低碳化学与化工2025，Vol.50Issue(4)：29-37,54,10.DOI:10.12434/j.issn.2097-2547.20240232
阶梯Cu(221)面催化还原CO制甲醇反应机理及其电子效应的理论研究
Theoretical study on reaction mechanisms and electron effects of CO catalytic reduction to methanol on stepped Cu(221)surface
摘要
Abstract
Cu based catalysts are one of efficient green catalysts for catalytic CO reduction to methanol,and different crystal surfaces of Cu based catalysts exhibit different catalytic performances.Therefore,clarifying the reaction mechanisms on different surfaces is crucial for design and development of catalysts.At present,the reaction mechanisms of stepped Cu(221)surface with the highest stability for CO hydrogenation to methanol are not clear.Based on density functional theory,the optimal pathway for methanol synthesis on the stepped Cu(221)surface was determined via compared activation energies and reaction heats of related elementary reactions.The rate determining step energy barriers during the optimal pathways of methanol synthesis over the terrace Cu(100)and Cu(111)surfaces with higher coordination numbers and stepped Cu(110),Cu(211),Cu(611)and Cu(221)surfaces with lower coordination numbers of Cu active sites were systematically compared(Cu(221):0.77 eV,Cu(611):0.88 eV,Cu(211):0.99 eV,Cu(110):1.04 eV,Cu(100):1.05 eV and Cu(111):1.21 eV).It is confirmed that stepped Cu(221)surface has the best methanol synthesis performance.Combined with Bader charge,density of state,differential charge density and Crystal Orbital Hamiltonian Popution,the CO activation and conversion process was further revealed at the microscopic electronic level.It is found that the strong electrostatic interaction between the step edge site with stronger electronegativity and key species is the essential reason for the high catalytic activity of the stepped Cu(221)surface.关键词
密度泛函理论/阶梯Cu(221)面/CO活化/甲醇/反应机理Key words
density functional theory/stepped Cu(221)surface/CO activation/methanol/reaction mechanisms分类
化学工程引用本文复制引用
刘婷婷,白慧,白冰,徐慧凯,刘勇军,黄伟..阶梯Cu(221)面催化还原CO制甲醇反应机理及其电子效应的理论研究[J].低碳化学与化工,2025,50(4):29-37,54,10.基金项目
山西省科技合作交流项目(202304041101027) （202304041101027）
山西省基础研究计划(202103021224044,202203021212264). （202103021224044,202203021212264）
