.2cm ³ g ^{- 1} , and the specific surface area is about 689m ² g ^-1 . Figure 1 is a scanning electron microscope photo of this material, which shows that its appearance is spherical and has a polyhedral internal morphology; Figure 2 is a transmission electron microscope photo of this mesoporous material, which shows that this material has regular internal morphology, and evenly distributed mesopores on the walls.

Example 2

Weigh 0.207g (0.5mmol) C ₁₈ GluA and 0.5g (0.69mmol) Brij-76 and disperse them into 21g (1.167mol) deionized water, stir at 50°C, add 0.179g (1mmol) APS to the solution at the same time and 1.56 g (7.5 mmol) TEOS. Stirring was stopped after 20 min, and aging was continued in a water bath at this temperature for 2 days. The resulting white powder was separated by filtration, dried overnight at 60°C, and calcined at 550°C for 6h to remove the surfactant. Its size is 600nm～2μm, it has a cubic bicontinuous diamond Pn-3m structure, and the inner surface is a {111} or {100} crystal plane; the pore diameter of the mesoporous material is 5.9nm, and the pore volume is about 1.3cm ³ g ^{- 1} , and the specific surface area is about 714m ² g ^-1 . Figure 3 is a transmission electron microscope photo of this material. It can be seen from the figure that this material has a polyhedral internal morphology, and mesoporous pores are evenly distributed on the walls.

Example 3

Weigh 0.207g (0.5mmol) C ₁₈ GluA and 0.5g (0.72mmol) Brij-56 and disperse them into 21g (1.167mol) deionized water, stir at 60°C, add 0.179g (1mmol) APS to the solution at the same time and 1.56 g (7.5 mmol) TEOS. Stirring was stopped after 20 min, and aging was continued in a water bath at this temperature for 2 days. The resulting white powder was separated by filtration, dried overnight at 60°C, and calcined at 550°C for 6h to remove the surfactant. Its size is 1-2 μm, and it has a cubic bicontinuous diamond Pn-3m structure, and the inner surface is a {111} or {100} crystal plane; the pore diameter of the mesoporous material is 5.5nm, and the pore volume is about 1.3cm ³ g ^{- 1} , and the specific surface area is about 694m ² g ^-1 . Figure 4 is a transmission electron microscope photo of this material. It can be seen from the figure that this material has a thinner spherical shell and polyhedral internal morphology, and the mesopores are evenly distributed on the walls.

Claims (10)

1. A preparation method for a polyhedral internal morphology silica mesoporous hollow sphere material, characterized in that an anionic surfactant and a nonionic surfactant are dissolved in deionized water earlier, and an alkaline silane with an amine group is added Co-structural directing agent and organosiloxane are separated by filtration and then calcined at a high temperature to obtain a silica mesoporous hollow sphere material with a polyhedral inner shape. 2. the preparation method of polyhedron internal morphology silica mesoporous hollow sphere material according to claim 1, is characterized in that, described anionic surfactant, nonionic surfactant, alkaline silane with amine group , organosilane and deionized water in a molar ratio of 1:1.4-1.5:2:15:2330. 3. The preparation method of the polyhedral internal morphology silica mesoporous hollow sphere material according to claim 1, characterized in that, said dissolving in deionized water refers to: stirring and dissolving in a 50-60°C environment deionized water. 4. according to the preparation method of the described polyhedron internal morphology silica mesoporous hollow sphere material of claim 1 or 2, it is characterized in that, described anionic surfactant, its structural formula is as follows:

Among them: R ₁ is a natural constant of C _n H _2n+1 , n=8-22; R ₂ is CH ₃ , COOH, C(CH ₃ ) ₂ , C(CH ₃ )CH ₂ CH ₃ , CHC ₆ H ₅ , CH ₂ CH ₂ SCH ₃ or (CH ₂ ) ₆ C ₆ H ₅ , R ₃ is H or CH ₃ , A is COO, CH ₂ COO, CH ₂ CH ₂ COO, OSO ₃ , OSO ₂ or OPO ₃ . 5. The preparation method of the polyhedral internal morphology silica mesoporous hollow sphere material according to claim 1 or 2, characterized in that the nonionic surfactant is C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₂ OH, C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₁₀ OH, C ₁₆ H ₃₃ (OCH ₂ CH ₂ ) ₂₀ OH, C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₂ OH, C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₁₀ OH or C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₂₀ OH. 6. the preparation method of polyhedron internal morphology silica mesoporous hollow sphere material according to claim 1, is characterized in that, described co-structure directing agent is the basic silane with amino group, and its structural formula is: ( R ₁ O) ₃ Si——R—NH ₂ , wherein: R ₁ is a C ₁ -C ₄ straight chain, branched chain alkyl group or a hydrogen atom, and R is a C ₁ -C ₄ straight chain or branched chain alkyl group. 7. The preparation method of the polyhedral internal morphology silica mesoporous hollow sphere material according to claim 1 or 6, characterized in that, the co-structure directing agent is 3-aminopropyltrimethoxysilane, 3 - Aminopropyltriethoxysilane or 4-aminobutyltrimethoxysilane. 8. The preparation method of the polyhedral internal morphology silica mesoporous hollow sphere material according to claim 1, characterized in that, the structural formula of the organosilane is: (R ₁ O) _m ——Si——R , wherein: m=2-4 integer, R ₁ is a C ₁ -C ₄ chain, a branched chain alkyl group or a hydrogen atom, and R is a C ₁ -C ₄ straight chain or branched chain alkyl group. 9. according to the preparation method of polyhedron internal morphology silica mesoporous hollow sphere material described in claim 1 or 6, it is characterized in that, described organosilane is tetramethoxysilane, tetraethoxysilane, tetraethoxysilane, Propoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydimethylsilane, trimethoxymethylsilane or dimethoxydiisopropylsilane. 10. The preparation method of the polyhedron internal morphology silica mesoporous hollow sphere material according to claim 1, characterized in that, the high-temperature roasting refers to: the prepared material is packed into a crucible, and immediately The furnace was heated to 550°C over 6 hours and kept for 6 hours to remove the surfactant molecules used to form mesoporous channels.

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