CN100360421C - Process for preparing zinc oxide nano-stick - Google Patents
Process for preparing zinc oxide nano-stick Download PDFInfo
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- CN100360421C CN100360421C CNB2006100527091A CN200610052709A CN100360421C CN 100360421 C CN100360421 C CN 100360421C CN B2006100527091 A CNB2006100527091 A CN B2006100527091A CN 200610052709 A CN200610052709 A CN 200610052709A CN 100360421 C CN100360421 C CN 100360421C
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- Prior art keywords
- zinc oxide
- oxide nano
- zno
- hydrazine hydrate
- rod
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000002073 nanorod Substances 0.000 claims abstract description 15
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 239000013543 active substance Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 4
- 229910021529 ammonia Inorganic materials 0.000 abstract 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002910 structure generation Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
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Abstract
This invention involves a preparation method for zinc oxide nanorods. In this method, hydrazine hydrate replaces sodium hydroxide or ammonia as an alkaline mineralizer, and zinc oxide nanorods are prepared by hydrothermal synthesis rapidly and simply. Compared with the conventional hydrothermal synthesis method with sodium hydroxide or ammonia as mineralizer, this method can control the size and morphology of zinc oxide by making use of the alkaline hydrazine hydrate and its coordination compound formed with zinc. Zinc oxide nanorods can be prepared quickly in the absence of any other surfactant and complexing agent.
Description
Technical field
The present invention relates to a kind of preparation method of zinc oxide nano rod.
Background technology
Zinc oxide (ZnO) is a kind of important semiconductor material with wide forbidden band, and energy gap is 3.37eV under the room temperature, and GaN compares with wide bandgap semiconductor, and ZnO has higher exciton forbidden band (60meV), has higher blue light luminous efficiency.As a kind of purposes functional materials very widely, zinc oxide has been widely used in photoelectric device, gas sensitive device, pressure-sensitive device, catalyzer, coating, important industrial technology Application Areas such as antibiotic.When the grain-size of ZnO was reduced to nano level, its surface electronic structure and crystalline structure generation noticeable change had produced the surface effects that macroscopical block materials did not have, small-size effect, quantum size effect and dielectric confinement effect.Therefore, the ZnO nanostructure has become a large focal spot in nanotechnology research field.
The One-Dimensional ZnO nanostructure mainly comprises nano belt, nano wire, nanometer rod and nanotube etc., in recent years, because the ZnO one dimension Nano structure has important use in fields such as photodiode, laser diodes, the preparation of its one-dimentional structure has caused global concern.At present, the method for preparing the ZnO nanometer rod is numerous, comprises thermal evaporation, physical vaporous deposition (PVD), Metalorganic Chemical Vapor Deposition (MOCVD), template and hydrothermal method etc.Hydrothermal method have equipment and simple to operate, environmental pollution is little and the characteristics of suitable scale operation, has become the important method of preparation ZnO nanometer rod.It is mineralizer that the technology of traditional water thermal synthesis zinc oxide nano rod generally adopts sodium hydroxide or ammoniacal liquor, usually need the auxiliary of tensio-active agent or complexing agent, used main tensio-active agent or complexing agent comprise cetyl trimethylammonium bromide (X.Sun et al.Mater.Chem.Phys., 78,99 (2003)), citric acid and Citrate trianion (H.Zhang et al.Mater.Lett., 59,1696 (2005)), quadrol (B.Liu et al.J.Am.Chem.Soc., 125,4430 (2003)) and vulkacit H (C.Liu et al.Thin Solid Films, 503,110 (2006)) etc.Simultaneously, the above hydrothermal method synthetic time is long, is generally more than ten hour to several days, and therefore, energy consumption is bigger.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of zinc oxide nano rod, is to utilize hydrazine hydrate to prepare zinc oxide nano rod for the hydro-thermal technology of mineralizer.Overcome traditional water thermal synthesis zinc oxide nano rod and needed problems such as tensio-active agent or complexing agent are assisted, long reaction time.
The step of the technical solution used in the present invention is as follows:
Zinc chloride and 1: 2 in molar ratio～1: 8 ratio of hydrazine hydrate are put into deionized water for stirring, and produce the precipitation of white pulpous state this moment, and promptly hydrazine hydrate and zinc chloride have formed the precipitation of being made up of coordination compound; After the stirring, the above-mentioned solution for preparing is put into autoclave, compactedness is 80～90%, handles 3～48 hours in 120～280 ℃ of temperature ranges, with solution centrifugal, the drying handled well, has just obtained zinc oxide nano rod then.
Realize the synthetic of ZnO nanometer rod under the situation that need not tensio-active agent or complexing agent, the diameter of nanometer rod is 70 nanometers, and length is 2～4 microns.
