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Amine-functionalized nanoporous materials can be prepared by the incorporation of diverse organic amine moieties into the pore structures of a range of support materials, such as mesoporous silica and alumina, zeolite, carbon and metal organic frameworks (MOFs), either by direct functionalization or post-synthesis through physical impregnation or grafting. These hybrid materials have great potential for practical applications, such as dry adsorbents for post-combustion CO capture, owing to their high CO capture capacity, high capture selectivity towards CO compared to other gases, and excellent stability. This paper summarizes the preparation methods and CO capture performance based on the equilibrium CO uptake of a range of amine-functionalized nanoporous materials. [ABSTRACT FROM AUTHOR]

Highlights: [•] Zinc hydroxides and oxides derived from organozinc complexes. [•] The preparation and structural variety of organozinc hydroxides. [•] Synthetic methods and structural types of zinc oxide clusters. [•] The relevance of zinc hydroxides and oxides to functional materials. [ABSTRACT FROM AUTHOR]

Hydrogen is a green energy carrier. Chemical looping reforming of biomass and its derivatives is a promising way for hydrogen production. However, the removal of carbon dioxide is costly and inefficient with the traditional chemical absorption methods. The objective of this article is to find a new material with low energy consumption and high capacity for carbon dioxide storage. A metal organic framework (MOF) material (e.g., CuBTC) was prepared using the hydrothermal synthesis method. The synthesized material was characterized by X-ray diffraction, −196 °C N adsorption/desorption isotherms, and thermogravimetry analysis to obtain its physical properties. Then BET, t-plot, and density functional theory (DFT) methods were used to acquire its specific surface area and pore textural properties. Its carbon dioxide adsorption capacity was evaluated using a micromeritics ASAP 2000 instrument. The results show that the decomposition temperature of the synthesized CuBTC material is 300 °C. Besides, high CO adsorption capacity (4 mmol g) and low N adsorption capacity were obtained at 0 °C and atmospheric pressure. These results indicate that the synthesized MOF material has a high efficiency for CO separation. From this study, it is expected that this MOF material could be used in adsorption and separation of carbon dioxide in chemical looping reforming process for hydrogen production in the near future. [ABSTRACT FROM AUTHOR]

The design and synthesis of boronate affinity materials that show high efficiency, high selectivity, and high enrichment performance have gained significant attention. The principle of boronate affinity relies on the reversible covalent reactions, including the formation of stable five-membered or six-membered cyclic esters with cis -diol-containing compounds in alkaline aqueous media and dissociation of cyclic esters in an acidic surrounding to release cis -diol-containing compounds. Recently, various boronate affinity materials have been synthesized and utilized for selective enrichment of these compounds. Metal organic frameworks (MOFs) and covalent organic frameworks (COFs) have been widely used in chromatographic separation and sample pretreatment because of their adjustable pore size, high porosity, high specific surface area, tunable skeleton structure, and favorable chemical and thermal stability. To promote the enrichment selectivity of MOFs and COFs for cis -diol-containing compounds, boronic acid-functionalized MOFs and COFs with various structures and categories have been synthesized. This review summarizes more than 80 investigations into the categories, synthetic strategies, and applications of boronic acid-functionalized MOFs and COFs from the Science Citation Index. These synthesis methods include metal ligand-fragment co-assembly, post-synthetic modification, and bottom-up modification of boronic acid-functionalized porous materials. Although two modification strategies (post-synthetic and metal ligand-fragment co-assembly) have been introduced for the preparation of boronic acid-functionalized MOFs, the latter is more commonly adopted as it improves the enrichment selectivity and enrichment efficiency of MOFs. The common limitations of MOFs such as aggregation and aperture issues were also resolved. Boron affinity MOFs possessing favorable properties according to the characteristics of cis -diol-containing compounds, have also been synthesized. Furthermore, to facilitate enrichment and separation, many boronic acid-functionalized magnetic material MOFs have been developed for the enrichment and analysis of cis -diol-containing compounds. Additionally, the luminescent properties of Ln-MOFs have been used in combination with boronic acid affinity for the enrichment, separation, and subsequent detection of cis -diol-containing compounds. Post-synthetic modification and the bottom-up strategy are the primary methods for the preparation of boronic acid-functionalized COFs. Boronic acid-functionalized COFs are less investigated than boronic acid-functionalized MOFs, likely due to the greater complexity of COF synthesis. This work aims to summarize the research advances, synthesis ideas, and synthesis methods related to boric acid-functionalized porous organic frameworks, which will provide theoretical guidance and technical support for its applications while accelerating the commercialization of such organic frameworks.

Metal organic frameworks (MOFs) are rarely used in the field of phase change heat storage, because their low thermal conductivity affects the practical application of composite phase change materials (PCMs). Three dimensional porous materials with good thermal conductivity and adsorption properties can be synthesized by cleverly combining high adsorption MOF with high thermal conductivity expanded graphite (EG). In this paper, ZIF-8 of zeolites with imidazole structure with high adsorption was prepared by method of co-precipitation. ZnO was prepared by carbonizing ZIF-8 in a vacuum tube furnace at 700°C. EG/CuS@ZnO was synthesized by compounding EG, the crosslinking agent polyvinylpyrrolidone (PVP) and photothermal materials (CuS). Finally, OC/EG/CuS@ZnO was prepared by stirring impregnation process according to four different proportions of octadecanol (OC) and compounding with EG/CuS@ZnO. The microstructure and thermal properties of the samples were characterized. The result shows that the enthalpy of composite phase change materials OC/EG/CuS@ZnO reaches 202.97 J/g, which greatly improves the adsorption performance of OC and improves the heat storage performance. The thermal conductivity test results show that the thermal conductivity of the composite PCMs with the ratio of ZnO to EG (1:8) is as high as about 11.77 W/(m·K). The results of photothermal experiments show that the composite PCM with CuS can improve its photothermal properties. • The material has high adsorption performance and heat storage performance. • The enthalpy value of the composite phase change material reached 202.97 J/g. • Composite PCM with CuS can improve its photothermal performance. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel covalently connected core–shell NH 2 -UiO-66@Br-COFs hybrid materials was prepared. • Abundant ultramicropores were generated at the core–shell interface. • The hybrid materials had high S BET (966 m2·g−1), V total (0.655 cm3·g−1) and V ultra (0.157 cm3·g−1). • The hybrid materials exhibited much higher CO 2 uptake (169.5 mg·g−1) than NH 2 -UiO-66 and Br-COFs. • The hybrid materials exhibited good I 2 vapor adsorption capacity (3.73 g·g−1). Metal organic frameworks (MOFs)@covalent organic frameworks (COFs) (MOFs@COFs) hybrid materials not only combine the advantages of MOFs and COFs, but the possible synergistic effect at the MOFs-COFs interface can improve the performance of the hybrid materials greatly. Herein, the Br-COFs shell was in-situ grown on the surface of the NH 2 -UiO-66 core by Schiff-based reaction and a kind of novel covalently connected core–shell NH 2 -UiO-66@Br-COFs hybrid materials were prepared accordingly. Unique structure was generated at the core–shell interface which could be effectively adjusted by the coating amount of Br-COFs. In particular, abundant ultramicropores were generated at the interfacial layers as compared with NH 2 -UiO-66 and Br-COFs, and the maximum ultramicropore volume (V ultra) was up to 0.157 cm3·g−1. These produced ultramicropores at the core–shell interface made a great positive contribution to the CO 2 capacity and the maximum CO 2 capacity of the hybrid materials was measured to be 169.5 mg·g−1 at 273 K and 1.0 bar, outperformed the corresponding single MOF and COF. Additionally, the highest I 2 vapor uptake of the hybrid materials was determined to be 3.73 g·g−1 and it increased with the increase of the coating amount of Br-COFs. This work presents the successful regulation of the adsorption performance by the rational fabrication of novel hybrid MOFs@COFs interface. [ABSTRACT FROM AUTHOR]

