CN1986402A - Mesoporous silica tube in homogeneous diameter and its preparing process - Google Patents
Mesoporous silica tube in homogeneous diameter and its preparing process Download PDFInfo
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- CN1986402A CN1986402A CN 200610119242 CN200610119242A CN1986402A CN 1986402 A CN1986402 A CN 1986402A CN 200610119242 CN200610119242 CN 200610119242 CN 200610119242 A CN200610119242 A CN 200610119242A CN 1986402 A CN1986402 A CN 1986402A
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Abstract
The present invention is mesoporous silica tube in homogeneous diameter and its preparation process. The mesoporous silica tube is prepared with organic silane as silica source, acid or salt anion surfactant as main structure guiding agent, and alkaline silane with amino radical or quaternary ammonium salt as assistant structure guiding agent, and in the presence of alkali or acid to form micellar structure. The prepared mesoporous silica tube has inside diameter of 30-120 nm, wall thickness of 30-200nm, vermiform mesopores of diameter 2.0-4.0 nm, specific surface area of 200-550 sq m/g, pore volume of 400-750 cu mm3/g, and homogeneous pore size.
Description
Technical field
The invention belongs to a kind of inorganic mesoporous material and preparation method thereof, particularly a kind of have mesoporous silica tube in homogeneous diameter and preparation method thereof.Be applied in microexamination nano-device, drug loading, atmosphere storage and catalytic field.
Background technology
Therefore nano-tube is used at microcosmic owing to have the characteristic of nano-material and nano-tube material concurrently, and the nanoelectronic apparatus has important use to be worth.And mesoporous silica tube because have big specific surface area and and pore volume, adjustable pore structure, adjustable aperture, the surface properties that can modify and the appearance that can control or the like, therefore in microexamination, nano-device, drug loading, atmosphere storage and catalytic field have very large application potential.At present, can prepare the silicone tube of the hollow of caliber from 300nm to 3 Xie with soft template, but not mesoporous silicone tube.At Langmuir, Vol.16, No.5 discloses a kind of cats product of using in 2000, and hexadecyl uncle ammonium is the hollow silicon nanowires that template is prepared, but pattern is inhomogeneous, and structure is uncontrollable; At Phys.Chem.Chem.Phys, 2001,3, a kind of cats product of using is disclosed among the 3486-3489, six alkyl trimethyl ammonium bromides are the silicone tube that template is prepared hollow, but impurity is many, the profile heterogeneity, and no mesoporous on the tube wall; At Mater.Chem., 2001,11, disclosing a kind of organic molecule with hand-type among the 2412-2419 is that template can be synthesized the tubular material of profile than homogeneous, but does not exist mesoporous on the tube wall.At nature, vol 429,20, the chirality rod meso pore silicon oxide material that utilizes anion surfactant successfully to synthesize among the may 2004 first to have special construction, proposing anion surfactant first and helping this synthesis condition of notion of structure directing agent is different temperature and acidity of control, make tensio-active agent form a kind of micella state, this micella state finally forms the chirality rod.The present invention makes tensio-active agent form gel by attemperation and acidity, makes synthetic profile more even, and the controlled tubulose mesoporous material of pipe range and caliber becomes possibility.
In a word, narrow with the synthesising mesoporous pore size distribution of simple template, pattern evenly single mesoporous silica tube with good external form still has certain difficulty.In addition, have amido or quaternary ammonium salt functional group, make it huge application potential be arranged owing to utilizing method of extraction on tube wall, to stay in catalysis and drug loading.
Summary of the invention
The objective of the invention is to propose that a kind of utilization acid or salt anionic surfactant are synthetic has homogeneous diameter, no organic group or have amido or the meso-porous nano tubular material of quaternary ammonium salt functional group and preparation method thereof on the tube wall.
The present invention has mesoporous silica tube in homogeneous diameter, with the organosilane is silica source, by acid or salt anionic surfactant as the main structure directed agents, formed micellar structure guide effect in the presence of alkali or acid, basic silane with band amido or quaternary ammonium salt is prepared both ends open for helping structure directing agent, and the inner and outer wall of pipe is smooth, the uniform meso-porous nano tube material of diameter, after the roasting, there is not functional group on the tube wall; Perhaps after the extraction, on tube wall, stay amido or quaternary ammonium salt functional group.
The feature that the present invention has mesoporous silica tube in homogeneous diameter is as follows:
With the organosilane is silica source, by acid or salt anionic surfactant as the main structure directed agents, formed micellar structure guide effect in the presence of alkali or acid, basic silane with band amido or quaternary ammonium salt is 0.1～25 Xie for helping structure directing agent to prepare pipe range, the inside pipe wall diameter is 30～120nm, and thickness of pipe is 30～200nm, and mesoporous is vermiform, its pore size distribution is 2.0～4.0nm, and specific surface area is 200～550m
2g
-1, pore volume is 400～750mm
3g
-1Both ends open, the inner and outer wall of pipe is smooth, and diameter is even, no organic group or have amido or the meso-porous nano tube material of quaternary ammonium salt functional group on the tube wall.
