CN102249286A

CN102249286A - Method for preparing zinc oxide micron sphere

Info

Publication number: CN102249286A
Application number: CN 201110160877
Authority: CN
Inventors: 王明松; 宋娟; 唐丽永
Original assignee: Jiangsu University
Current assignee: Jiangsu University
Priority date: 2011-06-16
Filing date: 2011-06-16
Publication date: 2011-11-23
Anticipated expiration: 2031-06-16
Also published as: CN102249286B

Abstract

The invention relates to a method for preparing a semiconductor oxide nano material, in particular to a method for preparing a zinc oxide micron sphere. In the method, ultrasonic activation treatment is not needed, the pH value of solution is adjusted and the appearance of a product is controlled by using NH4F, the solution is not needed to be diluted and the yield can be improved to the maximum extent; and the solution is not needed to be stirred in the water bath heat preservation process, the temperature of heat preservation can much lower than the boiling point of water, and the method contributes to large scale industrial production.

Description

A kind of preparation method of zinc oxide micrometer ball

Technical field

The present invention relates to the conductor oxidate preparation of nanomaterials, be specifically related to a kind of preparation method of zinc oxide micrometer ball.

Background technology

Zinc oxide (ZnO) is a kind of novel I I-VI family semiconductor material with wide forbidden band, nontoxicity, and raw material is cheap and easy to get, has excellent photoelectricity, piezoelectricity and dielectric characteristics; Nano-ZnO can be widely used as gas sensitive, catalytic material, anti-biotic material and photoelectric material etc., therefore become the popular research material in nanometer field over past ten years in the world, nano-ZnO is as air-sensitive, during photocatalyst material, require it to have big as far as possible specific surface area, to increase the contact area of ZnO and medium, thereby improve the sensitivity of gas sensor or strengthen the photochemical catalysis effect, the ZnO nanometer sheet of the tens of approximately nanometers of thickness is a kind of nanostructures with bigger serface, yet in use reduce effective contact area of ZnO and medium owing to the stack between nanometer sheet self, if the autonomous dress of nanometer sheet can be a kind of ball-like structure, then can keep the independence between each nanometer sheet, and can effectively overcome the reunion between ball and the ball, it will be a kind of ideal large-specific surface area nano structure, can be used for air-sensitive, field such as photochemical catalysis and dye sensitization solar battery, relevant nanometer sheet makes up the preparation of ZnO micron ball and has only a small amount of report, for example Chinese patent (CN 101249979 B) has been reported a kind of normal pressure water-bath preparation method of prickly sphere zinc oxide, this water-bath synthesis method needs the ultrasonic activation pre-treatment, solution needs thin up (efficient is low), bath temperature will reach boiling point and need and stir, offer (Journal of Crystal Growth 282 (2005) 165 – 172) in a separate paper and reported similar ZnO nanostructure, it is the solvent-thermal method of media that its preparation method adopts with the dehydrated alcohol, and solvent temperature is up to 190 ℃.

Summary of the invention

The object of the present invention is to provide a kind of nanometer sheet to make up the low temperature water-bath preparation method of ZnO micron ball, need not ultrasonic activation, stirring, this method energy consumption is little, equipment simple, need not solvent, productive rate height, good reproducibility, be easy to suitability for industrialized production.

For achieving the above object, in the technical scheme of the present invention, adopt low temperature water-bath legal system to be equipped with nanometer sheet and make up ZnO micron ball.

Above-mentioned a kind of nanometer sheet makes up the preparation method of ZnO micron ball, and concrete steps are:

1, the preparation of mixing solutions: with a certain amount of zinc salt, alkali and NH ₄F is dissolved in distilled water respectively, and above-mentioned solution is mixed, stirs, and makes mixed solution;

2, water bath heat preservation: the mixed solution that makes is left standstill insulation 10 ~ 24 hours in 60 ℃ ~ 100 ℃ water-bath;

3, cleaning-drying: will filter through the solution of water bath heat preservation, the cleaning and filtering thing, dry under 30 ℃ ~ 60 ℃ temperature.

Among the above-mentioned preparation method, zinc salt is Zn (NO in the step 1 ₃) ₂, Zn (CH ₃COO) ₂, ZnSO ₄, ZnCl ₂In a kind of; Alkali is a kind of among NaOH, the KOH.

Among the above-mentioned preparation method, the mol ratio of zinc salt and alkali is 0.1 ~ 0.3 in the step 1, NH ₄The mol ratio of F and alkali is 0.5 ~ 0.75.

Compared with the prior art, the invention has the advantages that:

Need not ultrasonic activation handles; With NH ₄F regulator solution pH value and control product pattern, solution need not dilution, can improve productive rate to greatest extent; Solution need not to stir in the water bath heat preservation process, and holding temperature can be convenient to large-scale industrial production far below the boiling point of water.

