Abstract
The dehydrogenation of benzene on Pt/ZnO(0001)−O model catalysts was studied with temperature-programmed desorption (TPD) and low-energy ion scattering spectroscopy (LEIS). Vapor-deposited Pt grows as two-dimensional (2D) islands on this oxygen-terminated ZnO(0001)−O surface up to ∼50% of a monolayer and as three-dimensional (3D) islands at higher coverage. The reactivity of these Pt islands is studied as a function of their thickness and coverage. Benzene desorbs molecularly at ∼250 K from Pt-free ZnO(0001)−O, unless the surface is preannealed in ultrahigh vacuum, in which case some of it dehydrogenates and populates the subsurface ZnO with H (or D when using perdeuterobenzene, c-C6D6). Subsurface H (or D) reappears as H2, HD, and D2 gas above ∼700 K in TPD, isotopically scrambled with the bulk H (D) reservoir. The ZnO defect sites active in benzene decomposition are passivated by annealing in O2. On Pt islands, most of the adsorbed benzene dehydrogenates in TPD, giving a broad H2 peak at ∼560 K with a s...
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