电化学2011，Vol.17Issue(2)：155-160,6.
CO2在Cu表面还原成碳氢化合物的DFT计算研究
DFT Study of CO2 Reduction to Hydrocarbons on Cu Surfaces
摘要
Abstract
The CO2 reduction on Cu( 111 ) single crystal surfaces was studied using DFT calculations on the reaction energies and the minimum energy paths. The results indicated that the possible reaction paths for CO2 reduction on Cu(111) surface are CO2(g) + H*→COOH*→(CO +OH) * ,(CO + H) *→CHO* ,CHO + H→ CH2O*→(CH2 +O) * ,CH2* +2H*→CH4 or 2CH2 *→C2 H4. On Cu(111) surface,the reaction rate is controlled by steps of CH2 O* →( CH2 + O) *, CO2 (g) + H * →COOH→( CO + OH) * and ( CO + H) *→CHO*. In addition, the reaction energies for various steps in the electrochemical reduction of CO2 were calculated under different electrode potentials. The results indicated that HCOO and CO are mainly formed when the potential is more positive than - 0.50 V (vs. RHE ). The hydrogenated dissociation of CO2 to form CO and the subsequent hydrogenation of CO become increasingly exothermic as the potential goes negative, so that hydrocarbons gradually become the favored products in the electrochemical reduction. Under electrochemical conditions, the CHO intermediate prefers to dissociate to form CH,rather than to form CH2O intermediate via protonation as does in gas phase reduction.关键词
密度泛函理论计算/CO2还原/反应路径Key words
density functional theory calculations/ carbon dioxide reduction/ the minimum energy paths分类
化学化工引用本文复制引用
欧利辉,陈胜利..CO2在Cu表面还原成碳氢化合物的DFT计算研究[J].电化学,2011,17(2):155-160,6.基金项目
国家自然科学基金(21073137,50632050)资助 （21073137,50632050）
