CN102826557A - Method for preparing silicon oxide nanotube and two-dimensional ordered assembly body thereof - Google Patents
Method for preparing silicon oxide nanotube and two-dimensional ordered assembly body thereof Download PDFInfo
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- CN102826557A CN102826557A CN2012103603891A CN201210360389A CN102826557A CN 102826557 A CN102826557 A CN 102826557A CN 2012103603891 A CN2012103603891 A CN 2012103603891A CN 201210360389 A CN201210360389 A CN 201210360389A CN 102826557 A CN102826557 A CN 102826557A
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Abstract
The invention belongs to the technical field of an advanced nano-composite material, and particularly relates to a method for preparing a silicon oxide nanotube and a two-dimensional ordered assembly body of the silicon oxide nanotube. In the method, two segmented copolymers prepared in the laboratory are used as a template agent, a solvent volatizing inducing gathering self-assembly method is adopted, and a silicon oxide nanotube material with even bore diameter and length is mildly synthesizing under room temperature by taking tetraethoxysilane and the like as a silicon source, wherein the diameter is approximately to be 50nm, and the mean length is approximately to be 500nm. Under the condition that a small quantity of organosilane is added, the obtained silicon oxide nanotube can be assembled to form into a two-dimensional ordered nanopore material. The synthesized silicon oxide nanotube has even one-dimensional closed pore channel, biocompatibility, photoluminescence property, surface paintability and the like, so that the silicon oxide nanotube is wide in application prospects in the aspects such as the heterogeneous catalysis, drug load, limited range synthesis, nano-electronic appliance and environment monitoring sensor. The raw materials are easy to obtain, and the method is simple in technology, controllable in reaction conditions, free from high-temperature reaction, and suitable for expanded production.
Description
Technical field
The invention belongs to advanced nano composite material technical field, be specially a kind of method for preparing monox nanometer pipe and sequential 2 D assembly thereof.
Background technology
As a kind of typical monodimension nanometer material, the monox nanometer pipe has attracted whole world scientist's extensive studies interest in recent years.Because the physicochemical property that the biocompatibility of monox nanometer tube material, pl-property, surface modificability or the like are remarkable; Can be applied to comprising that heterogeneous catalyst, drug loading, confinement are synthetic, nano electron device, environment monitoring sensor or the like field, shown wide application prospect.
Before this, the used template of preparation monox nanometer pipe is hard template such as carbon nanotube, metal oxide nano rod mostly, and the preparation process is complicated, cost is higher; The yardstick of the resulting monox nanometer pipe of the surfactants based soft template method of several examples few in number is inhomogeneous, is difficult to realize accurate control (Satishkumar, the B. C. to its diameter and length; Govindaraj, A.; Vogl, E. M.; Basumallick, L.; Rao, C. N. R.
J. Mater.Res.
1997,
12,604. Martin, C. R.
Science 1994,
266,1961. Gao, C. B.; Lu, Z. D.; Yin, Y. D.
Langmuir 2011,
27,12201. Harada, M.; Adachi, M.
Adv. Mater.
2000 , 12,839.).
Summary of the invention
The object of the present invention is to provide simple, the lower-cost method for preparing monox nanometer pipe and sequential 2 D assembly thereof of a kind of process.
The method for preparing monox nanometer pipe and sequential 2 D assembly thereof proposed by the invention; Be to utilize tetraethoxy etc. as the silicon source; With the di-block copolymer with T 46155 strong hydrophilicity block is template, under the condition that continues the stirring reaction system, realizes.Volatilization along with good solvent; The hydrolysis of silicon source forms the silicon-dioxide oligopolymer, and passes through hydrogen bond action with PEO, and silica dioxide granule is attached to the spherical micelle surface; Under the effect of stirring shearing force, spherical micelle collides and forms gradually " head is met and discussed " the one-dimensional rod-like structure each other; After removing template, obtain unidimensional monox nanometer pipe.If after adding the silicon source, add a small amount of organosilane to reaction system in the 2-6 h; On the then formed rod-shaped micelle outside finish organic group; Reduced the mutual hydrogen bond action power between the micella; Micella mutually " shoulder to shoulder " arrange and form two dimensional structure, remove template after, obtain the mano-porous material of monox nanometer pipe assembling can formation sequential 2 D.
Among the present invention, the diameter (20-60 nm) that can regulate the monox nanometer pipe through the size of regulating the hydrophobic block molecular weight.(under the condition of organosilane quality/tetraethoxy (or methyl silicate) quality=1:30-1:2), the monox nanometer pipe can be assembled the mano-porous material of formation sequential 2 D, and spacer does adding a small amount of organosilane
P6
Mm
The inventive method is applicable to PEO-
b-PS, PEO-
b-PI, PEO-
bMacromolecular template agent such as-PMMA.With methyl silicate or tetraethoxy is that precursor can obtain similar structure.
