Multiple Roles of Alkanethiolate‐Ligands in Direct Formation of H ₂ O ₂ over Pd Nanoparticles

Coadsorbed organic species including thiolates can promote direct synthesis of hydrogen peroxide from H2 and O2 over Pd particles. Here, density functional theory based kinetic modeling, augmented with activity measurements vibrational spectroscopy are used to provide atomistic understanding H2O2 formation alkylthiolate(RS) Pd. We find that the RS oxidized during reaction conditions yielding RSO2 as effective ligand. The ligand shows superior ability for proton transfer intermediate surface OOH, which accelerates H2O2. ligands selectivity also by blocking sites unselective water modifying electronic structure work rationalizes observations enhanced ligand-funtionalized nanoparticles engineering modifiers be desired routes.