CN102249285A - Method for preparing hollow spindle-shaped micro-structured zinc oxide - Google Patents
Method for preparing hollow spindle-shaped micro-structured zinc oxide Download PDFInfo
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- CN102249285A CN102249285A CN2011101362735A CN201110136273A CN102249285A CN 102249285 A CN102249285 A CN 102249285A CN 2011101362735 A CN2011101362735 A CN 2011101362735A CN 201110136273 A CN201110136273 A CN 201110136273A CN 102249285 A CN102249285 A CN 102249285A
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Abstract
The invention relates to a method for preparing hollow spindle-shaped micro-structured zinc oxide, and belongs to a method for preparing a semiconductor micro material. The method comprises the following steps of: dissolving soluble zinc salt in deionized water, and stirring to obtain uniform and transparent solution, wherein the total concentration of zinc ions is 0.01 to 0.50mol/L; adding sodium borohydride into the solution in a ratio, stirring, and preheating; and transferring the solution to a hydrothermal reaction kettle for reaction, naturally cooling to room temperature after the reaction is finished, and collecting, washing, and drying a product. The micro-structured zinc oxide has high dispersibility and crystallinity, a uniform shape and obvious cavities; and the reaction system is simple, and convenient to wash, the reaction is mild, cost is low, yield reaches 99.2 percent, and wide application prospects are achieved.
Description
Technical field
The present invention relates to a kind of preparation method of micrometer semiconductor material oxidation zinc of special appearance.
Background technology
Zinc oxide is the wide bandgap semiconductor materials with the high exciton bind energy of 60eV, can produce stronger exciton emission in the ultraviolet region during room temperature, unique photoelectric property and cheap cost, make it at short-wave LED, the room temperature ultraviolet laser diode, solar cell, UV light absorber, transparent conductor, Field Emission Display, piezoresistor and transmitter, field of semiconductor materials such as catalyzer and gas sensor widespread use (Wei Dong Zhou, Xiao Wu, Yong Cai Zhang et al. Materials Letters, 2007,61:2054 – 2057).On the other hand, the electricity of inorganic materials and optical property are subjected to the very big influence of size and pattern, select the size of suitable synthetic method controlled material, forward position and the focus that pattern is current investigation of materials according to people's wish.Up to the present, the ZnO material for preparing of success comprise that (poplar is closed feelings, Li Li for the nanometer sheet of nano wire, nanometer rod, nano-comb, nanometer spring, hexagonal shape and nano-rings and one-dimension zinc oxide nano-array, Song Yuzhe, et al. Chinese science B collects: chemistry, and 2007,37:417-425).Wherein, hollow ZnO bill of material reveals that density is low, specific surface area reaches superior special propertys such as optical characteristics greatly, these character have wide application prospect (Sun Ruixue in various fields such as medicament slow release/controlled release system, chromatographic separation, catalyzer, coating, microreactor and photoelectric materials, Li Musen, Lv Yupeng. the material Leader, 2005,19:19-22).Studying more synthetic method mainly contains: sacrifice template, microemulsion method, spray reaction method, supersonic method, template-interfacial reaction method, self-assembly method successively, but use maximum template that remains, as use the high molecular polymer polymethylmethacrylate to prepare Zinc oxide hollow microsphere (Chinese patent application number be 200910098778.X) as template.This method has been introduced organic compound, and not only production cost is higher, contaminate environment, and also the washing that may exist is unclean, makes impurity residual in product.
In pertinent literature, " a kind of preparation method of spindle-shaped nano ZnO monocrystal " (application number is 200810018192.3 Chinese invention patents), this method is with the synthetic spindle-shaped nano ZnO monocrystal of microwave-hydrothermal method, the non-hollow of this nano-ZnO monocrystalline fusiform structure.Document (Xueying Chu, Xia Hong, Xinghua Li, et al. J. Appl. Phys., 2009,
105: 123109) reported use vulkacit H and zinc acetate dihydrate as reactant, adopted hydrothermal method to synthesize fusiform ZnO, this method has not only been used the non-hollow of ZnO of the fusellar fabric of organic compound and its preparation.At present, the ZnO about hollow fusiform micrometer structure does not see relevant patent and bibliographical information.
