Auene‐Supported Transition‐Metal Single‐Atom Catalysts for Promising Electrocatalytic Nitrogen Reduction

The electrochemical nitrogen reduction reaction (NRR) provides a sustainable route to ammonia synthesis, but its efficiency is hindered by the inert N≡N bond and competing hydrogen evolution reaction (HER). Herein, we systematically screened 25 transition‐metal (TM) single‐atom catalysts (SACs) supported on goldene, denoted as TM@Auene, using density functional theory (DFT). Sixteen TM@Auene systems capable of end‐on N 2 adsorption were evaluated across distal, alternating, and mixed NRR pathways. Mo@Auene and Re@Auene exhibited high NRR catalytic activity with low limiting potentials of −0.04 and −0.10 V, respectively, associated with effective N 2 activation through synergistic σ‐donation and π*‐back‐donation. A volcano‐type relationship was established between NRR activity and occupied d‐electron number, positioning Mo and Re near the optimum. HER competition was assessed, with Nb@Auene, Mo@Auene, W@Auene, Re@Auene, and Os@Auene showing favorable NRR selectivity. For Mo@Auene and Re@Auene, Pourbaix diagram analysis and ab initio molecular dynamics (AIMD) simulations provide preliminary support for electrochemical stability and short‐timescale structural integrity under NRR‐relevant conditions. These results identify Mo@Auene as a promising NRR candidate and highlight Auene‐supported SACs as a descriptor‐guided platform for catalyst design.