Fabrication of easy separable and reusable MIL-125(Ti)/MIL-53(Fe) binary MOF/CNT/Alginate composite microbeads for tetracycline removal from water bodies.
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ABSTRACT:
SUBMITTER: Omer AM
PROVIDER: S-EPMC8664953 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:The flexibility of the MIL-53(M) metal-organic framework (MOF) has been elucidated through various characterization methodologies, particularly in gas and liquid adsorption processes. However, to the best of our knowledge, there has been no prior electron paramagnetic resonance (EPR) characterization of liquid-phase adsorption in the MOF MIL-53(M), which offers insights into local geometric changes at the oxygen octahedron containing the metal ions of the framework. In this study, we investigate, for the first time, the pore transformations within the MIL-53(Al0.99Cr0.01) framework during liquid-phase adsorption using EPR spectroscopy. Our investigation concentrates explicitly on the adsorption of pure solvents, including water, methanol, ethanol, isopropanol, pyridine, and mixed water/methanol phases. The EPR spectroscopy on the (Al0.99Cr0.01) MOF has allowed us to witness and comprehend the transitions between the narrow pore and large pore phases by examining changes in the zero-field splitting parameters of the S = 3/2 Cr(iii) species. Of all the solvents examined, a robust and distinct spectral feature observed during methanol adsorption unequivocally indicates the pore opening.
| S-EPMC10826799 | biostudies-literature
Project description:Tetracycline detection has been a great concern because of its overuse and difficulty in degrading. Here, a detection method with ratio fluorescence was developed by synthesizing Eu3+ doped nanocomposites with NH2-MIL-53(Al) nanosheets. After adding tetracycline, the fluorescence intensity at 616 nm characteristic emission peak of Eu3+ was sensitized by the antenna effect generated from coordinating Eu3+ with tetracycline, but the fluorescence of NH2-MIL-53(Al) at 433 nm was quenched by the fluorescence resonance energy transfer between the Eu3+-tetracycline composition and NH2-MIL-53(Al). Therefore, the efficient detection of tetracycline was achieved based on this change of ratio fluorescence signal. The experimental results show that Eu3+/NH2-MIL-53(Al) has excellent selectivity, a wider linear range and a lower detection limit for detecting tetracycline. This method can afford favorable ideas for developing advanced chemical and biological sensors.
| S-EPMC8693705 | biostudies-literature
Project description:The flavin derivatives 10-methyl-isoalloxazine (MIA) and 6-fluoro-10-methyl-isoalloxazine (6F-MIA) were incorporated in two alternative metal-organic frameworks, (MOFs) MIL-53(Al) and MOF-5. We used a post-synthetic, diffusion-based incorporation into microcrystalline MIL-53 powders with one-dimensional (1D) pores and an in-situ approach during the synthesis of MOF-5 with its 3D channel network. The maximum amount of flavin dye incorporation is 3.9 wt% for MIA@MIL-53(Al) and 1.5 wt% for 6F-MIA@MIL-53(Al), 0.85 wt% for MIA@MOF-5 and 5.2 wt% for 6F-MIA@MOF-5. For the high incorporation yields the probability to have more than one dye molecule in a pore volume is significant. As compared to the flavins in solution, the fluorescence spectrum of these flavin@MOF composites is broadened at the bathocromic side especially for MIA. Time-resolved spectroscopy showed that multi-exponential fluorescence lifetimes were needed to describe the decays. The fluorescence-weighted lifetime of flavin@MOF of 4 ± 1 ns also corresponds to those in solution but is significantly prolonged compared to the solid flavin dyes with less than 1 ns, thereby confirming the concept of "solid solutions" for dye@MOF composites. The fluorescence quantum yield (ΦF) of the flavin@MOF composites is about half of the solution but is significantly higher compared to the solid flavin dyes. Both the fluorescence lifetime and quantum yield of flavin@MOF decrease with the flavin loading in MIL-53 due to the formation of various J-aggregates. Theoretical calculations using plane-wave and QM/MM methods are in good correspondence with the experimental results and explain the electronic structures as well as the photophysical properties of crystalline MIA and the flavin@MOF composites. In the solid flavins, π-stacking interactions of the molecules lead to a charge transfer state with low oscillator strength resulting in aggregation-caused quenching (ACQ) with low lifetimes and quantum yields. In the MOF pores, single flavin molecules represent a major population and the computed MIA@MOF structures do not find π-stacking interactions with the pore walls but only weak van-der-Waals contacts which reasons the enhanced fluorescence lifetime and quantum yield of the flavins in the composites compared to their neat solid state. To analyze the orientation of flavins in MOFs, we measured fluorescence anisotropy images of single flavin@MOF-5 crystals and a static ensemble flavin@MIL53 microcrystals, respectively. Based on image information, anisotropy distributions and overall curve of the time-resolved anisotropy curves combined with theoretical calculations, we can prove that all fluorescent flavins species have a defined and rather homogeneous orientation in the MOF framework. In MIL-53, the transition dipole moments of flavins are orientated along the 1D channel axis, whereas in MOF-5 we resolved an average orientation that is tilted with respect to the cubic crystal lattice. Notably, the more hydrophobic 6F-MIA exhibits a higher degree order than MIA. The flexible MOF MIL-53(Al) was optimized essentially to the experimental large-pore form in the guest-free state with QuantumEspresso (QE) and with MIA molecules in the pores the structure contracted to close to the experimental narrow-pore form which was also confirmed by PXRD. In summary, the incorporation of flavins in MOFs yields solid-state materials with enhanced rigidity, stabilized conformation, defined orientation and reduced aggregations of the flavins, leading to increased fluorescence lifetime and quantum yield as controllable photo-luminescent and photo-physical properties.
