Enhancing Oxygen Reduction Reaction through Asymmetric Electronic Structure-Mediated d-π Interaction

Open AccessCCS ChemistryRESEARCH ARTICLES12 Dec 2024Enhancing Oxygen Reduction Reaction through Asymmetric Electronic Structure-Mediated d-π Interaction Zhe Zhang, Ziqi Zhang, Minggang Xie, Rui Tian, Chunxiao Chai, Ruian Xu, Xiao-bo Chen, Yujiang Song, Haiyan Lu, Zhan Shi and Shouhua Feng Zhe Zhang , Ziqi Zhang , Minggang Xie , Rui Tian , Chunxiao Chai , Ruian Xu , Xiao-bo Chen , Yujiang Song , Haiyan Lu , Zhan Shi and Shouhua Feng https://doi.org/10.31635/ccschem.024.202405248 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Non-precious transition metal (TM)-based materials have demonstrated tremendous potential as efficient oxygen reduction reaction (ORR) electrocatalysts. However, establishing reliable relationships between geometric/electronic structures and ORR performances, remains a great challenge to design and manufacture high-performance ORR catalysts. In this study, we propose and validate that reducing the symmetry of the coordination structure of TMs enhances d-π interactions, thereby strengthening their adsorption for key intermediates. Then, we manage the tuning of the metal center's spin state by substituents, which further optimizes the ORR performance. Such advancements are attributed to the orientation differences in d-orbital interactions as a result of asymmetric electronic structure. Based upon the understandings of such structureactivity relationships, we designed a covalent organic framework-based ORR electrocatalyst, which exhibits high activity, rapid kinetic response, and high four-electron transfer selectivity. This work validates an alternative strategy for enhanced ORR through managing d-π interactions by means of asymmetric coordination structures. It inspires the design of TM-based electrocatalysts by providing mechanistic insights through the precise control of the microchemical environments at TM active centers. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentNot Yet AssignedSupporting Information Copyright & Permissions© 2024 Chinese Chemical Society Downloaded 10 times PDF downloadLoading ...