Summary of the invention
The object of the invention is to provide a kind of preparation method of micron ZnO of hollow fusiform structure, is raw material with soluble zinc salt and solubility alkaline compound, adopts the synthetic hollow fusiform micron zinc oxide of hydrothermal method.
Reaction system of the present invention is simple, and raw material is easy to get, and is easy and simple to handle, productive rate height and environmental friendliness.
The present invention includes following steps for achieving the above object:
(1) soluble zinc salt is dissolved in the deionized water, stir make soluble zinc salt dissolve fully transparent and homogeneous solution, zine ion Zn
2+Concentration in solution is the 0.01-0.50 mol;
(2) with NaBH
4Add in the solution of step (1), continue to stir 0.1-2h, wherein, Zn
2+With NaBH
4The mole join
Than being 1:5-10:1;
(3) with step (2) gained solution at 40 ℃ to 60 ℃ following preheating 20-50 minutes, change in the hydrothermal synthesis reaction still heating 0.5-20h, Heating temperature to 60 ℃～200 ℃ over to;
(4) after step (3) finishes, naturally cool to room temperature;
(5) solution of filtration step (4) gained, collect resultant, washing, drying, obtain the micron ZnO of fusiform structure.
The soluble zinc salt of described step (1) is zinc nitrate or zinc acetate or zinc chloride.
The beneficial effect that the present invention has is:
The micron ZnO of the hollow fusiform structure that the present invention prepares has good dispersiveness, pattern rule homogeneous, its cavity obviously visible (accompanying drawing 2); And under the room temperature fluorescent emission is arranged, the emission peak position is positioned at visible region (accompanying drawing 3) about 427nm; The ZnO material that the present invention obtains has degree of crystallinity preferably, uses X-diffraction powdery diffractometry (XRD) that its thing is analyzed (accompanying drawing 1) mutually, go out the peak position at d=2.8177, d=2.6042, d=2.4767, d=1.9095, d=1.6245, d=1.4763, d=1.4068, d=1.3770, d=1.3589, d=1.3038, its corresponding standard of d=1.2381 d value is d=2.814, d=2.603, d=2.475, d=1.911, d=1.624, d=1.477, d=1.407, d=1.378, d=1.358, d=1.301, d=1.237, with the standard card proof of comparing, prepared ZnO material is pure hexagonal wurtzite structure.
The present invention uses and eco-friendly water as solvent, and does not use any template and organic solvent, thereby has simplified reaction system, and the reaction conditions gentleness, raw material is easy to get, and inclusion-free is introduced, convenient for washing, productive rate are up to 99.2%, and low production cost has been avoided environmental pollution.
The micron ZnO of the hollow fusiform structure of the present invention's preparation has wide application prospect in various fields such as medicament slow release/controlled release system, chromatographic separation, catalyzer, coating, microreactor and photoelectric materials.
Below in conjunction with drawings and Examples technical scheme of the present invention is further described.Following examples comprise but do not limit the scope of protection of the invention.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum of gained material of the present invention.
Fig. 2 is the SEM figure of the shuttle type structure ZnO of gained material of the present invention.Cavity illustration among the figure is clapped from the disruptive spindle body.
Fig. 3 is the room temperature fluorescence spectrogram of gained material of the present invention.Among the figure, the emission peak position of the micron ZnO of hollow fusiform structure is positioned at visible region about 427nm.
Embodiment
Embodiment 1
(1) zinc acetate is dissolved in the deionized water, stir make its dissolve fully transparent and homogeneous solution, zinc
Ionic concentration is 0.01 mol.
(2) the 0.1g sodium borohydride is added in the solution of (1), continue to stir 10 minutes.