The preparation method that the present invention has mesoporous silica tube in homogeneous diameter is as follows:
Earlier that the acidic anionic tensio-active agent is soluble in water, the aqueous solution of adding alkali; Or the salt analog anion surfactants is soluble in water, stirring at room temperature adds inorganic acid solution after dissolving fully; The basic silane that adds band amido or quaternary ammonium salt then, add organosilane again, 0-100 ℃ of reaction 0.5 hour-120 hours, through centrifugation or filtration, washing, drying, roasting or extraction, obtain having mesoporous silica tube in homogeneous diameter, wherein acid or salt anionic surfactant: ion exchanged water: mineral acid: the basic silane of band amido or quaternary ammonium salt: the mol ratio of organosilane is 1: 500-4000: 0.10-0.90: 0.05-2.0: 3-30.
Anion surfactant used in the present invention, its structural formula is as follows:
R
1-AH or
Wherein, R
1Be C
nH
2n+1, n=8-22; R
2Be CH
3, C (CH
3)
2, C (CH
3) CH
2CH
3, CHC
6H
5, CH
2CH
2SCH
3Or (CH
2)
6C
6H
5R
3Be H or CH
3A is COO, CH
2COO, CH
2CH
2COO, OSO
3, OSO
2Or OPO
3N-caprylic acid, n-capric acid, dodecyl carboxylic acid, tetradecyl carboxylic acid, hexadecyl carboxylic acid, octadecyl carboxylic acid, eicosyl carboxylic acid, docosane yl carboxylic acid are wherein arranged.N-octane base acyl for-L-L-Ala, N-n-decane alkyl acyl for-L-L-Ala, N-dodecyl acyl for-L-L-Ala, N-tetradecyl acyl for-L-L-Ala, N-hexadecyl acyl for-L-L-Ala, N-octadecyl acyl for-L-L-Ala, N-eicosyl acyl for-L-L-Ala, N-docosyl acyl for-L-L-Ala.N-octane base acyl for-D-L-Ala, N-n-decane alkyl acyl for-D-L-Ala, N-dodecyl acyl for-D-L-Ala, N-tetradecyl acyl for-D-L-Ala, N-hexadecyl acyl for-D-L-Ala, N-octadecyl acyl for-D-L-Ala, N-eicosyl acyl for-D-L-Ala, N-docosyl acyl for-D-L-Ala.N-octane base acyl for-L-third amidosulphuric acid, N-n-decane alkyl acyl for-L-third amidosulphuric acid, N-dodecyl acyl for-L-third amidosulphuric acid, N-tetradecyl acyl for-L-third amidosulphuric acid, N-hexadecyl acyl for-L-third amidosulphuric acid, N-octadecyl acyl for-L-third amidosulphuric acid, N-eicosyl acyl for-L-third amidosulphuric acid, N-docosyl acyl for-L-third amidosulphuric acid.N-octane base acyl for-D-third amidosulphuric acid, N-n-decane alkyl acyl for-D-third amidosulphuric acid, N-dodecyl acyl for-D-third amidosulphuric acid, N-tetradecyl acyl for-D-third amidosulphuric acid, N-hexadecyl acyl for-D-third amidosulphuric acid, N-octadecyl acyl for-D-third amidosulphuric acid, N-eicosyl acyl for-D-third amidosulphuric acid, N-docosyl acyl for-D-third amidosulphuric acid.N-octane base acyl for-L-Xie Ansuan, N-n-decane alkyl acyl for-L-Xie Ansuan, N-dodecyl acyl for-L-Xie Ansuan, N-tetradecyl acyl for-L-Xie Ansuan, N-hexadecyl acyl for-L-Xie Ansuan, N-octadecyl acyl for-L-Xie Ansuan, N-eicosyl acyl for-L-Xie Ansuan, N-docosyl acyl for-L-Xie Ansuan.N-octane base acyl for-D-Xie Ansuan, N-n-decane alkyl acyl for-D-Xie Ansuan, N-dodecyl acyl for-D-Xie Ansuan, N-tetradecyl acyl for-D-Xie Ansuan, N-hexadecyl acyl for-D-Xie Ansuan, N-octadecyl acyl for-D-Xie Ansuan, N-eicosyl acyl for-D-Xie Ansuan, N-docosyl acyl for-D-Xie Ansuan.N-octane base acyl replaces-the L-Isoleucine, N-n-decane alkyl acyl replaces-the L-Isoleucine, N-dodecyl acyl replaces-the L-Isoleucine, N-tetradecyl acyl replaces-the L-Isoleucine, N-hexadecyl acyl replaces-the L-Isoleucine, N-octadecyl acyl replaces-the L-Isoleucine, N-eicosyl acyl replaces-the L-Isoleucine, N-docosyl acyl replaces-the L-Isoleucine, N-octane base acyl replaces-the L-phenylalanine, N-n-decane alkyl acyl replaces-the