【作者】 李生英；

【导师】 高锦章； 杨武；

【作者基本信息】 西北师范大学 ， 分析化学， 2003， 硕士

【摘要】 材料的开发与应用在人类社会进步上起了极为关键的作用。人类文明史上的石器时代、铜器时代、铁器时代的划分就是以所用材料命名的。材料、能源、信息是当代技术的三大支柱，其中信息与能源技术的发展离不开材料技术的支持。 自1984年德国科学家H.V.Gleiter成功地采用惰性气体凝聚原位加压法制得纯物质的块状纳米材料后，纳米材料的研究及其制备技术引起了世界各国的普遍重视。在纳米材料中，由于纳米级尺寸与光波波长、德布罗意波长以及超导态的相干长度等物理特征尺寸相当或更小，使得晶体周期性的边界条件被破坏，纳米微粒的表面层附近的原子密度减小，电子的平均自由程很短，而局域性和相干性增强。尺寸下降还使纳米体系包含的原子数大大下降，宏观固定的准连续能带转变为离散的能级。这些导致纳米材料宏观的声、光、电、磁、热、力学等的物理效应与常规材料有所不同，体现为量子尺寸效应、小尺寸效应、表面效应和宏观隧道效应等。纳米材料的制备、结构、性能及其应用研究是目前材料科学研究的热点。纵观纳米材料的研究发展，不难看出，纳米材料的推广应用关键在于纳米材料的制备。因此，为使这种新型材料既有利于理论研究，又能在实际中拓宽其使用范围，探索高质量、低能耗、操作简单的纳米材料制备技术已成为纳米材料研究的关键之一。本研究采用微波辐射技术和低温固相反应法分别制备了SnO₂、PbO、NiO、ZnO等金属氧化物纳米材料，运用X射线粉末衍射、原子力显微镜、透射电镜、红外光谱分析、热重-差热分析等技术对产品进行了详细的表征，并对它们在纳米催化、纳米电极上的应用进行了探讨。本研究论文共分五个部分： 第一部分 文献综述 第一节 纳米技术的发展、应用及其展望 纳米技术是20世纪80年代初迅速发展起来的前沿学科，它使人们认识、改造微观世界的水平提高到了一个新的高度，是21世纪科技战略的制高点。本部分从纳米、纳米技术、纳米材料的概念出发，对纳米技术的发展历程进行了简要的综述，论述了纳米技术在社会活动中的应用和若干最新进展，提出纳米技术将会领导下一场工业革命。LIShe脚沙王ng:尸哪口心jon， Characterlzationand月PPlicotionofMetaloxidenan口m口terl’als第二节微波辐射技术在纳米材料制备中的应用 微波辐射技术因其具有特殊的热效应和非热效应，近年来引起了材料科学界的极大关注.与传统方法相比，微波辐射法具有反应速度快、反应条件温和、反应效率高等优点，而且产品具有较高的纯度、窄的粒径分布和均一的形态，并适于推广到大规模的工业生产中去，因而在纳米材料合成领域里显示了良好的发展态势和广阔的应用前景.本部分从微波致热的基本原理出发，简要介绍了微波辐射法制备纳米粒子的一些研究进展，主要是该方法在制备金属、金属氧化物和金属硫属化合物纳米粒子中的应用，并且对该领域未来的发展作了一些展望.第二部分微波辐射法制备Sno:纳米晶及其催化性能的研究 SnO:在陶瓷、气敏半导体材料及催化剂等方面被广泛应用，纳米级的SnOZ因具有明显的表面效应而受到关注，其制备方法也广受重视，本研究在微波辐射下，通过控制SnC玩与氨水在PVA存在条件下的水解反应，制得了纳米SnO2.实验表明，在微波辐射下结晶时间从常规水热合成的几小时减少到了11而n.随着微波辐射功率、时间及焙烧温度的不同，所得纳米晶的晶粒尺寸从3nm到24tun变化，从而预示了可以通过改变反应条件实现晶粒尺寸的控制.将所得纳米晶SnOZ应用于乙酸和乙醇的酷化反应，表现了优于大颗粒sn伍/s仇2一的催化性能.第三部分微波辐射法制备Pbo纳米颗粒及Pb0I)离子选择性电极的研制 本部分以硝酸铅为原料、尿素为沉淀剂，在微波辐射下合成了纳米级的碱式碳酸铅，在此基础上通过不同温度下的热分解，得到了红色四方晶相的a一Pbo（400℃焙烧Zh）和黄色正交晶相的尽Pbo（600℃焙烧Zh），晶粒尺寸分别为30nm和35 nln.将所得a一Pbo纳米颗粒与醋酸纤维素一同溶于丙酮中，溶剂蒸发后所得的a一Pbo纳米电极在2.sxlo一5到l.ox一。一1 mol·L一1 PbZ+浓度范围内表现29士zmV的Nenistian响应和1 05的响应时间，适宜的pH范围为2.0一8.0.第四部分固相合成纳米Nio微粒 室温或近室温条件下的固相化学反应是近年来发展起来的新研究领域，它以无溶剂、选择性高、产率高、能耗低、操作简单等优点，已被广泛用于合成化学.利用低温固相反应作为合成纳米材料的新途径受到了广泛的关注.本研究以NISO;·7玩O和NaoH为原料，用固相法合成了NIO纳米微粒.研究了不同焙烧温度及同一温度下不同焙烧时间对NIO纳米微晶的晶化过程的影响.用X射线衍射、透射电镜、热重一差热分析等方法对样品进行了表征.结果表明，固相法可以Post『aduate:LIShen盯ing SPeeiality:Ana】ytical ChemistlysSuPervisors:Rof Gao Jinzhang， Prof物ng WuLi巫旦翌{ngi望些叼竺丝旦生二互旦塑口吵旦生竺塑夕座丝些些些翌丛丝巫竺恻竺鲤些丝二一一一一制得平均粒径为Slnn的NIO纳米微粒，属六方晶系，形状为球形.与更多还原

