【作者】 曹亚丽；

【导师】 贾殿赠；

【作者基本信息】 新疆大学 ， 物理化学， 2004， 硕士

【摘要】 纳米结构因具有独特的性质以及潜在的应用前景引起了人们广泛的关注，特别是一维纳米结构以及空心纳米结构成为纳米材料研究领域的热点。已有制备一维纳米结构及空心纳米结构的方法往往需要多个步骤、较高的温度、特殊的仪器、苛刻的实验条件。本论文采用简单方便的表面活性剂聚乙二醇参加的低热固相化学反应法制备了一系列的一维纳米材料和空心纳米结构。与其它方法相比，此合成方法工艺简单，合成温度低，无需特殊的仪器，无溶剂依赖性，因而是一种较好的合成特殊形貌纳米材料的方法。 全文分为三部分，第一部分为绪论部分，该部分概述了纳米材料、纳米结构材料、一维纳米材料的一些基本概念，并介绍了合成一维纳米材料的方法并对其进行了展望。在简单介绍固相化学反应的发展史及特点后提出了本文选题的出发点并简单介绍了本论文的研究内容。 第二部分分为五章，分别为氧化物一维纳米棒、氢氧化物一维纳米棒、草酸金属配合物一维纳米棒、草酸金属配合物空心纳米结构、丙二酸及酒石酸金属配合物纳米结构的合成及其表征。 第一章利用锌盐与氢氧化钠的一步固相化学反应合成了氧化锌纳米球，并利用表面活性剂聚乙二醇400参加的锌、铅盐与氢氧化钠的一步固相化学反应合成了氧化锌及氧化铅纳米棒，借助X-射线衍射确定了样品的组成，并通过透射电镜和扫描电镜观察了样品的球形或棒状形貌。氧化锌样品的光化学性质通过红外分析、紫外分析以及荧光分析加以表征，发现样品与本体氧化锌相比，紫外吸收增强，红外及荧光峰发生蓝移。本章还讨论了金属盐与氢氧化钠或氢氧化钾的一步固相反应直接得到氧化物的反应历程及反应机理，并由此得出了这样的结论：对于金属盐与氢氧化钠或氢氧化钾的一步固相化学反应来说，如果相应金属氢氧化物的分解温度低或不稳定，那么该固相反应体系将一步得到氧化物，反之则得到氢氧化物。 第二章利用表面活性剂聚乙二醇400参加的镉、钴、锶盐与氢氧化钠的固相化学反应合成了氢氧化福、氢氧化钻及氢氧化铭纳米棒，利用X一射线衍射及热分析对产物的组成进行了表征，并通过透射电镜、扫描电镜观察了样品的棒状形貌，同时讨论了不同金属盐对产物形貌的影响。实验结果表明:不同结构的反应物盐得到的产物的形貌有很大的差异;对于钻盐和铭盐而言，除醋酸盐得到了形态较好的一维纳米棒外，其它反应物盐甚至不能得到一维纳米棒。 第二章利用表面活性剂聚乙二醇参加的钻盐、铜盐、醋酸镍和草酸的固相化学反应合成了一系列的草酸钻、草酸铜一维纳米棒及草酸镍一维纳米短棒，借助X一射线衍射、热分析确定了样品的组成，并通过透射电镜和扫描电镜观察了样品的棒状形貌。样品中的结构水通过热分析和红外分析得以确定，并通过红外分析研究了纳米棒与常规尺寸粒子的性质差异。同时讨论了不同金属盐作反应物、不同聚合度的聚乙二醇作表面活性剂对产物形貌的影。结果表明固相产物的形貌因选取不同金属盐作反应物有所不同;聚乙二醇分子链的长短也会影响产物的形貌。本章还讨论了纳米棒的形成机理，认为表面活性剂聚乙二醇在纳米棒的形成过程中起到关键的软模板作用并使产物粒子定向生长为一维纳米棒。 第四章利用了表面活性剂聚乙二醇400参加的锌盐、醋酸镁(锰、铭)和草酸的固相化学反应合成了草酸锌空心纳米球及纳米链、草酸镁空心纳米球及空心一维纳米棒、内含空泡的草酸锰空心纳米棒及草酸铭空心纳米球，借助X一射线衍射确定了样品的组成，同时利用透射电镜、高倍透射电镜观察样品的空心结构。通过热分析不仅进一步确证了样品的组成，推测了样品中的结构水，而且比较了空心结构纳米材料与常规材料热稳定性的差异。 第五章利用表面活性剂聚乙二醇400参加的醋酸钻、镍、锌、铭、镁和丙二酸的固相化学反应合成了等边三角形的丙二酸钻、棒状的丙二酸镍及空心球状的丙二酸锌、铭、镁纳米材料，借助X一射线衍射、红外分析及热分析确定了样品的组成，并借助了透射电镜观察了样品的形貌。同时利用了表面活性剂聚乙二醇400参加的醋酸锌、钻、镍、锰和酒石酸的固相化学反应合成了酒石酸锌、钻、镍、锰一维纳米短棒，并利用了X-射线衍射、红外及热分析对样品的组成进布」:了表征，还利用了透射电镜对样品的棒状形貌进行了表征。 第三部分为全文的结论，该部分通过表面活性剂聚乙二醇参加的固相化学反应的一系列实验结果总结了利用该方法制备特殊形貌纳米材料的规律，得出如下结论:(l)对于金属盐和氢氧化钠(钾)的固相化学反应体系而言，如果金属相应氢氧化物的分解温度低或不稳定，该金属与强碱固相反应时将一步生成氧化物，反之则生成氢氧化物。(2)对于表活剂PEG参加的醋酸盐与有机酸的固相反应体系而言，不同金属盐与不同有机酸反应得到的固相产物形貌各不相同，由此说明反应物结构的不同是影响固相产物呈不同形貌的原因。(3)对于一这种表活剂PEG参加的固相反应体系来说，表活剂PEG是得到一维纳米棒的关键，它在纳米棒的构筑过程中起到重要的类似软模板作用。更多还原

