Structure Revealing H/D Exchange with Co-Adsorbed Hydrogen and Water on Gold

A fundamental understanding of the interactions between coadsorbed water and hydrogen on metallic surfaces is critical to many chemical processes including catalysis and electrochemistry. Here, we report on the strong and intricate interactions between coadsorbed H/D and water on the close-packed (111) surface of gold. Deuterium isotopic labeling shows H/D exchange in H–D₂O and D–H₂O systems, indicating water dissociation and suggesting a nonrandom scrambling process by revealing the origin of hydrogen evolution (from surface H atoms or from water molecules) during annealing. In this reaction, the protonation of the H-bonding ice network (i.e., the formation of (H₂O)_<i>n</i>H⁺) is energetically favorable and is responsible for water dissociation. Density functional theory (DFT) modeling suggests that the thermodynamics and structure of the protonated clusters are predominant factors for yielding the traceable H₂ desorption features from the surface interaction with H atoms, providing insights into reaction mechanisms