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An atomic layer deposition process is used to modify size-selectedPt7/alumina model catalysts by Sn addition, both before and after Pt7 clusterdeposition. Surface science methods are used to probe the effects ofSn-modification on the electronic properties, reactivity, and morphology of theclusters. Sn addition, either before or after cluster deposition, is found tostrongly affect the binding properties of a model alkene, ethylene, changingthe number and type of binding sites, and suppressing decomposition leading tocarbon deposition and poisoning of the catalyst. Density functional theory on amodel system, Pt4Sn3/alumina, shows that the Sn and Pt atoms are mixed, formingalloy clusters with substantial electron transfer from Sn to Pt. The presenceof Sn also makes all the thermally accessible structures closed shell, suchthat ethylene binds only by {\pi}-bonding to a single Pt atom. The Sn-modifiedcatalysts are quite stable in repeated ethylene temperature programmed reactionexperiments, suggesting that the presence of Sn also reduces the tendency ofthe sub-nano-clusters to undergo thermal sintering.

Sn-modification of Pt7/alumina model catalysts: Suppression of carbon deposition and enhanced thermal stability