Ce配合物设计合成及其绿色高效催化芳烃硝化反应机理研究

硝基含能材料在我国国民经济、社会发展、军事及国家安全领域具有特殊的重要意义。本项目针对目前工业上硝硫混酸体系硝基芳烃含能材料制备过程中存在的产率低、安全性差以及环境污染严重等问题，拟采用绿色、高效、安全的Ce(IV)配合物体系制备硝基芳烃含能材料。以硝酸铈铵（CAN）体系芳烃硝化反应为模型，采用量子化学计算与在线监测等实验技术相结合的方法，研究CAN体系催化芳烃硝化反应机理，建立Ce(IV)配合物催化芳烃硝化反应机理模型；在此基础上，理论设计与制备Ce(IV)配合物，阐明Ce(IV)配合物结构与催化芳烃硝化反应活性和选择性的构效关系，获得高活性和高选择性的Ce(IV)配合物模型，揭示不同取代基对芳烃硝化反应的活性和选择性的影响规律。该研究将有助于推动Ce(IV)配合物体系硝基含能材料制备方法在工业上的应用与推广，为实现我国硝基含能材料的绿色、高效、安全制备奠定理论基础和技术支撑。

Nitro energetic materials are of especially great importance to the economic, social development, military affairs, and national security. In view that the problems of low yield, poor safety and serious environmental pollution existing in the current preparation process of nitro energetic materials by nitro-sulfur mixed acids in industry, a green, efficient and safe method with Ce(IV) complex is proposed for the preparation of nitro energetic materials. The nitration of aromatic with cerium ammonium nitrate (CAN) is used as a model to study the nitration mechanism. The combined method of quantum chemical calculation and on-line monitoring techniques is used in this project. The nitration mechanism is revealed from the molecular level in the preparation process of nitro-aromatic energetic materials. Thus, the nitration mechanism model of aromatics by Ce(IV)-catalyzed in Ce(IV) complex system is preliminarily established. Ce(IV) complex catalysts with different anionic ligands are theoretically designed and studied to reveal the structure-activity relationship between structure and catalytic activity of Ce(IV) complex, and establish high activity and high selectivity catalyst model of Ce(IV) complex. The effect of substituent on the activity and selectivity of nitration of aromatics is also revealed. The results gained from this project will help to promote the industrial application and promotion of the preparation method of nitro energetic materials with Ce(IV) complex system, and also will provide the theoretical foundation and technical support for realizing the green, efficient, and safe preparation of nitro energetic materials.