CN101498051A - Preparation of zinc oxide nano-wire array - Google Patents
Preparation of zinc oxide nano-wire array Download PDFInfo
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- CN101498051A CN101498051A CNA2009100771304A CN200910077130A CN101498051A CN 101498051 A CN101498051 A CN 101498051A CN A2009100771304 A CNA2009100771304 A CN A2009100771304A CN 200910077130 A CN200910077130 A CN 200910077130A CN 101498051 A CN101498051 A CN 101498051A
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Abstract
The invention discloses a method of preparing a zinc oxide nanometer wire array, which belongs to the field of nanometer material preparation. The method comprises the following steps: using metallic zinc as an anode and an inert electrode as a cathode in an alkalescent electrolyte for anode oxidation; carrying out high-temperature annealing treatment of a zinc salt nanometer wire array obtained on the oxidated anode to prepare the zinc oxide nanometer wire array; and preferably, cleaning and/or carrying out electrochemical polishing treatment to the metallic zinc anode before the anode oxidation or adding a surface active agent to the electrolyte. The zinc oxide nanometer wire array prepared in the invention has the advantages of low-price material, environmental protection, simple equipment and steps, short preparation period and easy mass synthesis, and nanometer wire prepared by the method is formed by assembling zinc oxide nanometer crystals and has higher slenderness ratio, specific surface area and favorable electric performance.
Description
Technical field
The present invention relates to the preparation method of zinc oxide nano-wire array, relate in particular to the method for preparing zinc oxide nano-wire array by the zinc anode oxidation, belong to field of nano material preparation.
Background technology
Zinc oxide is a kind of important wide-band-gap semiconductor material (3.37eV), has higher exciton bind energy (60meV).Nano zine oxide has a lot of special propertys, has at aspects such as optical equipment, heterogeneous catalyst and photochemical catalysis, solar cell preparations widely to use.
The simple branch of the preparation method of zinc oxide can be divided into vapor phase process and liquid phase method.Vapor phase process usually with zinc powder or oxide powder and zinc as starting material, under comparatively high temps,,, finally obtain the zinc oxide of different-shape then in suitable warm area deposition by vapor transportation.This method needs high temperature, and resulting zinc oxide pattern along with the deposition warm area difference and difference also needs to use catalyzer sometimes.Compare with vapor phase process, liquid phase method is another very common zinc oxide nano-wire array preparation method.Typical preparation method wants to prepare earlier the nanocrystalline as Seed Layer of one deck zinc oxide usually in substrate, soak the regular hour then in the zinc solution of 60-90 degree, thereby obtain zinc oxide nano-wire array.It is simple that this method has an experimental installation, and good stability is suitable for the advantage of large-area preparation.But the length-to-diameter ratio of the resultant zinc oxide nanowire of present most of synthesis technique is all less than 200.Though human liquid phase methods such as nearest Lu Chonghua are prepared the zinc oxide nano-wire array (Chem.Commun., 2006,3551-3553) of length-to-diameter ratio bigger (about 1000), its employed temperature higher (150 degree), the time is grown (two days).Be unsuitable for macro preparation.
Anodic oxidation is a kind of very common process of surface treatment, is mainly used in anticorrosive, the friction resistant ability that improve material surface, sometimes is in order to obtain certain specific decorative effect.This technology is mainly used in metals such as aluminium, titanium at present.But less about the anodic oxidation of zinc research.In the prior art, the pattern that anodic oxidation zinc obtains is mainly some porous, particulate state or laminate structure.As far back as the sixties in last century, US military provides a kind of anode oxidation process (MIL-A-81801) of zinc, uses phosphoric acid salt, chromic salt and fluorochemical as electrolytic solution, obtains the olive-green protective layer of 80 micron thickness under the voltage up to 200V.But this patent was cancelled in the nineties in last century.The present invention utilizes anode oxidation process, prepare the zinc oxide nano-wire array film that has than big L/D ratio first apace, simple and reliable, be very suitable for macro preparation, be applicable to technical fields such as solar battery light anode, gas sensor, thermal electric film, have broad application prospects.
