CN103771493B

CN103771493B - A kind of method preparing one-D nano zinc oxide

Info

Publication number: CN103771493B
Application number: CN201410051031.XA
Authority: CN
Inventors: 王茂华; 周芙; 张波
Original assignee: Changzhou University
Current assignee: XUZHOU RUNFENG NEW MATERIALS Co.,Ltd.
Priority date: 2014-02-14
Filing date: 2014-02-14
Publication date: 2016-01-27
Anticipated expiration: 2034-02-14
Also published as: CN103771493A

Abstract

The present invention relates to nano zine oxide, refer in particular to a kind of liquid phase preparation process of nano zine oxide, concrete steps are: preparation 0.5M zinc salt solution, the aqueous sodium hydroxide solution of 4M; Preparation PN mixing solutions, the mol ratio of extraction agent PC-88A and N1923 is 1-3:1; The mixing solutions of preparation PN and heptane, the massfraction of PN is 16%; Mixed with the zinc solution of 0.5M by PN-n-heptane solution, the volume ratio of PN-n-heptane solution and zinc solution is: 4:1-4:3, and stirred at ambient temperature fully mixes; Measure the NaOH aqueous solution of 4M, be slowly added drop-wise in mixing solutions, the volume ratio of zinc solution and NaOH solution is 2:1, stirring at room temperature; After question response, centrifugation, filters, and with ethanol, distilled water wash, is placed in baking oven dry, obtains the ZnO powder of white.Synthetic method of the present invention is simple, mild condition, and reaction at room temperature just can be carried out, without the need to calcining.

Description

A kind of method preparing one-D nano zinc oxide

Technical field

The present invention relates to nano zine oxide, specifically, what relate to is a kind of liquid phase preparation process of nano zine oxide.

Background technology

1-dimention nano ZnO structure is because of its special quantum size effect, interfacial effect and quantum limitation effect, in magnetic, light, power etc., possessed the many excellent properties not available for thin-film material, the preparation of various 1-dimention nano ZnO structure and performance study have become the focus of current Material Field research; Compared with other semiconductor nano material, the one dimension Nano structure of zinc oxide is easy to synthesis, and the configuration of surface provided is more, more due to its larger direct broad-band gap (3.37eV) and excellent piezoelectricity, pyroelectricity, it is preferably is applied to room temperature ultra-violet light-emitting, laserable material and opto-electronic device, to the exploitation of novel sensor, memory device and field-effect transistor etc., there is potential researching value, all dropped into the development work that sizable strength carries out One-Dimensional ZnO nanostructure both at home and abroad at present.

One-Dimensional ZnO nanostructure mainly comprises nano belt, nano wire, nanometer rod and nanotube etc., the method of current making ZnO nanostructure is numerous, comprise vapor phase process and liquid phase method, as thermal evaporation, physical vaporous deposition (PVD), Metalorganic Chemical Vapor Deposition (MOCVD), template and hydrothermal method etc.; Although the obtained product quality of vapor phase process is high, but apparatus expensive, cost of manufacture is high, and requirement for experiment condition is harsh, compared with vapor phase process, liquid phase method has the advantages such as technique is simple, easy and simple to handle, low for equipment requirements, easily mass-produced, and the nano-particle surface activity synthesized is good, product composition controllable precise, has more industrial prospect.

Reverse micelle extraction method mainly utilizes microemulsion system to extract by extraction agent and by the electrostatic interaction extracted between thing, and chemical reaction is carried out in " pond " that oil phase wraps up, to obtain good dispersity, and the nano material of pattern rule; The present invention is with 2-ethylhexyl phosphonic acid-mono--2-(ethyl hexyl) ester (PC-88A) and primary amine N1923 for extraction agent, and heptane is organic solvent, adopts W/O Microemulsion extraction system making ZnO monodimension nanometer material; Based on the interfacial property of extraction agent and the surface phenomenon of extraction system, multiple nanoscale molecular aggregate is there is in extracted organic phase, the special clustering phenomena of extraction system can be utilized to prepare the nano material of different surfaces performance to meet practical application needs, (the YangC.Eetal.J.Mater.Sci.Technol. such as Yang Zhuanfang, 11,217 (1995)) TBP-kerosene/HCl-ZrOCl is being studied in great detail ₂with TBP-kerosene/HNO ₃-ZrO (NO ₃) ₂system basis is successfully prepared ultra-fine ZrO ₂particle, from extraction system, directly preparing nanoparticle, it not only increases the charge capacity of metal, extraction process itself has carried out purifying to metal ion simultaneously, and extraction agent and organic solvent not easily run off in process of the test, be easy to reclaim, can reuse, provide for being transformed into industry efforts from laboratory study the thinking that well " was separated-prepared to apply " integration.

Summary of the invention

An object of the present invention is to provide single dispersing one-D nano zinc oxide particle, and the one-D nano zinc oxide particle dispersion obtained is good, and length-to-diameter ratio is larger.