L-phenylalanine, N-dodecyl acyl replaces-the L-phenylalanine, N-tetradecyl acyl replaces-the L-phenylalanine, N-hexadecyl acyl replaces-the L-phenylalanine, N-octadecyl acyl replaces-the L-phenylalanine, N-eicosyl acyl replaces-the L-phenylalanine, N-docosyl acyl replaces-the L-phenylalanine.N-octane base acyl for-D-phenylalanine, N-n-decane alkyl acyl for-D-phenylalanine, N-dodecyl acyl for-D-phenylalanine, N-tetradecyl acyl for-D-phenylalanine, N-hexadecyl acyl for-D-phenylalanine, N-octadecyl acyl for-D-phenylalanine, N-eicosyl acyl for-D-phenylalanine, N-docosyl acyl for-D-phenylalanine.N-octane base acyl for-DL-phenylalanine, N-n-decane alkyl acyl for-DL-phenylalanine, N-dodecyl acyl for-DL-phenylalanine, N-tetradecyl acyl for-DL-phenylalanine, N-hexadecyl acyl for-DL-phenylalanine, N-octadecyl acyl for-DL-phenylalanine, N-eicosyl acyl for-DL-phenylalanine, N-docosyl acyl for-DL-phenylalanine.N-octane base acyl for-L-methionine(Met), N-n-decane alkyl acyl for-L-methionine(Met), N-dodecyl acyl for-L-methionine(Met), N-tetradecyl acyl for-L-methionine(Met), N-hexadecyl acyl for-L-methionine(Met), N-octadecyl acyl for-L-methionine(Met), N-eicosyl acyl for-L-methionine(Met), N-docosyl acyl for-L-methionine(Met).N-octane base acyl for-D-methionine(Met), N-n-decane alkyl acyl for-D-methionine(Met), N-dodecyl acyl for-D-methionine(Met), N-tetradecyl acyl for-D-methionine(Met), N-hexadecyl acyl for-D-methionine(Met), N-octadecyl acyl for-D-methionine(Met), N-eicosyl acyl for-D-methionine(Met), N-docosyl acyl for-D-methionine(Met).N-octane base acyl for-L-proline(Pro), N-n-decane alkyl acyl for-L-proline(Pro), N-dodecyl acyl for-L-proline(Pro), N tetradecyl acyl for-L-proline(Pro), N-hexadecyl acyl for-L-proline(Pro), N-octadecyl acyl for-L-proline(Pro), N-eicosyl acyl for-L-proline(Pro), N-docosyl acyl for-L-proline(Pro).N-octane base acyl for-D-proline(Pro), N-n-decane alkyl acyl for-D-proline(Pro), N-dodecyl acyl for-D-proline(Pro), N-tetradecyl acyl for-D-proline(Pro), N-hexadecyl acyl for-D-proline(Pro), N-octadecyl acyl for-D-proline(Pro), N-eicosyl acyl for-D-proline(Pro) or N-docosyl acyl for-D-proline(Pro).
Salt anionic surfactant used in the present invention, its structural formula is as follows:
R
1-AB or
Wherein, R
1Be C
nH
2n+1, n=8-22; R
2Be CH
3, C (CH
3)
2, C (CH
3) CH
2CH
3, CHC
6H
5, CH
2CH
2SCH
3Or (CH
2)
6C
6H
5R
3Be H or CH
3A is COO, CH
2COO, CH
2CH
2COO, OSO
3, OSO
2Or OPO
3B is Na, K or NH
4N-caprylic acid sodium, n-capric acid sodium, dodecyl carboxylic acid sodium, tetradecyl carboxylic acid sodium, hexadecyl carboxylic acid sodium, octadecyl carboxylic acid sodium, eicosyl carboxylic acid sodium, docosyl carboxylic acid sodium are wherein arranged.Octane base sodium sulfate, n-decane base sodium sulfate, sodium lauryl sulphate, Trombovar, Sodium palmityl sulfate, sodium stearyl sulfate, eicosyl sodium sulfate, docosyl sodium sulfate.Octane base sodium sulfonate, n-decane base sodium sulfonate, sodium laurylsulfonate, tetradecyl sodium sulfonate, sodium cetanesulfonate, octadecyl sodium sulfonate, eicosyl sodium sulfonate, docosyl sodium sulfonate.Octane base sodium phosphate, n-decane base sodium phosphate, dodecylphosphoric acid sodium, tetradecyl sodium phosphate, hexadecyl sodium phosphate, octadecyl sodium phosphate, eicosyl sodium phosphate, docosyl sodium phosphate.N-octane base acyl for-L-Sodium L-alaninate, N-n-decane alkyl acyl for-L-Sodium L-alaninate, N-dodecyl acyl for-L-Sodium L-alaninate, N-tetradecyl acyl for-L-Sodium L-alaninate, N-hexadecyl acyl for-L-Sodium L-alaninate, N-octadecyl acyl for-L-Sodium L-alaninate, N-eicosyl acyl for-L-Sodium