Concrete steps of the present invention are following:
, and this template is dissolved in the good solvent as template with the di-block copolymer that contains polyoxyethylated strong hydrophilicity block,, obtains the solution of clear to wherein adding poor solvent and acid solution; Continuing under the stirring condition, normal pressure volatilization good solvent spends the night (being generally 6-16 h), and temperature is between 0-15 ℃; In reaction system, add inorganic species, continue to stir the volatilization good solvent; A large amount of white precipitates appear at last, after washing and the centrifugal collection, directly 0-40 ℃ of oven dry; And then hydrothermal treatment consists, collect the hydrothermal treatment consists product, oven dry; In retort furnace, calcine 4-8 h then, temperature perhaps utilizes solvent-extracted method to remove template between 450-900 ℃, promptly obtains unidimensional monox nanometer pipe.
In above-mentioned whole process; If in reaction system, also add a spot of organo-silicon ester in the 2-6 h behind the inorganic species of adding; The add-on of organo-silicon ester is: organo-silicon ester quality/inorganics mass=1:30-1:2; Other steps are identical with condition, then can prepare the sequential 2 D assembly of monox nanometer pipe.
Among the present invention, used good solvent is a THF, and poor solvent is water or simple alcohols material; Used acid is hydrochloric acid, nitric acid, acetic acid or sulfuric acid; Used inorganic species are the ester class, comprise methyl silicate or tetraethoxy; Used organo-silicon ester comprises organic silicone grease and methyl, ethyl, the substituted in various degree methyl silicate of propyl group or the tetraethyl silicate of various methyl, ethyl, propyl group, phenyl, xenyl or vinyl bridging.
The present invention adopts magnetic stirring apparatus to continue the stirring reaction system, and the magnetic agitation rotating speed is 100-1000 rev/min.
The temperature of hydrothermal treatment consists according to the invention is 80-150 ℃, and the hydro-thermal reaction time is 20-50 h.
The diameter that the present invention can regulate the monox nanometer pipe through the size of regulating the hydrophobic block molecular weight, monox nanometer pipe diameter is 20-60 nm.
The present invention can utilize solvent-extracted method to remove template, and to realize the recycle of template, the available solvent comprises Pottasium Hydroxide, sodium hydroxide, calcium hydroxide or soda-lime etc.
The monox nanometer tube material of preparing method's preparation of the present invention, diameter is approximately 50 nm, and mean length is approximately 500 nm.Under the condition that adds a small amount of organosilane, the monox nanometer pipe can be assembled the mano-porous material that forms sequential 2 D, and spacer does
P6
Mm
The synthetic monox nanometer pipe that obtains of the present invention has uniform one dimension sealing duct, biocompatibility, pl-property, surface modificability etc.; Aspects such as therefore, it is synthetic at heterogeneous catalyst, drug loading, confinement, nano electron device, environment monitoring sensor have broad application prospects.Raw material of the present invention is easy to get, and technology is simple, and the reaction conditions may command need not pyroreaction, is fit to enlarge produce.
Description of drawings
Fig. 1: the transmission electron microscope picture of monox nanometer pipe.
Fig. 2: the transmission electron microscope picture of the sequential 2 D assembly of monox nanometer pipe.Wherein, a, side-view; B, vertical view.
Embodiment
Embodiment 1: with 30 mg PEO-
b-PS is dissolved in the 8 g THFs, adds 1.5 g, the 2 M HCl aqueous solution, obtains the solution of clear, is about 5 ℃ in room temperature and stirs spend the night (12 h) that volatilize down; In above-mentioned solution, add 0.30 g tetraethoxy, continue to stir (rotating speed is 100 rev/mins) volatilization (if the sequential 2 D assembly of preparation monox nanometer pipe then adds 20 mg after adding tetraethoxy 5 h
1,2-two (triethoxy is silica-based) ethene), to a large amount of white precipitates of last appearance; After washing and the centrifugal collection, in 15 ℃ of oven dry; Redispersion is in the 2 M HCl aqueous solution, in 100 ℃ of hydro-thermal 24 h; Collect the hydro-thermal product, in 15 ℃ of oven dry; With resulting white solid 550 ℃ of calcining 5 h in retort furnace.
