Kurt Frey - Implications of coverage-dependent O adsorption for catalytic NO oxidation on the late transition metals

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      Publication Details (including relevant citation   information):

      Frey, Kurt, Schmidt, David J., Wolverton, C., Schneider, William   F. Catalysis Science & Technology  2014 4 (12) 4356-4365

      Abstract: Adsorbate interactions affect both the   energies and arrangements of adsorbates on surfaces and   consequently influence rates of surface chemical reactions. Here   we examine these effects for a rate-limiting O2 dissociation   model of catalytic NO oxidation on the late transition metals. We   report periodic density functional theory calculations of atomic   oxygen adsorption on the (0001) facets of Ru, Os, and Co, and the   (111) facets of Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au and correlate   these results using cluster expansion (CE) representations. We   use grand canonical Monte Carlo simulations implementing these CE   Hamiltonians to determine both the number and energetics of   first-nearest-neighbor binding site vacancies available for the   dissociative adsorption of O2 at conditions representative of   catalytic NO oxidation. We estimate steady-state turnover   frequencies and compare results to predictions using   non-interacting adsorbates. We show that coverage dependence   manifests itself in both the energetics and statistical   availability of reaction sites and causes rates to deviate   substantially from the coverage-independent limit.

      Address (URL): http://dx.doi.org/10.1039/C4CY00763H