CN102923757B - Method for preparing ZnO Nano-rods - Google Patents
Method for preparing ZnO Nano-rods Download PDFInfo
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- CN102923757B CN102923757B CN201210460686.3A CN201210460686A CN102923757B CN 102923757 B CN102923757 B CN 102923757B CN 201210460686 A CN201210460686 A CN 201210460686A CN 102923757 B CN102923757 B CN 102923757B
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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 a kind of application broad stopband (3.37eV) conductor oxidate more and more widely.Nano zine oxide is a kind of conventional nano material, and particle diameter, between 1 ~ 100nm, is also called superfine zinc oxide.The granular of particle, causes specific surface area sharply to increase, and gives small-size effect, surface effects, macro quanta tunnel effect, Dielectric confinement effect etc. not available for nano zine oxide common zinc oxide.Thus, nano zine oxide has the property and novelty teabag that general zinc oxide is unattainable in optical, electrical, magnetic, chemistry, physics, sensitivity etc., demonstrates wide application prospect in coating, 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 research is prepared for the zinc oxide of different-shape and studies, wherein zinc oxide nano rod shows the performance of many excellences due to it, and becomes one of focus of research at present.
Method at present for the preparation of zinc oxide nano rod mainly contains vapor phase process and liquid phase method two kinds, although wherein vapor phase process to obtain product quality high, apparatus expensive, energy consumption is higher, thus cost is very high and condition harsh.Liquid phase method has single stage method and two-step approach, and wherein in single stage method, hydrothermal method accounts for very large proportion, and two-step approach still needs high-temperature calcination and it is high to consume energy, the cycle is long; Hydrothermal method need adopt special high-pressure reactor, higher and there is potential safety hazard to equipment requirements.
Summary of the invention
Based on this, the preparation method of the zinc oxide nano rod providing a kind of reaction conditions gentle, low for equipment requirements.
Further, a kind of zinc oxide nano rod prepared by aforesaid method is provided.
A preparation method for zinc oxide nano rod, comprises the steps:
Organic Alcohol and deionized water are mixed to get alcohol-water mixture by 1 ~ 4:9 ~ 6 by volume;
Zinc salt and precipitation agent are dissolved in described alcohol-water mixture according to the mol ratio of 1:3 ~ 1:4 and obtain mixture;
The pH value of described mixture is regulated to be 1 ~ 4;
By described pH value be 1 ~ 4 mixture be heated to 80 DEG C ~ 100 DEG C, insulation reaction 2 hours ~ 8 hours;
Reacted mixture is filtered, washing filter residue drying obtains zinc oxide nano rod.
Wherein in an embodiment, described Organic Alcohol is dehydrated alcohol or anhydrous methanol.
Wherein in an embodiment, described zinc salt is zinc nitrate, zinc sulfate or zinc chloride.
Wherein in an embodiment, in described mixture, the concentration of described zinc salt is 0.01mol/L ~ 0.1mol/L.
Wherein in an embodiment, described precipitation agent is urea or hexamethylenetetramine.
Wherein in an embodiment, regulate the pH value of described mixture be 1 ~ 4 step be in described mixture, drip nitric acid regulate the pH value of described mixture to be 1 ~ 4.
Wherein in an embodiment, the step that described throw out carries out washing is specially and uses throw out described in deionized water and washing with alcohol successively repeatedly.
Adopt a zinc oxide nano rod prepared by the preparation method of above-mentioned zinc oxide nano rod, the minor axis diameter of described zinc oxide nano rod is 30 nanometer ~ 100 nanometers, and length-to-diameter ratio is 3 ~ 10:1.
The preparation method of above-mentioned zinc oxide nano rod is using zinc salt as raw material, under precipitation agent effect, at 80 DEG C ~ 100 DEG C, reaction generates zinc oxide, adopt alcohol-water mixture as morphology control agent, and adopt suitable zine ion and the proportioning of precipitation agent, generate the zinc oxide nano rod that pattern is homogeneous.The top temperature of this preparation method reaction is only 100 DEG C, and without the need to carrying out high-temperature calcination, reaction conditions is gentle.Reaction is carried out at ambient pressure, only needs simple reaction vessel and common heating equipment, without the need to adopting autoclave, lower to equipment requirements.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of the zinc oxide nano rod of an embodiment;
Fig. 2 is the SEM figure of zinc oxide nano rod prepared by embodiment 4;
Fig. 3 is the XRD diffractogram of zinc oxide nano rod prepared by embodiment 4.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the zinc oxide nano rod of an embodiment, comprises the steps:
Step S110: Organic Alcohol and deionized water are mixed to get alcohol-water mixture by 1 ~ 4:9 ~ 6 by volume.
Organic Alcohol as morphology control agent, for the pattern of controlled oxidization zinc bar.
Organic Alcohol is preferably dehydrated alcohol or anhydrous methanol.Dehydrated alcohol or anhydrous methanol viscosity little, price is low, can carry out regulator solution boiling point according to different ratios, thus ensure react at the same reaction temperature, make reaction be easy to control.