Another object of the present invention is the shortcomings and deficiencies for existing in prior art, a kind of preparation method of one-D nano zinc oxide is proposed, without the need to calcining, monodispersed one-D nano zinc oxide is directly prepared with extraction process, the present invention is achieved by the following technical solutions, the present invention includes following steps:

The first step, compound concentration is 0.5M zinc salt solution, and concentration is the aqueous sodium hydroxide solution of 4M.

Described zinc salt, selects zinc nitrate hexahydrate.

Second step, preparation PN mixing solutions.

In described PN mixing solutions, the mol ratio of extraction agent PC-88A and N1923 is 1-3:1.

3rd step, the mixing solutions of preparation PN and heptane, the massfraction of PN is 16%.

4th step, mixes PN-n-heptane solution with the zinc solution of 0.5M, and the volume ratio of PN-n-heptane solution and zinc solution is: 4:1-4:3, makes it abundant mixing in stirred at ambient temperature.

5th step, measures the NaOH aqueous solution of 4M, is slowly added drop-wise in mixing solutions, and the volume ratio of zinc solution and NaOH solution is 2:1, and stirring velocity is adjusted to 600 ~ 800 revs/min, room temperature Keep agitation 2 hours simultaneously.

6th step, after question response, centrifugation, filters, and with ethanol, distilled water wash, is placed in baking oven dry, obtains the ZnO powder of white.

7th step, by the mixing solutions purification process of the supernatant liquid PN that obtains after centrifugation and heptane, recycling.

In conventional microemulsion system, tensio-active agent and the organism of employing are difficult to recycling, and will obtain the experiment condition that monodispersed 1-dimention nano ZnO powder needs High Temperature High Pressure, and beneficial effect of the present invention is:

(1) these two kinds of extraction agents of PC-88A and N1923 are cheap and easy to get, and stable in properties, by recycling after centrifugation, greatly saved cost;

(2) synthetic method is simple, mild condition, and reaction at room temperature just can be carried out, and without the need to calcining, does not need large-scale precision equipment, is applicable to scale operation.

Accompanying drawing explanation

Fig. 1 is the XRD figure of gained one-D nano zinc oxide of the present invention:

As can be seen from XRD figure, the ZnO prepared is hexagonal system wurtzite structure, and all diffraction peaks all match with the standard diagram (PDF#65-3411) of ZnO, do not occur Zn (NO in figure ₃) ₂, Zn (OH) ₂deng other impurity peaks, illustrate that the purity of products obtained therefrom is very high, narrow and sharp-pointed diffraction peak shape shows that the crystallization quality of product is fine.

Fig. 2 is the TEM figure of the needle-shape nano zinc oxide of embodiment 1 gained, and better dispersed, length-to-diameter ratio is 13 ~ 15.

Fig. 3 is the TEM figure of the rod-like nano-zinc oxide of embodiment 2 gained, and pattern is petal-shaped, and length-to-diameter ratio is 2 ~ 3.

Fig. 4 is the TEM figure of the rod-like nano-zinc oxide of embodiment 3 gained, and very well dispersed, regular shape, length-to-diameter ratio can reach 15 ~ 20.

Fig. 5 is the TEM figure of the rod-like nano-zinc oxide of embodiment 4 gained, and pattern is corynebacterium, and length-to-diameter ratio is 3 ~ 4.

Embodiment

Embodiment 1

Compound concentration is the 0.5M zinc nitrate hexahydrate aqueous solution, concentration is the NaOH aqueous solution of 4M, the mol ratio of extraction agent PC-88A and N1923 is 1:1, the mixing solutions of preparation PN and heptane, the massfraction of PN is 16%, organic mixing solutions of 40mLPN and heptane is mixed with 10mL zinc salt solution, is placed in 250mL round-bottomed flask, stirring at room temperature 0.5h; Measure 5mLNaOH solution, be slowly added dropwise in mixing solutions, stirring velocity is adjusted to 600 revs/min, room temperature Keep agitation 2h simultaneously; After question response, centrifugation, filter, with ethanol, distilled water wash number time, be placed in baking oven 60 DEG C of dry 6h and obtain Zinc oxide powder, transmission electron microscope the results are shown in Figure 2.

Embodiment 2

Compound concentration is the 0.5M zinc nitrate hexahydrate aqueous solution, concentration is the NaOH aqueous solution of 4M, the mol ratio of extraction agent PC-88A and N1923 is 1:1, the mixing solutions of preparation PN and heptane, the massfraction of PN is 16%, organic mixing solutions of 40mLPN and heptane is mixed with 20mL zinc salt solution, is placed in 250mL round-bottomed flask, stirring at room temperature 0.5h; Measure 10mLNaOH solution, be slowly added dropwise in mixing solutions, stirring velocity is adjusted to 800 revs/min, room temperature Keep agitation 2h simultaneously; After question response, centrifugation, filter, with ethanol, distilled water wash number time, be placed in baking oven 60 DEG C of dry 6h and obtain Zinc oxide powder, transmission electron microscope the results are shown in Figure 3.

