Detailed analysis of transitions in the CO oxidation on palladium(111) under noisy conditions

Abstract

It has been shown that CO oxidation on Pd(111) under ultrahigh vacuum conditions can suffer rare transitions between two stable states triggered by weak intrinsic perturbations. Here we study the effects of adding controlled noise by varying the concentrations of O and CO that feed the vacuum chamber, while the total flux stays constant. In addition to the regime of rare transitions between states of different CO reaction rates induced by intrinsic fluctuations, we found three distinct effects of external noise depending on its strength: small noise suppresses transitions and stabilizes the upper rate state; medium noise induces bursting; and large noise gives rise to reversible transitions in both directions. To explain some of the features present in the dynamics, we propose an extended stochastic model that includes a global coupling through the gas phase to account for the removal of CO gas caused by the adsorption of the Pd surface. The numerical simulations based in the model show a qualitative agreement with the noise-induced transitions found in experiments, but suggest that more complex spatial phenomena are present in the observed fluctuations.

Competing ternary surface reaction CO + O2 + H2on Ir(111)

“…The restriction reduces the degrees of freedom and therefore decreases the number of parameters to control the reaction system. In this basic model, possible pressure effects such as global coupling [21,42] are neglected, thus adsorption depends directly on gas flow and is not influenced by changing partial pressures.…”

“…CO oxidation is the prototype reaction for a monomer-dimer surface reaction. It was, for example, intensively analysed on the non-reconstructing surfaces of the platinum group metals: platinum [15], rhodium [16,17], palladium [3,[18][19][20][21] and iridium [22][23][24][25][26][27][28]. Water formation is the prototype for a dimer-dimer surface reaction.…”