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

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 (T, p)-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.