Targeted drug delivery systems are effective ways to reduce side effects and enhance the therapeutic efficacy of drugs. Metal-organic frameworks are a new class of porous materials that have been recently used as high-performance nanocarriers in medical applications, such as drug storage and delivery due to high internal surface area, high porosity, low toxicity, high payloads, controlled drug release, their exceptional biocompatibility, and biodegradability. In this study, the loading of anti-cancer drugs Temozolomide, Alendronate, and 5-Fluorouracil inside UiO-66 nanocarrier cavities at the atomic level and different concentrations of the drug were investigated using the molecular dynamics simulation method. Drug interaction energies with UiO-66, two-dimensional density map, and drug mobility in all systems were investigated. It was found that all drugs in higher concentration systems have higher loads than less concentrated systems. Among the drugs used, Temozolomide was located closer to the center of UiO-66 which indicated more negative interaction energy. Therefore, Temozolomide has a more thermodynamic tendency to load inside the UiO-66 cavities than the other studied drugs. Two-dimensional density study showed that all drugs were mainly loaded on metal centers. Temozolomide and Alendronate were loaded on inner centers, although 5-Fluorouracil showed a higher tendency to load on surface metal centers. From studying the mobility of drugs, Temozolomide was less mobile than the other two drugs due to its stronger interaction with UiO-66. [Display omitted] •Loading of drugs into the UiO-66 occurred without any specific structural change. •5-Fluorouracil was loaded on metal centers of UiO-66 surface. •Loading of temozolomide was thermodynamically more favorable than two others. •Alendronate showed more hydrogen bonding with water. [ABSTRACT FROM AUTHOR]

p -Arsanilic acid (p -ASA), a feed additive in poultry and swine production, tends to be converted into more toxic inorganic arsenic in the environment, thus posing hazards to the environment and humans. In this work, novel ε -MnO 2 @MIL-100(Fe) nanocomposites were successfully synthesized by a wet impregnation method to remove p -ASA by simultaneously oxidation and adsorption. Batch experiments demonstrated that the ε-MnO 2 @MIL-100(Fe) had an outstanding adsorption capacity toward p -ASA and the oxidized products (486.99 μmol g-1), and the adsorption fitted well with pseudo-second-order kinetic model and Freundlich isotherm model, while intra-particle diffusion was a rate-limiting step. In the composites, manganese oxide was responsible for the oxidation of p -ASA and MIL-100(Fe) played a dominant role in the in-situ adsorption through a joined force from coordination, hydrogen bonding, and π-π stacking. Thus the combination of adsorption and oxidation resulted in excellent removal performances. Additionally, ε -MnO 2 @MIL-100(Fe) achieved good removal efficiency for p -ASA in a wide pH range (5−11) and was robust to some co-existing substances, which enables its good removal performance towards p -ASA in natural water bodies. The fixed-bed column experiments further confirmed the continuous removal of p -ASA from the water flow by ε -MnO 2 @MIL-100(Fe). [Display omitted] ● ε -MnO 2 @MIL-100(Fe) was designed and prepared via a wet impregnation method. ● ε -MnO 2 @MIL-100(Fe) exhibits excellent removal abilities toward p -arsanilic acid. ● ε -MnO 2 @MIL-100(Fe) applied in fixed-bed column exhibits potential large-scale application. [ABSTRACT FROM AUTHOR]

With large specific surface area, abundant adsorption sites, flexible pore structure, and good water stability, Materials of Institute Lavoisier frameworks (MILs) have attracted increasing attention as effective environmental adsorbents. This review systematically analyzes and recapitulates recent progress in the synthesis and application of MIL-based adsorbents for the removal of aqueous heavy metal ions. Commonly used solvothermal, microwave, electrochemical, ultrasonic, and mechanochemical syntheses of MILs are first summarized and compared. Instead of focusing on adsorption process parameters, adsorption performances and governing mechanisms of virgin MILs, functional MILs, MIL-based composites, and carbonized MILs to representative metal(loid) ions (chromium, arsenic, lead, cadmium, and mercury) in water under various conditions are then systematically reviewed and discussed. In the end, this work also outlines prospects and future directions to promote the applications of MILs in treating heavy metal contaminated water. [Display omitted] • Advantages and limitations of synthesis methods of MILs are summarized and compared. • Adsorption performances of MILs to aqueous metal(loid) ions are reviewed and compared. • Adsorption mechanisms of MILs to aqueous metal(loid) ions are analyzed and recapitulated. • Future perspectives of MILs in wastewater treatment are proposed. [ABSTRACT FROM AUTHOR]

Metal organic frameworks (MOFs) are porous crystalline materials of one-, two-, or three-dimensional networks constructed from metal ions/clusters and multidentate organic linkers via coordination bonding, which are emerging as an important group of materials for energy storage, CO adsorption, alkane/alkene separation, and catalysis. To introduce newcomers in chemical engineering discipline to the rapidly expanding MOF research works, this review presents a brief introduction to the currently available MOFs synthesis methods. Starting from the conventional solvothermal/hydrothermal synthesis, microwave-assisted, sonochemical, electrochemical, mechanochemical, ionothermal, drygel conversion, and microfluidic synthesis methods will be presented. Examples will be limited to those representative MOF structures that can be synthesized using common organic ligands of 1,4-benzenedicarboxylic acid (and its functionalized forms) and 1,3,5-benzenetricarboxylic acid, in conjunction with metal nodes of Zn, Cu, Cr, Al, Fe and Zr. Synthesis of widely-investigated zeolitic imidazolate framework (ZIF) structure, ZIF-8 is also included. [ABSTRACT FROM AUTHOR]

