Selective Oxidation of Methanol to Methyl Formate on Gold: The Role of Low-Coordinated Sites Revealed by Isothermal Pulsed Molecular Beam Experiments and AIMD Simulations

To elucidate the role of low-coordinated sites in the partial methanol oxidation to methyl formate (MeFo), the isothermal reactivity of flat Au(111) and stepped Au(332) in pulsed molecular beam experiments was compared for a broad range of reaction conditions. Low-coordinated step sites were found to enhance MeFo selectivity, especially at low coverage conditions, as found at higher temperatures. The analysis of the transient kinetics provides evidence for the essential role of Au$_x$O$_y$ phases for MeFo formation and the complex interplay of different oxygen species for the observed selectivity. Ab initio molecular dynamic simulations yielded microscopic insights in the formation of Au$_x$O$_y$ phases on flat and stepped gold surfaces emphasizing the role of low-coordinated sites in their formation. Moreover, associated surface restructuring provides atomic-scale insights which align with the experimentally observed transient kinetics in MeFo formation