CN100408480C

CN100408480C - A kind of preparation method of nano zinc oxide powder

Info

Publication number: CN100408480C
Application number: CNB2006100293671A
Authority: CN
Inventors: 储德韦; 曾宇平; 江东亮
Original assignee: Shanghai Institute of Ceramics of CAS
Current assignee: Shanghai Institute of Ceramics of CAS
Priority date: 2006-07-26
Filing date: 2006-07-26
Publication date: 2008-08-06
Anticipated expiration: 2026-07-26
Also published as: CN1887720A

Abstract

本发明涉及一种制备纳米氧化锌粉体的方法，其特征在于：将可溶解于无水乙醇的锌盐，溶解于无水乙醇中，配制成浓度为0.1wt%～10wt%的悬浊液；将氢氧化钾或氢氧化钠配制成摩尔浓度为3倍于锌盐的乙醇悬浊液；将十六烷基三甲基溴化铵表面活性剂加入到上述锌盐悬浊液中，加入量为锌盐质量的0.1wt%～1.0wt%；在60℃～70℃下，将锌盐溶液剧烈搅拌，并将强碱悬浊液逐滴加入锌盐悬浊液中，得到白色浑浊液。反应完全后，将浑浊溶液冷却至25℃，静置，分离反应溶液。用去离子水对分离物充分洗涤，再用无水乙醇对分离物充分洗涤、干燥。本发明只有一步反应，通过控制滴定速度，反应物浓度及反应温度，可以控制纳米氧化锌颗粒的大小。The invention relates to a method for preparing nanometer zinc oxide powder, which is characterized in that: dissolving zinc salt soluble in absolute ethanol in absolute ethanol, and preparing a suspension with a concentration of 0.1wt% to 10wt% Potassium hydroxide or sodium hydroxide is mixed with the ethanol suspension liquid that molar concentration is 3 times of zinc salt; Cetyltrimethylammonium bromide surfactant is joined in above-mentioned zinc salt suspension liquid, adds The amount is 0.1wt% to 1.0wt% of the zinc salt mass; at 60°C to 70°C, vigorously stir the zinc salt solution, and add the strong alkali suspension to the zinc salt suspension drop by drop to obtain a white turbid solution . After the reaction was complete, the cloudy solution was cooled to 25° C., allowed to stand, and the reaction solution was separated. Fully wash the isolate with deionized water, then fully wash the isolate with absolute ethanol, and dry. The invention has only one-step reaction, and can control the size of nanometer zinc oxide particles by controlling the titration speed, reactant concentration and reaction temperature.

Description

一种纳米氧化锌粉体的制备方法 A kind of preparation method of nano zinc oxide powder

技术领域 technical field

本发明涉及一种纳米氧化锌粉体的制备方法，属于纳米粉体领域。The invention relates to a preparation method of nano zinc oxide powder, which belongs to the field of nano powder.

背景技术 Background technique

纳米氧化锌粉体由于晶粒的细化，其表面电子结构和晶体结构发生变化，产生了宏观材料所不具有的表面效应、体积效应、量子尺寸效应和宏观隧道效应。同时氧化锌是一种多功能性的新型无机材料，在陶瓷、化工、纺织、电子、光学等许多领域有重要的用途。纳米氧化锌是一种典型的半导体材料，具有屏蔽红外线、吸收紫外线抗菌的功能，已被广泛应用于防晒化妆品、功能纤维、自洁抗菌玻璃、卫生洁具等产品中。此外纳米氧化锌还可以用作太阳能电池的电极材料。Due to the refinement of the crystal grains, the surface electronic structure and crystal structure of nano-zinc oxide powder change, resulting in surface effects, volume effects, quantum size effects and macroscopic tunnel effects that macroscopic materials do not have. At the same time, zinc oxide is a multifunctional new inorganic material, which has important uses in many fields such as ceramics, chemicals, textiles, electronics, and optics. Nano-zinc oxide is a typical semiconductor material, which has the functions of shielding infrared rays, absorbing ultraviolet rays and antibacterial, and has been widely used in sunscreen cosmetics, functional fibers, self-cleaning antibacterial glass, sanitary ware and other products. In addition, nano-zinc oxide can also be used as an electrode material for solar cells.

