Hydrogenation of “Readily Activated Molecule” for Glycine Electrosynthesis

Abstract The hydrogenation of glyoxylate oxime is the energy‐intensive step in glycine electrosynthesis. To date, there has been a lack of rational guidance for catalyst design specific to this step, and the unique characteristics of the oxime molecule have often been overlooked. In this study, we initiate a theoretical framework to elucidate the fundamental mechanisms of glycine electrosynthesis across typical transition metals. By comprehensively analyzing the competitive reactions, proton‐coupled electron transfer processes, and desorption steps, we identify the unique role of the glyoxylate oxime as a “readily activated molecule”. This inherent property positions Ag, featuring weak adsorption characteristics, as the “dream” catalyst for glycine electrosynthesis. Notably, a record‐low onset potential of −0.09 V versus RHE and an impressive glycine production rate of 1327 µmol h −1 are achieved when using an ultralight Ag foam electrode. This process enables gram‐scale glycine production within 20 h and can be widely adapted for synthesizing diverse amino acids. Our findings underscore the vital significance of considering the inherent characteristics of reaction intermediates in catalyst design.