CN101973573B - Method for preparing zinc oxide nano microspheres - Google Patents
Method for preparing zinc oxide nano microspheres Download PDFInfo
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- CN101973573B CN101973573B CN2010105298682A CN201010529868A CN101973573B CN 101973573 B CN101973573 B CN 101973573B CN 2010105298682 A CN2010105298682 A CN 2010105298682A CN 201010529868 A CN201010529868 A CN 201010529868A CN 101973573 B CN101973573 B CN 101973573B
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Abstract
The invention discloses a method for preparing zinc oxide nano microspheres, which comprises the following steps of: preparing aqueous solution of zinc acetate, aqueous solution of triethanolamine and aqueous solution of ethanol phosphotungstate; at room temperature, slowly adding a proper amount of aqueous solution of zinc acetate into a proper amount of solution of ethanol phosphotungstate, and stirring uniformly; slowly adding a proper amount of solution of triethanolamine, simultaneously raising the temperature to between 60 and 80 DEG C, and continuously reacting for 2 hours with magnetic stirring to generate milky solution; separating the milky solution by using a centrifugal machine, and washing; and finally drying in a drying oven at 70 DEG C for 24 hours to obtain the zinc oxide nano microspheres. By using a phosphotungstate additive, the preparation method for the nano microspheres is successfully changed from the common high-temperature hydrothermal method to the easily implemented low-temperature homogeneous precipitation method; and compared with the conventional method for preparing the nano microspheres, the method has the advantages that the temperature is low, the operation is simple, the method is environment-friendly and the like.
Description
Technical field
The present invention relates to have the semiconductor material of piezoelectricity and photoelectric characteristic, be specifically related to a kind of preparation method of zinc-oxide nano microballoon.
Background technology
At present, the main method for preparing spherical ZnO microballoon has hydrothermal method, vapor phase process and electrochemical process etc.Adopt Hydrothermal Preparation to go out the ZnO microballoons of adjustable grain like Shuang Xu etc. down at 160 ℃; People such as S.S.Hullavarad adopt direct vapor phase process, in the time of 800 ℃, evaporate pure zinc powder and are prepared into the ZnO microballoon; G.Vijaya Prakash team generates the ZnO nanoparticle with solution method earlier, successfully prepares the ZnO microballoon through electrochemical process again.
But these methods have certain deficiency, and are longer like the general solution reaction of the hydro-thermal reaction method time complicated, that react, and can be added with organic additive etc.; And vapor phase process is high to generating equipment requirements, severe reaction conditions; Last electrochemical process process is generally two steps realization etc.Deficiency on these preparing methods has all hindered the macro preparation and the application of ZnO microballoon, makes these methods be mainly used in breadboard research.
The related application of zinc-oxide nano microballoon preparation mainly contains one, i.e. " a kind of next step solid state reaction of nearly room temperature condition prepares the method for zinc oxide nanosphere and nanometer rod ", the patent No. is: CN03128748.4.This method is to have adopted the solid state reaction legal system to be equipped with zinc oxide nanosphere.This method has that technology is easy, mild condition, reaction do not need water or solvent, environmentally safe or of reduced contamination, productive rate is high, less cost of power.But, because what adopt is solid reaction process, cause product purity low, shortcoming such as size-grade distribution is inhomogeneous.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art, provide a kind of product purity high, the preparation method of the zinc-oxide nano microballoon of even particle size distribution.
The object of the invention is realized through following proposal:
A kind of preparation method of zinc-oxide nano microballoon comprises the steps:
(1) the trolamine aqueous solution of preparation 0.015mol/L～0.40mol/L zinc acetate aqueous solution and 0.050mol/L～0.200mol/L;
(2) get straight alcohol, add 1.00 * 10-3mol/L～2.00 * 10-3mol/L phospho-wolframic acid, stirring is fully dissolved it, obtains the phospho-wolframic acid ethanolic soln;
(3) measure 30ml～40.0ml zinc acetate aqueous solution, measure 30ml～40.0ml phospho-wolframic acid aqueous ethanolic solution, 30ml～40.0ml triethanolamine solution;
At ambient temperature, zinc acetate aqueous solution is slowly added in the phospho-wolframic acid ethanolic soln, after stirring, slowly splash into triethanolamine solution, be warming up to 60 ℃～80 ℃ simultaneously, under magnetic agitation, continue reaction 2h, generate milky solution;
(4) above-mentioned milky solution is separated, washs with whizzer, place 70 ℃～80 ℃ dry 24h of loft drier at last, obtain the zinc-oxide nano microballoon.