| S-EPMC10055669 | biostudies-literature
Project description:The role of breathing behavior in hydrated and dehydrated forms of MIL-53(Fe) is investigated here. The material can be used as an efficient electrocatalyst and photocatalyst for a hydrogen evolution reaction (HER) in an alkaline medium and the same was further tested for the degradation of organic pollutants. The as-synthesized MIL-53(Fe)/hydrated and dehydrated forms were characterized by different analytical techniques to study their structure, morphology, surface analysis, thermal, physical and chemical properties. The breathing behavior of the hydrated and dehydrated forms of MIL-53(Fe) was studied through BET surface analysis. Our results show a low onset potential (-0.155 V and -0.175 V), Tafel slope (71.6 mV per decade, 88.7 mV per decade) and a large exchange current density (1.6 × 10-4 mA cm-2 and 2.5 × 10-4 mA cm-2). Hydrated and dehydrated MIL-53(Fe) degraded an RhB dye solution within 30 minutes thus proving their efficiency as efficient photocatalysts.
| S-EPMC9059945 | biostudies-literature
Project description:In this study, hybrids of nanoporous MIL-101(Cr) and MIL-53(Al) were synthesized using a hydrothermal method for various time periods, ranging from 8 to 40 h. The prepared materials were characterized by powder X-ray diffraction (PXRD) and elemental analysis, and their specific surface areas were measured by N2 sorption at 77 K using the Brunauer-Emmett-Teller (BET) method. To investigate the practical application of these materials, the pure carbon dioxide and methane adsorption capacities of the samples were determined using the volumetric method. The Langmuir model was used to fit the CO2 and CH4 isotherms. Extended Langmuir (EL) equations and the ideal adsorbed solution theory (IAST) models were used to obtain the CO2/CH4 selectivity. The sample with the highest BET specific surface area was selected as a candidate for further investigations. The thermal stability of the selected sample was investigated by thermogravimetric analysis (TGA). Scanning electron microscopy (SEM) was used to characterize the sample morphology. XRD results showed that the sample synthesized over the shortest time corresponded to MIL-101(Cr), while the sample synthesized over the longest time was in agreement with MIL-53(Al). Samples synthesized for time periods between these two limits were assumed to be composites of both MIL-53(Al) and MIL-101(Cr). TGA results indicated that the hybrid materials were thermally stable at temperatures about 100 °C higher than for pure MIL-101(Cr). The BET specific surface area (1746 m2 g-1) and CO2 adsorption capacity (16 mmol g-1) of the selected hybrid sample were about 50% and 35% higher, respectively, compared with those of pure MIL-53(Al), but 30% and 20% lower, respectively, compared with those of pure MIL-101(Cr). Binary adsorption modeling showed the high selectivity of the MIL-101(Cr) and MIL-53(Al) hybrid material for CO2 with a minimum separation factor of about 60 at 298 K. This value was much higher than those reported previously and those observed in this work for the original MIL-101(Cr) or MIL-53(Al). These results demonstrated that the hybrid of MIL-101(Cr) and MIL-53(Al) was a promising material for selective CO2 capture from natural and biogas.
| S-EPMC9064224 | biostudies-literature
Project description:The vast structural and chemical diversity of metal-organic frameworks (MOFs) provides the exciting possibility of material's design with tailored properties for gas separation, storage and catalysis. However, after more than twenty years after first reports introducing MOFs, the discovery and control of their synthesis remains extremely challenging due to the lack of understanding of mechanisms of their nucleation and growth. Progress in deciphering crystallization pathways depends on the possibility to follow conversion of initial reagents to products at the molecular level, which is a particular challenge under solvothermal conditions. The present work introduces a detailed molecular-level mechanism of the formation of MIL-53(Al), unraveled by combining in situ time-resolved high-resolution mass-spectrometry, magic angle spinning nuclear magnetic resonance spectroscopy and X-ray diffraction. In contrast to the general belief, the crystallization of MIL-53 occurs via a solid-solid transformation mechanism, associated with the spontaneous release of monomeric aluminum. The role of DMF hydrolysis products, formate and dimethylamine, is established. Our study emphasizes the complexity of MOF crystallization chemistry, which requires case-by-case investigation using a combination of advanced in situ methods for following the induction period, the nucleation and growth across the time domain.
