CN101214990A - A kind of normal temperature synthetic method of nanometer zinc oxide - Google Patents
A kind of normal temperature synthetic method of nanometer zinc oxide Download PDFInfo
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- CN101214990A CN101214990A CNA2007101736239A CN200710173623A CN101214990A CN 101214990 A CN101214990 A CN 101214990A CN A2007101736239 A CNA2007101736239 A CN A2007101736239A CN 200710173623 A CN200710173623 A CN 200710173623A CN 101214990 A CN101214990 A CN 101214990A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title abstract description 33
- 239000011787 zinc oxide Substances 0.000 title abstract description 19
- 238000010189 synthetic method Methods 0.000 title 1
- 150000003751 zinc Chemical class 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000007530 organic bases Chemical class 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 5
- 239000011707 mineral Substances 0.000 claims 5
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 150000007529 inorganic bases Chemical class 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000004098 selected area electron diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001478 photoelectron diffraction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种纳米氧化锌的常温合成方法，属于属于纳米材料领域。本发明选用有机锌盐和无机碱或有机碱为原料，将有机锌盐加入去离子水中，搅拌溶解后，缓慢加入无机碱或有机碱，生成白色沉淀，继续搅拌1～10小时，离心分离后，用去离子水和无水乙醇洗涤沉淀，在烘箱中烘干，制得产品。本发明原料价便、工艺简单、操作方便、降低能耗，易于控制等特点。The invention relates to a method for synthesizing nano-zinc oxide at normal temperature, belonging to the field of nano-materials. The present invention selects organic zinc salt and inorganic base or organic base as raw materials, adds organic zinc salt into deionized water, after stirring and dissolving, slowly adds inorganic base or organic base to form white precipitate, continues to stir for 1 to 10 hours, and centrifuges , wash the precipitate with deionized water and absolute ethanol, and dry in an oven to obtain the product. The invention has the characteristics of cheap raw materials, simple process, convenient operation, reduced energy consumption, easy control and the like.
Description
技术领域technical field
本发明涉及一种纳米氧化锌的常温合成方法，属于纳米材料领域。The invention relates to a method for synthesizing nano-zinc oxide at normal temperature, which belongs to the field of nano-materials.
背景技术Background technique
氧化锌是当今各国高科技研究与开发前沿领域最重要的光电子半导体材料之一。世界各国，特别是美、日、韩三国的科学家都以极大的的热情相继投入了大量的研究。纳米氧化锌材料具有其本体块状材料所无法比拟的优异性能，如无毒和非迁移性、荧光性、压电性、吸收和散射紫外线能力等，在陶瓷、紫外屏蔽、纺织、橡胶、催化剂和光催化剂、传感器和吸波材料、荧光屏和电容器、图象记录材料等众多方面有着广泛的应用，颇受人们青睐，成为科技人员关注的焦点。材料的性能取决于组成材料的晶粒尺寸、分布和形貌，因而合成高纯度、粒径和形貌可控的纳米氧化锌粉体是制备高性能纳米材料的第一步。Zinc oxide is one of the most important optoelectronic semiconductor materials in the forefront of high-tech research and development in various countries. Scientists from all over the world, especially the United States, Japan and South Korea, have invested a lot of research with great enthusiasm. Nano-zinc oxide materials have excellent properties unmatched by their bulk materials, such as non-toxic and non-migratory, fluorescent, piezoelectric, ultraviolet absorption and scattering capabilities, etc., in ceramics, ultraviolet shielding, textiles, rubber, catalysts, etc. And photocatalysts, sensors and absorbing materials, fluorescent screens and capacitors, image recording materials and many other aspects have a wide range of applications, popular with people, and become the focus of scientific and technological personnel. The performance of materials depends on the grain size, distribution and morphology of the constituent materials, so synthesizing nano-zinc oxide powders with high purity, controllable particle size and morphology is the first step in the preparation of high-performance nanomaterials.