Embodiment 2: with 30 mg PEO-
b-PS is dissolved in the 10 g THFs, adds 2 g, the 2 M HCl aqueous solution, obtains the solution of clear, is about 10 ℃ in room temperature and stirs spend the night (8 h) that volatilize down; In above-mentioned solution, add 0.30 g methyl silicate, continue to stir (rotating speed is 200 rev/mins) volatilization (if the sequential 2 D assembly of preparation monox nanometer pipe then adds 50 mg after adding methyl silicate 4 h
1,2-two (triethoxy is silica-based) ethane), to a large amount of white precipitates of last appearance; After washing and the centrifugal collection, in 25 ℃ of oven dry; Redispersion is in the 2 M HCl aqueous solution, in 120 ℃ of hydro-thermal 20 h; Collect the hydro-thermal product, in 25 ℃ of oven dry; With resulting white solid 500 ℃ of calcining 6 h in retort furnace.
Embodiment 3: with 30 mg PEO-
b-PS is dissolved in the 10 g THFs, adds 1.5 g, the 2 M HCl aqueous solution, obtains the solution of clear, is about 10 ℃ in room temperature and stirs spend the night (10 h) that volatilize down; In above-mentioned solution, add 0.30 g tetraethoxy; Continue to stir (rotating speed is 200 rev/mins) volatilization (if sequential 2 D assembly of preparation monox nanometer pipe; Then after adding methyl silicate 3 h, add 30 mg diethylammonium diethoxy silanes), to a large amount of white precipitates of last appearance; After washing and the centrifugal collection, in 20 ℃ of oven dry; Redispersion is in the 2 M HCl aqueous solution, in 80 ℃ of hydro-thermal 30 h; Collect the hydro-thermal product, in 20 ℃ of oven dry; Resulting white solid is scattered in the excessive sodium hydroxide solution, is heated to 80-100 ℃ of backflow, to remove template; Centrifugal collection gained solid, dried after being washed is handled.
Embodiment 4: with 30 mg PEO-
b-PI is dissolved in the 12 g THFs, adds 2.0 g, the 2 M HCl aqueous solution, obtains the solution of clear, is about 10 ℃ in room temperature and stirs spend the night (8 h) that volatilize down; In above-mentioned solution, add 0.30 g methyl silicate; Continue to stir (rotating speed is 200 rev/mins) volatilization (if sequential 2 D assembly of preparation monox nanometer pipe; Then after adding methyl silicate 5 h, add 100 mg ethyl trimethoxy silanes), to a large amount of white precipitates of last appearance; After washing and the centrifugal collection, in 15 ℃ of oven dry; Redispersion is in the 2 M HCl aqueous solution, in 100 ℃ of hydro-thermal 30 h; Collect the hydro-thermal product, in 15 ℃ of oven dry; Resulting white solid is scattered in the excessive aqua calcis, is heated to 80-100 ℃ of backflow, to remove template; Centrifugal collection gained solid, dried after being washed is handled.
Embodiment 5: with 30 mg PEO-
b-PI is dissolved in the 10 g THFs, adds 1.5 g, the 2 M HCl aqueous solution, obtains the solution of clear, is about 5 ℃ in room temperature and stirs spend the night (10 h) that volatilize down; In above-mentioned solution, add 0.30 g tetraethoxy; Continue to stir (rotating speed is 150 rev/mins) volatilization (if sequential 2 D assembly of preparation monox nanometer pipe; Then after adding methyl silicate 6 h, add 30 mg dimethyldiethoxysilanes), to a large amount of white precipitates of last appearance; After washing and the centrifugal collection, in 15 ℃ of oven dry; Redispersion is in the 2 M HCl aqueous solution, in 80 ℃ of hydro-thermal 30 h; Collect the hydro-thermal product, in 15 ℃ of oven dry; With resulting white solid 600 ℃ of calcining 6 h in retort furnace.
Embodiment 6: with 30 mg PEO-
b-PMMA is dissolved in the 10 g THFs, adds 1.5 g, the 2 M HCl aqueous solution, obtains the solution of clear, is about 10 ℃ in room temperature and stirs spend the night (10 h) that volatilize down; In above-mentioned solution, add 0.30 g tetraethoxy; Continue to stir (rotating speed is 100 rev/mins) volatilization (if sequential 2 D assembly of preparation monox nanometer pipe; Then after adding methyl silicate 5 h, add 60 mg dimethyldimethoxysil,ne), to a large amount of white precipitates of last appearance; After washing and the centrifugal collection, in 40 ℃ of oven dry; Redispersion is in the 2 M HCl aqueous solution, in 80 ℃ of hydro-thermal 30 h; Collect the hydro-thermal product, in 40 ℃ of oven dry; With resulting white solid 600 ℃ of calcining 4 h in retort furnace.
