二维材料限域单原子催化剂活性中心本质及构效关系

活性中心物理本质一直二维材料限域单原子催化剂（two-dimensional materials confining single-atom catalysts, 2DM©SACs）研究的前沿焦点问题。尽管人们对2DM©SACs中心单元在催化反应前后的成键以及电子状态展开了大量研究。但是，在催化过程中，尤其是在额外施加光照、电极电压等工作条件下，活性中心单元的配位结构及其形成的微观机制依然不明确。本项目拟在普遍热力学及动力学框架下，通过第一性原理并结合分子动力学，深入研究2DM©SACs活性中心配位结构，重点围绕其在工作条件下的动态演化，揭示活性中心位本质；选取具有巨大应用前景的新型制氨工艺—光（电）催化固氮作为探针反应，总结成分-结构-性能的构效关系。本项目的研究有利于揭示2DM©SACs在工作条件下的新现象、新规律，丰富与发展光（电）催化的基础理论。

The physical nature of active center has always been the cutting-edge research focus in the community of two-dimensional materials confining single-atom catalysts (2DM©SACs). Great efforts have been made to uncover its bonding and electronic states before and/or after catalytic reaction. However, the detailed structural dynamic evolution under operation conditions, particularly illumination and electrode potential, and the underlying mechanism remain elusive. In this proposal, we will systematically investigate the local configurations of the active centers and especially their dynamic evolution under operation conditions in the framework of thermodynamics and dynamics. In addition, photo-/electro-catalytic N2 fixation will be selected as the probe reaction to disclose the structure–performance correlations of 2DM©SACs. The present project is expected to provide new guidelines for the development of practical 2DM©SACs and contribute to theoretical enrichment of basic understandings in photo-/electro-catalysis.