CN101785982A - Method for preparing hollow nanospheres by a hot emulsion method - Google Patents
Method for preparing hollow nanospheres by a hot emulsion method Download PDFInfo
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- CN101785982A CN101785982A CN201010108661A CN201010108661A CN101785982A CN 101785982 A CN101785982 A CN 101785982A CN 201010108661 A CN201010108661 A CN 201010108661A CN 201010108661 A CN201010108661 A CN 201010108661A CN 101785982 A CN101785982 A CN 101785982A
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Abstract
The invention relates to a method for preparing hollow nanospheres, i.e. a hot emulsion method. The method comprises the following technical steps: using metal salt water solution, surface active agents and the like as raw materials for preparing reverse microemulsion; carrying out constant-temperature crystallization in a hydro-thermal reaction kettle; and then, obtaining various hollow nanospheres through further roasting. The prepared nanosphere materials have the diameter between 100 and 300 nm and the sphere wall thickness about 200 nm. The method of the invention is applicable to the preparation of various hollow nanospheres such as copper oxide, zinc oxide, cerium oxide, nickel oxide, ferric oxide, tin oxide, copper sulphide and the like, and has the characteristics of mild reaction conditions, simple preparation process and the like.
Description
Technical field
The present invention relates to a kind of method for preparing hollow nanospheres, belong to the nano material preparation technical field.
Background technology
The hollow structure material since its wall thickness usually in the nanoscale scope, except that the special effects that nano material possessed, hollow material also has characteristics such as low-density, high-specific surface area, high Surface Permeability, thereby in fields such as chemistry, biotechnology, material science good application prospects is arranged.
Hard template method is a kind of method for preparing the hollow ball shell material.This method is chosen silica, carbon ball, polymer microballoon usually as template, utilizes the absorption of different metal particle at template surface, removes template by chemical etching or thermal decomposition process again, thus the different hollow ball shell materials of forming of preparation.Patent CN2008-10059885 adopts silica as template, document X.M.Sun, J.F.Liu, Y.D.Li.Chem.Eur.J.2006,12,2039-2047 utilizes the carbon ball as template, prepared the different hollow oxide nano spheres of forming such as tin oxide, aluminium oxide, nickel oxide respectively, but this method is destroyed the hollow structure of product easily in the process of removing template.
Document Adv.Mater.2006,18,2325-2329 and J.Cryst.Growth 2009,311,2285-2290 adopts hydro-thermal method, with water and ethanol as mixed solvent, with K
2SnO
33H
2O, PVP etc. have been feedstock production SnO
2And Cu
2O hollow nanospheres, but this method exists shortcomings such as the scope of application is single, severe reaction conditions.
Thereby the new method of inventing the synthetic hollow ball shell material of a kind of reaction condition gentleness, applied widely, easy operating is significant for the production and the application of nano material.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing the hollow ball nano material.
The present invention is a raw material preparation reverse micro emulsion with aqueous metal salt, surfactant, alkane etc., and it is carried out thermostatic crystallization in hydrothermal reaction kettle, can obtain the hollow ball nano material by further roasting again.It is simple that this method has a synthesis technique, advantage of wide range of application.By changing the reaction raw materials of aqueous phase, can prepare the different hollow ball nano materials of forming, and be easy to realize large-scale production.
Concrete steps of the present invention are as follows:
One, preparation reverse micro emulsion A
Oil phase, surfactant, cosurfactant and water are pressed 20-60: 3-10: 0.5-2: 0.5-2 percent by volume mixed preparing reverse micro emulsion A,
Wherein oil phase is that carbon number is the alkane of 5-10, preferably cyclohexane, n-hexane, pentane or normal heptane; Surfactant is triton x-100, Qu Latong X-114, tween or class of department; Cosurfactant is that carbon number is the alcohol of 4-8, preferably n-hexyl alcohol or n-butanol; Water is that concentration is 0.2～0.6mol/L soluble metal salting liquid, and described soluble metal salting liquid is copper nitrate, zinc nitrate, cerous nitrate, nickel nitrate, ferric nitrate, stannic chloride, copper chloride;
Two, preparation reverse micro emulsion B
Oil phase, surfactant, cosurfactant and water are pressed 20-60: 3-10: 0.5-2: 0.5-2 percent by volume mixed preparing reverse micro emulsion B,
Wherein oil phase is that carbon number is the alkane of 5-10, preferably cyclohexane, n-hexane, pentane or normal heptane; Surfactant is triton x-100, Qu Latong X-114, tween or class of department; Cosurfactant is that carbon number is the alcohol of 4-8, preferably n-hexyl alcohol or n-butanol; Water is that concentration is 0.2～1.5mol/L precipitant solution, and described precipitating reagent is ammoniacal liquor, carbonic hydroammonium, NaOH, vulcanized sodium;
Three, be 1: 1 ratio rapid mixing, stirring with reverse micro emulsion A and reverse micro emulsion B according to volume ratio, again mixed liquor be transferred in the hydrothermal reaction kettle, and carry out thermostatic crystallization that crystallization temperature is 100 ℃～200 ℃, crystallization time 6～48 hours; With the product that obtains after the crystallization,, can obtain the hollow ball nano material in 300 ℃～500 ℃ temperature roastings 2-7 hour.
