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- Title
Unraveling the electrocatalytic reduction mechanism of enols on copper in aqueous media.
- Authors
Cui, Zhihao; Dong, Xing'an; Cho, Sung Gu; Tegomoh, Modeste N.; Dai, Weidong; Dong, Fan; Co, Anne C.
- Abstract
Deoxygenation of aldehydes and their tautomers to alkenes and alkanes has implications in refining biomass-derived fuels for use as transportation fuel. Electrochemical deoxygenation in ambient, aqueous solution is also a potential green synthesis strategy for terminal olefins. In this manuscript, direct electrochemical conversion of vinyl alcohol and acetaldehyde on polycrystalline Cu to ethanol, ethylene and ethane; and propenol and propionaldehyde to propanol, propene and propane is reported. Sensitive detection was achieved using a rotating disk electrode coupled with gas chromatography-mass spectrometry. In-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy, and in-situ Raman spectroscopy confirmed the adsorption of the vinyl alcohol. Calculations using canonical and grand-canonical density functional theory and experimental findings suggest that the rate-determining step for ethylene and ethane formation is an electron transfer step to the adsorbed vinyl alcohol. Finally, we extend our conclusions to the enol reaction from higher-order soluble aldehyde and ketone. The products observed from the reduction reaction also sheds insights into plausible reaction pathways of CO2 to C2 and C3 products. Understanding the electrochemical deoxygenation pathway of aldehydes and ketones is important yet challenging. Here the authors use acetaldehyde as a model system to elucidate the role of enols in the electroreduction of aldehydes and ketones, which may shed light on the reaction pathway of CO2 to C2 and C3 products.
- Subjects
ACETALDEHYDE; PROPENE; KETONES; ROTATING disk electrodes; ENOLS; GAS chromatography/Mass spectrometry (GC-MS); INFRARED absorption; RAMAN spectroscopy
- Publication
Nature Communications, 2022, Vol 13, Issue 1, p1
- ISSN
2041-1723
- Publication type
Article
- DOI
10.1038/s41467-022-33620-2