Self-supported MOF/cellulose-nanocrystals materials designed from ultrafiltration

Abstract

Metal–organic-frameworks (MOFs) are promising materials for addressing critical issues such as petrochemical separation, water purification, energy storage and drug delivery. Their large-scale deployment, however, is hampered by a limited processability due to their powdery nature. Recently, the hybridization of MOFs with biopolymers has emerged as a greener, biocompatible strategy to shape MOFs composites into more processable membranes, films, and porous materials. In this work, cellulose nanocrystals (CNCs) were used in combination with ZIF-8 (a widely used synthetic zeolite) to produce hybrid composites through ultrafiltration. Results showed that small quantities of CNCs (1 to 20 CNC:ZIF-8 volume ratio) were sufficient to form a self-supported, dense deposit with high ZIF-8 loadings. Compared to classical MOF in situ growth strategies, this approach allowed the tuning of the composition of the final nanocomposite by controlling the nature and quantities of particles in the suspension. The fabrication of the deposit was strongly dependent on the physiochemical properties of the suspension, which were fully characterized with a set of complementary techniques, including in situ SAXS. This technique was employed to investigate the filtration process, which exhibited a homogeneous deposition of ZIF-8 particles mediated by CNC self-assembly. Finally, the available pore volume and integrity of the internal porosity of ZIF-8 were characterized by water porosimetry, demonstrating that the presence of CNCs did not alter the properties of the supported ZIF-8.