CN101920986B - Preparation method of zinc oxide nanosphere - Google Patents
Preparation method of zinc oxide nanosphere Download PDFInfo
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- CN101920986B CN101920986B CN 200910117086 CN200910117086A CN101920986B CN 101920986 B CN101920986 B CN 101920986B CN 200910117086 CN200910117086 CN 200910117086 CN 200910117086 A CN200910117086 A CN 200910117086A CN 101920986 B CN101920986 B CN 101920986B
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Abstract
The invention discloses a preparation method of a zinc oxide nanosphere which fills a gap of the prior art on a zinc oxide microsphere/ nanosphere. In the invention, the zinc oxide nanosphere is prepared by adopting a microwave chemical hydrothermal synthesis method, that is to say, the zinc oxide nanosphere is prepared by using an aqueous solution of simple zinc sources, such as zinc acetate, and the like and trolamine as a precursor solution through a microwave irradiation process. The preparation method of the zinc oxide nanosphere does not use any templates, additives and organic solvents, has a clean process, friendly environment, lower reaction temperature, and shorter reaction time, and microwave irradiation for 10 minutes at the temperature of 60 DEG C is enough, thereby saving energy sources with simplicity and high efficiency. The zinc oxide nanosphere product has even size distribution with the nanosphere diameter of 250-400nm, monodispersity, high production rate and low cost and is suitable for industrial production, and raw materials are easy to obtain.
Description
Technical field
The present invention relates to belong to the preparation field of nano material, specifically relate to the spherical preparation of nanomaterials of a kind of zinc oxide.
Background technology
Zinc oxide (ZnO) is as a kind of semiconductor material with wide forbidden band of direct band gap, its at room temperature energy gap be 3.37eV, and exciton bind energy is up to 60meV.The ZnO of nanoscale has light, electricity, magnetic, mechanics and the chemical property of a series of excellences, all is widely used in fields such as solar cell, photodiode, biosensor, photochemical catalysis, varistors.
In the preparation research of nanostructure, being assembled into the complicated orderly superstructure of two and three dimensions by a peacekeeping two-dimensional nanostructure unit is to have challenging research field.Because ZnO crystal has the polar growth characteristic, is oriented in monodimension nano stick and excellent aggregate structure.Therefore, preparing high symmetric ZnO micro-nano structure is the research focus that scientist constantly pursues.In recent years, the document of the spherical ZnO micro-nano structure of relevant preparation is very many.But existing document great majority all concentrate on two kinds technical: a kind of is pyrochemistry vapor transportation method; This method be earlier with the Zn powder at high-temperature gasification, fractional coagulation and oxidation finally obtain the ZnO micro-nano ball then; Though this technology process is simple, reaction mechanism clear, generally need special devices, high temperature (more than at least 500 ℃) and vacuum or protection gas atmosphere; Severe condition with respect to preceding a kind of technology; Another kind method is exactly the hot template of hydrothermal/solvent; This method is less demanding to equipment and envrionment temperature; But to want to overcome ZnO crystal polar growth habit in mutually at solution, just must introduce template and do the growth directed agents, no matter be to do hard template with sulfonation PS ball or zinc powder; Still adopt tensio-active agent such as polymkeric substance to do soft template, it is expensive (template generally all compare expensive), low output (when the removing template, bringing loss) and length consuming time (generally wanting several hrs at least) that this technology faces maximum difficulty.Therefore, at low temperature with do not rely under the spherical template situation, directly constructing spherical ZnO micro-nano structure is a very relevant challenge.
