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Water-metal interfaces are ubiquitous and play a key role in many chemicalprocesses, from catalysis to corrosion. Whereas water adlayers on atomicallyflat transition metal surfaces have been investigated in depth, little is knownabout the chemistry of water on stepped surfaces, commonly occurring inrealistic situations. Using first-principles simulations we study theadsorption of water on a stepped platinum surface. We find that water adsorbspreferentially at the step edge, forming linear clusters or chains, stabilizedby the cooperative effect of chemical bonds with the substrate and hydrogenbonds. In contrast with flat Pt, at steps water molecules dissociate formingmixed hydroxyl/water structures, through an autocatalytic mechanism promoted byhydrogen bonding. Nuclear quantum effects contribute to stabilize partiallydissociated cluster and chains. Together with the recently demonstratedattitude of water chains adsorbed on stepped Pt surfaces to transfer protonsvia thermally activated hopping, these findings candidate these systems asviable proton wires.

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