α-MnO2低温催化苯系物开环路径的晶面依赖性研究

低温催化氧化技术处理挥发性有机物（VOCs）具有极大的应用潜力，锰氧化物表现出较好的催化性能。本项目针对α-MnO2催化降解苯系物反应历程、开环路径晶面依赖性等关键科学问题，采用第一性原理计算与实验相结合的方法，可控合成不同暴露晶面的α-MnO2催化剂，归纳制备工艺与催化剂结构间的规律，并建立催化剂结构与催化性能间的构-效关系，计算苯系物降解过程中各中间产物活化能和基元反应反应速率，重点利用in-situ DRIFTS和PTR-TOF联用技术动态追踪反应物、中间产物和终产物演变过程，揭示α-MnO2催化剂催化降解苯系物反应机理，高度结合理论计算与实验结果，阐明α-MnO2暴露晶面对其降解苯系物反应历程和速率控制步骤开环反应路径的影响机制，明确开环路径对其晶面依赖性。本项目结果可为高效分解苯系物α-MnO2催化剂的理性设计提供理论指导，还可为低温催化氧化技术用于挥发性有机物分解提供理论支撑。

Low-temperature catalytic oxidation technology shows great potential in the treatment of volatile organic compounds (VOCs). Manganese oxides possess better catalytic activity. This project aims to solve the key scientific issues in the catalytic degradation mechanism and the facet dependency of the ring-opening pathways of benzene series catalytic decomposed by α-MnO2 catalysts. In this research, the first principles method and experimental characterizations will be combined. The proposal will optimize the preparation process conditions systematically and synthesize α-MnO2 catalysts with different facets controllably. The impact of preparation process on catalytic microstructure will be summarized. Meanwhile, the relationship between the microstructure of catalysts and catalytic performance will be established. The activation energy of intermediate products and reaction rate of elementary reaction during the benzene series decomposition will be calculated by the first principles method. In - situ DRIFTS and PTR - TOF will be used jointly in order to achieve dynamic tracking of the evolution process of reactant, intermediate and final products, and uncover the degradation reaction mechanism of benzene series over α-MnO2 catalysts. By combining the results of theoretical calculation and the experimental test highly, the influencing mechanism of exposed facet of α-MnO2 catalysts in the degradation reaction mechanism and open-ring pathways of benzene series will be clarified in the proposal. The facet dependency of the ring-opening pathways of benzene series catalyzed by α-MnO2 will also be illuminated. This research is valuable not only for rational design of α-MnO2 catalysts with excellent catalytic performance for benzene decomposition, but also for providing theoretical support for low-temperature catalytic oxidation technology applied in the decomposition of volatile organic compounds.