Step S120: zinc salt and precipitation agent are dissolved in described alcohol-water mixture according to the mol ratio of 1:3 ~ 1:4 and obtain mixture.
Zinc salt preferably adopts strong acid salt, as zinc nitrate, zinc sulfate, zinc chloride etc.This several zinc salt more soluble in water in.
In mixture, the concentration of zinc salt is 0.01mol/L ~ 0.1mol/L.Select this concentration can control the pattern of resultant further, ensure bar-shaped growth, and do not occur other patterns.
Present embodiment by adding the pattern of concentration two means controlled oxidization zinc of morphology control agent and zine ion, to ensure the product that finally the obtains rod-like nano-zinc oxide for the homogeneous rule of pattern, i.e. zinc oxide nano rod.
Precipitation agent is preferably urea (CO (NH
2)
2) or hexamethylenetetramine (HMTA).Urea and hexamethylenetetramine are slowly hydrolyzed within specified temperatures and discharge OH
-react.
In order to ensure to react completely, in mixture, the mol ratio of zinc salt and precipitation agent is 1:3 ~ 1:4.React under this mol ratio, be also conducive to generating the less zinc oxide precipitate of particle diameter.
Step S130: the pH value regulating compound is 1 ~ 4.
The pH value regulating mixing with nitric acid is 1 ~ 4.In other embodiments, hydrochloric acid, sulfuric acid etc. also can be adopted to regulate.
Under this pH value, carry out reaction 1 ~ 4, be conducive to generating the higher zinc oxide nano rod of topography uniformity.
Step S140: by pH value be 1 ~ 4 mixture be heated to 80 DEG C ~ 100 DEG C, insulation reaction 2 hours ~ 8 hours.
By pH value be 1 ~ 4 mixture be heated to 80 DEG C ~ 100 DEG C, urea and hexamethylenetetramine are slowly hydrolyzed.Insulation reaction 2 hours ~ 8 hours, makes precipitation agent fully be hydrolyzed to discharge OH-to react.
Preferably, reflux is adopted to carry out back flow reaction, to improve reaction efficiency and transformation efficiency.
In the mixture, metallic cation Zn
2+[Zn (OH is formed with water molecules effect
2)
n]
2+ion, is also hydrolyzed with precipitation agent the OH discharged simultaneously
-in conjunction with formation [Zn (OH
2)
n-p(OH)
p]
(2-p)+.Wherein Zn-OH
2bond polarity impels coordinated water deprotonation.The reaction bases such as polycondensation generate the metal oxide nuclei of crystallization and realizes crystal growth growth.
Concrete reaction process is as follows, and first join reaction by a hydroxyl and hydrated cation generation hydroxyl and formed one " ol bridge ", reaction formula is as follows:
Zn-OH+Zn-OH
2→Zn-OH-Zn+H
2O
Then by hydroxyls dehydrate generation oxolation, formed " oxo bridge ", obtain zinc oxide, reaction formula is as follows:
Zn-OH-Zn→Zn-O-Zn+H
2O
Step S150: filtered by reacted mixture, washs filter residue and drying obtains zinc oxide nano rod.
Reacted mixture is carried out filtration and obtains filter residue, filter residue is used deionized water and washing with alcohol repeatedly successively, fully to remove the negatively charged ion in filter residue, obtain pure white depositions.
By the vacuum-drying 2 hours ~ 8 hours at 60 DEG C ~ 100 DEG C of this pure white depositions, obtain zinc oxide nano rod.
Adopting the zinc oxide nano rod minor axis diameter prepared in this way is 30 nanometer ~ 100 nanometers, and length-to-diameter ratio is 3 ~ 10:1, and granularity is little, is evenly distributed.Minor axis diameter is 30 nanometer ~ 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 is using zinc salt as raw material, under precipitation agent effect, at 80 DEG C ~ 100 DEG C, reaction generates zinc oxide, adopt alcohol-water mixture as morphology control agent, and adopt suitable zine ion and the proportioning of precipitation agent, generate the zinc oxide nano rod that topography uniformity is good.This preparation method is only 100 DEG C by the top temperature of primary sedimentation formation reaction, and without the need to carrying out high-temperature calcination, reaction conditions is gentle.Reaction is carried out at ambient pressure, only needs simple reaction vessel and common heating equipment, without the need to adopting autoclave, 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 carry out reacting and generate other containing after the throw out of zinc, 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 is below specific embodiment.
Embodiment 1
Dehydrated alcohol and deionized water are mixed to get alcohol-water mixture for 1:9 by volume, by the zinc nitrate ((Zn (NO of 0.003mol
3)
26H
2and the urea of 0.0105mol (CO (NH O)
2)
2) be dissolved in successively in 100ml alcohol-water mixture and obtain mixture, in this mixture, drip concentrated nitric acid regulates the pH value of mixture to be 3, it is the mixture heated and stirred to 100 DEG C of 3 by pH value, at 100 DEG C, backflow obtains reaction solution in 6 hours, reacting liquid filtering is obtained white depositions, use the white depositions of deionized water and washing with alcohol gained respectively each three times, by the vacuum-drying 8 hours at 60 DEG C of the white depositions after washing, obtain zinc oxide nano rod.
