茂金属分子/金属有机框架微孔限域调控的过渡金属纳米异质结电催化性能研究

调控活性位点电子结构是实现材料电催化（氧析出和氧还原反应）性能高效提升的关键。当前对精细电子结构的有效调变仍面临极大挑战。针对这一关键科学问题，本项目设计合成一类新型的纳米异质结构，通过对异质界面结构的控制，深入解析从材料微结构调变电子结构的电催化反应机制。拟采用高度可设计的多孔化金属有机框架为限域载体，引入过渡族茂金属分子基团，通过有序微孔空间限域控制主客体配位金属及有机配体的演化过程，衍生构建多孔碳负载的Ni, Co, Fe, Mn基过渡金属纳米异质结构。深入研究从聚合物前体的空间拓扑结构到无机衍生物微结构的定向演化机制，通过有机框架载体多孔结构的理性设计和控制性衍生手段，对异质界面组分、形态、尺寸、原子排布、缺陷等进行有效调控，进而调变活性位点的精细电子结构和电催化反应能垒，揭示微结构-电子行为-催化活性之间的内在调制关系，为高效非贵金属电催化材料的可控设计和性能调控提供新的策略。

Controlling the electronic structure of the active sites is the key to improve the electrocatalytic performance （oxygen evolution and oxygen reduction reactio）of materials. At present, the effective modulation of fine electronic structure is still facing great challenges in methods and means. Aiming at this key scientific problem, this project designs and synthesizes a new type of nano heterostructure. The electrocatalytic reaction mechanism of electronic structure modulation by controlling of the heterogeneous interface structure will be deeply analyzed. It is proposed to use highly designable porous metal-organic frameworks as confinement template and introduce transition metallocene as confinement guest molecules. By controlling the evolution of host-guest coordination metals and organic ligands through ordered microporous space confinement, porous carbon supported Ni, Co, Fe, Mn based transition metal nanostructures are derived and constructed. The mechanism of rational design and evolution from the spatial topological structure of polymer precursor to the microstructure of inorganic derivative will be studied. The composition, morphology, size, atomic arrangement and defects of heterogeneous interface can be effectively controlled by reasonable design of porous structure of organic framework and controllable derivation method, so as to change the fine electronic structure and electrocatalytic reaction energy barrier of active sites. The internal regulatory relationship among the microstructure, electronic behavior and catalytic activity of materials is revealed, which provides a new strategy for the controllable design of high-efficiency non noble metal electrocatalytic materials.