现有的氧化锌纳米材料的制备方法很多，可归纳为固相法、液相法和气相法。其中液相法包括了直接沉淀法、均匀沉淀法、溶胶凝胶法等；气相法包括化学分解法和喷雾热解法等。制备方法不同，得到晶粒的尺寸和形貌各不相同。目前已经制备出从零维到三维的不同形貌的氧化锌纳米材料，包括纳米粒子(D.Qian，J.Z.Jiang，P.L.Hansen，Chem.Commun.(2003)1078)，纳米棒(B.Cheng，E.T.Samulski，Chem.Commun.(2004)986))，纳米带(J.H.Park，H.J.Choi，Y.J.Choi，S.H.Sohn，et al J.Mater.Chem.14(2004)3955)以及其他复杂的形貌。但是现有的制备方法，都需要在一定的条件下(如加热、微波辅助、超声处理等)促进反应的进行，造成合成过程中的能耗上升，提高成本，因此寻求低成本的有效控制氧化锌形貌的方法具有重要的现实意义。There are many methods for preparing zinc oxide nanomaterials, which can be classified into solid-phase method, liquid-phase method and gas-phase method. Among them, the liquid phase method includes direct precipitation method, uniform precipitation method, sol-gel method, etc.; the gas phase method includes chemical decomposition method and spray pyrolysis method, etc. Different preparation methods result in different grain sizes and shapes. At present, zinc oxide nanomaterials with different shapes from zero-dimensional to three-dimensional have been prepared, including nanoparticles (D. Qian, J.Z. Jiang, P. L. Hansen, Chem. Commun. (2003) 1078), nanorods (B. Cheng, E.T.Samulski, Chem.Commun.(2004)986)), nanoribbons (J.H.Park, H.J.Choi, Y.J.Choi, S.H.Sohn, et al J.Mater.Chem.14(2004)3955) and other complex topography. However, the existing preparation methods all need to promote the reaction under certain conditions (such as heating, microwave assistance, ultrasonic treatment, etc.), resulting in increased energy consumption in the synthesis process and increased costs. Therefore, it is necessary to seek effective oxidation control at low cost. The method of zinc morphology has important practical significance.
发明内容Contents of the invention
本发明的目的在于提供一种纳米氧化锌的常温合成方法。The object of the present invention is to provide a normal temperature synthesis method of nanometer zinc oxide.
为了实现上述目的，本发明通过以下步骤实现：In order to achieve the above object, the present invention realizes through the following steps:
(1)原料的准备：(1) Preparation of raw materials:
选用有机锌盐和无机碱或有机碱为原料。Organic zinc salts and inorganic bases or organic bases are selected as raw materials.
所述的有机锌盐优选醋酸锌；The preferred zinc acetate of the organic zinc salt;
所述的无机碱或有机碱为氢氧化钠或氢氧化钾或三乙胺，优选三乙胺。The inorganic base or organic base is sodium hydroxide or potassium hydroxide or triethylamine, preferably triethylamine.
(2)将有机锌盐加入去离子水中，搅拌溶解后，缓慢加入无机碱或有机碱，生成白色沉淀，继续搅拌1～10小时。(2) Add organic zinc salt into deionized water, stir to dissolve, then slowly add inorganic base or organic base to form white precipitate, and continue stirring for 1 to 10 hours.
有机锌盐的浓度为0.01～0.08mol/L，每升有机锌盐溶液中加入无机碱或有机碱0.01～0.5mol；The concentration of the organic zinc salt is 0.01-0.08mol/L, and 0.01-0.5mol of inorganic base or organic base is added to each liter of organic zinc salt solution;
(3)离心分离后，用去离子水和无水乙醇洗涤沉淀，在烘箱中烘干，制得产品。(3) After centrifugal separation, the precipitate is washed with deionized water and absolute ethanol, and dried in an oven to obtain the product.
