CN102363893B - Method for synchronically synthesizing two ZnO nanostructures - Google Patents
Method for synchronically synthesizing two ZnO nanostructures Download PDFInfo
- Publication number
- CN102363893B CN102363893B CN201110341451.8A CN201110341451A CN102363893B CN 102363893 B CN102363893 B CN 102363893B CN 201110341451 A CN201110341451 A CN 201110341451A CN 102363893 B CN102363893 B CN 102363893B
- Authority
- CN
- China
- Prior art keywords
- zno
- electrode
- fluorine
- doped
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
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 synchronous synthetic two kinds of ZnO nano-structures.
Background technology
ZnO, as a kind of important direct wide bandgap compound semiconductor oxide material, has excellent optics and electrology characteristic.At room temperature, ZnO energy gap is 3.37eV, and its exciton bind energy, up to 60meV, is applicable to being used as the ultraviolet light emission material under room temperature or higher temperature, all has broad application prospects at optical fields such as short-wave long light-emitting diodes simultaneously.ZnO also has piezoelectric property, field emission effect, the multiple special performance such as gas sensing property; Meanwhile, its preparation technology is simple, and growth temperature is lower; Abundant raw material, low production cost; In addition, ZnO is nontoxic, environmentally safe, is a kind of environment-friendly materials.Therefore, ZnO has very wide application prospect, becomes the study hotspot of semiconductor applications, gets most of the attention.
The ZnO of different-shape, has different character and application, and it is a study hotspot that ZnO is carried out to pattern regulation and control always.ZnO nanorod is one-dimentional structure, is conducive to electric transmission etc., having broad application prospects aspect photodiode, laser apparatus, ultraviolet detector, high frequency and high power device and related device thereof.And hollow out ZnO nano sheet has larger surface-area and adsorption site, be conducive to absorbing dye or other inorganic nano-particle, formation has many absorber portions (ZnO ultraviolet, inorganic nano-particle can be selected different wave length, as visible region CdS, infrared region PbS) matrix material, has good application at aspects such as solar cells.
Existing ZnO nanorod and ZnO hollow out nanometer sheet, must adopt respectively different preparation technologies, different equipment to make.As need, prepare these two kinds of ZnO nano-structures and must at least adopt two kinds of preparation technologies, two kinds of equipment, preparation process is loaded down with trivial details, efficiency is low.
Summary of the invention
The object of the invention is just to provide a kind of method of synchronous synthetic two kinds of ZnO nano-structures, the method can obtain the ZnO nano-structure 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 the technical scheme that the order of its invention adopts, a kind of method of synchronous synthetic two kinds of ZnO nano-structures, and its concrete practice is:
The cleaning of the SnO2 transparent conducting glass of a, doped with fluorine
(1) by square surface resistance, be the SnO2 transparent conducting glass of the doped with fluorine in 10-14 Europe, in the HCl of 0.1-0.3M solution, ultrasonic 30-40min removes mineral ion; (2), after rinsing well with deionized water, put into the washing powder solution of 5-10%, 70 ℃ of ultrasonic 2-2.5 hour; (3) use again the ultrasonic 30-40min of isopropanol solvent; (4) deionized water is cleaned, is dried;
B, galvanic deposit making ZnO hollow out nanometer sheet and nanometer rod
Adopt three-electrode cell system, platinized platinum is supporting electrode, and saturated calomel electrode is reference electrode, and the SnO2 transparent conducting glass of the doped with fluorine after cleaning is 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, deposit 1.5 hours in the situation of opened upper end, and temperature during deposition is 70 ℃, and voltage is-1.0V;
After deposition finishes, take out the SnO2 transparent conducting glass of doped with fluorine and get final product: the black deposit below liquid level is ZnO hollow out nanometer sheet, and white deposits more than liquid level is ZnO nanorod.
