CN101817548A - Method for preparing zinc oxide hollow spheres - Google Patents
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- CN101817548A CN101817548A CN 201010162308 CN201010162308A CN101817548A CN 101817548 A CN101817548 A CN 101817548A CN 201010162308 CN201010162308 CN 201010162308 CN 201010162308 A CN201010162308 A CN 201010162308A CN 101817548 A CN101817548 A CN 101817548A
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Abstract
本发明公开了一种氧化锌空心球的制备方法。本发明制备方法为超声法，包括如下步骤：(1)将锌盐溶解在有机溶剂和水的混合溶剂中，进行超声反应；(2)将产物离心分离，经过水洗、醇洗、干燥，得到氧化锌空心球。本发明方法简单、方便、快速、重现性好，制得的氧化锌空心球可广泛用于催化、化学反应载体、药物输运、化妆品、涂料、太阳能电池等领域。利用本发明氧化锌空心球制备染料敏化太阳能电池具有成本低，原材料丰富，无毒无污染，部分材料可以回收等优点，对环境保护具有重要意义，在大面积工业化生产中具有较大优势。
The invention discloses a preparation method of zinc oxide hollow spheres. The preparation method of the present invention is an ultrasonic method, comprising the following steps: (1) dissolving the zinc salt in a mixed solvent of an organic solvent and water, and performing an ultrasonic reaction; (2) centrifuging the product, washing with water, washing with alcohol, and drying to obtain Zinc oxide hollow spheres. The method of the invention is simple, convenient, fast and has good reproducibility, and the prepared zinc oxide hollow spheres can be widely used in the fields of catalysis, chemical reaction carrier, drug delivery, cosmetics, paint, solar cells and the like. The preparation of dye-sensitized solar cells by using the zinc oxide hollow spheres of the present invention has the advantages of low cost, rich raw materials, non-toxicity and pollution-free, and some materials can be recycled. It is of great significance to environmental protection and has great advantages in large-scale industrial production.
Description
Technical field
The present invention relates to the zinc oxide nano-particle field, be specifically related to a method for preparing zinc oxide hollow spheres.
Background technology
The preparation method of Zinc oxide hollow spheres mainly contains hydrothermal method, template agent method (hard mould agent or soft template), high temperature vapour deposition process etc., but its synthetic time-consuming and power consumption, and for the applied research of hollow ball also seldom.
Sonochemistry is widely used for preparing the nano material of various patterns as a kind of high efficient and convenient synthetic method." acoustic cavitation " effect that ultrasound wave irradiation produces, in the extremely short time, in the little space around the cavitation bubble, to produce high temperature 5000K and the high pressure (20MPa) of moment and surpass the speed of cooling of 1010K/S. and the shockwave of accompanied by intense, jet and photoelectric action, the high-temperature and high-pressure conditions that this moment produces has represented the incomparable advantage of additive method in novel material is synthetic. as effective control pattern, accelerate speed of reaction, productive rate height, easy to operate and clean environment firendly etc.If the sonochemistry method can be used to prepare Zinc oxide hollow spheres, might make the performance of Zinc oxide hollow spheres of gained better, and the preparation method is also simple before.
Summary of the invention
The objective of the invention is to synthetic loaded down with trivial detailsly according to what exist in the existing method that prepare Zinc oxide hollow spheres, the big shortcoming that consumes energy provides a kind of simple and convenient quick and can improve the preparation method of Zinc oxide hollow spheres performance.
The object of the invention is achieved by the following technical programs:
One method for preparing zinc oxide hollow spheres comprises the steps: that (1) is dissolved in zinc salt in the mixed solvent of organic solvent and water, carries out ultrasonic reaction; (2) with the product centrifugation, process washing, alcohol are washed, drying, obtain Zinc oxide hollow spheres.
Utilize ultrasonic method of the present invention to prepare by zinc oxide nano-particle (10～50nm) Zinc oxide hollow spheres of forming (100～1000nm).
As a kind of preferred version, among the above-mentioned preparation method, described zinc salt is zinc acetate, zinc nitrate, zinc chloride or zinc sulfate, and the volumetric molar concentration of zinc salt is 0.005～0.5mol/L.
As a kind of preferred version, among the above-mentioned preparation method, described organic solvent is dimethyl sulfoxide (DMSO), N, dinethylformamide, glycol ether, ethylene glycol or glycerol; Wherein, the volume of water accounts for 5～95 volume % of mixed solvent volume.
