Metal–organic frameworks and covalent organic frameworks as disruptive membrane materials for energy-efficient gas separation

In this Review we survey the molecular sieving behaviour of metal–organic framework (MOF) and covalent organic framework (COF) membranes, which is different from that of classical zeolite membranes. The nature of MOFs as inorganic–organic hybrid materials and COFs as purely organic materials is powerful and disruptive for the field of gas separation membranes. The possibility of growing neat MOFs and COFs on membrane supports, while also allowing successful blending into polymer–filler composites, has a huge advantage over classical zeolite molecular sieves. MOFs and COFs allow synthetic access to more than 100,000 different structures and tailor-made molecular gates. Additionally, soft evacuation below 100 °C is often enough to achieve pore activation. Therefore, a huge number of synthetic methods for supported MOF and COF membrane thin films, such as solvothermal synthesis, seed-mediated growth and counterdiffusion, exist. Among them, methods with high scale-up potential, for example, layer-by-layer dip- and spray-coating, chemical and physical vapour deposition, and electrochemical methods. Additionally, physical methods have been developed that involve external stimuli, such as electric fields and light. A particularly important point is their ability to react to stimuli, which has allowed the ‘drawbacks’ of the non-ideality of the molecular sieving properties to be exploited in a completely novel research direction. Controllable gas transport through membrane films is a next-level property of MOFs and COFs, leading towards adaptive process deviation. MOF and COF particles are highly compatible with polymers, which allows for mixed-matrix membranes. However, these membranes are not simple MOF–polymer blends, as they require improved polymer–filler interactions, such as cross-linking or surface functionalization.