Cost
competitive electroreduction of CO2 to CO requires
electrochemical systems that exhibit partial current density (j
CO) exceeding 150 mA cm–2 at cell overpotentials (|ηcell|) less than 1 V.
However, achieving such benchmarks remains difficult. Here, we report
the electroreduction of CO2 on a supported gold catalyst
in an alkaline flow electrolyzer with performance levels close to
the economic viability criteria. Onset of CO production occurred at
cell and cathode overpotentials of just −0.25 and −0.02
V, respectively. High j
CO (∼99,
158 mA cm–2) was obtained at low |ηcell| (∼0.70, 0.94 V) and high CO energetic efficiency
(∼63.8, 49.4%). The performance was stable for at least 8 h.
Additionally, the onset cathode potentials, kinetic isotope effect,
and Tafel slopes indicate the low overpotential production of CO in
alkaline media to be the result of a pH-independent rate-determining
step (i.e., electron transfer) in contrast to a pH-dependent overall
process.
Since 1995, Me(3)SiCF(2)H has been widely believed to be an inefficient difluoromethylating agent, which requires harsh reaction conditions to cleave its rather inert Si-CF(2)H bond. However, it has now been found that, by using a proper Lewis base activator, Me(3)SiCF(2)H can efficiently difluoromethylate various aldehydes, ketones, and imines to give the corresponding products in good to excellent yields at room temperature or even at -78 °C.
Difluoromethyltri(n-butyl)ammonium chloride 1 was found to be an effective difluorocarbene reagent for O-, S-, N-, C-difluoromethylation under basic conditions. It is particularly remarkable that, when only 1.2 equivalent of reagent 1 was used, the difluoromethylated products were obtained in moderate to excellent yields.
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