Pt-Embedded CuO_<i>x</i>–CeO₂ Multicore–Shell Composites: Interfacial Redox Reaction-Directed Synthesis and Composition-Dependent Performance for CO Oxidation

Abstract

Exploring the state-of-the-art heterogeneous catalysts has been a general concern for sustainable and clean energy. Here, Pt-embedded CuO _x-CeO₂ multicore-shell (Pt/CuO _x-CeO₂ MS) composites are fabricated at room temperature via a one-pot and template-free procedure for catalyzing CO oxidation, a classical probe reaction, showing a volcano-shaped relationship between the composition and catalytic activity. We experimentally unravel that the Pt/CuO _x-CeO₂ MS composites are derived from an interfacial autoredox process, where Pt nanoparticles (NPs) are in situ encapsulated by self-assembled ceria nanospheres with CuO _x clusters adhered through deposition/precipitation-calcination process. Only Cu-O and Pt-Pt coordination structures are determined for CuO _x clusters and Pt NPs in Pt/CuO _x-CeO₂ MS, respectively. Importantly, the close vicinity between Pt and CeO₂ benefits to more oxygen vacancies in CeO₂ counterparts and results in thin oxide layers on Pt NPs. Meanwhile, the introduction of CuO _x clusters is crucial for triggering synergistic catalysis, which leads to high resistance to aggregation of Pt NPs and improvement of catalytic performance. In CO oxidation reaction, both Pt^δ+-CO and Cu⁺-CO can act as active sites during CO adsorption and activation. Nonetheless, redundant content of Pt or Cu will induce a strongly bound Pt-O-Ce or Cu-[O _x]-Ce structures in air-calcinated Pt/CuO _x-CeO₂ MS composites, respectively, which are both deleterious to catalytic reactivity. As a result, the composition-dependent catalytic activity and superior durability of Pt/CuO _x-CeO₂ MS composites toward CO oxidation reaction are achieved. This work should be instructive for fabricating desirable multicomponent catalysts composed of noble metal and bimetallic oxide composites for diverse heterogeneous catalysis.