燃料化学学报（中英文）2025，Vol.53Issue(10)：1528-1539,中插13-中插19,19.DOI:10.1016/S1872-5813(25)60564-0
CeO2(110)表面上FLP催化C=C和C=O选择加氢反应机理的理论计算研究
Mechanistic understanding of the selective C=C and C=O hydrogenation catalyzed by frustrated Lewis pairs on CeO2(110)from theoretical perspectives
摘要
Abstract
Heterogeneous solid frustrated-Lewis-pair(FLP)catalyst is of great promise in practical hydrogenation applications.It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation.Consequently,it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO2 catalysts for the selective hydrogenation.In this work,the reaction mechanism of the hydrogenation of CH2=CH2 and CH3CH=O at the FLP sites constructed on CeO2(110)surface was investigated by density functional theory(DFT),with the classical Lewis acid-base pairs(CLP)site as the reference.The results illustrate that at the CLP site,the dissociated hydride(Hδ-)forms a stable H-O bond with the surface O atom,while at the FLP site,Hδ-is stabilized by Ce,displaying higher activity on the one hand.On the other hand,the electron cloud density of the Ce atom at the FLP site is higher,which can transfer more electrons to the adsorbed CC=C and OC=O atoms,leading to a higher degree of activation for C=C and C=O bonds,as indicated by the Bader charge analysis.Therefore,compared to the CLP site,the FLP site exhibits higher hydrogenation activity for CH2=CH2 and CH3CH=O.Furthermore,at the FLP sites,it demonstrates high efficiency in catalyzing the hydrogenation of CH2=CH2 with the rate-determining barrier of 1.04 eV,but it shows limited activity for the hydrogenation of CH3CH=O with the rate-determining barrier of 1.94 eV.It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis.The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO2(110)and reveal the relationship between the catalytic performance and the nature of the active site,which is of great benefit to development of rational design of heterogeneous FLP catalysts.关键词
CeO2(110)/受阻路易斯酸-碱对/CH2=CH2/CH3CH=O/加氢反应机理/密度泛函理论计算Key words
CeO2(110)/frustrated Lewis pairs(FLP)/CH2=CH2/CH3CH=O/the mechanism of hydrogenation/DFT calculation分类
化学化工引用本文复制引用
马宏,赵永祥,陈思情,陈佳敏,丁润龙,刘绍丽,田欣欣,武建兵,李海涛,王永钊..CeO2(110)表面上FLP催化C=C和C=O选择加氢反应机理的理论计算研究[J].燃料化学学报（中英文）,2025,53(10):1528-1539,中插13-中插19,19.基金项目
The project was supported by the National Natural Science Foundation of China(22302115,22072079)and the Fundamental Research Program of Shanxi Province(202303021221056). （22302115,22072079）
