Interfacial manipulation of MOFs/polymer mixed matrix membranes for gas separations: A review

Abstract

Membrane-based separation technology holds great promise to effectively address separation needs in chemical industries due to advantages in energy efficiency, scalability, and small footprint. Mixed matrix membranes based on polymer/metal organic frameworks (MOFs), which combine the ease of processability of polymer materials with the excellent adsorption characteristics of MOFs, have been widely investigated for gas separations. The preparation of gas separation membrane materials with both high flux and gas selectivity is the key to achieving efficient gas separation. Recent research results show that the permeability coefficient and gas pair selectivity of mixed matrix membrane materials are hardly improved simultaneously by adding second phase materials such as MOFs. When the loading of MOFs increases, most membranes have common problems such as particle agglomeration and non-selective interfacial defective structures, which lead to a significant decrease in separation performance. To resolve these issues, research scientists are devoted to tailoring the interfacial microstructure of mixed matrix membranes with an aim to exceed the Robeson upper limit. Many novel characterization techniques coupled with simulation studies were carried out to probe the filler dispersion behavior and interfacial structure within membranes in order to provide rules for rationally designing mixed matrix membranes. A variety of approaches have been proposed to finely tune the interfacial interaction by constructing hydrogen bonding and covalent bonding in the membranes. For example, synthesizing functionalized MOFs via mixed-linker or ligand exchange methods provides a good option to enhance interfacial adhesion within membranes. The amino groups, hydroxyl groups and other organic functional groups in MOFs have the capability to create hydrogen bonding. Moreover, these groups can preferentially adsorb specific gas molecules (such as CO2 molecules) to improve gas selectivity. Some researchers post-functionalized MOFs to graft reactive groups on their surface, incorporating them with cross-linkable polymers. Then the light/heat induced crosslinking reaction occurred within the membrane to seal its defective structure, thereby achieving a substantial improvement in membrane separation performance. The past publications on mixed matrix membranes in the decade demonstrated that the researchers have much more in-depth understanding and insights on the fabrication process, membrane morphology, and structure-property relationship of mixed matrix membrane materials. With respect to fundamental research, research scientists are committed to investigating the MOFs properties including crystal morphology, coordinated metal ion, functional groups on membrane performance. To yield high performance mixed matrix membranes, highly permeable polymers were rationally designed as the polymer matrix. However, to complement their widespread industrial application, scale-up of hollow fiber mixed matrix membranes needs to be further investigated. The membrane stability in humid gas feeds is required to be improved. It is also of importance to develop stable, cost-effective and scalable MOFs fillers. With a specific focus on interfacial manipulation of MOFs/polymer mixed matrix membranes for gas separations, this paper mainly reviewed the research progress in the fields of MOFs/polymer-based hybrid matrix membranes for gas separations. It focuses on three aspects: (1) Research progress on optimizing and characterizing the interfacial structure; (2) fundamental understanding of the influences of MOFs and polymers properties on membrane performance; (3) research progress on scale-up of mixed matrix membranes. Finally, the future development direction of mixed matrix membrane materials is proposed in order to provide research ideas for the rational design of high-performance mixed matrix membranes.