纳米氧化锌具有良好的功能性的前提是粒径小，颗粒分布均匀、分散性好。目前制备纳米氧化锌粉体的方法主要有沉淀法、水热法、溶胶-凝胶法、喷雾热解法等。这些方法由于所用的原料或设备价格较高而使工业化生产受到限制。同时需要解决批量生产时防止粉体硬团聚的问题。The premise of good functionality of nano-zinc oxide is that the particle size is small, the particle distribution is uniform, and the dispersion is good. At present, the methods for preparing nano zinc oxide powder mainly include precipitation method, hydrothermal method, sol-gel method, spray pyrolysis method and so on. These methods make industrial production limited due to the high price of raw materials or equipment used. At the same time, it is necessary to solve the problem of preventing hard agglomeration of powder during mass production.

直接沉淀法是上述制备方法中工艺最简单的一种纳米氧化锌粉体的制备方法，该法操作简便、对设备要求低，容易批量生产，适合工业化生产。但沉淀法的缺点是粉体很容易团聚。由于沉淀物中通常夹杂着各种无机离子(如Na⁺、OH^-、Cl^-、SO₄ ^2-等)，尤其是OH^-、Cl^-离子等极易使沉淀的颗粒在干燥过程中由于氢键、氯桥的作用而团聚在一起，煅烧后会形成难以分散的硬团聚体，如控制不当，会使产品团聚很严重。因此，设计合适的沉淀反应并研究防团聚工艺对改善沉淀法制备的纳米粉体的性能有重要意义。The direct precipitation method is the simplest method for preparing nano-zinc oxide powder among the above-mentioned preparation methods. This method is easy to operate, has low requirements on equipment, is easy to produce in batches, and is suitable for industrial production. But the disadvantage of the precipitation method is that the powder is easy to agglomerate. Since the precipitate is usually mixed with various inorganic ions (such as Na ⁺ , OH ^- , Cl ^- , SO ₄ ^2- , etc.), especially OH ^- , Cl ^- ions, etc., it is very easy for the precipitated particles to be damaged by hydrogen during the drying process. Bonds, chlorine bridges and agglomerates together, hard aggregates that are difficult to disperse will be formed after calcination, if not properly controlled, the product will be agglomerated seriously. Therefore, it is of great significance to design a suitable precipitation reaction and study the anti-agglomeration process to improve the performance of nanopowders prepared by precipitation.

本发明人设想能否利用廉价的锌盐和常见的强碱及乙醇为原料，在乙醇沸点以下直接沉淀得到纳米氧化锌粉体，不存在常见的沉淀法中前驱体团聚的问题；同时由于无需煅烧，也不存在煅烧后硬团聚的问题，而且减少设备和能源的投入，可显著降低生产成本，从而引导出本发明的构思。The present inventor imagines whether it is possible to use cheap zinc salts, common strong bases and ethanol as raw materials to obtain nano-zinc oxide powders by direct precipitation below the boiling point of ethanol, without the problem of precursor agglomeration in the common precipitation method; Calcination does not have the problem of hard agglomeration after calcination, and the investment in equipment and energy can be reduced, which can significantly reduce production costs, thereby leading to the idea of the present invention.

发明内容 Contents of the invention

本发明的目的在于提供一种简便的纳米氧化锌粉体的制备方法。The object of the present invention is to provide a kind of simple and convenient preparation method of nano-zinc oxide powder.

本发明的制备纳米氧化锌粉体的方法，其特征是包括以下制备步骤：The method for preparing nano zinc oxide powder of the present invention is characterized in that it comprises the following preparation steps:

(1)把可溶解于无水乙醇的锌盐，如醋酸锌，硝酸锌或氯化锌中的一种溶解于无水乙醇中，在20℃～30℃条件下充分搅拌，配制成浓度为0.1wt％～10wt％的悬浊液，选择此范围内的浓度的依据是，浓度低于0.1wt％时产量太低无实际意义，浓度高于10wt％后悬浊液分散困难，且所得的产物粒度不均匀；室温下将氢氧化钾或氢氧化钠等强碱配制成摩尔浓度3倍于锌盐的乙醇悬浊液；(1) Dissolve a zinc salt soluble in absolute ethanol, such as zinc acetate, zinc nitrate or zinc chloride, in absolute ethanol, fully stir at 20°C to 30°C, and prepare a concentration of 0.1wt% to 10wt% suspension, the basis for selecting the concentration within this range is that the yield is too low when the concentration is lower than 0.1wt%, and there is no practical significance, and the suspension is difficult to disperse after the concentration is higher than 10wt%, and the obtained The particle size of the product is uneven; at room temperature, a strong base such as potassium hydroxide or sodium hydroxide is prepared into an ethanol suspension with a molar concentration 3 times that of the zinc salt;

