Three-Dimensional-Printed Core-Shell Structured MFI-Type Zeolite Monoliths for Volatile Organic Compound Capture under Humid Conditions.

Crystalline aluminosilicate zeolites with high sorption capacity and low production cost have been recognized as a promising adsorbent for volatile organic compound (VOC) capture. However, the ubiquitous water vapor in the VOC streams may compete with VOCs during the practical separation process because of the hydrophilic property of aluminosilicate zeolites. Herein, a self-supporting core-shell structured MFI-type zeolite monolith was fabricated by 3D-printing aluminosilicate ZSM-5 zeolites as the core, followed by coating silicalite-1 zeolites as a hydrophobic shell via post-hydrothermal crystallization. Natural sepiolite nanofibers (SNFs) were employed as printing ink additives for reinforcing the mechanical stability of 3D-printed ZSM-5 monoliths. Colloidal silica was also introduced into the printing inks, affording continuous growth of silicalite-1 layers (with a thickness of ∼200 nm) over ZSM-5 crystals. Such core-shell structured MFI-type zeolite monoliths exhibited superior dynamic adsorption performance for toluene at 298 K under humid conditions (relative humidity: 50%), with a saturated adsorption capacity of 44.3 mg/g. This work provides a facile strategy for designing self-supporting zeolite monoliths with core-shell architectures for adsorption/separation and other advanced applications.