Interfacial Organic Electrosynthesis with Chemically Modified Electrodes

Abstract Synthetic electrochemistry is a sustainable alternative to traditional redox chemistry, using electricity from renewable sources in place of stoichiometric reagents. However, electrochemical reactions occur at electrode interfaces where the local environment and surface properties critically influence reaction outcomes. This review highlights recent advances in harnessing interfacial effects through chemically modified electrodes for organic electrosynthesis. Two complementary strategies are examined: (1) nanoparticle-modified electrodes that modulate electron transfer and can participate directly in bond-forming events, and (2) electrodes bearing immobilized molecular catalysts that provide well-defined active sites. Representative case studies illustrate how these approaches enable oxidations, reductions, and redox-neutral reactions with tunable selectivity and new reactivity. Mechanistic insights from surface characterization, electroanalytical techniques, and operando spectroscopy are used to establish relationships between structure and reactivity at the electrified interface. This review surveys representative studies from 2015 to 2025 and primarily includes examples that compare chemically modified electrodes with their unmodified counterparts.