含三个活性金属原子的团簇体系活化转化氮气分子的机理研究

本年度重大研究计划重点资助方向“团簇的功能与应用”继续关注“温和固氮及机制”的相关研究。温和条件下氮气还原反应（NRR）具有重要的应用价值。单原子、单团簇催化的发展为温和NRR的实现提供了可行的方向。本项目以团簇为模型体系，以包含三个活性金属原子的团簇为突破口，系统研究同核、异核金属碳化物、氮化物等团簇体系以及包含团簇载体的体系。以密度泛函理论为基础，使用概念密度泛函理论等分析方法，深入研究单原子类催化体系活性位点的电子结构信息，关注金属-金属、金属-氮气相互作用，在分子水平上研究氮气分子活化转化的微观机理。使用火山图、热度图、机器学习等方法探索影响催化反应活性的关键因素，提出合理预测催化性能的描述符。结合必要的实验和周期性模型方法以提高研究的可靠性。本项目充分发挥团簇模型系统性理论研究的优势，全面、深刻地揭示复杂催化反应的微观机制，为合理设计和实际合成NRR催化剂提供重要的理论指导。

One of the key research directions funded by the Major Research Plan this year, "the function and application of clusters", continues to support the research on "mild nitrogen fixation and its mechanisms". Nitrogen reduction reaction (NRR) under mild conditions is of great importance in applications. The progress of single-atom and single-cluster catalysis provides a feasible direction for NRR under mild conditions. In this project, we use clusters as the model systems, and select clusters with three active metal atoms as the starting point to break through. The research systems include homonuclear and heteronuclear metal compound clusters (e.g., carbides, nitrides) and systems with supporting clusters. Based on density functional theory calculations, the conceptual density functional theory and other analysis methods will be used to explore the electronic structure of active sites of single-atom/single-cluster catalysts, investigate the microscopic information of metal-metal and metal-nitrogen interactions, and reveal the microscopic mechanisms of the activation and conversion of dinitrogen at the molecular level. The essential factors affecting the catalytic activity will be explored using the volcano diagram method, heat map method and machine learning method, based on which descriptors will be proposed for reasonable prediction of catalytic performance. The necessary experiments and periodic model methods are combined to improve the reliability of the research. This project will take full advantage of systematic theoretical research with cluster models, gain a comprehensive and profound understanding of the microscopic nature of complicated catalytic reactions, and provide crucial theoretical guidance for the rational design and practical synthesis of NRR catalysts.