Carbon radical-promoted NH bond breaking for biomass-derived amino acids to nitriles on low-coordinated Ni centers

Cyanide-free electrosynthesis converts amino acids to nitriles with >90% FE. • Low-coordinated Ni sites promote NiOOH formation for decarboxylation–dehydrogenation. • Carbon radicals induce nitrogen lone-pair delocalization, facilitating N H cleavage. • Broad amino acid scope includes challenging aromatic substrates. Leveraging biomass for organic nitrogen synthesis can reduce dependency on fossil ammonia, streamline synthetic pathways, and decrease carbon footprint and contamination. However, the conversion is chemically disfavored owing to the competition with deamination, overoxidation, and crosslink. Herein, we report a novel electrochemical synthesis route for biomass-derived amino acid oxidation, using L-alanine as the representative example to produce acetonitrile with high selectivity in the electrolyte. Upon dynamic reconstruction, defect-rich NiO anchored on O-doped carbon interacts with carboxylate groups, thereby facilitating decarboxylation. The resulting carbon radical induces partial delocalization of the nitrogen lone pair electrons, which weakens the N H bond, ultimately promoting nitrile production. The optimized electrocatalyst delivers a Faradaic efficiency of up to 92.2% together with a high acetonitrile production rate of 580.1 mmol g cat −1  h −1 and excellent stability. Moreover, our strategy has proven to be applicable to multiple α-amino acids. This work reveals the fundamental mechanism of amino acid electrooxidation to nitriles and paves the way for green and sustainable nitrogen utilization. An electrochemical strategy to convert biomass-derived amino acids into value-added nitriles using low-coordinated Ni catalysts. The process initiates decarboxylation to generate carbon-centered radical, which reorganize the local C N bonding environment and lower the barrier for C N bond formation, providing a sustainable and cyanide-free route for nitrogen valorization from renewable feedstocks. Download: Download high-res image (72KB) Download: Download full-size image