This method is applicable to the hollow nanospheres of multiple materials such as preparation cupric oxide, zinc oxide, cerium oxide, nickel oxide, iron oxide, tin oxide, copper sulfide.
Result of study shows: the hot emulsion system that obtains under the above-mentioned condition helps the formation of spherical micelle, and then induces the generation of spherical intermediate product.Can be in metastable condition owing to centre of sphere part crystallite has higher surface,, can crystallization obtain the hollow ball shell material by the Ostwald ripening process.
Prepared product is carried out SEM, transmission electron microscope, powder x-ray diffraction analysis.The characterization result of product is seen Fig. 1-5,
Fig. 1 is embodiment 1 sample transmission electron microscope (TEM) figure, and lower right corner illustration is the partial enlarged drawing of sample.Fig. 1 shows that product has the hollow sphere structure, and diameter is 100～3000nm, and ball wall thickness is about 20nm.
Fig. 2 is X-ray diffraction (XRD) figure before and after the calcining of embodiment 1 sample, and the result shows that (Fig. 2 a) changes cupric oxide (Fig. 2 b) into after 300 ℃ of calcinings for cuprous oxide before the sample calcining.
Fig. 3 is the TEM figure of the cupric oxide that obtains after 300 ℃ of calcinings of embodiment 1 sample, calcines afterproduct as seen from Figure 3 and still has hollow structure, and partial enlarged drawing display ball wall is made up of nano microcrystalline.
Fig. 4 is embodiment 3 sample ESEMs (SEM), by the position of nanosphere partial fracture among Fig. 4 and depressed phenomenon as can be known product have hollow structure.
Fig. 5 is the TEM figure of the zinc oxide that obtains after 500 ℃ of calcinings of embodiment 3 samples, and the calcining afterproduct still has the hollow sphere structure.
The invention has the beneficial effects as follows: the present invention is a kind of new method of synthetic hollow nanospheres material, has the advantages that synthetic route is simple, easy to operate, be applicable to multiple nano material preparation.
Description of drawings
Fig. 1 is embodiment 1 sample TEM figure, and lower right corner illustration is the partial enlarged drawing of sample.
Fig. 2 is the XRD figure before and after the calcining of embodiment 1 sample.
Fig. 3 is the TEM figure of the cupric oxide that obtains after 300 ℃ of calcinings of embodiment 1 sample.
Fig. 4 is the SEM figure of embodiment 3 samples.
Fig. 5 is the TEM figure of the zinc oxide that obtains after 500 ℃ of calcinings of embodiment 3 samples.
The specific embodiment
Embodiment 1
(1) preparation reverse micro emulsion A
With the 40ml cyclohexane, the 4ml song draws logical X-114, the 2ml n-hexyl alcohol, and 1.5ml copper nitrate aqueous solution (0.6mol/L) mixing obtains reverse micro emulsion A;
(2) preparation reverse micro emulsion B.
Draw logical X-114,2ml n-hexyl alcohol and 1.5ml ammonia spirit (1.5mol/L) to mix 40ml cyclohexane, 4ml song and obtain reverse micro emulsion B.
(3) with above-mentioned reverse micro emulsion A and reverse micro emulsion B rapid mixing, mixed liquor is transferred in the hydrothermal reaction kettle after stirring, and carried out thermostatic crystallization 24 hours, crystallization temperature is 150 ℃, can get cuprous oxide hollow ball nano material, with the roasting 5 hours under 300 ℃ of conditions of the product that obtains, obtain cupric oxide hollow ball nano material.
Accompanying drawing 1 is the TEM figure of the cuprous oxide hollow ball nano material of the foregoing description preparation.As can be seen from the figure: product is the hollow sphere structure, and diameter is 100～2000nm, and wall thickness is about 20 nanometers.Fig. 2 a is the XRD figure before the calcining of embodiment 1 sample, and the result is cuprous oxide before showing the sample calcining.
