Enhanced CO2/N2 separation in hybrid composite membrane via dispersion of hollow defect‐engineered Zr‐MOF nanoparticles

Abstract High‐performance and durable membranes are being sought to enable energy‐efficient CO 2 capture. Although representing an appealing candidate for the above application, successful translation of distinct properties of MOF filler into hybrid composite membranes (HCMs) remains challenging. In this study, we synthesized uniform hollow defect‐engineered UiO‐66 nanoparticles as filler for enhancing the CO 2 /N 2 separation performance and durability of Pebax‐2533 membranes. The existence of missing‐linker defects in the framework not only endows HCMs with higher CO 2 /N 2 adsorption selectivity but also provides ultrafast CO 2 transport pathways; moreover, hollow structure of UiO‐66 not only contributes to better filler dispersibility in polymeric matrix but also reduces CO 2 diffusion path length. Obtained HCMs manifest concurrently increased CO 2 permeability (3100 Barrer) and CO 2 /N 2 separation factor (44), far exceeding state‐of‐the‐art 2019 upper bound for polymer membranes; moreover, our membranes exhibit enhanced resistance toward plasticization, physical aging, and water vapors under harsh operation conditions.