Atom by atom built subnanometer copper cluster catalyst for the highly selective oxidative dehydrogenation of cyclohexene

Abstract

The effect of particle size and support on the catalytic performance of supported subnanometer copper clusters was investigated in the oxidative dehydrogenation of cyclohexene. From among the investigated seven size-selected subnanometer copper particles between a single atom and clusters containing 2-7 atoms, the highest activity was observed for the titania-supported copper tetramer with 100% selectivity toward benzene production and being about an order of magnitude more active than not only all the other investigated cluster sizes on the same support but also the same tetramer on the other supports, Al₂O₃, SiO₂, and SnO₂. In addition to the profound effect of cluster size on activity and with Cu₄ outstanding from the studied series, Cu₄ clusters supported on SiO₂ provide an example of tuning selectivity through support effects when this particular catalyst also produces cyclohexadiene with about 30% selectivity. Titania-supported Cu₅ and Cu₇ clusters supported on TiO₂ produce a high fraction of cyclohexadiene in contrast to their neighbors, while Cu₄ and Cu₆ solely produce benzene without any combustion, thus representing odd-even oscillation of selectivity with the number of atoms in the cluster.