CN100567147C - A kind of synthetic method of organic-inorganic composite silicon oxide nano-line - Google Patents
A kind of synthetic method of organic-inorganic composite silicon oxide nano-line Download PDFInfo
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- CN100567147C CN100567147C CNB2007101725272A CN200710172527A CN100567147C CN 100567147 C CN100567147 C CN 100567147C CN B2007101725272 A CNB2007101725272 A CN B2007101725272A CN 200710172527 A CN200710172527 A CN 200710172527A CN 100567147 C CN100567147 C CN 100567147C
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Abstract
The invention belongs to polymeric material field, relate generally to a kind of method of synthesizing organic-inorganic composite silicon oxide nano-line.In this method with unformed silicon oxide as the silicon source, the liquid-solid phase reaction single step reaction by the organic amine aqueous solution in the presence of iron generates organic-inorganic composite silicon oxide nano-line.Simple synthetic method, cheapness.The silica white nano-wire of the organic and inorganic composite structure of gained is owing to have good fluorescence activity, higher specific surface area, the high electric insulation performance, abundant advantages such as surface silanol group, thereby have great application potential in fields such as micro-nano device assembling, nano-array research, nanocomposite optical transmission, the high insulation resistances of nanometer; This organic-inorganic composite silicon oxide nano-line brightens fields such as preventing ultraviolet at traditional Industrial Catalysis, macromolecular material reinforcement, makeup and also holds out broad prospects as a kind of emerging nano material simultaneously.
Description
Technical field
The present invention is a condition of utilizing the liquid-solid phase hydro-thermal reaction, in the aqueous solution of quadrol unformed silicon oxide is prepared into the silica white nano-wire with organic and inorganic composite structure; The silica white nano-wire of this organic and inorganic composite structure will be transformed into pure inorganic monox nanometer after overpickling or roasting.
Background technology
Along with since finding CNT (carbon nano-tube) the nineties in 20th century for the first time, the development of nano science is maked rapid progress.Pattern by nano material in the preparation of nano material can be divided into: zero-dimension nano material such as nanoparticle, monodimension nanometer material such as nano wire, nanotube, nanometer rod, nanometer spiral, two-dimensional nano material such as nanometer sheet, nano belt, three-dimensional manometer array or the like.The different nano material of various patterns is owing to have quantum effect on the microcosmic, thereby embodies the characteristic of traditional material different from the past at aspects such as light, electricity, magnetic.And nano material itself is also because pattern difference separately causes it to have different characteristics.
The one dimension silica white nano-wire is owing to have high-insulativity, good fluorescent effect, high surface-area, the abundant characteristics such as silicon hydroxyl in surface, thereby has great application potential in fields such as micro-nano device assembling, nano-array research, nanocomposite optical transmission, the high insulation resistances of nanometer, as a kind of emerging nano material, the one dimension silica white nano-wire brightens fields such as preventing ultraviolet at traditional Industrial Catalysis, macromolecular material reinforcement, makeup and also holds out broad prospects simultaneously.Thereby the Study of synthesis method of one dimension silica white nano-wire is one of material field research focus in recent years.
In the research of microtexture and synthesis mechanism, have organic and inorganic structure compound material become recent concern focus and emphasis (Th.Mayera, U.Weiler.Renewable Energy 2008,33,262; Xingwen Zhang, Lijiang Hu.Journal of Molecular Structure 2008,872,197; Jun-Wei Zhao, Shou-Tian Zheng.Journal of Solid State Chemistry 2007,180,3317; Cle ' ment Roux, Feng Chai.Biomolecular Engineering 2007,24,549; Yinzhuang Zhou, Haiping Qiao.Inorganic Chemistry Communications2007,10,1318; Je-Deok Kima, Toshiyuki Mori.Journal of Power Sources 2007,172,694).The material that causes this class to have the organic and inorganic composite nanostructure has had the performance different with pure inorganic materials on physicalies such as light, electricity, magnetic because organic and inorganic structurally mixes, this type of material of what is more important can have the characteristic of inorganic materials, and had both some performances of organic materials, aspect scientific research and the production practice great function is being arranged.