Above-mentioned steps (2) is measured the 40.0ml straight alcohol, adds 1.00 * 10-3mol/L～2.00 * 10-3mol/L phospho-wolframic acid, stirs it is fully dissolved, and obtains the phospho-wolframic acid ethanolic soln;
Above-mentioned steps (3) is measured the 35ml zinc acetate aqueous solution, is measured 35ml phospho-wolframic acid aqueous ethanolic solution, 35ml triethanolamine solution.
Above-mentioned steps (4) is separated above-mentioned milky solution, use distilled water wash with whizzer, places 70 ℃～80 ℃ dry 24h of loft drier at last, obtains the zinc-oxide nano microballoon.
Above-mentioned steps (4) with above-mentioned milky solution with whizzer separate, with distilled water wash 5 times, place 70 ℃～80 ℃ dry 24h of loft drier at last, obtain the zinc-oxide nano microballoon.
The application of above-mentioned zinc-oxide nano microballoon: be widely used in photonic crystal, pharmaceutical carrier, transmitter, solar cell.
Principle of the present invention is following
CH
3COO
-+HO-CH
2CH
3→OH
-+CH
3COOCH
2CH
3 (1)
Zn
2++2OH
-→ZnO↓+2H
2O (2)
The present invention generates the reaction mechanism of zinc oxide shown in equation (1), (2).There was the acetate of zinc acetate that esterification takes place in absolute ethyl alcohol before this, generated hydroxide ion; The hydroxide ion that generates generates zinc oxide fine particles with the zine ion reaction again.But the esterification process of equation (1) is slower, and the adding of phospho-wolframic acid can be played katalysis, and reaction (1) process is significantly improved, so will soon form many zinc-oxide nano particulates in the solution.
And three alcohol radical ions of the trolamine that adds can be adsorbed on the generation nano-particle surface.Stop particulate to be grown up on the one hand, reduce Ostwald slaking effect; The three alcohol radical ionic adsorption that have electrostatic force have on the other hand reduced each opposite sex of crystallite surface energy at nano-particle surface, have hindered particulate and have increased towards favourable growing direction, make the three-dimensional of crystallite increase equilibrium, and (Fig. 1) can find out from the XRD diffractogram.
Particulate in the solution is because to each other collision and self-organization each other forms the zinc oxide polycrystal.At the mutual collision process of particulate, can combine with the minimum mode of energy.Because ball-like structure has minimum surface energy, so particulate has formed the zinc-oxide nano microballoon through self-organization.
The present invention compared with prior art, advantage and effect are:
(1) through using the phospho-wolframic acid additive, the preparation that makes Nano microsphere is from general pyritous hydrothermal method, and successful transformation is for being prone to the low temperature homogeneous precipitation method of realization;
(2) the present invention compares with present Nano microsphere preparation method, have low temperature, simple to operate, pollute advantages such as low;
(3) the present invention directly generates nanometer, need not calcining, so that the Nano microsphere that makes has appearance is single, and uniform particle diameter, good dispersibility;
(4) the hydrothermal method requirement is in closed reaction kettle, to prepare, and can only be implemented in the preparation in the laboratory at present, and vapor phase process is higher to equipment requirements, needs the relevant equipment together of a cover.And the present invention to prepare process be general middle cryogenic fluid reaction, general conversion unit can satisfy.Therefore, the present invention has that technology is easy, mild condition, reaction do not need water or solvent, environmentally safe or of reduced contamination, plurality of advantages such as productive rate is high, less energy consumption.
