CN102923757A - Method for preparing ZnO Nano-rods - Google Patents
Method for preparing ZnO Nano-rods Download PDFInfo
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- CN102923757A CN102923757A CN2012104606863A CN201210460686A CN102923757A CN 102923757 A CN102923757 A CN 102923757A CN 2012104606863 A CN2012104606863 A CN 2012104606863A CN 201210460686 A CN201210460686 A CN 201210460686A CN 102923757 A CN102923757 A CN 102923757A
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Abstract
The invention provides a method for preparing ZnO Nano-rods. The method comprises the following steps: mixing the alcohol and deionized water in the volume ratio of (1-4):(9-6) to obtain an alcohol-water mixed solution; dissolving zinc salt and precipitant in the alcohol-water mixed solution in the molar ratio of (1-3):(1-4) to obtain a mixture; adjusting the pH value of the mixture to 1-4; heating the mixture with the pH value of 1-4 to 80-100 DEG C, and then performing thermal reaction for 2-8 hours; and filtering the mixture after reaction, washing and drying the filter residue to obtain the ZnO Nano-rods. The preparation method has the advantages of mild reaction condition and low demand on equipment. Furthermore, the invention further provides a ZnO Nano-rod prepared by adopting the method for preparing the ZnO Nano-rods.
Description
Technical field
The present invention relates to the synthesis technical field of nano material, particularly relate to a kind of preparation method of zinc oxide nano rod.
Background technology
Zinc oxide is more and more widely broad stopband (3.37eV) conductor oxidate of a kind of application.Nano zine oxide is a kind of nano material commonly used, and particle diameter is called again superfine zinc oxide between 1 ~ 100nm.The granular of particle causes specific surface area sharply to increase, and gives the not available small-size effect of nano zine oxide common zinc oxide, surface effects, macro quanta tunnel effect, Dielectric confinement effect etc.Thereby, nano zine oxide has property and the new purposes that general zinc oxide is unattainable at aspects such as light, electricity, magnetic, chemistry, physics, quick property, demonstrate wide application prospect in coating, printing ink, rubber, catalyzer, color stuffing, the cosmetics of super quality and medicine and other fields.And the factors such as the pattern of nano material, size have extremely important impact for its performance, therefore a lot of researchs prepare for the zinc oxide of different-shape and study, wherein zinc oxide nano rod shows the performance of many excellences owing to it, and becomes one of focus of present research.
At present mainly contain two kinds of vapor phase process and liquid phase methods for the preparation of the method for zinc oxide nano rod, although wherein product quality that vapor phase process obtains is high, apparatus expensive, energy consumption is higher, thus cost is very high and condition is harsh.Liquid phase method has single stage method and two-step approach, and wherein hydrothermal method accounts for very large proportion in the single stage method, and two-step approach still needs high-temperature calcination and it is high to consume energy, the cycle is long; Hydrothermal method need adopt the special high-pressure reactor, and is higher and have a potential safety hazard to equipment requirements.
Summary of the invention
Based on this, provide the preparation method of gentle, the low for equipment requirements zinc oxide nano rod of a kind of reaction conditions.
Further, provide a kind of zinc oxide nano rod that is prepared by aforesaid method.
A kind of preparation method of zinc oxide nano rod comprises the steps:
1 ~ 4:9 ~ 6 are mixed to get alcohol-water mixture with Organic Alcohol and deionized water by volume;
Zinc salt and precipitation agent be dissolved in the described alcohol-water mixture according to the mol ratio of 1:3 ~ 1:4 obtain mixture;
The pH value of regulating described mixture is 1 ~ 4;
Be 1 ~ 4 mixture heating up to 80 ℃ ~ 100 ℃ with described pH value, insulation reaction 2 hours ~ 8 hours;
Reacted mixture is filtered, and washing filter residue and drying obtain zinc oxide nano rod.
