CN101319388A - Preparation method of multicenter zinc aluminate nanometer pipe - Google Patents
Preparation method of multicenter zinc aluminate nanometer pipe Download PDFInfo
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- CN101319388A CN101319388A CNA2008100584036A CN200810058403A CN101319388A CN 101319388 A CN101319388 A CN 101319388A CN A2008100584036 A CNA2008100584036 A CN A2008100584036A CN 200810058403 A CN200810058403 A CN 200810058403A CN 101319388 A CN101319388 A CN 101319388A
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- zinc
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- multicenter
- zinc aluminate
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- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 54
- 239000011701 zinc Substances 0.000 title claims abstract description 54
- -1 zinc aluminate Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002070 nanowire Substances 0.000 claims abstract description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004070 electrodeposition Methods 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000009792 diffusion process Methods 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000009415 formwork Methods 0.000 claims description 27
- 238000000137 annealing Methods 0.000 claims description 24
- 238000005260 corrosion Methods 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 239000002071 nanotube Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract 3
- 239000002073 nanorod Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing a multichannel zinc aluminate nanotube, belonging to the multichannel nanotube preparation technical field. The preparation method comprises the following steps that: step 1, an alumina moulding board is prepared by a two-step anode oxidation method; step 2, a zinc nanowire is prepared in the alumina moulding board by an electrodeposition method; step 3, the alumina moulding board carried with the zinc nanowire is annealed under an atmospheric environment, the zinc nanowire is converted into a zinc oxide nanowire, and the solid state diffusion reaction is performed on the zinc oxide nanowire and the alumina to form zinc aluminate; and step 4, a sodium hydroxide solution is used to corrode the anneald sample to prepare the multichannel zinc aluminate nanotube. The prepared multichannel zinc aluminate nanotube has an appearance that the middle of a nanorod has cylindrical nano hole channels with certain number, the structure has high specific surface area and regular shape; moreover, the preparation method is simple, the environment is not polluted; therefore, the multichannel zinc aluminate nanotube can be used in the fields such as catalysis, nano devices and luminescent materials and has important potential application value.
Description
Technical field
The present invention relates to a kind of method that adopts electrochemical deposition and high temperature annealing to prepare multicenter zinc aluminate nanometer pipe, belong to the preparing technical field of hyperchannel nanotube.
Background technology
The nanometer zinc aluminate spinel is a kind of semiconductor material with wide forbidden band (≈ 4.0eV), have higher thermostability, anti-corrosion, wear-resisting and chemical stability, and its good insulating, thermal expansivity is little, hardness is high, have performances such as low surface acidity and UV separation, be widely used in industrial many fields.As making ceramic protective membrane, far infrared band window material, refractory materials, catalytic material and the fine ceramics vessel of insulation framework, alloy or the metal products of opto-electronic device, electronic devices and components with the nanometer Zinc aluminate, but also be outstanding bluish-green purple wave band of laser host crystal material.
Because the nanometer Zinc aluminate has purposes widely, become the focus of people's research gradually, people's research at present mainly concentrate on nanometer aluminic acid zinc powder manufacturing and catalysis and luminous aspect application.Usually preparation nanometer aluminic acid zinc powder method mainly contains: high-temperature calcination, coprecipitation method, sol-gel method, hydrothermal method etc.
Studies show that under nanoscale the pattern of material is because quantum size effect, interfacial effect and coupling effect are very big to its performance impact, how preparing the different nanometer Zinc aluminate of pattern and seeking new purposes is the emphasis of studying at present.As can increase substantially his catalytic effect by the specific area that improves the nanometer Zinc aluminate.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of multicenter zinc aluminate nanometer pipe, this multicenter zinc aluminate nanometer pipe profile is that the certain cylindrical nanometer duct of quantity is arranged in the middle of the nanometer rod, this structure has higher specific surface area, regular shape, and the preparation method is simple, environmentally safe.