As a kind of preferred version, among the above-mentioned preparation method, described ultrasonic reaction is finished by ultrasonic apparatus, and the power of ultrasonic apparatus is 50～500W, and amplitude is 10～90%.
As a kind of preferred version, among the above-mentioned preparation method, the time of described ultrasonic reaction is 1～180min.
As a kind of preferred version, among the above-mentioned preparation method, described exsiccant temperature is 20～100 ℃.
The Zinc oxide hollow spheres that the inventive method makes utilizes X-ray powder diffraction, scanning electron microscope, transmission electron microscope to carry out detailed sign.
The growth mechanism of described Zinc oxide hollow spheres is first through overbunching, is promptly assembled forming solid sphere by the zinc oxide nano-particle assembling, and then through the oersted maturing process, finally forms hollow ball structure.
The Zinc oxide hollow spheres that the inventive method makes can be widely used in fields such as catalysis, chemical reaction carrier, drug delivery, makeup, coating, solar cell.When especially being used for field of dye-sensitized solar cells, has higher photoelectric transformation efficiency than conventional zinc oxide nano-particle as the light anode.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention utilizes ultrasonic method to prepare the classification Zinc oxide hollow spheres, and the ultrasonic method of classification Zinc oxide hollow spheres has synthetic method and reaches high repeatability and other advantages simply, easily and fast;
(2) utilize institute's synthetic Zinc oxide hollow spheres to obtain the photoelectric transformation efficiency higher than conventional zinc oxide nano-particle, higher by 38.8% than traditional nanoparticle;
(3) Zinc oxide hollow spheres of preparation method's gained of the present invention can be used to prepare dye-sensitized solar cells; this battery mainly is an imitation photosynthesis principle; a kind of novel solar cell of developing; its main advantage is: abundant raw materials, cost is low, Technology is simple relatively; in the big area suitability for industrialized production, has bigger advantage; all raw material and production technique all are nontoxic, free of contamination simultaneously; the part material can be reclaimed fully, and the protection human environment is had great importance.
Description of drawings
Fig. 1 is the XRD figure of the Zinc oxide hollow spheres after the differential responses time; (a) 3min, (b) 10min, (c) 30min, (d) 1h;
Fig. 2 is the SEM of the Zinc oxide hollow spheres behind the ultrasonic reaction 30min, TEM figure; (a) scanning electron microscope (SEM) figure, (b) low power transmission electron microscope (TEM) figure, (c) TEM of single Zinc oxide hollow spheres figure, (d) high-resolution-ration transmission electric-lens (HRTEM) figure;
Fig. 3 is the sem photograph of different ultrasonic reaction time synthetic Zinc oxide hollow spheres; (a)～(b) 3min, (c)-(d) 10min, (e)～(f) 1h;
Fig. 4 is the relation of dye sensitization solar battery photoelectric transformation efficiency and Zinc oxide hollow spheres thickness.
Embodiment
Further explain the present invention below in conjunction with embodiment, but embodiment does not do any type of qualification to the present invention.
Embodiment
Utilize zinc acetate, dimethyl sulfoxide (DMSO), water as raw material, utilize ultrasound wave irradiation to synthesize the classification Zinc oxide hollow spheres.Claim the 1.098g zinc acetate to put into the beaker of a 100ml, add the 47.5ml dimethyl sulfoxide (DMSO), add 2.5ml water again, the probe of ultrasonic cell disruption instrument is put into beaker, and be 300W with its power regulation, it is 8s that ultrasound mode is set, the time is 1h, ultrasonic end back centrifugation extracting waste precipitation, washing, alcohol are washed each 3 times again.Get final product 60 ℃ of oven dry.
Dried white powder is directly used in the XRD test, judge its crystal formation, found that prepared zinc oxide is the wurtzite structure (see figure 1), observe its pattern with scanning electron microscope, measure its pattern and crystalline structure (Fig. 2) with transmission electron microscope, the classification Zinc oxide hollow spheres of finding submicron-scale is molecular by nanoparticle, and wherein nano-particles size is about 15 nanometers, and hollow ball is of a size of 500 nanometers.Observe the pattern (Fig. 3) of the sample of differential responses time by scanning electron microscope, and the growth mechanism of hollow ball is discussed, find that Zinc oxide hollow spheres forms through overbunching and oersted maturing process.
Ethyl cellulose, Terpineol 350 and ethanol are joined in the Zinc oxide hollow spheres, grind 30min and form slurry.