Description of drawings

Fig. 1 is the scanning electron microscope diagram that the nanometer sheet of embodiment 1 preparation makes up ZnO micron ball;

Fig. 2 is the EDS energy spectrum analysis figure that the nanometer sheet of embodiment 1 preparation makes up ZnO micron ball;

Fig. 3 is the scanning electron microscope diagram that the nanometer sheet of embodiment 2 preparations makes up ZnO micron ball;

Fig. 4 is the scanning electron microscope diagram that the nanometer sheet of embodiment 3 preparations makes up ZnO micron ball;

Fig. 5 is the scanning electron microscope diagram that the nanometer sheet of embodiment 4 preparations makes up ZnO micron ball.

Embodiment

The following examples are to further specify of the present invention, rather than limit the scope of the invention.

Embodiment 1:

1:0.1:0.75 takes by weighing a certain amount of NaOH, Zn (NO in molar ratio ₃) ₂, NH ₄F is dissolved in the distilled water respectively; Above-mentioned solution is mixed, stirs, make mixed solution; The mixed solution that makes is left standstill insulation 10 hours in 70 ℃ water-bath; To filter through the solution of water bath heat preservation, the cleaning and filtering thing, drying can obtain nanometer sheet and make up ZnO micron ball under 40 ℃ temperature; By shown in Figure 1, thick about 20 nm of nanometer sheet sheet, sphere diameter 1 ~ 4 μ m of the zinc oxide micrometer ball that is built into, Fig. 2 is the EDS energy spectrum analysis of this sample, does not detect impurity element, shows that prepared nanometer sheet makes up ZnO micron ball very high purity is arranged.

Embodiment 2:

1:0.15:0.6 takes by weighing a certain amount of NaOH, ZnSO in molar ratio ₄, NH ₄F is dissolved in the distilled water respectively; Above-mentioned solution is mixed, stirs, make mixed solution; The mixed solution that makes is left standstill insulation 15 hours in 80 ℃ water-bath; To filter cleaning and filtering thing, the dry ZnO micron ball that can obtain the nanometer sheet structure under 50 ℃ temperature through the solution of water bath heat preservation; As shown in Figure 3, thick about 20 nm of nanometer sheet, about 1.5 ~ 4 μ m of sphere diameter of micron ball.

Embodiment 3:

1:0.15:0.6 takes by weighing a certain amount of KOH, ZnCl in molar ratio ₂, NH ₄F is dissolved in the distilled water respectively; Above-mentioned solution is mixed, stirs, make mixed solution; The mixed solution that makes is left standstill insulation 10 hours in 90 ℃ water-bath; To filter through the solution of water bath heat preservation, the cleaning and filtering thing, drying can obtain nanometer sheet and make up ZnO micron ball under 40 ℃ temperature; As shown in Figure 4, thick about 20 nm of nanometer sheet sheet, about 1.5 ~ 4 μ m of sphere diameter of micron ball.

Embodiment 4:

1:0.2:0.5 takes by weighing a certain amount of NaOH, Zn (CH in molar ratio ₃COO) ₂, NH ₄F is dissolved in the distilled water respectively; Above-mentioned solution is mixed, stirs, make mixed solution; The mixed solution that makes is left standstill insulation 24 hours in 60 ℃ water-bath; To filter through the solution of water bath heat preservation, the cleaning and filtering thing, drying can obtain nanometer sheet and make up ZnO micron ball under 60 ℃ temperature; As shown in Figure 5, thick about 20 nm of nanometer sheet sheet sheet, about 1 ~ 2 μ m of sphere diameter.

Claims

1. the preparation method of a zinc oxide micrometer ball, described zinc oxide micrometer ball is made up by nanometer sheet and forms, and it is characterized in that comprising the steps:

(1) preparation of mixing solutions: with zinc salt, alkali and NH ₄F is dissolved in distilled water respectively, and above-mentioned solution is mixed, stirs, and makes mixed solution, and the mol ratio of zinc salt and alkali is 0.1 ~ 0.3, NH ₄The mol ratio of F and alkali is 0.5 ~ 0.75;

(2) water bath heat preservation: the mixed solution that makes is left standstill insulation 10 ~ 24 hours in 60 ℃ ~ 100 ℃ water-bath;

(3) cleaning-drying: will filter through the solution of water bath heat preservation, the cleaning and filtering thing, drying obtains the zinc oxide micrometer ball under 30 ℃ ~ 60 ℃ temperature.

2. the preparation method of a kind of zinc oxide micrometer ball as claimed in claim 1 is characterized in that: zinc salt is Zn (NO in the step (1) ₃) ₂, Zn (CH ₃COO) ₂, ZnSO ₄Or ZnCl ₂Alkali is NaOH or KOH.