Swelling-Resistant Functionalized 1T'-MoS2 Membranes for Crossover-Free Organic Electrosynthesis.

Abstract

Organic electrosynthesis offers a sustainable future for chemical manufacturing but is severely hindered by the instability of commercial polymer ion-exchange membranes in organic electrolytes. The excessive swelling of flexible polymer networks, such as Nafion, often results in massive reactant crossover and diminished product yields. In this study, we report a swelling-resistant membrane engineered from functionalized 1T' phase molybdenum disulfide (MoS2). By covalently grafting acetamide groups onto the electron-rich 1T'-MoS2, we create rigid nanochannels that physically exclude organic solvents while enabling efficient proton transport. This precise molecular sieving reduces organic permeability by an order of magnitude versus commercial Nafion 117, enabling near-quantitative yields (>96%) in diverse organic electrosynthesis reactions. Bridging the gap between lab and industrial application, we demonstrate scalable fabrication of this material via slot-die coating, with the resulting large-area membranes delivering robust stability and high productivity in a scaled-up electrolyzer stack. These findings establish functionalized 2D channels as a general platform for designing next-generation ion-conductive membranes capable of operating in aggressive organic media.