Blocking the Operando Formation of Single‐Atom Spectators by Interfacial Engineering

Aside from activity and selectivity, catalyst stability is a key focus in heterogeneous catalysis research. While sintering of metal species has been considered the primary cause for deactivation of metal catalysts, our study reveals that the loss of activity at low reaction temperatures in CeO2‐supported Pt (Pt/CeO2) catalysts in propane oxidation is due to the dispersion of Pt ensemble sites (nanoclusters) and their subsequent operando conversion into Pt single atoms under reaction conditions. These Pt single‐atom species exhibit low reactivity and act as spectators in the low‐temperature reaction region. To address this issue, we engineered the surface of CeO2 by introducing NbOx, which does not directly interact with Pt. Instead, NbOx blocks the strong binding sites for Pt on CeO2, thereby preventing Pt redispersion/fragmentation and preserving reactive Pt ensembles. This strategy led to a remarkable 37‐fold increase in the reaction rate compared to the Pt/CeO2 catalyst. Our findings emphasize the importance of suppressing the formation of noble metal single‐atom spectators through innovative surface engineering strategy. These mechanistic insights not only advance the understanding of materials science of Pt/CeO2 but also extend to critical technological fields such as energy conversion systems and environmental remediation technologies.