At present, the synthetic method of silica white nano-wire mainly contains physics method and chemical method.The physics method is mainly laser ablation method (Laser Ablation Method) (Y.Ding Appl.Phys.Lett 1998,73,3076 for D.P.Yu, Q.L.Hang).The laser ablation method is that silicon, silicon oxide and iron catalyst are mixed and made into target by a certain percentage, and then under the pyritous situation, utilizes laser ablation growing silicon oxide nano wire.This method needs very high temperature, and needs laser ablation, brings great difficulty to large-scale commercial production.The chemistry rule mainly comprises: and pyrochemistry steam sedimentation (chemistry vapor deposition) (Y.J.Chen, J.B.Li.Appl.Phys.A 2002,74, and 433; Y.Q.Zhu, W.K.Hsu, David R.M.Walton.J.Mater.Chem 1998,8,1859; H.F.Zhang, C.M.Wang, L.S.Wang Nano.Lett2003,3,577; B.Zheng, Y.Y.Wu, P.D.Yang, J.Liu.dver.Mater 2002,14, and 122; Z.L.Wang, Ruiping P.Gao.Adver.Mater 2000,12,1938; C.H.Liang, L.D.Zhang.J.Non-Cryst.Solids 2000,277,63), sol-gel (Sol-Gel) (M.Zhang, Y.Bando.J.Mater.Sci.Lett 1999,18,1911), carbon helps growth (Carbon-Assited Growth) (B.L.V.Prasad.J.A.C.S 2003,125,10488), gas-solid phase hydro-thermal is synthesized (Ping Chen, Songhai Xie.J.A.C.S 2006,128,1470) etc. method.The sedimentation of pyrochemistry steam is to make silicon mix growing silicon oxide nano wire under the effect of metal catalyst with metal catalyst (iron, cobalt, gold, nickel, gallium etc.) by the mode that blasts gas under the pyritous situation in these methods.This method can obtain silica white nano-wire easily but required reaction conditions is very harsh, can't reach the requirement of scale operation silica white nano-wire.Sol-gel method is the effect by silicon source and template, the growing silicon oxide nano wire, and then, finally obtain silica white nano-wire by roasting or chemical corrosion removal template.This method does not need very high temperature, can be under comparatively gentle condition grow nanowire, but need to consume template, synthetic cost height, and the roasting of template also can pollute environment and is not suitable for scale operation equally.Carbon help the growth be under the pyritous situation, with carbon as catalyzer growing silicon oxide nano wire.This method is the same with pyrochemistry steam settling process to need very high temperature, is difficult to reach scale operation equally.And hydro-thermal synthetic reaction conditions is gentle relatively, thereby is suitable for a large amount of preparations.But because catalytic metal needs roasting just can be written in the hydrothermal synthesis method in the past, this not only causes reactions steps loaded down with trivial details, and energy consumption increases, simultaneously because roasting makes the silicon source of Nano grade sintering, agglomeration occur.Reaction not exclusively causes product purity to descend in a large amount of preparation process, and productive rate is not high.We improve the hydro-thermal building-up process in this patent.Found a kind of and the synthetic diverse ways of hydro-thermal in the past, this method not only has hydro-thermal synthetic advantage, and what is more important has further improved productive rate, has increased output, is suitable for the demand of large-scale industrial production fully.
Summary of the invention
The objective of the invention is to propose that a kind of technology is simple, with low cost, productive rate is high, output is high, be fit to the liquid-solid phase hydrothermal synthesis method of the organic-inorganic composite silicon oxide nano-line of suitability for industrialized production; Resulting organic and inorganic composite structure silica white nano-wire can obtain pure inorganic silica white nano-wire after pickling or roasting; This method can be in a large number, convenient, cheap preparation silica white nano-wire, can conveniently be applied to commercial process.
The invention provides a kind of synthetic method of organic-inorganic composite silicon oxide nano-line, this method may further comprise the steps:
(1) be raw material with unformed silicon oxide, add ferro element concentration and be the molysite aqueous solution of 0.1～2mol/l or ironic hydroxide glue that iron level is 0.1～2mol/l and mix silicon: the molar ratio of iron is 1: 0.1～2.5;
(2) add quadrol in the mixed solution in (1), whole system mixes, and the volume ratio of quadrol and water is 1: 0.2 ~ 10 in the reaction soln; Unformed silicon oxide and quadrol mass ratio are 1: 0.02～0.2.
(3) react 0.5～30 day reaction times, temperature of reaction 160-250 ℃ among the mixed solution in (2) being changed over to the reactor of sealing;
(4) product in (3) is obtained organic-inorganic composite silicon oxide nano-line after water and organic solvent or wherein a kind of cleaning; Perhaps, obtain pure organic and inorganic silica white nano-wire with product cleanup acid treatment in (3).
Among the present invention, unformed silicon oxide is any in following: mesopore silicon oxide, white carbon black or silicon sol etc.
Among the present invention, amorphous silicon oxide is a silicon sol.
Among the present invention, used molysite is iron(ic) chloride, iron nitrate, ferric sulfate or iron acetate.
Among the present invention, molysite is an iron trichloride.
Among the present invention, with in (3) during product cleaning water and anhydrous acetic acid clean in turn.
Among the present invention, the volume ratio of quadrol and water is 1: 0.5～5.
Among the present invention, the temperature of reaction in (3) is 180～220 ℃, 3～8 days time.
Among the present invention, the organic solvent that is used to clean is ethanol, acetone, ether, methyl alcohol, benzene or toluene.