Embodiment 2
Anhydrous methanol and deionized water are mixed to get alcohol-water mixture for 2:8 by volume, by the zinc sulfate (ZnSO of 0.001mol
4) and the urea (CO (NH of 0.003mol
2)
2) be dissolved in successively in 100ml alcohol-water mixture and obtain mixture, in this mixture, drip concentrated nitric acid regulates the pH value of mixture to be 1, it is the mixture heated and stirred to 91 DEG C of 1 by pH value, at 91 DEG C, backflow obtains reaction solution in 8 hours, reacting liquid filtering is obtained white depositions, use the white depositions of deionized water and washing with alcohol gained respectively each three times, by the vacuum-drying 2 hours at 100 DEG C of the white depositions after washing, obtain zinc oxide nano rod.
Embodiment 3
Dehydrated alcohol and deionized water are mixed to get alcohol-water mixture for 3:7 by volume, by the zinc chloride (ZnCl of 0.003mol
2) and the hexamethylenetetramine (HMTA) of 0.009mol be dissolved in successively in 100ml alcohol-water mixture and obtain mixture, in this mixture, drip concentrated nitric acid regulates the pH value of mixture to be 4, it is the mixture heated and stirred to 89 DEG C of 3 by pH value, at 89 DEG C, backflow obtains reaction solution in 2 hours, reacting liquid filtering is obtained white depositions, use the white depositions of deionized water and washing with alcohol gained respectively each three times, by the vacuum-drying 8 hours at 80 DEG C of the white depositions after washing, obtain zinc oxide nano rod.
Embodiment 4
Dehydrated alcohol and deionized water are mixed to get alcohol-water mixture for 4:6 by volume, by the zinc nitrate (Zn (NO of 0.01mol
3)
26H
2urea (CO (the NH of O and 0.04mol
2)
2) be dissolved in successively in 100ml alcohol-water mixture and obtain mixture, in this mixture, drip concentrated nitric acid regulates the pH value of mixture to be 3, it is the mixture heated and stirred to 80 DEG C of 3 by pH value, at 80 DEG C, backflow obtains reaction solution in 4 hours, reacting liquid filtering is obtained white depositions, use the white depositions of deionized water and washing with alcohol gained respectively each three times, by the vacuum-drying 5 hours at 70 DEG C of the white depositions after washing, obtain zinc oxide nano rod.
Fig. 2 is the SEM figure of zinc oxide nano rod prepared by the present embodiment.As can be seen from Figure 2, it is even that embodiment 4 prepares zinc oxide nano rod pattern, 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, the zinc oxide that purity is higher is prepared.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It 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 (1)
1. a preparation method for zinc oxide nano rod, is characterized in that, comprises the steps:
Dehydrated alcohol and deionized water are mixed to get alcohol-water mixture for 1:9 by volume, by the zinc nitrate ((Zn (NO of 0.003mol
3)
26H
2and the urea of 0.0105mol (CO (NH O)
2)
2) be dissolved in successively in 100ml alcohol-water mixture and obtain mixture, in this mixture, drip concentrated nitric acid regulates the pH value of mixture to be 3, it is the mixture heated and stirred to 100 DEG C of 3 by pH value, at 100 DEG C, backflow obtains reaction solution in 6 hours, reacting liquid filtering is obtained white depositions, use the white depositions of deionized water and washing with alcohol gained respectively each three times, by the vacuum-drying 8 hours at 60 DEG C of the white depositions after washing, obtain zinc oxide nano rod.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310458B (en) * | 2014-10-10 | 2015-10-14 | 九江学院 | A kind of method preparing zinc oxide nano rod |
| 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 |
| 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 |
| CN106241858B (en) * | 2016-08-26 | 2018-01-23 | 广东工业大学 | A kind of preparation method of one-dimension zinc oxide crystal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1192991A (en) * | 1997-03-06 | 1998-09-16 | 西北大学 | Method for preparing nanometre-grade zinc oxide |
| CN1763263A (en) * | 2005-09-27 | 2006-04-26 | 清华大学 | Oriented ZnO nanorod or nanowire film and preparation process thereof |
| JP2008094695A (en) * | 2006-10-16 | 2008-04-24 | Sakai Chem Ind Co Ltd | Method for manufacturing needle zinc oxide |
-
2012
- 2012-11-15 CN CN201210460686.3A patent/CN102923757B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1192991A (en) * | 1997-03-06 | 1998-09-16 | 西北大学 | Method for preparing nanometre-grade zinc oxide |
| CN1763263A (en) * | 2005-09-27 | 2006-04-26 | 清华大学 | Oriented ZnO nanorod or nanowire film and preparation process thereof |
| JP2008094695A (en) * | 2006-10-16 | 2008-04-24 | Sakai Chem Ind Co Ltd | Method for manufacturing needle zinc oxide |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of small diameter ZnO nanorods via refluxing route in alcohol–water mixing solution containing zinc salt and urea;Jingwei Zhang etc.;《Materials Letters》;20060606;第592-594页 * |
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