CN100488875C - Batch synthesis method of hollow nanometer/micrometer zinc oxide ball - Google Patents
Batch synthesis method of hollow nanometer/micrometer zinc oxide ball Download PDFInfo
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- CN100488875C CN100488875C CNB2005101368011A CN200510136801A CN100488875C CN 100488875 C CN100488875 C CN 100488875C CN B2005101368011 A CNB2005101368011 A CN B2005101368011A CN 200510136801 A CN200510136801 A CN 200510136801A CN 100488875 C CN100488875 C CN 100488875C
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Abstract
The invention relates to the lot synthesis method for nano/micron ZnO hollow ball. Wherein, with Zn powder or ZnO powder as material, using simple chemical gas phase deposition to synthesize directly the product; adjusting the evaporating temperature of material, product deposition temperature or adding catalyst to realize original assembly synthesis. The product has well physical chemical performance and wide application in electronic device or other fields.
Description
Technical field
The invention belongs to nano material, inorganic synthetic chemistry crossed technical, relate to batch synthesis method with a kind of zinc-oxide nano/micrometre hollow sphere of CVD (Chemical Vapor Deposition) method synthesis of nano or micron zinc oxide functional materials.
Background technology
After ([Science, 282,1111,1998]) opened up soft template method synthetic silica hollow ball, the hollow ball synthetic technology obtained developing rapidly from Frank Cruso in 1998.
Hollow ball material has huge potential application foreground as a kind of special nanometer or micro materials in various fields, and one of its major function is exactly diffusion and the transmission that is used to control other material as a kind of packaged material.Particularly, these Nano/micron materials can be used for the release of control medicine in the guarantor's look, biological medicine of coating and pigment, also can be used as catalyzer and are used for the waste treatment aspect and are used for electron device as packaged material.
With regard to hollow ball material synthetic, the mode that generally adopts in the world is a template at present, this method at first forms spherical template, as micron or the solid bead of nanometer, colloid bead and phospholipid breast group etc., on these templates, adhere to other material then, mixture as materials such as metal or non-metal organic compound and these materials adopts heat treating method or chemical means to remove template at last and prepares hollow ball material.The shortcoming of template is that step is more, operation is longer.
Zinc oxide has very excellent in chemical crystal property, the forbidden band electronics energy gap and the higher exciton binding energy of better heat-resisting, weather-proof, unreactiveness, broad.The quantum self limiting of nanometer and micron zinc oxide material makes zinc oxide material show out better physical and chemical performance especially.These characteristics are basic reasons that zinc oxide material has wide application prospects in fields such as photodiode, piezoelectric, Field Emission Display, laser apparatus, rubber, medicine, catalyzer.At present, synthesizing in the whole world of the Nano/micron zinc oxide material of various forms is subjected to paying close attention to widely, and zinc oxide nano-belt, nanometer rod, nanotube, array and the zinc oxide material with various space structures emerge one after another.
In the synthesis technical field of Nano/micron hollow ball, also do not adopt the single stage method report of synthetic hollow ball in a large number at present.The present invention proposes to adopt monodimension nanometer material--the hollow zinc oxide sphere and the hemisphere material of a step chemical Vapor deposition process synthesizing zinc oxide, and its outstanding characteristics are technical parameters of control process more exactly.
Summary of the invention
Content of the present invention provides a kind of batch synthesis method of zinc-oxide nano/micrometre hollow sphere, it directly is raw material with the zinc powder, adopt simple direct synthesis of nano of one step of vapor deposition apparatus or micron Zinc oxide hollow spheres, hemisphere material, the technical parameter of control process more exactly.
The batch synthesis method of Zinc oxide hollow spheres is: (1) is higher than 99.2% zinc powder with pure zinc content and makes raw material, the order number of zinc powder is between the 500-1500 order, zinc powder is put into alcohol form mixture, the mass ratio of alcohol and zinc powder is between 0.1-0.5, directly be distributed on the surface of substrate then, the thickness of zinc powder is inserted in the chemical vapor deposition unit of being made up of quartz reactor, tube furnace, gas delivery regulation system then less than 2mm on the substrate;
(2) before the reaction, fully purge quartz reactor, require in the quartz reactor gas at least by displacement more than five times with argon gas or nitrogen.At flow velocity is under the protection of inert gas of 10-30m/h, the heat-up rate of control tube furnace is 50 ℃/min, be rapidly heated to temperature of reaction 500-800 ℃, when temperature reaches 400 ℃, the beginning aerating oxygen, the volumetric concentration of oxygen is controlled at the 0.01-0.1% of general gas flow, and the temperature of reaction that maintenance is scheduled to is constant, reaction times is 5-30min, and the Zinc oxide hollow spheres product of white original position on substrate generates;
The batch synthesis method of Zinc oxide hollow spheres, described substrate are any in graphite, silicon oxide or the silicon chip.Described temperature of reaction is 500-650 ℃.Described rare gas element is nitrogen or argon gas.
