Self-Sorting of Interfacial Compatibility in MOF-Based Mixed Matrix Membranes.

Metal-organic framework (MOF)-based mixed matrix membranes (MMMs) have shown great promises to overcome the performance upper limit of polymeric membranes for various gas separation processes. However, the gas separation properties of the MMMs largely depend on the MOF-polymer interfacial compatibility which is a metric difficult to quantify. In most cases, whether a MOF filler and a polymer matrix make a good pair is not revealed until the gas transport experiments are performed. This is because there is a lack of characterization techniques to directly probe the MOF-polymer interfacial compatibility. In this work, we demonstrate a self-sorting method to rank the interface compatibility among several MOF-polymer pairs. By mixing one MOF with two polymers in an MMM, the demixing of two polymers will form two polymer domains. The MOF particles will preferably partition into the "preferred" polymer domain due to their higher interfacial affinity. By scanning different polymer pairs, a rank of MOF-polymer interfacial compatibility from high to low can be obtained. Moreover, based on this ranking, it was also found that a highly compatible MOF-polymer pair suggested by this method also corresponds to a more predictable MMM gas separation performance.

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.

Establishing gas transport highways in MOF-based mixed matrix membranes.

Achieving percolation pathways in a metal-organic framework (MOF)-based mixed matrix membrane (MMM) without compromising its mechanical properties is challenging. We developed phase separated (PS)-MMMs with an interconnected MOF domain running across the whole membrane. Through demixing two immiscible polyimides, the MOF particles were selectively partitioned into one of the preferred polymer domains at over 50 volume % local packing density, leading to a percolated network at only 19 weight % MOF loading. The CO2 permeability of this PS-MMM is 6.6 times that of the pure polymer membrane, while the CO2/N2 and CO2/CH4 selectivity remain largely unchanged. Meanwhile, benefiting from its unique co-continuous morphology, the PS-MMM also exhibited markedly improved membrane ductility compared to the conventional MMM at similar MOF loading. PS-MMMs offer a practical solution to simultaneously achieve high membrane permeability and good mechanical properties.

Assessing Bone Quality of the Spine in Children with Scoliosis Using the Ultrasound Reflection Frequency Amplitude Index Method: A Preliminary Study.

Osteopenia is considered a common phenomenon in patients who have scoliosis. Quantitative ultrasound has been used to assess skeletal status for decades, and recently ultrasound imaging using reflection signals from vertebrae were as well applied to measure spinal curvatures in children with scoliosis. The objectives of this study were to develop a new method that can robustly extract a parameter from ultrasound spinal data for estimating bone quality of scoliotic patients and to investigate the potential of the parameter in predicting curve progression. The frequency amplitude index (FAI) was calculated based on the spectrum of the original radiofrequency signals reflected from the tissue-vertebra interface. The correlation between FAI and reflection coefficient was validated using decalcified bovine bone samples in vitro, and the FAIs of scoliotic subjects were investigated in vivo with reference to body mass index, Cobb angles and curve progression status. The results revealed that the intra-rater measures were highly reliable between different trials (intra-class correlation coefficient = 0.997). The FAI value was strongly correlated with the reflection coefficient of bone tissue (R2 = 0.824), and the lower FAI indicated the higher risk of curve progression for the non-mild scoliosis cases. This preliminary study found that the FAI method can provide a feasible and robust approach to assessment of the bone quality of spine and may be a promising factor in monitoring curve progression of patients who have adolescent idiopathic scoliosis.

Coating the Right Polymer: Achieving Ideal Metal-Organic Framework Particle Dispersibility in Polymer Matrixes Using a Coordinative Crosslinking Surface Modification Method.