L-alaninate, N-docosyl acyl for-L-Sodium L-alaninate.N-octane base acyl replaces-the D-Sodium L-alaninate, N-n-decane alkyl acyl replaces-the D-Sodium L-alaninate, N-dodecyl acyl replaces-the D-Sodium L-alaninate, N-tetradecyl acyl replaces-the D-Sodium L-alaninate, N-hexadecyl acyl replaces-the D-Sodium L-alaninate, N-octadecyl acyl replaces-the D-Sodium L-alaninate, N-eicosyl acyl replaces-the D-Sodium L-alaninate, N-docosyl acyl replaces-the D-Sodium L-alaninate, N-octane base acyl replaces-the L-third amidosulphuric acid sodium, N-n-decane alkyl acyl replaces-the L-third amidosulphuric acid sodium, N-dodecyl acyl replaces-the L-third amidosulphuric acid sodium, N-tetradecyl acyl replaces-the L-third amidosulphuric acid sodium, N-hexadecyl acyl replaces-the L-third amidosulphuric acid sodium, N-octadecyl acyl replaces-the L-third amidosulphuric acid sodium, N-eicosyl acyl replaces-the L-third amidosulphuric acid sodium, N-docosyl acyl replaces-the L-third amidosulphuric acid sodium.N-octane base acyl for the-D-third amidosulphuric acid sodium, N-n-decane alkyl acyl for the-D-third amidosulphuric acid sodium, N-dodecyl acyl for the-D-third amidosulphuric acid sodium, N-tetradecyl acyl for the-D-third amidosulphuric acid sodium, N-hexadecyl acyl for the-D-third amidosulphuric acid sodium, N-octadecyl acyl for the-D-third amidosulphuric acid sodium, N-eicosyl acyl for the-D-third amidosulphuric acid sodium, N-docosyl acyl for the-D-third amidosulphuric acid sodium.N-octane base acyl for the-L-third phosphoramidic acid sodium, N-n-decane alkyl acyl for the-L-third phosphoramidic acid sodium, N-dodecyl acyl for the-L-third phosphoramidic acid sodium, N-tetradecyl acyl for the-L-third phosphoramidic acid sodium, N-hexadecyl acyl for the-L-third phosphoramidic acid sodium, N-octadecyl acyl for the-L-third phosphoramidic acid sodium, N-eicosyl acyl for the-L-third phosphoramidic acid sodium, N-docosyl acyl for the-L-third phosphoramidic acid sodium.N-octane base acyl for the-D-third phosphoramidic acid sodium, N-n-decane alkyl acyl for the-D-third phosphoramidic acid sodium, N-dodecyl acyl for the-D-third phosphoramidic acid sodium, N-tetradecyl acyl for the-D-third phosphoramidic acid sodium, N-hexadecyl acyl for the-D-third phosphoramidic acid sodium, N-octadecyl acyl for the-D-third phosphoramidic acid sodium, N-eicosyl acyl for the-D-third phosphoramidic acid sodium, N-docosyl acyl for the-D-third phosphoramidic acid sodium.N-octane base acyl for-L-Valine sodium salt, N-n-decane alkyl acyl for-L-Valine sodium salt, N-dodecyl acyl for-L-Valine sodium salt, N-tetradecyl acyl for-L-Valine sodium salt, N-hexadecyl acyl for-L-Valine sodium salt, N-octadecyl acyl for-L-Valine sodium salt, N-eicosyl acyl for-L-Valine sodium salt, N-docosyl acyl for-L-Valine sodium salt.N-octane base acyl for-D-Valine sodium salt, N-n-decane alkyl acyl for-D-Valine sodium salt, N-dodecyl acyl for-D-Valine sodium salt, N-tetradecyl acyl for-D-Valine sodium salt, N-hexadecyl acyl for-D-Valine sodium salt, N-octadecyl acyl for-D-Valine sodium salt, N-eicosyl acyl for-D-Valine sodium salt, N-docosyl acyl for-D-Valine sodium salt.N-octane base acyl for-L-L-Isoleucine sodium salt, N-n-decane alkyl acyl for-L-L-Isoleucine sodium salt, N-dodecyl acyl for-L-L-Isoleucine sodium salt, N-tetradecyl acyl for-L-L-Isoleucine sodium salt, N-hexadecyl acyl for-L-L-Isoleucine sodium salt, N-octadecyl acyl for-L-L-Isoleucine sodium salt, N-eicosyl acyl for-L-L-Isoleucine sodium salt, N-docosyl acyl for-L-L-Isoleucine sodium salt.N-octane base acyl for-D-L-Isoleucine sodium salt, N-n-decane alkyl acyl for-D-L-Isoleucine