Metal Organic Framework

In this research, the Ciprofloxacin (CIP) adsorption process using chitosan/polyacrylamide/zeolitic imidazolate framework-8 (CPZ) was thoroughly investigated. The adsorbent underwent characterization through various techniques, e.g., SEM, FTIR, XRD, and BET/BJH analyses. The impact of parameters on the CIP adsorption, with statistical significance at p < 0.05, was systematically explored using the BBD matrix, encompassing CIP concentration, pH, CPZ mass, temperature, and contact time as variables. Considering ANOVA, it was determined that adsorbent mass and contact time were the most influential parameters affecting the CIP ion adsorption capacity. Conducting 46 experiments based on the BBD and subsequent ANOVA yielded an empirical formula to estimate the anticipated response. Calculation of optimum conditions was facilitated through the establishment of a quadratic correlation, revealing a high agreement between the R2 value (0.989) and adjusted R2 (0.984). The numerical optimization suggested optimal process conditions at CIP concentration of 55 mg/L, an adsorbent mass of 0.72 g/L, pH of 5.8, and a temperature of 47°C, achieving a maximum adsorption efficiency of 98.4% in 88 min. The model, supported by an F value of 345.2, exhibited robust predictive capability, offering valuable insights for process scale-up. Findings from equilibrium experiments suggested that the PSO kinetics and Langmuir isotherm displayed the highest conformity, supported by a lower error coefficient and significant regression coefficient. Additionally, the thermodynamic parameters pointed towards the spontaneous and endothermic nature of the experimental process.

Polyphenol-functionalized metal-organic frameworks (MOFs) have emerged as a revolutionary paradigm in cancer therapeutics, combining the structural versatility of MOFs with the bioactive and multifunctional properties of polyphenols. This review comprehensively analyzes recent advancements in the design, synthesis, and biomedical applications of polyphenol-MOF hybrids for targeted drug delivery and synergistic cancer therapy. By leveraging polyphenols such as tannic acid, epigallocatechin gallate (EGCG), gallic acid, and polydopamine, these hybrid systems exhibit enhanced biocompatibility, pH-responsive drug release, and tumor-targeting capabilities. Key innovations include the integration of polyphenol coatings or coordination networks with MOFs (e.g., ZIF-8, MIL-100, UiO-66) to enable stimuli-triggered cargo release, reactive oxygen species (ROS) generation, and multimodal therapeutic effects (chemodynamic, photothermal, and sonodynamic therapy). Case studies highlight the role of polyphenol-MOF hybrids in overcoming limitations of conventional chemotherapy, such as poor drug solubility, off-target toxicity, and multidrug resistance. Furthermore, in vitro and in vivo evaluations demonstrate their efficacy in inducing apoptosis, depleting glutathione (GSH), and enhancing immunotherapy responses. Challenges such as scalability, long-term biosafety, and clinical translation are critically discussed, alongside future directions for engineering next-generation polyphenol-MOF nanoplatforms. This review underscores the transformative potential of polyphenol-MOF hybrids in precision oncology and advocates for their integration into mainstream cancer treatment strategies.

Copper is a heavy metal that is utilized in a variety of sectors and is renowned for its severe environmental and health effects. With varied starting Cu+2 concentrations and pH levels, 5mg of MOF was applied to measure its ability in Cu+ 2 removals (5, 7 and 9). For starting concentrations of 5, 10, 15, and 20 ppm, the prepared MOF was able to remove Cu with 94.6 percent, 93 percent, 91.5 percent, and 92.5 percent, respectively. It also worked well at pH 5 and 7, with average removal rates of 93.9 percent and 95 percent for pH 5 and 7, respectively, for starting concentrations of 5, 10, and 15, indicating that the produced MOF has a strong capacity to remove Cu + 2 .

Copper is a heavy metal used in many industries and known for its negative impacts on the environment and human’s health. A novel structured metal organic framework (MOF) was used for copper adsorption for this work. SEM, EDAX, XRD and FTIR were done to confirm the structure of MOF prepared. MOF of 0.05 gm was used to examine its ability in Cu+ 2 removals with different initial concentrations of Cu+2 and pH values (5, 7 and 9). The prepared MOF was able to achieve Cu removal with 94.6%, 93%, 91.5%, and 92.5 % for the initial concentrations of 5, 10, 15, and 20 ppm respectively. It also performed very well for pH 5 and 7 with average removal ranging from 93.9%-95% for pH 5 and 7 for the initial concentrations of 5, 10, and 15 respectively which indicate that the prepared MOF is of high ability in Cu+ 2 removal.

furthest to the left representing 30 min of reaction. Upper row: photothermal synthesis. Middle row: a conventional synthesis with AuBPs. Bottom row: conventional synthesis without AuBPs. The vials have a length of 6 cm and radius of 1.75 cm. e Product mass as a function of time for PPRs at different temperatures. f PXRD results of products from PPRs in (e). g BET N 2 adsorption isotherms of products from PPRs in (e).

