Constructing sulfur and oxygen super-coordinated main-group electrocatalysts for selective and cumulative H 2 O 2 production.

Direct electrosynthesis of hydrogen peroxide (H 2 O 2 ) via the two-electron oxygen reduction reaction presents a burgeoning alternative to the conventional energy-intensive anthraquinone process for on-site applications. Nevertheless, its adoption is currently hindered by inferior H 2 O 2 selectivity and diminished H 2 O 2 yield induced by consecutive H 2 O 2 reduction or Fenton reactions. Herein, guided by theoretical calculations, we endeavor to overcome this challenge by activating a main-group Pb single-atom catalyst via a local micro-environment engineering strategy employing a sulfur and oxygen super-coordinated structure. The main-group catalyst, synthesized using a carbon dot-assisted pyrolysis technique, displays an industrial current density reaching 400 mA cm -2 and elevated accumulated H 2 O 2 concentrations (1358 mM) with remarkable Faradaic efficiencies. Both experimental results and theoretical simulations elucidate that S and O super-coordination directs a fraction of electrons from the main-group Pb sites to the coordinated oxygen atoms, consequently optimizing the *OOH binding energy and augmenting the 2e - oxygen reduction activity. This work unveils novel avenues for mitigating the production-depletion challenge in H 2 O 2 electrosynthesis through the rational design of main-group catalysts.