多孔固体中的电子转移机制与功效

Porous solids with various structures, compositions and morphologies have been widely used as catalysts, photocatalysts, and energy-storing materials. Electron tranfer usually plays an important part in the processes of catalysis, energy storage and conversion. Owing to the unique features of the porous frameworks, the electron transfer in a porous solid is different from in other solid materails. The investigation of electron transfer is of particular significance for the elucidation of reaction machanism involving a porous solid. Thus, the understanding of electron transfer which facilitates the exploration of new functions of porous solids is highly desirable. In this project, new porous solids with particular structures and compositions will be designed and prepared through well selected synthetic strategies and control of the reaction conditions. The catalytic, photovoltaic, and electrochemical performance of the porous solids will be systematically evaluated. More importantly, the process of electron transfer within the framework of a porous solid, or from the framework of a porous solid to guest species will be investigated. The driving forces for the electron transfer processes will be clarified. The impact of electron transfer on the functions of porous solids will be carefully elucidated. The investigation performed in this project on the mechanism and functions of electron transfer involving porous solids is of foundmental and practical significance for the rational design and construction of novel functional porous solids.

随着多孔固体在储能、催化等领域的应用，对相关反应机理的研究和新性能的开发已成为多孔材料研究领域的热点和前沿问题。由于存在特殊的骨架和孔道结构，多孔固体中的电子转移行为有别于其他固体材料。本项目拟从多孔固体的设计合成出发，发展具有特定组成和结构的多孔固体的可控制备；围绕电子在多孔骨架、骨架与客体分子或骨架与骨架之间的转移机制进行深入研究，明确电子转移的驱动力、影响因素及状态；针对电子转移过程在有机小分子的催化转化、电化学及光电化学等功能体系中的机制与功效进行系统探索，建立电子转移机制与反应功效之间的关系。本项目对于开发新型多孔固体材料、从原子和分子水平认识多孔固体中电子转移过程与功效、促进多孔固体在催化和电化学与光电化学体系中的实际应用具有重要意义。

本项目以多孔材料为研究对象，针对多孔材料在催化、储能等应用领域的关键指标，在具有特殊结构和组成的多孔固体的设计合成方面取得一系列可喜的成果：实现了分子筛晶体中微孔-介孔复合体系的构筑，优化了分子筛材料在催化应用中的物质传输效率和催化稳定性；通过在多孔晶体材料内引入功能化纳米粒子，实现了分子筛择形催化和纳米粒子高催化活性的集成；通过一维-二维等级碳结构的复合及多级孔结构的优化，获得了系列高效复合电催化材料和电极材料；无机纳米空心多孔结构的合理设计提升了该类材料的催化活性和作为能源材料的各项想能指标。基于多孔固体材料孔结构和组成的可控制备，本项目进一步研究了多孔固体材料中“电子布居与固体催化活性的构效关系”，利用多种组分与多孔材料的界面、化学相互作用的调控，实现了多孔固体材料中给电子能力、载流子密度和氧化还原能力的调控，进而调变材料在催化、储能等领域的应用性能。这些研究进展对于开发新型多孔固体材料、从原子和分子水平认识多孔固体中电子转移过程与功效、促进多孔固体在催化和电化学与光电化学体系中的实际应用具有重要意义。项目运行以来，共发表SCI论文83篇，其中影响因子大于10的期刊上发表论文21篇；申请国家发明专利28项，授权发明专利22项。在人才培养方面，共培养硕士博士研究生 40余人 人，已有32 人获得硕士/博士学位。