The possible mechanism of the inventive method is:
The reaction of b one-step electrochemistry deposition is
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 -
Due to capillary effect, the SnO2 transparent conducting glass (FTO) of doped with fluorine is poor with the liquid level that electrolytic solution meeting height of formation is h, because the voltage distribution at electrolytic solution different heights place is different, electrolytical concentration also may be different, cause the sedimentation velocity of ZnO on FTO different; Only there is deposition reaction in the FTO on liquid level, generates nanometer rod; All the time in subsurface FTO, first there is deposition reaction, after there is again etching reaction, finally generate hollow out nanometer sheet.Liquid level is because thermal evaporation causes decline, and therefore, the ZnO nanorod that the FTO on liquid level generates forms string shape.By adjusting the size of reaction vessel, can control the height that liquid level declines, 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 nano-structure 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 obtaining the occasion of these two kinds of prepared products simultaneously.
Two, adjust the size of reaction vessel, can control the height that liquid level declines, and then regulate and control the ratio of two kinds of products.Proportion of products regulation and control are convenient.
Three, adopt liquid-phase precipitation method, inorganic salt used are zinc nitrate, nontoxic, environmentally safe.
Four, X-ray test proof, ZnO hollow out nanometer sheet and two kinds of products of nanometer rod are all without dephasign, and purity is high.
Below in conjunction with accompanying drawing and concrete embodiment, the present invention is further detailed explanation.
Accompanying drawing explanation
Fig. 1 is the ZnO hollow out nanometer sheet (under liquid level) of the embodiment of the present invention one preparation and (XRD) of nanometer rod (on liquid level).
Fig. 2 is ZnO hollow out nanometer sheet (under the liquid level) stereoscan photograph of the embodiment of the present invention one preparation.
Fig. 3 is the stereoscan photograph of the nanometer rod (on liquid level) of the embodiment of the present 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 present invention two preparations.
Fig. 5 is the stereoscan photograph (depositing time 1.3 hours) of the nanometer rod (on liquid level) of the embodiment of the present invention two preparations.
Embodiment
Embodiment mono-
A kind of embodiment of the present invention is: a kind of method of synchronous synthetic two kinds of ZnO nano-structures, and its concrete practice is:
The cleaning of the SnO2 transparent conducting glass of a, doped with fluorine
(1) by square surface resistance, be the SnO2 transparent conducting glass of the doped with fluorine in 14 Europe, in the HCl of 0.1M solution, ultrasonic 30min removes mineral ion; (2) after rinsing well with deionized water, put into 5% washing powder solution, 70 ℃ ultrasonic 2 hours; (3) use again the ultrasonic 30min of isopropanol solvent; (4) deionized water is cleaned, is dried;
B, galvanic deposit making ZnO hollow out nanometer sheet and nanometer rod
Adopt three-electrode cell system, platinized platinum is supporting electrode, and saturated calomel electrode is reference electrode, and the SnO2 transparent conducting glass of the doped with fluorine after cleaning is 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, deposit 1.5 hours in the situation of opened upper end, and temperature during deposition is 70 ℃, and voltage is-1.0V;
After deposition finishes, take out the SnO2 transparent conducting glass of doped with fluorine and get final product: the black deposit below liquid level is ZnO hollow out nanometer sheet, and white deposits more than liquid level is ZnO nanorod.
Fig. 1 is the ZnO hollow out nanometer sheet (under liquid level) of embodiment mono-preparation and (XRD) of nanometer rod (on liquid level).Fig. 1 is visible, and the product that liquid level is upper and lower obtained is ZnO.
Fig. 2 is ZnO hollow out nanometer sheet (under the liquid level) stereoscan photograph of embodiment mono-preparation, and prepared product is the sheet structure of thickness 40nm as seen from Figure 2; And can see clearly the pattern of hollow out.
Fig. 3 is the stereoscan photograph of the nanometer rod (on liquid level) of embodiment mono-preparation, as seen from Figure 3, and the nanometer rod that products therefrom is bunchiness.