Abstract: Metal organic framework (MOF) structures of UIO-66, UIO-66-NH2, Mg-MOF-74, MIL-101, CuBTC, ZIF-8, IRMOF-3, and MOF-5 having different acid/base properties were prepared and tested for their catalytic activity in the CO2 cycloaddition to styrene epoxide using a high-pressure batch reactor. The high crystallinity and excellent textural properties of the prepared MOF materials were confirmed by XRD and the N2 adsorption–desorption isotherms at 77K. Their catalytic cycloaddition activities were found to be well correlated with the Lewis acid/base distributions of the materials examined by NH3- and CO2-TPD, respectively, such that the concurrent presence of Lewis acid and base sites were desirable for high catalytic activity. For a given catalyst weight, UIO-66-NH2 showed the best catalytic performance among the MOF samples tested with close to 100% selectivity to carbonate in chlorobenzene under relatively mild reaction conditions (2.0MPa, 373K). UIO-66-NH2 could be reused 3 times without losing catalytic activity in a truly heterogeneous mode without structural deterioration, and it also exhibited excellent cycloaddition activities for different epoxide substrates as well. [Copyright &y& Elsevier]

CuBTC (Copper(II) benzene-1,3,5-tricarboxylate) is one of the most well characterized and widely studied metal organic framework (MOF) structures for potential use in industrial applications due to its relatively easy synthesis and excellent textural and physicochemical properties. In this comprehensive review, a different perspective on MOF materials for future sustainability is presented by critically examining the recent works that have considered the synthesis and adsorption/catalytic applications of CuBTC as a model case. [ABSTRACT FROM AUTHOR]

The number of death due to cancer-related diseases each year is at the alarming level and is constantly growing. Tools that can effectively and conveniently detect cancer cell apoptosis can play a significant role in cancer research, cancer therapy, and other related industries. Herein, we fabricated, for the first time, an ultrasensitive, disposable, self-enhanced off-on electrochemiluminescence (ECL) biosensor based on ternary Ru-PEI@PCN-333(Al) system to determine caspase-3 activity, the biomarker of apoptosis. The biosensor had a low detection limit of 0.017 pg/mL and was able to enhance the ECL emission and stability. A solid-state (SS) ECL strategy was adopted to overcome the relatively weak ECL emission due to the long distance between electrochemiluminophore and electrode surface. The analysis requires only one incubation step, which can significantly reduce the operational complexity and time. The biosensor had higher sensitivity, and the off-on ECL mode was achieved using caspase-3 as a switch. The on-site and rapid detection capability of the biosensor was achieved by the introduction of disposable screen-printed electrodes (SPEs). This study lays a foundation for the development of more advanced, ingenious, portable and reliable ECL devices for biosensing not only caspase-3, but also other bioanalytes. [Display omitted] • We developed a disposable biosensor using the ECL technology to determination of caspase-3 activity. • The ternary Ru-PEI@PCN-333(Al) self-enhanced ECL system with excellent ECL performance was constructed for the first time. • The ECL biosensor had many advantages including on-site, rapid, disposable, low cost, simple batch production, and could effectively monitor the activity of caspase-3 during cell apoptosis. [ABSTRACT FROM AUTHOR]

Among various novel antimicrobial therapies, sonodynamic therapy (SDT) exhibits its advantages for the treatment of bacterial infections due to its high penetration depth and low side effects. In this study, a new nanosonosensitizer (HFH@ZIF-8) that loads sonosensitizer hematoporphyrin monomethyl ether (HMME) into zeolitic imidazolate framework-8 (ZIF-8), was constructed for killing multidrug-resistant (MDR) bacteria and treatment of in vivo infection diseases by SDT. In particular, the developed HFH@ZIF-8 exhibited enhanced water-solubility, good biocompatibility, and improved disease-targeting capability for delivering and releasing HMME and ablating the infected lesion. More importantly, the presence of oxygen-carrying hemoglobin for HFH@ZIF-8 can offer sufficient oxygen consumption by SDT, augmenting the efficacy of SDT by improving ROS generating efficiency against deep tissue multidrug-resistant bacterial infection. Therefore, this study paves a new avenue for treating infection disease, particularly for antibiotic resistant bacterial infection. [ABSTRACT FROM AUTHOR]

• MOFs as a promising biosensor due to high stability and easy tuning for synthesis. • MOFs as nanozymes for disease diagnostic and electrochemical for cancer marker. • MOFs for HIV, Zika and Covid-19 virus with curative immobilization biosensor. Metal-organic frameworks (MOFs) are garnering substantial interest due to their unique structural diversity, tunable pore size, luminescent properties and remarkable multifunction support for biosensing applications including immunoglobulin-M generated against the COVID-19. Recent developments have focused on RT nucleic probes, curative immobilization (enzyme, antibodies or nanoparticles), electrochemical and optical biosensors, along with noninvasive monitoring. In the following feature article, we present an overview of the key advances on MOFs biosensors from few of its branches. We also looked into the rich coordination chemistry between metal nodes and organic linkers which enables a diverse synthetic platform for the pragmatic design of MOF materials with anticipated geometries and properties. [ABSTRACT FROM AUTHOR]

Abstract: In this study, we synthesized 1,2-di(o-aminophenoxy)ethane, as the starting material, used in the preparation of a novel hexadentate OONNOO-donor macrocyclic ligand-1,4,11,14-tetraoxo-7,8-diaza-5,6:9,10;15,16:19,20-terabezocyclododeca-8,17-iene. It has twenty membered organic framework (OF), which has been designed, synthesized and characterized. Our main findings of this paper are related to the organic framework of ligand, its capacity to digest the metal ions and the stability of metal organic framework (MOFs) with cobalt(II), nickel(II) and manganese(II). The authenticity of the used organic framework and its metal complexes have been detected and observed in solid state as well as in aqueous solutions. The main observations were made on the basis of physiochemical measurements viz.: elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, 1H NMR, 13C NMR, mass spectroscopy, electronic, ESR spectroscopy. In addition, the magnetic susceptibility and electrochemistry measurements have been made. The 1H NMR spectra suggest stereochemistry and proton movement interaction. Considering the used organic framework there are a lot of carbon atoms in the molecule reflected by the 13C NMR spectrum. All these observations gave a clear view to confirming the encapsulation; arrive at the composition, structure and geometry of encapsulated complexes. In simple words, it confirms the host/guest coordination and its stability. Electrochemical properties of the complexes have been investigated to confirm the various changes in oxidation state of metals with change in potentials with respect to current at different scan rate. [Copyright &y& Elsevier]

