CN101618851B - Hexagonal mesoporous and nanowire complex and preparation method thereof - Google Patents
Hexagonal mesoporous and nanowire complex and preparation method thereof Download PDFInfo
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- CN101618851B CN101618851B CN2009100415812A CN200910041581A CN101618851B CN 101618851 B CN101618851 B CN 101618851B CN 2009100415812 A CN2009100415812 A CN 2009100415812A CN 200910041581 A CN200910041581 A CN 200910041581A CN 101618851 B CN101618851 B CN 101618851B
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Abstract
The invention discloses a hexagonal mesoporous and nanowire complex and a preparation method thereof. The preparation method comprises the following steps of: dissolving laurylamine into mixed solution of alcohol and deionized water, and adding nitrate solution dissolved with lanthanum oxide and tetraethoxysilane in sequence; stirring and reacting under room temperature, obtaining white precipitate, washing with water and extracting reactive products with an organic solvent, drying, then calcining and obtaining the hexagonal mesoporous and nanowire complex. The specific surface area and aperture of the hexagonal mesoporous and nanowire complex can be adjusted in a certain range, the synthesis technique thereof is simple, the nanowire has good dispersity, the mesoporous and liner structure is clear, and the hexagonal mesoporous and nanowire complex has great application potential in the fields of catalysis field, drug release, strength and toughness enhancement, bioengineering and the like.
Description
Technical field
The present invention relates to material, be specifically related to a kind of hexagonal mesoporous and nanowire complex and preparation method thereof as catalyst, pharmaceutical carrier.
Background technology
1992, the scientist of Mobil company is the mesoporous silicon oxide of synthetic high-sequential first.Because it has the mesoporous distribution (2-30nm) of big specific area (700-1500m2/g), regular size, higher chemistry and thermodynamic stability and because of there is a large amount of silicon hydroxyls other group of grafting easily in its surface, thereby makes it be widely used in fields such as absorption, catalysis, pharmaceutical carrier, Chemical Decomposition.
In recent years, the countries in the world scientist has synthesized panoramic Metaporous silicon dioxide material in order to excavate its potential application more fully.Such as spherical hollow silica material (Deng, Z.W etc., Langmuir.2006.22.6403-6407; Chen, M etc., Ad.Mater.2006.18.801-806; Masahiro Fujiwara etc., Nano Lett.2006.6.2925-2928); Mesopore film silica (Vijay R.Tirumala etc., Chem.Mater.2007.19.5868-5874); Have meso-hole structure the silica nanometer pipe (Xiaowei Wu etc., Chem.Mater.2007.19.1577-1583); Meso-porous titanium dioxide silicon nitride (Yifeng Shi etc., J.Phys.Chem.C 2008.112.112-116); Fibre-like silica (Shiori Kubo etc., Langmuir 2007.23.11761-11768 with meso-hole structure; Alpa C.Patel etc., Nano Lett.2006.6.1042-1046); Helical form silica (Thomas Delclos etc., Nano Lett.2008.8.1929-1935).
But also do not appear in the newspapers about mesoporous silicon oxide and nanowire complex both at home and abroad at present.Preparing the most frequently used method of mesoporous material is the method through the molecule self assembly.The molecule assembling is through weak covalency, non-covalent bond---hydrogen bond, ionic bond (electrostatic interaction), and hydrophobic interaction, the hydrogen bond of Van der Waals force and water produces.Although these keys are obviously isolated comparatively speaking, they together the time, are but controlling the formation and the intermolecular interaction (Zhang.S.G., nature biotechnology.2003.10.1171-1178) of macromolecular structure as an entire combination.People can control these intermolecular combinations, and (Reches.M is etc., Science.2003.300.625-637 to construct different shape and pattern nano material; Sang.O.K, etc., Nature.2003.424.411-414), and represent fabulous application prospect.As utilize the duct medicine carrying (Chen.J.F. etc. of mesoporous silicon oxide; Biomaterials; 2004.25.723-727), the functionalization appearance bonding drug molecule of one dimension CNT (Dwain.F.E, etc., Expert Opin.Biol.Ther.2003.3.655-663) etc.
