Tuning the Pyridine Units in Vinylene‐Linked Covalent Organic Frameworks Boosting 2e− Oxygen Reduction Reaction

Abstract The N‐doped carbon materials are supposed to be the efficient oxygen reduction reaction (ORR) catalysts with the undefined N‐doped carbon ring groups. It is essential to well define the role of the nitrogen atoms of these carbon structures in active behavior. Even though, the covalent organic frameworks (COFs) with precise structures are well developed, but unable to exclude the polar linkages influence. This study presents a series of pyridine‐containing COFs linked via nonpolar carbon–carbon double bonds (C = C). Their catalytic activity and selectivity for 2e− ORR are successfully modulated by locating the embedded pyridine nitrogen in the backbones through the linking modes of pyridine moieties within the frameworks. Such phenomena can be attributed to their different binding abilities toward O2, leading to the different binding strength of the intermediate OH* to the catalytic sites, also verified by the theoretical calculation. This work provides us a new insight to design high‐efficiency ORR catalysts through the exact location of pyridine nitrogen.