Fig. 2 b is the XRD figure after the calcining of embodiment 1 sample, and the result shows that sample changes cupric oxide into after 300 ℃ of calcinings.Fig. 3 is the TEM figure of the cupric oxide hollow ball nano material of the foregoing description preparation.
Embodiment 2
Change the dosage of surfactant in step (1) and (2) among the embodiment 1 into 6ml, cosurfactant changes n-butanol into, and precipitating reagent changes NaOH into; Change the crystallization temperature in the step (3) into 140 ℃, all the other are with embodiment 1.The product that obtains still is hollow cupric oxide nano ball.
Embodiment 3
(1) preparation reverse micro emulsion A and reverse micro emulsion B.
Reverse micro emulsion A:30ml cyclohexane, 4ml triton x-100,2ml n-hexyl alcohol, 1.5ml zinc nitrate aqueous solution (0.6mol/L);
(2) reverse micro emulsion B:30ml cyclohexane, 4ml triton x-100,2ml n-hexyl alcohol, 1.5ml ammonia spirit (1.2mol/L).
(3) with above-mentioned reverse micro emulsion A and reverse micro emulsion B rapid mixing, mixed liquor is transferred in the hydrothermal reaction kettle after stirring, thermostatic crystallization 24 hours, crystallization temperature are 150 ℃.With the roasting 5 hours under 500 ℃ of conditions of the above-mentioned product that obtains, can obtain zinc oxide hollow ball nano material.
Accompanying drawing 4 is the scanning electron microscope diagram sheet of the product of the foregoing description preparation.As can be seen from the figure: product is the hollow sphere structure, and diameter is 100～3000nm.Fig. 5 is the TEM figure of the zinc oxide hollow ball nano material that obtains after the roasting.
Embodiment 4
Change the metal salt solution in the step (1) among the embodiment 3 into the butter of tin aqueous solution, all the other can get tin oxide hollow ball nano material with embodiment 3.
Embodiment 5
With in the step (1) among the embodiment 3 metal salt solution change copper chloride solution into, precipitating reagent changes sodium sulfide solution in the step (2), all the other can get copper sulfide hollow ball nano material with embodiment 3.
Claims (4)
1. a hot emulsion legal system is equipped with the method for hollow nanospheres, and concrete steps are as follows:
One, preparation reverse micro emulsion A
Oil phase, surfactant, cosurfactant and water are pressed 20-60: 3-10: 0.5-2: the percent by volume mixed preparing reverse micro emulsion A of 0.5-2,
Wherein oil phase is that carbon number is the alkane of 5-10, and surfactant is triton x-100, Qu Latong X-114, tween or class of department; Cosurfactant is that carbon number is the alcohol of 4-8; Water is that concentration is the soluble metal salting liquid of 0.2～0.6mol/L;
Two, preparation reverse micro emulsion B
Oil phase, surfactant, cosurfactant and water are pressed 20-60: 3-10: 0.5-2: 0.5-2 percent by volume mixed preparing reverse micro emulsion B;
Wherein oil phase is that carbon number is the alkane of 5-10, and surfactant is triton x-100, Qu Latong X-114, tween or class of department, and cosurfactant is that carbon number is the alcohol of 4-8; Water is that concentration is 0.2～1.5mol/L precipitant solution;
Three, be 1: 1 ratio rapid mixing, stirring with reverse micro emulsion A and reverse micro emulsion B according to volume ratio, again mixed liquor be transferred in the hydrothermal reaction kettle, and carry out thermostatic crystallization that crystallization temperature is 100 ℃～200 ℃, crystallization time 6～48 hours; With the product that obtains after the crystallization,, obtain hollow nanospheres in 300 ℃～500 ℃ temperature roastings 2-7 hour.
2. hot emulsion legal system according to claim 1 is equipped with the method for hollow nanospheres, its feature be the oil phase described in step 1 and the step 2 be cyclohexane, n-hexane, pentane or normal heptane; Cosurfactant is n-hexyl alcohol or n-butanol.
3. hot emulsion legal system according to claim 1 is equipped with the method for hollow nanospheres, it is characterized in that the soluble metal salting liquid described in strong request 1 step 1 is copper nitrate, zinc nitrate, cerous nitrate, nickel nitrate, ferric nitrate, stannic chloride, copper chloride.