sodium salt, N-dodecyl acyl for-D-L-Isoleucine sodium salt, N-tetradecyl acyl for-D-L-Isoleucine sodium salt, N-hexadecyl acyl for-D-L-Isoleucine sodium salt, N-octadecyl acyl for-D-L-Isoleucine sodium salt, N-eicosyl acyl for-D-L-Isoleucine sodium salt, N-docosyl acyl for-D-L-Isoleucine sodium salt.N-octane base acyl for-L-Sodium phenylalaninate, N-n-decane alkyl acyl for-L-Sodium phenylalaninate, N-dodecyl acyl for-L-Sodium phenylalaninate, N-tetradecyl acyl for-L-Sodium phenylalaninate, N-hexadecyl acyl for-L-Sodium phenylalaninate, N-octadecyl acyl for-L-Sodium phenylalaninate, N-eicosyl acyl for-L-Sodium phenylalaninate, N-docosyl acyl for-L-Sodium phenylalaninate.N-octane base acyl for-D-Sodium phenylalaninate, N-n-decane alkyl acyl for-D-Sodium phenylalaninate, N-dodecyl acyl for-D-Sodium phenylalaninate, N-tetradecyl acyl for-D-Sodium phenylalaninate, N-hexadecyl acyl for-D-Sodium phenylalaninate, N-octadecyl acyl for-D-Sodium phenylalaninate, N-eicosyl acyl for-D-Sodium phenylalaninate, N-docosyl acyl for-D-Sodium phenylalaninate.N-octane base acyl for-DL-Sodium phenylalaninate, N-n-decane alkyl acyl for-DL-Sodium phenylalaninate, N-dodecyl acyl for-DL-Sodium phenylalaninate, N-tetradecyl acyl for-DL-Sodium phenylalaninate, N-hexadecyl acyl for-DL-Sodium phenylalaninate, N-octadecyl acyl for-DL-Sodium phenylalaninate, N-eicosyl acyl for-DL-Sodium phenylalaninate, N-docosyl acyl for-DL-Sodium phenylalaninate.N-octane base acyl for-L-methionine(Met) sodium, N-n-decane alkyl acyl for-L-methionine(Met) sodium, N-dodecyl acyl for-L-methionine(Met) sodium, N-tetradecyl acyl for-L-methionine(Met) sodium, N-hexadecyl acyl for-L-methionine(Met) sodium, N-octadecyl acyl for-L-methionine(Met) sodium, N-eicosyl acyl for-L-methionine(Met) sodium, N-docosyl acyl for-L-methionine(Met) sodium.N-octane base acyl for-D-methionine(Met) sodium, N-n-decane alkyl acyl for-D-methionine(Met) sodium, N-dodecyl acyl for-D-methionine(Met) sodium, N-tetradecyl acyl for-D-methionine(Met) sodium, N-hexadecyl acyl for-D-methionine(Met) sodium, N-octadecyl acyl for-D-methionine(Met) sodium, N-eicosyl acyl for-D-methionine(Met) sodium, N-docosyl acyl for-D-methionine(Met) sodium.N-octane base acyl for-L-Sodium proline, N-n-decane alkyl acyl for-L-Sodium proline, N-dodecyl acyl for-L-Sodium proline, N-tetradecyl acyl for-L-Sodium proline, N-hexadecyl acyl for-L-Sodium proline, N-octadecyl acyl for-L-Sodium proline, N-eicosyl acyl for-L-Sodium proline, N-docosyl acyl for-L-Sodium proline.N-octane base acyl for-D-Sodium proline, N-n-decane alkyl acyl for-D-Sodium proline, N-dodecyl acyl for-D-Sodium proline, N-tetradecyl acyl for-D-Sodium proline, N-hexadecyl acyl for-D-Sodium proline, N-octadecyl acyl for-D-Sodium proline, N-eicosyl acyl for-D-Sodium proline or N-docosyl acyl for-D-Sodium proline and their sylvite or ammonium salt.
The basic silane of band amido used in the present invention or quaternary ammonium salt, its structural formula is shown below:
(R
1O)
3Si-R-NR
2R
3Or (R
1O)
3Si-R-NR
2R
3R
4X
Wherein, R
1, R
2, R
3And R
4Be C
1-C
4Straight chain, branched chain alkyl or hydrogen atom; R is C
1-C
4Straight chain or branched chain alkane; X is chlorion or bromide anion.3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 4-ammonia butyl trimethoxy silane are wherein arranged; N-trimethoxy propyl silane-N-methylamine, N-trimethoxy propyl silane-N, N-dimethyl amine, N-triethoxy propyl silane-N, N-dipropylamine, N-triethoxy propyl silane-N-butylamine, N-trimethoxy propyl silane-N, N, N-trimethyl ammonium chloride or N-trimethoxy propyl silane-N, N, N-tributyl brometo de amonio etc.