Institute of the present invention synthetic Zinc oxide hollow spheres, be a kind of diameter between 500nm-20 μ m, wall thickness is between the hollow ball-shape zinc oxide material of 50-200nm.
Preparation method of the present invention adopts the chemical vapour deposition principle: the oxidation-evaporation original position building-up process that with the zinc powder is raw material.Feature of the present invention is, the oxygen concentration of oxidation stage and the temperature of evaporative process are the key factors of controlled oxidation zinc hollow ball growth, therefore can be by add-on, the flow rate of carrier gas and the growthhabit that vaporization temperature is come controlled oxidation zinc hollow ball of regulation and control oxygen.The volumetric concentration of oxygen is controlled at the 0.01-0.1% of general gas flow, and the control of oxidizing temperature and vaporization temperature is then according to the concrete product needs of different shape; Oxidizing temperature is controlled at 400-500 ℃, and its height directly influences the production rate and the wall thickness of hollow ball.The temperature of evaporation stage is controlled at 600-800 ℃, and it just determines the form of product.With the rising gradually of temperature, the product that can prepare successively is respectively: hollow ball, hollow hemisphere, cage shape ball and class ball fragment.
Employed zinc powder particle diameter directly determines the size of product Zinc oxide hollow spheres in of the present invention, and the content of pure zinc is greater than 99.2% in the zinc powder; Zinc powder at graphite substrate or other on-chip placement thickness less than 2mm.The characteristics of this process are that original position is synthetic, and the product purity of Zinc oxide hollow spheres and yield height, form are changeable.
Method of the present invention can be by the add-on of regulation and control oxygen, flow velocity, vaporization temperature and the reaction times of carrier gas, realize the self-assembled growth of hollow ball and one-dimensional zinc oxide nanometer material, comprise the assembling of zinc oxide nano rod/hollow ball and the assembling of zinc oxide nano-belt/hollow ball.The self-assembly principle that relates to is: after Zinc oxide hollow spheres forms, there are superfluous active zinc species and oxygen in the reactor, they can continue to form monodimension nanometer material at the surface deposition of Zinc oxide hollow spheres, and this process can very effectively be improved the room temperature luminous performance of zinc oxide.
The Zinc oxide hollow spheres degree of purity of production that synthetic method of the present invention obtains is all greater than 90%.
The invention has the beneficial effects as follows: the present invention adopts simple gas phase deposition technology method to substitute the various template synthesis method of step, and a step is directly from large batch of high-purity Zinc oxide hollow spheres, the hemisphere material prepared of zinc powder.Building-up process of the present invention is easy to regulation and control, the form that the flow by adjusting work gas and reaction gas or the mode of catalyst inducement are come the controlled target product, and then realize the selectivity controlledly synthesis of hollow hemisphere, georama, sea urchin shape zinc oxide material.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples.
Fig. 1 is the typical scan electromicroscopic photograph of products therefrom of the present invention, and demonstration can prepare regular Zinc oxide hollow spheres of form and hemisphere in a large number, and illustration is a typical hollow hemisphere.
Fig. 2 is the stereoscan photograph of gained sea urchin shape zinc oxide assembled material of the present invention, and demonstration can prepare sea urchin shape Zinc oxide hollow spheres and hollow hemisphere in a large number.
Embodiment
Embodiment 1
The diameter of reactor is 20mm, the length 200mm of electric furnace.Argon gas (99.9%) flow 115sccm, oxygen (99.9%) flow 0.1sccm, graphite material be as the container and the deposition substrate of zinc powder, and the particle diameter of zinc powder is less than 25 μ m (pure zinc content〉99.2%), about the placement thickness 1.5mm of zinc powder.680 ℃ of temperature of reaction, reaction times 20min.Batch preparations obtains purified hollow ball shape and semisphere zinc oxide, and the form of product as shown in Figure 1.