Description of drawings
Fig. 1 is the XRD spectrum of zinc-oxide nano microballoon of the present invention.
Fig. 2 is the SEM image of zinc-oxide nano microballoon of the present invention.
Fig. 3 is the uv-visible absorption spectroscopy of zinc-oxide nano microballoon of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done further explain, but embodiment of the present invention is not limited thereto.
Embodiment 1
(1) the trolamine aqueous solution of preparation 0.025mol/L zinc acetate aqueous solution and 0.100mol/L;
(2) preparation phospho-wolframic acid ethanolic soln: measure the 40.0ml ethanolic soln, add 1.00 * 10
-3The mol/L phospho-wolframic acid, stirring is fully dissolved it, obtains the phospho-wolframic acid ethanolic soln;
(3) measure the zinc acetate aqueous solution 40.0ml for preparing, measure the phospho-wolframic acid aqueous ethanolic solution 40.0ml for preparing, measure the trolamine aqueous solution 40.0ml for preparing; At ambient temperature, zinc acetate aqueous solution is slowly added in the phospho-wolframic acid ethanolic soln, after stirring; Slowly splash into triethanolamine solution; Be warming up to 75 ℃ simultaneously, under magnetic agitation, continue reaction 2h, generate milky solution;
(4) with above-mentioned milky solution with whizzer separate, distilled water wash 5 times, place 70 ℃ of dry 24h of loft drier at last, obtain the zinc-oxide nano microballoon.
Like Fig. 1, products therefrom can be known through X-ray diffraction check and is pure wurtzite zinc oxide;
Like Fig. 2, can know that through the electron-microscope scanning observation product pattern is spherical zinc oxide;
Like Fig. 3, can know that through the ultraviolet-visible light absorption experiment it has absorbing properties preferably.
Embodiment 2
(1) the trolamine aqueous solution of preparation 0.015mol/L zinc acetate aqueous solution and 0.050mol/L;
(2) preparation phospho-wolframic acid ethanolic soln: measure the 40.0ml straight alcohol, add 1.00 * 10
-3The mol/L phospho-wolframic acid, stirring is fully dissolved it, obtains the phospho-wolframic acid ethanolic soln;
(3) measure the zinc acetate aqueous solution 40.0ml for preparing, measure the phospho-wolframic acid aqueous ethanolic solution 40.0ml for preparing, measure the trolamine aqueous solution 40.0ml for preparing; At ambient temperature, zinc acetate aqueous solution is slowly added in the phospho-wolframic acid ethanolic soln, after stirring; Slowly splash into triethanolamine solution; Be warming up to 60 ℃ simultaneously, under magnetic agitation, continue reaction 2h, generate milky solution;
(4) with above-mentioned milky solution with whizzer separate, distilled water wash 5 times, place 70 ℃ of dry 24h of loft drier at last, obtain the zinc-oxide nano microballoon.
Like Fig. 1, products therefrom can be known through X-ray diffraction check and is pure wurtzite zinc oxide;
Like Fig. 2, can know that through the electron-microscope scanning observation product pattern is spherical zinc oxide;
Like Fig. 3, can know that through the ultraviolet-visible light absorption experiment it has absorbing properties preferably.
Embodiment 3
(1) the trolamine aqueous solution of preparation 0.40mol/L zinc acetate aqueous solution and 0.200mol/L;
(2) preparation phospho-wolframic acid ethanolic soln: measure the 40.0ml straight alcohol, add 1.00 * 10
-3The mol/L phospho-wolframic acid, stirring is fully dissolved it, obtains the phospho-wolframic acid ethanolic soln;
(3) measure the zinc acetate aqueous solution 40.0ml for preparing, measure the phospho-wolframic acid aqueous ethanolic solution 40.0ml for preparing, measure the trolamine aqueous solution 40.0ml for preparing; At ambient temperature, zinc acetate aqueous solution is slowly added in the phospho-wolframic acid ethanolic soln, after stirring; Slowly splash into triethanolamine solution; Be warming up to 80 ℃ simultaneously, under magnetic agitation, continue reaction 2h, generate milky solution;
(4) with above-mentioned milky solution with whizzer separate, distilled water wash 5 times, place 70 ℃ of dry 24h of loft drier at last, obtain the zinc-oxide nano microballoon.
