对共轭分子协同下金属有机框架化合物电催化性能的研究

Metal-organic framework (MOF) has been widely used in energy conversion and electrocatalysis due to the large specific surface area and high porous structure. It is difficult to increase the conductivity of MOF and improve its electrochemical property at a large extent. Organic compounds with π-conjugated structures are typical semiconductor materials owing to the high transmission of electric charges. This project proposes to apply the abovementioned organic ligands to undergo the facial exchange reaction with a series of pristine Co-MOF to get novel nano-MOF materials. It is supposed to enhance the conductivity and improve the electrochemical catalytic activity of as-prepared nano-MOF materials due to the accelerated electron transportation via coating π-conjugated molecules. The obtained materials will be investigated their electrocatalytic efficiency on oxygen evolution reaction. Furthermore, it will be explored the principle between the structures of different materials and their corresponding performances based on the obtained different nano-MOF materials. The underlying theory will be discussed in the perspective of molecular level. This project aims at obtaining porous nanomaterials with superior electrochemical properties and investigating the electrocatalytic theory of functional complexes. In addition, this project would provide a novel idea for the research of conductive complexes and lay theoretical foundation on electrochemical catalysis in the development of industrialization.

金属有机框架(MOF)化合物因其具有大比表面积和高孔隙率等特性，近年来常被应用在能量转化和电化学催化等领域。如何最大程度地提高MOF的导电性、改善电化学性能成为亟需解决的难题。含共轭大π结构的有机化合物因其电荷传输速率高，所以常被作为典型的半导体材料。本项目拟采用此类有机化合物与一系列Co-MOF进行表界面反应，合成表面具有共轭平面的新型纳米MOF复合材料。通过复合共轭有机分子增强电子的传输，可以提高MOF的导电性，改善MOF的电化学性质，从而增强MOF的电催化活性。本项目通过测试纳米MOF复合材料电催化析氧反应的效率，对比不同复合材料的电催化活性，从分子水平研究化合物的结构对材料电化学性能的影响，探索结构与性能之间的构效关系。本项目拟合成具有优良电化学催化性能的多孔纳米材料，探索功能型配合物的电催化机理，为导电配合物的研究提供新的思路，为电化学催化剂的工业化发展提供理论支撑。

MOFs（Metal-organic frameworks）是一种由金属离子和有机配体构筑的三维有序多孔配合物。由于MOFs孔隙率高、比表面积大、易功能化等优点，近年来被广泛应用于能源储存和转化领域，如气体储存和分离、多相催化、传感和药物输送等。然而，绝大多数MOFs是导电率极低的电绝缘体，这就限制了其在电化学领域的应用，因此制备具有良好导电性和电化学活性的新型MOFs受到广泛关注。MOFs复合纳米材料在过去几年中取得了巨大的进展，各种具有高电荷迁移率或导电性的二维和三维MOFs得以开发。科学研究者们通过多种策略实现了MOFs的高导电性。在该工作中，被资助人对较稳定的ZIF-67进行修饰，通过低温煅烧及掺杂活性Au纳米颗粒等手段提高了所得复合材料的导电性，改善了材料的电化学活性，并在析氧反应中表现出较好的催化活性；此外，被资助人构建了由导电MOFs和过渡金属化合物组成的复合纳米材料，从调节材料的形貌和尺寸出发，研究了对应材料的电化学活性，并成功地应用在了高性能超级电容器中。这项工作的结果将为开发MOFs纳米衍生物作为一种潜在的电化学活性器件材料提供了方向。