Among the present invention, the product in (3) is washed with the acid solution of 0.1～5mol/l and is handled except that behind the iron that unloads, and product is white powdery solid, 30～100 ℃ of cleanup acid treatment temperature, 0.2～10 hour time cleaned up this pressed powder water, obtained pure inorganic oxide silicon nanowires.
Among the present invention, acid solution is hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or acetum.
Among the present invention, acid concentration 0.5～5mol/l.
Among the present invention, the acid treatment temperature is 40～90 ℃, 0.5～3 hour time.
The silica white nano-wire of the inventive method preparation has organic and inorganic compound structure, and this structure not only helps to study the mechanism that nano wire forms, and makes nanowire surface have the character different with general silica material simultaneously.The silica white nano-wire of the inventive method preparation has unique organic and inorganic composite structure and causes its peculiar property that has such as high-insulativity, good fluorescent effect, high surface-area, the abundant characteristics such as silicon hydroxyl in surface, and therefore this silica white nano-wire is expected in biological example fluorescent mark, nano-device assembling, microcosmic conduction and optics, electricity and magnetics material in a lot of fields synthetic potential using value is arranged.Utilize the method steps of liquid-solid phase hydro-thermal synthesizing organic-inorganic composite silicon oxide nano-line simple, the processing condition cost is low, the product purity height, and output is bigger, and the technology of purchasing is simple, conversion unit, it is with low cost to purchase, and therefore is fit to very much extensive synthetic.
Description of drawings
Fig. 1 is silicon sol A
1SEM figure.
Fig. 2 is organic-inorganic composite silicon oxide nano-line A
2SEM figure.
Fig. 3 is pure inorganic oxide silicon nanowires A
3SEM figure.
Fig. 4 is the SEM figure of white carbon black B1.
Fig. 5 is a product B
2SEM figure.
Fig. 6 is a product B
3TEM figure.
Fig. 7 is HMS silicon oxide bead C
1SEM figure.
Fig. 8 is a products C
2SEM figure.
Fig. 9 is a products C
3SEM figure.
Figure 10 is product D
1SEM figure.
Figure 11 is a product A
2TEM figure.
Figure 12 is the high power TEM figure of product A 2.
Figure 13 is a product A
2XRD figure spectrum.
Figure 14 is a product A
3XRD figure spectrum.
Figure 15 is a product A
2Infared spectrum.
Figure 16 is a product A
3Infared spectrum.
Embodiment
Example 1
With 3.75g silicon sol (silica content is 40%) A
1Be dispersed in the 25ml 0.5mol/l liquor ferri trichloridi and shake, after the system for the treatment of mixes, add ethylenediamine solution 40ml, concussion, ultrasonic 15 minutes.The mixed solution that mixes changed over to have in the teflon-lined reactor, tighten reactor and be placed among 200 ℃ of baking ovens, reacted 5 days; The green solid that reaction is good takes out water and ethanol cleans respectively 5 times, will obtain a kind of silica white nano-wire A with organic and inorganic composite structure
2This silica white nano-wire with organic and inorganic composite structure is used 1mol/l hydrochloric acid soln stir process 1 hour, and temperature is 80 ℃; Last again with the cleaning of the solid water after the salt acid treatment three times, after drying, room temperature obtains the pure inorganic oxide silicon nanowires of white powder solid A
3
Example 2
Experimentize with the method identical with example 1, but with 3.75g silicon sol A
1Change the white carbon black B of 1.50g into
1, can get product B
2(before the pickling) B
3(after the pickling).
Example 3
Experimentize with the method identical with example 1, but with 3.75g silicon sol A
1Change 1.50g HMS silicon oxide bead C into
1Can get product C
2(before the pickling) C
3(after the pickling).
