Heteroatom‐tuned zeolite with reduced defect enables highly alcohol‐selective mixed‐matrix membranes

Abstract Pure‐silica MFI (Si‐MFI) zeolite, with its intrinsic hydrophobicity, has potential as a filler in polydimethylsiloxane (PDMS)‐based mixed matrix membranes (MMMs) for efficiently separating alcohol from its aqueous solution. The existence of silanol groups in MFI zeolite can restrict the separation performance of MMMs, while element tungsten can flexibly coordinate with Si via oxygen bridges to prevent silanol formation. Herein, we synthesized well‐crystallized W‐MFI zeolite via a one‐pot method and optimized its morphology and chemical properties. XRD, FT‐IR, XPS, and 29Si NMR characterizations confirmed the successful tungsten (W) doping and the elimination of silanol groups. The optimized membrane exhibited excellent pervaporation performance, achieving a flux of 1823 g·m −2 ·h −1 and a separation factor of 20.13 for 5 wt% ethanol/water, and 587 g·m −2 ·h −1 with a factor of 80.62 for 1 wt% n ‐butanol/water at 40°C. These results demonstrate that W‐MFI/PDMS MMMs are promising candidates for efficient alcohol recovery with high selectivity.