(2)将表面活性剂的一种，如十六烷基三甲基溴化铵加入到上述锌盐悬浊液中，加入量为锌盐质量的0.1wt％～1.0wt％。十六烷基三甲基溴化铵是一种表面活性剂，在粉体颗粒之间起空间位阻作用，可以提高产物的分散性，并使合成的氧化锌纳米粉体粒度更均匀.(2) Add one kind of surfactant, such as cetyltrimethylammonium bromide, to the zinc salt suspension, in an amount of 0.1wt% to 1.0wt% of the zinc salt mass. Cetyltrimethylammonium bromide is a surfactant that acts as a steric hindrance between powder particles, which can improve the dispersion of the product and make the particle size of the synthesized zinc oxide nanopowder more uniform.

(3)在60℃～70℃下，将锌盐悬浊液剧烈搅拌，并将氢氧化钾悬浊液或氢氧化钠等强碱悬浊液逐滴加入含表面活性剂的锌盐悬浊液中反应，温度维持在60-70℃之间，最后得到白色浑浊液。(3) Stir the zinc salt suspension vigorously at 60°C to 70°C, and add the strong alkali suspension such as potassium hydroxide or sodium hydroxide dropwise into the zinc salt suspension containing surfactant React in the liquid, the temperature is maintained between 60-70 ° C, and finally a white turbid liquid is obtained.

(4)反应完全后，将浑浊液冷却至25℃，静置，分离浑浊液。(4) After the reaction is complete, cool the turbid solution to 25°C, let it stand, and separate the turbid solution.

(5)用去离子水对分离物充分洗涤，再用无水乙醇对分离物充分洗涤，20℃～30℃下干燥，即可得到纳米氧化锌粉体。(5) Fully wash the isolate with deionized water, then fully wash the isolate with absolute ethanol, and dry at 20° C. to 30° C. to obtain nano zinc oxide powder.

本发明具有以下优点：The present invention has the following advantages:

1、制备纳米氧化锌的原料成本低廉，工艺非常简便，不需要复杂设备。1. The cost of raw materials for preparing nano-zinc oxide is low, the process is very simple, and no complicated equipment is required.

2、所制备纳米氧化锌的形貌均匀，分散性明显优于常规沉淀法制备的纳米氧化锌粉体，不存在常见的沉淀法中前驱体团聚的问题。颗粒直径在15-20nm左右，通过调节反应物浓度、滴定速度、搅拌速度可以控制纳米氧化锌颗粒的大小。在锌盐浓度从1％提高到5％时，产物粒径约增大10nm。滴定速度控制在0.5mol/min较合适.搅拌速度可控制在400-1000转/分。2. The morphology of the prepared nano-zinc oxide is uniform, and the dispersibility is obviously better than that of the nano-zinc oxide powder prepared by the conventional precipitation method, and there is no problem of precursor agglomeration in the common precipitation method. The diameter of the particles is about 15-20nm, and the size of the nano-zinc oxide particles can be controlled by adjusting the reactant concentration, titration speed, and stirring speed. When the zinc salt concentration increased from 1% to 5%, the particle size of the product increased by about 10nm. It is more appropriate to control the titration speed at 0.5mol/min. The stirring speed can be controlled at 400-1000 rpm.

3、反应温度低于乙醇的沸点，不产生污染物，乙醇可以回收利用。不存在沉淀法中前驱体团聚问题。3. The reaction temperature is lower than the boiling point of ethanol, no pollutants are produced, and ethanol can be recycled. There is no problem of precursor agglomeration in the precipitation method.

附图说明 Description of drawings

图1是产物的X射线衍射图谱，Fig. 1 is the X-ray diffraction pattern of product,

图2是产物的透射电子显微镜照片。Figure 2 is a transmission electron micrograph of the product.

具体实施方式 Detailed ways

下面通过具体实施例，进一步阐明本发明实质性特点和显著的进步。Below through specific embodiment, substantive characteristic and remarkable progress of the present invention are further illustrated.

