Two‐Dimensional Organometallic Frameworks with Pyridinic Single‐Metal‐Atom Sites for Bifunctional ORR/OER

Abstract Achieving efficient bifunctional oxygen reduction and evolution reactions (ORR/OER) on non‐noble metal catalysts is desirable but remains a significant challenge. Herein, inspired by the experimentally synthesized (phen 2 N 2 )FeCl molecule, a stable 2D organometallic framework, namely (phen 2 N 2 )FeCl monolayer, is proposed as a qualified candidate by means of constant‐potential first‐principles computations. Unlike most 2D organometallic frameworks that feature pyrrolic coordination, the (phen 2 N 2 )FeCl monolayer exhibits a pyridinic‐type FeN 4 ligation environment. The unique structure of the monolayer enables a high single‐atom Fe loading in a heterogeneous system, superior to the typical FeNC materials. Constant‐potential energy analysis and microkinetic modeling demonstrate that the monolayer holds great potential for facilitating bifunctional ORR/OER in both the acidic and alkaline conditions, showing theoretical activity higher than the FeNC materials, (phen 2 N 2 )FeCl molecule, and Pt/IrO 2 . Moreover, (phen 2 N 2 )MCl monolayers (M = Mn, Co, and Ni) are explored, and the (phen 2 N 2 )MnCl monolayer is also identified to have excellent bifunctional activity. This study highlights the rational design of local coordination environments for boosting the electrocatalytic performance of 2D organometallic frameworks.