With rapid population growth and increased water pollution, the global water situation is deteriorating. Due to this risk, it is now crucial to efficiently remove organic contaminants from water. Metal-organic frameworks (MOFs), due to their unique qualities including adjustable porosity, large pore volume, and excellent adsorption and regeneration properties have recently gained significant scientific interest in the field of water treatment. The knowledge mapping, classification, synthesis, and design of MOFs are described in this review of the literature in order to clarify the advancement of MOFs in the removal of organic contaminants from aqueous solutions. To generate fresh concepts for the use of MOFs in the treatment of organic pollutants, the mechanism of adsorption of organic pollutants in MOFs is described, the application trends of MOFs for the treatment of organic pollutants are reviewed, and the bottleneck issues and application prospects of MOFs are compiled. 

Organic pollutants removal from aqueous solutions using metal-organic frameworks (MOFs) as adsorbents: A review

Zirconium-based metal-organic framework (Zr-MOF) is considered as promising membrane candidate in terms of its tunable pore aperture, rich functionality, and excellent stability. In this study, we pioneered the fabrication of well-intergrown MOF-808 membrane via facile in situ solvothermal growth on porous α-Al2O3 tube. Owing to an appropriate hexagonal aperture window of 10.1 Å, prepared MOF-808 membrane possessed not only ultrahigh rejection rate for versatile dye molecules (e.g., 99.2% for Malachite green, 99.8% for Methyl blue, 99.6% for Congo red, and 99.3% for Calcein) with no loss in separation performance during 96 h of continuous operation, but also low rejection rate for simple salt (e.g., 6.3% for NaCl), rendering it suitable for efficient removal of various dyes from salt-containing wastewater. The resulting MOF-808 membrane achieved ultrahigh salt/dye separation factor of 287.3 with water permeance of 4.37 L m−2 h−1 bar−1. In addition, the MOF-808 membrane remained crack-free upon exposure to salt, acid, alkali solutions or hot water, indicating outstanding chemical stability, which held great promise for efficient dye extraction from textile wastewater. 

Fabrication of water-stable MOF-808 membrane for efficient salt/dye separation

Metal-organic frameworks (MOFs), as a subclass of porous crystalline materials with unique structures and multifunctional properties, play a pivotal role in various research domains. In recent years, significant attention has been directed toward composite materials based on MOFs, particularly MOF-on-MOF heterostructures. Compared to individual MOF materials, MOF-on-MOF structures harness the distinctive attributes of two or more different MOFs, enabling synergistic effects and allowing for the tailored design of diverse multilayered architectures to expand their application scope. However, the rational design and facile synthesis of MOF-on-MOF composite materials are in principle challenging due to the structural diversity and the intricate interfaces. Hence, this review primarily focuses on elucidating the factors that influence their interfacial growth, with a specific emphasis on the interfacial engineering of heterogeneous reactions, in which MOF-on-MOF hybrids can be conveniently obtained by using pre-fabricated MOF precursors. These factors are categorized as internal and external elements, encompassing inorganic metals, organic ligands, lattice matching, nucleation kinetics, thermodynamics, etc. Meanwhile, these intriguing MOF-on-MOF materials offer a wide range of advantages in various application fields, such as adsorption, separation, catalysis, and energy-related applications. Finally, this review highlights current complexities and challenges while providing a forward-looking perspective on future research directions.

Interfacial Engineering of Heterogeneous Reactions for MOF-on-MOF Heterostructures.

Phosphine-functionalized metal-organic frameworks (P-MOFs) as an emerging class of coordination polymers, have provided novel opportunities for the development of heterogeneous catalysts. Yet, compared with the ubiquitous phosphine systems in homogeneous catalysis, heterogenization of phosphines in MOFs is still at its early stage. In this Minireview, we summarize the synthetic strategies, characterization and catalytic reactions based on the P-MOFs reported in literature. In particular, various catalytic reactions are discussed in detail in terms of phosphine ligand structure-function relationship, including the potential obstacles for future development. Finally, we discuss the possible solutions, including new types of reactions and techniques as the perspectives for the development of P-MOF catalysts, highlighting the opportunities and challenges.

Bridging Homogeneous and Heterogeneous Catalysis: Phosphine-Functionalized Metal-Organic Frameworks.

