碳基小分子催化定向转化及外场与表界面效应的多尺度全程模拟研究

项目旨在完善与发展周期性边界条件的块定域波函数方法(PBC-BLW)和复杂表界面体系的QM/MM边界模型，建立研究复杂催化过程及其外场与表界面效应的多尺度计算模拟平台。重点研究原子和团簇分散负载催化剂催化CH4选择脱氢与C-C键偶联及外场诱导CO2氢化转化与还原生成碳氢燃料的反应机理及其热力学和动力学性质，探明调控原子分散负载催化剂稳定性、催化活性与选择性的表界面结构特征及其与外场环境的协同作用。调查CO2活化与催化直接还原过程中电子转移和能量转移的机制与调控因素，确定催化剂表界面结构、组成、配位修饰、表界面吸/脱附物种热力学性质等与催化活性和选择性的关联，发展表界面催化反应性的描述符。基于计算表征，构建并全面评估几类以氧化物、有机共价框架和二维类石墨烯新型材料为载体的高性能原子分散催化剂，为碳基小分子催化选择转化高性能负载金属催化剂设计和相关新催化体系的发展提供理论依据。

The project aims to develop the block-localized wave function method using the periodic boundary condition (PBC-BLW) and the QM/MM coupling scheme for the complex interface system, and build the computational platform for multiscale simulation of the interfacial catalysis. Plausible mechanisms and corresponding thermodynamic and kinetic properties of selective dehydrogenation and C-C bond coupling of CH4 and direct conversion of CO2 into liquid fuels catalyzed by the atomically dispersed supported metal catalysts will be explored theoretically. Based on extensive calculations and simulations, we try to elucidate the plausible mechanisms for electron/proton and energy transfers and regulating factors in the external electric field-induced reduction of CO2, as well as the electronic effects of surface-interface structure and surface coordination on the manipulation of stability, reactivity and selectivity of the supported metal catalysts, reveal correlations of the catalytic activity and selectivity with the interface structure, composition, adsorption energy of reactive species, and develop the reactivity descriptor. Based on the computational characterization, several kinds of high-performance atomically dispersed metal catalysts supported by oxides, covalent organic frameworks, and two-dimensional graphene-like new materials will be designed and evaluated for selective catalytic conversions of carbon-based small molecules.