The beneficial effect that the present invention has is: traditional zinc oxide nano rod hydro-thermal synthesis process is made alkaline mineralizer with sodium hydroxide or ammoniacal liquor, has long reaction time (being generally more than ten hour to several days) and needs tensio-active agent or shortcoming such as complexing agent (as cetyl trimethylammonium bromide, citric acid and quadrol etc.) is auxiliary.Maximum characteristics of the present invention are to adopt cheap hydrazine hydrate (N
2H
4H
2O) replace sodium hydroxide or ammoniacal liquor, following without any assisting of tensio-active agent or complexing agent, realized the zinc oxide nano rod quick preparation of (diameter is about 70 nanometers, and length is 2～4 microns), as long as the reaction times is 3 hours.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 gained ZnO nanometer rod;
Fig. 2 is the stereoscan photograph of embodiment 1 gained ZnO nanometer rod, (a) macrograph; (b) enlarged photograph.
Fig. 3 is the transmission electron microscope photo of embodiment 1 gained ZnO nanometer rod, (a) many nanometer rod; (b) single nanometer rod and electron diffraction pattern.
Fig. 4 is the stereoscan photograph of embodiment 2 gained sword shape ZnO nanometer rod.
Fig. 5 is the stereoscan photograph of the shaggy ZnO nanometer rod of embodiment 3 gained.
Fig. 6 is the stereoscan photograph of the ZnO nano particle of comparative example 1 gained.
Embodiment
Embodiment 1:
With 0.87 gram zinc chloride (ZnCl
2) and 0.64 gram concentration be 85% hydrazine hydrate (N
2H
4H
2O) put into 160 milliliters deionized water respectively, magnetic agitation was put into the above-mentioned solution for preparing in the polytetrafluoroethyllining lining of autoclave after 10 minutes, and the liner volume is 200 milliliters, and promptly compactedness is 80%.This solution was handled 8 hours down at 150 ℃, and solution centrifugal of handling well and drying, the acquisition diameter is about 70 nanometers, length is the nanometer rod of 2～4 microns ZnO.Fig. 1 is the XRD figure spectrum of the nanometer rod of this ZnO, follows the standard card (JCPDS no.76-0704) of ZnO to fit like a glove, and illustrates that product is pure zinc oxide.Fig. 2 is the stereoscan photograph of this ZnO nanometer rod, and as can be seen from Figure 2 the product of gained is the nanometer rod of comparison rule.Fig. 3 is the transmission electron microscope photo of this ZnO nanometer rod, and as can be seen from Figure 3 the product diameter of gained is about 70 nanometers, and length is about 2～4 microns.
Embodiment 2:
With 0.87 gram zinc chloride (ZnCl
2) and 0.64 gram concentration be 85% hydrazine hydrate (N
2H
4H
2O) put into 160 milliliters deionized water respectively, magnetic agitation was put into the above-mentioned solution for preparing in the polytetrafluoroethyllining lining of autoclave after 10 minutes, and the liner volume is 200 milliliters, and promptly compactedness is 80%.This solution was handled 24 hours down at 250 ℃, and solution centrifugal of handling well and drying, the acquisition diameter is about 70 nanometers, length is the nanometer rod of 2～4 microns ZnO.As different from Example 1, embodiment 2 obtains the structure that product presents sword shape, and its stereoscan photograph is seen Fig. 4.
Embodiment 3:
With 0.87 gram zinc chloride (ZnCl
2) and 2.56 gram concentration be 85% hydrazine hydrate (N
2H
4H
20) put into 160 milliliters deionized water respectively, magnetic agitation was put into the above-mentioned solution for preparing in the polytetrafluoroethyllining lining of autoclave after 10 minutes, and the liner volume is 200 milliliters, and promptly compactedness is 90%.This solution was handled 3 hours down at 120 ℃, and solution centrifugal of handling well and drying, the acquisition diameter is about 70 nanometers, length is the nanometer rod of 2～4 microns ZnO.Different with embodiment 1 and 2 is, it is more coarse that embodiment 3 obtains the product surface ratio, and its stereoscan photograph is seen Fig. 5.
Comparative example:
With 0.87 gram zinc chloride (ZnCl
2) and 0.44 the gram sodium hydroxide (NaOH) put into 160 milliliters deionized water respectively, magnetic agitation was put into the above-mentioned solution for preparing in the polytetrafluoroethyllining lining of autoclave after 10 minutes, the liner volume is 200 milliliters, promptly compactedness is 80%.This solution was handled 24 hours down at 150 ℃, and solution centrifugal of handling well and drying, obtaining product is the nano particle (see figure 6) of ZnO, does not obtain the ZnO nanometer rod.This explanation is under the situation that does not have tensio-active agent or complexing agent, and tradition is the impossible ZnO of generation of the hydro-thermal technology nanometer rod of mineralizer with sodium hydroxide or ammoniacal liquor.