Summary of the invention
The objective of the invention is to overcome problems of the prior art, propose a kind of new method for preparing zinc oxide nano-wire array, the zinc oxide nano-wire array that makes by the inventive method has better material characteristic and wide application prospect.
In order to reach above-mentioned technical purpose, the inventive method adopts following technique means:
In weakly alkaline electrolytic solution with metallic zinc as anode, carry out anodic oxidation with noble electrode as negative electrode, following reaction takes place in the anode oxidation process, wherein reaction (1) and (2) is respectively in negative electrode and anode generation:
2H
++ 2e
-→ H
2(g) reaction (1)
Zn-2e
-→ Zn
2+Reaction (2)
Zn
2++ 2OH
-→ Zn (OH)
2(s) reaction (3)
Zn (OH)
2+ 2OH
-→ Zn (OH)
4 2-Reaction (4)
5Zn
2++ 2HCO
3 -+ 6H
2O → Zn
5(OH)
6(CO
3)
2(s)+8H
+Reaction (5)
Ion that produces in the reaction or nano particle are assembled into the zinc salt nano-wire array at anode automatically under electric field action, and these nano-wire arrays at high temperature decompose and can form zinc oxide nano-wire array.
In aforesaid method, weakly alkaline electrolytic solution is preferably supercarbonate, such as sodium bicarbonate, saleratus or bicarbonate of ammonia, the aqueous solution, the pH value preferably between 8-9, concentration be preferably the 5-20 mmole/liter; In electrolytic solution, can also optionally add an amount of tensio-active agent,,, improve the speed of response of electrolytic solution/zinc to reduce solution surface tension as Silwet408, alcohol or the like; Strictly speaking, alcohol is not thought tensio-active agent, but after alcohol and water mixes, can greatly reduce the surface tension of the aqueous solution, therefore herein with alcohol as tensio-active agent.Different types of tensio-active agent can use separately also can mix use.
As the anodic metallic zinc can be to be deposited on substrate, such as transparent conducting glass substrate or flexible polymer substrate, on metallic zinc, also can directly use zinc metal sheet;
In addition, in order to increase the density of zinc oxide nano-wire array, preferably before anodic oxidation, the metallic zinc anode is cleaned and/or electrochemical polishing treatment.The electrochemical polishing treatment of zinc metal sheet uses phosphoric acid spirituous solution (370 milliliters of strong phosphoric acid and 630 milliliters of raw spirits mix) as polishing fluid usually, polished zinc metal sheet is cooked anode, graphite cake is done negative electrode, and polishing voltage is the 18-20V direct current, and the time is about 30 minutes.Polishing process needs constantly powerful the stirring.Zinc metal sheet after the polished finish can reach mirror effect.
Described noble electrode can be Graphite Electrodes or platinum electrode; And preferably with anode and the vertically opposite placement of negative electrode;
Further, above-mentioned anodic oxidation operation is preferably carried out under following condition: constant voltage (such as normal pressure), temperature are in 0-50 ℃ scope, and anodic oxidation voltage is in the scope of 5-20V, and anodizing time is in 1-4 hour scope;
Above-mentioned high temperature annealing is preferably carrying out under the following condition: temperature is more than 250 ℃, and ambiance is an air or oxygen, and annealing time was about more than half an hour.With regard to temperature, 250 ℃ is that the zinc salt that is obtained decomposes the minimum temperature that is transformed into ZnO, therefore, is higher than this temperature in theory and all can; Temperature is too high or temperature rise rate is too fast, may cause film cracking or peels off, and is unfavorable for that the later stage uses, and therefore suitable temperature range is 250-300 ℃; With regard to annealing time, get final product about 30 minutes, overlong time does not have too big meaning, and comparatively suitable annealing time is about 0.5-2 hour.
