Electrochemical carbon-carbon coupling with enhanced activity and racemate stereoselectivity by microenvironment regulation.

Enzymes are characteristic of catalytic efficiency and specificity by maneuvering multiple components in concert at a confined nanoscale space. However, achieving such a configuration in artificial catalysts remains challenging. Herein, we report a microenvironment regulation strategy by modifying carbon paper with hexadecyltrimethylammonium cations, delivering electrochemical carbon-carbon coupling of benzaldehyde with enhanced activity and racemate stereoselectivity. The modified electrode-electrolyte interface creates an optimal microenvironment for electrocatalysis-it engenders dipolar interaction with the reaction intermediate, giving a 2.2-fold higher reaction rate (from 0.13 to 0.28 mmol h -1 cm -2 ); Moreover, it repels interfacial water and modulates the conformational specificity of reaction intermediate by facilitating intermolecular hydrogen bonding, affording 2.5-fold higher diastereomeric ratio of racemate to mesomer (from 0.73 to 1.82). We expect that the microenvironment regulation strategy will lead to the advanced design of electrode-electrolyte interface for enhanced activity and (stereo)selectivity that mimics enzymes.