燃料化学学报（中英文）2024，Vol.52Issue(4)：553-564,12.DOI:10.1016/S1872-5813(23)60399-8
铜催化草酸二甲酯加氢副产物1,2-丙二醇生成机理的DFT研究
A DFT study on the formation mechanism of side product 1,2-propanediol in the hydrogenation of dimethyl oxalate over copper catalyst
摘要
Abstract
The costly separation of 1,2-propanediol(1,2-PDO),an unavoidable byproduct in the hydrogenation of dimethyl oxalate(DMO),significantly hampers the economic viability of coal-to-ethylene glycol(EG)technology.To address this challenge,the formation mechanism of the side product 1,2-PDO on the Cu(111)and Cu2O(111)surfaces during DMO hydrogenation was investigated,which focused on the active sites of copper catalyst and the dominant pathway through density functional theory calculation.The thermodynamics of each elementary step and the adsorption behavior of various species involved in the reaction network along with the local density of states and charge density difference were systematically analyzed.The results indicate that 1,2-PDO is generated more favorably on the Cu2O(111)surface than that on the Cu(lll)surface,owing to the Lewis acid-base pairs,i.e.Cuus+ and Osuf-sites,present on the Cu2O(111)surface,which strengthens the binding of reactants,products,and reaction intermediates to the substrate.EG reacts primarily with methanol(MeOH)to form 1,2-PDO through Guerbet alcohol condensation reaction through three consecutive steps:alcohol dehydrogenation,aldol condensation,and unsaturated aldehyde hydrogenation.The Osuf-sites promote the dehydrogenation of alcohols into aldehydes,the generation of enolates during aldol condensation and the hydrogenation of unsaturated aldehydes,while the Cuus+ sites are responsible for the C-C coupling reaction.These findings may shed light on the mechanism of 1,2-PDO formation over Cu catalyst and provide fundamental knowledge for the development of more efficient catalysts and process optimization.关键词
草酸二甲酯加氢/Cu催化剂/1,2-丙二醇/密度泛函理论/反应机理Key words
dimethyl oxalate hydrogenation/Cu catalyst/1,2-propanediol/density functional theory/reaction mechanism分类
化学化工引用本文复制引用
伦国栋,严伟琦,周静红,朱贻安,李伟..铜催化草酸二甲酯加氢副产物1,2-丙二醇生成机理的DFT研究[J].燃料化学学报（中英文）,2024,52(4):553-564,12.基金项目
The project was supported by National Key Research and Development Plan(2018YFB0604700)and National Natural Science Foundation of China(22178102).国家重点研发计划(2018YFB0604700)和国家自然科学基金(22178102)资助 （2018YFB0604700）
