CN100360420C - Method of growing nano-tube shaped zinc oxide by hydrothermal decomposition - Google Patents
Method of growing nano-tube shaped zinc oxide by hydrothermal decomposition Download PDFInfo
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- CN100360420C CN100360420C CNB2005100951690A CN200510095169A CN100360420C CN 100360420 C CN100360420 C CN 100360420C CN B2005100951690 A CNB2005100951690 A CN B2005100951690A CN 200510095169 A CN200510095169 A CN 200510095169A CN 100360420 C CN100360420 C CN 100360420C
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Abstract
The present invention relates to a method for growing nano-tube shaped zinc oxide by hydrothermal decomposition, which has the advantages of simple operation, mild preparation condition, good repeatability, uniform shape of the prepared zinc oxide nano-tube. The method for growing nano-tube shaped zinc oxide by hydrothermal decomposition in the present invention comprises the following steps that step 1, concentrated ammonia water is dripped into the solution of zinc chloride with the concentration of 0.06 to 0.15m to be fully stirred, and the solution is sealed after the pH value of the mixed solution is regulated to 9 to 11; step2, ultrasonic processing is carried out to the sealed solution; step3, a clean substrate with electric conductive performance is put in the solution; the solution is sealed again, put in the environment at the temperature of 80 to 98 DEG C for still standing, and subsequently cooled naturally to the room temperature kept for a plurality of hours to make the solution aged; the substrate with the electric conductive performance is taken out, flushed with deionized water and naturally aired, and the zinc oxide with nano-tube crystal structure is obtained on the surface of the substrate with electric conductive performance. The method of the present invention has the advantages of low cost, simple experimental operation, shortened formation time of tubular structure, mild preparation condition, good repeatability, uniform shape of the prepared zinc oxide nano-tube, etc.
Description
Technical field
The present invention relates to a kind of preparation method of zinc oxide, relate in particular to a kind of method of growing nano-tube shaped zinc oxide by hydrothermal decomposition.
Background technology
Nano material's structure and pattern have very big influence to the performance and the application of nano material.The nano crystal material of preparing ad hoc structure and pattern has important meaning for the frontier of developing nano ZnO.
In numerous nano materials, the nanostructure of zinc oxide has caused general interest.Zinc oxide is that a kind of 60meV of having exciton bind energy and direct band gap width are the wide bandgap semiconductor of 3.37eV.And the nano zine oxide of tubular structure enjoys attention owing to its high voidage and bigger surface-area and good light, electricity, magnetic property, and it is expected in fields such as biosensor, gas sensor, storage hydrogen device, metal-ionization cell, electric chemical super electric capacity, photocell, flat pannel display good application prospects to be arranged.
The preparation method of zinc oxide nano mitron comprises template method, pyrolysis method, chemical reaction method method or the like at present.Compare with the present invention, at present there are shortcomings such as temperature of reaction height, equipment complexity, cost height, efficient are low in these methods of report.Therefore, the tubular looks uniform method of zinc-oxide nano of work out a kind of simple to operate, cheap, good reproducibility, preparing there is significance.
Summary of the invention
The present invention be a kind of simple to operate, preparation condition is gentle, the method for good reproducibility, the uniform growing nano-tube shaped zinc oxide by hydrothermal decomposition of the tubular looks of zinc-oxide nano prepared.
The present invention adopts following technical scheme:
A kind of method of growing nano-tube shaped zinc oxide by hydrothermal decomposition:
The first step: with mass percent concentration be 25% strong aqua to be added drop-wise to concentration be to stir in 0.06～0.15M liquor zinci chloridi and fully, the pH to 9-11 of regulator solution, then that solution is airtight;
Second step: airtight solution was carried out supersound process 25～35 minutes;
The 3rd step: the conductivity substrate after will cleaning is put into above-mentioned solution and airtight once more solution, again should airtight solution putting into 80～98 ℃ of environment left standstill 45～90 minutes, naturally cool to room temperature subsequently and kept 5-9 hour, make it aging, again conductivity substrate is taken out, use deionized water rinsing, can on the surface of conductivity substrate, obtain the zinc oxide of nanotube crystalline structure after drying naturally.
Compared with prior art, the present invention has following advantage:
The present invention is dissolved in zinc chloride and ammoniacal liquor in the deionized water according to certain concentration, then this solution is used supersound process 25～35 minutes, substrate after cleaning is put into solution and airtight solution, and the baking oven of subsequently this encloses container being put into 90～98 ℃ left standstill 45～90 minutes.Reduce oven temperature at last, keep the zinc oxide nano mitron that can obtain to have even dense arrangement in 5-9 hour.Because the varieties of reagent that the present invention adopts is few, cost is low, experimental implementation is simple, growth time is short, can obtain uniform nano tubular structure in big area.The zinc oxide nano mitron mean diameter that obtains is 550nm, and thickness of pipe is less than 50nm, and the nanotube mean length is 3 μ m.