(3) with step (2) gained solution 40 ℃ of following preheatings 50 minutes.
(4) solution with (3) changes in the hydrothermal synthesis reaction still, and 60 ℃ are heated 10h down.
(5) after step (4) finishes, naturally cool to room temperature.
(6) solution of filtration step (5) gained, collection resultant, washing, drying obtain fusiform
The micron ZnO of structure.
Embodiment 2
(1) zinc acetate is dissolved in the deionized water, stir make its dissolve fully transparent and homogeneous solution, the concentration of zine ion is 0.01 mol.
(2) the 0.2g sodium borohydride is added in the solution of (1), continue to stir 10 minutes.
(3) with step (2) gained solution 60 ℃ of following preheatings 40 minutes.
(4) solution with (3) changes in the hydrothermal synthesis reaction still, and 60 ℃ are heated 20h down.
(5) after step (4) finishes, naturally cool to room temperature.
(6) solution of filtration step (5) gained, collection resultant, washing, drying obtain fusiform
The micron ZnO of structure.
Embodiment 3
(1) zinc acetate is dissolved in the deionized water, stir make its dissolve fully transparent and homogeneous solution, the concentration of zine ion is 0.01 mol.
(2) the 0.2g sodium borohydride is added in the solution of (1), continue to stir 1h.
(3) with step (2) gained solution 60 ℃ of following preheatings 30 minutes.
(4) solution with (3) changes in the hydrothermal synthesis reaction still, and 120 ℃ are heated 10h down.
(5) after step (4) finishes, naturally cool to room temperature.
(6) solution of filtration step (5) gained, collection resultant, washing, drying obtain fusiform
The micron ZnO of structure.
Embodiment 4
(1) zinc acetate is dissolved in the deionized water, stir make its dissolve fully transparent and homogeneous solution, the concentration of zine ion is 0.1 mol.
(2) the 0.2g sodium borohydride is added in the solution of (1), continue to stir 1h.
(3) with step (2) gained solution 40 ℃ of following preheatings 30 minutes.
(4) solution with (3) changes in the hydrothermal synthesis reaction still, and 180 ℃ are heated 1h down.
(5) after step (4) finishes, naturally cool to room temperature.
(6) solution of filtration step (5) gained, collection resultant, washing, drying obtain fusiform
The micron ZnO of structure.
Embodiment 5
(1) zinc acetate is dissolved in the deionized water, stir make its dissolve fully transparent and homogeneous solution, the concentration of zine ion is 0.3 mol.
(2) the 1.0g sodium borohydride is added in the solution of (1), continue to stir 1h.
(3) with step (2) gained solution 60 ℃ of following preheatings 30 minutes.
(4) solution with (3) changes in the hydrothermal synthesis reaction still, and 180 ℃ are heated 1h down.
(5) after step (4) finishes, naturally cool to room temperature.
(6) solution of filtration step (5) gained, collection resultant, washing, drying obtain fusiform
The micron ZnO of structure.
Embodiment 6
(1) zinc acetate is dissolved in the deionized water, stir make its dissolve fully transparent and homogeneous solution, the concentration of zine ion is 0.5 mol.
(2) the 2.0g sodium borohydride is added in the solution of (1), continue to stir 1h.
(3) with step (2) gained solution 40 ℃ of following preheatings 40 minutes.
(4) solution with (3) changes in the hydrothermal synthesis reaction still, and 180 ℃ are heated 1h down.
(5) after step (4) finishes, naturally cool to room temperature.
(6) solution of filtration step (5) gained, collection resultant, washing, drying obtain fusiform
The micron ZnO of structure.