本发明所制备的氧化锌纳米粒子的形貌随着所选用的碱的不同有很大的差异。以氢氧化钠为沉淀剂时得到针簇状的氧化锌纳米多晶，其粒径在100～200nm(见图2A)；以氢氧化钾为沉淀剂时，得到均匀分布的棒状的氧化锌，直径大约200nm，长度为600nm(见图2B)；而以三乙胺为沉淀剂时，得到的是一种三角状的氧化锌单晶，粒径在100～150nm(见图2C和D)。以三乙胺为沉淀剂时，氧化锌的颗粒尺寸随反应溶液中锌盐浓度的降低而减小至50nm以下。这种50nm的三角状氧化锌产物可以在乙醇中形成稳定的分散液。这种分散液经过一个月以上的放置，也不会发生明显沉降。The morphology of the zinc oxide nanoparticles prepared by the present invention is very different with the selected alkali. When sodium hydroxide is used as the precipitating agent, needle-clustered zinc oxide nano-polycrystals are obtained, with a particle size of 100-200 nm (see Figure 2A); when potassium hydroxide is used as the precipitating agent, evenly distributed rod-shaped zinc oxide is obtained, The diameter is about 200nm and the length is 600nm (see Figure 2B). When triethylamine is used as the precipitant, a triangular zinc oxide single crystal with a particle size of 100-150nm is obtained (see Figure 2C and D). When triethylamine is used as precipitant, the particle size of zinc oxide decreases to less than 50nm with the decrease of zinc salt concentration in the reaction solution. The 50nm triangular zinc oxide product can form a stable dispersion in ethanol. This dispersion will not settle significantly after being placed for more than one month.
本发明方法简单，能耗低，操作方便，选用的原料易得。另外，室温制备法也可以扩大纳米氧化锌在不同应用领域和应用条件下的工艺适应性，有利于材料性能的提高。The method of the invention is simple, low in energy consumption, convenient in operation, and the selected raw materials are easy to obtain. In addition, the room temperature preparation method can also expand the process adaptability of nano-zinc oxide in different application fields and application conditions, which is beneficial to the improvement of material properties.
附图说明Description of drawings
图1是本发明制备工艺流程图。Fig. 1 is a flow chart of the preparation process of the present invention.
图2是本发明根据实施例1、例2、例3的产物的SEM照片。图2a和图2c中***的是选区电子衍射图。Fig. 2 is the SEM photograph of the product of the present invention according to embodiment 1, example 2, example 3. Inserted in Figures 2a and 2c are selected area electron diffraction patterns.
具体实施方式Detailed ways
实施例1Example 1
准确称量0.440g(2mmol)二水合乙酸锌，室温下搅拌溶解于50ml去离子水中，再准确称取0.352g氢氧化钠(8.5mmol)，缓慢加入上述溶液中，室温下继续搅拌2h。反应溶液进行离心分离，沉淀分别用去离子水和无水乙醇洗涤，并于60℃下干燥，得到白色粉末。产物为针簇状的氧化锌纳米多晶，直径大小在100～200nm，其SEM照片以及选区电子衍射图列于图2a中。Accurately weigh 0.440g (2mmol) of zinc acetate dihydrate, stir and dissolve in 50ml of deionized water at room temperature, then accurately weigh 0.352g of sodium hydroxide (8.5mmol), slowly add to the above solution, and continue stirring at room temperature for 2h. The reaction solution was centrifuged, and the precipitate was washed with deionized water and absolute ethanol respectively, and dried at 60° C. to obtain a white powder. The product is a needle-like zinc oxide nanopolycrystal with a diameter of 100-200nm, and its SEM photo and selected area electron diffraction pattern are shown in Figure 2a.
