CN1539741A - Bar type zinc oxide granule, preparation method and usage - Google Patents
Bar type zinc oxide granule, preparation method and usage Download PDFInfo
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- CN1539741A CN1539741A CNA031097995A CN03109799A CN1539741A CN 1539741 A CN1539741 A CN 1539741A CN A031097995 A CNA031097995 A CN A031097995A CN 03109799 A CN03109799 A CN 03109799A CN 1539741 A CN1539741 A CN 1539741A
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Abstract
A rod-shaped zinc oxdie particle (tens nm-several microns) is prepared through preparing the aqueous solution of zinc salt, preparing the aqueous solution of ammonium alcoholate, proportionally mixing them in the preheated secondary water solvent, reaction, ageing, and centrifugal separation. It can be used for preparing photoelectric device, chemical sensor, atomic microscope, or scan tunnel microscope.
Description
Technical field
The invention belongs to field of semiconductor inorganic materials, particularly relate to tens nanometers to long bar-shaped one-dimension zinc oxide (ZnO) particle and liquid phase preparation process and the purposes of several microns.
Background technology
ZnO popular name zinc white, semi-conductor as a kind of broad stopband, it is a kind of more high function fine inorganic material of studying, owing to its excellent physical chemistry and at stupalith, optoelectronic equipment, catalysis, varistor, chemical industry, coating, rubber industry, industries such as pharmacy and makeup are able to widespread use.At present because factors such as structure (microstructure), size and pattern to the material impact that material behavior and application thereof have, have caused people's very big interest to the morphology control research of inorganic materials.This not only requires to give full play to the intrinsic properties of material, also needs by size and morphology control to inorganic materials its character to be reduced and adjusted.Further enlarge its application in order to improve its performance, just be necessary pattern and the size of ZnO are controlled.At present, more complete for the preparation method of spheric zinc oxide particle, then less relatively for the report of bar-shaped One-Dimensional ZnO particle.But because good intensity, rigidity and the chemical stability of small size one dimension or accurate one-dimension zinc oxide, it has caused great concern as the complex intensifying material in industrial application, its preparation and application have also been begun research, but can predict the development along with nanotechnology, one dimension and accurate One-Dimensional ZnO thereof also will have more wide application prospect.
At present, mainly adopt vapor phase process and liquid phase method to prepare bar-shaped one-dimension zinc oxide.Though the product quality height that vapor phase process makes, apparatus expensive, cost of manufacture height, and requirement for experiment condition harshness.Liquid phase method has mainly adopted high-temperature sintering process and hydrothermal method etc. at present.People such as Matijevic have prepared earlier bar-shaped zinc subcarbonate under 90 ℃, making bar-shaped length-to-diameter ratio in 4 hours 300 ℃ of following calcinations subsequently is 1～8 ZnO[Castellano M.and Matijevic E.Chem.Mater., and 1989,1,78.].People such as Zhang also utilize autoclave to decompose Zn (OH) under 180 ℃ in ethanol system
1 2-It is 1～5 ZnO[Zhang J. that precursor has synthesized bar-shaped length-to-diameter ratio, Sun L.D, Yin J.L., Su H.L., Liao C.S., and Yan C.H.Chem.Mater., 2002,14,4172.].People such as Kamata are the complex compound of hydrolysis Acetyl Acetone acid zinc salt at first, with after 80 ℃ of sintering have prepared bar-shaped ZnO[Kamata K., and Hosono H., Maeda Y.and Miyokawa K.Chem.Lett., 1984,2021.].Yet above preparation method's preparation process complexity, strict to equipment, the temperature requirement height, the experiment condition harshness needs last handling process, and the length-to-diameter ratio of gained ZnO rod is less.Thereby the preparation method of the big bar-shaped one-dimension zinc oxide of the length-to-diameter ratio scope of good reproducibility that is necessary to develop simple mild condition.
Summary of the invention
One of purpose of the present invention provides bar-shaped Zinc oxide particles, makes the bar-shaped Zinc oxide particles purity height that obtains, and diameter can reach 30～600 nanometers, and length can reach 50 nanometers～5 micron, and length-to-diameter ratio is in 1～30 scope.
Another object of the present invention provides the liquid phase preparation process of bar-shaped Zinc oxide particles, and with mild condition, process is simple, and the preparation method of good reproducibility obtains bar-shaped Zinc oxide particles, and Zinc oxide particles purity height.
