铱系氧化物纳米晶涂层电极电催化合成绿色硝化剂N2O5的作用机制

项目名称： 铱系氧化物纳米晶涂层电极电催化合成绿色硝化剂N2O5的作用机制

项目编号： No.21203137

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 物理化学

项目作者： 王庆法

作者单位： 天津大学

项目金额： 27万元

中文摘要： 为克服传统硝化的缺点，基于N2O5的新型硝化技术是未来合成有机原料和含能材料的主要方法，N2O5合成是其关键。目前，电化学法是合成N2O5的研究热点，而该过程受到电极材料发展的制约。由于对电极材料的影响规律及反应机理目前尚不清晰，严重影响了新型电极材料及电化学合成N2O5过程的开发。本工作拟通过研究钌铱氧化物纳米晶的析形和生长机理以及钛基体梯度化涂层的预处理技术，建立晶体形貌、取向和大小可控的高稳定钌铱氧化物纳米晶涂层电极制备技术；开展不同形貌钌铱纳米晶电极制备及电催化N2O4氧化性能研究，构建铱系氧化物纳米晶的形貌与其电催化性能的构效关系；研究铱系纳米晶涂层电极在N2O4/HNO3溶液中的电化学特性，建立电催化N2O4氧化反应机理，获得纳米晶电极材料的电催化N2O4氧化作用机制。本研究旨在揭示铱系氧化物涂层电极的电催化本质，以期为新型高效DSA类电极材料的设计、开发及应用提供理论指导。

中文关键词： 铱系氧化物纳米晶；择形调控；电催化；四氧化二氮氧化；机理及构效关系

英文摘要： In order to overcome the disadvantages of traditional nitration process, the novel nitration technology using dinitrogen pentoxide(N2O5) is becoming the main method to synthesize the organic materials and energetic materials and the synthesis of N2O5 is crucial for this technology.Nowadays the electrochemical route has been focused on the synthesis of N2O5.However,the development of this electrochemical process has been limited by the critical materials- electrode materials. Up to now, the understandings on the effects of anode materials and the electrode reaction mechanism are still ambiguous, which severely affect the developments of novel electrode materials and electrosynthesis routes. In this work, the preparation method of the shape-,oriention- and size-controlled iridium and ruthenium binary oxide nanocrystal electrodes will be developed by investigating the mechanism of shape-evolution and crystal growth of IrRu oxides as well as the pre-treatment method of Ti substrate by coating gradient IrRu oxides. The structry-activity relationship of iridium oxide-based nanocrystal will be constituted by preparation of different shapes of IrRu oxides nanocrystal electrode and by investigating the electrocatalytic oxidation of N2O4 on the obtained electrodes. The reaction mechanism of electrocatalytic oxidation of N

英文关键词： Ir-based oxides nanocrystal；shape control；electrocatalysis；N2O4 oxidation；reaction mechanism and structure-activity