Electrode Surface Heating with Organic Films Improves CO Reduction Kinetics on Copper.

Management of the electrode surface temperature is an understudied aspect of (photo)electrode reactor design for complex reactions, such as CO reduction. In this work, we study the impact of local electrode heating on electrochemical reduction of CO reduction. Using the ferri/ferrocyanide open circuit voltage as a reporter of the effective reaction temperature, we reveal how the interplay of surface heating and convective cooling presents an opportunity for cooptimizing mass transport and thermal assistance of electrochemical reactions, where we focus on reduction of CO to carbon-coupled (C) products.

Organic Additive-derived Films on Cu Electrodes Promote Electrochemical CO Reduction to C Products Under Strongly Acidic Conditions.

Electrochemical CO reduction (CO R) at low pH is desired for high CO utilization; the competing hydrogen evolution reaction (HER) remains a challenge. High alkali cation concentration at a high operating current density has recently been used to promote electrochemical CO R at low pH. Herein we report an alternative approach to selective CO R (>70 % Faradaic efficiency for C products, FE ) at low pH (pH 2; H PO /KH PO ) and low potassium concentration ([K ]=0.

Breaking Scaling Relationships in CO Reduction on Copper Alloys with Organic Additives.

Boundary conditions for catalyst performance in the conversion of common precursors such as N, O, HO, and CO are governed by linear free energy and scaling relationships. Knowledge of these limits offers an impetus for designing strategies to alter reaction mechanisms to improve performance. Typically, experimental demonstrations of linear trends and deviations from them are composed of a small number of data points constrained by inherent experimental limitations.

Desymmetrization of difluoromethylene groups by C-F bond activation.

Tertiary stereogenic centres containing one fluorine atom are valuable for medicinal chemistry because they mimic common tertiary stereogenic centres containing one hydrogen atom, but they possess distinct charge distribution, lipophilicity, conformation and metabolic stability. Although tertiary stereogenic centres containing one hydrogen atom are often set by enantioselective desymmetrization reactions at one of the two carbon-hydrogen (C-H) bonds of a methylene group, tertiary stereocentres containing fluorine have not yet been constructed by the analogous desymmetrization reaction at one of the two carbon-fluorine (C-F) bonds of a difluoromethylene group. Fluorine atoms are similar in size to hydrogen atoms but have distinct electronic properties, causing C-F bonds to be exceptionally strong and geminal C-F bonds to strengthen one another.