CN102060321A - Preparation method of tin dioxide self-assembly nanostructure microsphere - Google Patents
Preparation method of tin dioxide self-assembly nanostructure microsphere Download PDFInfo
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Abstract
The invention discloses a preparation method of a tin dioxide self-assembly nanostructure microsphere, belonging to the preparation method of inorganic advanced nanometer materials. The preparation method comprises the following steps of: a, adding sodium stannate trihydrate and surfactant to a mixed solvent of alcohol and water, and then adding ethanolamine, wherein the mol ratio of the sodium stannate trihydrate to the surfactant is 1:2-1:3, the volume ratio of the alcohol to the water in the mixed solvent is 1:3.5-3:1, the amount of the added ethanolamine is 2-5ml in each 1mmol sodium stannate trihydrate; b, mixing the solvent and the solute at the step a by using a glass bar to obtain a uniformly distributed mixed solution; c, arranging the obtained mixed solution of the step b into a reaction kettle to carry out the hydrothermal reaction for 1-48h at 140-200 DEG C, and then naturally cooling to the room temperature after the reaction is finished; and d, centrifugally washing the obtained precipitation of the step c with water and anhydrous alcohol to obtain the tin dioxide self-assembly nanostructure microsphere. In the preparation method, the synthesis is carried out under the condition of solvent heat, the method is simple; and the tin dioxide self-assembly nanostructure microsphere has the advantages of low cost, even structure, uniform size distribution, universality and controllability, and also provides wide application prospect for gas sensitive devices.
Description
Technical field
The present invention relates to the preparation method of tindioxide self-assembled nano structures microballoon, particularly the preparation method of nanocone self-assembly ball belongs to inorganic advanced nano material preparation Technology field.
Background technology
A highly developed information society, sensor element is being played the part of more and more important role.Gas sensor is exactly wherein a kind of, it drive when intoxicated, aspect such as coal mining, fire alarm prevention bringing into play the effect that can not be substituted.Tindioxide be wide can gap semiconductor important member in the family, belong to the n N-type semiconductorN, its energy gap width reaches 3.6ev.It is the earliest, and is most important applications in one of material of air-sensitive.SnO
2Gas sensor has satisfactory stability, can work, check advantages such as gaseous species is more to become one of emphasis of gas sensor exploitation under lower working temperature because of it.
As everyone knows, at nanoscale, the pattern of material and size and their performance have the contact of countless ties, and the performance decision is used, and has the material of application just to be worth research.Therefore, the material of large-area homogeneous structural and even size distribution becomes the emphasis of our research.Present stage, various pattern SnO have been reported
2Nanocrystalline is synthetic: and nano wire (Cryst.Growth Des.2009,9,3958-3963.), nanometer rod (Cryst.Growth Des.2006,6,1584-1587), nano belt (Angew.Chem.Int.Ed.2002,41,2405-2408), ball (the Nanotechnology2007 of sea urchin shape, 18,355604), and meso-hole structure (Microporous MesoporousMater.2001,49,171-178) etc.Various nano SnO
2Synthetic method, (J.Phys.Chem.C 2008,112,11645-11649) as microwave auxiliary agent heating method, CVD (Langmuir 2005,21,7937-7944), and alumina formwork method (Actuators, B 2008,131,313-317) or the like, all there is the scientific research personnel to explore.Yet wet method is synthesized (Adv.Mater.2003,15,1022-1025; J.Am.Chem.Soc.2004,126,5972-5973; Adv.Mater.2005,17,1546-1548) owing to the product structure homogeneous, controllability is good, energy consumption is low, operate advantages such as simple and easy relatively, becomes the emphasis of research material performance.
Compare with other pattern, hollow ball (Chem.Eur.J.2006,12,2039-2047) have special structure, its advantage is that intermediate hollow nuclear part can coat big quality and large-sized guest molecule, is easy to adsorption desorption, and hollow ball is because the good spreadability of spheroidal particle, with other nano materials than easier assembling film forming, help the transmission of electronics, therefore in for some time, become the focus of research.Yet, have what material also better than the air-sensitive performance of hollow ball?
