A Computational Study of Transition Metal Atom Embedded‐Pd(111) as Efficient Electrocatalysts for N ₂ Reduction

ABSTRACT Currently, there is a significant demand for NH 3 in both industrial and agricultural sectors. However, traditional industrial synthesis of NH 3 primarily relies on the Haber−Bosch process, which operates under harsh conditions, consumes substantial energy, and produces considerable greenhouse gas emissions. Therefore, it is imperative to find new catalysts that can reduce N 2 to NH 3 under ambient conditions. The green advantage of electrochemical synthesis of NH 3 in reactions using renewable resources. However, challenges such as high overpotential and competition from hydrogen evolution reactions necessitate exploration into low‐cost yet high‐performance NH 3 catalytic materials. Herein, this work systematically investigates the structural stability, catalytic activity, and selectivity of TM@Pd(111) catalysts formed by intercalating a transition metal (TM) atom into the Pd(111) surface, using density functional theory. Through screening various TM atoms, it is found that Os@Pd(111) exhibits excellent thermodynamic and electrochemical stability, as well as outstanding catalytic activity for the nitrogen reduction reaction. Moreover, it can effectively suppress the hydrogen evolution reaction, with a limiting potential of −0.487 V. The intrinsic reasons for the excellent catalytic activity of Os@Pd(111) are analyzed by calculating electronic properties. Thus, Os@Pd(111) is expected to become an efficient catalyst and provide guidance for experimental and theoretical research on nitrogen fixation catalysts.