The role of oxygenated species in the catalytic self-coupling of MeOH on O pre-covered Au(111).

The oxidation of alcohols plays a central role in the valorisation of biomass, in particular when performed with a non-toxic oxidant such as O. Aerobic oxidation of methanol on gold has attracted attention lately and the main steps of its mechanism have been described experimentally. However, the exact role of O and OH on each elementary step and the effect of the interactions between adsorbates are still not completely understood. Here we investigate the mechanism of methanol oxidation to HCOOCH and CO. We use Density Functional Theory (DFT) to assess the energetics of the underlying pathways, and subsequently build lattice kinetic Monte Carlo (kMC) models of increasing complexity, to elucidate the role of different oxygenates. Detailed comparisons of our simulation results with experimental temperature programmed desorption (TPD) spectra enable us to validate the mechanism and identify rate determining steps. Crucially, taking into account dispersion (van der Waals forces) and adsorbate-adsorbate lateral interactions are both important for reproducing the experimental data.