Modulating the Electronic Structure of Cobalt in Molecular Catalysts via Coordination Environment Regulation for Highly Efficient Heterogeneous Nitrate Reduction

Abstract Ammonia (NH 3 ) is pivotal in modern industry and represents a promising next‐generation carbon‐free energy carrier. Electrocatalytic nitrate reduction reaction (eNO 3 RR) presents viable solutions for NH 3 production and removal of ambient nitrate pollutants. However, the development of eNO 3 RR is hindered by lacking the efficient electrocatalysts. To address this challenge, we synthesized a series of macrocyclic molecular catalysts for the heterogeneous eNO 3 RR. These materials possess different coordination environments around metal centers by surrounding subunits. Consequently, electronic structures of the active centers can be altered, enabling tunable activity towards eNO 3 RR. Our investigation reveals that metal center with an N 2 (pyrrole)‐N 2 (pyridine) configuration demonstrates superior activity over the others and achieves a high NH 3 Faradaic efficiency (FE) of over 90 % within the tested range, where the highest FE of approximately 94 % is obtained. Furthermore, it achieves a production rate of 11.28 mg mg cat −1 h −1 , and a turnover frequency of up to 3.28 s −1 . Further tests disclose that these molecular catalysts with diverse coordination environments showed different magnetic moments. Theoretical calculation results indicate that variated coordination environments can result in a d‐band center variation which eventually affects rate‐determining step energy and calculated magnetic moments, thus establishing a correlation between electronic structure, experimental activity, and computational parameters.