Among embodiment, described Organic Alcohol is dehydrated alcohol or anhydrous methanol therein.
Among embodiment, described zinc salt is zinc nitrate, zinc sulfate or zinc chloride therein.
Among embodiment, in the described mixture, the concentration of described zinc salt is 0.01mol/L ~ 0.1mol/L therein.
Among embodiment, described precipitation agent is urea or hexamethylenetetramine therein.
Therein among embodiment, the pH value of regulating described mixture is 1 ~ 4 step to regulate the pH value of described mixture be 1 ~ 4 in order to drip nitric acid in described mixture.
Therein among embodiment, the step that described throw out is washed is specially uses deionized water and the described throw out of washing with alcohol repeatedly successively.
A kind of zinc oxide nano rod that adopts preparation method's preparation of above-mentioned zinc oxide nano rod, the minor axis diameter of described zinc oxide nano rod is 30 nanometers ~ 100 nanometers, length-to-diameter ratio is 3 ~ 10:1.
The preparation method of above-mentioned zinc oxide nano rod with zinc salt as raw material, under the precipitation agent effect, generate zinc oxide in 80 ℃ ~ 100 ℃ lower reactions, adopt alcohol-water mixture as the morphology control agent, and adopt the proportioning of suitable zine ion and precipitation agent, generate the zinc oxide nano rod of pattern homogeneous.The top temperature of this preparation method's reaction is 100 ℃ only, need not to carry out high-temperature calcination, and reaction conditions is gentle.Reaction is carried out under normal pressure, only needs simple reaction vessel and common heating equipment, need not to adopt autoclave, and is lower to equipment requirements.
Description of drawings
Fig. 1 is preparation method's schema of the zinc oxide nano rod of an embodiment;
Fig. 2 is the SEM figure of the zinc oxide nano rod of embodiment 4 preparations;
Fig. 3 is the XRD diffractogram of the zinc oxide nano rod of embodiment 4 preparations.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can be in the situation that do similar improvement without prejudice to intension of the present invention, so the present invention is not subjected to the restriction of following public implementation.
See also Fig. 1, the preparation method of the zinc oxide nano rod of an embodiment comprises the steps:
Step S110: 1 ~ 4:9 ~ 6 are mixed to get alcohol-water mixture with Organic Alcohol and deionized water by volume.
Organic Alcohol is used for the pattern of control oxidation zinc bar as the morphology control agent.
Organic Alcohol is preferably dehydrated alcohol or anhydrous methanol.Dehydrated alcohol or anhydrous methanol viscosity are little, and price is low, can come the regulator solution boiling point according to different ratios, thereby guarantee to react under identical temperature of reaction, make reaction be easy to control.
Step S120: zinc salt and precipitation agent be dissolved in the described alcohol-water mixture according to the mol ratio of 1:3 ~ 1:4 obtain mixture.
Zinc salt preferably adopts strong acid salt, such as zinc nitrate, zinc sulfate, zinc chloride etc.In this several zinc salts more soluble in water.
In the mixture, the concentration of zinc salt is 0.01mol/L ~ 0.1mol/L.Select this concentration can further control the pattern of resultant, guarantee bar-shaped growth, and other patterns do not occur.
The pattern of concentration two the means control zinc oxide of present embodiment by adding morphology control agent and zine ion, the rod-like nano-zinc oxide take the product that guarantees finally to obtain as the rule of pattern homogeneous, i.e. zinc oxide nano rod.
Precipitation agent is preferably urea (CO (NH
2)
2) or hexamethylenetetramine (HMTA).Urea and hexamethylenetetramine slowly are hydrolyzed under specific temperature and discharge OH
-React.
In order to guarantee to react completely, in the mixture, the mol ratio of zinc salt and precipitation agent is 1:3 ~ 1:4.Under this mol ratio, react, also be conducive to generate the less zinc oxide precipitation of particle diameter.
