Adsorption and reaction of methanethiol on the Ru(0001)-p(2x2)O surface:: A TPD and XPS study

Methanethiol adsorbed on Ru(0 0 0 1)-p(2 x 2)O has been studied by TPD and XPS. The dissociation of methanethiol to methylthiolate and hydrogen at 90 K is evidenced by the observation of hydroxyl and water. The saturation coverage of methylthiolate is similar to 0.15 ML, measured by both XPS and TPD. A detailed analysis suggests that only the hcp-hollow sites have been occupied. Upon annealing the surface, water and hydroxyl desorb from the surface at similar to 210 K. Methylthiolate decomposes to methyl radical and atomic sulphur via C-S cleavage between 350 and 450 K. Some methyl radicals (0.05 ML) have been transferred to Ru atoms before they decompose to carbon and hydrogen. The rest of methyl radicals desorb as gaseous phase. No evidence for the transfer of methyl radical to surface oxygen has been found. (c) 2007 Elsevier B.V. All rights reserved.