Genesis of Active Pt/CeO₂ Catalyst for Dry Reforming of Methane by Reduction and Aggregation of Isolated Platinum Atoms into Clusters

Abstract Atomically dispersed metal catalysts offer the advantages of efficient metal utilization and high selectivities for reactions of technological importance. Such catalysts have been suggested to be strong candidates for dry reforming of methane (DRM), offering prospects of high selectivity for synthesis gas without coke formation, which requires ensembles of metal sites and is a challenge to overcome in DRM catalysis. However, investigations of the structures of isolated metal sites on metal oxide supports under DRM conditions are lacking, and the catalytically active sites remain undetermined. Data characterizing the DRM reaction‐driven structural evolution of a cerium oxide‐supported catalyst, initially incorporating atomically dispersed platinum, and the corresponding changes in catalyst performance are reported. X‐ray absorption and infrared spectra show that the reduction and agglomeration of isolated cationic platinum atoms to form small platinum clusters/nanoparticles are necessary for DRM activity. Density functional theory calculations of the energy barriers for methane dissociation on atomically dispersed platinum and on platinum clusters support these observations. The results emphasize the need for in‐operando experiments to assess the active sites in such catalysts. The inferences about the catalytically active species are suggested to pertain to a broad class of catalytic conversions involving the rate‐limiting dissociation of light alkanes.