Step S130: the pH value of regulating compound is 1 ~ 4.
Regulating the pH value of mixing with nitric acid is 1 ~ 4.In other embodiments, also can adopt hydrochloric acid, sulfuric acid etc. to regulate.
Under this pH value, react 1 ~ 4, be conducive to generate the higher zinc oxide nano rod of pattern homogeneity.
Step S140: be 1 ~ 4 mixture heating up to 80 ℃ ~ 100 ℃ with the pH value, insulation reaction 2 hours ~ 8 hours.
Be 1 ~ 4 mixture heating up to 80 ℃ ~ 100 ℃ with the pH value, urea and hexamethylenetetramine slowly are hydrolyzed.Insulation reaction 2 hours ~ 8 hours fully is hydrolyzed precipitation agent to discharge OH-and reacts.
Preferably, adopt reflux to carry out back flow reaction, to improve reaction efficiency and transformation efficiency.
In mixture, metallic cation Zn
2+Form [Zn (OH with the water molecules effect
2)
n]
2+Ion also is hydrolyzed the OH that discharges with precipitation agent simultaneously
-In conjunction with forming [Zn (OH
2)
N-p(OH)
p]
(2-p)+Zn-OH wherein
2Bond polarity impels the coordinated water deprotonation.Generate the metal oxide nuclei of crystallization on reaction bases such as polycondensations and realized crystal growth growth.
Concrete reaction process is as follows, at first forms one " ol bridge " by a hydroxyl and the reaction of hydrated cation generation hydroxyl connection, and reaction formula is as follows:
Zn-OH+Zn-OH
2→Zn-OH-Zn+H
2O
Then by the hydroxyl dehydration oxolation occurs, form " oxo bridge ", obtain zinc oxide, reaction formula is as follows:
Zn-OH-Zn→Zn-O-Zn+H
2O
Step S150: reacted mixture is filtered, and washing filter residue and drying obtain zinc oxide nano rod.
Reacted mixture filtered obtain filter residue, filter residue is used deionized water and washing with alcohol repeatedly successively, fully to remove the negatively charged ion in the filter residue, obtain pure white depositions.
The white depositions that this is pure obtains zinc oxide nano rod in 60 ℃ ~ 100 ℃ lower vacuum-dryings 2 hours ~ 8 hours.
The zinc oxide nano rod minor axis diameter that adopts this method to prepare is 30 nanometers ~ 100 nanometers, and length-to-diameter ratio is 3 ~ 10:1, and granularity is little, is evenly distributed.The minor axis diameter is 30 nanometers ~ 100 nanometers, and length-to-diameter ratio is that the zinc oxide nano rod of 3 ~ 10:1 has excellent electric property, has a extensive future.
The preparation method of above-mentioned zinc oxide nano rod with zinc salt as raw material, under the precipitation agent effect, generate zinc oxide in 80 ℃ ~ 100 ℃ lower reactions, adopt alcohol-water mixture as the morphology control agent, and adopt the proportioning of suitable zine ion and precipitation agent, generate the good zinc oxide nano rod of pattern homogeneity.This preparation method is 100 ℃ only by the top temperature of primary sedimentation formation reaction, need not to carry out high-temperature calcination, and reaction conditions is gentle.Reaction is carried out under normal pressure, only needs simple reaction vessel and common heating equipment, need not to adopt autoclave, and is lower to equipment requirements.
And, the preparation method of above-mentioned zinc oxide nano rod directly obtains zinc oxide by a step precipitation, and need not react generate other and contain the throw out of zinc after, such as zinc hydroxide, zinc carbonate, zinc subcarbonate etc., and then carry out high-temperature calcination and obtain zinc oxide.This method is comparatively simple, and energy consumption is low, and preparation cost is low, and raw materials cost is low, and the reaction times is short, is easy to suitability for industrialized production, has a extensive future.
It below is specific embodiment.