We have invented a kind of method of easy synthetic tindioxide self-assembled nano structures microballoon here, this method be a kind of be structural promoter with the tensio-active agent, utilize the controlled hydrolysis reaction of pink salt under the solvent thermal condition, prepare the tindioxide microballoon.Empirical tests, anion surfactant as Sodium dodecylbenzene sulfonate (SDBS), sodium lauryl sulphate (SDS) and cationic tensio-active agent, as cetyl trimethylammonium bromide (CTAB) etc., can be induced the formation of microballoon.Except tensio-active agent, we find the ratio of ethanol and water in the solvent, and the reaction times etc. are to SnO
2The control of nanometer ball pattern also plays an important role.This be since the ratio adjusting of ethanol and water can cause polarity of solvent and solubility change (Chem.Mater.2008,20,1841-1846): for example, sodium stannate trihydrate is water-soluble, be insoluble to ethanol, the increase of proportion of ethanol can improve the tendency that sodium stannate is separated out; And tensio-active agent such as CATB are dissolved in ethanol, hot water, but are insoluble to warm water, and attemperation then can change the solvability of tensio-active agent.These all can control SnO
2Nanoparticle nucleated process of growth, thereby the SnO of acquisition different internal structure
2Self-assembly microspheres.Comprise that mainly nanocone is assembled microballoon, nanometer rod assembles microballoon and nanometer rod is assembled three kinds of tiny balloons.And we find that its sensitivity of ball that nanocone is formed will be higher than hollow ball, and detectability is very low, and this development for gas sensitive device provides a good material and method.Being also advantageous in that under the hydrothermal condition of this method is synthetic, and method is simple, and is with low cost, the structure homogeneous, and even size distribution, and possess universality, controllability.Empirical tests, is specially adapted to drive when intoxicated etc. detect and uses at the detection medium sensitivity height to alcohol by the prepared gas sensor of this material.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of tindioxide self-assembled nano structures microballoon.
For achieving the above object, the present invention adopts following technical scheme:
The preparation method of tindioxide self-assembled nano structures microballoon is characterized in that the concrete steps of this method are:
A kind of preparation method of tindioxide self-assembled nano structures microballoon is characterized in that, this method is carried out as follows:
A. be 1 with mol ratio: 2-1: 3 sodium stannate trihydrates and tensio-active agent join in the mixed solvent of ethanol and water, and ethanol and water volume ratio are 1 in the mixed solvent: 3.5-3: 1; Add thanomin then, the thanomin add-on is every 1mmol sodium stannate trihydrate 2-5ml thanomin;
B. the solvent solute among the step a is mixed with glass stick and stir, obtain finely dispersed mixing solutions;
C. with step b gained mixing solutions 140-200 ℃ of temperature hydro-thermal 1-48h in reactor, reaction naturally cools to room temperature after finishing;
D. with step c gained precipitation water and dehydrated alcohol centrifuge washing, remove impurity, get final product tindioxide self-assembled nano structures microballoon.
Tensio-active agent described in the step a is that cetyl trimethyl bromine (chlorine) is changed ammonium, dodecyl trimethylammonium bromine (chlorine) is changed ammonium, tetradecyl trimethylammonium bromine (chlorine) change ammonium, octadecyl trimethylammonium bromine (chlorine) change ammonium, Sodium dodecylbenzene sulfonate or sodium laurylsulfonate etc.
By regulating the ratio of ethanol and water, reach synthetic various tindioxide self-assembled nano structures microballoons; When the ratio of ethanol and water is 1: 3.5, obtain the ball of nanocone assembling; When the ratio of ethanol and water is 2: 1, obtain the hollow ball of nanometer rod assembling; When the ratio of ethanol and water is 3: 1, obtain the solid sphere of nanometer rod assembling; When ethanol and water are other ratio, obtained the mixture of some other irregular structures or said structure.
