Ordered hydroxyls on Ca₃Ru₂O₇(001)

As complex ternary perovskite-type oxides are increasingly used in solid oxide fuel cells, electrolysis and catalysis, it is desirable to obtain a better understanding of their surface chemical properties. Here we report a pronounced ordering of hydroxyls on the cleaved (001) surface of the Ruddlesden-Popper perovskite Ca₃Ru₂O₇ upon water adsorption at 105 K and subsequent annealing to room temperature. Density functional theory calculations predict the dissociative adsorption of a single water molecule (E _ads = 1.64 eV), forming an (OH)_ads group adsorbed in a Ca-Ca bridge site, with an H transferred to a neighboring surface oxygen atom, O_surf. Scanning tunneling microscopy images show a pronounced ordering of the hydroxyls with (2 × 1), c(2 × 6), (1 × 3), and (1 × 1) periodicity. The present work demonstrates the importance of octahedral rotation and tilt in perovskites, for influencing surface reactivity, which here induces the ordering of the observed OH overlayers.As ternary perovskite-type oxides are increasingly used in fuel cells and catalysis, greater understanding of their surface chemical properties is required. Here the authors report a pronounced ordering of hydroxyls on the cleaved (001) surface of Ca₃Ru₂O₇ perovskite induced by O-octahedral rotation and tilt.