Solving the processing step that technical problem of the present invention adopts is: the first step is equipped with alumina formwork with the two-step anodic oxidization legal system and (sees Masuda H for details, Fukuda K.Science, 1995,268 (9): 146), second step utilized electro-deposition method to prepare the zinc nano wire in alumina formwork, the 3rd step annealed under atmospheric environment to the alumina formwork that is loaded with the zinc nano wire, make the zinc nano wire be converted into zinc oxide nanowire earlier, the reaction of zinc oxide nanowire and aluminum oxide generation solid-state diffusion forms Zinc aluminate then, sample after the 4th step utilized sodium hydroxide solution to annealing corrodes, and obtains multicenter zinc aluminate nanometer pipe.
Concrete technical data of the present invention is: the zinc nano wire annealing process standard of galvanic deposit is, under atmospheric environment, the alumina formwork that is loaded with the zinc nano wire was heated to 300 ℃～350 ℃ by room temperature through 20 minutes～50 minutes, be incubated 30 hours～40 hours, be heated to 650 ℃～700 ℃ insulations 10 hours～15 hours through 20 minutes～30 minutes by this temperature again, be as cold as room temperature with stove at last.The starting material that the making alumina formwork is used adopt the rafifinal of purity 〉=99.999%, the cold rolled sheet of thickness 0.2～0.25mm, and before anodic oxidation, adopted the vacuum annealing processing, annealing process is for to be heated to 500 ℃ by room temperature through 50 minutes～70 minutes, be incubated 5 hours～6 hours, be as cold as room temperature with stove again.The zinc nanowire diameter that adopts electro-deposition method to prepare in alumina formwork is 20 nanometers～180 nanometers.To the sodium hydroxide solution immersion corrosion of the sample after the annealing with 3mol, 50 ℃～60 ℃ of treatment temps, 50 minutes～70 minutes treatment time.
The invention has the beneficial effects as follows: the multicenter zinc aluminate nanometer pipe profile of preparation is that the certain cylindrical nanometer duct of quantity is arranged in the middle of the nanometer rod, this structure has higher specific surface area, regular shape, preparation technology is simple, course of processing environmentally safe, output height, and the singularity of this structure can have important purposes in fields such as catalysis, nano-device, luminescent materials.
Embodiment
Embodiment 1
The first step: starting material and annealing starting material are selected rafifinal (99.999%), the cold rolled sheet of thickness 0.25mm, and carry out vacuum annealing and handle, the annealing standard is as follows: be heated to 500 ℃ by room temperature through 1 hour, be incubated 5 hours, be as cold as room temperature with stove.
Second step: make alumina formwork and utilize the two-step anodic oxidization legal system to be equipped with alumina formwork, electrolytic solution adopts the oxalic acid solution of 0.3M, anode voltage 50V, and the alumina formwork aperture that obtains after reaming is 80～90 nanometers.
The 3rd step: the galvanic deposit nano wire utilizes electro-deposition method to prepare the zinc nano wire in alumina formwork.
The 4th step: sample annealing is annealed to the alumina formwork that is loaded with the zinc nano wire, the annealing process standard is: under atmospheric environment, the alumina formwork that is loaded with the zinc nano wire was heated to 320 ℃ by room temperature through 20 minutes, be incubated 40 hours, be heated to 700 ℃ of insulations 10 hours through 20 minutes by this temperature again, be as cold as room temperature with stove at last.Making zinc nano wire oxidation conversion in annealing process earlier is zinc oxide nanowire, and the reaction of zinc oxide and aluminum oxide generation solid-state diffusion forms Zinc aluminate then.
The 5th step: corrosion treatment is carried out corrosion treatment to the sample after annealing, and the sodium hydroxide solution of employing 3mol soaks the sample after the annealing, 50 ℃ of soaking temperatures, soak time 60 minutes.Handle after cleaning obtains multicenter zinc aluminate nanometer pipe.