This work describes the first generalizable method to modify various metal-organic framework (MOF) surfaces with polyimide, polysulfone, polycarbonate, and polymer of intrinsic microporosity-1 (PIM-1). The method first utilizes electrostatic adsorption to rapidly decorate positively charged MOF surfaces with a layer of negatively charged metal-organic nanocapsule, PgC5 Cu. After mixing with the polymer, the copper open metal sites on PgC5 Cu can coordinatively crosslink the polar functional groups on the surface polymer upon thermal activation thereby resulting in the immobilization of a uniform sub-10 nm polymer coating. We quantitatively analyzed the distribution of free path spacing between MOF particles and demonstrated that when the surface polymer matches the matrix polymer, the MOF dispersion was not only visually improved but also found to align perfectly with a theoretically predicted ideal dispersion model where no aggregation driving force was present.

Reverse synthesis of yolk-shell metal-organic frameworks.

We report the first examples of yolk-shell metal-organic framework (MOF) heterostructures based on topologically distinct MOFs: ZIF-8/ZIF-67 and UiO-66. This was accomplished through an innovative reverse synthesis strategy: A hollow UiO-66 was first constructed; the precusors of the ZIFs were then loaded into the cavity of hollow UiO-66 through a mixed solvent impregnation method; subsequent crystallization under solvothermal condition led to the formation of yolk-shell MOFs containing one or multiple ZIF particles confined within a chemically robust single crystalline UiO-66 shell.

A Physical Entangling Strategy for Simultaneous Interior and Exterior Modification of Metal-Organic Framework with Polymers.

A new strategy uses a common feature of metal-organic frameworks (MOFs), namely porosity rather than functionality, to achieve simultaneous interior and exterior modification of a MOF with polymers. We demonstrate that an anhydride-terminated polyimide oligomer can be covalently grafted to the amine-functionalized methacrylate polymer backbone residing underneath the MOF surface and physically entangled within the 3D nanochannels. The MOF particles were evenly coated with a thin layer of polyimide brushes on the surface thereby exhibiting increased dispersibility in solvent media as well as in polymer matrix. The MOF pores were decorated with aliphatic amine groups to endow the MOF with higher CO2 affinity at low pressure. The polyimide-grafted surface allowed MOF particles to interact favorably with the polyimide matrix, producing defect-free MMM with drastically improved CO2 permeability and maintaining the inherent CO2 /N2 and CO2 /CH4 selectivity of the neat polymeric membrane.

The residual tetracycline in pharmaceutical wastewater was effectively removed by using MnO2/graphene nanocomposite.

The object of this study was to remove the tetracycline (TC) residue in pharmaceutical wastewater after flocculation treatment. MnO2/graphene nanocomposite was synthesized by an in situ hydrothermal method and its TC removal rate was up to 99.4%. This nanocomposite had excellent water solubility. More importantly, the introduction of MnO2 nanorods allowed the avoidance of excessive stacking of treated graphene sheets during the adsorption process, which made the TC molecules to have more opportunities to make contact with the adsorbents. In order to eliminate the interference factors, the adsorption isotherm, kinetics, thermodynamics and mechanism were all studied in TC aqueous solution. The influence of solution pH, contact time, MnO2 loading amount, temperature and solution concentration on the adsorption process were also assessed. The main adsorption mechanism contributed to the complexation of Mn(IV) and π-π interactions of the benzene ring structure on treated graphene sheets with TC molecules.

Interfacial Engineering in Metal-Organic Framework-Based Mixed Matrix Membranes Using Covalently Grafted Polyimide Brushes.

Good interfacial compatibility is the key to realize the full potential of metal-organic framework-based mix matrix membranes for gas separation. Here we report a new approach that uses polyimide brushes covalently grafted on the MOF surface to engineer the MOF-polymer interface. Benefiting from the strong brush-brush interaction, polyimide grafted MOF particles can form a stand-alone membrane at 88 wt % MOF loading without the addition of polymeric matrix. Compared to traditional mixed-matrix membranes, the modified membranes exhibit improved ductility up to 472%, reduced interfacial tearing phenomenon under shear force, decreased matrix chain mobility, and improved plasticization resistance against CO2. Most importantly, with increasing MOF loading, only the modified membranes exhibit simultaneous increase of selectivity and permeability for CO2/N2 and CO2/CH4 separation, following the trend predicted by the modified Maxwell model.