10288-08-1Relevant academic research and scientific papers
Electrochemical CO Reduction Builds Solvent Water into Oxygenate Products
Lum, Yanwei,Cheng, Tao,Goddard, William A.,Ager, Joel W.
, p. 9337 - 9340 (2018)
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, C16O reduction was performed in H218O electrolyte. Surprisingly, we found that 60-70% of the ethanol contained 18O, which must have originated from the solvent. We extended our previous all-solvent density functional theory metadynamics 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(18OH), subsequently leading to (18O)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.
Highly efficient visible-light photocatalytic ethane oxidation into ethyl hydroperoxide as a radical reservoir
Zhu, Yao,Fang, Siyuan,Chen, Shaoqin,Tong, Youjie,Wang, Chunling,Hu, Yun Hang
, p. 5825 - 5833 (2021/05/07)
Photocatalytic ethane conversion into value-added chemicals is a great challenge especially under visible light irradiation. The production of ethyl hydroperoxide (CH3CH2OOH), which is a promising radical reservoir for regulating the oxidative stress in cells, is even more challenging due to its facile decomposition. Here, we demonstrated a design of a highly efficient visible-light-responsive photocatalyst, Au/WO3, for ethane oxidation into CH3CH2OOH, achieving an impressive yield of 1887 μmol gcat?1in two hours under visible light irradiation at room temperature for the first time. Furthermore, thermal energy was introduced into the photocatalytic system to increase the driving force for ethane oxidation, enhancing CH3CH2OOH production by six times to 11?233 μmol gcat?1at 100 °C and achieving a significant apparent quantum efficiency of 17.9% at 450 nm. In addition, trapping active species and isotope-labeling reactants revealed the reaction pathway. These findings pave the way for scalable ethane conversion into CH3CH2OOH as a potential anticancer drug.
