While the reactivity of metallic nanoparticles, as function of shape, size, composition and support has been the subject of many investigations, more recently attention has focused on the role of interfacial and perimeter sites as they may facilitate strong mixing of the wave functions of the reactants, nanoparticle, and the substrate atoms. However subtle differences in the local electronic structure at the interface may control whether the active sites lie there or elsewhere in the system. Given the recent interest in single layer MoS2 and the large number of studies already carried out on titania, we present here a comparative examination of the microscopic details of CO oxidation and methanol decomposition on sub-nanometer sized metal nanoparticles (Au, Ag, Pt), supported on single layer MoS2 and on TiO2(110). Calculations of activation energy barriers, reaction pathways, and pre-exponential factors are based on density functional theory (DFT). Reaction rates for selected cases (for which experimental data is available) are obtained from kinetic Monte Carlo simulations performed with energetics obtained from DFT. The role of charge transfer at the interface, charge redistribution on the nanoparticle and their impact on the formation and scission of specific bonds will be presented in detail. In particular, activation mechanisms which were found to be applicable for both CO oxidation and methanol decomposition at the interface of Au/TiO2 [1] will be probed for the same reactions on the nanoparticle-MoS2 interface to check for their generality.[1] S. Hong and T. S. Rahman, J. Am. Chem. Soc. 135, 7629 (2013).Work supported in part by DOE grant DE-FG02-07ER15842.

Reactivity of oxide and sulfide supported metal nanoparticles: Role of the interface

248th National Meeting (2014)

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