Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products

被引:215
作者
Lum, Yanwei [1 ,2 ,3 ]
Cheng, Tao [4 ,5 ]
Goddard, William A., III [4 ,5 ]
Ager, Joel W. [1 ,2 ,3 ]
机构
[1] Lawrence Berkeley Natl Lab, Joint Ctr Artificial Photosynth, Berkeley, CA 94720 USA
[2] Lawrence Berkeley Natl Lab, Div Mat Sci, Berkeley, CA 94720 USA
[3] Univ Calif Berkeley, Dept Mat Sci & Engn, Berkeley, CA 94720 USA
[4] CALTECH, Joint Ctr Artificial Photosynth, Pasadena, CA 91125 USA
[5] CALTECH, Mat & Proc Simulat Ctr MC139 74, Pasadena, CA 91125 USA
基金
美国国家科学基金会;
关键词
CARBON-DIOXIDE; ELECTROREDUCTION; CU(100); HYDROCARBONS; INSIGHTS; KINETICS; FUELS;
D O I
10.1021/jacs.8b03986
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Numerous studies have examined the electrochemical reduction of CO (COR) to oxygenates (e.g., ethanol). None have considered the possibility that oxygen in the product might arise from water rather than from CO. To test this assumption, (CO)-O-16 reduction was performed in (H2O)-O-18 electrolyte. Surprisingly, we found that 60-70% of the ethanol contained O-18, which must have originated from the solvent. We extended our previous all-solvent density functional theory metady-namics calculations to consider the possibility of incorporating water, and indeed, we found a new mechanism involving a Grotthuss chain of six water molecules in a concerted reaction with the *C-CH intermediate to form *CH-CH((OH)-O-18), subsequently leading to (O-18)ethanol. This competes with the formation of ethylene that also arises from *C-CH. These unforeseen results suggest that all previous studies of COR under aqueous conditions must be reexamined.
引用
收藏
页码:9337 / 9340
页数:4
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