Single Molecular Reaction of Water on a ZnO Surface.

The dissociation of a single water molecule on a ZnO(101̅0) surface has been investigated at the atomic level by low temperature STM manipulation combined with DFT calculations. The positive pulses applied from the tip inject electrons into the system and break the bonding between water and the ZnO surface, thus leading to the hopping of water molecules. Negative pulses inject holes wherein the lower energy ones split the free O-H bond pointing out of the surface whereas the higher energy ones split the second O-H bond that is directed to the surface through hydrogen bonding. Moreover, the yielded proton and hydroxyl species present distinctly charged status through different reaction pathways, manifesting their unique impacts on tailoring the surface properties of the metal oxide.

Unveiling the Atomic Structure and Growth Dynamics of One-Dimensional Water on ZnO(10-10).

The adsorption and organization state of water on the metal oxide surface is of critical importance for wide fields where interface chemistry dominates. On the technically important ZnO(10-10) surface, we found water assembles into an one-dimensional (1D) chain structure at submonolayer coverage instead of the well-known half-dissociated two-dimensional (2D) island. With a combination of high resolution scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, we clearly distinguished the single and double water chains, which are composed of dissociated monomers and half-dissociated dimers, respectively. Moreover, we unambiguously determined that single water molecules dissociate spontaneously before agglomerating into ordered phase, which is contrary to the proposition of previous studies. These results have deepened our understandings of the adsorbed water species on the ZnO surface, which may bring new insights into the mechanisms of water-stimulated surface reactions.

Tailoring the Dispersion of Metals on ZnO with Preadsorbed Water.

The dispersity of metal particles over oxide surfaces is generally critical for the applications of the metal/oxide hybridized systems. In this work, we have experimentally investigated the hydration effect of preadsorbed water species over the Cu and Pd particles deposited on the ZnO(10-10) surface. Using scanning tunneling microscopy (STM), we clearly saw that both Cu and Pd grow as three-dimensional particles on the clean ZnO(10-10) surface but disperse into single atoms and few-atom clusters on the water-covered surfaces. Moreover, X-ray photoelectron spectroscopy (XPS) measurements revealed that Cu is readily oxidized by interacting with the molecular water while Pd tends to bind the surface hydroxyls and keep neutral status. Our work has demonstrated the effective role of the surface water in tuning the morphologies as well as electronic states of the supported metals, which may bring new insights to a number of important surface processes with water in presence.