Abstract
Using high temperature CO oxidation as the example, trends in the reactivity of transition metals are discussed on the basis of density functional theory (DFT) calculations. Volcano type relations between the catalytic rate and adsorption energies of important intermediates are introduced and the effect of adsorbate–adsorbate interaction on the trends is discussed. We find that adsorbate–adsorbate interactions significantly increase the activity of strong binding metals (left side of the volcano) but the interactions do not change the relative activity of different metals and have a very small influence on the position of the top of the volcano, that is, on which metal is the best catalyst.
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Notes
Self-consistent, periodic density functional theory (DFT) calculations were performed using the Dacapo total energy code using the RPBE exchange-correlation functional [53]. Ultrasoft Vanderbilt pseudopotentials are used to describe the core electrons and the Kohn-Sham one electron valence states are expanded in a plane wave basis set with a kinetic energy cutoff below 408 eV [54]. The electron density is determined by iterative diagonalization of the Kohn-Sham Hamiltonian, Fermi population of the Kohn-Sham states (kbT = 0.1 eV), and Pulay mixing of the resulting electron density [55]. Total energies are then extrapolated to kbT = 0 eV [56]. Sampling of the surface Brillouin zone was done using a 6 × 4 × 1 Monkhorst-Pack k-point set [57]. Fcc(111) surfaces of Au, Ag, Cu, Pd, Pt, Ni, and Rh were modeled as slabs with a (2 × 3) unit cell and four atomic layers. A vacuum of 10 Å separates successive slabs along the normal direction of the surface. The top two layers were allowed to relax, while the bottom two layers were kept fixed in their bulk truncated positions
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Acknowledgments
The center for Atomic-scale Materials Design is supported by the Lundbeck Foundation. In addition we thank the Danish Research Council for the Technical Sciences and the NABIIT program for financial support, and the Danish Center for Scientific Computing for computer time.
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Grabow, L.C., Hvolbæk, B. & Nørskov, J.K. Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals. Top Catal 53, 298–310 (2010). https://doi.org/10.1007/s11244-010-9455-2
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DOI: https://doi.org/10.1007/s11244-010-9455-2