CeO2表面氧吸附的第一性原理计算OA

This study employs first-principles calculations to systematically investigate molecular oxygen adsorption at three distinct adsorbed sites(bridge,hollow,and top)on CeO2(100)and(111)surfaces,thereby providing atomic-level insights into the oxygen reduction reaction(ORR)adsorption mechanism.Firstly,the computed results demonstrate a lower intrinsic surface energy for the(111)surface,whereas the(100)surface shows more favorable oxygen adsorption thermodynamics.Secondly,multiscale electronic structure analyses reveal that,in contrast to the(111)surface,the pronounced O2p-Ce4f orbital hybridization during adsorption on the(100)surface leads to the emergence of a pseudogap,which further enhances charge transfer between O and Ce.Thirdly,when O2 is adsorbed at the hollow position of the(100)surface and bridge site of the(111)surface,the p-band center is close to the Fermi level and work function reaches its minimum value,which can be regarded as the main reason for thehybridization of Ce and O.Finally,the rate-determining step for adsorption process is *O→*OH step at(100)surface and *OOH →*O step at(111)surface.This work elucidates the fundamental properties of distinct crystallographic surfaces in CeO2,providing referential insights for the rational design of high-performance catalysts.