【Abstract】 Nanostructured materials are a focused research field due to their unusual properties and potential applications ranging from mesoscopic research to the development of nanodevices. Especially, all sorts of nanoscale materials with specific structure or interesting morphology, such as one-dimensional (ID) nanomaterials and hollow nanostructures have become the focus of materials research. These reported methods for preparing ID nanomaterials and hollow nanostructures usually require multi-process, higher temperature, special instruments and rigorous conditions. In this paper, a series of ID nanomaterials and hollow nanostructures were prepared by simple and convenient low-heating solid-state chemical reaction methods with the assistance of a nonionic surfactant, polyethylene glycol (PEG). Compared with these reported methods, surfactant-assisted solid-state chemical reaction is a good synthetic method for nanomaterials with special morphologies because of its advantages such ’as simple technique, low temperature, no special instrument et al.This paper is divided into three parts. The first part introduces some basically conception of nanomaterials, nanostructured materials and ID nanomaterials. The synthetic method and the developing foreground for ID nanomaterials were also presented. The history and advantages of low-heating solid-state chemical reaction were introduced. Based on the advantages of solid-state chemical reaction method, the investigative subject of the paper was proposed.The second part includes five chapter: synthesis and characterization of ID oxide nanorods, ID hydroxide nanorods, ID metal oxalate complex nanorods, hollow metallic oxalate complex nanostructures, metallic malonate and tartratecomplex nanostructure with special morphologies.In the first chapter, ZnO nanospheres was prepared by one-step solid-state chemical reaction of zinc salt and sodium hydroxide, ZnO and PbO nanorods were synthesized by solid-state chemical reaction of zinc (lead) salt and NaOH in the presence of PEG 400. The compositions of samples were determined by XRD. The sphere-like or rod-like morphology of samples were observed by TEM and SEM. The optical properties of ZnO were studied by IR, UV and PL. Results show that the ultraviolet absorption intension of nanoscale ZnO was stronger than bulk ZnO, and the peaks in IR and PL of nanoscale ZnO become blue-shift. The reactive processes and mechanisms of one-step solid-state reaction were discussed. It can be summarized that oxide can be directly obtained by solid-state reaction of metallic salt and NaOH or KOH if corresponding metal hydroxides have low decomposition temperature or are of unsteadiness.In the second chapter, Cd(OH)2, Co(OH)2 and Sr(OH)a nanorods were synthesized by solid-state chemical reaction of metallic salt and NaOH in the presence of PEG 400. The compositions of samples were characterization by XRD and TG. The rod-like morphologies of samples were observed by TEM and SEM. The morphologies of samples were also investigated when different salts were selected as reactants. Results show that the morphologies of samples are different when reactants have different structures.In the third chapter, CoC2O4-2H2O, CuC2O4, and NiC2O4-2H2O nanorods were synthesized by solid-state chemical reaction of metallic salts and oxalic acid in the presence of PEG. The compositions of samples were characterization by XRD and TG. The rod-like morphologies of samples were observed by TEM and SEM. The structural water was determined by TG and IR. The morphologies of samples were also investigated when different salts were selected as reactants andPEG with different degree of polymerization were selected as surfactant, and found different. The formational mechanism of nanorods was also discussed. It was found that the surfactant plays an important soft-template role in the growth process of nanorods.In the forth chapter, hollow ZnC2O4-2H2O, MgC2O4-2H2O, MnC2O4-2H2O and SrC2O2H2O nanostructures with different morphologies were synthesized by solid-state chemical更多还原