Multiple Roles of Alkanethiolate-Ligands in Direct Formation of H₂ O₂ 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 and vibrational spectroscopy are used to provide atomistic understanding of direct H₂ O₂ formation over alkylthiolate(RS) Pd. We find that the RS species are oxidized during reaction conditions yielding RSO₂ as the effective ligand. The RSO₂ ligand shows superior ability for proton transfer to the intermediate surface species OOH, which accelerates the formation of H₂ O₂ . The ligands promote the selectivity also by blocking sites for unselective water formation and by modifying the electronic structure of Pd. The work rationalizes observations of enhanced selectivity of direct H₂ O₂ formation over ligand-funtionalized Pd nanoparticles and shows that engineering of organic surface modifiers can be used to promote desired hydrogen transfer routes.