光响应多孔催化材料的构建及其在甲烷选择性官能化中的应用研究

甲烷作为重要的C1资源，如何实现甲烷的选择性官能团化，是科学上目前面临的主要挑战也是化学化工研究领域的“圣杯”。本项目针对甲烷活化过程中反应温度高、选择性低，以及催化剂昂贵且易失活等关键问题，通过气相团簇反应模型考察铈金属与不同金属间的轨道杂化情况对甲烷活化的影响，初步筛选掺杂金属；在此基础上，利用金属铈的光响应特点和MOFs材料空间的限域效应，将具光催化活化甲烷能力的铈金属和掺杂组分直接引入到MOFs材料中，形成具有高催化活性和高选择性的光响应双金属多孔催化材料。围绕甲烷官能团化的效率和选择性等核心问题，建立和发展新型光响应催化体系，从反应动力学和反应机理出发研究具有光响应催化材料的关键调控因素，研究成果有望为温和条件下甲烷的官能团化提供科学基础和应用参考。

As an important C1 resource，how to realize the selective functionalization of methane is one of the main scientific challenges and the “Holy Grail” in the field of chemical engineering. The proposed work aims at solving the vital issues of high reaction temperature, low selectivity, and the use of precious metals during methane activation. Initially, the gas phase cluster reaction model will be used to screen doped metals by investigating the orbital hybridization between cerium and different metals and its effect on activation. Considering the features of optical response characteristic of cerium metal and confinement effect of MOFs, Photoresponsive bimetal porous catalytic materials with high catalytic activity are fabricated by simply introduction of cerium metal and doped metals into the framework of MOFs. Given the core issues of the efficiency and selectivity of methane activation, the proposal focuses on the construction and development of a new type of photocatalytic MOFs system through detailed investigation of their key regulatory factors and mechanism in methane activation and subsequent functionalization. The successful implementation of this project is expected to provide scientific basis and practical applications for the efficient and clean preparation of value-added methane derivatives under mild conditions.