Utilize silk screen print method that zinc oxide slurry is coated in through on the conductive glass that cleans, then 500 ℃ of calcination, the thickness of zinc oxide can be regulated and control by printing different number of times.
Being coated in Zinc oxide film on the conductive glass through calcining is placed in the N719 dyestuff of 0.5mM and soaks 15～24h, conductive glass (counter electrode) with deposition Pt fits together then, and the adding ionogen (prescription of electrolytic solution: 0.6mol/L PMII, 0.03mol/L I
2, it is in 85: 15 the acetonitrile and valeronitrile mixed solution that 0.05mol/L LiI, 0.1mol/L Guanidiniumthiocyanate (GuSCN), 0.5mol/L 4-tert-butylpyridine (TBP) are dissolved in volume ratio), promptly can be used to the testing photoelectronic efficiency of conversion.The photoelectric transformation efficiency of gained and the thickness of Zinc oxide hollow spheres have the (see figure 4) of relation, the highest photoelectric transformation efficiency is 4.33%, it is based on the Zinc oxide hollow spheres of 9.1 micron thickness, than with the photoelectric transformation efficiency (3.12%) of the zinc oxide nano-particle of 9.0 micron thickness high about 38.8%.
Claims (8)
1. a method for preparing zinc oxide hollow spheres is characterized in that described preparation method is a ultrasonic method, comprises the steps: that (1) is dissolved in zinc salt in the mixed solvent of organic solvent and water, carries out ultrasonic reaction; (2) with the product centrifugation, process washing, alcohol are washed, drying, obtain Zinc oxide hollow spheres.
2. according to the preparation method of the described Zinc oxide hollow spheres of claim 1, it is characterized in that described Zinc oxide hollow spheres is of a size of 100～1000nm, the nano-particles size of forming hollow ball is 10～50nm.
3. according to the preparation method of the described Zinc oxide hollow spheres of claim 1, it is characterized in that described zinc salt is zinc acetate, zinc nitrate, zinc chloride or zinc sulfate, the volumetric molar concentration of zinc salt is 0.005～0.5mol/L.
4. according to the preparation method of the described Zinc oxide hollow spheres of claim 1, the mixed solvent that it is characterized in that described organic solvent and water is dimethyl sulfoxide (DMSO), N, the mixed solvent of dinethylformamide, glycol ether, ethylene glycol or glycerol and water.
5. according to the preparation method of claim 1 or 4 described Zinc oxide hollow spheres, it is characterized in that in the mixed solvent of described organic solvent and water that the volume of water accounts for 5～95 volume % of mixed solvent volume.
6. according to the preparation method of the described Zinc oxide hollow spheres of claim 1, it is characterized in that described ultrasonic reaction finishes by ultrasonic apparatus, the power of ultrasonic apparatus is 50～500W, amplitude is 10～90%.
7. according to the preparation method of the described Zinc oxide hollow spheres of claim 1, the time that it is characterized in that described ultrasonic reaction is 1～180min.
8. according to the preparation method of the described Zinc oxide hollow spheres of claim 1, it is characterized in that described exsiccant temperature is 20～100 ℃.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102005305A (en) * | 2010-12-01 | 2011-04-06 | 北京科技大学 | Preparation Method of Al2O3 Modified ZnO Nanoporous Thin Film Composite Electrode |
| CN102311142A (en) * | 2011-07-22 | 2012-01-11 | 哈尔滨工程大学 | Method for preparing zinc oxide hollow ball with in situ gas growth |
| CN102398916A (en) * | 2010-09-07 | 2012-04-04 | 中国科学院上海硅酸盐研究所 | Low-temperature synthesis method of zinc oxide hollow ball |
| CN102807249A (en) * | 2011-06-01 | 2012-12-05 | 国家纳米科学中心 | Method for controlling shapes of zinc oxide nanoparticles |
| CN102849780A (en) * | 2012-09-11 | 2013-01-02 | 南京工业大学 | Method for synthesizing ZnO nanostructure by using organic weak base |