Incorporating chiral molecules in the covalent organic frameworks (COFs) with uniformly ordered pores results in chiral COFs, which have been highly promising candidates for enantioseparation. Herein, a homochiral COF nanochannel membrane is reported by introducing chiral centers (L-phenylalanine methyl ester) into one of the organic ligands for the enantioseparation of chiral amino acids. The separation results show that the D-isomer is preferentially transported through the porous membrane channel. This composite membrane exhibits excellent selectivity for racemic phenylalanine with the highest enantiomeric excess value of up to 99.4 %. The adsorption and molecular modeling studies substantiate the experiment results by showing higher bonding affinity towards D-isomer over L-isomer. The excellent enantioselective gating performance unveils the porous COF skeleton with chiral selectors and the size-matching synergy for stereoselective interactions with chiral isomers.

Hybrid metal-organic frameworks (MOFs) have many positive features like high porosity, surface area, and conductivity as compared to other materials. They have better potential than pristine ones due to the reason that hybrid materials have good faradic responses due to variable metal oxidation states. These all-favorable factors make hybrid MOFs more potential electrodes for energy storage. In this study, hybrid Ni-Co MOFs presented good specific capacitance of 745 F g-1 (447 C g-1 @ 1 A g-1) in comparison with pristine Co MOFs of 109 F g-1 (65.5 C g-1 @ 1 A g-1). Also, the hybrid MOFs showed superior electrical conductivity of 1353.3 S cm-1 as compared to pristine MOFs. The charge transfer resistance (Rct) of hybrid MOFs was 2.271 Ω pretty much greater than pristine MOF and other closely related studies. The best electrochemical performance was attributed to the synergic effect of Ni, Co, and organic ligand.

In this research, a method was presented for synthesizing magnetic nanoparticles and modifying them with a new group of porous nanomaterials. Initially, Iron oxide nanoparticles were prepared by co-precipitation method which modified by (3-aminopropyl) trimethoxysilane in toluene, followed by stabilization by the Cu-Benzen 1,3dicarboxylic acid (BDC) metal-organic. The product examined for structural properties using infrared Fourier spectroscopy (FT-IR), powder X-ray diffraction (PXRD), thermal gravimetric analysis (TGA), elemental analysis (EA), vibrational sampling magnetometer (VSM), and field-emission scanning electron microscopy. The operational parameters like pH, absorption time, and the adsorbent capacity determined the naproxen content in human urine which successfully extracted and determined by HPLC. Moreover, the adsorption process examined by three isotherms models of Langmuir, Freundlich, and Temkin. It was found that each gram of the synthesized adsorbent was able to adsorb 1.5 mg of naproxen. The average particle size of the synthesized adsorbent reported to be 20-50 nm. The loading capacity and the release kinetics in simulated gastric showed that both of these parameters were affected by the surface properties of the mesoporous silica material. Approximately 50% of naproxen was released in the simulated gastric fluid at pH=5 less than 5 minutes. Results of the absorption process of naproxen by Fe 3 O 4 /Cu (BDC) were congruent with the results of Higuchi model, one of the drug release theories from a degradable surface.

More than 47,000 articles have been published in the area of Metal-Organic Framework since its seminal discovery in 1995, exemplifying the intense research carried out in this short span of time. Among other applications, gas adsorption and storage are perceived as central to the MOFs research, and more than 10,000 MOFs structures are reported to date to utilize them for various gas storage/separation applications. Molecular modeling, particularly based on density functional theory, played a key role in (i) understanding the nature of interactions between the gas and the MOFs geometry (ii) establishing various binding pockets and relative binding energies, and (iii) offering design clues to improve the gas uptake capacity of existing MOF architectures. In this review, we have looked at various MOFs that are studied thoroughly using DFT/ periodic DFT (pDFT) methods for CO 2 , H 2 , O 2 , and CH 4 gases to provide a birds-eye-view on how various exchange-correlation functionals perform in estimating the binding energy for various gases and how factors such as nature of the (i) metal ion, (ii) linkers, (iii) ligand, (iv) spin state and (v) spin-couplings play a role in this process with selected examples. While there is still room for improvement, the rewards offered by the molecular modelling of MOFs were already substantial that we advocate experimental and theoretical studies to go hand-in-hand to undercut the trial-and-error approach that is often perceived in the selection of MOFs and gas partners in this area.

Metal-organic frameworks (MOFs)--tunable, nano-porous materials--are alluring recognition elements for gas sensing. Mimicking human olfaction, an array of cross-sensitive, MOF-based sensors could enable analyte detection in complex, variable gas mixtures containing confounding gas species. Herein, we address the question: given a set of MOF candidates and their adsorption properties, how do we select the optimal subset to compose a sensor array that accurately and robustly predicts the gas composition via monitoring the adsorbed mass in each MOF? We first mathematically formulate the MOF-based sensor array problem under dilute conditions. Instructively, the sensor array can be viewed as a linear map from gas composition space to sensor array response space defined by the matrix H of Henry coefficients of the gases in the MOFs. Characterizing this mapping, the singular value decomposition of H is a useful tool for evaluating MOF subsets for sensor arrays, as it determines the sensitivity of the predicted gas composition to measurement error, quantifies the magnitude of the response to changes in composition, and recovers which direction in gas composition space elicits the largest/smallest response. To illustrate, on the basis of experimental adsorption data, we curate MOFs for a sensor array with the objective of determining the concentration of CO 2 and SO 2 in the gas phase. download file view on ChemRxiv Curating_MOFs_for_sensor_arrays.pdf (18.39 MiB) download file view on ChemRxiv Curating_MOFs_for_sensor_arrays_SI.pdf (2.10 MiB)

A novel thorium(IV) metal-organic framework (MOF), Th(2,6-naphtalenedicarboxylate) 2 , has been synthesized via solvothermal reaction of thorium nitrate and 2,6naphtalendicarboxilyc acid. This compound shows a new structural arrangement with an interesting topology and an excellent thermal resistance, as the framework is stable in air up to 450 °C. Most notably, this MOF, combining the radioactivity of its metal center and the scintillation property of the ligand, has been proven capable of spontaneous photon emission.