Its diameter of ball of nanocone assembling is controlled at 300～1500nm, and the hollow ball diameter of nanometer rod assembling is controlled at 150～350nm, and the diameter of solid sphere of nanometer rod assembling is controlled at 100～300nm.
Further, the compactedness of mixing solutions in reactor is 35-72% among the step c.
Further, the temperature of reaction described in the step c is 160-180 ℃; Reaction times is 24-36h.
Method of the present invention is under the condition of solvent thermal, regulates polarity of solvent and solubleness by the ratio that changes ethanol and water, has carried out different maturing process, thereby can obtain several different SnO
2The self-assembled nano structures microballoon.The advantage of this method is under the solvent thermal condition synthetic, and method is simple, and is with low cost, the structure homogeneous, and even size distribution, and possess universality, controllability.Method provided by the present invention provides wide application prospect for the development of gas sensitive device.
Description of drawings
Fig. 1 is that ethanol and water volume ratio are to obtain SnO at 1: 3.5 in the embodiment of the invention one
2TEM figure.
Fig. 2 A is that ethanol and water volume ratio are to obtain SnO at 1: 3.5 in the embodiment of the invention one
2Low power SEM figure; Figure B is the SEM figure .. under the high power of this embodiment
Fig. 3 A is that ethanol and water volume ratio are to obtain SnO at 1: 3.5 in the embodiment of the invention one
2Air-sensitive test pattern figure B be the sensitivity curve of this embodiment.
Fig. 4 is that ethanol and water volume ratio are to obtain SnO at 2: 1 in the embodiment of the invention two
2TEM figure.
Fig. 5 A is that ethanol and water volume ratio are to obtain SnO at 2: 1 in the embodiment of the invention two
2Low power SEM figure; Figure B is the SEM figure under the high power of this embodiment.Fig. 6 A is that ethanol and water volume ratio are to obtain SnO at 2: 1 in the embodiment of the invention two
2The air-sensitive test pattern; Figure B is the SEM figure under the high power of this embodiment.
Fig. 7 is that ethanol and water volume ratio are to obtain SnO at 3: 1 in the embodiment of the invention three
2TEM figure.
Fig. 8 A is that ethanol and water volume ratio are to obtain SnO at 3: 1 in the embodiment of the invention three
2SEM figure; Figure B is the SEM figure .. under the high power of this embodiment
Fig. 9 A is that ethanol and water volume ratio are to obtain SnO at 3: 1 in the embodiment of the invention three
2The air-sensitive test pattern; Figure B is the sensitivity curve of this embodiment.
Figure 10 is that tensio-active agent is the SnO that Sodium dodecylbenzene sulfonate obtains in the embodiment of the invention four
2SEM figure.
Figure 11 A is the SnO that obtains in the embodiment of the invention four
2The air-sensitive test pattern; Figure B is the sensitivity curve of this embodiment.
Figure 12 is product S nO in the embodiment of the invention five
2SEM figure.
Figure 13 A is the SnO that obtains in the embodiment of the invention five
2The air-sensitive test pattern; Figure B is the sensitivity curve of this embodiment.
Figure 14 is product S nO in the embodiment of the invention six
2TEM figure.
Figure 15 A is the SnO that obtains in the embodiment of the invention six
2The air-sensitive test pattern; Figure B is the sensitivity curve of this embodiment.
Figure 16 is product S nO in the embodiment of the invention seven
2SEM figure.
Figure 17 A is the SnO that obtains in the embodiment of the invention seven
2The air-sensitive test pattern; Figure B is the sensitivity curve of this embodiment.
Figure 18 is product S nO in the embodiment of the invention eight
2TEM figure.
Figure 19 A is the SnO that obtains in the embodiment of the invention eight
2The air-sensitive test pattern; Figure B is the sensitivity curve of this embodiment.
Figure 20 is product S nO in the embodiment of the invention nine
2SEM figure.
Figure 21 A is the SnO that obtains in the embodiment of the invention nine
2The air-sensitive test pattern; Figure B is the sensitivity curve of this embodiment.