Herein, a strategy of synergetic dual-metal-ion centers to boost transition-metal-based metal organic framework (MOF) alloy nanomaterials as active oxygen reduction reaction (ORR) electrocatalysts for efficient hydrogen peroxide (H 2 O 2 ) generation is proposed. Through a facile one-pot wet chemical method, a series of MOF alloys with unique Ni-M (M-Co, Cu, Zn) synergetic centers are synthesized, where the strong metallic ions 3d-3d synergy can effectively inhibit O 2 cleavage on Ni sites toward a favorable two-electron ORR pathway. Impressively, the well-designed NiZn MOF alloy catalysts show an excellent H 2 O 2 selectivity up to 90% during ORR, evidently outperforming that of NiCo MOF (45%), and NiCu MOF (55%). Moreover, it sustains efficient activity and robust stability under a continuous longterm ORR operation. The correlative in situ synchrotron radiation X-ray adsorption fine structure and Fourier transform infrared spectroscopy analyses reveal at the atomic level that, the higher Ni oxidation states species, regulated via adjacent Zn 2+ ions, are favorable for optimizing the adsorption energetics of key *OOH intermediates toward fast two electron ORR kinetics., (© 2022 Wiley-VCH GmbH.)

Recent progress in synthetic strategies, analysis techniques, and computational modeling assist researchers to develop more active catalysts including metallic clusters to single-atom active sites (SACs). Metal coordinated N-doped carbons (M-N-C) are the most auspicious, with a large number of atomic sites, markedly performing for a series of electrochemical reactions. This perspective sums up the latest innovative and computational comprehension, while giving credit to earlier/pioneering work in carbonaceous assembly materials towards robust electrocatalytic activity for proton exchange membrane fuel cells via inclusive performance assessment of the oxygen reduction reaction (ORR). M-N x -C y are exclusively defined active sites for ORR, so there is a unique possibility to intellectually design the relatively new catalysts with much improved activity, selectivity, and durability. Moreover, some SACs structures provide better performance in fuel cells testing with long-term durability. The efforts to understand the connection in SACs based M-N x -C y moieties and how these relate to catalytic ORR performance are also conveyed. Owing to comprehensive practical application in the field, this study has covered very encouraging aspects to the current durability status of M-N-C based catalysts for fuel cells followed by degradation mechanisms such as macro-, microdegradation, catalytic poisoning, and future challenges., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

The insufficient contact between two phases in the heterostructure weakens the coupling interaction effect, which makes it difficult to effectively improve the electrochemical performance. Herein, a Co-carbonate hydroxide@ Ni-metal organic frameworks (Co-CH@Ni-MOFs) composite with super uniform core-shell heterostructure is fabricated by adopting 1D Co-CH nanowires as structuredirecting agents to induce the coating of Ni-MOFs. Both experimental and theoretical calculation results demonstrate that the heterostructure plays a vital role in the high performance of the as-prepared materials. On the one hand, the construction of super uniform core-shell heterostructure can create a large number of interfacial active sites and take advantages of the electrochemical characteristics of each component. On the other hand, the heterostructure can increase the adsorption energy of OH - ions and promote the electrochemical activity for improving the reversible redox reaction kinetics. Based on the aforementioned advantages, the as-fabricated Co-CH@Ni-MOFs electrode exhibits a high specific capacity of 173.1 mAh g -1 (1246 F g -1 ) at 1 A g -1 , an ultrahigh rate capability of 70.3% at 150 A g -1 and excellent cycling stability with 90.1% capacity retention after 10 000 cycles at 10 A g -1 . This study may offer a versatile design for fabricating a MOFs-based heterostructure as energy storage electrodes., (© 2022 Wiley-VCH GmbH.)

[Display omitted] • Structure tunable bimetallic Fe-Al-based MOF was prepared for arsenic removal. • The second metal doping can significantly enhance the absorption of arsenic. • The adsorption mechanism of arsenic on bimetallic MOF was proposed. • The adsorbent with excellent performance has water stability and renewability. • Fe-Al-based MOF is efficient for arsenic treatment in contaminated spring water. Arsenic pollution of groundwater and surface water has come to the attention of the public. To explore economically affordable and efficient adsorbents for the treatment of arsenic, bimetallic MOFs based on trivalent iron and aluminum were synthesized and used to capture arsenic from wastewater. Characterization methods including SEM, EDX, XRD, and N 2 adsorption–desorption were applied to analyze the morphology and element content, crystal structure, porosity and specific surface area of the Fe/Al-BDC-NH 2 materials. The microstructures of bimetallic MOFs were tuned through changing the ratio of Al and Fe in the precursor material. Adsorption results show that introducing aluminum into the iron-based material formed bimetallic Fe/Al-BDC-NH 2 MOFs that had much better adsorption performance for arsenic than the monometallic Fe-BDC-NH 2 or Al-BDC-NH 2 MOF. The adsorption isotherm of bimetallic MOF materials for arsenic is in accordance with the Langmuir isotherm model, and the maximum adsorption capability of Fe/Al-BDC-NH 2 (1:1) at 298 K was 146.8 mg g−1. The kinetics of arsenic adsorption follow the pseudo-second-order model. Also, the thermodynamics indicate that arsenic adsorption is endothermic. Fe/Al-BDC-NH 2 (1:1) is suitable for removal of arsenic from wastewater in a relatively wide pH range (5.0–9.0). Within this pH range, Fe and Al are hardly dissolved in water after arsenic capture, and this indicates that Fe/Al-BDC-NH 2 (1:1) is very stable and suitable for arsenic capture from water without generating secondary pollution. Furthermore, through FTIR and XPS analysis, ligand exchange was identified as the main adsorption mechanism of Fe/Al-BDC-NH 2 (1:1) for arsenic. [ABSTRACT FROM AUTHOR]

