Key Laboratory of Poyang Lake Environment and Resource Utilization of Ministry of Education, School of Resources Environmental and Chemical Engineering , Nanchang University , Nanchang , Jiangxi 330031 , P. R. China.
ACS Appl Mater Interfaces. 2018 Oct 10;10(40):34640-34645. doi: 10.1021/acsami.8b12556. Epub 2018 Sep 28.
Mixed-matrix membranes (MMMs) with excellent mechanical and separation performance are usually challenging to be fabricated due to the significant incompatibility between nanofillers and the polymer matrix. This work provides a facile technique to construct MMMs through covalently attaching metal-organic frameworks (MOFs) within the polymer matrix via ring-opening metathesis polymerization. Norbornene-modified UiO-66-NH was successfully copolymerized into polynorbornene matrix in less than 10 min. Owing to strong covalent interaction among MOFs and polymers, exceptional toughening effects for MMMs through cavitation were observed. For MMMs with 20 wt % MOF loading, 520 times improvement in mechanical toughness was realized in comparison with neat polymers (52 vs 0.1 MJ/m), far exceeding most of the previous MMMs. Such MMMs exhibited excellent gas separation performance for H/CO and H/N with high H permeability at 91-230 barrers and H/N and H/CO selectivity at >1000 and 6-7, respectively, surpassing the 2008 Robeson Upper Bound. As a proof for the scalable preparation of MMMs, a large and thin MMM (dimension: 98 × 165 cm; thickness: 3-5 μm) was also prepared in the factory for gas separation.
混合基质膜（MMMs）具有优异的机械性能和分离性能，但由于纳米填料与聚合物基体之间存在显著的不相容性，因此通常难以制备。本工作通过开环易位聚合将金属-有机骨架（MOFs）共价键合到聚合物基体中，提供了一种制备 MMMs 的简便技术。成功地在不到 10 分钟内将硝硼烯改性的 UiO-66-NH 共聚到聚硝硼烯基质中。由于 MOFs 和聚合物之间存在强烈的共价相互作用，通过空化观察到 MMMs 的出色增韧效果。对于负载 20wt% MOF 的 MMMs，与纯聚合物相比，力学韧性提高了 520 倍（52 对 0.1MJ/m），远远超过了大多数以前的 MMMs。这些 MMMs 表现出优异的 H/CO 和 H/N 气体分离性能，具有 91-230 巴的高气透过率和 >1000 的 H/N 和 H/CO 选择性，分别超过了 2008 年的 Robeson 上限。作为大规模制备 MMMs 的证明，还在工厂中制备了大而薄的 MMM（尺寸：98×165cm；厚度：3-5μm）用于气体分离。