Embodiment
Embodiment one:
(1) at first, take by weighing the sodium stannate trihydrate of 1mmol and the cetyl trimethylammonium bromide of 2mmol and join 5ml ethanol, in the mixed solvent of 17.5ml water.
(2) get in the mixing solutions that the 5ml ethanolamine solutions joins (1), stir with glass stick and mixed to solution in 5 minutes.(3) solution being transferred to volume is that 45ml has in the teflon-lined stainless steel autoclave, and compactedness is 61%, inserts baking oven and carries out hydro-thermal reaction, temperature is 180 ℃, reaction times is 24 hours, and reaction is reduced to room temperature, centrifuge washing still bottom product after finishing.
(4) the still bottom product adds dehydrated alcohol centrifugal 5min under rotating speed 4500r/min, remove supernatant liquor and add deionized water centrifugal 5min under rotating speed 4500r/min again, remove supernatant liquor and add dehydrated alcohol centrifugal 5min under rotating speed 4500r/min again, finally obtain the pattern homogeneous, the SnO of the nanocone assembling of even size distribution
2Ball.
(5) product is made gas sensor, test its ethanol air-sensitive performance, its sensitivity is 67.1 under the 200ppm alcohol vapour.
Referring to Fig. 1-3.
Change reaction parameter, 140～200 ℃ of temperature of reaction, reaction times 1～48h can obtain similar results, changes tensio-active agent and can get similar results as palmityl trimethyl ammonium chloride, dodecyl trimethylammonium bromine ammonium chloride, Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride.
Embodiment two:
(1) at first, take by weighing the sodium stannate trihydrate of 1mmol and the cetyl trimethylammonium bromide of 2mmol and join 15ml ethanol, in the mixed solvent of 7.5ml water.
(2) get in the mixing solutions that the 5ml ethanolamine solutions joins (1), stir with glass stick and mixed to solution in 5 minutes.
(3) solution being transferred to volume is that 45ml has in the teflon-lined stainless steel autoclave, and compactedness is 61%, inserts baking oven and carries out hydro-thermal reaction, temperature is 180 ℃, reaction times is 24 hours, and reaction is reduced to room temperature, centrifuge washing still bottom product after finishing.
(4) the still bottom product adds dehydrated alcohol centrifugal 5min under rotating speed 4500r/min, remove supernatant liquor and add deionized water centrifugal 5min under rotating speed 4500r/min again, remove supernatant liquor and add dehydrated alcohol centrifugal 5min under rotating speed 4500r/min again, finally obtain the pattern homogeneous, the SnO of the nanometer rod assembling of even size distribution
2Hollow ball.
(5) product is made gas sensor, test its ethanol air-sensitive performance, its sensitivity is 34.9 under the 200ppm alcohol vapour.
Referring to Fig. 4-6.
Change reaction parameter, 140～200 ℃ of temperature of reaction, reaction times 1～48h can obtain similar results, changes tensio-active agent and can get similar results as palmityl trimethyl ammonium chloride, dodecyl trimethylammonium bromine ammonium chloride, Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride.
Embodiment three:
(1) at first, take by weighing the sodium stannate trihydrate of 1mmol and the cetyl trimethylammonium bromide of 2mmol and join 17ml ethanol, in the mixed solvent of 5.5ml water.
(2) get in the mixing solutions that the 5ml ethanolamine solutions joins (1), stir with glass stick and mixed to solution in 5 minutes.
(3) solution being transferred to volume is that 45ml has in the teflon-lined stainless steel autoclave, and compactedness is 61%, inserts baking oven and carries out hydro-thermal reaction, temperature is 180 ℃, reaction times is 24 hours, and reaction is reduced to room temperature, centrifuge washing still bottom product after finishing.
(4) the still bottom product adds dehydrated alcohol centrifugal 5min under rotating speed 4500r/min, remove supernatant liquor and add deionized water centrifugal 5min under rotating speed 4500r/min again, remove supernatant liquor and add dehydrated alcohol centrifugal 5min under rotating speed 4500r/min again, finally obtain the pattern homogeneous, the SnO of the nanometer rod assembling of even size distribution
2Solid sphere.
