Active sites and effects of co-adsorbed H2O on isolated methanol dehydrogenation over Pt/γ-Al2O3.

[Display omitted] • Infrared spectra of CO adsorbed on Pt particles with varying size distributions revealed several sites with distinct reactivity. • Larger Pt particles dehydrogenate methanol faster and at lower temperatures than smaller Pt particles with or without co-adsorbed H 2 O. • Even on smaller Pt particles, methanol appears to dehydrogenate on the metal sites of highest coordination first. • Co-adsorbed H 2 O promotes the formation of bridging CO but hinders dehydrogenation on small Pt particles. Dehydrogenation is the first reaction of the aqueous phase reforming (APR) mechanism of polyols, and its rate is likely affected by the environment at the active site. This study focuses on reactions of methanol on benchmark Pt/γ-Al 2 O 3 catalysts probed by infrared spectroscopy under high vacuum. CO in linear and bridging coordination are the dominant surface species on metal sites. Pt particle sizes and reaction temperatures are varied to identify the kinetically preferred active site for methanol dehydrogenation as either lowly coordinated (edges, corners, interface) or highly coordinated (terraces) metal atoms. Interpretation of temperature-dependent IR spectra up to 450 °C show that larger Pt particles produce more CO at lower temperatures from complete methanol dehydrogenation. Similarly, time-resolved isothermal experiments at 150 °C showed equilibrium conversion occurred much faster on larger Pt particles than smaller ones. Features of evolving ν(C≡O) bands (shape, vibrational frequencies, integrals) suggest that, even on small Pt particles, CO first forms on the scarcely available terraces, or possibly in the form of islands. We have thus experimentally identified highly coordinated Pt metal as the more active site in overall methanol dehydrogenation. The electronic and chemical effects of co-adsorbed water and hydrogen on dehydrogenation activity and the CO spectra are discussed. The co-adsorption of water, an abundant APR component needed for the water-gas shift reaction, does not appear to affect methanol dehydrogenation on large Pt particles but hinders the reaction on small Pt particles as evident by limited growth in the respective ν(C≡O) bands. [ABSTRACT FROM AUTHOR]