Hinged Carboxylate in the Artificial Distal Pocket of an Iron Porphyrin Enhances CO₂ Electroreduction at Low Overpotential.

ABSTRACT: To efficiently capture, activate, and transform small molecules, metalloenzymes have evolved to integrate a well-organized pocket around the active metal center. Within this cavity, second coordination sphere functionalities are precisely positioned to optimize the rate, selectivity, and energy cost of catalytic reactions. Inspired by this strategy, an artificial distal pocket defined by a preorganized 3D strap is introduced on an iron-porphyrin catalyst (sc-Fe) for the CO₂-to-CO electrocatalytic reduction. Combined electrochemical, kinetic, and computational studies demonstrate that the adequate positioning of a carboxylate/carboxylic group acting in synergy with a trapped water molecule within this distal pocket remarkably enhances the reaction turnover frequency (TOF) by four

SUBMITTER: Smith A 

PROVIDER: S-EPMC11923859 | biostudies-literature | 2025 Mar

REPOSITORIES: biostudies-literature