Autocatalytic and cooperatively-stabilized dissociation of water on a stepped platinum surface

TL;DR

This study uses first-principles simulations to reveal how water interacts with stepped platinum surfaces, showing preferential adsorption, dissociation via autocatalytic mechanisms, and potential for proton transfer, which are less understood on flat surfaces.

Contribution

It uncovers the unique dissociation and stabilization mechanisms of water on stepped platinum surfaces, highlighting autocatalytic effects and proton transfer potential not observed on flat surfaces.

Findings

Water adsorbs at step edges forming chains and clusters.

Water dissociates at steps via autocatalytic mechanisms.

Water chains can transfer protons through thermally activated hopping.

Abstract

Water-metal interfaces are ubiquitous and play a key role in many chemical processes, from catalysis to corrosion. Whereas water adlayers on atomically flat transition metal surfaces have been investigated in depth, little is known about the chemistry of water on stepped surfaces, commonly occurring in realistic situations. Using first-principles simulations we study the adsorption of water on a stepped platinum surface. We find that water adsorbs preferentially at the step edge, forming linear clusters or chains, stabilized by the cooperative effect of chemical bonds with the substrate and hydrogen bonds. In contrast with flat Pt, at steps water molecules dissociate forming mixed hydroxyl/water structures, through an autocatalytic mechanism promoted by hydrogen bonding. Nuclear quantum effects contribute to stabilize partially dissociated cluster and chains. Together with the recently demonstrated attitude of water chains adsorbed on stepped Pt surfaces to transfer protons via thermally activated hopping, these findings candidate these systems as viable proton wires.