Membrane-based separations have garnered considerable attention owing to their high energy efficiency, low capital cost, small carbon footprint, and continuous operation mode. As a class of highly porous crystalline materials with well-defined pore systems and rich chemical functionalities, metal-organic frameworks (MOFs) have demonstrated great potential as promising membrane materials over the past few years. Different types of MOF-based membranes, including polycrystalline membranes, mixed matrix membranes (MMMs), and nanosheet-based membranes, have been developed for diversified applications with remarkable separation performances. In this comprehensive review, we first discuss the general classification of membranes and outline the historical development of MOF-based membranes. Subsequently, particular attention is devoted to design strategies for MOF-based membranes, along with detailed discussions on the latest advances on these membranes for various gas and liquid separation processes. Finally, challenges and future opportunities for the industrial implementation of these membranes are identified and outlined with the intent of providing insightful guidance on the design and fabrication of high-performance membranes in the future.

Advances in metal-organic framework-based membranes.

The booming of global environmental awareness has driven the scientific community to search for alternative sustainable approaches. This is accentuated in the 13th sustainable development goal (SDG13), climate action, where urgent efforts are salient in combating the drastic effects of climate change. Membrane separation is one of the indispensable gas purification technologies that effectively reduces the carbon footprint and is energy-efficient for large-scale integration. Metal-organic frameworks (MOFs) are recognized as promising fillers embedded in mixed matrix membranes (MMMs) to enhance gas separation performance. Tremendous research studies on MOFs-based MMMs have been conducted. Herein, this review offers a critical summary of the MOFs-based MMMs developed in the past 3 years. The basic models to estimate gas transport, preparation methods, and challenges in developing MMMs are discussed. Subsequently, the application and separation performance of a variety of MOFs-based MMMs including those of advanced MOFs materials are summarized. To accommodate industrial needs and resolve commercialization hurdles, the latest exploration of MOF materials for a harsh operating condition is emphasized. Along with the contemplation on the outlook, future perspective, and opportunities of MMMs, it is anticipated that this review will serve as a stepping stone for the coming MMMs research on sustainable and benign environmental application.

Metal-Organic Frameworks (MOFs)-Based Mixed Matrix Membranes (MMMs) for Gas Separation: A Review on Advanced Materials in Harsh Environmental Applications.

In the mixed matrix membrane (MMM), the interface between the filler and the polymer matrix will directly affect the gas separation performance of the membranes. Reasonable interfacial design in MMMs is thus important and necessary. In this work, metal-organic coordination interaction is used to construct the interface in metal-organic framework (MOF) nanosheet-based polyimide MMMs where ultrathin Co-benzenedicarboxylate MOF nanosheets (CBMNs) with a thickness less than 5 nm and a lateral size more than 5 μm are synthesized as fillers and a carboxyl-functionalized polyimide (6FDA-durene-DABA) is used as a polymer matrix. Because of the high aspect ratio (>1000) of CBMNs, abundant metal-organic coordination bonds are formed between Co2+ in CBMNs and the -COOH group in 6FDA-durene-DABA. As a result, the 6FDA-durene-DABA/CBMN MMMs exhibit improved separation performance for the CO2/CH4 and H2/CH4 gas pairs with H2/CH4 and CO2/CH4 selectivities up to 42.0 ± 4.0 and 33.6 ± 3.0, respectively. The enhanced interfacial interaction leads to the comprehensive separation performance of CO2/CH4 and H2/CH4 gas pairs approaching or surpassing the 2008 Robeson upper bound. In addition, the CO2 plasticization pressure of the MMMs is significantly enhanced up to ∼20 bar, which is 2 times that of the pure 6FDA-durene-DABA membrane. When separating a mixed gas of CO2/CH4, the selectivity of CO2/CH4 remains stable at around 23 and the CO2 permeability keeps around 400 barrer during the long-term test.

MOF Nanosheet-Based Mixed Matrix Membranes with Metal-Organic Coordination Interfacial Interaction for Gas Separation.

Metal-organic frameworks (MOFs) have attracted extensive research interest because of their high specific surface area, tunable microporosity, low skeleton density and good stability, and they are seen as ideal functional materials for the detection and removal of metal ions. Current research is mainly focused on the trade-off between the permeability and selectivity, and the development of MOFs composites with superior performance to obtain satisfactory adsorption and separation capacity, such as MOFs membranes. In this review, we first summarize the various design and synthesis strategies for MOFs and MOF membrane materials, including with/without solvent, the mechanochemical method, the primary growth method and the secondary growth method. The recent advances in MOFs and MOFs membranes for the adsorption and removal of different types of metal ions are then highlighted. Finally, the opportunities and challenges for the future development of MOFs and MOFs membranes are proposed. This review aims to provide a deep understanding of the rational design and application research of MOFs and MOF membranes and promote development and progress in MOF hybrid materials.

Recent advances in metal-organic frameworks/membranes for adsorption and removal of metal ions

Imputation of missing gas permeability data for polymer membranes using machine learning

Zn(II)-modified imidazole containing polyimide/ZIF-8 mixed matrix membranes for gas separations

Performance optimization of imidazole containing copolyimide/functionalized ZIF-8 mixed matrix membrane for gas separations

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Zn(II)-modified imidazole containing polyimide/ZIF-8 mixed matrix membranes for gas separations

Performance optimization of imidazole containing copolyimide/functionalized ZIF-8 mixed matrix membrane for gas separations