Compare with prior art, the present invention has following advantage:
1) production cost is low: the used equipment of the present invention is fairly simple, does not need special manufacturing; The used chemical reagent of preparation electrolytic solution is cheapness but also environmental friendliness not only; Current consumption is minimum.
2) processing step is simple: step involved in the present invention is fairly simple, mainly comprises pre-treatment, anodic oxidation and three steps of annealing.
3) be easy to macro preparation: change the electrolyzer size, increase the amount of counter electrode size and electrolytic solution, than the anodic oxidation zinc preparation that is easier to realize large-size.
4) preparation cycle is short: the present invention can realize 30 microns long zinc oxide nano-wire arrays of growth in 1 hour.
5) prepared nano-wire array has high length-to-diameter ratio: the anodic oxidation of the present invention by 1-4 hour can obtain length-to-diameter ratio greater than 1000 zinc oxide nano-wire array.And other arts demand of realizing same length-to-diameter ratio reaches 48 hours.
Generally speaking, the zinc oxide nano-wire array film material requested cheapness of the present invention's preparation, environmental friendliness, equipment used and step are simple, preparation cycle is short, be easy to extensive synthesizing, and the prepared nano wire of this kind method is to be assembled by zinc oxide nanocrystalline, have higher length-to-diameter ratio and specific surface area, good electric property.
Description of drawings
The stereoscan photograph of the zinc oxide nano-wire array (film) that Fig. 1 makes for embodiment 1, a are the low power stereoscan photograph that anodic oxidation in 1 hour obtains zinc oxide nanowire; B is the high power stereoscan photograph that anodic oxidation in 1 hour obtains zinc oxide nanowire; C is the high power stereoscan photograph that anodic oxidation in 4 hours obtains zinc oxide nanowire.
The X-ray diffraction spectrum (XRD) of the zinc oxide nano-wire array film that Fig. 2 makes for embodiment 1.
The transmission electron microscope photo of the zinc oxide nano-wire array that Fig. 3 makes for embodiment 1, a are the low power transmission electron microscope photo; B is the high-resolution-ration transmission electric-lens photo.
Fig. 4 has shown the electrical performance testing result of the single zinc oxide nanowire in the zinc oxide nano-wire array that embodiment 1 makes.
Fig. 5 has shown the influence of polished finish to zinc oxide nano-wire array, a carries out anodised situation again for anode among the embodiment 1 after polished finish, resulting nano-wire array is dense, b directly carries out anodised situation for anode among the embodiment 2 without polished finish, and the nano wire that obtains is more sparse.
Fig. 6 has shown a larger area zinc oxide nano-wire array.Anodic oxidation treatment is not carried out in the zone that red glyphs covered.
Embodiment
Below by specific embodiments and the drawings the inventive method is further described.
Embodiment 1
Present embodiment directly carries out anodic oxidation with zinc metal sheet as anode, comprises the following steps:
1) preparation electrolytic solution: prepare 500 ml concns and be 15 mmoles/liter sodium bicarbonate aqueous solution, add 50 ml ethanols, fully stir then and make it dissolving and mix, with the solution that obtains as electrolytic solution;
2) zinc metal sheet pre-treatment: use raw spirit and acetone ultrasonic cleaning zinc metal sheet successively, dry up, carry out behind the electrochemical etching as anodised anode;
3) zinc metal sheet anodic oxidation: pretreated zinc metal sheet is installed on the specimen holder, it simultaneously is exposed in the solution, another side links to each other with positive pole, counter electrode (negative electrode) graphite cake of 7cm * 5cm; Use the anodic oxidation 4 hours under the operating voltage of 10V of DH1720-2 type dc constant voltage source then;
4) anneal: after anodic oxidation finishes, zinc metal sheet is taken out, rinse well, then oven dry with deionized water; Be placed on and slowly be warming up to 250 degree in the tube furnace, annealing is 30 minutes to 2 hours under atmospheric environment;
Obtain the zinc oxide nano-wire array of film like after the above-mentioned processing, to the sign of product shown in accompanying drawing 1-4.Fig. 1 is the stereoscan photograph of product, and a, b are the situation of anodic oxidation after 1 hour, and c is the situation of anodic oxidation after 4 hours; Fig. 2,3 is respectively the X-ray diffraction spectrum and the transmission electron microscope photo of product; Fig. 4 has then shown the electrical performance testing result of single zinc oxide nanowire.