4. hot emulsion legal system according to claim 1 is equipped with the method for hollow nanospheres, it is characterized in that the described precipitating reagent described in strong request 1 step 2 is ammoniacal liquor, carbonic hydroammonium, NaOH, vulcanized sodium.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145914A (en) * | 2011-03-02 | 2011-08-10 | 上海大学 | Method for preparing nano zinc oxide |
| CN103058259A (en) * | 2012-12-21 | 2013-04-24 | 湘潭大学 | Preparation method for chestnut-shaped copper sulphide hollow micron sphere composed of nanosheets |
| CN104004186A (en) * | 2014-05-16 | 2014-08-27 | 福州大学 | Hollow copper sulphide/polypyrrole nanometer compound and application thereof |
| CN105016374A (en) * | 2015-08-14 | 2015-11-04 | 天津城建大学 | Method for preparing CuS micro-spheres of hierarchic structures |
| CN105127435A (en) * | 2015-09-24 | 2015-12-09 | 桂林电子科技大学 | Low-temperature sintering nano-silver paste and preparation process thereof |
| CN105622066A (en) * | 2016-01-27 | 2016-06-01 | 中国科学院新疆理化技术研究所 | Method for preparing thermistor powdered material by microemulsion-hydrothermal synthesis |
| CN106868475A (en) * | 2017-01-10 | 2017-06-20 | 广西大学 | The preparation method of cupric oxide self assembly multilevel hierarchy array material |
| CN110861178A (en) * | 2019-11-05 | 2020-03-06 | 浙江农林大学 | Composite CuS preservative, preparation method and application |
| CN110861179A (en) * | 2019-11-05 | 2020-03-06 | 浙江农林大学 | Novel anti-leaching CuS preservative, preparation method and application |
| CN114832865A (en) * | 2022-06-15 | 2022-08-02 | 中国石油大学(华东) | Preparation method of molybdenum-based microemulsion catalyst applied to hydrocracking |
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2010
- 2010-02-05 CN CN201010108661A patent/CN101785982A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145914A (en) * | 2011-03-02 | 2011-08-10 | 上海大学 | Method for preparing nano zinc oxide |
| CN103058259A (en) * | 2012-12-21 | 2013-04-24 | 湘潭大学 | Preparation method for chestnut-shaped copper sulphide hollow micron sphere composed of nanosheets |
| CN104004186B (en) * | 2014-05-16 | 2016-06-29 | 福州大学 | A kind of hollow copper sulfide/polypyrrole nano-complex and application thereof |
| CN104004186A (en) * | 2014-05-16 | 2014-08-27 | 福州大学 | Hollow copper sulphide/polypyrrole nanometer compound and application thereof |
| CN105016374A (en) * | 2015-08-14 | 2015-11-04 | 天津城建大学 | Method for preparing CuS micro-spheres of hierarchic structures |
| CN105127435B (en) * | 2015-09-24 | 2017-06-23 | 桂林电子科技大学 | A kind of low temperature-sintered nano silver paste and preparation technology |
| CN105127435A (en) * | 2015-09-24 | 2015-12-09 | 桂林电子科技大学 | Low-temperature sintering nano-silver paste and preparation process thereof |
| CN105622066A (en) * | 2016-01-27 | 2016-06-01 | 中国科学院新疆理化技术研究所 | Method for preparing thermistor powdered material by microemulsion-hydrothermal synthesis |
| CN105622066B (en) * | 2016-01-27 | 2019-03-05 | 中国科学院新疆理化技术研究所 | A kind of preparation method of micro emulsion-hydro-thermal method synthesis thermistor powder body material |
| CN106868475A (en) * | 2017-01-10 | 2017-06-20 | 广西大学 | The preparation method of cupric oxide self assembly multilevel hierarchy array material |
| CN110861178A (en) * | 2019-11-05 | 2020-03-06 | 浙江农林大学 | Composite CuS preservative, preparation method and application |
| CN110861179A (en) * | 2019-11-05 | 2020-03-06 | 浙江农林大学 | Novel anti-leaching CuS preservative, preparation method and application |
| CN110861179B (en) * | 2019-11-05 | 2022-10-28 | 浙江农林大学 | Novel anti-leaching CuS preservative, preparation method and application |
| CN110861178B (en) * | 2019-11-05 | 2022-10-28 | 浙江农林大学 | Composite CuS preservative, preparation method and application |
| CN114832865A (en) * | 2022-06-15 | 2022-08-02 | 中国石油大学(华东) | Preparation method of molybdenum-based microemulsion catalyst applied to hydrocracking |
| CN114832865B (en) * | 2022-06-15 | 2023-08-22 | 中国石油大学(华东) | Preparation method of molybdenum-based microemulsion catalyst applied to hydrocracking |
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Open date: 20100728 |