Embodiment 1
For 1:9 dehydrated alcohol and deionized water are mixed to get alcohol-water mixture by volume, with the zinc nitrate ((Zn (NO of 0.003mol
3)
26H
2O) and the urea of 0.0105mol (CO (NH
2)
2) be dissolved in successively in the 100ml alcohol-water mixture and obtain mixture, dripping concentrated nitric acid in this mixture, to regulate the pH value of mixture be 3, be that 3 mixture heating up is stirred to 100 ℃ with the pH value, obtained reaction solution in 6 hours 100 ℃ of lower backflows, reacting liquid filtering is obtained white depositions, use respectively deionized water and washing with alcohol gained white depositions each three times, with the washing after white depositions in 60 ℃ of lower vacuum-dryings 8 hours, obtain zinc oxide nano rod.
Embodiment 2
For 2:8 anhydrous methanol and deionized water are mixed to get alcohol-water mixture by volume, with the zinc sulfate (ZnSO of 0.001mol
4) and the urea (CO (NH of 0.003mol
2)
2) be dissolved in successively in the 100ml alcohol-water mixture and obtain mixture, dripping concentrated nitric acid in this mixture, to regulate the pH value of mixture be 1, be that 1 mixture heating up is stirred to 91 ℃ with the pH value, obtained reaction solution in 8 hours 91 ℃ of lower backflows, reacting liquid filtering is obtained white depositions, use respectively deionized water and washing with alcohol gained white depositions each three times, with the washing after white depositions in 100 ℃ of lower vacuum-dryings 2 hours, obtain zinc oxide nano rod.
Embodiment 3
For 3:7 dehydrated alcohol and deionized water are mixed to get alcohol-water mixture by volume, with the zinc chloride (ZnCl of 0.003mol
2) and the hexamethylenetetramine (HMTA) of 0.009mol be dissolved in successively in the 100ml alcohol-water mixture and obtain mixture, dripping concentrated nitric acid in this mixture, to regulate the pH value of mixture be 4, be that 3 mixture heating up is stirred to 89 ℃ with the pH value, obtained reaction solution in 2 hours 89 ℃ of lower backflows, reacting liquid filtering is obtained white depositions, use respectively deionized water and washing with alcohol gained white depositions each three times, white depositions after the washing in 80 ℃ of lower vacuum-dryings 8 hours, is obtained zinc oxide nano rod.
Embodiment 4
For 4:6 dehydrated alcohol and deionized water are mixed to get alcohol-water mixture by volume, with the zinc nitrate (Zn (NO of 0.01mol
3)
26H
2The urea of O and 0.04mol (CO (NH
2)
2) be dissolved in successively in the 100ml alcohol-water mixture and obtain mixture, dripping concentrated nitric acid in this mixture, to regulate the pH value of mixture be 3, be that 3 mixture heating up is stirred to 80 ℃ with the pH value, obtained reaction solution in 4 hours 80 ℃ of lower backflows, reacting liquid filtering is obtained white depositions, use respectively deionized water and washing with alcohol gained white depositions each three times, with the washing after white depositions in 70 ℃ of lower vacuum-dryings 5 hours, obtain zinc oxide nano rod.
Fig. 2 is the SEM figure of the zinc oxide nano rod of the present embodiment preparation.As can be seen from Figure 2, embodiment 4 prepares that the zinc oxide nano rod pattern is even, and granularity is little, is evenly distributed, and minor axis length is 30 ~ 100 nanometers, and length-to-diameter ratio is 5:1 ~ 10:1.