At present existing materials chemistry Research Scientists have realized this conception.The macromolecular science Shaanxi Province key lab poplar of Shaanxi Normal University is closed feelings etc. through zinc acetate and water and terepthaloyl moietie mixed solvent (V
Water/ V
Terepthaloyl moietie=1/20) synthesized the ZnO solid microsphere at 100 ℃ of hydro-thermal reaction 6h, diameter is 1～4 μ m; Prolonging the reaction times has obtained the ZnO tiny balloon to 12h, and the diameter of tiny balloon is 2～5 μ m, is formed by the nanometer sheet self-assembly of 10～20nm that (poplar is closed feelings; Li Li; Song Yuzhe etc., the no template Hydrothermal Preparation of ZnO nanometer sheet self-assembly tiny balloon and luminosity [J], Chinese science B collects: chemistry; 2007,37 (5): 417～425.); Be equally poplar close feelings etc. through zinc metal sheet and water in terepthaloyl moietie 120 ℃ react 12h, directly original position has synthesized the ZnO microballoon on zinc metal sheet, little 0.3～2 μ m of microsphere diameter; Also be nanometer sheet self-assembly by 30～50nm form (Li Li, poplar is closed feelings, Yu Jie etc.; Synthetic and the pl-[J] of the control of zinc oxide microballoon and stratiform aggregate; The chemistry journal, 2008,66 (3): 335～342.); The Shen Weizhuo of Shanghai Communications University etc. are raw material has synthesized core/shell structure under 85 ℃ of hydrothermal conditions ZnO microballoon (Zhu Y F with zinc nitrate, hexamethylenetetramine and Supragil GN; Fan D H; Shen W Z.Template-free synthesis of zinc oxide hollowmicrospheres in aqueous solution at low temperature [J], J.Phys.Chem.C, 2007; 111,18629～18635.); The Xu Changshan at the advanced photoelectric functional investigation of materials center of Northeast Normal University etc. are the zinc source with the zinc nitrate, and hexamethyl time amine is auxiliary reagent, and sodium hydroxide is alkali; Ethanol is solvent, at 70 ℃ of following solvent thermal reaction 5h, has synthesized nanometer ball (the Xu H T by the self-assembly of 20～30nm particle; Ning Y H; Liang J Q, et al.The structural and optical properties ofZnO nano-spheres synthesized via solvothermal method [J], Chinese J.Luminesence; 2008,29 (3): 513～518.).Broken away from the constraint of template though more than work, all selected organic solvent or other additives for use, and temperature of reaction is about 70～120 ℃, the reaction times is long, and the size of the ZnO microballoon of acquisition is bigger, and majority reaches micron order.
Our invention provides a kind of technology of preparing route of simpler and more direct zinc oxide nanosphere efficiently; Promptly adopt the microwave chemical hydrothermal synthesis method; The aqueous solution with simple zinc source such as zinc acetate and trolamine is precursor solution, goes on foot the microwave exposure process through one and can make the ZnO nanometer ball.The maximum characteristics of this invention are: do not use any template, additive and organic solvent, process cleaning, environmental friendliness; Temperature of reaction is lower, and the reaction times is shorter, get final product at 60 ℃ of microwave exposure 10min, and save energy, simple and direct efficient; Product cut size is evenly distributed, and the nanometer ball diameter is at 250～400nm, and list disperses; Productive rate is high, and raw material is easy to get, and is with low cost, suitability for industrialized production.Up to the present, the domestic and international step microwave chemical hydrothermal synthesis method that do not appear in the newspapers is as yet prepared the research contents of zinc oxide nanosphere.
Summary of the invention
The object of the present invention is to provide a kind of technology of preparing route of simple and direct zinc oxide nanosphere efficiently.
The objective of the invention is to realize through following technical scheme.
Technical scheme of the present invention is to adopt following procedure of processing to prepare zinc oxide nanosphere:
1) the simple zinc salt such as zinc acetate that takes by weighing 1mmol is mixed with Zn with deionized water
2+Solution A;
2) measure a certain amount of trolamine and be mixed with solution B with deionized water, the mol ratio of zinc salt and trolamine is 1: 3～1: 25;
3) under stirring state, solution A is joined in the solution B, form reaction liquid C, the reaction solution TV is 60mL;
4) reaction liquid C is placed microwave generator microwave exposure 5～25min, have a large amount of white precipitates to generate;
5) taking-up is cooled to room temperature, and filtering precipitate is with water washing 3 times;
6) place baking oven to heat 6～12h throw out, temperature is 40～60 ℃, collects white products and promptly obtains zinc oxide nanosphere of the present invention.
In the technique scheme, described simple zinc salt comprises zinc acetate, zinc nitrate, zinc chloride, zinc sulfate and Zinic stearas etc.
The working parameter of described microwave generator: power is 300W, and temperature is 60 ℃, and irradiation time is 10min.
Peach or apricot in the similar fruit of described zinc oxide nanosphere, the single dispersion, the nanometer ball diameter is formed by more tiny nanoparticle self-assembly at 250～400nm, and the particle diameter of nanoparticle is about 20nm.
Said that preparation technology's flow sheet equipment is simple, envrionment temperature is low, and is easy and simple to handle, good reproducibility; Do not adopt organic solvent and tensio-active agent to do template, the environmental friendliness cleaning; With short production cycle, productive rate is high, raw material sources are extensive, and are with low cost, suitability for industrialized production.
