Effects of inert species in the gas phase in a model for the catalytic oxidation of CO

TL;DR

This study uses kinetic Monte Carlo simulations to analyze how inert gas-phase impurities affect the catalytic oxidation of CO on surfaces, revealing that non-desorbing impurities eliminate the reactive phase, while desorbing impurities restore it.

Contribution

The paper introduces a modified ZGB model incorporating inert gas-phase impurities and explores their impact on catalytic oxidation behavior.

Findings

Non-desorbing impurities eliminate the reactive window.

Desorbing impurities restore the reactive window depending on their concentration and desorption rate.

The presence of inert impurities changes the nature of phase transitions in the model.

Abstract

We study by kinetic Monte Carlo simulations the catalytic oxidation of carbon monoxide on a surface in the presence of contaminants in the gas phase. The process is simulated by a Ziff-Gulari-Barshad (ZGB) model that has been modified to include the effect of the contaminants and to eliminate the unphysical oxygen-poisoned phase. The impurities can adsorb and desorb on the surface, but otherwise remain inert. We find that, if the impurities can not desorb, no matter how small their proportion in the gas mixture, the first order transition and the reactive window that characterize the ZGB model disappear. The coverages become continuous, and once the surface has reached a steady state there is no production of CO$_2$. This is quite different from the behavior of a system in which the surface presents a fixed percentage of impurities. When the contaminants are allowed to desorb, the reactive window appears again, and disappears at a value that depends on the proportion of contaminants in the gas and on their desorption rate.