Claims (2)
1, a kind of preparation method of zinc oxide nano rod, the step that it is characterized in that this method is as follows: zinc chloride and 1: 2 in molar ratio～1: 8 ratio of hydrazine hydrate are put into deionized water for stirring, produce the precipitation of white pulpous state this moment, and promptly hydrazine hydrate and zinc chloride have formed the precipitation of being made up of coordination compound; After the stirring, the above-mentioned solution for preparing is put into autoclave, compactedness is 80～90%, handles 3～48 hours in 120～280 ℃ of temperature ranges, with solution centrifugal, the drying handled well, has just obtained zinc oxide nano rod then.
2, the preparation method of a kind of zinc oxide nano rod according to claim 1 is characterized in that: realize the synthetic of ZnO nanometer rod under the situation that need not tensio-active agent or complexing agent, the diameter of nanometer rod is 70 nanometers, and length is 2～4 microns.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100527091A CN100360421C (en) | 2006-07-31 | 2006-07-31 | Process for preparing zinc oxide nano-stick |
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|---|---|---|---|
| CNB2006100527091A CN100360421C (en) | 2006-07-31 | 2006-07-31 | Process for preparing zinc oxide nano-stick |
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| CN1907861A CN1907861A (en) | 2007-02-07 |
| CN100360421C true CN100360421C (en) | 2008-01-09 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358973B (en) * | 2007-08-02 | 2012-07-04 | 四川大学 | Hepatocarcinoma early diagnosis kit based on ZnO nano-bar array |
| CN101407334B (en) * | 2007-10-12 | 2010-09-29 | 新疆大学 | Method for synthesizing rod-like nano-zinc oxide |
| CN101891239B (en) * | 2009-05-18 | 2012-04-25 | 合肥学院 | Method for preparing red zinc oxide nano powder |
| CN102219254A (en) * | 2011-06-20 | 2011-10-19 | 厦门大学 | Preparation method of zinc oxide nanorod |
| CN104528802B (en) * | 2014-12-11 | 2016-01-06 | 北京化工大学 | A kind of tubulose multilevel-structure zinc oxide and preparation method thereof |
| CN105036176A (en) * | 2015-06-30 | 2015-11-11 | 长安大学 | Growth method of ZnO nanorod |
| CN106430285A (en) * | 2016-09-13 | 2017-02-22 | 苏州市泽镁新材料科技有限公司 | Preparation method of nano zinc oxide capable of realizing uniform dispersion of particles |
| CN107649115A (en) * | 2017-10-16 | 2018-02-02 | 陕西科技大学 | A kind of Zn2SnO4/ ZnO composite photo-catalysts and preparation method thereof |
| CN107824178B (en) * | 2017-10-16 | 2020-09-01 | 陕西科技大学 | Spherical Zn2SnO4Hexagonal prism-shaped ZnO in-situ generated composite photocatalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006008175A1 (en) * | 2004-07-23 | 2006-01-26 | Eth Zurich | Rapid flame synthesis of doped zno nanorods with controlled aspect ration |
| CN1752013A (en) * | 2005-11-02 | 2006-03-29 | 东南大学 | Method of growing nano-rod shaped zinc oxide by hydrothermal decomposition |
| CN1781850A (en) * | 2004-12-03 | 2006-06-07 | 中国科学技术大学 | Tactic zinc oxide granular one dimension mesoporous nano belt and precursor and its preparing method |
| CN1789137A (en) * | 2005-12-07 | 2006-06-21 | 天津大学 | Method for preparing nano-rod of zinc oxide or its ordered structure |
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2006
- 2006-07-31 CN CNB2006100527091A patent/CN100360421C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006008175A1 (en) * | 2004-07-23 | 2006-01-26 | Eth Zurich | Rapid flame synthesis of doped zno nanorods with controlled aspect ration |
| CN1781850A (en) * | 2004-12-03 | 2006-06-07 | 中国科学技术大学 | Tactic zinc oxide granular one dimension mesoporous nano belt and precursor and its preparing method |
| CN1752013A (en) * | 2005-11-02 | 2006-03-29 | 东南大学 | Method of growing nano-rod shaped zinc oxide by hydrothermal decomposition |
| CN1789137A (en) * | 2005-12-07 | 2006-06-21 | 天津大学 | Method for preparing nano-rod of zinc oxide or its ordered structure |
Non-Patent Citations (1)
| Title |
|---|
| ZnO纳米棒的低温湿化学制备. 刘秀兰，李佳，赵晓鹏.功能材料，第36卷第4期. 2005 * |
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| CN1907861A (en) | 2007-02-07 |
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