Embodiment 2
Press embodiment 1 the first step, second step, the 3rd step preparation alumina formwork and electrodepositing zinc nano wire, the alumina formwork sample that is loaded with the zinc nano wire is carried out anneal, the annealing process standard is: under atmospheric environment, the alumina formwork that is loaded with the zinc nano wire was heated to 350 ℃ by room temperature through 30 minutes, be incubated 40 hours, be heated to 650 ℃ of insulations 15 hours through 30 minutes by this temperature again, be as cold as room temperature with stove at last.Go on foot the multicenter zinc aluminate nanometer pipe that corrosion treatment obtains by embodiment 1 the 5th,
Embodiment 3
The first step: starting material are selected identical with embodiment 1, and starting material annealing standard is as follows: be heated to 500 ℃ by room temperature through 70 minutes, be incubated 6 hours, be as cold as room temperature with stove.
Second step: make alumina formwork and utilize the two-step anodic oxidization legal system to be equipped with alumina formwork, electrolytic solution adopts the oxalic acid solution of 0.3M, anode voltage 40V, and the alumina formwork aperture that obtains after reaming is 60～70 nanometers.
The 3rd step: the galvanic deposit nano wire utilizes electro-deposition method to prepare the zinc nano wire in alumina formwork.
The 4th step: sample annealing is annealed to the alumina formwork that is loaded with the zinc nano wire, the annealing process standard is: under atmospheric environment, the alumina formwork that is loaded with the zinc nano wire was heated to 300 ℃ by room temperature through 50 minutes, be incubated 35 hours, be heated to 700 ℃ of insulations 15 hours through 50 minutes by this temperature again.
The 5th step: corrosion treatment is carried out corrosion treatment to the sample after annealing, and the sodium hydroxide solution of employing 3mol soaks the sample after the annealing, 60 ℃ of soaking temperatures, soak time 70 minutes.Handle after cleaning obtains multicenter zinc aluminate nanometer pipe.
Claims (5)
1, a kind of preparation method of multicenter zinc aluminate nanometer pipe, it is characterized in that: the first step is equipped with alumina formwork with the two-step anodic oxidization legal system, second step utilized electro-deposition method to prepare the zinc nano wire in alumina formwork, the 3rd step annealed under atmospheric environment to the alumina formwork that is loaded with the zinc nano wire, make the zinc nano wire be converted into zinc oxide nanowire earlier, the reaction of zinc oxide nanowire and aluminum oxide generation solid-state diffusion forms Zinc aluminate then, sample after the 4th step utilized sodium hydroxide solution to annealing corrodes, and obtains multicenter zinc aluminate nanometer pipe.
2, preparation method of multicenter zinc aluminate nanometer pipe according to claim 1, it is characterized in that: the zinc nano wire annealing process standard of galvanic deposit is, under atmospheric environment, the alumina formwork that is loaded with the zinc nano wire was heated to 300 ℃～350 ℃ by room temperature through 20 minutes～50 minutes, be incubated 30 hours～40 hours, be heated to 650 ℃～700 ℃ insulations 10 hours～15 hours through 20 minutes～30 minutes by this temperature again, be as cold as room temperature with stove at last.
3, preparation method of multicenter zinc aluminate nanometer pipe according to claim 1, it is characterized in that: the starting material that the making alumina formwork is used adopt the rafifinal of purity 〉=99.999%, the cold rolled sheet of thickness 0.2～0.25mm, and before anodic oxidation, adopted the vacuum annealing processing, be heated to 500 ℃ by room temperature through 50 minutes～70 minutes, be incubated 5 hours～6 hours, be as cold as room temperature with stove again.
4, preparation method of multicenter zinc aluminate nanometer pipe according to claim 1 is characterized in that: the zinc nanowire diameter that adopts electro-deposition method to prepare in alumina formwork is 20 nanometers～180 nanometers.