Description of drawings
Fig. 1 is the low power field scan electromicroscopic photograph of the prepared zinc oxide nanosphere of one embodiment of the invention;
Fig. 2 is the high power field scan electromicroscopic photograph of the prepared zinc oxide nanosphere of one embodiment of the invention;
Fig. 3 is the X-ray diffraction analysis figure of the prepared zinc oxide nanosphere of one embodiment of the invention;
Fig. 4 is the energy dispersion X-ray analysis figure of the prepared zinc oxide nanosphere of one embodiment of the invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further description:
Embodiment 1:
Take by weighing the 0.219g zinc acetate in the high pin beaker of 60mL, add the 10mL deionized water, stirring and dissolving; Measure the 1.98mL trolamine again to Erlenmeyer flask, add the 50mL deionized water, stirring and dissolving; Then zinc acetate aqueous solution is joined in the Erlenmeyer flask, continue to stir, have a small amount of white flocks to generate when beginning to mix; The Erlenmeyer flask that will fill reaction mixture is again inserted and is carried out microwave exposure in the microwave generator, sets microwave power 300W, 60 ℃ of temperature of reaction, microwave time 10min; Reaction naturally cools to room temperature after finishing, and has a large amount of white precipitates to generate, and filtering precipitate is with water washing 3 times; Throw out places baking oven to heat 8h, and temperature is 60 ℃, collects white products and promptly obtains zinc oxide nanosphere of the present invention.
Referring to accompanying drawing 1, the low power field scan electromicroscopic photograph of the zinc oxide nanosphere that makes by embodiment 1 described method.As can be seen from the figure ZnO nanometer ball output is high, good dispersivity, and size distribution is even.
Referring to accompanying drawing 2, the high power field scan electromicroscopic photograph of the zinc oxide nanosphere that makes by embodiment 1 described method.As can be seen from the figure ZnO nanometer ball diameter is between 250～400nm, and single nanometer ball is assembled by a large amount of more tiny nano particles, and the particle diameter of nano particle is about 20nm.
Referring to accompanying drawing 3; The X-ray diffraction analysis figure of the zinc oxide nanosphere that makes by embodiment 1 described method; The spectral line peak position is corresponding one by one with (100), (002), (101), (102), (110), (103), (200), (112), (201) diffraction crystal face of JCPDF standard card (05-664) among the figure; Be the ZnO of hexagonal wurtzite structure, spacer P6
3Mc.All diffraction peaks are strong and sharp-pointed, do not have the dephasign peak, show good crystallinity, the purity height of powder, and more obvious wideization of the peak width at half of diffraction peak shows that the particle diameter of powder is less.In conjunction with electronic microscope photos, show that also the ZnO nanometer ball is formed by the nano particle self-assembly.
Referring to accompanying drawing 4; The energy dispersion X-ray analysis figure of the zinc oxide nanosphere that makes by embodiment 1 described method; Show Zn, O and three kinds of elements of Al among the figure; Wherein the Al element derives from aluminium flake matrix, is approximately 1: 1 through the atomicity ratio that calculates Zn: O, shows that its chemical ingredients consists of ZnO.
Embodiment 2:
Take by weighing the 0.220g zinc acetate in the high pin beaker of 60mL, add the 10mL deionized water, stirring and dissolving; Measure the 1.32mL trolamine again to Erlenmeyer flask, add the 50mL deionized water, stirring and dissolving; Then zinc acetate aqueous solution is joined in the Erlenmeyer flask, continue to stir, have a small amount of white flocks to generate when beginning to mix; The Erlenmeyer flask that will fill reaction mixture is again inserted and is carried out microwave exposure in the microwave generator, sets microwave power 300W, 60 ℃ of temperature of reaction, microwave time 10min; Reaction naturally cools to room temperature after finishing, and has a large amount of white precipitates to generate, and filtering precipitate is with water washing 3 times; Throw out places baking oven to heat 8h, and temperature is 60 ℃, collects white products and promptly obtains zinc oxide nanosphere of the present invention.
Embodiment 3:
Take by weighing the 0.291g zinc nitrate in the high pin beaker of 60mL, add the 10mL deionized water, stirring and dissolving; Measure the 1.32mL trolamine again to Erlenmeyer flask, add the 50mL deionized water, stirring and dissolving; Then zinc acetate aqueous solution is joined in the Erlenmeyer flask, continue to stir, have a small amount of white flocks to generate when beginning to mix; The Erlenmeyer flask that will fill reaction mixture is again inserted and is carried out microwave exposure in the microwave generator, sets microwave power 300W, 60 ℃ of temperature of reaction, microwave time 10min; Reaction naturally cools to room temperature after finishing, and has a large amount of white precipitates to generate, and filtering precipitate is with water washing 3 times; Throw out places baking oven to heat 8h, and temperature is 60 ℃, collects white products and promptly obtains zinc oxide nanosphere of the present invention.