A further object of the present invention provides the purposes of bar-shaped Zinc oxide particles.
The objective of the invention is to realize by following technical scheme:
In solution system under 50～100 ℃ of temperature directly deposition synthesized bar-shaped One-Dimensional ZnO particle, the diameter that obtains bar-shaped Zinc oxide particles reaches 30～600 nanometers, length reaches 50 nanometers～5 micron, length-to-diameter ratio is in 1～30 scope.
The liquid phase preparation process step of bar-shaped Zinc oxide particles of the present invention comprises:
1.. the aqueous solution of preparing metal zinc salt, its volumetric molar concentration is 0.001～0.5mol/L, is preferably 0.005～0.1mol/L, recently determines the volumetric molar concentration and the consumption thereof of metal zinc salt according to the major diameter of the one-dimension zinc oxide rod that requires.
2.. the aqueous solution of preparation alcohol amine compound, its volumetric molar concentration is 0.001～5mol/L, is preferably 0.01～1mol/L, and recently determines its volumetric molar concentration and consumption thereof according to the major diameter of the one-dimension zinc oxide rod that requires.
3.. get two simultaneously notes of the alcohol amine compound aqueous solution that 2. metallic zinc salts solution that 1. step prepare and step prepare and join in the secondary water solvent that is preheating to 60～100 ℃, wherein, the consumption of metal zinc salt and alcohol amine compound solution requires to determine that alcohol amine compound in the mixed solution: the mol ratio of metal zinc salt is 0.5: 1～50: 1 according to the length-to-diameter ratio of one-dimension zinc oxide rod.
4.. with 3. mixed solution stirring reaction 0.5～3 hour of step, reaction back ageing 0.5～10 hour.
5.. with step mixed solution centrifugation 4., throw out is washed with secondary water washing, washs afterwards centrifugation more at every turn and goes out particle, obtains bar-shaped one-dimension zinc oxide particle particle, and length-to-diameter ratio is in 1～30 scope.
6.. with 5. gained Zinc oxide particles centrifugation of step, but the vacuum-drying of gained precipitation is used.
Described metal zinc salt is zinc nitrate, zinc chloride, zinc sulfate or zinc acetate etc., is preferably zinc acetate.
Described alcohol amine compound (replacing conventional used potassium hydroxide, sodium hydroxide or ammonium hydroxide) is preferably trolamine for diethanolamine or trolamine etc.
The used metallic zinc salt solution of the present invention solution energy consumption is low, the product purity height, and particulate size, the big I of length-to-diameter ratio are controlled by reaction conditions.
What the present invention was significantly different with technology of preparing in the past is, present method mild condition, and process is simple, the oxidized zinc products purity height of preparation, the length-to-diameter ratio scope is big.
Bar-shaped Zinc oxide particles of the present invention, it is a kind of novel high function fine inorganic material, be important pottery, semi-conductor and catalytic material are widely used in fields such as chemical industry, electronics, biology, coating, transmitter, dielectric materials, plastics, printing ink, papermaking, chemical fibre, rubber.Bar-shaped Zinc oxide particles purity height of the present invention, the particulate controllable size can be used for the product of high platform, is to be used to prepare optoelectronic equipment, chemical sensor, the material of atomic force microscope and scanning tunnel microscope etc.
The liquid phase preparation process of bar-shaped Zinc oxide particles of the present invention has:
1. reaction conditions gentleness prepares simplely, is easy to apply.
2. by selecting the consumption of zinc salt and alcohol amine compound, be easy to prepare the bar-shaped Zinc oxide particles product of different length-to-diameter ratios.
3. products obtained therefrom purity height does not need last handling process.
Description of drawings
Fig. 1. the bar-shaped Zinc oxide particles electromicroscopic photograph of the embodiment of the invention 1;
Fig. 2. the bar-shaped Zinc oxide particles electromicroscopic photograph of the embodiment of the invention 2;
Fig. 3. the bar-shaped Zinc oxide particles electromicroscopic photograph of the embodiment of the invention 3.