Like Fig. 1, products therefrom can be known through X-ray diffraction check and is pure wurtzite zinc oxide;
Like Fig. 2, can know that through the electron-microscope scanning observation product pattern is spherical zinc oxide;
Like Fig. 3, can know that through the ultraviolet-visible light absorption experiment it has absorbing properties preferably.
Embodiment 4
(1) the trolamine aqueous solution of preparation 0.025mol/L zinc acetate aqueous solution and 0.100mol/L;
(2) preparation phospho-wolframic acid ethanolic soln: measure the 40.0ml straight alcohol, add 2.00 * 10
-3The mol/L phospho-wolframic acid, stirring is fully dissolved it, obtains the phospho-wolframic acid ethanolic soln;
(3) measure the zinc acetate aqueous solution 40.0ml for preparing, measure the phospho-wolframic acid aqueous ethanolic solution 40.0ml for preparing, measure the trolamine aqueous solution 40.0ml for preparing; At ambient temperature, zinc acetate aqueous solution is slowly added in the phospho-wolframic acid ethanolic soln, after stirring; Slowly splash into triethanolamine solution; Be warming up to 60 ℃ simultaneously, under magnetic agitation, continue reaction 2h, generate milky solution;
(4) with above-mentioned milky solution with whizzer separate, distilled water wash 5 times, place 70 ℃ of dry 24h of loft drier at last, obtain the zinc-oxide nano microballoon.
Like Fig. 1, products therefrom can be known through X-ray diffraction check and is pure wurtzite zinc oxide;
Like Fig. 2, can know that through the electron-microscope scanning observation product pattern is spherical zinc oxide;
Like Fig. 3, can know that through the ultraviolet-visible light absorption experiment it has absorbing properties preferably.
Embodiment 5
(1) the trolamine aqueous solution of preparation 0.3mol/L zinc acetate aqueous solution and 0.100mol/L;
(2) preparation phospho-wolframic acid ethanolic soln: measure the 40.0ml straight alcohol, add 2.00 * 10
-3The mol/L phospho-wolframic acid, stirring is fully dissolved it, obtains the phospho-wolframic acid ethanolic soln;
(3) measure the zinc acetate aqueous solution 30.0ml for preparing, measure the phospho-wolframic acid aqueous ethanolic solution 30.0ml for preparing, measure the trolamine aqueous solution 30.0ml for preparing; At ambient temperature, zinc acetate aqueous solution is slowly added in the phospho-wolframic acid ethanolic soln, after stirring; Slowly splash into triethanolamine solution; Be warming up to 60 ℃ simultaneously, under magnetic agitation, continue reaction 2h, generate milky solution;
(4) with above-mentioned milky solution with whizzer separate, distilled water wash 5 times, place 70 ℃ of dry 24h of loft drier at last, obtain the zinc-oxide nano microballoon.
Like Fig. 1, products therefrom can be known through X-ray diffraction check and is pure wurtzite zinc oxide;
Like Fig. 2, can know that through the electron-microscope scanning observation product pattern is spherical zinc oxide;
Like Fig. 3, can know that through the ultraviolet-visible light absorption experiment it has absorbing properties preferably.
Embodiment 6
(1) the trolamine aqueous solution of preparation 0.3mol/L zinc acetate aqueous solution and 0.050mol/L;
(2) preparation phospho-wolframic acid ethanolic soln: measure the 30.0ml straight alcohol, add 2.00 * 10
-3The mol/L phospho-wolframic acid, stirring is fully dissolved it, obtains the phospho-wolframic acid ethanolic soln;
(3) measure the zinc acetate aqueous solution 30.0ml for preparing, measure the phospho-wolframic acid aqueous ethanolic solution 30.0ml for preparing, measure the trolamine aqueous solution 40.0ml for preparing; At ambient temperature, zinc acetate aqueous solution is slowly added in the phospho-wolframic acid ethanolic soln, after stirring; Slowly splash into triethanolamine solution; Be warming up to 60 ℃ simultaneously, under magnetic agitation, continue reaction 2h, generate milky solution;
(4) with above-mentioned milky solution with whizzer separate, distilled water wash 5 times, place 75 ℃ of dry 24h of loft drier at last, obtain the zinc-oxide nano microballoon.