【Abstract】 Stone, bronze, iron: civilization has always been defined by Man’s relationship with materials. Nowadays, materials have become an integral part of our society, as well as our daily life. Much of the technological progress is directly or indirectly dependent on the availability of advanced materials with improved functions. Nanomaterials is a new class of materials that has been making a silent revolution in the last decade. It is the foundation of the nanotechnology, and is causing an extensive concern of all over the world. The properties of the nanomaterials show remarkable improvement or deviation from the properties exhibited by the coarser grained materials. They exhibit unique optical, magnetic, electric, or catalytic properties. These properties are attributed to the significant increase in grain boundary area due to the small grain size, and are neither corresponds to those of the free atoms or molecules making up the particle nor to those of the bulk solids with identical chemical composition. Areas of application that can be foreseen to benefit from the small size include quantum electronics, nonlinear optics, photonics, chemoselective sensing, and information storage and processing, adsorbents, catalysis, solar cells, magnetic recording devices, superplastic ceramics, superhard metals, metastable alloys and so, on.In general, researches in nanomaterials are mainly concerned with the development of new synthesis methods, new ways of identifying and characterizing materials, and the applications of them. Of course, the first step is the synthesis of the required material. In the last few years, the key direction of nanomaterials lay in the search for new synthesis methods of nanomaterials with desired and controllable properties. At the same time, the characterization of materials is a critical ingredient to progress, because it provides guidance for further research efforts. This thesis reports on the study of the preparation, characterization, and application of metal oxide nanomaterials. With high quality and low cost, microwave irradiation techniques have been applied to the preparation of SnO2 nanocrystals and PbO nanoparticles. Low-temperature solid-state reaction method was used to prepared NiO nanoparticles and ZnO nanopowders. Theinfluences of experimental conditions on structures, components and sizes of the products and characterization of nanomaterials have also been studied. The ami is to enhance the overall performance of the nanoparticles for targeted applications. The main content consists of five parts. Part I. Literature ReviewChapter 1. Development, Application and Prospects of NanotechnologyIn this section, some primary concept of the nanotechnology and the hottest development of nanotechnology and nanomaterials were reviewed. The applications and the foreground of nanotechnology in some fields such as electronics, biology were described and prospected. The industrialization status of nanotechnology in the world was also introduced briefly.Chapter 2. Applications of Microwave Irradiation Technique to the Preparation of NanomaterialsThis review presented the latest advances in the application of microwave technique to the preparation of nanomaterials. The fundamental principles of microwave field interaction with the matter were presented briefly and their significance for the material science was discussed. A separate section described the examples of the usage of microwave technique in the preparation of nanomaterials including metals, metal oxides, and metal chalogenides. The prospect of this technique was also discussed. Part II. Preparation of SnO: Nanocrystals by Microwave Irradiation and Their Catalytic ActivityMicrowave irradiation technique was applied to the preparation of SnO2 nanocrystals by the hydrolysis of tin (IV) chloride. The time of crystallization was shortened drastically to 11 min from several hours of classical hydrothermal synthesis method. The products were characterized by XRD, AFM, TEM, and TG-DTA. The crystals size changed from 3nm to更多还原