The lanthanide functionalized MOFs with an exceptional performance for early diagnosis of pheochromocytomas and paragangliomas was constructed as a multifunctional sensing platform based on postsynthetic modification strategy. [Display omitted] • It is the first report in designing a luminescent sensor to determine the biomarker 3-methoxytyramine. • The proposed sensor Eu3+@Al-MOF is applicable in the detection of 3-methoxytyramine in urine system with excellent performance. • The test paper creates a portable analysis tool for visual and selectivity detection of 3-methoxytyramine. As a main extracellular metabolite of dopamine, 3-methoxytyramine (3-MT) is considered a potential biomarker of pheochromocytomas and paragangliomas. Therefore, the determination of 3-MT is of great significance in the early diagnosis of disease. However, it remains challenging for detecting 3-MT in consideration of sensitivity and accuracy. Here, a luminescent Eu3+ functionalized metal-organic frameworks （Eu3+@Al-MOF）with ultra-high chemical stability was constructed based on postsynthetic modification. Such a rational design greatly enhances the fluorescence signal of Eu3+@Al-MOF and it is endowed with excellent properties as a luminescent sensor to detect 3-MT in urine system. Intriguingly, the strong red emitting derived from antenna effect was significantly interdicted upon addition of 3-MT through the interaction between 3-MT and the ligand. The proposed sensing system exhibited many appealing analytical performances, such as excellent selectivity, high sensitivity and quick response. Remarkably, the developed paper-based sensor not only provides a portable and reliable strategy for direct detection of 3-MT but also expands the application of visual analysis tools. This work represents the first effort in designing a luminescent sensor to determine the metabolite biomarker 3-MT level and provides a new method for biomedical analysis. [ABSTRACT FROM AUTHOR]

Sonodynamic therapy, which utilizes ultrasound (US) to produce cytotoxic reactive oxygen species (ROS), can overcome the critical drawbacks of photodynamic therapy, such as limited tissue penetration depth. However, the development of sonosensitizers having superior sonodynamic effects and desirable biocompatibility remains a major challenge. In this study, nanoscale zirconium-based porphyrinic metal organic frameworks (MOFs) (PCN-222) were developed as safe and effective nanosonosensitizers. Polyethylene glycol (PEG)-coated PCN-222 (PEG-PCN) was loaded with a pro-oxidant drug, piperlongumine (PL), to enable tumor-specific chemo-photodynamic combination therapy. Both PEG-PCN and PL-incorporated PEG-PCN (PL-PEG-PCN) showed high colloidal stability in biological media. In addition, nanoscale PL-PEG-PCN was efficiently internalized by breast cancer cells, leading to substantially increased ROS generation under US exposure. The effective intracellular delivery of PL by PEG-PCN further elevated the level of intracellular ROS in breast cancer cells owing to the pro-oxidative activity of PL. Therefore, PL-PEG-PCN revealed significantly higher sonotoxicity than free PL and PEG-PCN. Owing to the cancer-specific apoptosis triggered by PL, PL-PEG-PCN showed cancer-selective cell death in breast cancer cells compared with normal fibroblast cells. This study demonstrates that pro-oxidant drug-loaded porphyrinic MOFs are biocompatible and effective sonosensitizers for cancer-targeted chemo-sonodynamic combination therapy. Nanoscale zirconium-based porphyrinic metal organic frameworks (MOFs) were developed as safe and effective nanosonosensitizers. Pro-oxidant drug-loaded, PEG-coated porphyrinic MOFs under US irradiation excessively increased intracellular ROS levels in breast cancer cells, leading to efficient and cancer-targeted chemo-sonodynamic combination therapy. [Display omitted] ● Nanoscale zirconium-based porphyrinic metal organic frameworks (PEG-PCN) were developed as sonosensitizers. ● PL-loaded PEG-PCN showed higher sonotoxicity against MCF-7 breast cancer cells than normal hDFB cells. ● PL-loaded PEG-PCN excessively increased intracellular ROS in breast cancer cells under US irradiation. ● PL-loaded PEG-PCN achieved cancer-specific chemo-sonodynamic combination therapy. [ABSTRACT FROM AUTHOR]

[Display omitted] • CuZn-MOFs as self-sacrificing template could enhance Cu-ZnO interaction. • MOFs-templated strategy could facilitate generation of CuZn alloy. • Cu-ZnO/NC-BMOFs delivered high selectivity to imines and/or amines. Tuning of the metal–metal/oxide interaction is a vital route to enhance the performance of the supported catalysts. In this study, a Cu/Zn bimetallic MOFs was synthesized through a simple solvothermal method by using an adenine rigid biomolecule acted as organic linker. Furthermore, a ZnO/nitrogen-doped carbon composite supported Cu catalyst (named as Cu-ZnO/NC-BMOFs) derived from the bimetallic CuZn-MOFs was obtained via one-pot pyrolysis method. The developed Cu-ZnO/NC-BMOFs catalyst was tested for hydrogenation-amination tandem reaction. The bimetallic CuZn-MOFs with the uniformly dispersed Cu and Zn centers acted as a self-sacrificing template, which could facilitate the derived catalyst with strengthened Cu-ZnO interaction, high dispersity, and more N species. All of these advantages give the developed Cu-ZnO/NC-BMOFs catalyst with higher performance in hydrogenation-amination tandem reaction compared with traditional Cu/ZnO/NC-IWI (synthesized by incipient wetness impregnation) catalyst. The Cu-ZnO/NC-BMOFs exhibits good stability for the recycling experiments with a negligible loss in its performance. More importantly, the Cu-ZnO/NC-BMOFs catalyst could convert nitroarenes into the corresponding imines or secondary amines with excellent selectivity (>90.0%). This bimetallic MOFs-derived strategy may provide a way for fabricating NC supported catalysts in other tandem reactions. [ABSTRACT FROM AUTHOR]

Four new isostructural 3d-4f mixed metal organic frameworks (MOFs) Cu Gd2 (BDC)4, compound 1, Cu Ho2 (BDC)4, compound 2, Cu Eu2 (BDC)4, compound 3, and Cu Dy2 (BDC)4, compound 4 were successfully synthesized. The structure, stability, and magnetic properties were analyzed. Each MOF has two lanthanide ions and one copper ion node with terephthalic acid as the organic linker. The lanthanide ions form a dimer with each having a capped trigonal prismatic geometry while the copper ion has a square planar geometry. Each of these MOFs shows varying degrees of antiferromagnetic interactions. [ABSTRACT FROM AUTHOR]

Metal organic frameworks (MOFs), which constitute a new class of porous organic-inorganic hybrid materials, have gained considerable attention in the fields of electrochemical energy storage and conversion devices owing to their open topological structures, large surface areas, tunable morphologies, and extreme redox activity. A synthesis protocol that comprises coprecipitation followed by controlled calcination processes to design a battery-type electrode is used. This electrode consists of three-dimensional (3D), ant cave-like polyhedrons of nickel-cobalt alloy on graphitic carbon (GC; NiCo@GC) nanostructures; trimesic acid is used as a potential MOF-linker. The developed NiCo@GC sample exhibits mesoporous characteristics with the maximum surface area of 94.08 m 2 g -1 at 77 K. In addition, the redox activity at different sweep rates reveals the battery-type charge storage behavior of the NiCo@GC electrode; its three-electrode assembly provides 444 C g -1 specific capacity at 2 A g -1 with long-term capacity retention. The constructed supercapattery (SC) devices (i.e., AC//NiCo@GC) achieved capacity, specific energy, and specific power are 74.3 mAh g -1 , 39.5 Wh kg -1 , and 665 W kg -1 , respectively. Owing to its reasonable electrochemical characteristics, the prepared NiCo@GC material is a promising candidate for supercapattery electrodes for portable electronic devices., (© 2022 Wiley-VCH GmbH.)