Embodiment 3

Compound concentration is the 0.5M zinc nitrate hexahydrate aqueous solution, concentration is the NaOH aqueous solution of 4M, the mol ratio of extraction agent PC-88A and N1923 is 1:1, the mixing solutions of preparation PN and heptane, the massfraction of PN is 16%, organic mixing solutions of 40mLPN and heptane is mixed with 30mL zinc salt solution, is placed in 250mL round-bottomed flask, stirring at room temperature 0.5h; Measure 15mLNaOH solution, be slowly added dropwise in mixing solutions, stirring velocity is adjusted to 700 revs/min, room temperature Keep agitation 2h simultaneously; After question response, centrifugation, filter, with ethanol, distilled water wash number time, be placed in baking oven 60 DEG C of dry 6h and obtain Zinc oxide powder, transmission electron microscope the results are shown in Figure 4.

Embodiment 4

Compound concentration is the 0.5M zinc nitrate hexahydrate aqueous solution, concentration is the NaOH aqueous solution of 4M, the mol ratio of extraction agent PC-88A and N1923 is 3:1, the mixing solutions of preparation PN and heptane, the massfraction of PN is 16%, organic mixing solutions of 40mLPN and heptane is mixed with 20mL zinc salt solution, is placed in 250mL round-bottomed flask, stirring at room temperature 0.5h; Measure 10mLNaOH solution, be slowly added dropwise in mixing solutions, stirring velocity is adjusted to 800 revs/min, room temperature Keep agitation 2h simultaneously; After question response, centrifugation, filter, with ethanol, distilled water wash number time, be placed in baking oven 60 DEG C of dry 6h and obtain Zinc oxide powder, transmission electron microscope the results are shown in Figure 5.

Embodiment 5

Compound concentration is the 0.5M zinc nitrate hexahydrate aqueous solution, concentration is the NaOH aqueous solution of 4M, the mol ratio of extraction agent PC-88A and N1923 is 2:1, the mixing solutions of preparation PN and heptane, the massfraction of PN is 16%, organic mixing solutions of 40mLPN and heptane is mixed with 20mL zinc salt solution, is placed in 250mL round-bottomed flask, stirring at room temperature 0.5h; Measure 10mLNaOH solution, be slowly added dropwise in mixing solutions, stirring velocity is adjusted to 800 revs/min, room temperature Keep agitation 2h simultaneously; After question response, centrifugation, filter, with ethanol, distilled water wash number time, be placed in baking oven 60 DEG C of dry 6h and obtain Zinc oxide powder, be rod-like nano-zinc oxide, length-to-diameter ratio is 5 ~ 8.

Embodiment 6

Compound concentration is the 0.5M zinc nitrate hexahydrate aqueous solution, concentration is the NaOH aqueous solution of 4M, the mol ratio of extraction agent PC-88A and N1923 is 2:1, the mixing solutions of preparation PN and heptane, the massfraction of PN is 16%, organic mixing solutions of 40mLPN and heptane is mixed with 10mL zinc salt solution, is placed in 250mL round-bottomed flask, stirring at room temperature 0.5h; Measure 5mLNaOH solution, be slowly added dropwise in mixing solutions, stirring velocity is adjusted to 600 revs/min, room temperature Keep agitation 2h simultaneously; After question response, centrifugation, filter, with ethanol, distilled water wash number time, be placed in baking oven 60 DEG C of dry 6h and obtain Zinc oxide powder, be rod-like nano-zinc oxide, length-to-diameter ratio is 9 ~ 12.

Claims

1. prepare a method for one-D nano zinc oxide, it is characterized in that comprising the steps:

(1) compound concentration is 0.5M zinc salt solution, and concentration is the aqueous sodium hydroxide solution of 4M;

(2) PN mixing solutions is prepared; In described PN mixing solutions, the mol ratio of extraction agent 2-ethylhexyl phosphonic acid-mono--2-(ethyl hexyl) ester and primary amine N1923 is 1-3:1;

(3) prepare the mixing solutions of PN and heptane, the massfraction of PN is 16%;

(4) mixed with the zinc solution of 0.5M by PN-n-heptane solution, the volume ratio of PN-n-heptane solution and zinc solution is: 4:1-4:3, makes it abundant mixing in stirred at ambient temperature;

(5) measure the NaOH aqueous solution of 4M, be slowly added drop-wise in mixing solutions, the volume ratio of zinc solution and NaOH solution is 2:1, stirring at room temperature;

(6) after question response, centrifugation, filters, and with ethanol, distilled water wash, is placed in baking oven dry, obtains the ZnO powder of white; Described drying refers to be placed in baking oven 60 DEG C of dry 6h.

2. a kind of method preparing one-D nano zinc oxide as claimed in claim 1, is characterized in that: described zinc salt, selects zinc nitrate hexahydrate.

3. a kind of method preparing one-D nano zinc oxide as claimed in claim 1, is characterized in that: the speed of the stirring at room temperature in described step 5 is 600 ~ 800 revs/min, and churning time is 2h.

4. a kind of method preparing one-D nano zinc oxide as claimed in claim 1, is characterized in that: the supernatant liquid PN obtained after described centrifugation and the mixing solutions purification process of heptane, recycling.

5. a kind of method preparing one-D nano zinc oxide as claimed in claim 1, is characterized in that: the length-to-diameter ratio of described one-D nano zinc oxide is 2-20.