Cu‐Sn Biphasic Alloy Heterostructure With <i>p‐d</i> Orbital Hybridization for Efficient Electrosynthesis of Amino Acids

ABSTRACT The electrocatalytic conversion of NO x species into amino acids is an attractive approach. However, significant challenges lie in the matching kinetics of C−N coupling and high selectivity for the target product. Herein, a Cu 3 Sn/Cu 6 Sn 5 biphasic alloy heterostructure (Cu‐Sn BAH) with p‐d orbital hybridization has been constructed by phase control engineering for enhanced amino acid electrosynthesis, delivering a remarkable glycine Faradaic efficiency of 80% and a selectivity of 93% at −0.8 V vs. RHE. Experimental and mechanistic studies reveal that the strong p‐d orbital hybridization between d ‐block Cu and p ‐block Sn effectively modulates interfacial electronic structure between Cu 3 Sn and Cu 6 Sn 5 biphasic alloys, promoting the electron transfer and optimizing the adsorption of NO 3– and glyoxylic acid, and thus facilitating the generation of *NH 2 OH with reduced energy barriers and subsequent oxime hydrogenation. This work offers a distinctive electrocatalyst design strategy for highly selective amino acid synthesis via orbital engineering and heterostructure construction, and also encourages the development of C−N coupling systems.