Density functional theory calculations corrected for on-site Coulomb interactions (DFT + U) have been performed to study the mechanism of catalytic at Rh/CeO2(111) surfaces. The purpose of this study was to explore the catalytic mechanism of single-atom rhodium-supported ceria surface for methane oxidation and the regulation mechanism of catalytic activity. According to DFT calculation, it has been found that a Rh atom loaded to CeO2(111) surface would produce one Ce3+ species. And the results also evidenced that the activation of O2 mainly occurs at Rh sties and it’s not affected by the coverage of single atom Rh. However, the methane activation mainly occurs at Ce3+ sites and was greatly affected by the coverage of single Rh atoms. These results also show that the activities of methane oxidation of the system can be significantly changed by increasing the coverage of rhodium atoms on CeO2(111) surface, and the change is nonlinear, and this change relationship is likely to originate from the synergy between active sites (such as Rh and Ce). In addition, we also studied the mechanism of the formation of active H species on the Rh/CeO2 system, and explored the catalytic properties of the CeO2 system for selective hydrogenation reactions. Notably, we found that the mechanism of catalytic reactions on Rh/CeO2 surfaces is similar to that of homogeneous catalysis of rhodium-based catalysts, which may provide guidance for the design of heterogenization of homogeneous catalysts.

Theoretical study for activation of methane on ceria surfaces supported with single-atom Rh

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