Like Fig. 1, products therefrom can be known through X-ray diffraction check and is pure wurtzite zinc oxide;
Like Fig. 2, can know that through the electron-microscope scanning observation product pattern is spherical zinc oxide;
Like Fig. 3, can know that through the ultraviolet-visible light absorption experiment it has absorbing properties preferably.
Embodiment 7
(1) the trolamine aqueous solution of preparation 0.025mol/L zinc acetate aqueous solution and 0.015mol/L;
(2) preparation phospho-wolframic acid ethanolic soln: measure the 40.0ml straight alcohol, add 2.00 * 10
-3The mol/L phospho-wolframic acid, stirring is fully dissolved it, obtains the phospho-wolframic acid ethanolic soln;
(3) measure the zinc acetate aqueous solution 40.0ml for preparing, measure the phospho-wolframic acid aqueous ethanolic solution 40.0ml for preparing, measure the trolamine aqueous solution 40.0ml for preparing; At ambient temperature, zinc acetate aqueous solution is slowly added in the phospho-wolframic acid ethanolic soln, after stirring; Slowly splash into triethanolamine solution; Be warming up to 60 ℃ simultaneously, under magnetic agitation, continue reaction 2h, generate milky solution;
(4) with above-mentioned milky solution with whizzer separate, distilled water wash 5 times, place 80 ℃ of dry 24h of loft drier at last, obtain the zinc-oxide nano microballoon.
Like Fig. 1, products therefrom can be known through X-ray diffraction check and is pure wurtzite zinc oxide;
Like Fig. 2, can know that through the electron-microscope scanning observation product pattern is spherical zinc oxide;
Like Fig. 3, can know that through the ultraviolet-visible light absorption experiment it has absorbing properties preferably.
Embodiment 8
(1) the trolamine aqueous solution of preparation 0.4mol/L zinc acetate aqueous solution and 0.015mol/L;
(2) preparation phospho-wolframic acid ethanolic soln: measure the 40.0ml straight alcohol, add 2.00 * 10
-3The mol/L phospho-wolframic acid, stirring is fully dissolved it, obtains the phospho-wolframic acid ethanolic soln;
(3) measure the zinc acetate aqueous solution 40.0ml for preparing, measure the phospho-wolframic acid aqueous ethanolic solution 40.0ml for preparing, measure the trolamine aqueous solution 40.0ml for preparing; At ambient temperature, zinc acetate aqueous solution is slowly added in the phospho-wolframic acid ethanolic soln, after stirring; Slowly splash into triethanolamine solution; Be warming up to 60 ℃ simultaneously, under magnetic agitation, continue reaction 2h, generate milky solution;
(4) with above-mentioned milky solution with whizzer separate, distilled water wash 5 times, place 75 ℃ of dry 24h of loft drier at last, obtain the zinc-oxide nano microballoon.
Like Fig. 1, products therefrom can be known through X-ray diffraction check and is pure wurtzite zinc oxide;
Like Fig. 2, can know that through the electron-microscope scanning observation product pattern is spherical zinc oxide;
Like Fig. 3, can know that through the ultraviolet-visible light absorption experiment it has absorbing properties preferably.
Principle of the present invention is following
CH
3COO
-+HO-CH
2CH
3→OH
-+CH
3COOCH
2CH
3 (1)
Zn
2++2OH
-→ZnO↓+2H
2O (2)
The present invention generates the reaction mechanism of zinc oxide shown in equation (1), (2).There was the acetate of zinc acetate that esterification takes place in absolute ethyl alcohol before this, generated hydroxide ion; The hydroxide ion that generates generates zinc oxide fine particles with the zine ion reaction again.But the esterification process of equation (1) is slower, and the adding of phospho-wolframic acid can be played katalysis, and reaction (1) process is significantly improved, so will soon form many zinc-oxide nano particulates in the solution.