All reagents and solvents were used as received from commercial suppliers without further purification. 1 H NMR and 13 C NMR spectra were recorded on a Varian Mercury 300 MHz spectrometer. Tetramethylsilane (TMS) and deuterated solvents (CDCl 3 , δ = 77.0 ppm; DMSO-d 6 , δ = 39.5 ppm) were used as internal standards in 1 H NMR and 13 C NMR experiments, respectively. The coupling constants were reported in Hertz. FTIR spectra were performed on a Bruker Vector 22 spectrometer at room temperature. The elemental analyses were performed with Perkin-Elmer 240 CHN analyzers from Galbraith Laboratories, Knoxville. Thermogravimetric analyses (TGA) were measured using a Shimadzu TGA-50 analyzer under a nitrogen atmosphere with a heating rate of 3 o C min -1 . Powder X-ray diffraction (PXRD) patterns were recorded by a Rigaku Ultima IV diffractometer operated at 40 kV and 44 mA with a scan rate of 1.0 deg min -1 . The crystallographic measurement was made on a Bruker SMART Apex II CCD-based X-ray diffractometer system equipped with a Motarget X-ray tube (λ = 0.71073 Å) operated at 2000 watts power (50 kV, 40 mA). The structure was solved by direct method and refined to convergence by least squares method on F 2 using the SHELXTL software suit. A Micromeritics ASAP 2020 surface area analyzer was used to measure gas adsorption isotherms. To have a guest-free framework, the fresh sample was guest-exchanged with

The adsorption of Pb(II), Ni(II), and Cd(II) metal ions onto Fe3O4@SiO2-TMPDT adsorbent was carried out through batch experiments. In this study, Fe3O4@SiO2-TMPDT adsorbent was synthesized through a sol-gel process using sodium silicate extracted from rice husk ash (Na2SiO3)RHA with the addition of magnetite (Fe3O4) and modifier N 1 -(3-trimethoxysilylpropyl) diethylenetriamine (TMPDT). The synthesized adsorbent was then characterized by FTIR. The Fe3O4@SiO2-TMPDT adsorbent was prepared with suspension Fe3O4:(Na2SiO3)RHA ratios (v/v) of 1:4, 2:3, and 1:1, and varying the amounts of TMPDT of 1; 2.5 and 5 mL. The optimum pH to perform conditions adsorption for Pb(II) metal ions was determined to be 4, while Ni(II) and Cd(II) were 5. In addition, the adsorption process followed a pseudo-second-order kinetic model, and the adsorption isotherm was consistent with the Langmuir isotherm. The adsorption capacities for Pb(II), Ni(II), and Cd(II) were 11.760 mg/g, 1.864 mg/g, and 1.888 mg/g, respectively.

Double-stage molecular diffusion control is achieved in an ‘organic-graphene hydrogel’ biphasic system to yield tunable MOF-based functional hydrogel-hybrids, with excellent water oxidation performance (with a low onset potential and Tafel slope of 44.3 mV dec−1).

After a short introduction highlighting the potentialities of metal-organic frameworks (MOFs) and the power of X-ray absorption spectroscopies (XAS), a list of selected examples follows. The first part of this review provides the basic concepts that are behind the most used XAS techniques: Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near Edge Structure (XANES) spectroscopies. Moreover, it reports also the basis of an innovative approach to the EXAFS data analysis based on the wavelet transform approach, that allows a more solid attribution to the different paths contributing to the overall signal. The second part is devoted to provide a section of examples where EXAFS and XANES techniques have been determinant in understanding the structural and electronic properties of metal centers in MOFs. The selected examples have been ordered in subsections related to the application foreseen for the investigated MOFs materials: MOFs functionalization for catalytic applications; MOFs as single site catalyst; MOFs as photocatalysts; MOFs for gas sorption and storage; MOFs for energy application. Conclusions and perspectives are provided at the end.

Three new Metal-Organic Frameworks, containing mesitylene tribenzoic acid as a linker and zinc (1) or cadmium as metals (2,3), were synthesized through solvothermal reactions, using DMF/ethanol/water as solvents, at temperatures of 80 °C (structures 1 and 3) and 120 °C (structure 2). Following single-crystal X-ray diffraction, it was found that 1 and 3 crystallize in the P21/c and C2/c space groups and form 2D networks, while 2 crystallizes in the Fdd2 space group, forming a 3D network. All three frameworks, upon heating, were found to be stable up to 350 °C. N2 sorption isotherms revealed that 1 displays a BET area of 906 m2/g. Moreover, the porosity of this framework is still present after five cycles of sorption/desorption, with a reduction of 14% of the BET area, down to 784 m2/g, after the fifth cycle. The CO2 loading capacity of 1 was found to be 2.9 mmol/g at 0 °C.

