CN102363893A - Method for synchronically synthesizing two ZnO nanostructures - Google Patents
Method for synchronically synthesizing two ZnO nanostructures Download PDFInfo
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- CN102363893A CN102363893A CN2011103414518A CN201110341451A CN102363893A CN 102363893 A CN102363893 A CN 102363893A CN 2011103414518 A CN2011103414518 A CN 2011103414518A CN 201110341451 A CN201110341451 A CN 201110341451A CN 102363893 A CN102363893 A CN 102363893A
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Abstract
The invention relates to a method for synchronically synthesizing two ZnO nanostructures. The method comprises steps that: fluorine-doped SnO2 transparent conductive glass with a square resistance of 10 to 14ohm is sequentially washed by using an HCl solution, a washing powder solution, and an isopropyl alcohol solution under ultrasonic sound; the glass is dried by air; a three-electrode electrolytic cell system is adopted, wherein a platinum sheet is adopted as an auxiliary electrode, a saturated calomel electrode is adopted as a reference electrode, the fluorine-doped SnO2 transparent conductive glass is adopted as a working electrode, and an electrolyte is a mixed solution of Zn(NO3)2 and KCl with concentrations of 0.3M; the electrolytic cell is deposed for 1.3 to 1.5 hours under an open state, wherein a deposition temperature is 70 DEG C, and a voltage is -1.0V; after deposition, black deposit under a liquid surface is hollowed nano-sheets of ZnO, and white deposit on the liquid surface is ZnO nano-rods. With the method provided by the invention, ZnO nanostructures with two different forms which are ZnO hollowed nano-sheets and ZnO nano-rods can be obtained simultaneously. The method is simple and energy saving. The operation of the method is easy, the cost is low, and the purities of the products are high.
Description
Technical field
The present invention relates to a kind of method of synchronously synthetic two kinds of ZnO nanostructures.
Background technology
ZnO has excellent optics and electrology characteristic as a kind of important direct wide bandgap compound semiconductor oxide material.At room temperature, the ZnO energy gap is 3.37eV, and its exciton bind energy is fit to be used as the ultraviolet light emission material under room temperature or the higher temperature up to 60meV, at optical fields such as short-wave long light-emitting diodes wide application prospect is arranged all simultaneously.ZnO also has piezoelectric property, field emission effect, multiple special performances such as gas sensing property; Simultaneously, its preparation technology is simple, and growth temperature is lower; Abundant raw material, low production cost; In addition, nontoxic, the environmentally safe of ZnO is a kind of environment-friendly materials.Therefore, ZnO has very wide application prospect, becomes the research focus of semiconductor applications, gets most of the attention.
The ZnO of different-shape has different character and application, and it is a research focus that ZnO is carried out the pattern regulation and control always.The ZnO nanometer rod is an one-dimentional structure, helps electric transmission etc., in the wide application prospect that has aspect photodiode, laser apparatus, ultraviolet detector, high frequency and high power device and the related device thereof.And hollow out ZnO nanometer sheet has bigger surface-area and adsorption site; Help absorbing dye or other inorganic nano-particle; Formation have many absorber portions (the ZnO ultraviolet, inorganic nano-particle can be selected different wave length, like visible region CdS; Infrared region PbS) matrix material has good application at aspects such as solar cells.
Existing ZnO nanometer rod and ZnO hollow out nanometer sheet must adopt different preparation technologies, different equipment to make respectively.Then must adopt two kinds of preparation technologies, two kinds of equipment at least like these two kinds of ZnO nanostructures of need preparation, the preparation process is loaded down with trivial details, efficient is low.
Summary of the invention
The object of the invention just provides a kind of method of synchronously synthetic two kinds of ZnO nanostructures; This method can obtain the ZnO nanostructure of ZnO hollow out nanometer sheet and two kinds of different-shapes of nanometer rod simultaneously, and its method is simple, energy-conservation, processing ease; Cost is low, and the purity of prepared product is high.
The present invention realizes that the technical scheme that order adopted of its invention is, a kind of method of synchronously synthetic two kinds of ZnO nanostructures, and its concrete practice is:
The cleaning of the SnO2 transparent conducting glass of a, doped with fluorine
(1) be the SnO2 transparent conducting glass of the doped with fluorine in 10-14 Europe with square face resistance, in the HCl of 0.1-0.3M solution, ultrasonic 30-40min removes mineral ion; (2) rinse well with deionized water after, put into the washing powder solution of 5-10%, 70 ℃ ultrasonic 2-2.5 hour; (3) use the ultrasonic 30-40min of isopropanol solvent again; (4) deionized water is cleaned, is dried;
B, prepared by electrodeposition ZnO hollow out nanometer sheet and nanometer rod
Adopt the three-electrode cell system, platinized platinum is a supporting electrode, and SCE is a reference electrode, and the SnO2 transparent conducting glass of the doped with fluorine after the cleaning is a working electrode, and electrolytic solution is the Zn (NO of deionized water preparation
3)
2Be the mixed solution of 0.3M with the concentration of KCl; Electrolyzer does not stir, the situation deposit of opened upper end 1.5 hours, and the temperature during deposition is 70 ℃, and voltage is-1.0V;
After deposition finished, the SnO2 transparent conducting glass that takes out doped with fluorine promptly got: the black deposit below the liquid level is a ZnO hollow out nanometer sheet, and the above white deposits of liquid level is the ZnO nanometer rod.
