CN102101695A - Preparation method of hierarchical structural zinc oxide hollow microsphere - Google Patents
Preparation method of hierarchical structural zinc oxide hollow microsphere Download PDFInfo
- Publication number
- CN102101695A CN102101695A CN201110086689.0A CN201110086689A CN102101695A CN 102101695 A CN102101695 A CN 102101695A CN 201110086689 A CN201110086689 A CN 201110086689A CN 102101695 A CN102101695 A CN 102101695A
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- China
- Prior art keywords
- zinc oxide
- hollow microsphere
- oxide hollow
- zinc
- ethanol
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004005 microsphere Substances 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- 239000011701 zinc Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005498 polishing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002073 nanorod Substances 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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Abstract
The invention discloses a liquid-phase preparation method of a hierarchical structural zinc oxide hollow microsphere, comprising the following steps of: firstly soaking a zinc sheet in a 1:10-1:15 diluted hydrochloric acid by taking ethanol/AMP-95 mixed liquor as a solvent and the metallic zinc sheet as a zinc source, and then polishing by using a levigation sandpaper of 800-2000 meshes; placing the processed zinc sheet into the ethanol/AMP-95 mixed solvent, and reacting in a high-pressure reaction kettle lined with polytetrafluoroethylene; and after reaction is finished, washing obtained product zinc oxide by using water and ethanol, and drying to obtain the zinc oxide hollow microsphere which consists of uniform radial nanorods. The preparation method of the hierarchical structural zinc oxide hollow microsphere has the advantages of simplicity, convenience for operation, uniform size of the zinc oxide hollow microsphere and easiness for control of dimension and shape of the zinc oxide hollow microsphere.
Description
Technical field
The present invention relates to a kind of preparation method of Zinc oxide hollow microsphere, belong to the micro Nano material technical field, specifically, relate to a kind of liquid phase preparation process of the hierarchy Zinc oxide hollow microsphere of constructing by nanometer rod.
Background technology
In recent years, people have carried out many research for add various form styles to inorganic materials on be situated between sight and even micro-meter scale, and this is because form and the structure importance on the decision material property.
Zinc oxide is a kind of novel broad stopband group material, and its energy gap is 3.37 eV under the room temperature.Have characteristics such as good characteristic of semiconductor, photoelectric characteristic, catalysis and photochemical catalysis and abundant morphological structure receives much concern owing to zinc oxide itself, at aspects such as solar cell, gas sensor, transparency electrode, short-wavelength light electrical part and laser apparatus very big application prospect is arranged, make it become the focus of various countries' research.Up to the present, the zinc oxide micron/nano structure of various new patterns constantly is produced out, as micro nano structures such as zinc oxide nano-particle, nanometer rod, nano wire, nanotube, nano belt and flower-shaped, the pectination of being made up of them, bridge shape, windmill shapes.The preparation method of ZnO nanostructure also presents diversity, can be by sacrificing template, soft template method, gas chemistry oxidation style etc. as tiny balloon.Yet existing method needs the reactions steps of complexity, higher temperature of reaction or long reaction times usually.And the performance of zinc oxide micron/nano structure can be regulated and control by regulating its size, pattern and microstructure, and the synthetic uniform hierarchy Zinc oxide hollow microsphere of particle diameter is significant to exploitation Zinc oxide-base new function material.
The objective of the invention is to overcome the weak point of existing zinc oxide micron/nano structure technology of preparing, provide that a kind of technology is simple relatively, reaction conditions is gentle, and can prepare the new reaction system of novel zinc oxide micron/nano structure.
Summary of the invention
The present invention is directed to the prior art processes complexity, problems such as raw material is expensive, proposed that a kind of technology is simple relatively, reaction conditions is gentle, the liquid phase preparation process of the hierarchy tiny balloon that preparation is made up of zinc oxide nano rod, and be expected to be widely used in fields such as photoelectricity, catalysis, air-sensitive, biologies.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions.
A kind of liquid phase preparation process of the hierarchy tiny balloon of being made up of zinc oxide nano rod is characterized in that using ethanol/AMP-95 mixed solution to be solvent, and described method comprises the steps:
(1) with after zinc metal sheet 1:10～1:15 dilute hydrochloric acid immersion, again with the polishing of 800-2000 order silicon carbide paper;
(2) zinc metal sheet of handling well is put into ethanol/AMP-95 mixed solvent, under 25 ℃, left standstill 12-24 h;
(3) in the autoclave of inner liner polytetrafluoroethylene, 160～180 ℃ are reacted 5～10 h down.
(4) after reaction finishes,, obtain the tiny balloon of forming by radial zinc oxide nano rod with products therefrom zinc oxide difference water and twice of washing with alcohol and dry.
2. the liquid phase preparation process of zinc oxide hierarchy tiny balloon according to claim 1 is characterized in that, in step (2), AMP-95 and alcoholic acid volume ratio are 1:1～1:2.
Description of drawings
Fig. 1 utilizes the method for the invention to prepare the X ray diffracting spectrum (XRD) of zinc oxide hierarchy tiny balloon.The peak position of diffraction peak all consistent with the standard spectrogram of wurtzite structure zinc oxide (JCPDS No. 36-1451) shows that prepared product is a zinc oxide in the spectrogram.
Fig. 2 is the electron scanning micrograph (SEM) that utilizes the hierarchy tiny balloon of being made up of radial zinc oxide nano rod of the method for the invention preparation.From figure a as can be seen, the size distribution of zinc oxide microballoon is even, and the about 2 μ m of size can see that from the photo b of magnification gained zinc oxide microballoon has the hierarchy that radial nanometer rod is formed, and the zinc oxide nano rod even thickness, about 50-80 nm.Figure c is the spherical shell of a fragmentation, as can be seen the hollow structure of microballoon.