New metal-organic frameworks (MOF) with lanthanum(III), cerium(III), neodymium(III), europium(III), gadolinium(III), dysprosium(III), and holmium(III)] and the ligand precursor 1,3,5-tris(4-carboxyphenyl)-2,4,6-trimethylbenzene (H3L) were synthesized under solvothermal conditions. Single crystal x-ray analysis confirmed the formation of three-dimensional frameworks of [LnL(H2O)2]n·xDMF·yH2O for Ln = La, Ce, and Nd. From the nitrogen sorption experiments, the compounds showed permanent porosity with Brunauer-Emmett-Teller (BET) surface areas of about 400 m2/g, and thermal stability up to 500 °C. Further investigations showed that these Ln-MOFs exhibit catalytic activity, paving the way for potential applications within the field of catalysis.

X-ray diffraction (XRD) and electron paramagnetic resonance spectroscopy (EPR) were combined to study the structural transformations induced by temperature, pressure and air humidity of the &quot;breathing&quot; metal-organic framework (MOF) MIL-53(Al), doped with paramagnetic V(IV) ions, after activation. The correlation between in situ XRD and thermogravimetric analysis measurements showed that upon heating this MOF in air, starting from ambient temperature and pressure, the narrow pore framework first dehydrates and after that makes the transition to a large pore state (lp). The EPR spectra of V(IV)[double bond, length as m-dash]O molecular ions, replacing Al-OH in the structure, also allow to distinguish the as synthesized, hydrated (np-h) and dehydrated narrow pore (np-d), and lp states of MIL-53(Al). A careful analysis of EPR spectra recorded at microwave frequencies between 9.5 and 275 GHz demonstrates that all V(IV)[double bond, length as m-dash]O in the np-d and lp states a...

Syntheses, structural characterizations, photoluminescence, and adsorption properties of three new azo-functionalized Cd(II)-MOFs, namely, {[Cd(azbpy)(msuc)]·2.5(H2O)}n (2), {[Cd(azbpy)(mglu)]·5(H2O)}n (3), and {[Cd1.5(azbpy)2(glu)]·(NO3)·MeOH}n (4) [where msuc2- = methylsuccinate; mglut2- = methylglutarate; glut2- = glutarate; azbpy = 4,4&#39;-azobispyridine] have been reported. The compounds show different structures only with the variation of aliphatic dicarboxylates. The photoswitching behavior for the above-mentioned newly synthesized Cd(II)-MOFs along with one of our previously reported other azo-functionalized Cd(II)-MOF, namely, {[Cd(azbpy)(suc)]·2(H2O)}n (1), has been studied extensively. At photoilluminated condition, the conductivity values can draw a clear structure-property relationship among the structures of compounds 1-4. Single crystal structural analysis reveals that all the compounds exhibit a three-dimensional (3D) framework connected by azbpy linker and respecti...

Adsorption and desorption of hydrogen from nanoporous materials, such as activated carbon, is usually fully reversible. We have prepared nanoporous metal-organic framework materials with flexible linkers in which the pore openings, as characterized in the static structures, appear to be too small to allow H 2 to pass. We observe hysteresis in their adsorption and desorption kinetics above the supercritical temperature of H 2 that reflects the dynamical opening of the “windows” between pores. This behavior would allow H 2 to be adsorbed at high pressures but stored at lower pressures.

Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.

BACKGROUNDVery recently, metal‐organic framework (MOF) materials have been postulated as emerging supports to achieve solid‐state enzyme‐contained biocatalysts. In this work, post‐synthesis and in situ strategies to immobilize β‐glucosidase and laccase on different MOF materials were studied. The MOF‐based supports, i.e. MIL‐53(Al), NH2‐MIL‐53(Al) and Mg‐MOF‐74, were prepared under soft and sustainable conditions (room temperature and pH values compatible with enzymatic activity), allowing development of the in situ strategy.RESULTSIn both post‐synthesis and in situ approaches, the intercrystalline mesoporosity of the MOF‐based support favored the immobilization efficiency or the specific activity. The latter expressed as units per milligram of immobilized enzyme was higher in the post‐synthesis immobilization, whereas the biocatalysts prepared in situ gave much higher enzyme loading (over 85%) and lower enzyme leaching (around 5%). The in situ approach even worked in a non‐aqueous ...

A flexible metal‐organic framework selectively sorbs para‐ (pX) over meta‐xylene (mX) by synergic restructuring around pX coupled with generation of unused void space upon mX loading. The nature of the structural change suggests more generally that flexible structures which are initially mismatched in terms of fit and capacity to the preferred guest are strong candidates for effective molecular separations.