Claims (4)
1. the preparation method of a zinc oxide nanosphere is characterized in that, said method comprises following concrete steps:
1) the simple zinc salt such as zinc acetate that takes by weighing 1mmol is mixed with Zn with deionized water
2+Solution A;
2) measure a certain amount of trolamine and be mixed with solution B with deionized water, the mol ratio of zinc salt and trolamine is 1: 3～1: 25;
3) under stirring state, solution A is joined in the solution B, form reaction liquid C, the reaction solution TV is 60mL;
4) reaction liquid C is placed microwave generator microwave exposure 5～25min, have a large amount of white precipitates to generate;
5) taking-up is cooled to room temperature, and filtering precipitate is with water washing 3 times;
6) place baking oven to heat 6～12h throw out, temperature is 40～60 ℃, collects white products and promptly obtains zinc oxide nanosphere of the present invention.
2. the preparation method of a kind of zinc oxide nanosphere according to claim 1 is characterized in that, the simple zinc salt described in the step (1) comprises zinc acetate, zinc nitrate, zinc chloride, zinc sulfate and Zinic stearas etc.
3. the preparation method of a kind of zinc oxide nanosphere according to claim 1 is characterized in that, the working parameter of the microwave generator described in the step (4): power is 300W, and temperature is 60 ℃, and irradiation time is 10min.
4. the preparation method of a kind of zinc oxide nanosphere according to claim 1; It is characterized in that; Peach or apricot in the similar fruit of described zinc oxide nanosphere, the single dispersion, the nanometer ball diameter is at 250～400nm; Nanoparticle self-assembly by more tiny forms, and the particle diameter of nanoparticle is about 20nm.
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| CN102324309B (en) * | 2011-06-30 | 2013-05-08 | 东南大学 | Zinc oxide composite nano structure for dye sensitized solar cell photoanode and preparation method of zinc oxide composite nano structure |
| CN102881462B (en) * | 2012-09-20 | 2015-12-16 | 太原理工大学 | A kind of preparation method of ZnO nano rod array/nano grain cluster microballoon sphere composite film |
| CN103789765A (en) * | 2014-01-02 | 2014-05-14 | 上海大学 | Method for forming Ag/ZnO core-shell structure on silicon substrate through inclination angle method |
| CN106379930A (en) * | 2016-11-09 | 2017-02-08 | 上海天地涂料有限公司 | Interface microwave preparation method of zinc oxide nanometer material |
| CN106495128A (en) * | 2016-11-09 | 2017-03-15 | 江苏理工学院 | A kind of single dispersing N doping hollow carbon nanometer polyhedral and preparation method thereof |
| CN108187660A (en) * | 2018-01-22 | 2018-06-22 | 新疆大学 | A kind of method that liquid phase prepares witch culture zinc oxide nanosphere |
| CN111100302B (en) * | 2018-10-26 | 2022-07-08 | 中国石油化工股份有限公司 | Preparation method of metal particle @ ZIFs core-shell particle |
| CN109820001B (en) * | 2019-02-18 | 2023-11-17 | 江苏理工学院 | Cu (copper) alloy 2 Preparation method of O/ZnO composite nano material and application of material |
| CN111217601A (en) * | 2020-01-19 | 2020-06-02 | 常州市创捷防雷电子有限公司 | Preparation method of monodisperse ZnO composite powder |
| CN112777626B (en) * | 2021-01-11 | 2022-04-12 | 大连理工大学 | Highly uniform zinc oxide submicron spheres with controllable particle size and preparation method thereof |
| CN113174147A (en) * | 2021-04-12 | 2021-07-27 | 华南理工大学 | Submicron spherical zinc oxide particle and preparation method thereof |
| CN113305958B (en) * | 2021-06-10 | 2023-01-17 | 广东省林业科学研究院 | Method for in-situ synthesis of nano zinc oxide in wood by utilizing microwave |
| CN113735158A (en) * | 2021-09-09 | 2021-12-03 | 陕西科技大学 | Method for preparing high-dispersity spherical nano zinc oxide by microwave hydrothermal method |
| CN113861961A (en) * | 2021-09-30 | 2021-12-31 | 哈尔滨工业大学 | Preparation method of carbon quantum dot loaded ZnO pigment and application of product thereof |
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| CN1657415A (en) * | 2005-02-02 | 2005-08-24 | 苏州大学 | Preparation method of nanometer zinc oxide |
| CN1974486A (en) * | 2006-11-21 | 2007-06-06 | 浙江大学 | Process of preparing carbon nanotube/nanometer zinc oxide sphere heterojunction |
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| CN1657415A (en) * | 2005-02-02 | 2005-08-24 | 苏州大学 | Preparation method of nanometer zinc oxide |
| CN1974486A (en) * | 2006-11-21 | 2007-06-06 | 浙江大学 | Process of preparing carbon nanotube/nanometer zinc oxide sphere heterojunction |
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