Abstract
In a previous paper, (Chen, N.; Blowers, P.; Masel, R. I. Surf. Sci. 1998, 418, 329−341.) we found that methoxonium ions (CH3OH2)+ can form when methanol and hydrogen coadsorb on Pt(110). In this paper, we characterize the chemistry of methoxonium on (2 × 1)Pt(110) using mainly TPD. We observe three reaction pathways: a simple dehydrogenation to CO and hydrogen; an SN1 pathway to form water, methane, and adsorbed CHx groups; and an SN2 pathway yielding dimethyl ether. The SN1 pathway shows a strong secondary isotope effect implying that the transition state is ionic. The SN2 pathway is seen at high hydrogen coverages and shows kinetics typical for an SN2 process. This work demonstrates for the first time that cationic species on surfaces react via the same SN1 and SN2 pathways seen during reactions of cations in solution.
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