Constructing sulfur and oxygen super-coordinated main-group electrocatalysts for selective and cumulative H2O2 production
Xiao Zhou, Yuan Min, Changming Zhao, Cai Chen, Ming‐Kun Ke, Shilin Xu, Jie‐Jie Chen, Yuen Wu, Han‐Qing Yu
Abstract
Abstract 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.