Embodiment 2
The diameter of reactor is 20mm, the length 200mm of electric furnace.Argon gas (99.9%) flow 80sccm, oxygen (99.9%) flow 8sccm, graphite material be as the container and the deposition substrate of zinc powder, and the particle diameter of zinc powder is less than 25 μ m (pure zinc content〉99.2%), and the placement thickness of zinc powder is 3mm; 600 ℃ of temperature of reaction, reaction times 40min.Batch preparations obtains sea urchin shape zinc oxide hollow ball material, and this material is the assembly of zinc oxide nanowire and hollow ball, and the form of product as shown in Figure 2.
Claims (4)
1, a kind of batch synthesis method of zinc-oxide nano/micrometre hollow sphere, it is characterized in that: be higher than 99.2% zinc powder with pure zinc content and make raw material, the order number of zinc powder is between the 500-1500 order, zinc powder is put into alcohol form mixture, the mass ratio of alcohol and zinc powder is between 0.1-0.5, directly be distributed to then on the surface of substrate, the thickness of zinc powder is inserted in the chemical vapor deposition unit of being made up of quartz reactor, tube furnace and gas delivery regulation system then less than 2mm on the substrate; Before the reaction, fully purge quartz reactor, require in the quartz reactor atmosphere at least by displacement more than five times with rare gas element; Under the protection of rare gas element, the flow velocity of rare gas element is between 10-30m/h, and the heat-up rate of control tube furnace is 50 ℃/min, is rapidly heated to temperature of reaction 500-800 ℃; When temperature reaches 400 ℃, the beginning aerating oxygen, the volumetric concentration of oxygen is controlled at the 0.01-0.1% of general gas flow, and the temperature of reaction that maintenance is scheduled to is constant, reaction times is 5-30min, and the Zinc oxide hollow spheres product of white original position on substrate generates, when gas velocity is lower than 15m/h, zinc powder thickness surpasses after the 2mm on the substrate, can realize the self-assembled growth of hollow ball and one-dimension zinc oxide nanometer rod.
2, the batch synthesis method of a kind of zinc-oxide nano/micrometre hollow sphere according to claim 1 is characterized in that, described substrate is any in graphite, silicon oxide or the silicon chip.
3, the batch synthesis method of a kind of zinc-oxide nano/micrometre hollow sphere according to claim 1 is characterized in that, described temperature of reaction is 500-650 ℃.
4, the batch synthesis method of a kind of zinc-oxide nano/micrometre hollow sphere according to claim 1 is characterized in that, described rare gas element is nitrogen or argon gas.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101368011A CN100488875C (en) | 2005-12-29 | 2005-12-29 | Batch synthesis method of hollow nanometer/micrometer zinc oxide ball |
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| CNB2005101368011A CN100488875C (en) | 2005-12-29 | 2005-12-29 | Batch synthesis method of hollow nanometer/micrometer zinc oxide ball |
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| CN1803624A CN1803624A (en) | 2006-07-19 |
| CN100488875C true CN100488875C (en) | 2009-05-20 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497127B (en) * | 2008-02-03 | 2010-12-22 | 中国科学院金属研究所 | Method for preparing zinc-zinc oxide composite nanostructure |
| CN101704667B (en) * | 2009-11-13 | 2012-02-29 | 无锡泰达纺织科技有限公司 | Method for preparing magnetic ferrite hollow spheres used for removing microcystin |
| EP2361887A1 (en) * | 2010-02-25 | 2011-08-31 | Corning Incorporated | A process for manufacturing a doped or non-doped zno material and said material |
| CN107774266B (en) * | 2017-11-13 | 2020-03-17 | 山西洁泰达煤化工工程有限公司 | Preparation method and application of hollow zinc oxide coated copper catalyst |
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2005
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Non-Patent Citations (4)
| Title |
|---|
| Growth and Physical Characterization of Polygon PrismaticHollow Zn-ZnO Crystals. Kun-Ho Liu et al.Crystal Growth & Design,Vol.5 No.2. 2004 |
| Growth and Physical Characterization of Polygon PrismaticHollow Zn-ZnO Crystals. Kun-Ho Liu et al.Crystal Growth & Design,Vol.5 No.2. 2004 * |
| Mesoporous Polyhedral Cages and Shells Formed byTextured Self-Assembly of ZnO Nanocrystals. Pu Xian Gao et al.J.AM.CHEM.SOC,Vol.125 . 2003 |
| Mesoporous Polyhedral Cages and Shells Formed byTextured Self-Assembly of ZnO Nanocrystals. Pu Xian Gao et al.J.AM.CHEM.SOC,Vol.125 . 2003 * |
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