Effect of surface nanostructure on temperature programmed reaction spectroscopy: First-principles kinetic Monte Carlo simulations of CO oxidation at RuO2(110)

TL;DR

This study uses first-principles kinetic Monte Carlo simulations to show how nanostructure-induced site correlations on RuO2(110) surfaces affect temperature programmed reaction spectroscopy data, revealing inhomogeneities overlooked by traditional analysis.

Contribution

It demonstrates that nanostructure alone can cause significant inhomogeneities in reaction data, challenging mean-field analysis assumptions.

Findings

Nanostructure causes inhomogeneities in reaction data.

Mean-field analysis may lead to incorrect conclusions.

Surface site correlations significantly impact reactivity interpretations.

Abstract

Using the catalytic CO oxidation at RuO2(110) as a showcase, we employ first-principles kinetic Monte Carlo simulations to illustrate the intricate effects on temperature programmed reaction spectroscopy data brought about by the mere correlations between the locations of the active sites at a nanostructured surface. Even in the absence of lateral interactions, this nanostructure alone can cause inhomogeneities that cannot be grasped by prevalent mean-field data analysis procedures, which thus lead to wrong conclusions on the reactivity of the different surface species.