The possible mechanism of the inventive method is:
The sedimentary reaction of b one-step electrochemistry does
The cathodic reaction formula is:
NO
3 -+H
2O+2e
-→NO
2 -+2OH
-
Zn
2++2OH
-→Zn(OH)
2→ZnO+H
2O
Total reaction equation is:
Zn
2++NO
3 -+2e
-→ZnO+NO
2 -
Because capillary effect; The SnO2 transparent conducting glass (FTO) of doped with fluorine and electrolytic solution can form highly poor for the liquid level of h; Because the voltage at electrolytic solution different heights place distributes different, electrolytical concentration also maybe be different, cause the sedimentation velocity of ZnO on FTO different; Deposition reaction only takes place in the FTO on the liquid level, generates nanometer rod; All the time be in subsurface FTO deposition reaction then take place earlier, after etching reaction takes place again, generate the hollow out nanometer sheet at last.Liquid level causes decline owing to thermal evaporation, therefore, and the ZnO nanorod shaped bunchiness shape that the FTO on the liquid level generates.Through the area size of adjustment reaction vessel, can control the height that liquid level descends, and then regulate and control the ratio of two kinds of products.
Compared with prior art, the invention has the beneficial effects as follows:
One, only use a kind of method, a kind of equipment, obtain the ZnO nanostructure of ZnO hollow out nanometer sheet and two kinds of different-shapes of nanometer rod simultaneously, its method is simple, energy-conservation, processing ease, and cost is low.Be particularly useful for to obtain simultaneously the occasion of these two kinds of prepared products.
Two, the area size of adjustment reaction vessel, i.e. the height that descends of may command liquid level, and then regulate and control the ratio of two kinds of products.The proportion of products convenient regulation and control.
Three, adopt liquid-phase precipitation method, used inorganic salt are zinc nitrate, nontoxic, environmentally safe.
Four, X-ray test proof, ZnO hollow out nanometer sheet and two kinds of products of nanometer rod all do not have dephasign, and purity is high.
Below in conjunction with accompanying drawing and concrete embodiment, the present invention is done further detailed explanation.
Description of drawings
Fig. 1 is the ZnO hollow out nanometer sheet (under the liquid level) of the embodiment of the invention one preparation and (XRD) of nanometer rod (on the liquid level).
Fig. 2 is ZnO hollow out nanometer sheet (under the liquid level) stereoscan photograph of the embodiment of the invention one preparation.
Fig. 3 is the stereoscan photograph of the nanometer rod (on the liquid level) of the embodiment of the invention one preparation.
Fig. 4 is ZnO hollow out nanometer sheet (under the liquid level) stereoscan photograph (depositing time 1.3 hours) of the embodiment of the invention two preparations.
Fig. 5 is the stereoscan photograph (depositing time 1.3 hours) of the nanometer rod (on the liquid level) of the embodiment of the invention two preparations.
Embodiment
Embodiment one
A kind of embodiment of the present invention is: a kind of method of synchronously synthetic two kinds of ZnO nanostructures, and its concrete practice is:
The cleaning of the SnO2 transparent conducting glass of a, doped with fluorine
(1) be the SnO2 transparent conducting glass of the doped with fluorine in 14 Europe with square face resistance, in the HCl of 0.1M solution, ultrasonic 30min removes mineral ion; (2) rinse well with deionized water after, put into 5% washing powder solution, 70 ℃ ultrasonic 2 hours; (3) use the ultrasonic 30min of isopropanol solvent again; (4) deionized water is cleaned, is dried;
B, prepared by electrodeposition ZnO hollow out nanometer sheet and nanometer rod
Adopt the three-electrode cell system, platinized platinum is a supporting electrode, and SCE is a reference electrode, and the SnO2 transparent conducting glass of the doped with fluorine after the cleaning is a working electrode, and electrolytic solution is the Zn (NO of deionized water preparation
3)
2Be the mixed solution of 0.3M with the concentration of KCl; Electrolyzer does not stir, the situation deposit of opened upper end 1.5 hours, and the temperature during deposition is 70 ℃, and voltage is-1.0V;
After deposition finished, the SnO2 transparent conducting glass that takes out doped with fluorine promptly got: the black deposit below the liquid level is a ZnO hollow out nanometer sheet, and the above white deposits of liquid level is the ZnO nanometer rod.