Embodiment
Embodiment 1
The secondary water of 10ml is heated to 90 ℃, be 1: 1 trolamine and acetic acid zinc solution simultaneously with two notes dropping molar concentration rates in this solvent, the initial molar ratio that makes trolamine-zinc acetate is 1: 1, its dropping time is 20 minutes, stirring reaction is 30 minutes under this temperature, ageing 2.0 hours, obtain white opacity solution, centrifugation, the centrifugal product vacuum-drying of gained obtains bar-shaped one-dimension zinc oxide particle, diameter can reach 200～400 nanometers, length can reach 2 microns～5 microns, and length-to-diameter ratio can be used for preparing the material of atomic force microscope and scanning tunnel microscope etc. in 5～20 scopes.See accompanying drawing 1.
Embodiment 2
The secondary water of 8mL is heated to 60 ℃, be 2: 1 trolamine and acetic acid zinc solution simultaneously with two notes dropping molar concentration rates in this solvent, the initial molar ratio that makes trolamine-zinc acetate is 2: 1, its dropping time is 10 minutes, keep this temperature and stir reaction down 120 minutes, ageing 1.0 hours, obtain white opacity solution, centrifugation, the centrifugal product vacuum-drying of gained obtains bar-shaped Zinc oxide particles, diameter can reach 30～60 nanometers, length can reach 60 nanometers～120 nanometers, and length-to-diameter ratio can be used for preparing the material of optoelectronic equipment in 1～4 scope.See accompanying drawing 2.
Embodiment 3
The secondary water of 15mL is heated to 90 ℃, be 40: 1 trolamine and acetic acid zinc solution simultaneously with two notes dropping molar concentration rates in this solvent, the initial molar ratio that makes trolamine-zinc acetate is 40: 1, its dropping time is 25 minutes, keep this temperature and stir reaction down 60 minutes, ageing 1.0 hours, obtain white opacity solution, centrifugation, the centrifugal product vacuum-drying of gained obtains bar-shaped Zinc oxide particles, diameter can reach 600 nanometers, length can reach 1～2 micron, and length-to-diameter ratio can be used for preparing the material of chemical sensor in 1～4 scope.See accompanying drawing 3.
Embodiment 4
The secondary water of 10mL is heated to 80 ℃, be 20: 1 trolamine and acetic acid zinc solution simultaneously with two notes dropping molar concentration rates in this solvent, the initial molar ratio that makes trolamine-zinc acetate is 20: 1, its dropping time is 40 minutes, keep this temperature and stir reaction down 30 minutes, ageing 1.5 hours obtains white opacity solution, centrifugation, the centrifugal product vacuum-drying of gained, obtain bar-shaped Zinc oxide particles, diameter can reach 80～100 nanometers, and length can reach 700～900 nanometers, length-to-diameter ratio is in 7～10 scopes, can be used for preparing optoelectronic equipment, chemical sensor, the material of atomic force microscope and scanning tunnel microscope etc.
Claims (9)
1. bar-shaped Zinc oxide particles, it is characterized in that: the diameter of described bar-shaped Zinc oxide particles is 30～600 nanometers, and length is 50 nanometers～5 micron, and length-to-diameter ratio is in 1～30 scope.
2. the preparation method of a bar-shaped Zinc oxide particles as claimed in claim 1, it is characterized in that: the step of this method comprises:
1.. the aqueous solution of preparing metal zinc salt;
2.. the aqueous solution of preparation alcohol amine compound;
3.. get two simultaneously notes of the alcohol amine compound aqueous solution that 2. metallic zinc salts solution that 1. step prepare and step prepare and join in the secondary water solvent that is preheating to 60～100 ℃, wherein, alcohol amine compound in the mixed solution: the mol ratio of metal zinc salt is 0.5: 1～50: 1;
4.. with 3. mixed solution stirring reaction of step, reaction back ageing;
5.. step mixed solution is 4. separated, and throw out is washed with secondary water washing, isolates particle, obtains bar-shaped one-dimension zinc oxide particle.
3. method as claimed in claim 2 is characterized in that: the diameter of described bar-shaped Zinc oxide particles is 30～600 nanometers, and length is 50 nanometers～5 micron, and length-to-diameter ratio is in 1～30 scope.
4. method as claimed in claim 2 is characterized in that: the volumetric molar concentration of the metallic zinc salt brine solution that 1. described step is prepared is 0.001～0.5mol/L.
5. method as claimed in claim 2 is characterized in that: the volumetric molar concentration of the alcohol amine compound aqueous solution that 2. described step is prepared is 0.001～5mol/L.
