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

The electrocatalytic conversion of NOx 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 Cu₃Sn/Cu₆Sn₅ 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 Cu₃Sn and Cu₆Sn₅ biphasic alloys, promoting the electron transfer and optimizing the adsorption of NO₃₋ and glyoxylic acid, and thus facilitating the generation of *NH₂OH 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.