Oxide supported gold catalysts (e.g.,
Au/TiO2) are of great significance in heterogeneous catalysis
owing to their extraordinary catalytic activity. Study of heteronuclear
metal oxide clusters (HMOCs, e.g., Au
x
Ti
y
O
z
q
) is an important way to uncover the molecular-level
mechanisms of gold catalysis in the related heterogeneous catalytic
systems. However, the current studies of HMOCs are focused on charged
clusters with little attention paid to neutral species. The reactivity
study of neutral HMOCs is vital to have a comprehensive understanding
of heterogeneous catalysis, but it is experimentally challenging because
of the difficulty of cluster ionization and detection without fragmentation.
Herein, benefiting from a homemade time-of-flight mass spectrometer
coupled with a vacuum ultraviolet laser system, the reactivity of
neutral Au1-doped titanium oxide clusters AuTi2O3–6 in catalytic CO oxidation by O2 has been successfully identified. The mechanistic details of the
catalysis have been elucidated by quantum chemistry calculations.
The crucial roles of the mobile AuCO species that can facilitate not
only the process of CO oxidation but also the process of O2 activation have been discovered in the cluster catalysis. The fascinating
results are of substantial importance to understand the mechanisms
of CO oxidation over Au/TiO2, one type of the best studied
gold catalysts.