Embodiment
The present invention is further detailed explanation below in conjunction with accompanying drawing, and present embodiment has provided detailed embodiment being to implement under the prerequisite with the technical solution of the present invention, but the present invention is not limited only to these embodiment.
Embodiment one:
(1) dilute hydrochloric acid with 1:10 soaks zinc metal sheet, again with 800 order silicon carbide papers polishing zinc metal sheet;
(2) measuring 12 ml ethanol with graduated cylinder is reaction medium, adds the AMP-95 of 8 ml, stirs in reactor, obtains mixed solvent;
(3) zinc metal sheet that obtains in the step (1) is put into solvent, under 25 ℃, leave standstill 18 h, at 170 ℃ of reaction 5 h, obtain target product then;
(4) with after the above-mentioned reaction solution cooling, twice of gained sample difference water and ethanol repeated washing.
Embodiment two:
(1) dilute hydrochloric acid with 1:10 soaks zinc metal sheet, again with 800 order silicon carbide papers polishing zinc metal sheet;
(2) measuring 12 ml ethanol with graduated cylinder is reaction medium, adds the AMP-95 of 8 ml, stirs in reactor, obtains mixed solvent;
(3) zinc metal sheet that obtains in the step (1) is put into solvent, under 25 ℃, leave standstill 18 h, at 170 ℃ of reaction 8 h, obtain target product then;
(4) with after the above-mentioned reaction solution cooling, twice of gained sample difference water and ethanol repeated washing.
Embodiment three:
(1) dilute hydrochloric acid with 1:10 soaks zinc metal sheet, again with 800 order silicon carbide papers polishing zinc metal sheet;
(2) measuring 10 ml ethanol with graduated cylinder is reaction medium, adds the AMP-95 of 10 ml, stirs in reactor, obtains mixed solvent;
(3) zinc metal sheet that obtains in the step (1) is put into mixed solvent, under 25 ℃, leave standstill 18 h, at 170 ℃ of reaction 8 h, obtain target product then;
(4) with after the cooling of above-mentioned reaction solution, gained sample water and ethanol respectively repeats to wash twice.
Claims (2)
1. plant the liquid phase preparation process of hierarchy Zinc oxide hollow microsphere, it is characterized in that using ethanol/AMP-95 mixed solution to be solvent, described method comprises the steps:
(1) with after zinc metal sheet 1:10～1:15 dilute hydrochloric acid immersion, again with the polishing of 800-2000 order silicon carbide paper;
(2) zinc metal sheet of handling well is put into ethanol/AMP-95 mixed solvent, under 25 ℃, left standstill 12-24 h;
(3) in the autoclave of inner liner polytetrafluoroethylene, 160～180 ℃ are reacted 5～10 h down;
(4) after reaction finishes,, obtain the Zinc oxide hollow microsphere of forming by radial nanometer rod with products therefrom zinc oxide difference water and twice of washing with alcohol and dry.
2. the liquid phase preparation process of hierarchy Zinc oxide hollow microsphere according to claim 1 is characterized in that, in step (2), AMP-95 and alcoholic acid volume ratio are 1:1～1:2.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100866890A CN102101695B (en) | 2011-04-07 | 2011-04-07 | Preparation method of hierarchical structural zinc oxide hollow microsphere |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100866890A CN102101695B (en) | 2011-04-07 | 2011-04-07 | Preparation method of hierarchical structural zinc oxide hollow microsphere |
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| CN102101695A true CN102101695A (en) | 2011-06-22 |
| CN102101695B CN102101695B (en) | 2012-07-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103364453A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Tin oxide-zinc oxide composite hollow microsphere air-sensitive sensing device and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807254A (en) * | 2006-01-26 | 2006-07-26 | 徐志兵 | Zinc oxide hollow microsphere preparation method |
| CN101559974A (en) * | 2009-05-14 | 2009-10-21 | 浙江理工大学 | Method for preparing zinc oxide hollow microspheres |
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- 2011-04-07 CN CN2011100866890A patent/CN102101695B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807254A (en) * | 2006-01-26 | 2006-07-26 | 徐志兵 | Zinc oxide hollow microsphere preparation method |
| CN101559974A (en) * | 2009-05-14 | 2009-10-21 | 浙江理工大学 | Method for preparing zinc oxide hollow microspheres |
Non-Patent Citations (3)
| Title |
|---|
| 《Journal of Alloys and Compounds》 20080103 Mahyar Mazloumi et al. Self-assembly of ZnO nanoparticles and subsequent formation of hollow microspheres 303-307 1-2 第468卷, 2 * |
| 《Solid State Sciences》 20100213 Debao Wang et al. Synthesis and properties of cuboid-shaped ZnO hierarchical structures 776-782 1-2 第12卷, 2 * |
| 《青岛科技大学学报(自然科学版)》 20091231 李立岩 等 溶剂热法制备纳米氧化锌及其光学性能研究 487-490 1-2 第30卷, 第6期 2 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103364453A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Tin oxide-zinc oxide composite hollow microsphere air-sensitive sensing device and preparation method thereof |
| CN103364453B (en) * | 2013-06-28 | 2016-05-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Tin oxide-zinc oxide compound hollow microballoon gas-sensitive sensor device and preparation method |
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| CN102101695B (en) | 2012-07-04 |
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Inventor after: Liu Jian Inventor before: Song Caixia Inventor before: Wang Debao Inventor before: Hu Zhengshui |
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Effective date of registration: 20170821 Address after: 301, room 2, building 8, 42 Changqing Road, 075000 West Bridge, Hebei, Zhangjiakou Patentee after: Liu Jian Address before: 266061 Shandong Province, Qingdao city Laoshan District Songling Road No. 99 Patentee before: Qingdao University of Science & Technology |
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