6. method as claimed in claim 2 is characterized in that: described metal zinc salt is zinc nitrate, zinc chloride, zinc sulfate or zinc acetate.
7. method as claimed in claim 2 is characterized in that: described alcohol amine compound is diethanolamine or trolamine.
8. method as claimed in claim 2 is characterized in that: the described step stirring reaction time 4. is 0.5～3 hour.
9. the purposes of a bar-shaped Zinc oxide particles as claimed in claim 1, it is characterized in that: described bar-shaped Zinc oxide particles is to be used to prepare optoelectronic equipment, chemical sensor, the material of atomic force microscope and scanning tunnel microscope.
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| CN 03109799 CN1286730C (en) | 2003-04-21 | 2003-04-21 | Bar type zinc oxide granule, preparation method and usage |
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| CN 03109799 CN1286730C (en) | 2003-04-21 | 2003-04-21 | Bar type zinc oxide granule, preparation method and usage |
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| CN1539741A true CN1539741A (en) | 2004-10-27 |
| CN1286730C CN1286730C (en) | 2006-11-29 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301217C (en) * | 2004-11-03 | 2007-02-21 | 西北工业大学 | Method for chemically preparing zinc oxide nanometer rod using low temperature wet method |
| CN1314593C (en) * | 2004-12-03 | 2007-05-09 | 中国科学技术大学 | Tactic zinc oxide granular one dimension mesoporous nano belt and precursor and its preparing method |
| CN100344542C (en) * | 2005-12-16 | 2007-10-24 | 厦门大学 | Method for inhibiting C axial growth of zinc oxide nano-wire |
| CN100372777C (en) * | 2006-01-19 | 2008-03-05 | 浙江大学 | Method for preparing different shaped nano zinc oxide by thermal decomposition |
| CN100503741C (en) * | 2006-05-12 | 2009-06-24 | 中国科学院理化技术研究所 | Dumb-bell-like zinc oxide particles and preparing method and use |
| CN101559975B (en) * | 2009-05-14 | 2011-01-05 | 浙江理工大学 | Method for preparing zinc oxide micron rods by using solution method |
| CN102134091A (en) * | 2011-01-21 | 2011-07-27 | 陕西师范大学 | Method for preparing micro structural zinc oxide by hydrothermal method |
| CN107513196A (en) * | 2016-06-17 | 2017-12-26 | 常州百思通复合材料有限公司 | A kind of method using microwave high-efficiency heating high molecular polymer |
-
2003
- 2003-04-21 CN CN 03109799 patent/CN1286730C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301217C (en) * | 2004-11-03 | 2007-02-21 | 西北工业大学 | Method for chemically preparing zinc oxide nanometer rod using low temperature wet method |
| CN1314593C (en) * | 2004-12-03 | 2007-05-09 | 中国科学技术大学 | Tactic zinc oxide granular one dimension mesoporous nano belt and precursor and its preparing method |
| CN100344542C (en) * | 2005-12-16 | 2007-10-24 | 厦门大学 | Method for inhibiting C axial growth of zinc oxide nano-wire |
| CN100372777C (en) * | 2006-01-19 | 2008-03-05 | 浙江大学 | Method for preparing different shaped nano zinc oxide by thermal decomposition |
| CN100503741C (en) * | 2006-05-12 | 2009-06-24 | 中国科学院理化技术研究所 | Dumb-bell-like zinc oxide particles and preparing method and use |
| CN101559975B (en) * | 2009-05-14 | 2011-01-05 | 浙江理工大学 | Method for preparing zinc oxide micron rods by using solution method |
| CN102134091A (en) * | 2011-01-21 | 2011-07-27 | 陕西师范大学 | Method for preparing micro structural zinc oxide by hydrothermal method |
| CN102134091B (en) * | 2011-01-21 | 2013-04-17 | 陕西师范大学 | Method for preparing micro structural zinc oxide by hydrothermal method |
| CN107513196A (en) * | 2016-06-17 | 2017-12-26 | 常州百思通复合材料有限公司 | A kind of method using microwave high-efficiency heating high molecular polymer |
| CN107513196B (en) * | 2016-06-17 | 2020-04-14 | 常州百思通复合材料有限公司 | Method for efficiently heating high-molecular polymer by using microwaves |
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| CN1286730C (en) | 2006-11-29 |
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