Abstract The molecular heterogeneity of extracellular vesicles (EVs) and the co‐isolation of physically similar particles, such as lipoproteins (LPs), confounds and limits the sensitivity of EV bulk biomarker characterization. Herein, we present a single‐EV and particle (siEVP) protein and RNA assay ( siEVP PRA) to simultaneously detect mRNAs, miRNAs, and proteins in subpopulations of EVs and LPs. The siEVP PRA immobilizes and sorts particles via positive immunoselection onto micropatterns and focuses biomolecular signals in situ. By detecting EVPs at a single‐particle resolution, the siEVP PRA outperformed the sensitivities of bulk‐analysis benchmark assays for RNA and protein. To assess the specificity of RNA detection in complex biofluids, EVs from various glioma cell lines were processed with small RNA sequencing, whereby two mRNAs and two miRNAs associated with glioblastoma multiforme (GBM) were chosen for cross‐validation. Despite the presence of single‐EV‐LP co‐isolates in serum, the siEVP PRA detected GBM‐associated vesicular RNA profiles in GBM patient siEVPs. The siEVP PRA effectively examines intravesicular, intervesicular, and interparticle heterogeneity with diagnostic promise. 

Engineering a tunable micropattern‐array assay to sort single extracellular vesicles and particles to detect RNA and protein in situ

The majority of commercial polyolefins are produced by coordination polymerization using early or late transition metal catalysts. Molecular catalysts containing these transition metals (Ti, Zr, Cr, Ni, and Fe, etc.) are loaded on supports for controlled polymerization behavior and polymer morphology in slurry or gas phase processes. Within the last few years, metal-organic frameworks (MOFs), a class of unique porous crystalline materials constructed from metal ions/clusters and organic ligands, have been designed and utilized as excellent supports for heterogeneous polymerization catalysis whose high density and uniform distribution of active sites would benefit the modulations of molecular weight distributions of high-performance olefin oligomers and (co)polymers. Impressive efforts have been made to modulate the microenvironment surrounding the active centers at the atomic level for improved activities of MOFs-based catalysts and controlled selectivity of olefin insertion. This review aims to draw a comprehensive picture of MOFs for coordination olefin oligomerization and (co)polymerization in the past decades with respect to different transition metal active centers, various incorporation sites, and finally microenvironment modulation. In consideration of more efforts are needed to overcome challenges for further industrial and commercial application, a brief outlook is provided.

Microenvironment Modulation of Metal-Organic Frameworks (MOFs) for Coordination Olefin Oligomerization and (co)Polymerization.

Superparamagnetic nanobeads offer several advantages over microbeads for immunocapture of nanocarriers (extracellular vesicles, lipoproteins, and viruses) in a bioassay: high-yield capture, reduction in incubation time, and higher capture capacity. However, nanobeads are difficult to "pull-down" because their superparamagnetic feature requires high nanoscale magnetic field gradients. Here, an electrodeposited track-etched membrane is shown to produce a unique superparamagnetic nano-edge ring with multiple edges around nanopores. With a uniform external magnetic field, the induced monopole and dipole of this nano edge junction combine to produce a 10× higher nanobead trapping force. A dense nanobead suspension can be filtered through the magnetic nanoporous membrane (MNM) at high throughput with a 99% bead capture rate. The yield of specific nanocarriers in heterogeneous media by nanobeads/MNM exceeds 80%. Reproducibility, low loss, and concentration-independent capture rates are also demonstrated. This MNM material hence expands the application of nanobead immunocapture to physiological samples. 

/pdf/electrodeposited-magnetic-nanoporous-membrane-for-high-yield-2w1acwj0.pdf

Electrodeposited magnetic nanoporous membrane for high-yield and high-throughput immunocapture of extracellular vesicles and lipoproteins

As nanoscale extracellular vesicles secreted by cells, small extracellular vesicles (sEVs) have enormous potential as safe and effective vehicles to deliver drugs into lesion locations. Despite promising advances with sEV-based drug delivery systems, there are still challenges to drug loading into sEVs, which hinder the clinical applications of sEVs. Herein, we report an exogenous drug-agnostic chiral graphene quantum dots (GQDs) sEV-loading platform, based on chirality matching with the sEV lipid bilayer. Both hydrophobic and hydrophilic chemical and biological drugs can be functionalized or adsorbed onto GQDs by π-π stacking and van der Waals interactions. By tuning the ligands and GQD size to optimize its chirality, we demonstrate drug loading efficiency of 66.3% and 64.1% for doxorubicin and siRNA, which is significantly higher than other reported sEV loading techniques.

Chiral Graphene Quantum Dots Enhanced Drug Loading into Small Extracellular Vesicles.

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Papers

Microenvironment Modulation of Metal-Organic Frameworks (MOFs) for Coordination Olefin Oligomerization and (co)Polymerization.

Electrodeposited magnetic nanoporous membrane for high-yield and high-throughput immunocapture of extracellular vesicles and lipoproteins

Chiral Graphene Quantum Dots Enhanced Drug Loading into Small Extracellular Vesicles.