1. the present invention has only adopted zinc chloride and strong aqua, and the chemical reagent that adopts than similar preparation nanostructure aqueous process reduces.On the one hand, preparation process is further oversimplified, further reduced preparation cost simultaneously; On the other hand, reduce the ionic species in the solution, reduced the adverse influence factor, also improved sample purity.
2. the said substrate of the present invention is a conductivity substrate, as: metal substrate such as copper, aluminium, iron or stainless steel also can be silicon, Teflon or the semiconducter substrate that is coated with above-mentioned metal.。Selecting for use of conductivity substrate, for the various electrical measurements of nano structure membrane subsequently provide convenience, in addition, the nano zine oxide structure that is grown on the metal substrate more helps making various transmitters and other device, as gas/liquid transmitter and feds.
3. the present invention adopts cryogenic weathering process, and the formation time of tubular structure is reduced.
Description of drawings
Fig. 1 is by embodiment 1 resulting zinc oxide nano mitron scanning electron microscopy (SEM) image.
Fig. 2 is by embodiment 1 resulting zinc oxide nano mitron scanning electron microscopy (SEM) image (amplifying the back).
Fig. 3 is by embodiment 1 resulting zinc oxide nano mitron X-ray diffraction (XRD) image.
Embodiment
The following examples is to further specify of the present invention, rather than limits the scope of the invention.
Embodiment 1
A kind of method of growing nano-tube shaped zinc oxide by hydrothermal decomposition:
The first step: with mass percent concentration is that to be added drop-wise to concentration be to stir in 0.06～0.15M liquor zinci chloridi and fully for 25% strong aqua, the pH to 9-11 of regulator solution, then that solution is airtight, present embodiment can be chosen in 0.08,0.10,0.12 or the 0.15M liquor zinci chloridi in drip strong aqua, and make the pH value of solution be adjusted into 9,9.5,9.7,10.1 or 11;
Second step: airtight solution was carried out supersound process 25～35 minutes, and in the present embodiment, the time of supersound process is 25,28,32 or 35 minutes;
The 3rd step: the conductivity substrate after will cleaning is put into above-mentioned solution and airtight once more solution, again should airtight solution putting into 80～98 ℃ of environment left standstill 45～90 minutes, in the present embodiment, airtight solution can be placed 90,95 or 98 ℃ environment left standstill 45,51,62 or 70 minutes, naturally cool to room temperature subsequently and kept 5-9 hour, hold-time is 5,7 or 9 hours, make it aging, again conductivity substrate is taken out, use deionized water rinsing, can on the surface of conductivity substrate, obtain the zinc oxide of nanotube crystalline structure after drying naturally.
In the present embodiment, the clean of conductivity substrate is to clean with acetone, uses acetone, deionized water ultrasonic cleaning subsequently successively again.
Embodiment 2
1. at first stainless steel substrates is cleaned with acetone, used acetone, deionized water ultrasonic cleaning each 15 minutes subsequently successively again;
2. be that to be added drop-wise to 40ml concentration be to stir in the 0.10M liquor zinci chloridi and fully for 25% strong aqua 3ml with mass ratio; Solution places in the glass bottle that is threaded flap.
2. the processing of film growth liquid: supersound process 35 minutes are used in the airtight back of above-mentioned solution;
4. the substrate after will cleaning is put into solution and airtight once more solution.The baking oven of immediately this encloses container being put into 95 ℃ left standstill 60 minutes.Reduce oven temperature subsequently, keep 6 hours substrate taking-up, the zinc oxide nano mitron that can obtain to have even dense arrangement with natural airing behind the deionized water rinsing.
The XRD figure line of Fig. 3 shows that resulting sample is a zincite crystal, does not have other impurity.
Fig. 1, Fig. 2 show that the zinc oxide that obtains is hexagonal structure.The zinc oxide nano mitron mean diameter that obtains is 550nm, and thickness of pipe is less than 50nm, and the nanotube mean length is 3 μ m.
Embodiment 3
1. the selection of substrate and processing: at first the zinc-plated silicon substrate of wide strip is cleaned with acetone, used acetone, deionized water ultrasonic cleaning each 15 minutes subsequently successively again;
2. the preparation of film growth liquid: with mass ratio is that to be added drop-wise to 50ml concentration be to stir in the 0.12M liquor zinci chloridi and fully for 25% strong aqua 3ml; Solution places in the glass bottle that is threaded flap.
