作为一类特殊的锡氧化物，晶态混合价（II，IV）锡-氧簇合物在电催化CO2还原制甲酸领域极具先天优势，然而目前晶态混合价（II，IV）锡-氧簇合物的结构类型匮乏，合成方法相对单一、Sn4+/Sn2+组成缺乏有效调控。针对上述问题，本项目以电催化CO2还原制甲酸为功能导向，拟采用配位活性位点诱导组装策略，以富含O给体的配体（包括含有杂原子F、N等）为有机组件，在具有配位活性位点的锡-氧簇单元合成条件中原位组装或将其作为反应物分步组装构筑目标簇合物，丰富该类簇合物的结构类型，总结合成规律，发展新的策略和合成方法；同时，探究簇核结构、核数、Sn4+/Sn2+组成、配体或基团对电催化CO2还原制甲酸性能的影响规律，揭示组成、结构与电催化还原性能之间的内在关系，阐明电催化CO2还原制甲酸机理，实现高性能晶态混合价（II，IV）锡-氧簇合物的创制，丰富簇化学、配位化学、结构化学、合成化学的研究内容。

As the molecular mixed-valence tin oxide, crystalline mixed-valence (II, IV) tin-oxo clusters have many advantages in the preparation of HCOOH through electrocatalytic CO2 reduction. However, there are some important issues to be resolved in the researches of mixed-valence (II, IV) tin-oxo clusters, including the less developed structural diversities, the simple synthetic methods, and the unregulated component of Sn4+/Sn2+. Herein, this project will use the coordination sites of different tin (IV)-oxo clusters and the different functionalized O-containing ligands to synthesize mixed-valence (II, IV) tin-oxo clusters and aggregations via one-pot or two-step method. The relationship between syntheses and structures will be summarized. Furthermore, the influences of cluster cores, component of Sn4+/Sn2+ and ligands on the electrocatalytic CO2 reduction properties will be investigated. The relationship among compositions, structures and properties will also be summarized. The mechanism of electrocatalytic CO2 reduction will be elucidated. This project will not only obtain a diversity of mixed-valence (II, IV) tin-oxo clusters with excellent performances of electrocatalytic CO2 reduction, but also enrich the researches of the cluster chemistry, coordination chemistry, structural chemistry and synthetic chemistry.