Here we successfully synthesize hexagonal mesoporous in an individual system and complex nano wire through the molecule self assembly.Its good thermal stability has broad application prospects.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency that prior art exists, hexagonal mesoporous and nanowire complex and preparation method thereof are provided.The present invention realizes through following technical scheme:
The preparation method of hexagonal mesoporous and nanowire complex comprises the steps:
(1) lauryl amine is dissolved in ethanol and the deionized water, adds the salpeter solution that is dissolved with lanthana, add ethyl orthosilicate again;
(2) stirring reaction under the room temperature gets white precipitate, uses water washing, uses residual lauryl amine in the organic solvent extraction gained white precipitate again, and white precipitate is dried after calcining promptly obtains hexagonal mesoporous and nanowire complex.
Among the preparation method of above-mentioned hexagonal mesoporous and nanowire complex, add that each constituent content is in the mixture of gained after the ethyl orthosilicate: deionized water 18.025～24.139molL in the step (1)
-1, lanthana 0.004～0.014molL
-1, NO
3 -0.023～0.094molL
-1, ethanol 5.589～7.419molL
-1, lauryl amine 0.131～0.235molL
-1, ethyl orthosilicate 0.727～0.901molL
-1
Among the preparation method of above-mentioned hexagonal mesoporous and nanowire complex, step (1) is dissolved in lauryl amine that the rotating speed with 500～700 rev/mins stirs more than 5 minutes in the process of ethanol and deionized water.
Among the preparation method of above-mentioned hexagonal mesoporous and nanowire complex, step (1) is dissolved in lauryl amine that the rotating speed with 500～700 rev/mins stirred 5～50 minutes in the process of ethanol and deionized water.
Among the preparation method of above-mentioned hexagonal mesoporous and nanowire complex, step (1) is to drip ethyl orthosilicate under the 850-1000 rev/min of stirring condition at rotating speed.
Among the preparation method of above-mentioned hexagonal mesoporous and nanowire complex, stirring reaction got white precipitate more than 8 hours under the middle room temperature of step (2), through filtering, spent the deionised water filtration product again.
Among the preparation method of above-mentioned hexagonal mesoporous and nanowire complex, the rotating speed of the said stirring of step (2) is 600～700 rev/mins.
Among the preparation method of above-mentioned hexagonal mesoporous and nanowire complex, stirring reaction is 8～30 hours under the middle room temperature of step (2), gets white precipitate, through filtering, spends the deionised water filtration product again.
Among the preparation method of above-mentioned hexagonal mesoporous and nanowire complex, filtration product after room temperature is dried, is used ethanol extraction again, 40～80 ℃ of oven dry down, obtained said hexagonal mesoporous and nanowire complex in 2～5 hours in 600～740 ℃ of insulations more then.
The present invention adopts numerator self-assembly technique, synthesizes the composite of the mesoporous and nano wire that obtains good thermal stability as template according to the assembling of surfactant.It is mesoporous clear with linear structure, and line length is 100～250nm, and diameter is 3～4nm; Specific area is 960～1098m
2G
-1, average pore size is 2.7～3.5nm.Discharge, strengthen toughness reinforcing, bioengineering field at catalytic field, medicine very big application potential is arranged.
The present invention adopts numerator self-assembly technique, selects for use suitable surfactant as template, the synthetic hexagonal mesoporous and nanowire complex material through sol-gal process, and its synthesis technique is simple, and good dispersion generally speaking has following advantage and effect:
1, synthetic first hexagonal mesoporous and nanowire complex, entire reaction is at room temperature carried out, and technology is simple, and medicine sources such as ethyl orthosilicate, ethanol are abundant, and are cheap, help large-scale industrial production.
2, adopt sol-gal process synthetic, pass through the process conditions that provided, make nano wire in hexagonal mesoporous, evenly distribute,
Transmission electron microscope picture (Fig. 3) shows that the contained nano wire of this complex has than big L/D ratio, and the hexagonal hole hole distributes all
Even; This complex of nitrogen suction-desorption test shows has bigger specific area, is 960～1098m
2G
-1
Description of drawings
Fig. 1～Fig. 3 is the transmission electron microscope photo of hexagonal mesoporous and nanowire complex under three kinds of different amplification for preparing in the embodiment.
Fig. 4 is the small angle X-ray diffraction figure of the hexagonal mesoporous and nanowire complex for preparing in the embodiment.
Fig. 5 is the FFIR figure of the hexagonal mesoporous and nanowire complex for preparing in the embodiment.
Fig. 6 is the nitrogen suction-desorption isotherm of the hexagonal mesoporous and nanowire complex for preparing in the embodiment.
Fig. 7 is the pore size distribution curve of the hexagonal mesoporous and nanowire complex for preparing in the embodiment.
The specific embodiment
Following embodiment further specifies of the present invention, is not limitation of the present invention.
