Metal–Support Electronic Coupling in Re 2 /NiO Enables Early N≡N Bond Cleavage and Dissociative N 2 Reduction

Designing catalysts that can efficiently cleave the inert N≡N bond while suppressing competing hydrogen evolution reaction (HER) is a long-standing challenge in electrochemical nitrogen electroreduction (NRR). Here, inspired by the recent experiments that utilize NiO as support to disperse transition metal atoms, we propose Re 2 /NiO as a promising NRR catalyst, which dissociates N 2 with a barrier of only 0.66 eV, driving NRR to proceed through a dissociative mechanism. This is distinct from the conventional associative pathway, where N 2 is protonated to form *NNH first, which usually serves as the rate-limiting step with a barrier greater than 1 eV. Electronic structure analyses further demonstrate strong metal–support interactions and dynamic charge redistribution that underlie the catalyst’s superior activity and selectivity. Surface Pourbaix diagram and kinetic analyses confirm the intrinsic suppression of HER on Re 2 /NiO, while ab initio molecular dynamics (AIMD) and machine learning molecular dynamics (MLMD) simulations validate its excellent thermal and dynamic stability under realistic NRR conditions. This work establishes Re 2 /NiO as an advanced NRR catalyst and provides new insights for designing dual-site catalysts for challenging bond activation reactions.