实施例1Example 1

将醋酸锌溶解于无水乙醇中，25℃下充分搅拌配制成浓度为1.0％的悬浊液，同时在20℃室温下将氢氧化钠溶解于无水乙醇中，配制成3.0％的氢氧化钠悬浊液。用分液漏斗将氢氧化钠溶液逐滴滴加到搅拌着的70℃醋酸锌溶液，滴定速度为0.5mol/min混合溶液维持在70℃。反应完全后将上述溶液离心分离，白色沉淀用去离子水和无水乙醇充分洗涤，30℃干燥，即获得纳米氧化锌粉体。产物的X射线衍射图谱及透射电子显微镜(TEM)照片见图1，2。Dissolve zinc acetate in absolute ethanol, stir well at 25°C to prepare a suspension with a concentration of 1.0%, and at the same time dissolve sodium hydroxide in absolute ethanol at 20°C to prepare a 3.0% hydroxide sodium suspension. Use a separatory funnel to add the sodium hydroxide solution dropwise to the stirred zinc acetate solution at 70°C, the titration rate is 0.5mol/min and the mixed solution is maintained at 70°C. After the reaction is complete, the above solution is centrifuged, the white precipitate is fully washed with deionized water and absolute ethanol, and dried at 30°C to obtain nano zinc oxide powder. The X-ray diffraction patterns and transmission electron microscope (TEM) photos of the product are shown in Figures 1 and 2.

实施例2Example 2

将硝酸锌替代醋酸锌，其余同实施例1。所得纳米ZnO的X衍射图和TEM照片与图1、图2雷同。Zinc nitrate is replaced zinc acetate, all the other are with embodiment 1. The X-ray diffractogram and TEM photo of the obtained nano-ZnO are the same as those in Fig. 1 and Fig. 2 .

Claims

1. 一种纳米氧化锌粉体的制备方法，其特征在于：1. A preparation method of nano zinc oxide powder, characterized in that:

(1)将可溶解于无水乙醇的锌盐中一种溶解于无水乙醇中，经搅拌，配制成浓度为0.1wt％-10wt％的悬浊液；(1) dissolving one of the zinc salts soluble in absolute ethanol in absolute ethanol, and stirring to prepare a suspension with a concentration of 0.1wt%-10wt%;

(2)将KOH或NaOH配制成摩尔浓度3倍于步骤(1)配制的乙醇悬浊液；(2) KOH or NaOH are mixed into the ethanol suspension that the molar concentration is 3 times that of step (1) preparation;

(3)将十六烷基三甲基溴化胺表面活性剂加入到步骤(1)配制的锌盐悬浊液中，加入量为锌盐质量的0.1wt％-10wt％；(3) Add cetyltrimethylammonium bromide surfactant to the zinc salt suspension prepared in step (1), in an amount of 0.1wt%-10wt% of the zinc salt quality;

(4)在60℃～70℃下，将锌盐悬浊液剧烈搅拌，并将氢氧化钾或氢氧化钠悬浊液逐滴加入步骤(3)含表面活性剂的锌盐悬浊液中反应，得到白色浑浊液；(4) Stir the zinc salt suspension vigorously at 60°C to 70°C, and add potassium hydroxide or sodium hydroxide suspension dropwise into the zinc salt suspension containing surfactant in step (3) reaction to obtain a white turbid liquid;

(5)反应完全后，将浑浊溶液冷却至25℃，静置、分离浑浊液；(5) After the reaction is complete, cool the turbid solution to 25°C, let stand, and separate the turbid solution;

(6)用去离子水对分离物充分洗涤，再用无水乙醇对分离物充分洗涤，20℃～30℃下干燥，即可得到纳米氧化锌粉体。(6) Fully wash the isolate with deionized water, then fully wash the isolate with absolute ethanol, and dry at 20° C. to 30° C. to obtain nanometer zinc oxide powder.

2. 按权利要求1所述的纳米氧化锌粉体的制备方法，其特征在于所述的锌盐为醋酸锌、硝酸锌或氯化锌。2. by the preparation method of the described nano zinc oxide powder of claim 1, it is characterized in that described zinc salt is zinc acetate, zinc nitrate or zinc chloride.

3. 按权利要求1所述的纳米氧化锌粉体的制备方法，其特征在于KOH或NaOH乙醇悬浊液加入时的滴定速度为0.5mol/min。3. by the preparation method of the described nano-zinc oxide powder of claim 1, the titration rate when it is characterized in that KOH or NaOH ethanol suspension adds is 0.5mol/min.

4. 按权利要求1所述的纳米氧化锌粉体的制备方法，其特征在于步骤(4)搅拌速度为400-1000转/分。4. by the preparation method of the nano-zinc oxide powder as claimed in claim 1, it is characterized in that step (4) stirring speed is 400-1000 rev/min.

5. 按权利要求1所述的纳米氧化锌粉体的制备方法，其特征在于步骤(1)搅拌时是在20℃-30℃条件下进行的。5. according to the preparation method of the nano-zinc oxide powder described in claim 1, it is characterized in that step (1) is carried out under the condition of 20 ℃-30 ℃ when stirring.