3. the processing of film growth liquid: supersound process 30 minutes are used in the airtight back of above-mentioned solution;
4. the substrate level after will cleaning is inserted in the solution and airtight once more solution.The baking oven of immediately this encloses container being put into 95 ℃ left standstill 50 minutes.Reduce oven temperature subsequently, keep 6 hours substrate taking-up, the zinc oxide nano mitron that can obtain to have even dense arrangement with natural airing behind the deionized water rinsing.
Claims (2)
1. the method for a growing nano-tube shaped zinc oxide by hydrothermal decomposition is characterized in that:
The first step: with mass percent concentration be 25% strong aqua to be added drop-wise to concentration be to stir in 0.06～0.15M liquor zinci chloridi and fully, the pH to 9-11 of regulator solution, then that solution is airtight;
Second step: airtight solution was carried out supersound process 25～35 minutes;
The 3rd step: the conductivity substrate after will cleaning is put into above-mentioned solution and airtight once more solution, again should airtight solution putting into 80～98 ℃ of environment left standstill 45～90 minutes, naturally cool to room temperature subsequently and kept 5-9 hour, make it aging, again conductivity substrate is taken out, use deionized water rinsing, can on the surface of conductivity substrate, obtain the zinc oxide of nanotube crystalline structure after drying naturally.
2, the method for growing nano-tube shaped zinc oxide by hydrothermal decomposition according to claim 1 is characterized in that the clean of conductivity substrate is to clean with acetone, uses acetone, deionized water ultrasonic cleaning subsequently successively again.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100360719C (en) * | 2006-03-31 | 2008-01-09 | 中国科学院上海光学精密机械研究所 | Hydrothermal method growth process for self-assembling ZnO array |
| JP4967120B2 (en) * | 2006-04-24 | 2012-07-04 | 国立大学法人 名古屋工業大学 | Method for producing ZnO-based nanotube |
| CN100447089C (en) * | 2006-10-25 | 2008-12-31 | 哈尔滨工程大学 | Zinc oxide nano tube and its supersonically preparing method |
| CN101455960B (en) * | 2007-12-14 | 2010-11-17 | 中国科学院合肥物质科学研究院 | Porous zinc bloom nanometer tube with high photocatalysis activity and preparation method thereof |
| CN101271078B (en) * | 2008-04-03 | 2010-12-15 | 东南大学 | Production method of biological chemistry sensor |
| WO2010050430A1 (en) * | 2008-10-27 | 2010-05-06 | 国立大学法人名古屋工業大学 | Columnar zno particle manufacturing method and columnar zno particles obtained using the same |
| CN103395823B (en) * | 2013-07-22 | 2015-02-11 | 中国计量学院 | Preparation method for nano-zinc oxide directional array |
| CN104386736A (en) * | 2014-11-20 | 2015-03-04 | 信阳师范学院 | Method for preparing zinc oxide nanotubes |
| CN105372897B (en) * | 2015-11-27 | 2018-07-13 | 南京邮电大学 | Electrochromic device and preparation method thereof based on ZnO nanotube/ |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415545A (en) * | 2001-11-01 | 2003-05-07 | 北京化工大学 | Method for preparing nano zinc oxide |
| US6710091B1 (en) * | 1999-02-23 | 2004-03-23 | Bayer Aktiengesellschaft | Nanoparticulate, redispersible zinc oxide gels |
| CN1557718A (en) * | 2004-01-19 | 2004-12-29 | 上海交通大学 | Method for preparing zinc oxide nanometer material with orientation arrangement nano-tubes |
| CN1590302A (en) * | 2003-08-29 | 2005-03-09 | 中国科学院过程工程研究所 | Coprecipitation method for preparing ultra fine zinc oxide powder possessing high electric conductivity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6710091B1 (en) * | 1999-02-23 | 2004-03-23 | Bayer Aktiengesellschaft | Nanoparticulate, redispersible zinc oxide gels |
| CN1415545A (en) * | 2001-11-01 | 2003-05-07 | 北京化工大学 | Method for preparing nano zinc oxide |
| CN1590302A (en) * | 2003-08-29 | 2005-03-09 | 中国科学院过程工程研究所 | Coprecipitation method for preparing ultra fine zinc oxide powder possessing high electric conductivity |
| CN1557718A (en) * | 2004-01-19 | 2004-12-29 | 上海交通大学 | Method for preparing zinc oxide nanometer material with orientation arrangement nano-tubes |
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