武汉大学汪成团队报道了促进基于卟啉的sp2碳共轭共价有机框架的能量转移途径，用于选择性光催化硫化物氧化。相关研究成果于2024年4月10日发表在《结构化学》。

具有完全π共轭晶格和高化学稳定性的sp²碳共轭共价有机框架（COFs），有希望实现多相光催化剂，但具有挑战性。

该文中，研究人员报道了一种新型的基于钯卟啉的sp²碳共轭COF（PdPor-sp2c-COF）的设计和合成，该COF具有AA堆叠2D结构。有趣的是，PdPor-sp²c-COF显示出高结晶度、良好的化学稳定性和对可见光的宽吸收。此外，与之前报道的不含金属的Por-sp²c-COF相比，PdPor-sp²c-COF在绿光照射下对硫化物的选择性好氧氧化中表现出改进的光催化性能。

系统的机理研究表明，PdPor-sp²c-COF在光催化过程中促进了能量转移，从而提高了光催化性能。研究清楚地表明，使用金属卟啉基分子构建块有利于促进sp²碳共轭COFs中的能量转移途径，以提高其光催化性能，这将启发人们设计和合成用于选择性好氧氧化的新型基于COFs的光催化剂。

附：英文原文

Title: Promoting energy transfer pathway in porphyrin-based sp2 carbon-conjugated covalent organic frameworks for selective photocatalytic oxidation of sulfide

Author: Weixu Li, Yuexin Wang, Lin Li, Xinyi Huang, Mengdi Liu, Bo Gui, Xianjun Lang, Cheng Wang

Issue&Volume: 2024-04-10

Abstract: The sp2 carbon-conjugated covalent organic frameworks (COFs) with fully π-conjugated lattice and high chemical stability are promising but challenging to achieve heterogeneous photocatalysts. Herein, we report the design and synthesis of a novel palladium porphyrin-based sp2 carbon-conjugated COF (PdPor-sp2c-COF) with an eclipsed AA stacking 2D structure. Interestingly, PdPor-sp2c-COF showed high crystallinity, good chemical stability, and a broad absorption of visible light. Moreover, compared to our previously reported metal-free Por-sp2c-COF, PdPor-sp2c-COF displayed an improved photocatalytic performance in the selective aerobic oxidation of sulfides under green light irradiation. The systematic mechanism studies testified that the enhanced photocatalytic performance can be ascribed to the promoted energy transfer pathway by PdPor-sp2c-COF during photocatalytic process. Our study clearly demonstrated that it is favorable to promote the energy transfer pathway in sp2 carbon-conjugated COFs to enhance the photocatalytic property by using metalloporphyrin-based molecular building blocks, which will inspire us to design and synthesize novel photocatalyst based on COFs for the selective aerobic oxidation.

DOI: 10.1016/j.cjsc.2024.100299

Source: http://cjsc.ac.cn/cms/issues/597