CN101805013A - Synthesis method for grenade-shaped nanometer zinc oxide with low-temperature control - Google Patents

Synthesis method for grenade-shaped nanometer zinc oxide with low-temperature control Download PDF

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Publication number
CN101805013A
CN101805013A CN201010149062A CN201010149062A CN101805013A CN 101805013 A CN101805013 A CN 101805013A CN 201010149062 A CN201010149062 A CN 201010149062A CN 201010149062 A CN201010149062 A CN 201010149062A CN 101805013 A CN101805013 A CN 101805013A
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microemulsion
grenade
zinc oxide
aqueous solution
temperature control
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黄在银
姜俊颖
米艳
刘绍刚
周泽广
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Northwest Minzu University
Guangxi University for Nationalities
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Guangxi University for Nationalities
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention provides a synthesis method for grenade-shaped nanometer zinc oxide with low-temperature control. The method of invention uses quatermary microemulsion composed of nonionic surfactant alkyl polyoxyethylene (10) ether, cyclohexane, n-octanol and aqueous phase, with zinc acetate and sodium hydroxide as reactants. After mixing the components of the anti-phase microemulsion, the mixture is churned by the magnetic stirring apparatus under room temperature to produce even, transparent and stable anti-phase microemulsion. Then, sodium hydroxide water solution is added to the zinc acetate microemulsion to make the two components to react in a limited space. After supercritical water reaction and centrifugal separation, evenly-shaped grenade-shaped nanometer zinc oxide nanometer structure can be prepared by the repeated washings of acetone, twice distilled water and ethanol. The method of the invention makes use of patterns and domain-limiting functions of the reverse micelle microemulsion to fabricate grenade-shaped nanometer zinc oxide structure. The method is simple in productive technology, safe in production process. While the products do not easily coacervate, so that the invention can be widely used for fabrication of inorganic function materials with grenade-shaped structures.

