Air Oxidation of Self-Assembled Monolayers on Polycrystalline Gold:  The Role of the Gold Substrate

Alkanethiolates in self-assembled monolayers on gold oxidize in air, in the dark, to form sulfinates and sulfonates. The kinetics of oxidation, however, vary depending on the morphology of the underlying gold, with the rate of oxidation increasing dramatically with a decrease in the size of the grains and the amount of Au(111) on the surface. This difference in kinetics of oxidation is sufficiently great that it may provide insight into discrepancies among previous reports in the literature regarding the inertness of these SAMs in air. The oxidized products also desorb readily, and these species decompose under prolonged X-ray irradiation in ultrahigh vacuum.