The interaction of size-selected Ru3 clusters with RF-deposited TiO2: probing Ru–CO binding sites with CO-temperature programmed desorption

Abstract

Small Ru clusters are efficient catalysts for chemical reactions such as CO hydrogenation. In this study 3-atom Ru₃ clusters were deposited onto radio frequency (RF)-deposited TiO₂ which is an inexpensive, nanoparticulate form of TiO₂. TiO₂ substrates are notable in that they form strong metal–substrate interactions with clusters. Using temperature programmed desorption to probe Ru–CO binding sites, and X-ray photoelectron spectroscopy to provide chemical information on clusters, differences in cluster–support interactions were studied for Ru₃ deposited using both an ultra-high vacuum cluster source and chemical vapour deposition of Ru₃(CO)₁₂. The TiO₂ was treated with different Ar⁺ sputter doses prior to cluster depositions, and SiO₂ was also used as a comparison substrate. For cluster source-deposited Ru₃, heating to 800 K caused cluster agglomeration on SiO₂ and oxidation on non-sputtered TiO₂. For cluster source-deposited Ru₃ on sputtered TiO₂ substrates, all Ru–CO binding sites were blocked as-deposited and it was concluded that for the binding sites to be preserved for potential catalytic benefit, sputtering of TiO₂ before cluster deposition cannot be applied. Conversely, for Ru₃(CO)₁₂ on sputtered TiO₂ the clusters were protected by their ligands and Ru–CO binding sites were only blocked once the sample was heated to 723 K. The mechanism for complete blocking of CO sites on sputtered TiO₂ could not be directly determined; however, comparisons to the literature indicate that the likely reasons for blocking of the CO adsorption sites are encapsulation into the TiO_x layer reduced through sputtering and also partial oxidation of the Ru clusters.