Nature of selenium sub-monolayer effect on the oxygen electro-reduction reaction activity of Ru(0001)

TL;DR

This study uses first principles calculations to show that selenium modification on Ru(0001) surfaces reduces oxygen and hydroxyl binding energies, significantly enhancing the oxygen electro-reduction reaction activity by electrostatic effects and charge transfer.

Contribution

It provides the first detailed computational analysis of how sub-monolayer selenium modifies Ru(0001) surfaces to improve ORR catalytic activity.

Findings

Se reduces O and OH binding energies on Ru(0001).

Se atoms become negatively charged and repel O/OH intermediates.

Se modification dramatically improves ORR rate on Ru.

Abstract

I present here the results of the first principles studies of the adsorption energetics of the intermediates of the oxygen electro-reduction reaction (ORR) on the Se modified Ru(0001) surface. The calculations were performed for the 1/3 ML and 1/6 ML coverage of Se, as well as for the clean Ru(0001) as a reference. The binding energies of O and OH on Ru(0001) are found to decrease significantly upon the presence of the Se and this effect to be increasing with the Se coverage. The Se surface modification is found not to change Ru LDOS noticeably. However, Se atoms accept electronic charge from the surface and thus become negatively charged. As a result, they repeal electrostatically the adsorbed negatively charged O and OH intermediates, and this way reduce their binding energies. This effect provide an alternative way of tuning reactivity of the catalyst surfaces. Since for the Ru case, reduction of the O and OH binding energies makes ORR energetically favorable, Se modification dramatically improve the ORR rate on Ru. Adsorption of O2 and co-adsorption of the ORR intermediates and water have also been studied. The effect of the co-adsorption on the binding energies of O and OH are discussed.