UCLA

Supported sub-nano clusters hold great promise as economical and highly active catalysts. However, they tend to deactivate rapidly by poisoning and sintering, impeding their widespread use. We find that self-limiting poisoning can stabilize and promote cluster catalysis, that is, poisoning is not always detrimental but can sometimes be exploited. Specifically, Pt-Ge alloy clusters supported on alumina undergo slow and self-limiting coking (carbon deposition) under conditions of thermal dehydrogenation, modifying the cluster framework and electronic properties but preserving the Pt sites required for strong ethylene binding. For the case of Pt4Ge/alumina, theory shows a number of thermally populated isomers, one of which catalyzes carbon deposition. Because the clusters are fluxional at high temperatures, this isomer acts as a gateway, slowly converting all clusters to Pt4GeC2. The surprising result is that Pt4GeC2 is highly catalytically active and selective against further coking, that is, coking produces functional, stable catalytic clusters. Ge and C2 have synergistic electronic effects, leading to efficient and highly selective catalytic dehydrogenation that stops at alkenes and improving stability. Thus, under reaction conditions, the clusters develop into a robust catalyst, suggesting an approach to practicable cluster catalysis.