Tuning the Coordination Microenvironment of Central Fe Active Site to Boost Water Electrolysis and Oxygen Reduction Activity

Abstract In heterogeneous catalysis, single‐atom catalysts are the frontier and important prototypes for many reactions, and revealing the intrinsic structure–activity relationship is presently a critical task, but remains challenging. In this work, water electrolysis and oxygen reduction performances of FeXY_iN_3‐i (X, Y = B, C, O, P and S; i = 0, 1) moiety in Fe–porphyrin are studied by the first‐principles calculations, aiming at unraveling how and why tuning the coordination microenvironment of the active metal atom can improve the activity. It can be concluded that breaking the coordination shell symmetry breaks the well‐accepted standard scaling relationship, adjusts *O adsorption behavior and thus optimizes the oxygen evolution reaction (OER) activity, for example, to an extremely low overpotential of 0.17 V. In combination with the Fe atom spin configuration and ligand field theory, the dramatically improved OER activity can be well explained. In the present work, the significance of the coordination microenvironment of central metal atom in studies of electrocatalysis is highlighted.