The interaction of size-selected Ru3 clusters with RF-deposited TiO2: probing Ru-CO binding sites with CO-Temperature Programmed Desorption

Liam Howard-Fabretto, Timothy J. Gorey, Guangjing Li, Siriluck Tesana, Gregory F. Metha, Scott L. Anderson, Gunther G. Andersson

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Small Ru clusters are efficient catalysts for chemical reactions such as CO hydrogenation. In this study 3-atom Ru 3clusters were deposited onto radio frequency (RF)-deposited TiO 2which is an inexpensive, nanoparticulate form of TiO 2. TiO 2substrates 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 Ru 3deposited using both an ultra-high vacuum cluster source and chemical vapour deposition of Ru 3(CO) 12. The TiO 2was treated with different Ar +sputter doses prior to cluster depositions, and SiO 2was also used as a comparison substrate. For cluster source-deposited Ru 3, heating to 800 K caused cluster agglomeration on SiO 2and oxidation on non-sputtered TiO 2. For cluster source-deposited Ru 3on sputtered TiO 2substrates, 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 TiO 2before cluster deposition cannot be applied. Conversely, for Ru 3(CO) 12on sputtered TiO 2the 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 TiO 2could 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 xlayer reduced through sputtering and also partial oxidation of the Ru clusters.

Original languageEnglish
Pages (from-to)3537-3553
Number of pages17
JournalNanoscale Advances
Issue number12
Early online date26 Apr 2021
Publication statusPublished - 21 Jun 2021


  • Small Ru clusters
  • catalyst
  • CO hydrogenation


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