Electro‐Organic Synthesis at a Stable Oil/Water/Solid Three‐Phase Interface Reactor

ABSTRACT Electro‐organic synthesis offers a green and efficient method to produce high‐value organic chemicals under mild conditions, but it suffers from poor water solubility of organic reactant(s) and tedious separation processes for organic product(s) in the conventional electrochemical reaction systems. Herein, we report a porous membrane electrode (PME) reactor design that allows electro‐organic synthesis with concentrated or neat organic reactant(s), achieving product concentrations above 6 M in representative reactions with simplified separation. The PME reactor is demonstrated across several representative electro‐organic transformations, including reduction, oxidation, and oxidation–reduction coupled reactions. The PME reactor can be run at a low operating voltage (∼2 V) with excellent long‐term stability (for more than 400 h) and has achieved the synthesis of pharmaceutical intermediate on a 500‐g scale. The exceptional performance of the PME reactor is associated with its unique interfacial structure, which can create a stable oil/water/solid three‐phase electrochemical reaction interface.