The development of effective and precious‐metal‐free electrocatalysts for the oxygen evolution reaction (OER) represents a major bottleneck to unlock a renewable energy scenario based on water splitting technologies. Materials uniting the electrical conductivity of conjugated graphitic nanomaterials with the chemical regularity of metal‐organic‐framework (MOF) crystals are promising precursors for such electrocatalysts. Nanoscale integration of these two materials is challenging. A new synthesis route is developed that integrates 2D MOF nanocrystals and graphitic carbon nanolamellae into layered composites. The graphitic carrier contributes excellent charge–transport properties, and the 2D macromolecular MOF precursor provides a suitable shuttle for introducing highly dispersed metal species. Furthermore their direct chemical environment can be controlled via selection of organic linker. Thermal decomposition of 2D cobalt tetrafluoro benzene‐dicarboxylate MOF nanocrystals within suc...

In this work, we have successfully synthesized a bimetallic (Zinc and Cobalt) Zeolitic Imidazolate Framework (Zn50Co50-ZIF), a class in a wider microporous Metal-Organic Framework (MOF) family. The synthesized nanostructures maintain both water stability like ZIF-8 (solely Zn containing) and charge transfer electronic band in the visible optical spectrum as ZIF-67 (solely Co containing). Crystal structure from XRD, high resolution transmission electron microscopy (HRTEM) followed by elemental mapping (EDAX) confirm structural stability and omnipresence of the metal atoms (Zn and Co) across the nanomaterial with equal proportion. Existence of charge transfer state consistent with ZIF67 and intact ultrafast excited state dynamics of the imidazolate moiety in both ZIF-8 and ZIF-67, is evidenced from steady state and time resolved optical spectroscopy. The thermal and aqueous stabilities of Zn50Co50-ZIF are found to be better than ZIF-67 but comparable to ZIF-8 as evidenced by solubilit...

We report a novel catalyst comprising palladium supported on thioether functionalized Schiff-base conjugated covalent organic frameworks, which significantly enhances the semi-hydrogenation conversion and selectivity of phenylacetylene. Theoretical calculations substantiate that the imide and thioether groups modify the electron density around Pd, reducing the energy barriers for phenylacetylene adsorption and styrene desorption, thereby improving the conversion and selectivity of the catalyst.

etal-organic coordination networks (MOCNs) have attracted wide interest because they provide a novel route towards porous materials that may find applications in molecular recognition, catalysis, gas storage and separation 1,2 . The so-called rational design principle-synthesis of materials with predictable structures and properties-has been explored using appropriate organic molecular linkers connecting to metal nodes to control pore size and functionality of open coordination networks 3-9 . Here we demonstrate the fabrication of surface-supported MOCNs comprising tailored pore sizes and chemical functionality by the modular assembly of polytopic organic carboxylate linker molecules and iron atoms on a Cu(100) surface under ultra-high-vacuum conditions. These arrays provide versatile templates for the handling and organization of functional species at the nanoscale, as is demonstrated by their use to accommodate C 60 guest molecules. Temperature-controlled studies reveal, at the single-molecule level, how pore size and chemical functionality determine the host-guest interactions. Transition metal carboxylates are widely used as constituents for nanoporous supramolecular materials 8,10-14 . The linker molecules used for the present study are 1,4-dicarboxylic benzoic acid (terephthalic acid, TPA), 1,2,4-tricarboxylic benzoic acid (trimellitic acid, TMLA) and 4,1′,4′,1′′-terphenyl-1,4′′-dicarboxylic acid (TDA), as depicted in Fig. . Our previous studies revealed that on deposition on a Cu(100) surface at room temperature, such species readily undergo complexation with coadsorbed Fe . In particular, on the engagement of the endgroups in Fe-carboxylate formation, the linear linkages allow for the construction of MOCNs comprising surfacesupported nanometre-size cavities with specific topology. They represent two-dimensional (2D) analogues to previously described 3D porous metal-organic framework structures . The different backbone length (∼7 Å for TPA and TMLA; ∼15 Å for TDA) controls the cavity dimensions,whereas the additional side group of TMLA bestows a specific chemical functionality to the cavities. The tuning of 2D metal-organic networks using Fe and TPA or TDA is demonstrated by the scanning tunnelling microscopy (STM) data reproduced in Fig. .The identification of the organic molecules and Fe atoms in the MOCNs is based on a thorough analysis of carboxylate nanostructures from related benzoic acids and transition metal atoms at Cu(100) . Their symmetry and shape is induced by the atomic arrangement of the underlying Cu atomic lattice, which induces the orientation along the principal directions of the substrate. The positioning of the flat-lying molecular species and the bonding of Fe atoms to their functional groups gives rise to networks comprising nanocavities of distinct shape and size. The overview image in Fig. shows the mesoscopic ordering of Fe-TPA MOCNs in domains extending up to 50 nm. In the highresolution data in Fig. , the formation of ladder-type and fully 2D interconnected networks is shown,the formation of which is controlled by the amount and ratio of the materials deposited (a complete account of the system is given elsewhere 17 ).With the Fe concentration kept small, ladder-type structures with elongated cavities evolve (Fig. ). In such cases, not all carboxylate groups can participate in coordinating Fe atoms; presumably they form hydrogen-bridges (marked by dotted lines in Fig. ) with adjacent phenyl rings to stabilize the network structures further. On complete 2D Fe-carboxylate reticulation, a trellis

Chemical separation has great importance in industrial applications. Separation of xylene isomers still prevails to be one of the most important challenges in chemical industry, due to the large amount of commercial use of p-xylene in the production of beverage bottles, fibers and films. A novel Zn(II)-based dynamic coordination framework based on flexible ether-linkage, exhibiting selective adsorption of p-Xylene over its congener C 8 -alkyl aromatic isomers at ambient conditions is reported. Notably, no dynamic structure based MOF compound is known in the literature which shows clear preference of p-xylene over other isomers. This type of framework-breathing and guest-induced reversible solid-state structural transformations with unique adsorption selectivity can be exploited purposefully to develop smart functional host materials capable of industrially important chemical separations.