Embodiment 1
Take by weighing the 10g lauryl amine and be dissolved in 105.5ml ethanol and 106.7ml deionized water, and stirred 5 minutes, then the 1.40g lanthana is dissolved in the 5molL of 5.16ml with the speed of 700 commentaries on classics per minutes
-1Salpeter solution and mix with above-mentioned mixed liquor.The speed that changes with 1000 commentaries on classics per minutes stirs, and dropwise adds the 44.6ml ethyl orthosilicate again.Then the speed with 700 commentaries on classics per minutes continues to stir 24 hours, with its filtration, with 800ml deionized water washing and filtering product, after room temperature is dried, uses the 800ml ethanol extraction again 4 hours.Then 80 ℃ of oven dry 4 hours.Obtained mesoporous and nanowire complex white powder in 4 hours 640 ℃ of calcinings at last.Its specific area is 978m
2G
-1, pore volume is 0.60cm
3G
-1, average pore size is 2.7nm.Like Fig. 1～shown in Figure 3, the nano wire of TEM photo clear display and hexagonal mesoporous structure, line length is 100-250nm, and its diameter is about 3-4nm, and the hexagonal hole road evenly distributes.As shown in Figure 4,2 times of angles of diffraction equal 2.32 degree places occur diffraction maximum show this complex have the rule hexagonal hole road structure.Fig. 5 shows 1500cm
-1The weak absorption band at place is relevant with lanthanum element.Fig. 6 is the nitrogen suction-desorption isotherm of the hexagonal mesoporous and nanowire complex of preparation, and significantly hysteresis loop has proved absolutely the existence of meso-hole structure.Fig. 7 is the pore size distribution curve of the hexagonal mesoporous and nanowire complex of preparation, and its aperture mainly is distributed between 2～3.2nm.
Take by weighing the 12g lauryl amine and be dissolved in 90ml ethanol and 120ml deionized water, and stirred 30 minutes, then the 0.326g lanthana is dissolved in the 5molL of 1.2ml with the speed of 600 commentaries on classics per minutes
-1Salpeter solution also mixes with above-mentioned mixed liquor.The speed that changes with 900 commentaries on classics per minutes stirs, and dropwise adds the 44.6ml ethyl orthosilicate again.Then the speed with 600 commentaries on classics per minutes continues to stir 30 hours, with its filtration, with 600ml deionized water washing and filtering product, after room temperature is dried, uses the 700ml ethanol extraction again 4 hours.Then 40 ℃ of oven dry 9 hours.Obtained mesoporous and nanowire complex white powder in 5 hours 700 ℃ of calcinings at last.Its specific area is 980m
2G
-1, pore volume is 0.68cm
3G
-1, average pore size is 3nm.
The nano wire of TEM photo clear display and hexagonal mesoporous structure, line length are 100-150nm, and its diameter is about 3-4nm, and the duct evenly distributes.
Embodiment 3
Take by weighing the 8g lauryl amine and be dissolved in 120ml ethanol and 90ml deionized water, and stirred 20 minutes, then the 0.652g lanthana is dissolved in the 5molL of 2.4ml with the speed of 500 commentaries on classics per minutes
-1Salpeter solution also mixes with above-mentioned mixed liquor.The speed that changes with 900 commentaries on classics per minutes stirs, and dropwise adds the 44.6ml ethyl orthosilicate again.Then the speed with 600 commentaries on classics per minutes continues to stir 26 hours, with its filtration, with 700ml deionized water washing and filtering product, after room temperature is dried, uses the 500ml ethanol extraction again 4 hours.Then 70 ℃ of oven dry 5 hours.Obtained mesoporous and nanowire complex white powder in 2 hours 600 ℃ of insulations at last.Its specific area is 1098m
2G
-1, pore volume is 0.62cm
3G
-1, average pore size is 3.5nm.
The nano wire of TEM photo clear display and hexagonal mesoporous structure, line length are 120-250nm, and its diameter is about 3-4nm, and the hexagonal hole road evenly distributes.
