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多金属氧酸盐辅助下水溶液的氧化锌纳米材料的合成、表征及光学性质研究

Aqueous Solution Synthesis, Characterization, and Optical Property of Zinc Oxide Nanomaterials with Polyoxometalates

【作者】 王春蕾

【导师】 王恩波;

【作者基本信息】 东北师范大学 , 无机化学, 2008, 博士

【摘要】 氧化锌是一种重要的Ⅱ-Ⅳ族宽带隙半导体材料。氧化锌在光学、光电、传导、传感、以及生物等不同领域有许多潜在的应用。纳米氧化锌是近年来开发的一种新型无机功能材料。当前,制备氧化锌纳米材料的方法主要分为物理和化学的方法。其中,基于水溶液的化学合成方法由于温和的反应温度,简单的操作和高产率受到了广泛的青睐。本文中,采用水溶液的化学合成方法,通过控制反应的化学环境,成功的合成出了多种形貌的氧化锌纳米材料。工作主要分为以下几个方面:(1)通过将多金属氧酸盐引入到反应体系中,利用水溶液的电化学方法,使用价格低廉的锌片,成功的合成出了氧化锌的纳米中空球。探讨了中空球的生长成核过程,并进一步对其光催化性质进行了研究,发现中空球对染料显示了良好的光催化性质。进一步,利用多金属氧酸盐辅助的水热合成的方法,成功的制备出了氧化锌纳米棒,纳米片和纳米捆。同时对以上纳米结构的光致发光性质进行了研究。(2)利用醇热的合成方法,通过加入表面活性剂合成出了氧化锌纳米棒,纳米粒子和星状纳米晶。探讨了表面活性剂对产物形貌的影响。进一步,利用溶剂热的合成方法,通过须状氧化锌纳米前驱体进一步合成出了分散性良好的氧化锌纳米粒子。通过水热的合成方法,不借助任何模板,合成出了氧化锌纳米管。并研究了反应时间对管质量的影响。(3)从合成中得到启示,以锌粉末和碘粉末为原料,合成出了分散性较好的氧化锌纳米粒子。并研究了碘在整个化学反应过程中的重要作用。利用层接层技术,通过硝酸锌溶液和氨水的交替沉积,在聚合物膜里合成出了氧化锌纳米粒子,并通过控制反应条件,得到氧化锌链状纳米粒子。

【Abstract】 ZnO is one of the most important wide -band-gap II-IV semiconductors. Its considerable applications in optical, optoelectonic, conductor, gas sensor and biology have initiated intensive research. ZnO nanomaterials are a kind of inorganic functional materials with special properties compared with buld ZnO. Physical and chemical methods are two main methods for the fabrication of ZnO nanomaterials. Thereinto, solution chemical methods have proven to be appealing because of their mild reaction temperature, simply manipulation and large scale-up production.In this dissertation, various morphologies of ZnO nanomaterials have been fabricated through solution chemical method by controlling the reaction conditions. The main contents are listed below:(1) Uniform ZnO hollow nanospheres were fabricated controllably by using cheap zinc foils a simply one-step, polyxometalate-assisted, electrochemical mthod. Reasonable mechanisms were also discussed to explain the results in detail. The photocatalytic investigation indicated that the as-prepared ZnO hollow nanospheres had good photocatalytic activity. Furthermore, with the help of polyxometalate, single crystalline ZnO with the morphologies, including nanorods, nanosheets and nanobundles were successfully obtained by hydrothermal method. At the same time, the optical properties of the ZnO nanostructures have also been discussed.(2) An alcohol thermal process was developed of the controllable syntheses of ZnO nanorods, nanoparticles and starlike nanocrystals at a low temperature. The effect of the surfactant to the morphologies of the ZnO nanostructures has also been discussed. Furthermore, growth of uniform ZnO nanoparticles from a nanowhisker precursor was realized with a simple solvothermal route. An attractive template-free hydrothermal method was developed to synthesize ZnO nanotubes. The effect of the reaction time to the morphology of the ZnO nanotubes has also been discussed.(3) A novel reaction was developed for the synthesis of ZnO nanoparticles with nearly uniform spherical morphology by directly oxidizing zinc powders with iodine in ethanol. The effect of iodine during the reaction has also been researched. Furthermore, facile synthesis of ZnO nanoparticles in polyelectrolyte multilayer films was presented using the in situ layer-by-layer nucleation and growth method. The morphologies of the particles were controlled from the nanoparticles to the one dimensional nanocrystals through changing the precipitation reaction cycles.

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