In order to cope with the environmental crisis and the depletion of non-renewable resources, the combination of metal-organic framework (MOF) and biomass materials has become an important breakthrough in sustainable materials science. With its unique pore structure and adjustable performance, MOF significantly improves the thermal stability and mechanical strength of biomass materials, and broadens its application in energy, material manufacturing and other fields. MOF-biomass composites show excellent properties in carbon capture, water treatment and biomedicine, which is of great significance to environmental protection and green chemical industry. This paper summarizes the latest research progress of MOF-biomass composites, including their application in wastewater treatment, air purification, food packaging and other fields, and discusses the green synthesis method, biological interface integration strategy and its potential in biocatalysis, sensing and medical fields. The development and application of MOF-biomass composites provide a new way to solve environmental problems and promote sustainable development. Furthermore, we critically analyze the key challenges and future directions. Our sincere hope is that this review will stimulate greater research interest in applications of biomass/MOF composites, and offer valuable insights for their design and utilization strategies.

Developing advanced porous materials possessing both a high storage capacity and selectivity for acetylene (C2H2) remains challenging but a sought-after endeavor. Herein we show a strategy involving synergic combination of spatial confinement and commensurate stacking for enhanced C2H2 storage and capture via maximizing the host—guest and guest—guest interactions. Two ultramicroporous metal-organic frameworks (MOFs), MIL-160 and MOF-303 are elaborately constructed to exhibit ultrahigh C2H2 uptakes of 235 and 195 cm3·g−1, respectively, due to the confinement effect of the suitable pore sizes and periodically dispersed molecular recognition sites. Specially, C2H2 capacity of MIL-160 sets a new benchmark for C2H2 storage. The exceptional separation performances of two materials for C2H2 over both CO2 and ethylene (C2H4), which is rarely observed, outperform most of the benchmark materials for C2H2 capture. We scrutinized the origins of ultrahigh C2H2 loading in the confined channels vi...

Metal-organic framework (MOF)-based sensors for the detection of various analyte molecules has been a subject of absolute importance. However, most of these sensors rely on the turn-off (quenching) transduction response, while those reporting turn-on response are very rare. Here, we present two new MOF-based sensors, {[Zn2(oxdz)2(tpbn)]•14H2O}n (1) and {[Zn2(oxdz)2(tpxn)]•10H2O•2C2H5OH}n (2), via the self-assembly of Zn(II) metal ions, a fluorogenic oxdz2-linker, and bis(tridentate) ligands (tpbn and tpxn) under ambient conditions. Their formation from such a self-assembly process has been evaluated on the basis of the geometry around the fivecoordinated Zn(II), preferential meridional binding of the bis(tridentate) ligands, and diverse binding of the carboxylate groups in oxdz2-studied using single-crystal X-ray diffraction. The bulk phase purity and the similarity of the bulk materials of 1 and 2 is studied through powder X-ray diffraction analysis. Although 1 and 2 are isostructural, a difference in the transduction mechanism for the sensing of acetylacetone in organic solvents (turnon for 1 and turn-off for 2) is observed and can be attributed to the spacer in the bis(tridentate) ligands. We have demonstrated the competing effect of the nonradiative interactions and photoinduced electron transfer toward the sensing mechanism. The results are well-supported by the Fourier transform infrared spectroscopy study, intensity versus concentration plots, spectral overlap measurements, time-resolved fluorescence studies, and MM2 and density functional theory calculations. Furthermore, we have showcased the utilization of 1 for the sensing of trace amounts of water in organic solvents. Figure

Metal-organic framework (MOF)-based sensors for the detection of various analyte molecules has been a subject of absolute importance. However, most of these sensors rely on the turn-off (quenching) transduction response, while those reporting turn-on response are very rare. Here, we present two new MOF-based sensors, {[Zn2(oxdz)2(tpbn)]•14H2O}n (1) and {[Zn2(oxdz)2(tpxn)]•10H2O•2C2H5OH}n (2), via the self-assembly of Zn(II) metal ions, a fluorogenic oxdz2-linker, and bis(tridentate) ligands (tpbn and tpxn) under ambient conditions. Their formation from such a self-assembly process has been evaluated on the basis of the geometry around the fivecoordinated Zn(II), preferential meridional binding of the bis(tridentate) ligands, and diverse binding of the carboxylate groups in oxdz2-studied using single-crystal X-ray diffraction. The bulk phase purity and the similarity of the bulk materials of 1 and 2 is studied through powder X-ray diffraction analysis. Although 1 and 2 are isostructural, a difference in the transduction mechanism for the sensing of acetylacetone in organic solvents (turnon for 1 and turn-off for 2) is observed and can be attributed to the spacer in the bis(tridentate) ligands. We have demonstrated the competing effect of the nonradiative interactions and photoinduced electron transfer toward the sensing mechanism. The results are well-supported by the Fourier transform infrared spectroscopy study, intensity versus concentration plots, spectral overlap measurements, time-resolved fluorescence studies, and MM2 and density functional theory calculations. Furthermore, we have showcased the utilization of 1 for the sensing of trace amounts of water in organic solvents. Figure

