The steady-state of heterogeneous catalysis, studied by first-principles statistical mechanics

TL;DR

This paper uses first-principles statistical mechanics to calculate the steady-state catalytic oxidation rate of CO on RuO2(110), providing detailed insights into the atomic-scale mechanisms and thermodynamics of heterogeneous catalysis.

Contribution

It introduces a comprehensive ab initio statistical mechanics approach to study the steady-state behavior of heterogeneous catalysis, linking energetics to reaction rates.

Findings

Calculated CO2 formation rate as a function of temperature and partial pressures.

Visualized atomic motions and reactions over multiple time scales.

Provided detailed insights into the mechanisms governing heterogeneous catalysis.

Abstract

The turn-over frequency of the catalytic oxidation of CO at RuO2(110) was calculated as function of temperature and partial pressures using ab initio statistical mechanics. The underlying energetics of the gas-phase molecules, dissociation, adsorption, surface diffusion, surface chemical reactions, and desorption were obtained by all-electron density-functional theory. The resulting CO2 formation rate [in the full (T, p_CO, p_O2)-space], the movies displaying the atomic motion and reactions over times scales from picoseconds to seconds, and the statistical analyses provide insights into the concerted actions ruling heterogeneous catalysis and open thermodynamic systems in general.