CO Oxidation Promoted by the Gold Dimer in Au2VO3− and Au2VO4− Clusters

Investigations on the reactivity of atomic clusters have led to the identification of the elementary steps involved in catalytic CO oxidation, a prototypical reaction in heterogeneous catalysis. The atomic oxygen species O.− and O2− bonded to early‐transition‐metal oxide clusters have been shown to oxidize CO. This study reports that when an Au2 dimer is incorporated within the cluster, the molecular oxygen species O22− bonded to vanadium can be activated to oxidize CO under thermal collision conditions. The gold dimer was doped into Au2VO4− cluster ions which then reacted with CO in an ion‐trap reactor to produce Au2VO3− and then Au2VO2−. The dynamic nature of gold in terms of electron storage and release promotes CO oxidation and OO bond reduction. The oxidation of CO by atomic clusters in this study parallels similar behavior reported for the oxidation of CO by supported gold catalysts. Gold in action: The cluster Au2VO4−, doped with a gold dimer, can activate the peroxide species O22− bonded to the vanadium center to oxidize CO molecules under thermal collision conditions. The CO oxidation mechanism parallels similar behavior for oxide‐supported gold catalysts.