Computational insights into the zeolite-supported gold nanocluster-catalyzed ethanol dehydrogenation to acetaldehyde

Zeolite-supported gold nanoclusters play increasingly important roles in heterogeneous catalysis and exhibit unique catalytic properties for ethanol dehydrogenation to acetaldehyde. Nevertheless, the reaction mechanism and potential roles of the zeolite-encapsulated gold nanoclusters during the catalytic process remain unclear. Herein, computational studies were carried out to gain mechanistic insights into ethanol dehydrogenation to acetaldehyde under both aerobic and anaerobic conditions catalyzed by a silicalite-1 zeolite-encapsulated Au₃ cluster cation (Au₃⁺-S1). The presence of O₂ can significantly promote the ethanol dehydrogenation catalyzed by Au₃⁺-S1. A feasible mechanistic pathway could be initiated via the O₂ induced H-atom transfer (HAT) step from the hydrogen of the hydroxyl group to afford ethoxy and OOH radical species. Subsequently, the OOH induced second HAT from α-C-H of the ethoxy intermediate could follow to afford the acetaldehyde product. Moreover, the possible confinement and stabilization effect of the zeolite channels on the ethanol dehydrogenation reaction was discussed.