MMENT>Computational study of complete methanol dehydrogenation on Au(100) and Au(310) surfaces: Dominant role of atomic oxygen

Methanol dehydrogenation to CO and H2 has been systematically investigated on Au(100) and Au(310) surfaces using density functional theory (DFT). All possible intermediates involved are calculated. Methanol and formaldehyde being saturated molecules adsorb weakly on both the surfaces. The thermochemistry and kinetics of the decomposition via sequential hydrogen abstraction are both found to be highly unfavorable for these species. Nevertheless, atomic oxygen pre-covered surfaces substantially enhance CH3OH and CH2O (resulting in CH2O2 complex formation) interaction with Au and offer weak activation barrier for methanol disintegration into CH3O and H. On the other hand, methoxy, formyl, and atomic hydrogen are predicted to make strong chemical bonds with the clean Au surfaces. The abstraction of hydrogen from the methoxy intermediate on bare gold surfaces is practical, while formyl splits instantaneously during optimization. A feasible mechanism on oxygen pre-covered surfaces for complete methanol dehydrogenation has been presented.