Fig. 3 is the XRD diffractogram of the zinc oxide nano rod of this enforcement preparation.As seen from Figure 3, prepare the higher zinc oxide of purity.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (8)
1. the preparation method of a zinc oxide nano rod is characterized in that, comprises the steps:
1 ~ 4:9 ~ 6 are mixed to get alcohol-water mixture with Organic Alcohol and deionized water by volume;
Zinc salt and precipitation agent be dissolved in the described alcohol-water mixture according to the mol ratio of 1:3 ~ 1:4 obtain mixture;
The pH value of regulating described mixture is 1 ~ 4;
Be 1 ~ 4 mixture heating up to 80 ℃ ~ 100 ℃ with described pH value, insulation reaction 2 hours ~ 8 hours;
Reacted mixture is filtered, and washing filter residue and drying obtain zinc oxide nano rod.
2. the preparation method of zinc oxide nano rod according to claim 1 is characterized in that, described Organic Alcohol is dehydrated alcohol or anhydrous methanol.
3. the preparation method of zinc oxide nano rod according to claim 1 is characterized in that, described zinc salt is zinc nitrate, zinc sulfate or zinc chloride.
4. the preparation method of zinc oxide nano rod according to claim 1 is characterized in that, in the described mixture, the concentration of described zinc salt is 0.01mol/L ~ 0.1mol/L.
5. the preparation method of zinc oxide nano rod according to claim 1 is characterized in that, described precipitation agent is urea or hexamethylenetetramine.
6. the preparation method of zinc oxide nano rod according to claim 1 is characterized in that, the pH value of regulating described mixture is 1 ~ 4 step to regulate the pH value of described mixture be 1 ~ 4 in order to drip nitric acid in described mixture.
7. the preparation method of zinc oxide nano rod according to claim 1 is characterized in that, the step that described throw out is washed is specially uses deionized water and the described throw out of washing with alcohol repeatedly successively.
8. the zinc oxide nano rod of the preparation method of an employing such as each described zinc oxide nano rod of claim 1 ~ 7 preparation is characterized in that, the minor axis diameter of described zinc oxide nano rod is 30 nanometers ~ 100 nanometers, and length-to-diameter ratio is 3 ~ 10:1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310458A (en) * | 2014-10-10 | 2015-01-28 | 九江学院 | Method for preparing zinc oxide nanorod |
| CN105289582A (en) * | 2015-10-30 | 2016-02-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for zinc oxide nanometer rod supported manganese-oxide-base catalyst |
| CN106186047A (en) * | 2016-08-05 | 2016-12-07 | 武汉理工大学 | A kind of based on secondary nanosphere hierarchical Z nO nano material and preparation method thereof |
| CN106241858A (en) * | 2016-08-26 | 2016-12-21 | 广东工业大学 | A kind of preparation method of one-dimension zinc oxide crystal |
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| CN1192991A (en) * | 1997-03-06 | 1998-09-16 | 西北大学 | Method for preparing nanometre-grade zinc oxide |
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| CN1192991A (en) * | 1997-03-06 | 1998-09-16 | 西北大学 | Method for preparing nanometre-grade zinc oxide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310458A (en) * | 2014-10-10 | 2015-01-28 | 九江学院 | Method for preparing zinc oxide nanorod |
| CN104310458B (en) * | 2014-10-10 | 2015-10-14 | 九江学院 | A kind of method preparing zinc oxide nano rod |
| CN105289582A (en) * | 2015-10-30 | 2016-02-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for zinc oxide nanometer rod supported manganese-oxide-base catalyst |
| CN105289582B (en) * | 2015-10-30 | 2017-11-10 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of zinc oxide nano rod supports the preparation method of oxidation manganese-based catalyst |
| CN106186047A (en) * | 2016-08-05 | 2016-12-07 | 武汉理工大学 | A kind of based on secondary nanosphere hierarchical Z nO nano material and preparation method thereof |
| CN106186047B (en) * | 2016-08-05 | 2017-12-05 | 武汉理工大学 | One kind is based on secondary nanosphere hierarchical Z nO nano materials and preparation method thereof |
| CN106241858A (en) * | 2016-08-26 | 2016-12-21 | 广东工业大学 | A kind of preparation method of one-dimension zinc oxide crystal |
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