Take by weighing the 6g lauryl amine and be dissolved in 90ml ethanol and 106.7ml deionized water, and stirred 50 minutes, then the 0.977g lanthana is dissolved in the 5molL of 3.6ml with the speed of 650 commentaries on classics per minutes
-1Salpeter solution also mixes with above-mentioned mixed liquor.The speed that changes with 850 commentaries on classics per minutes stirs, and dropwise adds the 44.6ml ethyl orthosilicate again.Then the speed with 650 commentaries on classics per minutes continues to stir 8 hours, with its filtration, with 500ml deionized water washing and filtering product, after room temperature is dried, uses the 500ml ethanol extraction again 4 hours.Then 60 ℃ of oven dry 7 hours.Obtained mesoporous and nanowire complex white powder in 3 hours 740 ℃ of insulations at last.Its specific area is 960m
2G
-1, pore volume is 0.58cm
3G
-1, average pore size is 3.1nm.
The nano wire of TEM photo clear display and hexagonal mesoporous structure, line length is 100-180nm, the duct evenly distributes.
Claims (8)
1. the preparation method of hexagonal mesoporous and nanowire complex is characterized in that comprising the steps:
(1) lauryl amine is dissolved in ethanol and the deionized water, adds the salpeter solution that is dissolved with lanthana, add ethyl orthosilicate again; Add that each constituent content is in the mixture of gained after the ethyl orthosilicate: deionized water 18.025～24.139molL
-1, lanthana 0.004～0.014molL
-1,
Ethanol 5.589～7.419molL
-1, lauryl amine 0.131～0.235molL
-1, ethyl orthosilicate 0.727～0.901molL
-1
(2) stirring reaction under the room temperature gets white precipitate, uses water washing; With the said white precipitate that filtration obtains, after room temperature is dried, use ethanol extraction; 40～80 ℃ of oven dry down, obtained said hexagonal mesoporous and nanowire complex in 2～5 hours in 600～740 ℃ of calcinings more then.
2. the preparation method of hexagonal mesoporous and nanowire complex according to claim 1 is characterized in that step (1) is dissolved in lauryl amine in the process of ethanol and deionized water with 500～700 rev/mins rotating speed stirring more than 5 minutes.
3. the preparation method of hexagonal mesoporous and nanowire complex according to claim 1 is characterized in that step (1) is dissolved in lauryl amine in the process of ethanol and deionized water with 500～700 rev/mins rotating speed stirring 5～50 minutes.
4. the preparation method of hexagonal mesoporous and nanowire complex according to claim 1 is characterized in that step (1) is to drip ethyl orthosilicate under 850～1000 rev/mins of stirring condition at rotating speed.
5. the preparation method of hexagonal mesoporous and nanowire complex according to claim 5; It is characterized in that described in the step (2) that the time of stirring reaction is more than 8 hours under the room temperature; Through filtering said white precipitate, spend the deionised water white precipitate, said organic solvent adopts ethanol.
6. the preparation method of hexagonal mesoporous and nanowire complex according to claim 5 is characterized in that the rotating speed that the said stirring of step (2) is adopted is 600～700 rev/mins.
7. the preparation method of hexagonal mesoporous and nanowire complex according to claim 6 is characterized in that described in the step (2) that the time of stirring reaction is 8～30 hours under the room temperature.
8. the hexagonal mesoporous and nanowire complex that is made by the said preparation method of claim 1 is characterized in that the nanometer line length that is comprised is 100～250nm, and diameter is 3～4nm, and specific area is 960～1098m
2G
-1, average pore size is 2.7～3.5nm.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1532230A (en) * | 2003-03-20 | 2004-09-29 | 中国科学院固体物理研究所 | Nano tin dioxide/silica dioxide mesoporous composite body and preparing method |
| US20060116284A1 (en) * | 2004-11-04 | 2006-06-01 | Pak Chan-Ho | Mesoporous carbon composite containing carbon nanotube |
| CN101205420A (en) * | 2007-12-06 | 2008-06-25 | 复旦大学 | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1532230A (en) * | 2003-03-20 | 2004-09-29 | 中国科学院固体物理研究所 | Nano tin dioxide/silica dioxide mesoporous composite body and preparing method |
| US20060116284A1 (en) * | 2004-11-04 | 2006-06-01 | Pak Chan-Ho | Mesoporous carbon composite containing carbon nanotube |
| CN101205420A (en) * | 2007-12-06 | 2008-06-25 | 复旦大学 | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof |
Non-Patent Citations (2)
| Title |
|---|
| 吴玉程，等.纳米镍_介孔二氧化硅复合材料的组装及结构和_省略_米镍/介孔二氧化硅复合材料的制.《复合材料学报》.2005,第22卷(第6期),21-26. * |
| 陆斌,等.高活性铈银介孔复合抗菌剂的制备.《中国稀土学报》.2008,第26卷(第1期),125-128. * |
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