Embodiment bis-
This routine specific practice is:
The cleaning of the SnO2 transparent conducting glass of a, doped with fluorine
(1) by square surface resistance, be the SnO2 transparent conducting glass of the doped with fluorine in 10 Europe, in the HCl of 0.3M solution, ultrasonic 40min removes mineral ion; (2) after rinsing well with deionized water, put into 10% washing powder solution, 70 ℃ ultrasonic 2.5 hours; (3) use again the ultrasonic 40min of isopropanol solvent; (4) deionized water is cleaned, is dried;
B, galvanic deposit making ZnO hollow out nanometer sheet and nanometer rod
Adopt three-electrode cell system, platinized platinum is supporting electrode, and saturated calomel electrode is reference electrode, and the SnO2 transparent conducting glass of the doped with fluorine after cleaning is 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, deposit 1.3 hours in the situation of opened upper end, and temperature during deposition is 70 ℃, and voltage is-1.0V;
After deposition finishes, take out the SnO2 transparent conducting glass of doped with fluorine and get final product: the black deposit below liquid level is ZnO hollow out nanometer sheet, and white deposits more than liquid level is ZnO nanorod.
Fig. 4 is ZnO hollow out nanometer sheet (under the liquid level) stereoscan photograph of embodiment mono-preparation, and prepared product is sheet structure as seen from Figure 4; And can see clearly the pattern of hollow out.
Fig. 5 is the stereoscan photograph of the nanometer rod (on liquid level) of embodiment mono-preparation, as seen from Figure 5, and the nanometer rod that products therefrom is bunchiness.
Embodiment tri-
This routine specific practice is:
The cleaning of the SnO2 transparent conducting glass of a, doped with fluorine
(1) by square surface resistance, be the SnO2 transparent conducting glass of the doped with fluorine in 12 Europe, in the HCl of 0.2M solution, ultrasonic 35min removes mineral ion; (2) after rinsing well with deionized water, put into 8% washing powder solution, 70 ℃ ultrasonic 2.3 hours; (3) use again the ultrasonic 38min of isopropanol solvent; (4) deionized water is cleaned, is dried;
B, galvanic deposit making ZnO hollow out nanometer sheet and nanometer rod
Adopt three-electrode cell system, platinized platinum is supporting electrode, and saturated calomel electrode is reference electrode, and the SnO2 transparent conducting glass of the doped with fluorine after cleaning is 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, deposit 1.4 hours in the situation of opened upper end, and temperature during deposition is 70 ℃, and voltage is-1.0V;
After deposition finishes, take out the SnO2 transparent conducting glass of doped with fluorine and get final product: the black deposit below liquid level is ZnO hollow out nanometer sheet, and white deposits more than liquid level is ZnO nanorod.
Claims (1)
1. synchronously synthesize a method for two kinds of ZnO nano-structures, its concrete practice is:
The SnO of a, doped with fluorine
2the cleaning of transparent conducting glass
(1) by square surface resistance, be the SnO of the doped with fluorine in 10-14 Europe
2transparent conducting glass, in the HCl of 0.1-0.3M solution, ultrasonic 30-40min removes mineral ion; (2), after rinsing well with deionized water, put into the washing powder solution of 5-10%, 70 ℃ of ultrasonic 2-2.5 hour; (3) use again the ultrasonic 30-40min of isopropanol solvent; (4) deionized water is cleaned, is dried;
B, galvanic deposit making ZnO hollow out nanometer sheet and nanometer rod
Adopt three-electrode cell system, platinized platinum is supporting electrode, and saturated calomel electrode is reference electrode, the SnO of the doped with fluorine after cleaning
2transparent conducting glass is 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, deposit 1.3-1.5 hour in the situation of opened upper end, and temperature during deposition is 70 ℃, and voltage is-1.0V;
After deposition finishes, take out the SnO of doped with fluorine
2transparent conducting glass and get final product: the black deposit below liquid level is ZnO hollow out nanometer sheet, and white deposits more than liquid level is ZnO nanorod.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110341451.8A CN102363893B (en) | 2011-11-02 | 2011-11-02 | Method for synchronically synthesizing two ZnO nanostructures |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110341451.8A CN102363893B (en) | 2011-11-02 | 2011-11-02 | Method for synchronically synthesizing two ZnO nanostructures |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102363893A CN102363893A (en) | 2012-02-29 |
