Edge‐Rich Graphene Nanomesh Thermally Self‐Exfoliated From Metal‐Organic Frameworks for Boosting CO ₂ Electroreduction

Abstract Atomic‐level metal sites at the edges of graphene‐like carbon supports are considered more active for CO 2 electrocatalysis than those in‐plane. However, creating high‐density edge‐dominating metal sites, particularly in a simple, scalable, and self‐templated fashion, presents a significant challenge. Herein, a MOF‐mediated self‐exfoliation strategy is reported to preferentially integrate edge‐type FeN 4 sites onto the ultrathin edge‐rich N‐doped graphene nanomesh (e‐Fe‐NGM). Theoretical calculations, finite element method (FEM) simulations, together with a series of in situ spectro‐electrochemical experiments corroborate that the edge‐dominating FeN 4 sites can not only optimize the electronic structure of catalysts, facilitating the formation of * COOH and desorption of * CO, but also effectively induce a strong local electrostatic field, promoting the interfacial H 2 O supply and thereby accelerating the protonation process of CO 2 . Thus‐prepared e‐Fe‐NGM delivers a remarkable CO Faraday efficiency (FE) of above 98% over an ultra‐wide potential window of 500 mV and a high turnover frequency of 6648 h −1 , much superior to that of the controlled sample with dominant plane‐type sites. Moreover, this self‐exfoliated, non‐catalyzed approach is readily scalable and can be used to produce large‐size edge‐rich graphene nanomesh at industrial levels.