Energy-efficient alternative desalination and cooling systems are pivotal in addressing the incredible increase in energy and water demands worldwide. Sorption-based technology is a unique system that could help in solving the energy and water crisis and cut down the overall carbon footprint. Such systems' performance relies on the adsorption characteristics of the employed nanoporous adsorbent. Although different nanoporous materials were developed, metal-organic frameworks (MOFs) are fast becoming a key working substance in water capture applications due to their interesting adsorption characteristics. Owing to the chemical tunability of MOFs, scientists developed thousands of MOFs in the last few decades. With the increasing interest in MOFs, this review paper provides a comprehensive survey of MOFs adsorbents and their roles in cooling and water desalination systems. Herein, three aspects are covered, the synthesis processes, the adsorption characteristics, and the implementation of MOFs at the system level. Many challenges are discussed, such as mass production, the energy demand for synthesis, and the chemical modulation of MOFs to enhance their adsorption characteristics. Many MOFs are presented, but the sorption characteristics of most of them have not been tested yet. Subsequently, a small number of the presented MOFs have been employed in sorption applications. Accordingly, a gap should be filled to test and employ the MOFs in sorption applications. • Progress of MOFs adsorbents in cooling and water desalination is summarized. • Adsorption capacities and isotherms of different MOFs are presented. • Hybridizing MIL-101(Cr) with inorganic salts lead to better cooling application. • Applications and challenges of MOFs in sorption cooling and desalination discussed. [ABSTRACT FROM AUTHOR]

A new type of Eu-based metal organic framework (Eu-MOF) characterized with ability of arsenate ion luminescence sensing and entrapping was constructed via solvothermal method based on the optimization of the organic ligand. The Eu-MOF aqueous dispersion sample displayed arsenate-triggered augment in luminescence emission intensity with appreciable contrast and detection sensitivity with limit of detection down to 17.8 nM toward arsenate ion, which is less than one-fourth of the upper limit concentration of arsenic in drinking water that the World Health Organization (WHO) set for public health, 72 nM. Additionally, the excellent recognition specificity Eu-MOF toward arsenate species over various potential interfering anions and cations was also confirmed. The rapid adsorption ability of Eu-MOF nanostructures toward arsenate in aqueous milieu that plausibly originated from its nature of chemical adsorption and the adsorption feature conforming to the Langmuir model was also verified. The advantages that Eu-MOF nanostructure displays in terms of high sensitivity and recognition specificity in luminescence sensing of arsenate ion and the desired arsenate entrapping ability in aqueous milieu is expected to impart it potential for sensing and entrapping trace amount of arsenate in water in practical applications. • The Eu-based MOFs characterized with ability of arsenate ion luminescence sensing and entrapping. • Arsenate ion sensing with detection limit down to 17.8 nM, much lower than the upper limit that WHO set for public health. • High recognition specificity in luminescence sensing and rate in adsorption of arsenate ions. [ABSTRACT FROM AUTHOR]

[Display omitted] • Ternary NiFeZr MOFs were first synthesized by one-step solvothermal method. • Ternary NiFeZr MOFs displayed an enhanced OER performance compared with bimetallic NiFe MOFs. • The data of zeta potential of catalysts provided a powerful evidence for the OER mechanism. Highly efficient electrocatalysts for the oxygen evolution reaction (OER) are strongly desired in oxygen involved technologies such as water splitting and metal-air batteries. Recently, metal organic frames (MOFs) have become one kind of OER electrocatalysts. To obtain MOFs with high OER activity, the ternary NiFeZr MOFs were synthesized and prepared by a simple solvothermal method. The results show that the OER performance of ternary NiFeZr MOFs is better than the corresponding bimetallic NiFe MOFs due to the doping of Zr. At the optimal dosage of Zr of 0.12 mmol, the overpotential at 10 mA/cm2 (η 10) of NiFeZr MOFs-0.12 on the glass carbon electrode is only 288 mV. The reasons behind were explored from the aspects of electrochemical surface area (ECSA), electrochemical impedance spectroscopy (EIS), electronic structure and zeta potential of catalysts and the OER mechanism on NiFeZr MOFs was also revealed. To further improve the OER activity, the NiFeZr MOFs-0.12 was grown in-situ on the nickel foam (NF), which exhibits an overpotential at 50 mA/cm2 (η 50) of only 345 mV and good stability. This study proves that the reasonable incorporation of metal into OER active MOFs is effective to improve their OER activity. [ABSTRACT FROM AUTHOR]

Antibiotic abuse has led to serious water pollution and severe harm to human health; therefore, there is an urgent need for antibiotic removal from water sources. Adsorption and photodegradation are two ideal water treatment methods because they are cheap, simple to operate, and reusable. Metal organic frameworks (MOFs) are excellent adsorbents and photocatalysts because of their high porosity, adaptability, and good crystal form. The aim of this study is to suggest ways to overcome the limitations of adsorption and photocatalysis treatment methods by reviewing previous applications of MOFs to antibiotic adsorption and photocatalysis. The different factors influencing these processes are also discussed, as well as the various adsorption and photocatalysis mechanisms. This study provides a valuable resource for researchers intending to use MOFs to remove antibiotics from water bodies. [Display omitted] • MOFs exhibit good adsorption and photodegradation efficiency for antibiotics. • Factors to improve their adsorption and photodegradation efficiency are identified. • MOFs recovery can be aided by carriers and magnetic/hydrophobic/nanofiber materials. • The dominant adsorption/photocatalytic degradation mechanisms are summaried. • Future research should focus on applying MOFs to antibiotic removal from water. [ABSTRACT FROM AUTHOR]