实施例2Example 2
准确称量0.440g(2mmol)二水合乙酸锌，室温下搅拌溶解于50ml去离子水中，加入0.476g氢氧化钾(8.5mmol)，室温下继续搅拌2h。反应溶液进行离心分离，沉淀分别用去离子水和无水乙醇进行洗涤，然后在60℃下干燥。图2b是产物的TEM照片。照片表明产物为均匀分布的棒状氧化锌纳米晶粒，粒径为200nm，长度为600nm。Accurately weigh 0.440 g (2 mmol) of zinc acetate dihydrate, stir and dissolve in 50 ml of deionized water at room temperature, add 0.476 g of potassium hydroxide (8.5 mmol), and continue stirring at room temperature for 2 h. The reaction solution was centrifuged, and the precipitate was washed with deionized water and absolute ethanol, and then dried at 60°C. Figure 2b is a TEM photo of the product. The photo shows that the product is uniformly distributed rod-shaped zinc oxide nanocrystals with a particle size of 200nm and a length of 600nm.
实施例3Example 3
准确称量0.440g(2mmol)二水合乙酸锌，室温下搅拌溶解于50ml去离子水中，加入2.5ml三乙胺，室温下继续搅拌8h。反应溶液进行离心分离，沉淀分别用去离子水和无水乙醇进行洗涤，然后在60℃下干燥。从图2c、d以看出，产物为三角状的氧化锌纳米单晶，粒径大小在100～150nm之间。Accurately weigh 0.440 g (2 mmol) of zinc acetate dihydrate, stir and dissolve in 50 ml of deionized water at room temperature, add 2.5 ml of triethylamine, and continue stirring at room temperature for 8 h. The reaction solution was centrifuged, and the precipitate was washed with deionized water and absolute ethanol, and then dried at 60°C. It can be seen from Figure 2c and d that the product is a triangular zinc oxide nano single crystal with a particle size between 100 and 150nm.
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| CN102275977A (en) * | 2011-07-19 | 2011-12-14 | 西安交通大学 | Preparation method of zinc oxide mesoscopic crystal with adjustable aspect ratio |
| CN102608170A (en) * | 2011-10-08 | 2012-07-25 | 北京中科微纳物联网技术股份有限公司 | High-performance gas sensor |
| 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 |
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- 2007-12-28 CN CN2007101736239A patent/CN101214990B/en not_active Expired - Fee Related
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| CN102275977A (en) * | 2011-07-19 | 2011-12-14 | 西安交通大学 | Preparation method of zinc oxide mesoscopic crystal with adjustable aspect ratio |
| CN102275977B (en) * | 2011-07-19 | 2013-01-02 | 西安交通大学 | Preparation method of zinc oxide mesoscopic crystal with adjustable aspect ratio |
| CN102608170A (en) * | 2011-10-08 | 2012-07-25 | 北京中科微纳物联网技术股份有限公司 | High-performance gas sensor |
| 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 |
| CN107441778A (en) * | 2017-09-08 | 2017-12-08 | 宣城市聚源精细化工有限公司 | One kind defoams rapid defoamer |
| CN108570850A (en) * | 2018-02-15 | 2018-09-25 | 湖北大学 | A kind of preparation method of the excellent super wetting woven fabric of stabilization patience for water-oil separating |
| CN108570850B (en) * | 2018-02-15 | 2021-03-02 | 湖北大学 | Preparation method of super-wetting woven fabric with excellent stability and tolerance for oil-water separation |
| CN110903582A (en) * | 2019-11-27 | 2020-03-24 | 桂林理工大学 | A kind of polyvinyl alcohol/starch nanocomposite material with ultraviolet blocking function and preparation method thereof |
| CN111514937A (en) * | 2020-05-13 | 2020-08-11 | 中国石油大学(华东) | Preparation method of porphyrin-based metal organic framework material sensitized oxide catalyst |
| CN116282127A (en) * | 2023-02-28 | 2023-06-23 | 安徽工程大学 | Balsam pear type nano zinc oxide and preparation method and application thereof |
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