| S-EPMC9243051 | biostudies-literature
Project description:The breathing behavior of the MIL-53(Cr) metal-organic framework (MOF) has been explored previously upon guest-adsorption and thermal and mechanical stimuli. Here, advanced molecular simulations based on the use of an accurate force field to describe the flexibility of this porous framework demonstrate that the application of an electrical field induces the structural switching of this MOF leading to a first-order transition and a volume change of more than 40%. This motivated us to electrically tune the pore size of MIL-53(Cr) with the idea to propose a new concept to selectively capture CO2 over CH4 via a molecular sieving that paves the way toward the optimization of current separation-based processes.
| S-EPMC5445524 | biostudies-literature
Project description:A promising hierarchical nanocomposite of MIL-53(Al)/ZnO was synthesized as a visible-light-driven photocatalyst to investigate the degradation of amoxicillin (AMX). MIL-53(Al)/ZnO ultrafine nanoparticles were obtained by preparing Zn-free MIL-53Al and employing it as a reactive template under hydrothermal and chemical conditions. The synthesized nanocomposite (MIL-53(Al)/ZnO) has a low content of Al > 1.5% with significantly different characterizations of the parent compounds elucidated by various analyses such as SEM, TEM, XRD, EDX, and UV-Vis. The effect of operational parameters (catalyst dose (0.2-1.0 g/L), solution pH (3-11), and initial AMX concentration (10-90 mg/L)) on the AMX removal efficiency was studied and optimized by the response surface methodology. A reasonable goodness-of-fit between the expected and experimental values was confirmed with correlation coefficient (R2) equal to 0.96. Under the optimal values, i.e., initial AMX concentration = 10 mg/L, solution pH ~ 4.5, and catalyst dose = 1.0 g/L, 100% AMX removal was achieved after reaction time = 60 min. The degradation mechanism and oxidation pathway were vigorously examined. The AMX degradation ratios slightly decreased after five consecutive cycles (from 78.19 to 62.05%), revealing the high reusability of MIL-53(Al)/ZnO. The AMX removal ratio was improved with enhancers in order ([Formula: see text]> H2O2 > S2O8-2). The results proved that 94.12 and 98.23% reduction of COD were obtained after 60 and 75 min, respectively. The amortization and operating costs were estimated at 3.3 $/m3 for a large-scale photocatalytic system.
| S-EPMC9508224 | biostudies-literature
Project description:Although metal-organic framework (MOF) photocatalysts have become ubiquitous, basic aspects of their photoredox mechanisms remain elusive. Nanosizing MOFs enables solution-state techniques to probe size-dependent properties and molecular reactivity, but few MOFs have been prepared as nanoparticles (nanoMOFs) with sufficiently small sizes. Here, we report a rapid reflux-based synthesis of the photoredox-active MOF Ti8O8(OH)4(terephthalate)6 (MIL-125) to achieve diameters below 30 nm in less than 2 hours. Whereas MOFs generally require ex situ analysis by solid-state techniques, sub-30 nm diameters ensure colloidal stability for weeks and minimal light scattering, permitting in situ analysis by solution-state methods. Optical absorption and photoluminescence spectra of free-standing colloids provide direct evidence that the photoredox chemistry of MIL-125 involves Ti3+ trapping and charge accumulation onto the Ti-oxo clusters. Solution-state potentiometry collected during the photochemical process also allows simultaneous measurement of MOF Fermi-level energies in situ. Finally, by leveraging the solution-processability of these nanoparticles, we demonstrate facile preparation of mixed-matrix membranes with high MOF loadings that retain the reversible photochromism. Taken together, these results demonstrate the feasibility of a rapid nanoMOF synthesis and fabrication of a photoactive membrane, and the fundamental insights they offer into heterogeneous photoredox chemistry.
| S-EPMC10445466 | biostudies-literature
Project description:MIL-53(Al) is a member of the most extensively studied metal-organic framework (MOF) families owing to its "flexible" framework and superior stability. 17 O solid-state NMR (SSNMR) spectroscopy is an ideal site-specific characterization tool as it probes local oxygen environments. Because oxygen local structure is often altered during phase change, 17 O SSNMR can be used to follow phase transitions. However, 17 O is a challenging nucleus to study via SSNMR due to its low sensitivity and resolution arising from the very low natural abundance of 17 O isotope and its quadrupolar nature. In this work, we describe that by using 17 O isotopic enrichment and performing 17 O SSNMR experiments at an ultrahigh magnetic field of 35.2 T, all chemically and crystallographically inequivalent oxygen sites in two representative MIL-53(Al) (as-made and water adsorbed) phases can be completely resolved. The number of signals in each phase is consistent with that predicted from the space group refined from powder X-ray diffraction data. The 17 O 1D magic-angle spinning (MAS) and 2D triple-quantum MAS (3QMAS) spectra at 35.2 T furnish fine information about the host-guest interactions and the structural changes associated with phase transition. The ability to completely resolve multiple chemically and crystallographically inequivalent oxygen sites in MOFs at very high magnetic field, as illustrated in this work, significantly enhances the potential for using the NMR crystallography approach to determine crystal structures of new MOFs and verify the structures of existing MOFs obtained from refining powder X-ray diffraction data.
| S-EPMC8192589 | biostudies-literature