1-ethyl-3-methylimidazolium diethyl phosphate ([EMIM][DEP]) was incorporated into copper benzene-1,3,5-tricarboxylate, CuBTC. Consequences of molecular interactions on the CO 2 separation performance of CuBTC were investigated. Scanning electron microscopy and X-ray diffraction results showed that the surface morphology and crystal structure of CuBTC remained intact upon the incorporation of the ionic liquid (IL); and the results of thermogravimetric analysis and infrared spectroscopy indicated the presence of interactions between the anion of the IL and the open metal sites of CuBTC. Gas adsorption measurements for the pristine CuBTC and IL-incorporated CuBTC were performed at 25 °C in a pressure range of 0.1–1 bar. Data showed that ideal CO 2 /CH 4 and CO 2 /N 2 selectivities of IL-incorporated CuBTC were 1.6- and 2.4-times higher compared to those of the pristine CuBTC at 0.01 bar, respectively. Moreover, for the CO 2 /CH 4 :50/50 and CO 2 /N 2 :15/85 mixtures, the corresponding selectivities were improved by more than 1.5- and 1.9-times compared to that of pristine CuBTC at 0.01 bar, respectively. Image 1 • [EMIM][DEP]-incorporated CuBTC was prepared via wet-impregnation method. • Direct interactions between the IL and the open metal sites of CuBTC were revealed. • CO 2 , CH 4 , and N 2 adsorption isotherms in [EMIM][DEP]/CuBTC composite were measured. • CO 2 /CH 4 selectivity of composite was 1.6-times of that of CuBTC at low pressures. • CO 2 /N 2 selectivity of composite was 2.4-times of that of CuBTC at low pressures. [ABSTRACT FROM AUTHOR]

Cover Feature: Recent Advances in Electrocatalysis of Oxygen Evolution Reaction using Noble-Metal, Transition-Metal, and Carbon-Based Materials (ChemElectroChem 3/2021) Keywords: Electrocatalysts; Hydrogen production; Oxygen Evolution Reaction (OER); Activity parameters; Metal Organic Frameworks (MOFs) EN Electrocatalysts Hydrogen production Oxygen Evolution Reaction (OER) Activity parameters Metal Organic Frameworks (MOFs) 427 427 1 02/13/21 20210201 NES 210201 B The Cover Feature b illustrates noble-metal, transition-metal, and carbon-based compounds effectively utilized for oxygen evolution reaction electrocatalysis. Electrocatalysts, Hydrogen production, Oxygen Evolution Reaction (OER), Activity parameters, Metal Organic Frameworks (MOFs). [Extracted from the article]

Libraries of extremely localized molecular orbitals (ELMOs) have been recently assembled to reconstruct approximate wavefunctions of very large biological systems, such as polypeptides and proteins. In this paper, we investigate for the first time the possibility of using ELMO transferability to also quickly obtain wavefunctions, electron densities, and electrostatic potentials of three-dimensional coordination polymers such as metal organic frameworks (MOFs). To accomplish this task, we propose a protocol that, in addition to exploiting the usual exportability of extremely localized molecular orbitals, also takes advantage of the novel QM/ELMO (quantum mechanics/extremely localized molecular orbital) approach to properly describe the secondary building units of MOFs. As a benchmark test, our technique has been applied to the well-known metal organic framework HKUST-1 ({Cu3(BTC)2}n, with BTC=1,3,5-benzenetricarboxylate) to quickly calculate electrostatic potential maps in the small and large cavities inside the network. On the basis of the obtained results, we envisage further improvements and applications of this strategy, which can be also seen as a starting point to perform less computationally expensive quantum mechanical calculations on metal organic frameworks with the goal of investigating transformation phenomena such as chemisorption. [ABSTRACT FROM AUTHOR]

In this study, zeolitic imidazolate framework (ZIF-67) derived nano-porous carbon structures that were further hybridized with MnO2 were tested for oxygen reduction reaction (ORR) as cathode material for fuel cells. The prepared electrocatalyst was characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and Energy Dispersive X-ray Analysis (EDX). Cyclic voltammetry was performed on these materials at different scan rates under dissolved oxygen in basic media (0.1 M KOH), inert and oxygen rich conditions to obtain their I–V curves. Electrochemical impedance spectroscopy (EIS) and Chronoamperometry was also performed to observe the materials' impedance and stability. We report improved performance of hybridized catalyst for ORR based on cyclic voltammetry and EIS results, which show that it can be a potential candidate for fuel cell applications. [ABSTRACT FROM AUTHOR]

• MOFs show high catalytic capacity in heterogeneous Fenton-like oxidation process. • Physical/chemical MOFs modification can effectively enhance catalytic functions. • Efficient e− transfer and e−-h+ pairs separation mainly promotes catalytic reactions. • Influencing factors and stability/reusability are prerequisite in MOFs application. • The future developments and suggestions of MOFs-based catalysts are highlighted. Advanced oxidation process (AOP), with a high oxidation efficiency, fast reaction speed (relatively no secondary pollution), has become one of the core technologies of industrial wastewater and advanced drinking water treatment. Heterogeneous Fenton-like oxidation process (HFOP) is a kind of AOP, which developed rapidly in recent years in such a way to overcome the disadvantages of traditional Fenton reaction. Metal-organic frameworks (MOFs) and their derivatives become essential heterogeneous catalysts for organics mineralization due to the large specific surface area, abundant active sites, and ease of structural regulation. However, the knowledge gap on the mechanism and the fate of heterogeneous catalyst species during organics degradation activities by MOFs presents considerable impediments, particularly for a wide application and scaling up the process. This work has the potential to provide guidance and ideas for researchers and engineers in the fields of environmental remediation, environmental catalysis and functional materials. This review focuses on clarifying the critical mechanism of •OH production from MOFs and derivatives as well as its action on the organic's degradation process. The recent developments in MOF based HFOP are compared, and more attention is paid for the following aspects in this review: (1) classifies systematically progressive modification methods of MOFs by chemical and physical treatments; (2) analyzes the fate of catalytic species during treating organic wastewater; (3) proposes design ideas and principles for improving the performance of MOFs catalysts; (4) discusses the main factors influencing the catalytic properties and practical application; (5) summarizes the possible research challenges and directions for MOFs and their derivatives as catalysts applied to wastewater treatment in the future. [ABSTRACT FROM AUTHOR]

