Constructing sulfur and oxygen super-coordinated main-group electrocatalysts for selective and cumulative H<sub>2</sub>O<sub>2</sub> production.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 38167494.
- Also identified by DOI 10.1038/s41467-023-44585-1 and PMC identifier 10761824.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Direct electrosynthesis of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) 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<sub>2</sub>O<sub>2</sub> selectivity and diminished H<sub>2</sub>O<sub>2</sub> yield induced by consecutive H<sub>2</sub>O<sub>2</sub> 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<sup>-2</sup> and elevated accumulated H<sub>2</sub>O<sub>2</sub> 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<sup>-</sup> oxygen reduction activity. This work unveils novel avenues for mitigating the production-depletion challenge in H<sub>2</sub>O<sub>2</sub> electrosynthesis through the rational design of main-group catalysts.