Through four hours anodic oxidation treatment, the length of zinc oxide nanowire surpassed 100 microns, and diameter is less than 100 nanometers, and length-to-diameter ratio is greater than 1000.Electricity performance measurement to single nano-wire shows, as shown in Figure 4, parameters such as its electronic mobility and the carrier concentration (M.Law that can match in excellence or beauty with the single-crystal zinc-oxide nano line of other method preparation, L.E.Greene, J.C.Johnson, R.Saykally, P.D.Yang, Nature Mater.2005,4,455).
If change the size of zinc metal sheet and Graphite Electrodes, increase the amount of electrolytic solution simultaneously, can prepare the anodic oxidation zinc of large-size, as shown in Figure 6 the anodic oxidation zinc of 40mm * 80mm.Simultaneously can be than the anodic oxidation zinc that is easier to prepare different pattern.
Embodiment 2
Present embodiment adopts the preparation method identical with embodiment 1, and difference is that before the anodic oxidation, antianode does not carry out electrochemical polishing treatment.
As shown in Figure 5, embodiment 1 product is dense, and embodiment 2 products are then more sparse, and as seen, the electrochemical polishing treatment before the anodic oxidation has tangible influence to the compactness of the finished product.
Present embodiment adopts the preparation method identical with embodiment 1, and difference is that ITO (perhaps FTO) glass of anode employing magnetron sputtering zinc-plated (perhaps electrochemical deposition zinc) can obtain required zinc oxide nano-wire array equally.
Embodiment 4
Present embodiment adopts the preparation method identical with embodiment 1, and difference is that anode adopts the compliant conductive polymeric film of electrodepositing zinc, and anneal employing microwave heating can obtain required zinc oxide nano-wire array equally.
Present embodiment adopts the preparation method identical with embodiment 1, difference is, electrolytic solution adopted 500 ml concns be 15 mmoles/liter ammonium bicarbonate aqueous solution, add 50 ml ethanols, fully stir then and make it dissolving and mix, with the solution that obtains as electrolytic solution.Can obtain required zinc oxide nano-wire array equally.
Claims (10)
1, a kind of preparation method of zinc oxide nano-wire array is characterized in that, in weakly alkaline electrolytic solution with metallic zinc as anode, carry out anodic oxidation with noble electrode as negative electrode; After the anodic oxidation, the zinc salt nano-wire array that antianode obtains carries out The high temperature anneal, obtains zinc oxide nano-wire array.
2, preparation method as claimed in claim 1 is characterized in that, described weakly alkaline electrolytic solution be the 5-20 mmole/liter bicarbonate aqueous solution.
3, preparation method as claimed in claim 2 is characterized in that, described supercarbonate is one or more in sodium bicarbonate, saleratus or the bicarbonate of ammonia.
4, preparation method as claimed in claim 1 or 2 is characterized in that, adds tensio-active agent in the described weakly alkaline electrolytic solution.
5, preparation method as claimed in claim 1 is characterized in that, described metallic zinc is to be deposited on suprabasil metallic zinc, or zinc metal sheet.
6, preparation method as claimed in claim 5 is characterized in that, described substrate is transparent conducting glass substrate or flexible polymer substrate.
7, as claim 1 or 5 or 6 described preparation methods, it is characterized in that, before the anodic oxidation, described metallic zinc anode is cleaned and/or electrochemical polishing treatment.
8, preparation method as claimed in claim 1 is characterized in that, described noble electrode is Graphite Electrodes or platinum electrode; The vertically opposite placement of described anode and negative electrode.
