Single‐Site vs. Cluster Catalysis in High Temperature Oxidations

The behavior of single Pt atoms and small Pt clusters was investigated for high‐temperature oxidations. The high stability of these molecular sites in CHA is a key to intrinsic structure–performance descriptions of elemental steps such as O 2 dissociation, and subsequent oxidation catalysis. Subtle changes in the atomic structure of Pt are responsible for drastic changes in performance driven by specific gas/metal/support interactions. Whereas single Pt atoms and Pt clusters (> ca. 1 nm) are unable to activate, scramble, and desorb two O 2 molecules at moderate T (200 °C), clusters <1 nm do so catalytically, but undergo oxidative fragmentation. Oxidation of alkanes at high T is attributed to stable single Pt atoms, and the C‐H cleavage is inferred to be rate‐determining and less sensitive to changes in metal nuclearity compared to its effect on O 2 scrambling. In contrast, when combustion involves CO, catalysis is dominated by metal clusters, not single Pt atoms.