Catalytic CO Oxidation by O2 Mediated with Single Gold Atom Doped Titanium Oxide Cluster Anions AuTi2 O4-6.

Gas-phase studies on catalytic CO oxidation by O2 mediated with gold-containing heteronuclear metal oxide clusters are vital to obtain the structure-reactivity relationship of supported gold catalysts, while it is challenging to trigger the reactivity of clusters with closed-shell electronic structure in O2 activation. Herein, we identified that CO oxidation by O2 can be catalyzed by the AuTi2 O4-6 - clusters, among which AuTi2 O4 - with closed-shell electronic structure can effectively activate O2 . The reactions were characterized by mass spectrometry and quantum chemical calculations. Theoretical calculations showed that in the initial stage of O2 activation, the Ti2 O4 moiety in AuTi2 O4 - contributes dominantly to activate O2 into superoxide (O2 - ⋅) without participation of the Au atom. In subsequent steps, the intimate charge transfer interaction between Au and the Ti2 O4 moiety drives the direct dissociation of the O2 - ⋅ unit.