(5) product is made gas sensor, test its ethanol air-sensitive performance, its sensitivity is 5.7 under the 200ppm alcohol vapour.
Referring to Fig. 7-9.
Change reaction parameter, 140～200 ℃ of temperature of reaction, reaction times 1～48h can obtain similar results, changes tensio-active agent and can get similar results as palmityl trimethyl ammonium chloride, dodecyl trimethylammonium bromine ammonium chloride, Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride.
Embodiment four:
(1) at first, take by weighing the sodium stannate trihydrate of 1mmol and the Sodium dodecylbenzene sulfonate of 0.70g and join 7.5ml ethanol, in the mixed solvent of 7.5ml water.
(2) get in the mixing solutions that the 5ml ethanolamine solutions joins (1), stir with glass stick and mixed to solution in 5 minutes.
(3) solution being transferred to volume is that 45ml has in the teflon-lined stainless steel autoclave, and compactedness is 44%, inserts baking oven and carries out hydro-thermal reaction, temperature is 170 ℃, reaction times is 36 hours, and reaction is reduced to room temperature, centrifuge washing still bottom product after finishing.
(4) the still bottom product adds dehydrated alcohol centrifugal 5min under rotating speed 4500r/min, remove supernatant liquor and add deionized water centrifugal 5min under rotating speed 4500r/min again, remove supernatant liquor and add dehydrated alcohol centrifugal 5min under rotating speed 4500r/min again, finally obtain the pattern homogeneous, the SnO of even size distribution
2Nanocone.
(5) product is made gas sensor, test its ethanol air-sensitive performance, its sensitivity is 60.6 under the 200ppm alcohol vapour.
Referring to Figure 10-11.
Use the tensio-active agent sodium laurylsulfonate instead and can get similar results.
Embodiment five:
(1) at first, take by weighing the sodium stannate trihydrate of 2mmol and the cetyl trimethylammonium bromide of 6mmol and join 11.25ml ethanol, in the mixed solvent of 11.25ml water.
(2) get in the mixing solutions that the 10ml ethanolamine solutions joins (1), stir with glass stick and mixed to solution in 5 minutes.
(3) solution being transferred to volume is that 45ml has in the teflon-lined stainless steel autoclave, and compactedness is 72%, inserts baking oven and carries out hydro-thermal reaction, temperature is 170 ℃, reaction times is 24 hours, and reaction is reduced to room temperature, centrifuge washing still bottom product after finishing.
(4) the still bottom product adds dehydrated alcohol centrifugal 5min under rotating speed 4500r/min, remove supernatant liquor and add deionized water centrifugal 5min under rotating speed 4500r/min again, remove supernatant liquor and add dehydrated alcohol centrifugal 5min under rotating speed 4500r/min again, finally obtain the pattern homogeneous, the SnO of the nanocone assembling of even size distribution
2Ball.
(5) product is made gas sensor, test its ethanol air-sensitive performance, its sensitivity is 62.2 under the 200ppm alcohol vapour.
Referring to Figure 12-13.
Embodiment six:
(1) at first, take by weighing the sodium stannate trihydrate of 1mmol and the cetyl trimethylammonium bromide of 2mmol and join 16.5ml ethanol, in the mixed solvent of 6.5ml water.
(2) get in the mixing solutions that the 5ml ethanolamine solutions joins (1), stir with glass stick and mixed to solution in 5 minutes.
(3) solution being transferred to volume is that 45ml has in the teflon-lined stainless steel autoclave, and compactedness is 62%, inserts baking oven and carries out hydro-thermal reaction, temperature is 170 ℃, reaction times is 24 hours, and reaction is reduced to room temperature, centrifuge washing still bottom product after finishing.