Mercury is one of the most hazardous environmental pollutants due to its immediate health implications on humans. With pollution risks of water bodies due to industrial and natural release of mercury, there is a need to assess the contamination of sea water to ensure its safety and sustainability to effectively prevent health deterioration due to mercury absorption through seafood consumption. Metal organic frameworks (MOFs) have emerged as a new class of crystalline porous materials with potential deployment for chemical detection thanks to their outstanding features including high specific surface areas, tunable pore size, and easy functionalization of the organic part upon selection of different metal ions and organic bridging ligands. In the present study, a novel MOF namely NH 2 -Cd-BDC was successfully developed and investigated toward mercury detection in a competitive aqueous medium in presence of other metal ions. NH 2 -Cd-BDC is composed of Cadmium ions (Cd2+) as the metal cluster and 2-aminoterephthalic acid (NH 2 -H 2 BDC) as the organic linker. The luminescent property of the MOF provides a cost-effective and nondestructive method for testing the detection ability of the MOF using fluoro-spectroscopy. The experiments showed that the developed MOF has a limit of detection of 0.58 μM and demonstrated the superiority of mercury detection in comparison to other metal ions including Na+, K+, Ca2+, Cr3+, Cd2+, Cu2+, Pb2+ and Fe3+. Several characterization tests of the novel developed MOF were executed including XRD, FTIR, TGA, FE-SEM and SEM to inspect its crystalline structure and thermal stability. The experimental study revealed that the MOF has a crystalline sea-shell shape, providing a large pore size for the mercury to be trapped in. [ABSTRACT FROM AUTHOR]

Adsorption is considered as one of the eco-friendly methods to effectively remove pollutants from water environment. 1 , namely ([Zn 3 (dpcp) 2 (1,4′-bmib) 2 ] n , dpcp ​= ​3-(3,5-dicarboxylphenoxy)-5-carboxylpyridine and 1,4′-bmib = 1,4-bis(2-methylimidazol-1-yl) butane), was synthesized under simple solvothermal method and characterized by XRD, PXRD, TGA, FTIR, BET and Zeta potential. The influence of temperature and pH of the solution and the dye initial concentration on the adsorption process of 1 was investigated using Congo red (CR) as the adsorption object. Pseudo second-order kinetics and Langmuir isotherms more accurately described the adsorption process of 1. The maximum adsorption capacity measured in the adsorption experiment was about 262.2 ​mg ​g-1. Thermodynamic studies showed that the entire adsorption process was spontaneous. In addition, 1 released the CR dye by a simple organic solvent (ethanol solution of NaOH) and exhibited stable and high adsorption performance over 5 cycles. The subtle hydrogen bond between 1 and the dye promotes its selective adsorption of CR. A Zn-based MOF, namely [Zn 3 (dpcp) 2 (1,4′-bmib) 2 ] n , highly selective and rapid adsorption of CR dyes through subtle hydrogen bonds, with an adsorption capacity of up to 262.2 ​mg ​L-1. Image 1 • A new Zn-based MOF synthesized by solvothermal method is reported. • The adsorption data is more accurately described by pseudo-second-order kinetics and Langmuir isotherms. • Zn-MOF has an adsorption capacity of 262.2 ​mg ​g-1 for Congo red (CR). • Highly efficient and selective adsorption of CR via hydrogen bonding. [ABSTRACT FROM AUTHOR]

We investigated the influences of the changes in the electronic structure and size of the anion of an imidazolium ionic liquid (IL) on gas adsorption and separation performance of the IL/ZIF-8 (zeolitic imidazolate framework) composites. We studied four different imidazolium ILs having the same cation, 1- n -butyl-3-methylimidazolium, [BMIM]+, with anions having structures allowing a systematic comparison of the changes in the electronic structure and size. To examine the influence of changes in the electronic structure, we considered anions representing the fluorination on the anion, methanesulfonate, [MeSO 3 ]−, and trifluoromethanesulfonate, [CF 3 SO 3 ]−. To investigate the change in the anion size, methyl sulfate, [MeSO 4 ]−, and octyl sulfate, [OcSO 4 ]−, were studied. Characterization of IL/ZIF-8 composites demonstrated successful incorporation of each IL in ZIF-8 without causing any detectable changes in the crystal structure and morphology of ZIF-8. Thermogravimetric analysis and infrared (IR) spectroscopy indicated the presence of direct interactions between ILs and ZIF-8, which directly control gas separation performance of the composite. Gas adsorption measurements illustrated that incorporation of ILs significantly improves the gas separation performance of the pristine ZIF-8. [BMIM][MeSO 4 ]/ZIF-8 composite had 3.3- and 1.8-times higher CO 2 /N 2 and CH 4 /N 2 selectivities compared to ZIF-8, respectively, at 1 bar. When the IL has a fluorinated anion, CO 2 /CH 4 selectivity improved 3-times compared to its non-fluorinated counterpart. Upon the incorporation of IL with a small anion, IL/ZIF-8 composite showed higher CO 2 /N 2 and CH 4 /N 2 selectivities compared to the composite having an IL with a bulky anion. These results will contribute in guiding rational design of IL/MOF composites for different gas separations. Image 1 • IL-incorporated ZIF-8 composites were prepared by wet-impregnation method. • Impacts of change in electronic structure and anion size of IL were investigated. • Composite with a fluorinated anion showed an improved CO 2 /CH 4 selectivity. • Significantly improved selectivities were observed when the anion of IL is small. [ABSTRACT FROM AUTHOR]

A novel zinc(II) porous 3D framework with a new 4,6-connected binodal topology constructed by 4,4′-bipyridine and sulfate anion has been successfully isolated, and its usage as catalyst in Friedel–Crafts alkylation reaction has been reported. • An unprecedented 3D Zn(II)-MOF showing a new 4,6-connected topology is repoorted. • A new Cu(II)-MOF activated by PSE can be used as catalyst for Friedel–Crafts reaction. • This work enriches the field of MOFs constructed by inorganic sulfate anions. An unprecedented three-dimensional supramolecular MOF, namely [Zn 3 (bpy) 3 (SO 4) 4 ]·(Me 2 NH 2) 2 ·DMF·9H 2 O (1 , where bpy = 4,4′-bipyridine, DMF = N,N′-dimethylformamide), has been efficaciously synthesized under the solvothermal reaction. A single-crystal structure determination showed that the wavelike [Zn 3 (bpy)(SO4) 4 ] layers are pillared by pairs of bpy ligands to give a new 4,6-connected binodal self-penetrated network with overall (4264)(42687382) topology. 1 also has been fully identified characterized by thermogravimetric analysis, gas adsorption properties and so on. In addition, a new Cu(II)-MOF (cat1) was further prepared by postsynthetic exchange (PSE) synthetic approach based on compound 1 , which is proved to be an active catalyst for the Friedel–Crafts reaction of indole with β -nitrostyrenes. The result from this work provides a new attempt to describe the crystallization of inorganic sulfate anion link to the organic functional group, and the functionalization-induced MOF gain insights for designing new functional MOF. [ABSTRACT FROM AUTHOR]