Alkali used in the present invention is sodium hydroxide, potassium hydroxide or C
1-C
4Straight chain, the short chain amine of branched chain alkyl; Mineral acid is sulfuric acid, hydrochloric acid, Hydrogen bromide or nitric acid.
Organosilane used in the present invention, its structural formula is shown below:
(R
1O)
m-Si-R
Wherein, the integer of m=2-4; R
1Be C
1-C
4Straight chain, branched chain alkyl or hydrogen atom; R is C
1-C
4Straight chain or branched chain alkyl.Tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes, dimethoxy dimethylsilane, trimethoxymethylsila,e or dimethoxy di-isopropyl silane etc. are wherein arranged.
The present invention have mesoporous silica tube in homogeneous diameter with anion surfactant or its sodium salt as the main structure directed agents, amido or quaternary ammonium salt silane are as helping structure directing agent, preparation at room temperature has mesoporous silica tube in homogeneous diameter.Synthesis mechanism is that the main structure directed agents of electronegative tensio-active agent and positively charged interacts, and forms tubulose under certain temperature, acidity influence.Mesoporous for vermiform be because the adding of mineral acid has reduced tensio-active agent and the interaction that helps structure directing agent.
The synthetic first uniform mesoporous silica tube of pattern of the present invention.Make it form gel state by controlling acidity and temperature.Usually under the lower situation of acidity comparatively high temps, form gel; Under acidity lesser temps condition with higher, form micella.Material is under the micella state, and what finally easily form is the chirality rod.And under gel state, might form pipe.And the present invention has mesoporous silica tube in homogeneous diameter is to utilize anionic gel state to prepare tubulose meso-porous nano material first.
It is both ends open that the present invention has mesoporous silica tube in homogeneous diameter, and the inner and outer wall of pipe is smooth, homogeneous diameter, no organic group or have amido or quaternary ammonium salt functional group on the tube wall; Pipe range is 0.1～25 Xie, and the inside pipe wall diameter is 30～120nm, and thickness of pipe is 30～200nm, and mesoporous is vermiform, and its pore size distribution is 2.0～4.0nm, and specific surface area is 50～550m
2g
-1, pore volume is 400～750mm
3g
-1
The present invention has mesoporous silica tube in homogeneous diameter will be in atmosphere storage, catalysis, and drug loading, support of the catalyst, hard template method prepare in the fields such as mesoporous pipe and have wide practical use.
Description of drawings
The scanning electron microscope sem of the mesoporous silica tube that obtains in Fig. 1 example 1,2 and transmission electron microscope TEM figure.
The N of the mesoporous silica tube that obtains in Fig. 2 example 1,2
2Absorption figure.
The nuclear magnetic resonance map of the mesoporous silica tube that obtains in Fig. 3 example 1.
Embodiment
Following examples are to further specify of the present invention, rather than limit the scope of the invention.
Earlier 0.32g (1mmol) tetradecyl acyl is dissolved in the 17.1g ion exchanged water for the L-Ala sodium salt, at room temperature dispersed with stirring is even; Add 4.5g (0.45mmol) 0.1M hydrochloric acid soln, at room temperature dispersed with stirring is even; Add 1.46g tetraethoxysilane (TEOS) and 0.154g (0.3mmol) then and help structure directing agent N-trimethoxy propyl silane-N, N, the mixture of N-trimethyl ammonium chloride (TMAPS) was room temperature reaction 10 minutes.Placed 4 days for 30 ℃.Through centrifugation, washing, drying, extraction obtains having mesoporous silica tube in homogeneous diameter.Resulting have mesoporous silica tube in homogeneous diameter and have both ends open, and the inner and outer wall of pipe is smooth, the uniform structure of diameter.Have quaternary ammonium salt functional group on the tube wall of this material, pipe range is 1-2 μ m, and thickness of pipe is 25nm, and the aperture of this material is the 3.0nm aperture, and pore volume is 554mm
3g
-1, specific surface area is 260m
2g
-1
A among Fig. 1
1Scanning electron microscope sem figure for the mesoporous silica tube that obtains in the example 1 therefrom finds out, mesoporous silica tube pattern homogeneous, and diameter is even, has good shapes; a
2, a
3Transmission electron microscope TEM figure for the mesoporous silica tube that obtains in the example 1 therefrom finds out, mesoporous silica tube, and mesoporous being evenly distributed on the tube wall, mesoporous silica tube has the good profile and the diameter of homogeneous.
Curve a among Fig. 2 is the N of the mesoporous silica tube that obtains in the example 1
2Adsorption curve and graph of pore diameter distribution obtain specific surface area, pore volume and the pore size distribution of the mesoporous silica tube in the example 1.
Fig. 3 is the nucleus magnetic resonance curve N MR of the mesoporous silica tube that obtains in the example 1, therefrom draws to have quaternary ammonium salt functional group on the tube wall.