Description

The method of the synthetic grenade-shaped nanometer zinc oxide of a kind of low temperature control
Technical field
The present invention relates to a kind of preparation of inorganic functional material, particularly a kind of method that adopts low temperature reverse micro emulsion assisting alcohol-hydrothermal method to prepare the controlled grenade-shaped nanometer zinc oxide of particle diameter.
Background technology
Zinc oxide (ZnO) is a kind of important semiconductor material with wide forbidden band, bandwidth can reach 3.37eV, very big exciton bind energy (60meV) is arranged, have performances such as excellent in chemical character and thermostability and good luminous, opto-electronic conversion, make it potential widely application be arranged in various fields, for example can be used for luminescent material, photoelectric conversion material, coating and daily-use chemical industry material, can be used for making honourable electrode, transformer and multiple Optical devices.Simultaneously ZnO still is a kind of Biosafety and the good material of Bc, can be used for the carrier of biological medicine or biosensor etc.Nano material shows special light, electricity, magnetic and catalytic performance owing to having quantum size and macro quanta tunnel effect etc., caused the great interest of people, the research of its preparation and performance has become field very active in the present material science, and the size of the performance of material and particle and pattern are closely related.Therefore, when synthesis of nano ZnO particle, control very important that its pattern, size and distribution of sizes just show.The growth mechanism of research ZnO nano material, and regulate and control the basis that its growth is the micro-nano device of preparation future feature.Synthetic existing a lot of reports of relevant ZnO nano material, comprise physical sputtering sedimentation, chemical Vapor deposition process, electrochemical synthesis method, thermal evaporation, metal organic vapor (MOVPE) technology, laser method, microemulsion method, solvent thermal are synthetic, hydro-thermal is synthetic with the template synthesis method etc., have synthesized nano wire, nanometer rod, nano belt, nanotube, nano-rings, nanometer bow, nanometer flower, nanometer sheet of ZnO or the like.
Sui etc. [X.M.Sui, Y.C.Liu.Chemical Physics Letters.2006,424,340] adopt microemulsion method to synthesize the nano-ZnO of hexa-prism; Zhang etc. [J.Zhang, L.D.Sun.New J.Chem.2002,26,33] adopt the microemulsion assisting alcohol-hydrothermal method to synthesize the nano wire of ZnO; Guo etc. [L.Guo, Y.L.Ji.J.AM.CHEM.SOC.2002,124,14864] utilize the microemulsion approach to synthesize the nanometer rod of uniform ZnO; Inoguchi etc. [M.Inoguchi, K.Suzuki.J.Am.Ceram.Soc.2008,91,3850] utilize microemulsion method to synthesize the ZnO nano particle of granularity less than 10nm; Needle-like, column and ball-like structure that Li etc. [X.C.Li, G.H.He.Journal ofColloid and Interface Science.2009,333,465] adopt the microemulsion assisting alcohol-hydrothermal method to synthesize nano-ZnO; Zhang etc. [H.Zhang, D.Yang, D.S.Li.Crystal Growth and Design.2005,5,547] utilize end-capping reagent molecule assisting alcohol-hydrothermal method to synthesize the ZnO crystallite of dumbbell shaped structure; Zhao etc. [M.Zhao, D.P.Wu, J.L.Chang.Materials Chemistry and Physics.2009,117,422] adopt bromination n-Hexadecane trimethyl ammonium assisting alcohol-hydrothermal method to prepare the ZnO crystallite of cup-like structure.At present, do not see the bibliographical information that comes synthesis of nano ZnO grenade structure by simple microemulsion assisting alcohol-hydrothermal method.
Summary of the invention
The objective of the invention is to provide that a kind of production technique is simple, safety in order to overcome the defective that above-mentioned prior art exists, product particle pattern, controlled amount, be uniformly dispersed, the preparation method of the grenade-shaped nano structure of zinc oxide that product performance are good, this method is to carry out at low temperatures simultaneously, reaction conditions is gentle relatively, does not need to get final product with the direct centrifugation of emulsion splitter.
Purpose of the present invention can be achieved through the following technical solutions: the method for the synthetic grenade-shaped nano structure of zinc oxide of a kind of low temperature control is characterized in that this preparation method selects raw material nonionogenic tenside alkyl polyoxyethylene (10) ether, hexanaphthene, n-Octanol, Zn (Ac) for use 2The aqueous solution forms microemulsion, after each component of forming microemulsion is mixed, is prepared into the reverse micro emulsion of homogeneous transparent, the aqueous solution of NaOH is dropwise added contain Zn (Ac) again 2Microemulsion in, Zn (Ac) 2With NaOH at confinement space internal reaction, after auxiliary water thermal response, centrifugation, washing make grenade-shaped nano structure of zinc oxide.Concrete preparation process is as follows:
1), with raw material alkyl polyoxyethylene (10) ether, hexanaphthene, n-Octanol and Zn (Ac) 2The aqueous solution is inserted in the beaker of 50ml, selected alkyl polyoxyethylene (10) ether surface active agent and pure blended quality percentage composition, Zn (Ac) 2The ratio ω of the amount of substance of the amount of substance of the aqueous solution and alkyl polyoxyethylene (10) ether, Zn (Ac) 2The concentration of the aqueous solution after above-mentioned each component mixing, stirred 10 minutes on constant temperature blender with magnetic force under the room temperature, was mixed with uniform Zn (Ac) 2Microemulsion;
2), with Zn (Ac) 2Microemulsion places on the constant temperature blender with magnetic force, at room temperature dropwise drips the NaOH aqueous solution, and along with the adding of the NaOH aqueous solution, microemulsion becomes white gradually, dropwises the back and continues to stir 30 minutes;
