Glutathione-Mediated Biomimetic NO Activation with Coordination Capsules for NH ₃ and α-Amino Acid Electrosynthesis

The conversion of nitrogen oxides into nitrogen-containing chemicals is critical to the global nitrogen cycle, but utilizing resources derived from NOx gas presents significant challenges. Herein we report a biomimetic strategy to incorporate a catalytic partner into coordination capsules for efficient N–O bond cleavage and α-amino acid synthesis. This strategy includes the generation of NO adducts via glutathione-mediated NO binding and enzymatic NO activation via the formation of substrate-involved intermediates. The metal centers interact with the NO adducts, anodically shifting the redox potential up to −0.34 VNHE. Under the optimized conditions, the enzymatic manifold facilitates an ammonia conversion rate of 182.16 μmol·h–1·cm–1 and a Faradaic efficiency (FE) of 87.1% with the lowest overpotential of −0.3 VRHE, surpassing the performance of most reported electrocatalysts. When both the α-keto acid and the NO adduct were incorporated within the capsules, efficient electrocatalytic conversion of NO into amino acids was achieved with a high FE of 55.2%, providing an attractive way to elucidate enzyme-like activation dynamics.