Example 4
Experimentize with the method identical with example 1, but change quadrol into 1, the 6-hexanediamine will obtain the product D of partial reaction
1
Example 5
Experimentize with the method identical, but change iron trichloride into ironic hydroxide with example 1, iron nitrate, ferric sulfate can obtain having the silica white nano-wire E of organic and inorganic composite structure respectively after the reaction
1, E
2, E
3
Example 6
Experimentize with the method identical, but the volume ratio of quadrol and water was changed to 1: 5 o'clock by 1: 0.625 in the system, obtained having the silica white nano-wire F of organic and inorganic composite structure after the reaction with example 1
1
Example 7
Experimentize with the method identical, but when when reaction, temperature of reaction being changed to 170 ℃ and 22 ℃ respectively by 200 ℃, also can obtain organic-inorganic composite silicon oxide nano-line G respectively after the reaction with example 1
1, G
2
Example 8
Experimentize with the method identical, but when reaction, the reaction times was changed to 3 days by 5 days, 15 days, also can obtain organic-inorganic composite silicon oxide nano-line H respectively after the reaction with example 1
1, H
2
Example 9
Experimentize with the method identical with example 1, but when product is cleaned ethanol is changed to toluene respectively, ether cleans behind the acetone, also can obtain organic-inorganic composite silicon oxide nano-line I
1, I
2, I
3
Example 10
Experimentize with the method identical with example 1, but change hydrochloric acid soln into salpeter solution when pickling, sulphuric acid soln also can obtain pure inorganic silica white nano-wire J respectively after the pickling
1, J
2
Example 11
Experimentize with the method identical with example 1, but when pickling concentration of hydrochloric acid solution is changed to 0.5mol/l by 1mol/l, 4mol/l also can obtain pure inorganic silica white nano-wire K respectively after the pickling
1, K
2
Example 12
Experimentize with the method identical, but when pickling, pickling temperature is changed to 50 ℃ by 80 ℃, also can obtain pure inorganic silica white nano-wire L after the pickling with example 1
1
Example 13
Experimentize with the method identical, but do not add quadrol, then can not get the product nano wire after the reaction to reaction system with example 1.
Example 14
Experimentize with the method identical, but in reaction system, do not have the iron trichloride of adding, then can not get the product nano wire after the reaction with example 1.
The stereoscan photograph of the said products (SEM) all absorbs on Philips XL30 D6716 instrument, and lens photo (TEM) absorbs on JEOL JEM-2010 instrument.By Fig. 2,3,5,6 and 8,9 product A as can be seen
2, A
3, B
2, B
3, C
2, C
3Has the traditional thread binding structure of one dimension.With the product A of XRD (on Rigaku D/Max-IIA type X-ray diffractometer, carry out, see Figure 13,14) to gained
2, A
3Characterize.Use the product A of infrared spectroscopy (on Nicolet Nexus 470 class infrared spectrometer, carrying out) simultaneously to gained
2, A
3Characterize.Product A as can be seen from Figure 15
2Have organic and inorganic compound structure, Figure 16 shows the product A after overpickling
3Become pure inorganic nano thread structure; The product B that example 2 and 3 obtains
3, C
3With A
3Also identical, belong to same substance.
Claims (8)
1. the synthetic method of an organic-inorganic composite silicon oxide nano-line is characterized in that, this method may further comprise the steps:
(1) be raw material with unformed silicon oxide, add ferro element concentration and be the molysite aqueous solution of 0.1～2mol/l or ironic hydroxide glue that iron level is 0.1～2mol/l and mix silicon: the molar ratio of iron is 1: 0.1～2.5;
(2) add quadrol in the mixed solution in (1), whole system mixes, and the volume ratio of quadrol and water is 1: 0.2 ~ 10 in the reaction soln; Unformed silicon oxide and quadrol mass ratio are 1: 0.02～0.2;
(3) react 0.5～30 day reaction times, temperature of reaction 160-250 ℃ among the mixed solution in (2) being changed over to the reactor of sealing;
(4) product in (3) is obtained organic-inorganic composite silicon oxide nano-line after water and organic solvent or wherein a kind of cleaning.
2. synthetic method according to claim 1 is characterized in that unformed silicon oxide is any in following: mesopore silicon oxide, white carbon black or silicon sol.
3. synthetic method according to claim 2 is characterized in that amorphous silicon oxide is a silicon sol.
4. synthetic method according to claim 1 is characterized in that used molysite is iron(ic) chloride, iron nitrate, ferric sulfate or iron acetate.
5. synthetic method according to claim 4 is characterized in that molysite is an iron trichloride.
6. synthetic method according to claim 1, the volume ratio that it is characterized in that quadrol and water are 1: 0.5～5.
7. synthetic method according to claim 1 is characterized in that the temperature of reaction in (3) is 180～220 ℃, 3～8 days time.
8. synthetic method according to claim 1 is characterized in that the organic solvent that is used to clean is ethanol, acetone, ether, methyl alcohol, benzene or toluene.
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| CN103159501B (en) * | 2012-11-15 | 2014-08-20 | 中国科学院理化技术研究所 | Preparation method of core shell Si/Fe2O3 nanowire array |
| CN104310461B (en) * | 2014-09-28 | 2016-08-17 | 南京欣益浩化学科技有限公司 | A kind of preparation method of germania nanoparticles line |
| CN105502413B (en) * | 2015-12-08 | 2017-08-11 | 渤海大学 | A kind of SiO2The preparation method of amorphous nanometer wire and nanocrystal |
| CN105600793A (en) * | 2015-12-29 | 2016-05-25 | 中国石油化工股份有限公司 | Method for preparing silicon oxide nanofiber |
| CN106927471A (en) * | 2015-12-31 | 2017-07-07 | 新材料与产业技术北京研究院 | A kind of preparation method of nanometer silica line |
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