Spin Control at Bi–Bi ₂ O ₃ Heterointerfaces for Highly Efficient Electrosynthesis of Glycine

ABSTRACT Electrocatalytic C─N coupling offers an efficient and sustainable pathway for glycine synthesis; however, its efficiency is limited by key intermediates conversion involving spin‐state reconfiguration. Herein, we develop a heterostructured catalyst that can induce a high density of Bi (OVs) sites with localized magnetic moments via oxygen‐vacancy formation at the Bi/Bi ₂ O ₃ interfaces. Within the eBi–Bi ₂ O ₃ catalyst, Bi sites serve as the primary adsorption sites for NO ₃ ⁻ and the conversions of closed‐shell intermediates, while Bi (OVs) sites selectively facilitate the spin‐state reconfiguration of the adsorbed *NO to *NHO. This synergistic Bi/Bi (OVs) configuration promotes the subsequent formation of hydroxylamine as a crucial reaction intermediate and steers the reaction pathway toward favorable glycine synthesis. The eBi–Bi ₂ O ₃ catalyst exhibits an attractive Faradaic efficiency of 80.32% and yield rate of approximate 1000 µmol h ⁻¹ cm ⁻² for glycine synthesis, establishing one of the best overall performances reported to date. This work offers a pioneering strategy for developing spin catalysts applicable to electrochemical reactions involving complex multi‐step pathways.