Topics in Catalysis

, Volume 57, Issue 1–4, pp 159–170 | Cite as

CO Oxidation on Pd(100) Versus PdO(101)-\((\sqrt{5}\times \sqrt{5})R27^{\circ}\): First-Principles Kinetic Phase Diagrams and Bistability Conditions

  • Max J. Hoffmann
  • Karsten ReuterEmail author
Original Paper


We present first-principles kinetic Monte Carlo (1p-kMC) simulations addressing the CO oxidation reaction at Pd(100) for gas-phase conditions ranging from ultra-high vacuum to ambient pressures and elevated temperatures. For the latter technologically relevant regime there is a long-standing debate regarding the nature of the active surface. The pristine metallic surface, an ultra-thin \((\sqrt{5}\times \sqrt{5})R27^{\circ}\)PdO(101) surface oxide, and thicker oxide layers have each been suggested as the active state. We investigate these hypotheses with 1p-kMC simulations focusing on either the Pd(100) surface or the PdO(101) surface oxide and intriguingly obtain a range of (Tp)-conditions where both terminations appear metastable. The predicted bistability regime nicely ties in with oscillatory behavior reported experimentally by Hendriksen et al. (Catal Today 105:234, 2005). Within this regime we find that both surface terminations exhibit very similar intrinsic reactivity, which puts doubts on attempts to assign the catalytic function to just one active state.


First-principles kinetic Monte Carlo Bistability CO oxidation catalysis Density-functional theory In situ characterization 



We gratefully acknowledge support from the German Research Council (DFG) and the TUM Faculty Graduate Center Chemistry, as well as generous computing time at the Supercomputing Center of the Max-Planck-Society, Garching. We thank Matthias Scheffler for insightful discussions and his continued support for this project.


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Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  1. 1.Department ChemieTechnische Universität MünchenGarchingGermany

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