【作者】 张娜；

【导师】 彭笑刚； 金一政；

【作者基本信息】 浙江大学 ， 化学， 2014， 硕士

【摘要】 本文用反注入法,以傅里叶变换红外光谱(FTIR)为工具,对羧酸盐与十八醇(ODA)在非配位溶剂十八烯(ODE)中的醇解反应进行化学动力学研究。在此基础上,研究前驱体反应活性和Mg掺杂ZnO纳米晶的形貌、性质之间的联系。所获得的这些知识对纳米晶的可控合成有一定的指导作用。本文内容如下：1.对纯ZnO和MgO纳米晶合成时的醇解反应进行化学反应动力学研究。以FTIR为工具定量检测产物酯的浓度,获得相应的反应动力学数据,并指导掺杂纳米晶的合成。2.改变反应物前驱体中硬脂酸锌(Zn(St)2)与硬脂酸镁(Mg(St)2)的比例和掺杂反应的温度以得到不同形貌和性质的纳米晶。实验结果表明纳米晶的最终形貌与反应前驱体中Zn(St)2和Mg(St)2的相对反应活性有关,而反应活性又受到反应温度与掺杂物在前驱体中所占的比例影响。我们以超细纳米线的合成为例证明可以通过同时调节反应温度和镁前驱体的比例来控制产物的形貌和性质。3.改变羧酸锌的种类以改变锌前驱体的反应活性来研究化学反应动力学在掺杂纳米晶中的应用。首先,合成Zn(My)2和Zn(De)2两种前驱体,并进行红外光谱和热重分析。其次,用它们合成纯ZnO纳米晶并检测其初始反应速率。最后,根据反应动力学数据选择超细纳米线合成的条件并获得预期的实验结果。另外,对比实验的结果也说明掺杂纳米晶的形貌并不受外加羧酸的影响。更多还原

【Abstract】 We reported a quantitative method based on FTIR to study the chemical kinetics of the alcoholysis reactions associated with the formation of Mg-doped zinc oxide nanocrystals. The correlations between the chemical kinetics of the precursor conversion reactions and the morphologies and properties of the doped oxide nanocrystals were investigated. The understanding underpins the advancement of the synthesis of doped nanocrystals and should be useful for future rational design of new synthetic systems.The main contents are as follows:1. We studied the chemical kinetics of alcoholysis reaction associated with the formation of pure ZnO and MgO nanocrystals. FTIR was employed to quantitatively measure the corresponding chemical kinetics parameters.2. Changing the ratio of Zn(St)2to Mg(St)2and the reaction temperature to synthesize doped nanocrystals with different morphologies and properties. Based on the experimental results, we show that the ultrathin nanowires were obtained by adjusting the relative reactivity of Zn(St)2to Mg(St)2. The morphologies and properties of the doped nanocrystals are affected by the relative reactivity of Zn(St)2to Mg(St)2which is determined by the reaction temperature and dopant ratio. Therefore, we can get ultrathin nanowires by adjusting the reaction conditions. Meanwhile, we also verified that the ultrathin nanowires exhibited almost identical properties.3. We employed another two kinds of zinc carboxylate as precursors to study the reaction kinetics. The obtained kinetics data were used to guide the synthesis of ultrathin nanowires, revealing that our understanding can be used to guide the synthesis of doped nanocrystals with well-defined shapes and properties. Furthermore, we found that adding free acid as additional coordination ligands did not change the morphology and properties of the products.更多还原