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Spatially Nonuniform Reaction Rates during Selective Oxidation on Gold

Xu, Fang, Madix, Robert J., Friend, Cynthia M.
Journal of the American Chemical Society 2018 v.140 no.38 pp. 12210-12215
gold, isopropyl alcohol, methanol, oxidation, oxygen, oxygen consumption, reaction kinetics, scanning tunneling microscopy
The nonuniform reactivity of adsorbed oxygen during the selective oxidation of methanol on Au(110)-(1×2) was demonstrated using in situ scanning tunneling microscopy (STM), establishing the importance of both atomic and mesoscale structure in determining reaction kinetics. At coverages above 0.06 ML, oxygen consumption occurs preferentially along [11̅0] direction, creating local regions completely devoid of oxygen between oxygen islands. The directionally specific reactivity is attributed to a combination of the weaker binding of oxygen atoms at chain termini and the release of surface strain induced by O bonding to Au. The generality of this phenomenon is illustrated by analogous, but kinetically contrasting behavior, for reaction of 2-propanol with oxygen covered Au(110)-(1×2). Even at low O coverages, there are structurally related changes in the reactivity for the reaction with methanol. With decreasing O coverage, a slow reaction period is followed by a fast reaction period, the latter starting when oxygen coverage decreases to ∼0.06 monolayer, independent of the initial coverage. This increase in reactivity is attributed to a sudden destabilization of the island structure. These results demonstrate that both local and mesocale structures can affect reactivity.