燃料化学学报（中英文）2025，Vol.53Issue(6)：906-917,12.DOI:10.1016/S1872-5813(24)60512-8
CO与Cu掺杂CeO2(111)不同晶格氧的反应性:DFT研究
The reactivity of CO with different lattice oxygens on Cu doped CeO2(111):A DFT study
摘要
Abstract
The adsorption of CO on different lattice oxygen sites in Cu doped CeO2(111)was studied by DFT method,and the geometrical structure and electronic properties of adsorption systems were analyzed.The results showed that CO interacted with lattice oxygen on the first layer formed CO2.However,when adsorbed on the second layer lattice oxygen,carbonate species were formed with the participation of first layer lattice oxygens,i.e.,CO co-adsorbed on first and second layer lattice oxygens.For the second layer adsorption,the absolute CO adsorption energy was big on the Oss nearby Cu.This kind of carbonates was thermodynamically stable,and it was attributed to the facilitation of Cu on CO adsorption,manifested by an electron migration behavior from the C 2p orbitals to the Cu 3d orbitals.However,the absolute CO adsorption energy on the Oss away from Cu was small.Compared to the formation of carbonates,the formation CO2 had very small absolute adsorption energy,suggesting the formed carbonates on second layer was stable.Further,when CO adsorbed on the systems with a carbonate,the absolute CO adsorption energy was significantly smaller than that of the non-carbonated system,indicating that the formation of carbonates inhibited CO oxidation on Cu/CeO2(111).Therefore,the formation of carbonates was unfavorable for CO oxidation reaction on Cu/CeO2(111).The results of this study provide theoretical support for the negative effect of CO2 on ceria-based catalysts.关键词
Cu/CeO2(111)/CO吸附/碳酸盐/晶格氧Key words
Cu/CeO2(111)/CO adsorption/carbonate/lattice oxygen分类
化学化工引用本文复制引用
李媛,郑亦凇,王浩,王宏浩,张财顺,胡绍争,韩蛟,张磊,高志贤..CO与Cu掺杂CeO2(111)不同晶格氧的反应性:DFT研究[J].燃料化学学报（中英文）,2025,53(6):906-917,12.基金项目
The project was supported by National Natural Science Foundation of China(22379059),Applied Basic Research Program Project of Liaoning Province(2023JH2/101300224),Service Local Project of the Education Department of Liaoning Province(Enlisting and Leading)(LJKFZ20220201),General Project of the Educational Department of Liaoning Province(LJKMZ20220728),supported by Talent Scientific Research Fund of Liaoning Petrochemical University(2019-XJJL-028),Collaborative Innovation Project of Beijing-Tianjin-Hebei(Tianjin)(22PTXTHZ00020),Basic scientific research project of Liaoning Provincial Department of Education(LJ212410148019). （22379059）