3), with step 2) microemulsion that obtains is transferred to that to carry out hydro-thermal in the 25mL teflon-lined autoclave auxiliary, design temperature and time, reaction naturally cools to room temperature after finishing;
4), white precipitate centrifugation that step 3) is obtained, again with acetone, redistilled water and dehydrated alcohol repeatedly wash with
Remove unnecessary tensio-active agent and water, thereby obtain grenade-shaped ZnO nanostructure.Compared with prior art, the present invention has following characteristics:
1, the grenade-shaped nano structure of zinc oxide among the present invention is formed in the microemulsion water nuclear, by the parameter that forms microemulsion is adjusted, and then the particle diameter and the structure of control microemulsion water nuclear, obtains the nano structure of zinc oxide of desired pattern.
2, the present invention carries out at low temperatures, gentle relatively, the easily control of condition, and energy expenditure is little, and cost is low.
3, the present invention can be widely used in the preparation of other grenade-shaped inorganic functional materials.
Description of drawings
Fig. 1 is the SEM figure of the grenade-shaped nanometer zinc oxide of the embodiment of the invention 1 preparation;
Fig. 2 is the SEM figure of the grenade-shaped nanometer zinc oxide of the embodiment of the invention 2 preparations;
Fig. 3 is the SEM figure of the grenade-shaped nanometer zinc oxide of the embodiment of the invention 3 preparations;
Fig. 4 is the SEM figure of the grenade-shaped nanometer zinc oxide of the embodiment of the invention 4 preparations;
The X-ray diffractogram (XRD) of the grenade-shaped nanometer zinc oxide that Fig. 5 makes for the inventive method.
Embodiment
The invention will be further described below in conjunction with specific embodiment, and the description of embodiment is only for ease of understanding the present invention, but not to the restriction of the present invention's protection.
Embodiment 1
Preparation comprises 0.1mol/L Zn 2+Zn (Ac) 2Microemulsion, wherein the amount of substance concentration of tensio-active agent (alkyl polyoxyethylene (10) ether) is 0.25mol/L, and the mol ratio ω of water and tensio-active agent is 2.5, and all the other are oil phase content; Configuration 0.2mol/L OH -The NaOH aqueous solution.Under the stirring at room condition, will with used Zn (Ac) 2The isopyknic NaOH aqueous solution of the aqueous solution dropwise joins Zn (Ac) 2In the microemulsion, dropwise the back and continue to stir 30 minutes, then it is transferred to that to carry out hydro-thermal in the autoclave of 25mL inner liner polytetrafluoroethylene auxiliary, 120 ℃ of design temperatures, time 12h, reaction naturally cools to room temperature after finishing.The white precipitate centrifugation that obtains is repeatedly washed removing unnecessary tensio-active agent and water with acetone, distilled water and dehydrated alcohol, thereby is obtained grenade-shaped nanometer ZnO, as Fig. 1.
Embodiment 2
Preparation comprises 0.1mol/L Zn 2+Zn (Ac) 2Microemulsion, wherein the amount of substance concentration of tensio-active agent (alkyl polyoxyethylene (10) ether) is 0.25mol/L, and the mol ratio ω of water and tensio-active agent is 5.0, and all the other are oil phase content; Configuration 0.2mol/L OH -The NaOH aqueous solution.Under the stirring at room condition, will with used Zn (Ac) 2The isopyknic NaOH aqueous solution of the aqueous solution dropwise joins Zn (Ac) 2In the microemulsion, dropwise the back and continue to stir 30 minutes, then it is transferred to that to carry out hydro-thermal in the 25mL teflon-lined autoclave auxiliary, 120 ℃ of design temperatures, time 12h, reaction naturally cools to room temperature after finishing.The white precipitate centrifugation that obtains is repeatedly washed removing unnecessary tensio-active agent and water with acetone, distilled water and dehydrated alcohol, thereby is obtained grenade-shaped nanometer ZnO, as Fig. 2.
Embodiment 3
Preparation comprises 0.1mol/L Zn 2+Zn (Ac) 2Microemulsion, wherein the amount of substance concentration of tensio-active agent (alkyl polyoxyethylene (10) ether) is 0.25mol/L, and the mol ratio ω of water and tensio-active agent is 7.5, and all the other are oil phase content; Configuration 0.2mol/L OH -The NaOH aqueous solution.Under the stirring at room condition, will dropwise join Zn (Ac) with the isopyknic NaOH aqueous solution of used Zn (Ac) 2 aqueous solution 2In the microemulsion, dropwise the back and continue to stir 30 minutes, then it is transferred to that to carry out hydro-thermal in the 25mL teflon-lined autoclave auxiliary, 120 ℃ of design temperatures, time 12h, reaction naturally cools to room temperature after finishing.The white precipitate centrifugation that obtains is repeatedly washed removing unnecessary tensio-active agent and water with acetone, distilled water and dehydrated alcohol, thereby is obtained grenade-shaped nanometer ZnO, as Fig. 3.
Embodiment 4
Preparation comprises 0.1mol/L Zn 2+Zn (Ac) 2Microemulsion, wherein the amount of substance concentration of tensio-active agent (alkyl polyoxyethylene (10) ether) is 0.25mol/L, and the mol ratio ω of water and tensio-active agent is 10, and all the other are oil phase content; Configuration 0.2mol/L OH -The NaOH aqueous solution.Under the stirring at room condition, will with used Zn (Ac) 2The isopyknic NaOH aqueous solution of the aqueous solution dropwise joins Zn (Ac) 2In the microemulsion, dropwise the back and continue to stir 30 minutes, then it is transferred to that to carry out hydro-thermal in the 25mL teflon-lined autoclave auxiliary, 120 ℃ of design temperatures, time 12h, reaction naturally cools to room temperature after finishing.The white precipitate centrifugation that obtains is repeatedly washed removing unnecessary tensio-active agent and water with acetone, distilled water and dehydrated alcohol, thereby is obtained grenade-shaped nanometer ZnO, as Fig. 4.