Earlier 0.32g (1mmol) tetradecyl acyl is dissolved in the 17.1g ion exchanged water for the L-Ala sodium salt, at room temperature dispersed with stirring is even; Add 5g (0.5mmol) 0.1M hydrochloric acid soln, at room temperature dispersed with stirring is even; Add 1.46g tetraethoxysilane (TEOS) and 0.205g (0.4mmol) then and help structure directing agent N-trimethoxy propyl silane-N, N, the mixture of N-trimethyl ammonium chloride (TMAPS) was room temperature reaction 10 minutes.Placed 4 days for 30 ℃.Through centrifugation, washing, drying, roasting obtains having mesoporous silica tube in homogeneous diameter.Resulting have mesoporous silica tube in homogeneous diameter and have both ends open, and the inner and outer wall of pipe is smooth, the uniform structure of diameter.Do not contain functional group on this material tube wall, pipe range is 5-10 μ m, and thickness of pipe is 50nm, and the aperture is the 3.0nm aperture, and pore volume is 556mm
3g
-1, specific surface area is 340m
2g
-1
B among Fig. 1
1Scanning electron microscope sem figure for the mesoporous silica tube that obtains in the example 2 therefrom finds out, mesoporous silica tube pattern homogeneous, and diameter is even, has good shapes; b
2, b
3Transmission electron microscope TEM figure for the mesoporous silica tube that obtains in the example 2 therefrom finds out mesoporous silica tube, mesoporous being evenly distributed on the tube wall, and mesoporous silica tube has the good profile and the diameter of homogeneous.
Curve b among Fig. 2 is the N of the mesoporous silica tube that obtains in the example 2
2Adsorption curve and graph of pore diameter distribution obtain specific surface area, pore volume and the pore size distribution of the mesoporous silica tube in the example 2.
Embodiment 3
Earlier 0.35g (1mmol) hexadecyl acyl is dissolved in the 30.5g ion exchanged water for the Xie Ansuan sodium salt, at room temperature dispersed with stirring is even; Add 5g (0.45mmol) 0.1M hydrochloric acid soln, at room temperature dispersed with stirring is even; Add 1.46g tetraethoxysilane (TEOS) and 0.257g (0.3mmol) then and help structure directing agent N-trimethoxy propyl silane-N, N, the mixture of N-trimethyl ammonium chloride (TMAPS) was room temperature reaction 10 minutes.Placed 4 days for 30 ℃.Through centrifugation, washing, drying, roasting obtains having mesoporous silica tube in homogeneous diameter.Resulting have mesoporous silica tube in homogeneous diameter and have both ends open, and the inner and outer wall of pipe is smooth, the uniform pattern of diameter.Do not contain functional group on this material tube wall, pipe range is 10-20 μ m, and thickness of pipe is 40nm, and the aperture is the 3.0nm aperture, and pore volume is 560mm
3g
-1, specific surface area is 360m
2g
-1
Earlier 0.35g (1mmol) hexadecyl acyl is dissolved in the 30.5g ion exchanged water for the L-Ala sodium salt; Add 1g (0.50mmol) 0.1M hydrochloric acid soln, at room temperature dispersed with stirring is even; Add mixture that 1.46g tetraethoxysilane (TEOS) and 0.20g (0.1mmol) help structure directing agent 3-aminopropyl triethoxysilane (APES) then room temperature reaction 10 minutes.Room temperature was placed 12 hours.Through centrifugation, washing, drying, extraction obtains having mesoporous silica tube in homogeneous diameter.Resulting have mesoporous silica tube in homogeneous diameter and have both ends open, and the inner and outer wall of pipe is smooth, the uniform pattern of diameter.Amino-contained functional group on this material tube wall, pipe range is 10-20 μ m, and thickness of pipe is 40nm, and the aperture is the 2.5nm aperture, and pore volume is 510mm
3g
-1, specific surface area is 200m
2g
-1
Claims (7)
1. has mesoporous silica tube in homogeneous diameter, it is characterized in that with the organosilane being silica source, by acid or salt anionic surfactant as the main structure directed agents, formed micellar structure guide effect in the presence of alkali or acid, basic silane with band amido or quaternary ammonium salt is 0.1～25 Xie for helping structure directing agent to prepare pipe range, the inside pipe wall diameter is 30～120nm, thickness of pipe is 30～200nm, mesoporous is vermiform, its pore size distribution is 2.0～4.0nm, and specific surface area is 50～550m
2g
-1, pore volume is 400～750mm
3g
-1Both ends open, the inner and outer wall of pipe is smooth, and diameter is even, no organic group or have amido or the meso-porous nano tube material of quaternary ammonium salt functional group on the tube wall.
