Boosting Selective Nitrogen Reduction via Geometric Coordination Engineering on Single‐Tungsten‐Atom Catalysts

Abstract Atomic interface regulation that can efficiently optimize the performance of single‐atom catalysts (SACs) is a worthwhile research topic. The challenge lies in deeply understanding the structure–properties correlation based on control of the coordination chemistry of individual atoms. Herein, a new kind of W SACs with oxygen and nitrogen coordination (W‐NO/NC) and a high metal loading over 10 wt% is facilely prepared by introducing an oxygen‐bridged [WO 4 ] tetrahedron. The local structure and coordination environment of the W SACs are confirmed by high‐angle annular dark‐field scanning transmission electron microscopy, X‐ray photoelectron spectroscopy, and extended X‐ray absorption fine structure. The catalyst shows excellent selectivity and activity for the electrochemical nitrogen reduction reaction (NRR). Density functional theory calculation reveals that unique electronic structures of the N and O dual‐coordinated W sites optimize the binding energy of the NRR intermediate, resulting in facilitating the electrocatalytic NRR. This work opens an avenue toward exploring the correlation between coordination structure and properties.