This study successfully encapsulated palladium nanoparticles within the metal-organic framework material UiO-66 using a straightforward method. Utilizing a microwave-assisted process, the pores of UiO-66 were activated, and the metal precursors were simultaneously reduced in the presence of a reducing agent. The morphological and physicochemical properties of the resulting material were thoroughly analyzed using various techniques, including EDX, SEM, XRD, TGA, BET, and ICP-OES. UiO-66-NH 2-Pd demonstrated highly efficient catalytic activity in CO cross-coupling reactions under mild conditions. Moreover, this nanostructured material offers notable advantages, such as high reaction efficiency, a simple preparation process, and environmentally friendly characteristics. The catalyst was easily recovered via centrifugation and recycled five times without significant palladium leaching or any substantial loss in activity.

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Metal Organic Frame works (MOFs) are being widely used in carbon capture through adsorption and membrane techniques, which are yet to be commercialized. This is due to their high affinity towards acidic gases and exceptional characteristics such as crystallinity, structural stability, high surface area and flexible pore dimensions. In this review, wide range of topics viz., synthesis protocols, modifications employed to further improve their attributes, comprehensive comparison of different MOFs used in carbon capture, thermo-kinetics modelling studies, contactors and material screening. Every section has been discussed in detail in terms of developmental trends, future challenges and prospects besides summarizing in the form of comprehensive tables at a glance for the benefit of the readers. Solvo-thermal method was found to be the most effective synthesis method besides ultra-sonication and microwave assisted methods, which also gave very good crystalline structures. The copper ligand based unmodified Cu-BTC MOF gave the maximum CO 2 uptake value of 9.59 mmol/g at 273 K and 1 atm. Zn(Bmic)(AT) MOF was the only species to be tested at 353 K. Alternatively, a photo-responsive MOF, Mg-IRMOF-74-III functionalized with azopyridine gave a CO 2 uptake of 89 cc/g which is comparable to many of the conventional MOFs. Kinetics indicate MOF adsorption mostly follows pseudo second order reactions either along with Toth isotherms or modified Langmuir isotherms. Fixed and fluidized bed reactors perform the best in terms of carbon capture studies. Moisture affinity, active sites and crystallinity were found to be the best factors considered whilst screening of proper MOFs. Abbreviations: CC, Carbon dioxide Capture; SA, Surface area; PV, Pore volume; DMF, N,N-Dimethylformamide; mmol/g, millimoles of CO 2 per gram of adsorbent; cc/g, cubic centimeters of CO 2 per gram of adsorbent; CLC, Chemical Looping Combustion.

The pursuit of rapid development in the area of catalysis, solar energy, environmental remediation, wastewater treatment and other aspects of ecological and sustainable chemistry has prompted substantial research by material chemists, physicists, academics and other scientists for the development of porous material. A lot of energy had been invested in this course by scientist, research organizations and public sector agencies from antiquity, but the resulting solution has been somewhat undesirable until two decades ago when Metal-Organic Frameworks (MOFs) appears to offer a glimpse of solution to those challenging issues. The adaptability, flexibility, uniqueness and usability of the metal-organic frameworks material, and its suitability to every facet of scientific and technological advancement has since triggered an incredible upsurge in studies aimed at uncovering more of the inherent influential properties of the materials, and its improvement for the betterment of material sci...

The infection with multiple-drug-resistant bacteria and fungi has become a significant challenge in wound care management. Microbial infections significantly increase mortality rates and healthcare costs for patients with diabetic wounds. Therefore, the design of effective antimicrobial materials for wound healing is critically important. Zeolitic imidazole frameworks (ZIFs) are highly tunable and effective materials for biomedical applications. In this study, we present a chitosan-coated bimetallic ZIF-Ni nanocomposite designed for antimicrobial and wound healing applications. The material characteristics of the CS@ZIF-Ni nanocomposite were systematically investigated using various spectroscopic and microscopic techniques. The surface coating of the biopolymer chitosan enhances the biological activity and biocompatibility of the CS@ZIF-Ni nanocomposite. Antimicrobial assays confirmed that the combination of bimetallic zeolitic imidazole and chitosan effectively eradicates multidrug-resistant pathogenic bacteria and fungi. Results from cytotoxicity assays on human skin cells indicated that the CS@ZIF-Ni is a highly biocompatible material. The presence of zinc and nickel promotes reactive oxygen species (ROS)-mediated microbial cell death and creates optimal conditions for cell regeneration. Additionally, the chitosan bioactive molecules stimulate antimicrobial activity and enhance the migration rate of wounded cells. The synergistic effects of CS@ZIF-Ni, including its high stability, biosafety, antimicrobial efficacy, and ability to support cell regeneration based on in vitro experiments, make it an excellent therapeutic option for wound

