应用化学2026，Vol.43Issue(7)：1094-1102,9.DOI:10.19894/j.issn.1000-0518.250402
CeO2表面氧吸附的第一性原理计算
Adsorption Mechanism of Oxygen on CeO2 Surface by Using First-Principles Calculations
摘要
Abstract
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.关键词
第一性原理计算/表面吸附/吸附位点/吉布斯自由能/氧还原反应机理Key words
First-principles calculations/Surface adsorption/Adsorption site/Gibbs free energy/Oxygen reduction reaction mechanism分类
化学化工引用本文复制引用
周爽,孟君玲,姚芬,徐娜,赵丽娜,徐兰兰..CeO2表面氧吸附的第一性原理计算[J].应用化学,2026,43(7):1094-1102,9.基金项目
国家自然科学基金(No.52202238)和吉林省科技发展计划(No.YDZJ202601ZYTS108)资助 Supported by the National Natural Science Foundation of China(No.52202238)and Provincial Natural Science Foundation of Jilin(No.YDZJ202601ZYTS108) （No.52202238）