(4) the still bottom product adds dehydrated alcohol centrifugal 5min under rotating speed 4500r/min, remove supernatant liquor and add deionized water centrifugal 5min under rotating speed 4500r/min again, remove supernatant liquor and add dehydrated alcohol centrifugal 5min under rotating speed 4500r/min again, finally obtain the pattern homogeneous, the SnO of even size distribution
2Hollow ball.
(5) product is made gas sensor, test its ethanol air-sensitive performance, its sensitivity is 72.7 under the 200ppm alcohol vapour.
Referring to Figure 14-15.
Embodiment seven:
(1) at first, take by weighing the sodium stannate trihydrate of 1mmol and the cetyl trimethylammonium bromide of 2mmol and join 5ml ethanol, in the mixed solvent of 17.5ml water.
(2) get in the mixing solutions that the 5ml ethanolamine solutions joins (1), stir with glass stick and mixed to solution in 5 minutes.
(3) solution being transferred to volume is that 45ml has in the teflon-lined stainless steel autoclave, and compactedness is 61%, inserts baking oven and carries out hydro-thermal reaction, temperature is 140 ℃, reaction times is 48 hours, and reaction is reduced to room temperature, centrifuge washing still bottom product after finishing.
(4) the still bottom product adds dehydrated alcohol centrifugal 5min under rotating speed 4500r/min, remove supernatant liquor and add deionized water centrifugal 5min under rotating speed 4500r/min again, remove supernatant liquor and add dehydrated alcohol centrifugal 5min under rotating speed 4500r/min again, finally obtain the pattern homogeneous, the SnO of even size distribution
2The nanometer conisphere.
(5) product is made gas sensor, test its ethanol air-sensitive performance, its sensitivity is 45.4 under the 200ppm alcohol vapour.
Referring to Figure 16-17.
Embodiment eight:
(1) at first, take by weighing the sodium stannate trihydrate of 1mmol and the cetyl trimethylammonium bromide of 2mmol and join 15ml ethanol, in the mixed solvent of 7.5ml water.
(2) get in the mixing solutions that the 5ml ethanolamine solutions joins (1), stir with glass stick and mixed to solution in 5 minutes.
(3) solution being transferred to volume is that 45ml has in the teflon-lined stainless steel autoclave, and compactedness is 61%, inserts baking oven and carries out hydro-thermal reaction, temperature is 170 ℃, reaction times is 24 hours, and reaction is reduced to room temperature, centrifuge washing still bottom product after finishing.
(4) the still bottom product adds dehydrated alcohol centrifugal 5min under rotating speed 4500r/min, remove supernatant liquor and add deionized water centrifugal 5min under rotating speed 4500r/min again, remove supernatant liquor and add dehydrated alcohol centrifugal 5min under rotating speed 4500r/min again, finally obtain the SnO that pattern is a nanometer ball
2
(5) product is made gas sensor, test its ethanol air-sensitive performance, its sensitivity is 7.9 under the 200ppm alcohol vapour.
Referring to Figure 18-19.
Embodiment nine:
(1) at first, take by weighing the sodium stannate trihydrate of 0.5mmol and the cetyl trimethylammonium bromide of 1mmol and join 7.5ml ethanol, in the mixed solvent of 7.5ml water.
(2) get in the mixing solutions that the 1ml ethanolamine solutions joins (1), stir with glass stick and mixed to solution in 5 minutes.
(3) solution being transferred to volume is that 45ml has in the teflon-lined stainless steel autoclave, and compactedness is 35%, inserts baking oven and carries out hydro-thermal reaction, temperature is 200 ℃, reaction times is 1 hour, and reaction is reduced to room temperature, centrifuge washing still bottom product after finishing.
(4) the still bottom product adds dehydrated alcohol centrifugal 5min under rotating speed 4500r/min, remove supernatant liquor and add deionized water centrifugal 5min under rotating speed 4500r/min again, remove supernatant liquor and add dehydrated alcohol centrifugal 5min under rotating speed 4500r/min again, finally obtain the SnO that the part pattern is a cavity ring
2
(5) product is made gas sensor, test its ethanol air-sensitive performance, its sensitivity is 29.19 under the 200ppm alcohol vapour.