5, preparation method of multicenter zinc aluminate nanometer pipe according to claim 1 is characterized in that: to the sodium hydroxide solution immersion corrosion of the sample after the annealing with 3mol, 50 ℃～60 ℃ of treatment temps, 50 minutes～70 minutes treatment time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2008100584036A CN101319388B (en) | 2008-05-16 | 2008-05-16 | Preparation method of multicenter zinc aluminate nanometer pipe |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100584036A CN101319388B (en) | 2008-05-16 | 2008-05-16 | Preparation method of multicenter zinc aluminate nanometer pipe |
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| Publication Number | Publication Date |
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| CN101319388A true CN101319388A (en) | 2008-12-10 |
| CN101319388B CN101319388B (en) | 2011-06-08 |
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| CN2008100584036A Expired - Fee Related CN101319388B (en) | 2008-05-16 | 2008-05-16 | Preparation method of multicenter zinc aluminate nanometer pipe |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010114403A1 (en) * | 2009-04-03 | 2010-10-07 | Universidade De Aveiro | LUMINESCENT BERYLLIUM, MAGNESIUM, CALCIUM, STRONTIUM OR BARIUM ALUMINATE NANOTUBES DOPED WITH CERIUM (III) AND CO-DOPED WITH OTHER LANTHANIDE IONS M(1-x-y)N2O4: Cex, Lny |
| CN101629314B (en) * | 2009-07-30 | 2011-06-15 | 上海交通大学 | Aluminate-metal-aluminum oxide composite material coating and preparation method thereof |
| CN102274976A (en) * | 2011-05-16 | 2011-12-14 | 云南师范大学 | Method for preparing nanomaterials by using anodized aluminum oxide template |
| CN104005070A (en) * | 2014-05-04 | 2014-08-27 | 昆明理工大学 | Preparation method of zinc aluminate nanopore array template |
| CN104152915A (en) * | 2014-05-04 | 2014-11-19 | 昆明理工大学 | Preparation method of zinc aluminate protective layer |
| CN105819849A (en) * | 2016-05-04 | 2016-08-03 | 武汉工程大学 | Zinc aluminate nanometer powder and preparing method thereof |
-
2008
- 2008-05-16 CN CN2008100584036A patent/CN101319388B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010114403A1 (en) * | 2009-04-03 | 2010-10-07 | Universidade De Aveiro | LUMINESCENT BERYLLIUM, MAGNESIUM, CALCIUM, STRONTIUM OR BARIUM ALUMINATE NANOTUBES DOPED WITH CERIUM (III) AND CO-DOPED WITH OTHER LANTHANIDE IONS M(1-x-y)N2O4: Cex, Lny |
| CN101629314B (en) * | 2009-07-30 | 2011-06-15 | 上海交通大学 | Aluminate-metal-aluminum oxide composite material coating and preparation method thereof |
| CN102274976A (en) * | 2011-05-16 | 2011-12-14 | 云南师范大学 | Method for preparing nanomaterials by using anodized aluminum oxide template |
| CN102274976B (en) * | 2011-05-16 | 2013-05-29 | 云南师范大学 | Method for preparing nanomaterials by using anodized aluminum oxide template |
| CN104005070A (en) * | 2014-05-04 | 2014-08-27 | 昆明理工大学 | Preparation method of zinc aluminate nanopore array template |
| CN104152915A (en) * | 2014-05-04 | 2014-11-19 | 昆明理工大学 | Preparation method of zinc aluminate protective layer |
| CN104152915B (en) * | 2014-05-04 | 2017-09-26 | 昆明理工大学 | A kind of preparation method of aluminic acid zinc protective layer |
| CN105819849A (en) * | 2016-05-04 | 2016-08-03 | 武汉工程大学 | Zinc aluminate nanometer powder and preparing method thereof |
| CN105819849B (en) * | 2016-05-04 | 2019-02-01 | 武汉工程大学 | A kind of zinc aluminate nano-powder and preparation method thereof |
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| Publication number | Publication date |
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| CN101319388B (en) | 2011-06-08 |
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Granted publication date: 20110608 Termination date: 20130516 |