The sensitivity, or insensitivity, of catalysed reactions to catalyst structure is a commonly employed fundamental concept. Here we report on the nature of nano-catalysed ethylene hydrogenation, investigated through experiments on size-selected Pt_n (n=8–15) clusters soft-landed on magnesia and first-principles simulations, yielding benchmark information about the validity of structure sensitivity/insensitivity at the bottom of the catalyst size range. Both ethylene-hydrogenation-to-ethane and the parallel hydrogenation–dehydrogenation ethylidyne-producing route are considered, uncovering that at the 150 K, with maximum room temperature reactivity observed for Pt₁₃. Structure insensitivity, inherent for specific cluster sizes, is induced in the more active Pt₁₃ by a temperature increase up to 400 K leading to ethylidyne formation. Control of sub-nanometre particle size may be used for tuning catalysed hydrogenation activity and selectivity.

First results of investigations are presented, where size-selected metal clusters generated in ultra high vacuum (UHV) are transferred to ambient conditions and tested for suitable electrochemical applications. As demonstrated, the transfer allows for the characterization of clusters by transmission electron microscopy (TEM) as well as catalytic measurements, which is exemplified by the application of electrochemical measurements. It is demonstrated that well known electrochemical processes on the carbon supported Pt clusters are detected, and thus Pt clusters can be characterized with respect to their accessible surface area, an essential requirement for the study of catalytic processes. Furthermore, as an example for an important electrocatalytic process, it is shown that the oxygen reduction reaction can be probed on the cluster samples featuring a detrimental particle size effect, previously reported for industrial catalysts as well.