| CN102363893B true CN102363893B (en) | 2014-03-12 |
Family
ID=45690486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110341451.8A Expired - Fee Related CN102363893B (en) | 2011-11-02 | 2011-11-02 | Method for synchronically synthesizing two ZnO nanostructures |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102363893B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002356400A (en) * | 2001-03-22 | 2002-12-13 | Canon Inc | Manufacturing method for needle structural zinc oxide body, and battery and photoelectric transducer using it |
| 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 |
| KR101322708B1 (en) * | 2006-01-02 | 2013-10-29 | 삼성전자주식회사 | Method for Manufacturing Zinc Oxide Nanowires and Nanowires Manufactured therefrom |
| US20110048956A1 (en) * | 2008-02-21 | 2011-03-03 | Helmholtz-Zentrum Berlin Für Materialien Und Energ | Electrodeposition method for the production of nanostructured zno |
| US8366974B2 (en) * | 2008-12-04 | 2013-02-05 | Northwestern University | Nanoscale lamellar photoconductor hybrids and methods of making same |
| CN102061498B (en) * | 2010-12-28 | 2012-04-18 | 东南大学 | Preparation method of injector-shaped ZnO nanostructural array for field emission |
| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102363893A (en) | 2012-02-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102107850B (en) | Method for preparing nuclear-shell-structured rutile monocrystal titanium dioxide nanowire array with surface-cladding carbon layer | |
| CN102220615B (en) | Method for preparing CdS/ZnO nanotube array photoelectrode | |
| Gan et al. | Vertically aligned In 2 O 3 nanorods on FTO substrates for photoelectrochemical applications | |
| CN103400878B (en) | A kind of zinc-oxide nano pencil array electrode and its preparation method and application | |
| CN104362412A (en) | ZnO/g-C3N4 nanocomposite and preparation method thereof | |
| CN109473489B (en) | Self-powered photoelectric detector capable of distinguishing ultraviolet bands | |
| Guo et al. | Hierarchical TiO 2–CuInS 2 core–shell nanoarrays for photoelectrochemical water splitting | |
| CN110205634B (en) | ZnO/ZnS/CdS photo-anode film and preparation method thereof | |
| CN103132119B (en) | Preparation method of graphene/TiO2 flower-like nano-clusters | |
| CN104795456B (en) | Electrodeposition process prepares the method for three band gap Fe2O3 doping copper gallium sulphur solar cell materials | |
| CN102303901B (en) | Preparation method, product and use of micro/nano heretically-structured insert octahedral Zn2SnO4 | |
| CN1763261A (en) | Titanium dioxide nano material film and preparation method thereof | |
| Feng et al. | Nickel hydroxide decorated hydrogenated zinc oxide nanorod arrays with enhanced photoelectrochemical performance | |
| CN103943721A (en) | Copper-zinc-tin-sulfur (CZTS) thin film and preparation method and purposes thereof | |
| CN109706478A (en) | The thin layer titanium carbide of hydrogen reducing loads photoelectrolysis water cuprous oxide photocathode material and preparation method thereof | |
| CN102881462A (en) | Preparation method of ZnO nano rod array/nano grain cluster microballoon sphere composite film | |
| CN109103282A (en) | A kind of optical electro-chemistry type solar blind ultraviolet detector based on gallium oxide nano column array | |
| CN110241439B (en) | Plasma treatment for preparing surface hydroxylation WO3Method for preparing thin film photoelectrode material | |
| CN100552099C (en) | Improved electrochemical deposition process prepares the single c-axle oriented zinc oxide film method | |
| CN104628262B (en) | Method for preparing matchstick-shaped TiO2 nanoparticle and nanorod composite array | |
| CN102418130B (en) | Preparation method of gridded CuxS/Cu2O (x is 1.75-2) composite pyramid-like film | |
| Chen et al. | ZnO hemisphere pits nanowire/CdS photoelectrode for high-efficiency photoelectrochemical water splitting | |
| CN105568309A (en) | Preparation method for photoelectrode of photoelectrochemical cell | |
| CN102363893B (en) | Method for synchronically synthesizing two ZnO nanostructures | |
| CN101863507B (en) | Preparation method of gradated stannic oxide octahedrons |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140312 Termination date: 20161102 |