And three alcohol radical ions of the trolamine that adds can be adsorbed on the generation nano-particle surface.Stop particulate to be grown up on the one hand, reduce Ostwald slaking effect; The three alcohol radical ionic adsorption that have electrostatic force have on the other hand reduced each opposite sex of crystallite surface energy at nano-particle surface, have hindered particulate and have increased towards favourable growing direction, make the three-dimensional of crystallite increase equilibrium, and (Fig. 1) can find out from the XRD diffractogram.
Particulate in the solution is because to each other collision and self-organization each other forms the zinc oxide polycrystal.At the mutual collision process of particulate, can combine with the minimum mode of energy.Because ball-like structure has minimum surface energy, so particulate has formed the zinc-oxide nano microballoon through self-organization.
The application of the prepared zinc-oxide nano microballoon of the inventive method: be widely used in photonic crystal, pharmaceutical carrier, transmitter, solar cell.
The foregoing description is merely preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other are any not to deviate from change, the modification done under spirit of the present invention and the principle, substitute, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. the preparation method of a zinc-oxide nano microballoon is characterized in that comprising the steps:
(1) the trolamine aqueous solution of preparation 0.015mol/L～0.40mol/L zinc acetate aqueous solution and 0.050mol/L～0.200mol/L;
(2) get straight alcohol, add 1.00 * 10
-3Mol/L～2.00 * 10
-3The mol/L phospho-wolframic acid, stirring is fully dissolved it, obtains the phospho-wolframic acid aqueous ethanolic solution;
(3) measure 30ml～40.0ml zinc acetate aqueous solution, measure 30ml～40.0ml phospho-wolframic acid aqueous ethanolic solution, the 30ml～40.0ml trolamine aqueous solution; At ambient temperature, zinc acetate aqueous solution is slowly added in the phospho-wolframic acid aqueous ethanolic solution, after stirring, slowly splash into the trolamine aqueous solution, be warming up to 60 ℃～80 ℃ simultaneously, under magnetic agitation, continue reaction 2h, generate milky solution;
(4) above-mentioned milky solution is separated, washs with whizzer, place 70 ℃～80 ℃ dry 24h of loft drier at last, obtain the zinc-oxide nano microballoon.
2. according to the preparation method of the said zinc-oxide nano microballoon of claim 1, it is characterized in that said step (2) is measured the 40.0ml straight alcohol, add 1.00 * 10
-3Mol/L～2.00 * 10
-3The mol/L phospho-wolframic acid, stirring is fully dissolved it, obtains the phospho-wolframic acid aqueous ethanolic solution;
3. according to the preparation method of the said zinc-oxide nano microballoon of claim 1, it is characterized in that said step (3) is measured the 35ml zinc acetate aqueous solution, measured 35ml phospho-wolframic acid aqueous ethanolic solution, the 35ml trolamine aqueous solution.
4. according to the preparation method of the said zinc-oxide nano microballoon of claim 1; It is characterized in that; Said step (4) is separated above-mentioned milky solution, use distilled water wash with whizzer, places 70 ℃～80 ℃ dry 24h of loft drier at last, obtains the zinc-oxide nano microballoon.
5. according to the preparation method of the said zinc-oxide nano microballoon of claim 4; It is characterized in that; Said step (4) with above-mentioned milky solution with whizzer separate, with distilled water wash 5 times, place 70 ℃～80 ℃ dry 24h of loft drier at last, obtain the zinc-oxide nano microballoon.
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| 姜秀平等.一维纳米结构ZnO 的制备.《中北大学学报(自然科学版)》.2008,第29卷(第2期),147-150. * |
| 李平等.表面活性剂对氧化锌微晶形貌的影响.《无机盐工业》.2007,第39卷(第7期),18-19,32. * |
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