甲烷作为一种重要的碳基能源分子，其高效转化利用对于优化能源结构、减少大气污染具有重要意义。硅化物晶格限域的单铁中心催化剂的成功构建，使甲烷直接转化制备乙烯和芳烃（包氏转化法）取得了重大突破。但是，反应温度高和催化剂表面单铁中心覆盖度低在一定程度上制约了其工业化应用进程。本申请项目围绕甲烷无氧直接转化工艺，在“包氏转化法”基础上，借助现代理论与计算化学研究方法，探究单铁中心催化剂催化甲烷无氧偶联反应的活性位及动态反应机理，阐明包氏转化法中“反应温度高”的原因，并开展负载型单/多金属中心催化剂的优化设计、性能预测以及高通量筛选，进而采用先进的气相和表面负载团簇反应实验手段，对所预测性能优异的催化剂进行高覆盖度精准制备和催化反应性能研究，期望在分子、原子水平上获得催化剂活性中心的设计依据和调控策略，为开发新型、高性能、具有工业应用前景的甲烷无氧直接转化催化剂提供重要的理论依据。

Methane is one of the most important carbon-based energy resources in modern chemical industry. Its efficient conversion and utilization will significantly contribute to the optimization of energy structure and the reduction of air pollution. Recently, significant advance in direct methane conversion has been achieved by Bao et al., where they used a lattice-confined single-iron catalyst embedded in a silica matrix to achieve the direct conversion of methane to ethylene and aromatics, which is the so-called “Bao process”. However, the industrialization of this process is limited due to the high reaction temperature and low concentration of active iron sites. In this proposal, we plan to investigate the direct conversion of methane based on “Bao process”, and use a series of modern theoretical and computational chemistry methods to elucidate the role of the active centers and dynamic catalytic mechanisms. Specifically, we will focus on explaining the origin of the high reaction temperature (>1200 K), analyzing the nature of reaction mechanism, predicting the catalytic performance, computationally screening the catalysts with different compositions, and finally designing the catalysts with high performance from atomic level. An additional experimental effort will focus on studying the supported surface clusters for relevant catalytic reactions. This work will provide theoretical guidance for rational design of advanced catalysts for direct, nonoxidative conversion of methane.