9, preparation method as claimed in claim 1 is characterized in that, described anodic oxidation was carried out under the volts DS of 5-20V 1-4 hour under 0-50 ℃ temperature.
10, preparation method as claimed in claim 1 is characterized in that, described high temperature annealing carried out under air or oxygen atmosphere 0.5-2 hour under 250-300 ℃ temperature.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181911A (en) * | 2011-04-21 | 2011-09-14 | 河北联合大学 | Method for preparing ZnO nano-band array |
| CN102220596A (en) * | 2011-05-19 | 2011-10-19 | 中国原子能科学研究院 | Preparation method of nano zinc oxide wire |
| CN102220603A (en) * | 2010-04-16 | 2011-10-19 | 中国石油大学(北京) | NbTi nanowires and preparation method thereof |
| CN103021821A (en) * | 2012-11-27 | 2013-04-03 | 复旦大学 | Metal or semiconductor structure on flexible substrate and annealing method of metal or semiconductor |
| CN103243371A (en) * | 2013-05-16 | 2013-08-14 | 中国船舶重工集团公司第七二五研究所 | Preparation method of zinc anode oxidation film layer |
| CN106006715A (en) * | 2016-05-20 | 2016-10-12 | 西北师范大学 | Method for preparing nano zinc oxide by using liquid diaphragm discharge plasma |
| CN114016048A (en) * | 2021-12-16 | 2022-02-08 | 西北师范大学 | Zn (OH) with micro-nano structure2And a controllable preparation method of ZnO |
| CN116479498A (en) * | 2023-04-04 | 2023-07-25 | 扬州新达再生资源科技有限公司 | Low-energy-consumption clean processing technology for preparing active zinc oxide from zinc ash |
-
2009
- 2009-01-16 CN CN2009100771304A patent/CN101498051B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220603A (en) * | 2010-04-16 | 2011-10-19 | 中国石油大学(北京) | NbTi nanowires and preparation method thereof |
| CN102220603B (en) * | 2010-04-16 | 2013-11-06 | 中国石油大学(北京) | NbTi nanowires and preparation method thereof |
| CN102181911B (en) * | 2011-04-21 | 2012-10-10 | 河北联合大学 | Method for preparing ZnO nano-band array |
| CN102181911A (en) * | 2011-04-21 | 2011-09-14 | 河北联合大学 | Method for preparing ZnO nano-band array |
| CN102220596A (en) * | 2011-05-19 | 2011-10-19 | 中国原子能科学研究院 | Preparation method of nano zinc oxide wire |
| CN103021821A (en) * | 2012-11-27 | 2013-04-03 | 复旦大学 | Metal or semiconductor structure on flexible substrate and annealing method of metal or semiconductor |
| CN103021821B (en) * | 2012-11-27 | 2016-09-28 | 复旦大学 | The method for annealing of the semiconductor structure being positioned in flexible substrate |
| CN103243371A (en) * | 2013-05-16 | 2013-08-14 | 中国船舶重工集团公司第七二五研究所 | Preparation method of zinc anode oxidation film layer |
| CN103243371B (en) * | 2013-05-16 | 2015-06-17 | 中国船舶重工集团公司第七二五研究所 | Preparation method of zinc anode oxidation film layer |
| CN106006715A (en) * | 2016-05-20 | 2016-10-12 | 西北师范大学 | Method for preparing nano zinc oxide by using liquid diaphragm discharge plasma |
| CN114016048A (en) * | 2021-12-16 | 2022-02-08 | 西北师范大学 | Zn (OH) with micro-nano structure2And a controllable preparation method of ZnO |
| CN116479498A (en) * | 2023-04-04 | 2023-07-25 | 扬州新达再生资源科技有限公司 | Low-energy-consumption clean processing technology for preparing active zinc oxide from zinc ash |
| CN116479498B (en) * | 2023-04-04 | 2023-10-20 | 扬州新达再生资源科技有限公司 | Low-energy-consumption clean processing technology for preparing active zinc oxide from zinc ash |
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