Effects of Subsurface Oxide on Cu₁/CeO₂ Single-Atom Catalysts for CO Oxidation: A Theoretical Investigation

Supported atomic dispersion metals are of great interest, and the interfacial effect between isolated metal atoms and supports is crucial in heterogeneous catalysis. Herein, the behavior of single-atom Cu catalysts dispersed on CeO₂ (100), (110), and (111) surfaces has been studied by DFT + U calculations. The interactions between ceria crystal planes and isolated Cu atoms together with their corresponding catalytic activities for CO oxidation are investigated. The CeO₂ (100) and (111) surfaces can stabilize active Cu⁺ species, while Cu exists as Cu²⁺ on the (110) surface. Cu⁺ is certified as the most active site for CO adsorption, which can promote the formation of the reaction intermediates and reduce reaction energy barriers. For the CeO₂ (100) surface, the interaction between CO and Cu is weak and the CO adsorbate is more likely to activate the subsurface oxygen. The catalytic performance is closely related to the binding strength of CO to the active Cu single atoms on the different subsurfaces. These results bring a significant insight into the rational design of single metal atoms on ceria and other reducible oxides.