Biradical-mediated synergistic electrocatalysis using metal-free redox molecular catalysts.

ABSTRACT: Nature's redox enzymes achieve remarkable selectivity by organizing active sites with precise spatial control, an ability difficult to replicate in synthetic systems. Inspired by this, we report a class of stable, metal-free bicarbenium-based molecular catalysts that undergo electrochemical two-electron reduction to form biradical intermediates. These biradicals are confined within a rigid xanthene bridge ( ~ 4.3 Å), creating a spatially defined pocket that engages paramagnetic substrates, such as O₂ and NO, resembling nature's synergistic catalysis. This biradical-mediated synergistic catalysis enables highly selective two-electron oxygen reduction (99.3% H₂O₂ selectivity, 96.8% Faradaic efficiency, 2.21 mol g⁻¹_cat h⁻¹ productivity) and three-electron nitr

SUBMITTER: Fu D 

PROVIDER: S-EPMC12749437 | biostudies-literature | 2025 Dec

REPOSITORIES: biostudies-literature