28 Metal-organic frameworks (MOFs) act as versatile coordinators for the 29 subsequent synthesis of high-performance electrochemical catalysts by 30 providing dispersed metal-ion distribution, initial coordination condition, and 31 modular dopant atom ratios, etc. In this work, a copper-based crystalline MOF 32 trans-[Cu(NO 3 ) 2 (Him) 4 ] was synthesized as a novel precursor of a 33 carbon-based electrochemical valence-alternating NC@Cu x O catalyst. 34 Through simple temperature modulation of the pyrolysis procedure, the 35 gradual transformation towards highly-active catalytic nanocomposite was 36 characterized and investigated to ascertain the signal enhancing mechanism 37 during H 2 O 2 detection. Owing to its proprietary structure and ensuing 38 electrochemical reduction activity, a proof-of-principle sensor using 39 NC@Cu x O as transducer was able to provide an amplified sensitivity of 2330 40 μA mM -1 cm -2 . In addition, its facile one-vessel preparation and the intrinsic 41 non-enzymatic nature suggests a wide range of potential applications in 42 medical settings.

Metal–organic frameworks (MOFs), as high-surface-area materials, have shown promise in various areas of application, such as chiral sensing and separation, due to their flexibility in design and organized porous cages. Researchers have been striving to design and develop high-performance enantiorecognition and separation analytical techniques in chiral science fields. The main aim of this review is to provide a comprehensive overview of chirality, state-of-the-art MOFs in chirality, and chiral analysis in the past decade, 2012–2022. The classification of this review includes chirality, principles of chiral analysis, the attraction of functional materials in chirality, MOFs in chiral analysis, MOFs for designing enantioselective sensors (fluorescence, circular dichroism, quartz crystal microbalance, electrochemical), and MOFs as chiral stationary phases (CSPs) for chromatographic enantioseparation (high-performance liquid chromatography, gas chromatography, and capillary electrochrom...

Adsorption and controlled release of agrochemicals has been studied widely using different nanomaterials and a variety of formulations. However, the potential for application of high surface-area metal-organic frameworks (MOFs) for the controlled release of agrochemicals has not been thoroughly explored. Herein, we report controlled and sustainable release of a widely used herbicide (2-methyl-4-chlorophenoxyacetic acid, MCPA) via incorporation in a range of zirconiumbased MOFs and their biodegradable polymer composites. Three Zr-based MOFs, viz., UiO-66, UiO-66-NH 2 , and UiO-67 were loaded with MCPA either postsynthetically or in situ during synthesis of the MOFs. The MCPA-loaded MOFs were then incorporated into a biodegradable polycaprolactone (PCL) composite membrane. All three MOFs and their PCL composites were thoroughly characterized using FT-IR, TGA, SEM, PXRD, BET, and mass spectrometry. Release of MCPA from each of these MOFs and their PCL composites was then studied in both distilled water and in ethanol for up to 72 h using HPLC. The best performance for MCPA release was observed for the postsynthetically loaded MOFs, with PS-MCPA@UiO-66-NH 2 showing the highest MCPA concentrations in ethanol and water of 0.056 and 0.037 mg/mL, respectively. Enhanced release of MCPA was observed in distilled water when the MOFs were incorporated in PCL. The concentrations of herbicides in the release studies provide us with a range of inhibitory concentrations that can be utilized depending on the crop, making this class of composite materials a promising new route for future agricultural applications.

In the past century, the global temperature rose by 0.7 K. CO2 concentration in the atmosphere, contributing by more than 60% to global warming, overcame 410 ppm in 2019. MOFs are a potential alternative to all-inorganic materials in applications requiring gas adsorption. Their performances can be optimized using one properly functionalized ligand or a mixture therefrom. The four mixed-ligand MOFs Zn-H/NO2, Zn-H/NH2, Zn-NO2/NH2 and Zn-H/NO2/NH2, synthesized employing 4,4'bipyrazole, 3-nitro-4,4'-bipyrazole and 3-amino-4,4'-bipyrazole, were characterized in the solid state. Their crystal structures were assessed by PXRD, they are isoreticular to the end-members Zn-H [1], Zn-NO2 [2] and Zn-NH2 [3], showing a 3-D open frameworks with 1-D square/rhombic channels. The ligand stoichiometric ratio was determined independently, with an excellent agreement, by 13C CPMAS solid-state NMR and PXRD. DSC and PXRD, upon application of the Vegard law, confirmed the formation of solid solutions. The four MOFs are thermally stable (Tdec = 708-726 K) and, as proved by variable-temperature PXRD, show permanent porosity. N2 adsorption at 77 K revealed BET surface areas in the range 400-600 m2/g. CO2 adsorption capacity, isosteric heat of adsorption (Qst) and CO2/N2 selectivity (at 1 bar and 298 K), were compared with those of their end-members. The amino-decorated compounds show higher Qst values and better selectivity vs. the nitro-tagged analogues; moreover, tag "dilution" is beneficial compared to the end-members.