Fig. 1 is the ZnO hollow out nanometer sheet (under the liquid level) of embodiment one preparation and (XRD) of nanometer rod (on the liquid level).Fig. 1 is visible, and the product that liquid level is obtained up and down is ZnO.
Fig. 2 is ZnO hollow out nanometer sheet (under the liquid level) stereoscan photograph of embodiment one preparation, is the sheet structure of thickness 40nm by the visible prepared product of Fig. 2; And can see the pattern of hollow out clearly.
Fig. 3 is the stereoscan photograph of the nanometer rod (on the liquid level) of embodiment one preparation, and visible by Fig. 3, products therefrom is the nanometer rod of bunchiness.
Embodiment two
This routine specific practice is:
The cleaning of the SnO2 transparent conducting glass of a, doped with fluorine
(1) be the SnO2 transparent conducting glass of the doped with fluorine in 10 Europe with square face resistance, in the HCl of 0.3M solution, ultrasonic 40min removes mineral ion; (2) rinse well with deionized water after, put into 10% washing powder solution, 70 ℃ ultrasonic 2.5 hours; (3) use the ultrasonic 40min of isopropanol solvent again; (4) deionized water is cleaned, is dried;
B, prepared by electrodeposition ZnO hollow out nanometer sheet and nanometer rod
Adopt the three-electrode cell system, platinized platinum is a supporting electrode, and SCE is a reference electrode, and the SnO2 transparent conducting glass of the doped with fluorine after the cleaning is a working electrode, and electrolytic solution is the Zn (NO of deionized water preparation
3)
2Be the mixed solution of 0.3M with the concentration of KCl; Electrolyzer does not stir, the situation deposit of opened upper end 1.3 hours, and the temperature during deposition is 70 ℃, and voltage is-1.0V;
After deposition finished, the SnO2 transparent conducting glass that takes out doped with fluorine promptly got: the black deposit below the liquid level is a ZnO hollow out nanometer sheet, and the above white deposits of liquid level is the ZnO nanometer rod.
Fig. 4 is ZnO hollow out nanometer sheet (under the liquid level) stereoscan photograph of embodiment one preparation, is sheet structure by the visible prepared product of Fig. 4; And can see the pattern of hollow out clearly.
Fig. 5 is the stereoscan photograph of the nanometer rod (on the liquid level) of embodiment one preparation, and visible by Fig. 5, products therefrom is the nanometer rod of bunchiness.
Embodiment three
This routine specific practice is:
The cleaning of the SnO2 transparent conducting glass of a, doped with fluorine
(1) be the SnO2 transparent conducting glass of the doped with fluorine in 12 Europe with square face resistance, in the HCl of 0.2M solution, ultrasonic 35min removes mineral ion; (2) rinse well with deionized water after, put into 8% washing powder solution, 70 ℃ ultrasonic 2.3 hours; (3) use the ultrasonic 38min of isopropanol solvent again; (4) deionized water is cleaned, is dried;
B, prepared by electrodeposition ZnO hollow out nanometer sheet and nanometer rod
Adopt the three-electrode cell system, platinized platinum is a supporting electrode, and SCE is a reference electrode, and the SnO2 transparent conducting glass of the doped with fluorine after the cleaning is a working electrode, and electrolytic solution is the Zn (NO of deionized water preparation
3)
2Be the mixed solution of 0.3M with the concentration of KCl; Electrolyzer does not stir, the situation deposit of opened upper end 1.4 hours, and the temperature during deposition is 70 ℃, and voltage is-1.0V;
After deposition finished, the SnO2 transparent conducting glass that takes out doped with fluorine promptly got: the black deposit below the liquid level is a ZnO hollow out nanometer sheet, and the above white deposits of liquid level is the ZnO nanometer rod.
