Salt-Free Glycine Electrosynthesis via Carbon–Nitrogen Coupling Boosted by the Lattice Strain in Atomically Thin <i>p</i> -Block Bismuthene

Electrochemical carbon–nitrogen (C–N) coupling using simple inorganic feedstocks offers a sustainable route to valuable organonitrogen compounds such as amino acids. Herein, we present an atomically thin and acid-resistant p -block bismuthene (Bi-ene) derived via the reconstruction of a Bi-based metal–organic framework, where the enriched atomic misarrangement induces significant lattice strain that modulates the local electronic structure of the resultant Bi-ene, significantly boosting its electrocatalytic activity. Such defective Bi-ene exhibits an exceptional electrocatalytic performance for reductive C–N coupling in a salt-free acidic system, achieving a Faradaic efficiency (FE) of 95.7% and an ultrahigh yield rate of 1161 μmol cm –2 h –1 for NH 2 OH generation via the nitrate reduction reaction (NtrRR). Further, the efficient coreduction of HNO 3 and oxalic acid (OA) over Bi-ene simultaneously generates NH 2 OH and glyoxylic acid (GX) respectively, which undergo effective C–N coupling to produce glycine with a high yield of 455.4 μmol cm –2 h –1 . Moreover, the Bi-ene demonstrates stable performance for over 120 h at an industrial-relevant current density of 200 mA cm –2 . Operando spectroscopy and calculations reveal that the strain in lattice-distorted Bi-ene optimizes the intermediate adsorption through modulating local electronic structure and thus enhances the efficacy for glycine electrosynthesis.