| CN103771490A (en) * | 2014-01-04 | 2014-05-07 | 东华理工大学 | Simple method for preparing micrometer/nanometer zinc oxide by stirring at room temperature |
| US8795695B2 (en) | 2011-08-15 | 2014-08-05 | The Procter & Gamble Company | Personal care methods |
| CN105645458A (en) * | 2016-01-12 | 2016-06-08 | 浙江师范大学 | Monodisperse ZnO micro/nano material, and preparation method and application thereof |
| CN106366817A (en) * | 2016-09-30 | 2017-02-01 | 陕西科技大学 | Preparation method of polyacrylate and peanut-shaped hollow zinc oxide composited leather finishing agent |
| CN108101101A (en) * | 2018-02-06 | 2018-06-01 | 西安理工大学 | A kind of preparation method of porous coniform ZnO nano powder |
| CN109081368A (en) * | 2018-08-10 | 2018-12-25 | 浙江大学 | A kind of preparation method of BTA- zinc oxide composite powder |
| CN110078112A (en) * | 2019-05-08 | 2019-08-02 | 中国航空发动机研究院 | By the preparation method for the ZnO microsphere that nano dot forms |
| CN113135586A (en) * | 2021-04-21 | 2021-07-20 | 内蒙古大学 | Zinc oxide micron ball, electrode and preparation method thereof |
-
2010
- 2010-04-27 CN CN 201010162308 patent/CN101817548A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 《Materials Letters》 20100120 Chonghai Deng et al. Facile template-free sonochemical fabrication of hollow ZnO spherical structures "2.Experimental"部分、第853页第29～53行、图2a,2b,3a-3d 1～8 第64卷, 2 * |
| 《Ultrasonics Sonochemistry》 20090926 Xiaohua Jia et al. Using sonochemistry for the fabrication of hollow ZnO microspheres 第284～287页 1～8 第17卷, 2 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102398916A (en) * | 2010-09-07 | 2012-04-04 | 中国科学院上海硅酸盐研究所 | Low-temperature synthesis method of zinc oxide hollow ball |
| CN102398916B (en) * | 2010-09-07 | 2013-10-30 | 中国科学院上海硅酸盐研究所 | Low-temperature synthesis method of zinc oxide hollow ball |
| CN102005305B (en) * | 2010-12-01 | 2012-12-05 | 北京科技大学 | Preparation Method of Al2O3 Modified ZnO Nanoporous Thin Film Composite Electrode |
| CN102005305A (en) * | 2010-12-01 | 2011-04-06 | 北京科技大学 | Preparation Method of Al2O3 Modified ZnO Nanoporous Thin Film Composite Electrode |
| CN102807249A (en) * | 2011-06-01 | 2012-12-05 | 国家纳米科学中心 | Method for controlling shapes of zinc oxide nanoparticles |
| CN102807249B (en) * | 2011-06-01 | 2014-04-16 | 国家纳米科学中心 | Method for controlling shapes of zinc oxide nanoparticles |
| CN102311142A (en) * | 2011-07-22 | 2012-01-11 | 哈尔滨工程大学 | Method for preparing zinc oxide hollow ball with in situ gas growth |
| US8795695B2 (en) | 2011-08-15 | 2014-08-05 | The Procter & Gamble Company | Personal care methods |
| CN102849780A (en) * | 2012-09-11 | 2013-01-02 | 南京工业大学 | Method for synthesizing ZnO nanostructure by using organic weak base |
| CN103771490A (en) * | 2014-01-04 | 2014-05-07 | 东华理工大学 | Simple method for preparing micrometer/nanometer zinc oxide by stirring at room temperature |
| CN103771490B (en) * | 2014-01-04 | 2015-08-19 | 东华理工大学 | A kind of simple and easy stirring at room temperature prepares the method for micro-/ nano zinc oxide |
| CN105645458A (en) * | 2016-01-12 | 2016-06-08 | 浙江师范大学 | Monodisperse ZnO micro/nano material, and preparation method and application thereof |
| CN106366817A (en) * | 2016-09-30 | 2017-02-01 | 陕西科技大学 | Preparation method of polyacrylate and peanut-shaped hollow zinc oxide composited leather finishing agent |
| CN106366817B (en) * | 2016-09-30 | 2019-02-01 | 陕西科技大学 | A kind of preparation method of polyacrylate/peanut shape hollow zinc composite leather coating agent |
| CN108101101A (en) * | 2018-02-06 | 2018-06-01 | 西安理工大学 | A kind of preparation method of porous coniform ZnO nano powder |
| CN109081368A (en) * | 2018-08-10 | 2018-12-25 | 浙江大学 | A kind of preparation method of BTA- zinc oxide composite powder |
| CN110078112A (en) * | 2019-05-08 | 2019-08-02 | 中国航空发动机研究院 | By the preparation method for the ZnO microsphere that nano dot forms |
| CN113135586A (en) * | 2021-04-21 | 2021-07-20 | 内蒙古大学 | Zinc oxide micron ball, electrode and preparation method thereof |
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Open date: 20100901 |