Claims (8)
1. the preparation method of monox nanometer pipe and sequential 2 D assembly thereof is characterized in that concrete steps are following:
, and this template is dissolved in the good solvent as template with the di-block copolymer that contains polyoxyethylated strong hydrophilicity block,, obtains the solution of clear to wherein adding poor solvent and acid solution; Continuing under the stirring condition, normal pressure volatilization good solvent spends the night, and temperature is between 0-15 ℃; In reaction system, add inorganic species, continue to stir the volatilization good solvent; A large amount of white precipitates appear at last, after washing and the centrifugal collection, directly 0-40 ℃ of oven dry; And then hydrothermal treatment consists, collect the hydrothermal treatment consists product, oven dry; In retort furnace, calcine 4-8 h then, temperature perhaps utilizes solvent-extracted method to remove template between 450-900 ℃, promptly obtains unidimensional monox nanometer pipe;
In above-mentioned whole process; If in reaction system, also add a spot of organo-silicon ester in the 2-6 h behind the inorganic species of adding; The add-on of organo-silicon ester is: organo-silicon ester quality/inorganics mass=1:30-1:2; Other steps are identical with condition, then can prepare the sequential 2 D assembly of monox nanometer pipe.
2. preparation method according to claim 1 is characterized in that used template is selected from PEO-
b-PS, PEO-
b-PI or PEO-
b-PMMA.
3. preparation method according to claim 1 is characterized in that used good solvent is a THF, and poor solvent is water or alcohols material, and used acid is hydrochloric acid, nitric acid, acetic acid or sulfuric acid.
4. preparation method according to claim 1; It is characterized in that used inorganic species are the ester class; Comprise methyl silicate or tetraethoxy; Used organo-silicon ester comprises organic silicone grease of various methyl, ethyl, propyl group, phenyl, xenyl or vinyl bridging, and methyl, ethyl, the substituted in various degree methyl silicate of propyl group or tetraethyl silicate.
5. preparation method according to claim 1 is characterized in that described magnetic agitation rotating speed is 100-1000 rev/min.
6. preparation method according to claim 1, the temperature that it is characterized in that said hydrothermal treatment consists is 80-150 ℃, the hydro-thermal reaction time is 20-50 h.
7. preparation method according to claim 1, when it is characterized in that removing template with solvent-extracted method, said solvent is Pottasium Hydroxide, sodium hydroxide, calcium hydroxide or soda-lime.
8. preparation method according to claim 1 is characterized in that the diameter of regulating the monox nanometer pipe through the size of regulating the hydrophobic block molecular weight, and monox nanometer pipe diameter is 20-60 nm.
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Cited By (4)
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| CN104692398A (en) * | 2015-02-03 | 2015-06-10 | 天津大学 | Preparation method for three-dimensional continuous silicon dioxide nanotube |
| CN106588829A (en) * | 2016-11-03 | 2017-04-26 | 天津大学 | Tetrahydrofuran C-H multiphase oxidation method |
| CN106582845A (en) * | 2016-11-03 | 2017-04-26 | 天津大学 | Iridium based dipyridine-organic silicon nanotube heterogeneous catalyst and preparation method thereof |
| CN110203935A (en) * | 2019-05-31 | 2019-09-06 | 武汉纺织大学 | Tube wall is in the right-handed helix nano-tube material and preparation method for radiating hole arrangement |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104692398A (en) * | 2015-02-03 | 2015-06-10 | 天津大学 | Preparation method for three-dimensional continuous silicon dioxide nanotube |
| CN104692398B (en) * | 2015-02-03 | 2016-11-02 | 天津大学 | A kind of preparation method of the continuous Silica Nanotube of three-dimensional |
| CN106588829A (en) * | 2016-11-03 | 2017-04-26 | 天津大学 | Tetrahydrofuran C-H multiphase oxidation method |
| CN106582845A (en) * | 2016-11-03 | 2017-04-26 | 天津大学 | Iridium based dipyridine-organic silicon nanotube heterogeneous catalyst and preparation method thereof |
| CN106588829B (en) * | 2016-11-03 | 2019-03-05 | 天津大学 | Tetrahydrofuran C-H heterogeneous oxidation method |
| CN106582845B (en) * | 2016-11-03 | 2019-09-17 | 天津大学 | Iridium base bipyridyl-organic silicon nano pipe heterogeneous catalyst and preparation method |
| CN110203935A (en) * | 2019-05-31 | 2019-09-06 | 武汉纺织大学 | Tube wall is in the right-handed helix nano-tube material and preparation method for radiating hole arrangement |
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Application publication date: 20121219 |