Metal-organic framework glass composites.

The melting phenomenon in metal-organic frameworks (MOFs) has been recognised as one of the fourth generation MOF paradigm behaviours. Molten MOFs have high processibility for producing mechanically robust glassy MOF macrostructures, and they also offer highly tunable interfacial characteristics when combined with other types of functional materials, such as crystalline MOFs, inorganic glass and metal halide perovskites. As a result, MOF glass composites have emerged as a family of functional materials with dynamic properties and hierarchical structural control. These nanocomposites allow for sophisticated materials science studies as well as the fabrication of next-generation separation, catalysis, optical, and biomedical devices. Here, we review the approaches for designing, fabricating, and characterising MOF glass composites. We determine the key application opportunities enabled by these composites and explore the remaining hurdles, such as improving thermal and chemical compatibility, regulating interfacial properties, and scalability.

Recent advances in the interfacial engineering of MOF-based mixed matrix membranes for gas separation.

The membrane process stands as a promising and transformative technology for efficient gas separation due to its high energy efficiency, operational simplicity, low environmental impact, and easy up-and-down scaling. Metal-organic framework (MOF)-polymer mixed matrix membranes (MMMs) combine MOFs' superior gas-separation performance with polymers' processing versatility, offering the opportunity to address the limitations of pure polymer or inorganic membranes for large-scale integration. However, the incompatibility between the rigid MOFs and flexible polymer chains poses a challenge in MOF MMM fabrication, which can cause issues such as MOF agglomeration, sedimentation, and interfacial defects, substantially weakening membrane separation efficiency and mechanical properties, particularly gas separation. This review focuses on engineering MMMs' interfaces, detailing recent strategies for reducing interfacial defects, improving MOF dispersion, and enhancing MOF loading. Advanced characterisation techniques for understanding membrane properties, specifically the MOF-polymer interface, are outlined. Lastly, it explores the remaining challenges in MMM research and outlines potential future research directions.

Bioinspired Angstrom-Scale Heterogeneous MOF-on-MOF Membrane for Osmotic Energy Harvesting.

Membrane-based salinity gradient energy generation from the osmotic potential at the interface of a river and seawater through reverse electrodialysis is a promising route for realizing clean, abundant, and sustainable energy. Membrane permeability and selective ion transport are crucial for efficient osmotic energy harvesting. However, balancing these two parameters in the membrane design and synthesis remains challenging. Herein, a hybridized bilayer metal-organic frameworks (MOF-on-MOF) membrane is fabricated for efficient transmembrane conductance for enhanced osmotic power generation. The heterogeneous membrane is constructed from imidazolate framework-8 (ZIF-8) deposited on a UiO-66-NH2 membrane intercalated with poly(sodium-4-styrenesulfonate) (PSS). The angstrom-scale cavities in the ZIF-8 layer promote ion selectivity by size exclusion, and the PSS-intercalated UiO-66-NH2 film ensures cation permeability. The synergistic effect is a simultaneous improvement in ion transport and selectivity from an overlapped electric double layer generating 40.01 W/m2 and 665 A/m2 permeability from a 500-fold concentration gradient interface at 3 KΩ and 9.20 W/m2 from mixing of real sea-river water. This work demonstrates a rational design strategy for hybrid membranes with improved ion selectivity and permeability for the water-energy nexus.

Recent advances in enzymatic biofuel cells enabled by innovative materials and techniques.

The past few decades have seen increasingly rapid advances in the field of sustainable energy technologies. As a new bio- and eco-friendly energy source, enzymatic biofuel cells (EBFCs) have garnered significant research interest due to their capacity to power implantable bioelectronics, portable devices, and biosensors by utilizing biomass as fuel under mild circumstances. Nonetheless, numerous obstacles impeded the commercialization of EBFCs, including their relatively modest power output and poor long-term stability of enzymes. To depict the current progress of EBFC and address the challenges it faces, this review traces back the evolution of EBFC and focuses on contemporary advances such as newly emerged multi or single enzyme systems, various porous framework-enzyme composites techniques, and innovative applications. Besides emphasizing current achievements in this field, from our perspective part we also introduced novel electrode and cell design for highly effective EBFC fabrication. We believe this review will assist readers in comprehending the basic research and applications of EBFCs as well as potentially spark interdisciplinary collaboration for addressing the pressing issues in this field.

Phase control of ZIF-7 nanoparticles via mechanochemical synthesis.

Mechanochemical synthesis is a greener synthesis route to form functional metal organic frameworks (MOFs) compared to the typical solvothermal method. Here we demonstrate the crystal phase control of a widely functional zeolitic imidazolate framework, ZIF-7, and its variations via the mechanochemical synthesis route.

Designing Angstrom-Scale Asymmetric MOF-on-MOF Cavities for High Monovalent Ion Selectivity.

Biological ion channels feature angstrom-scale asymmetrical cavity structures, which are the key to achieving highly efficient separation and sensing of alkali metal ions from aqueous resources. The clean energy future and lithium-based energy storage systems heavily rely on highly efficient ionic separations. However, artificial recreation of such a sophisticated biostructure has been technically challenging. Here, a highly tunable design concept is introduced to fabricate monovalent ion-selective membranes with asymmetric sub-nanometer pores in which energy barriers are implanted. The energy barriers act against ionic movements, which hold the target ion while facilitating the transport of competing ions. The membrane consists of bilayer metal-organic frameworks (MOF-on-MOF), possessing a 6 to 3.4-angstrom passable cavity structure. The ionic current measurements exhibit an unprecedented ionic current rectification ratio of above 100 with exceptionally high selectivity ratios of 84 and 80 for K+ /Li+ and Na+ / Li+ , respectively (1.14 Li+ mol m-2 h-1 ). Furthermore, using quantum mechanics/molecular mechanics, it is shown that the combined effect of spatial hindrance and nucleophilic entrapment to induce energy surge baffles is responsible for the membrane's ultrahigh selectivity and ion rectification. This work demonstrates a striking advance in developing monovalent ion-selective channels and has implications in sensing, energy storage, and separation technologies.