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.

Adsorption technology based on ethane-selective materials is a promising alternative to energy-intensive cryogenic distillation for separating ethane (C2H6) and ethylene (C2H4). We employed pore engineering strategy to tune pore environment of metal-organic framework (MOF) through organic functional groups and boosted the C2H6/C2H4 separation of MOF. Introduction of amino (-NH2) groups into Tb-MOF-76 not only decreased pore sizes but also facilitated multiple guest-host interactions in confined pores. The NH2-functionalized Tb-MOF-76(NH2) has increased C2H6 and C2H4 uptakes and C2H6/C2H4 selectivity. The results of experimental and simulated transient breakthroughs reveal that Tb-MOF-76(NH2) has significantly improved one-step separation performance for  C2H6/C2H4 mixtures with a high C2H4 (>99.95%) productivity of 17.66 L kg-1 compared to 7.53 L kg-1 by Tb-MOF-76, resulting from the suitable pore confinement and accissible -NH2 groups on pore surfaces.

Boosting Ethane/Ethylene Separation by MOFs through the Amino-Functionalization of Pores.

Electrocatalytic technology opens a new path to solve the existing problems in fossil fuel consumption and environmental pollution as well as efficient energy use. Metal-organic frameworks (MOFs), a class of...

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Recent Progress in Metal-Organic Frameworks (MOFs) for Electrocatalysis

Eliminating lattice defects in metal–organic framework molecular-sieving membranes

Zeolites and metal-organic frameworks (MOFs) represent an attractive class of crystalline porous materials that possesses regular pore structures. The inherent porosity of these materials has led to an increasing focus on gas separation applications, encompassing adsorption and membrane separation techniques. Here, a brief overview of the critical properties and fabrication approaches for zeolites and MOFs as adsorbents and membranes is given. The separation mechanisms, based on pore sizes and the chemical properties of nanochannels, are explored in depth, considering the distinct characteristics of adsorption and membrane separation. Recommendations for judicious selection and design of zeolites and MOFs for gas separation purposes are emphasized. By examining the similarities and differences between the roles of nanoporous materials as adsorbents and membranes, the feasibility of zeolites and MOFs from adsorption separation to membrane separation is discussed. With the rapid development of zeolites and MOFs towards adsorption and membrane separation, challenges and perspectives of this cutting-edge area are also addressed.

Zeolites and metal-organic frameworks for gas separation: the possibility of translating adsorbents into membranes.

Asymmetric pore windows in MOF membranes for natural gas valorization

Here, this work reports an innovative strategy for the synthesis of chemically robust metal–organic frameworks (MOFs), and applies them as catalysts for the electrocatalytic oxygen evolution reaction (OER). A bimetallic squarate‐based MOF (Sq‐MOF) with a zbr topology serves as an excellent platform for electrocatalytic OER owing to its open porous structure, high affinity toward water, and presence of catalytically active 1D metal hydroxide strips. By regulating the Ni2+ content in a bimetallic squarate MOF system, the electrochemical structural stability toward OER can be improved. The screening of various metal ratios demonstrates that Ni3Fe1 and Ni2Fe1 Sq‐zbr‐MOFs show the best performance for electrocatalytic OER in terms of catalytic activity and structural stability. Ni2Fe1 Sq‐zbr‐MOF shows a low overpotential of 230 mV (at 10 mA cm−2) and a small Tafel slope of 37.7 mV dec−1, with an excellent long‐term electrochemical stability for the OER. Remarkably, these overpotential values of Ni2Fe1 Sq‐zbr‐MOF are comparable with those of the best‐performing layered double hydroxide (LDH) systems and outperforms the commercially available noble‐metal‐based RuO2 catalyst for OER under identical operational conditions.

Unveiling Chemically Robust Bimetallic Squarate‐Based Metal–Organic Frameworks for Electrocatalytic Oxygen Evolution Reaction

•Oriented KAUST-7 membranes with aligned 1D channels were obtained •Steam-assisted surface reorganization to stabilize grain boundary structure •The unique CO2-recognition transportation behavior •Cooperative separation based on adsorption affinity and molecular sieving The steady removal of carbon dioxide (CO2) from diverse gas streams is a critical step toward achieving the blueprint of carbon neutrality and clean energy production. However, the associated energy and capital inputs are considerably high, necessitating the development of effective technologies for CO2 separation. Here, we report a special CO2-recognition membrane based on a fluorinated metal-organic framework (KAUST-7) for efficient CO2 capture from various mixtures including CO2/H2, CO2/CH4, and CO2/N2. Uniquely, the appropriate CO2 affinity cooperating with the confined aperture of KAUST-7 enables the membrane with the right orientation to be nearly only permeable to CO2, showing unprecedented CO2 separation selectivity over both smaller (H2) and larger (N2, CH4) molecules. The extraordinary performance is maintained after treatment with corrosive hydrogen sulfide or humid atmospheres, swing temperatures or pressures, and long-term operations, pinpointing the potential for high-throughput CO2 capture in a continuous mode. The steady removal of carbon dioxide (CO2) from diverse gas streams is a critical step toward achieving the blueprint of carbon neutrality and clean energy production. However, the associated energy and capital inputs are considerably high, necessitating the development of effective technologies for CO2 separation. Here, we report a special CO2-recognition membrane based on a fluorinated metal-organic framework (KAUST-7) for efficient CO2 capture from various mixtures including CO2/H2, CO2/CH4, and CO2/N2. Uniquely, the appropriate CO2 affinity cooperating with the confined aperture of KAUST-7 enables the membrane with the right orientation to be nearly only permeable to CO2, showing unprecedented CO2 separation selectivity over both smaller (H2) and larger (N2, CH4) molecules. The extraordinary performance is maintained after treatment with corrosive hydrogen sulfide or humid atmospheres, swing temperatures or pressures, and long-term operations, pinpointing the potential for high-throughput CO2 capture in a continuous mode. 

A CO2-recognition metal-organic framework membrane for continuous carbon capture

In spite of massive progress in oil-water separation, attributable to the use of advanced materials, the separation process faces challenges such as low permeance and fouling problems. Therefore, superwettable materials used in several fields are considered potential candidates for oily wastewater treatment. Metal-organic frameworks (MOFs) are receiving more and more interest in various separation applications due to their wide potential applications. Nevertheless, MOFs have been rarely explored for separating stabilized oil-in-water emulsions due to the difficulty in finding highly hydrolytic stable MOF candidates for this application. Furthermore, oil can clog water-stable materials owing to its high density, causing the degradation of MOF particles. As a result, there is a need to develop better MOF materials that can fulfill these requirements. Herein, we have explored Cr-soc-MOF-1 as a candidate for this application and deployed it as a membrane, which exhibited superhydrophilicity and underwater superoleophobicity for separating stabilized oil-in-water emulsions. The Cr-soc-MOF-1 membranes were synthesized by assembling the as-prepared MOF particles on a mixed cellulose ester substrate using a vacuum-assisted self-assembly technique. The Cr-soc-MOF-1 membrane exhibited ultrahigh water permeance (7465.9 L·m-2·h-1·bar-1), very high oil rejection (99.9%), and excellent anti-oil-fouling properties. The Cr-soc-MOF-1 membranes also exhibited excellent recyclability over 10 continuous separation cycles. Further, they exhibited an outstanding performance in separating various surfactant-stabilized oil-in-water emulsions. Thus, the Cr-soc-MOF-1 membranes exhibit a high potential in treating oily wastewater.

Deployment of Superhydrophilic and Super-antifouling Cr-soc-MOF-1-Based Membrane for Ultrafast Separation of Stabilized Oil-in-Water Emulsions.

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