燃料化学学报（中英文）2025，Vol.53Issue(7)：1061-1071,11.DOI:10.1016/S1872-5813(24)60527-X
单原子镍催化剂上CO还原NO反应机理:密度泛函理论与微观动力学研究
Mechanism of NO reduction by CO over single atomic nickel catalyst:DFT and microkinetic study
摘要
Abstract
The microscopic reaction mechanism of NO reduction by CO on the graphene-supported single-atom Ni catalyst(Ni/G)was investigated by using density functional theory(DFT)and microkinetic modeling.The results indicate that as the most probably pathway for the NO reduction by CO over the Ni/G catalyst,two NO molecules adsorb onto the Ni atoms via the Langmuir-Hinshelwood mechanism and then transform to N2O and active oxygen(O*).Subsequently,N2O is adsorbed on the Ni surface and reduced to N2 and O*.Finally,CO reduces O*to form CO2,releasing the active Ni sites.From the energy barrier perspective,the transformation of NO to N2O and O*has a higher energy barrier,which controls the NO reduction reaction rate.From the microkinetic perspective,the reaction temperature has a significant effect on the rate of O*reduction with CO,which is lower than that of N2O reduction.As a result,the Ni atoms are gradually occupied by O*,which may inhibit the adsorption and reduction of NOx leading to the deactivation of the Ni/G catalyst.关键词
单原子Ni催化剂/NO还原/催化反应机理/密度泛函理论/微观动力学Key words
single-atom Ni catalyst/NO reduction/catalytic reaction mechanism/density functional theory/microkinetic分类
能源科技引用本文复制引用
赵妍,李响,王焕然,朱亚明,李先春..单原子镍催化剂上CO还原NO反应机理:密度泛函理论与微观动力学研究[J].燃料化学学报（中英文）,2025,53(7):1061-1071,11.基金项目
The project was supported by Key Technologies Research and Development Program(2022YFE0208100),Graduate Education Reform and Technological Innovation and Entrepreneurship Project of University of Science and Technology Liaoning(LKDYC202424).国家重点研发计划(2022YFE0208100)和辽宁科技大学研究生科技创新项目(LKDYC202424)资助 （2022YFE0208100）
