Our studies of small (n=2−40) gas phase transition metal clusters (cations, neutrals and anions) have revealed a number of size-dependent chemical and physical properties. This paper will discuss results involving activated dissociative molecular chemisorption of hydrogen (deuterium) and small alkanes on cationic, neutral and anionic platinum and gold clusters. For example, we have yet to find any size gold cluster anion to exhibit measurable reactivity towards di-deuterium, but reactivity is observed on small (n<15) gold cations and very small (n<9) neutral gold clusters. Methane or ethane chemisorption occurs most readily only on small Pt and Au cluster cations and least rapidly, if at all, on cluster anions. The larger Pt and Au clusters are found to be non-reactive towards the alkanes under our experimental conditions.
At the other extreme, at steady state, small clusters of Pt, Rh, Ni, Pd, V, Nb, and Ta are hydrogen “rich” exhibiting H/M stoichiometrics >> 1. These results are consistent with a limited data base on supported clsutes obtained via EXAFS measurements and have important implications for catalytic reactions involving hydrogen and light hydrocarbons.