Claims (6)

1. the method for the synthetic grenade-shaped nanometer zinc oxide of low temperature control is characterized in that this preparation method selects raw material nonionogenic tenside alkyl polyoxyethylene (10) ether, hexanaphthene, n-Octanol, Zn (Ac) for use 2The aqueous solution forms microemulsion, after each component of forming microemulsion is mixed, is prepared into the reverse micro emulsion of homogeneous transparent, the NaOH aqueous solution is dropwise added contain Zn (Ac) again 2Microemulsion in, Zn (Ac) 2With NaOH at confinement space internal reaction, after auxiliary water thermal response, centrifugation, washing make grenade-shaped nanometer zinc oxide, concrete preparation process is as follows:
1), with raw material alkyl polyoxyethylene (10) ether, hexanaphthene, n-Octanol and Zn (Ac) 2The aqueous solution is inserted in the beaker of 50ml, selected alkyl polyoxyethylene (10) ether surface active agent and pure blended quality percentage composition, Zn (Ac) 2The ratio ω of the amount of substance of the amount of substance of the aqueous solution and alkyl polyoxyethylene (10) ether, Zn (Ac) 2The concentration of the aqueous solution after above-mentioned each component mixing, stirred 10 minutes on constant temperature blender with magnetic force under the room temperature, was mixed with uniform Zn (Ac) 2Microemulsion;
2), with Zn (Ac) 2Microemulsion places on the constant temperature blender with magnetic force, at room temperature dropwise drips the certain density NaOH aqueous solution, and along with the adding of the NaOH aqueous solution, microemulsion becomes white gradually, dropwises the back and continues to stir 30 minutes;
3), with step 2) microemulsion that obtains is transferred in the stainless steel cauldron of 25mL inner liner polytetrafluoroethylene, design temperature and time, carry out the hydro-thermal assisted reaction, reaction naturally cools to room temperature after finishing;
4), with the white precipitate centrifugation that step 3) obtains, wash with acetone, distilled water and dehydrated alcohol again, thereby obtain grenade-shaped nanometer ZnO.
2. the preparation method of low temperature control synthesizing zinc oxide nanometer grenade according to claim 1 is characterized in that the amount of substance concentration of tensio-active agent alkyl polyoxyethylene (10) ether in the microemulsion system is 0.25mol/L.
3. the preparation method of low temperature control synthesizing zinc oxide nanometer grenade according to claim 1 is characterized in that the mol ratio ω of water and tensio-active agent is 2.5～10 in the described step 1).
4. the preparation method of low temperature control synthesizing zinc oxide nanometer grenade according to claim 1 is characterized in that described step 2) middle Zn 2+With the mol ratio of NaOH be 1: 2.
5. the preparation method of low temperature control synthesizing zinc oxide nanometer grenade according to claim 1 is characterized in that the reaction times in the described step 3) is 12 hours.
6. the preparation method of low temperature control synthesizing zinc oxide nanometer grenade according to claim 1 is characterized in that the temperature of reaction in the described step 3) is 120 ℃.
CN201010149062A 2010-04-19 2010-04-19 Synthesis method for grenade-shaped nanometer zinc oxide with low-temperature control Pending CN101805013A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102259907A (en) * 2011-06-30 2011-11-30 上海大学 Porous zinc oxide nano material and preparation method thereof
CN102838159A (en) * 2012-09-26 2012-12-26 内蒙古科技大学 Method for synthesizing nano-zinc oxide by micro-emulsion carbon black adsorption precipitation method
CN105924148A (en) * 2016-04-13 2016-09-07 南方科技大学 Forming method of ceramic powder

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1613774A (en) * 2004-11-16 2005-05-11 浙江大学 Preparation for zinc oxide nanometer material
WO2005044722A1 (en) * 2003-11-06 2005-05-19 Nanohybrid Co., Ltd. Method for forming zno nano-array and zno nanowall for uv laser on silicon substrate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005044722A1 (en) * 2003-11-06 2005-05-19 Nanohybrid Co., Ltd. Method for forming zno nano-array and zno nanowall for uv laser on silicon substrate
CN1613774A (en) * 2004-11-16 2005-05-11 浙江大学 Preparation for zinc oxide nanometer material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《合成化学》 20091231 胡寒梅等 室温超声合成哑铃状纳米氧化锌 第236-238页 1-6 第17卷, 第2期 2 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102259907A (en) * 2011-06-30 2011-11-30 上海大学 Porous zinc oxide nano material and preparation method thereof
CN102259907B (en) * 2011-06-30 2014-05-14 上海大学 Porous zinc oxide nano material and preparation method thereof
CN102838159A (en) * 2012-09-26 2012-12-26 内蒙古科技大学 Method for synthesizing nano-zinc oxide by micro-emulsion carbon black adsorption precipitation method
CN105924148A (en) * 2016-04-13 2016-09-07 南方科技大学 Forming method of ceramic powder
CN105924148B (en) * 2016-04-13 2018-12-21 南方科技大学 A kind of forming method of ceramic powders

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Open date: 20100818