Operando Spectroscopy Unveils the Catalytic Role of Different Palladium Oxidation States in CO Oxidation on Pd/CeO₂ Catalysts

Aiming at knowledge‐driven design of novel metal–ceria catalysts for automotive exhaust abatement, current efforts mostly pertain to the synthesis and understanding of well‐defined systems. In contrast, technical catalysts are often heterogeneous in their metal speciation. Here, we unveiled rich structural dynamics of a conventional impregnated Pd/CeO 2 catalyst during CO oxidation. In situ X‐ray photoelectron spectroscopy and operando X‐ray absorption spectroscopy revealed the presence of metallic and oxidic Pd states during the reaction. Using transient operando infrared spectroscopy, we probed the nature and reactivity of the surface intermediates involved in CO oxidation. We found that while low‐temperature activity is associated with sub‐oxidized and interfacial Pd sites, the reaction at elevated temperatures involves metallic Pd. These results highlight the utility of the multi‐technique operando approach for establishing structure–activity relationships of technical catalysts.