Materials that bind strongly to water structure the contact layer, modifying its chemical and physical properties in a manner that depends on the symmetry and reactivity of the surface. Although detailed models have been developed for several inert surfaces, much less is known about reactive surfaces, particularly those with a symmetry different from that of ice. Here we investigate water adsorption on a rectangular surface, Ni(110), an active re-forming catalyst that interacts strongly with water. Instead of forming a network of H-bonded cyclic rings, water forms flat 1D water chains, leaving half the Ni atoms exposed. Second layer water also follows the surface symmetry, forming chains of alternating pentamer and heptamer rings in preference to an extended 2D structure. This behavior is different from that found on other surfaces studied previously and is driven by the short lattice spacing of the solid and the strength of the Ni–water bond.
Nickel is an active catalyst for hydrogenation and re-forming reactions, with the reactions showing a strong dependence on the surface exposed. Here, we describe the mixed hydroxyl–water phases formed during water dissociation on Ni(110) using scanning tunneling microscopy and low-current low-energy electron diffraction. Water dissociation starts between 150 and 180 K as the H-bond structure evolves from linear one-dimensional (1D) chains of intact water into a two-dimensional (2D) network containing short rows of face-sharing hexagonal rings. As further water desorbs, the hexagonal rows adopt a local (2 × 3) arrangement, forming small, disordered domains separated by strain relief features. Decomposition of this phase occurs near 220 K to form linear 1D structures consisting of flat, zigzag water chains, with each water stabilized by donating one H to hydroxyl to form a branched chain structure. The OH–H 2 O chains repel each other, with the saturation layer ordering into a (2 0, 1 4) structure that decomposes to OH near 245 K as further water desorbs. The structure of the mixed OH/H 2 O phases is discussed and contrasted with those found on the related Cu(110) surface, with the differences attributed to strain in the 2D H-bond network caused by the short Ni lattice spacing and strong bond to OH/H 2 O.
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.
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