Early N─O Bond Cleavage Unlocks Barrier‐Free Nitric Oxide Electroreduction to Ammonia on B‐Doped GeS 2 Monolayer: A Comprehensive Density Functional Theory Study

Electrochemical reduction of nitric oxide (NO) to ammonia (NH 3 ) integrates pollutant abatement with green chemical synthesis. Using density functional theory with the computational hydrogen electrode model, we investigate NO electroreduction on a boron‐doped GeS 2 monolayer (B@S‐GeS 2 ) containing complementary Ge and B active centers. At the Ge site, the distal pathway operates as the minimum‐energy pathway under gas‐ and aqueous‐phase conditions, achieving a barrier‐free limiting potential ( U L = 0 V vs. RHE) driven by early N─O bond cleavage following double O‐end protonation. Conversely, the electron‐deficient B site exhibits stronger NO binding ( E ads = −2.14 eV). Although strong postcleavage N stabilization yields U L = −0.218 V, implicit solvation stabilizes polar intermediates, establishing a near‐degenerate dual‐pathway mechanism (Δ U L = 0.027 V). Both sites intrinsically suppress the hydrogen evolution reaction via severe H overbinding (Δ G H = −0.93 to −1.57 eV) and competitive NO adsorption. Additionally, competing N 2 O/N 2 formation pathways are kinetically and thermodynamically disfavored (Δ G PDS = +0.61 to +2.19 eV). Outperforming benchmark 2D catalysts, B@S‐GeS 2 presents a highly selective, dual‐site platform for ambient NO‐to‐NH 3 valorization.