Claims (1)
1. synchronous method of synthetic two kinds of ZnO nanostructures, its concrete practice is:
The cleaning of the SnO2 transparent conducting glass of a, doped with fluorine
(1) be the SnO2 transparent conducting glass of the doped with fluorine in 10-14 Europe with square face resistance, in the HCl of 0.1-0.3M solution, ultrasonic 30-40min removes mineral ion; (2) rinse well with deionized water after, put into the washing powder solution of 5-10%, 70 ℃ ultrasonic 2-2.5 hour; (3) use the ultrasonic 30-40min of isopropanol solvent again; (4) deionized water is cleaned, is dried;
B, prepared by electrodeposition ZnO hollow out nanometer sheet and nanometer rod
Adopt the three-electrode cell system, platinized platinum is a supporting electrode, and SCE is a reference electrode, and the SnO2 transparent conducting glass of the doped with fluorine after the cleaning is a working electrode, and electrolytic solution is the Zn (NO of deionized water preparation
3)
2Be the mixed solution of 0.3M with the concentration of KCl; Electrolyzer does not stir, the situation deposit of opened upper end 1.3-1.5 hour, and the temperature during deposition is 70 ℃, and voltage is-1.0V;
After deposition finished, the SnO2 transparent conducting glass that takes out doped with fluorine promptly got: the black deposit below the liquid level is a ZnO hollow out nanometer sheet, and the above white deposits of liquid level is the ZnO nanometer rod.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040016646A1 (en) * | 2002-07-29 | 2004-01-29 | Stucky Galen D. | Electrochemical synthesis of mesoporous metal/metal oxide flims using a low percentage surfactant solution by cooperative templating mechanism |
| US20050081912A1 (en) * | 2001-03-22 | 2005-04-21 | Canon Kabushiki Kaisha | Zinc oxide with acicular structure, process for its production, and photoelectric conversion device |
| US20070154385A1 (en) * | 2006-01-02 | 2007-07-05 | Min Yo-Sep | Method for manufacturing zinc oxide nanowires and device having the same |
| CN101162739A (en) * | 2007-11-13 | 2008-04-16 | 清华大学 | ZnO electric pole of dye sensitization solar cell and method for producing the same |
| US20100143679A1 (en) * | 2008-12-04 | 2010-06-10 | Northwestern University | Nanoscale lamellar photoconductor hybrids and methods of making same |
| US20110048956A1 (en) * | 2008-02-21 | 2011-03-03 | Helmholtz-Zentrum Berlin Für Materialien Und Energ | Electrodeposition method for the production of nanostructured zno |
| CN102024573A (en) * | 2010-12-18 | 2011-04-20 | 西南交通大学 | Method for preparing sensitized ZnO nano-plate photo-anode of PbS quantum dot |
| CN102061498A (en) * | 2010-12-28 | 2011-05-18 | 东南大学 | Preparation method of injector-shaped ZnO nanostructural array for field emission |
| CN102220615A (en) * | 2011-05-13 | 2011-10-19 | 中国科学院理化技术研究所 | Method for preparing CdS/ZnO nanotube array photoelectrode |
| CN102691084A (en) * | 2012-06-26 | 2012-09-26 | 上海大学 | Method for preparing ZnO nano-rod array through one-step electro-deposition |
-
2011
- 2011-11-02 CN CN201110341451.8A patent/CN102363893B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050081912A1 (en) * | 2001-03-22 | 2005-04-21 | Canon Kabushiki Kaisha | Zinc oxide with acicular structure, process for its production, and photoelectric conversion device |
| US20040016646A1 (en) * | 2002-07-29 | 2004-01-29 | Stucky Galen D. | Electrochemical synthesis of mesoporous metal/metal oxide flims using a low percentage surfactant solution by cooperative templating mechanism |
| US20070154385A1 (en) * | 2006-01-02 | 2007-07-05 | Min Yo-Sep | Method for manufacturing zinc oxide nanowires and device having the same |
| CN101162739A (en) * | 2007-11-13 | 2008-04-16 | 清华大学 | ZnO electric pole of dye sensitization solar cell and method for producing the same |
| US20110048956A1 (en) * | 2008-02-21 | 2011-03-03 | Helmholtz-Zentrum Berlin Für Materialien Und Energ | Electrodeposition method for the production of nanostructured zno |
| US20100143679A1 (en) * | 2008-12-04 | 2010-06-10 | Northwestern University | Nanoscale lamellar photoconductor hybrids and methods of making same |
| CN102024573A (en) * | 2010-12-18 | 2011-04-20 | 西南交通大学 | Method for preparing sensitized ZnO nano-plate photo-anode of PbS quantum dot |
| CN102061498A (en) * | 2010-12-28 | 2011-05-18 | 东南大学 | Preparation method of injector-shaped ZnO nanostructural array for field emission |
| CN102220615A (en) * | 2011-05-13 | 2011-10-19 | 中国科学院理化技术研究所 | Method for preparing CdS/ZnO nanotube array photoelectrode |
| CN102691084A (en) * | 2012-06-26 | 2012-09-26 | 上海大学 | Method for preparing ZnO nano-rod array through one-step electro-deposition |
Non-Patent Citations (1)
| Title |
|---|
| 李鹏等: "微/纳米多孔氧化锌薄膜的电化学制备及其光催化性能", 《中国有色金属学报》, vol. 19, no. 09, 15 September 2009 (2009-09-15) * |
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