Referring to Figure 20-21.
Claims (4)
1. the preparation method of a tindioxide self-assembled nano structures microballoon is characterized in that, this method is carried out as follows:
A. be 1 with mol ratio: 2-1: 3 sodium stannate trihydrates and tensio-active agent join in the mixed solvent of ethanol and water, and ethanol and water volume ratio are 1 in the mixed solvent: 3.5-3: 1; Add thanomin then, the thanomin add-on is every 1mmol sodium stannate trihydrate 2-5ml thanomin;
B. the solvent solute among the step a is mixed with glass stick and stir, obtain finely dispersed mixing solutions;
C. with step b gained mixing solutions 140-200 ℃ of temperature hydro-thermal 1-48h in reactor, reaction naturally cools to room temperature after finishing;
D. with step c gained precipitation water and dehydrated alcohol centrifuge washing, remove impurity, get final product tindioxide self-assembled nano structures microballoon.
2. the preparation method of a kind of tindioxide self-assembled nano structures microballoon according to claim 1 is characterized in that: the tensio-active agent described in the step a is cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, Trimethyllaurylammonium bromide, Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, tetradecyl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, Sodium dodecylbenzene sulfonate or sodium laurylsulfonate.
3. the preparation method of a kind of tindioxide self-assembled nano structures microballoon according to claim 1 is characterized in that: the compactedness of mixing solutions in reactor is 35-72% among the step c.
4. the preparation method of a kind of tindioxide self-assembled nano structures microballoon according to claim 1 is characterized in that: the temperature of reaction described in the step c is 160-180 ℃; Reaction times is 24-36h.
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| CN102671652A (en) * | 2012-05-23 | 2012-09-19 | 上海师范大学 | Preparation method of SnO2 nanometer particle photocatalyst with controllable size |
| CN102874872A (en) * | 2012-10-26 | 2013-01-16 | 黑龙江大学 | Preparation method of multistage-structured flower-shaped molybdenum dioxide |
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| CN102671652A (en) * | 2012-05-23 | 2012-09-19 | 上海师范大学 | Preparation method of SnO2 nanometer particle photocatalyst with controllable size |
| CN102874872A (en) * | 2012-10-26 | 2013-01-16 | 黑龙江大学 | Preparation method of multistage-structured flower-shaped molybdenum dioxide |
| CN102874874A (en) * | 2012-10-26 | 2013-01-16 | 黑龙江大学 | Preparation method and application of multistage-structured flower-shaped molybdenum trioxide |
| CN102874872B (en) * | 2012-10-26 | 2014-07-23 | 黑龙江大学 | Preparation method of multistage-structured flower-shaped molybdenum dioxide |
| CN104176768A (en) * | 2013-05-22 | 2014-12-03 | 北京化工大学 | Metal-doped tin oxide transparent dispersion and preparation method |
| CN104176768B (en) * | 2013-05-22 | 2016-04-20 | 北京化工大学 | A kind of metal-doped tin oxide transparent dispersion and preparation method thereof |
| CN103364453A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Tin oxide-zinc oxide composite hollow microsphere air-sensitive sensing device and preparation method thereof |
| CN103364453B (en) * | 2013-06-28 | 2016-05-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Tin oxide-zinc oxide compound hollow microballoon gas-sensitive sensor device and preparation method |
| CN104445376A (en) * | 2014-11-05 | 2015-03-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Olivary porous stannic oxide sensitive to hydrogen sulfide as well as preparation and application |
| CN104445376B (en) * | 2014-11-05 | 2016-01-20 | 上海纳米技术及应用国家工程研究中心有限公司 | The olive shape porous oxidation tin of hydrogen sulfide sensitivity and Synthesis and applications |
| CN105271374A (en) * | 2015-11-21 | 2016-01-27 | 河南师范大学 | Preparation method of stannic oxide microspheres of oriented connection microstructure |
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