Claims (2)
1. the preparation method of a hollow fusiform micrometer structure zinc oxide may further comprise the steps:
(1) soluble zinc salt is dissolved in the deionized water, stir make soluble zinc salt dissolve fully transparent and homogeneous solution, zine ion Zn
2+Concentration in solution is 0.01～0.50 mol;
(2) with NaBH
4Add in the solution of step (1), continue to stir 0.1～2h, wherein, Zn
2+With NaBH
4The mole join
Than being 1:5～10:1;
(3) with step (2) gained solution 40 ℃ to 60 ℃ following preheatings 20～50 minutes, change in the hydrothermal synthesis reaction still heating 0.5～20h, Heating temperature to 60 ℃～200 ℃ over to;
(4) after step (3) finishes, naturally cool to room temperature;
(5) solution of filtration step (4) gained, collect resultant, washing, drying, obtain the micron ZnO of hollow fusiform structure.
2. preparation method according to claim 1, the soluble zinc salt that it is characterized in that step (1) is zinc nitrate or zinc acetate or zinc chloride.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006706A (en) * | 2016-05-19 | 2016-10-12 | 青岛大学 | Preparation method of dumbbell-shaped ZnO micro-ring gas-sensitive material |
| CN107367527A (en) * | 2017-06-29 | 2017-11-21 | 滨州学院 | It is a kind of that there is highly sensitive spindle zinc oxide gas sensitive to triethylamine |
| CN107597174A (en) * | 2017-10-18 | 2018-01-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of heterogeneous ozone catalyst and products thereof and application |
| CN107673398A (en) * | 2017-10-11 | 2018-02-09 | 北京振兴华龙制冷设备有限责任公司 | A kind of preparation method of Nanometer-sized Rods ZnO and its application for preparing ventilating duct for air-conditioner |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3167756B2 (en) * | 1991-11-13 | 2001-05-21 | 花王株式会社 | Hollow fine particles of zinc oxide, method for producing the same and apparatus therefor |
| CN101319371A (en) * | 2008-05-14 | 2008-12-10 | 陕西科技大学 | Production method of spindle-shaped nano ZnO monocrystal |
| CN101774632A (en) * | 2010-03-18 | 2010-07-14 | 哈尔滨师范大学 | Method for preparing zinc oxide of spindle-shaped structure |
-
2011
- 2011-05-25 CN CN201110136273A patent/CN102249285B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3167756B2 (en) * | 1991-11-13 | 2001-05-21 | 花王株式会社 | Hollow fine particles of zinc oxide, method for producing the same and apparatus therefor |
| CN101319371A (en) * | 2008-05-14 | 2008-12-10 | 陕西科技大学 | Production method of spindle-shaped nano ZnO monocrystal |
| CN101774632A (en) * | 2010-03-18 | 2010-07-14 | 哈尔滨师范大学 | Method for preparing zinc oxide of spindle-shaped structure |
Non-Patent Citations (1)
| Title |
|---|
| 乔靓等: "水热合成纺锤状ZnO及其光致发光性质研究", 《长春大学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006706A (en) * | 2016-05-19 | 2016-10-12 | 青岛大学 | Preparation method of dumbbell-shaped ZnO micro-ring gas-sensitive material |
| CN107367527A (en) * | 2017-06-29 | 2017-11-21 | 滨州学院 | It is a kind of that there is highly sensitive spindle zinc oxide gas sensitive to triethylamine |
| CN107673398A (en) * | 2017-10-11 | 2018-02-09 | 北京振兴华龙制冷设备有限责任公司 | A kind of preparation method of Nanometer-sized Rods ZnO and its application for preparing ventilating duct for air-conditioner |
| CN107673398B (en) * | 2017-10-11 | 2019-05-14 | 北京振兴华龙制冷设备有限责任公司 | A kind of preparation method of Nanometer-sized Rods ZnO and its application for being used to prepare ventilating duct for air-conditioner |
| CN107597174A (en) * | 2017-10-18 | 2018-01-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of heterogeneous ozone catalyst and products thereof and application |
| CN107597174B (en) * | 2017-10-18 | 2019-11-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of heterogeneous ozone catalyst and products thereof and application |
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Granted publication date: 20121024 Termination date: 20130525 |