2. the preparation method with mesoporous silica tube in homogeneous diameter as claimed in claim 1 is characterized in that the preparation method is as follows:
Earlier that the acidic anionic tensio-active agent is soluble in water, the aqueous solution of adding alkali; Or the salt analog anion surfactants is soluble in water, stirring at room temperature adds inorganic acid solution after dissolving fully; The basic silane that adds band amido or quaternary ammonium salt then, add organosilane again, 0-100 ℃ of reaction 0.5 hour-120 hours, through centrifugation or filtration, washing, drying, roasting or extraction, obtain having mesoporous silica tube in homogeneous diameter, wherein acid or salt anionic surfactant: ion exchanged water: mineral acid: the basic silane of band amido or quaternary ammonium salt: the mol ratio of organosilane is 1: 500-4000: 0.10-0.90: 0.05-2.0: 3-30.
3. the preparation method with mesoporous silica tube in homogeneous diameter according to claim 2 is characterized in that acidic anionic surfactant structure formula is as follows:
R
1-AH or
Wherein, R
1Be C
nH
2n+1, n=8-22; R
2Be CH
3, C (CH
3)
2, C (CH
3) CH
2CH
3, CHC
6H
5, CH
2CH
2S CH
3Or (CH
2)
6C
6H
5R
3Be H or CH
3A is COO, CH
2COO, CH
2CH
2COO, OSO
3, OSO
2Or OPO
3
4. the preparation method with mesoporous silica tube in homogeneous diameter according to claim 2 is characterized in that the anion surfactant structural formula of salt is as follows:
R
1-AB or
Wherein, R
1Be C
nH
2n+1, n=8-22; R
2Be CH
3, C (CH
3)
2, C (CH
3) CH
2CH
3, CHC
6H
5, CH
2CH
2SCH
3Or (CH
2)
6C
6H
5R
3Be H or CH
3A is COO, CH
2COO, CH
2CH
2COO, OSO
3, OSO
2Or OPO
3B is Na, K or NH
4
5 preparation methods with mesoporous silica tube in homogeneous diameter according to claim 2 is characterized in that alkali is sodium hydroxide, potassium hydroxide or C
1-C
4Straight chain, the short chain amine of branched chain alkyl; Mineral acid is sulfuric acid, hydrochloric acid, Hydrogen bromide or nitric acid.
6. the preparation method with mesoporous silica tube in homogeneous diameter according to claim 2, it is characterized in that helping structure directing agent is the silane of band amido or quaternary ammonium salt, its structural formula is shown below:
(R
1O)
3Si-R-NR
2R
3Or (R
1O)
3Si-R-NR
2R
3R
4X
Wherein, R
1, R
2, R
3And R
4Be C
1-C
4Straight chain, branched chain alkyl or hydrogen atom; R is C
1-C
4Straight chain or branched chain alkane; X is the chlorine or bromine ion.
7. the preparation method with mesoporous silica tube in homogeneous diameter according to claim 2 is characterized in that organosilane is shown below:
(R
1O)
m-Si-R
Wherein, m is the integer of 2-4; R
1Be C
1-C
4Straight chain, branched chain alkyl or hydrogen atom; R is C
1-C
4Straight chain or branched chain alkyl.
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| CN101891211A (en) * | 2010-07-02 | 2010-11-24 | 上海第二工业大学 | Silicon dioxide mesoporous material with multilayer sleeve structure and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891211A (en) * | 2010-07-02 | 2010-11-24 | 上海第二工业大学 | Silicon dioxide mesoporous material with multilayer sleeve structure and preparation thereof |
| CN101891211B (en) * | 2010-07-02 | 2012-07-11 | 上海第二工业大学 | Silicon dioxide mesoporous material with multilayer sleeve structure and preparation thereof |
| CN103449450A (en) * | 2013-08-29 | 2013-12-18 | 华南理工大学 | Preparation method of hollow mesoporous silica material |
| CN105312051A (en) * | 2014-07-15 | 2016-02-10 | 中国科学院大连化学物理研究所 | Nano gold-mesoporous silica composite nanotube, preparation and applications thereof |
| CN105312051B (en) * | 2014-07-15 | 2017-10-27 | 中国科学院大连化学物理研究所 | A kind of nanometer mesoporous gold silica composite nano tube and its preparation and application |
| CN107696776A (en) * | 2017-11-13 | 2018-02-16 | 浙江工贸职业技术学院 | A kind of preparation method of woodwork word text wound suspension member |
| CN107696776B (en) * | 2017-11-13 | 2019-11-08 | 浙江工贸职业技术学院 | A kind of production method of woodwork word text wound pendant |
| CN113502153A (en) * | 2021-07-07 | 2021-10-15 | 哈尔滨工程大学 | Non-aromatic luminous micromolecule/SiO2Hybrid fluorescent nano material and preparation method and application thereof |
| CN113502153B (en) * | 2021-07-07 | 2023-02-14 | 哈尔滨工程大学 | Non-aromatic luminous micromolecule/SiO 2 Hybrid fluorescent nano material and preparation method and application thereof |
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