Synergistic Chemistry Between Supported Platinum Atoms and Nanoclusters in Hydrocarbon Oxidation

Abstract Delineating the specific role of supported metal atoms and nanoclusters as well as their synergistic effect is particularly challenging but crucial for thermal catalytic oxidation. A programmed atomic layer deposition method is herein devised for the precise synthesis of Pt single atoms and nanoclusters coexisting on the surface of CeO 2 (Pt 1 ‐Pt n /CeO 2 ) with controllable ratios and proximity, permitting a careful optimization of the distribution and relative proportions of these Pt species. The 80%Pt 1 ‐20%Pt n /CeO 2 catalyst with an average separation of ≈3.7 nm between single atoms and nanoclusters exhibits unprecedented performance in hydrocarbon oxidation reaction, far superior to Pt 1 /CeO 2 or Pt n /CeO 2 catalysts and outperforming all so‐far‐known Pt nano‐catalysts, this can also be extended to Pt 1 ‐Pt n /TiO 2 and Pt 1 ‐Pt n /ZrO 2 catalysts. The intrinsic investigations reveal a synergistic dual‐active‐site catalytic mechanism, involving that the polarized Pt atoms enable the fast dissociation and migration of activated hydrocarbons toward the nanoclusters center to further react with the surrounding excited oxygen. The synthesis strategy and synergistic chemistry demonstrated in this work provide a generalizable platform for the future design of well‐defined complex multi‐competent‐site catalysts for efficient thermo‐catalytic oxidation reactions.