Spectroscopic Monitoring of the Acidity of Water Films on Ru(0001): Orientation-Specific Acidity of Adsorbed Water

We examined the acid–base properties of water films adsorbed onto a Ru(0001) substrate by using surface spectroscopic methods in vacuum environments. Ammonia adsorption experiments combined with low‐energy sputtering (LES), reactive ion scattering (RIS), reflection–absorption infrared spectroscopy (RAIRS) and temperature‐programmed desorption (TPD) measurements showed that the adsorbed water is acidic enough to transfer protons to ammonia. Only the water molecules in an intact water monolayer and water clusters larger than the hexamer exhibit such acidity, whereas small clusters, a thick ice film or a partially dissociated water monolayer that contains OH, H2O and H species are not acidic. The observations indicate the orientation‐specific acidity of adsorbed water. The acidity stems from water molecules with H‐down adsorption geometry present in the monolayer. However, the dissociation of water into H and OH on the surface does not promote but rather suppresses the proton transfer to ammonia. Acidic water: Adsorbed water molecules exhibit orientation‐specific acidity. Spectroscopic investigations of water films adsorbed on Ru(0001) indicate strong acidity of the water monolayer on Ru(0001), which stems from water molecules adsorbed with H‐down geometry (see figure). Surprisingly, the dissociation of water into H and OH on the surface decreases the acidity of the water layer.