title: Why is silver catalytically active for NO reduction? A unique pathway via an inverted (NO)2 dimer.
abstract: NO reduction on the noble metal Ag has been studied using density functional theory calculations. It was found that monomeric NO dissociation is subject to prohibitive barriers on Ag metal and is thus unlikely to account for the experimental observations for NO reduction over Ag-based catalysts. For the first time, a mechanism via an inverted (NO)(2) dimer is identified, which can explain both the high activity and the selectivity of this catalytic system. N(2)O is the major reduction product of the inverted (NO)(2) dimer, in accord with experiment. The physical origin of the Ag metallic state as a good catalyst is furthermore identified: Ag surfaces, including small clusters, have little or no covalent bonding ability but can bond ionically with adsorbates. We conclude that the variation of the ionic bonding strength of Ag toward different reactants determines its catalytic selectivity.
authors.affiliation: Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK.
authors.forename: Zhi-Pan
authors.initials: ZP
authors.lastname: Liu
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Jenkins
authors.forename: David A
authors.initials: DA
authors.lastname: King