Wetting of a Stepped Platinum (211) Surface.

Steps stabilize water adsorption on metal surfaces, providing favorable binding sites for water during wetting or ice nucleation, but there is limited understanding of the local water arrangements formed on such surfaces. Here we describe the structural evolution of water on the stepped Pt(211) surface using thermal desorption, low-energy electron diffraction, and scanning tunneling microscopy to probe the water structure. At low coverage water forms linear structures comprising zigzag chains along the steps that are decorated by H-bonded rings every one or two units along the terrace. Simple 2-coordinate H-bonded chains are not observed, indicating the Pt step binds too weakly to compensate entirely for a low water H-bond coordination number. As the coverage increases, water chains assemble into a disordered (2 × 1) structure, likely made up of the same narrow water chains along the steps with little or no H-bonding between adjacent structures. The chain structure disappears as water adsorption saturates the surface to form an incommensurate, disordered network of water rings of different size. Although the steps on Pt(211) clearly stabilize water adsorption and direct growth, the surface does not support the simple 1D chains previously proposed or an ordered 2D network such as seen on other surfaces. We discuss reasons for this and the factors that determine the behavior of the first water layer on stepped metal surfaces.