Tackling antibiotic contaminations in wastewater with novel Modified-MOF nanostructures: A study of molecular simulations and DFT calculations.

The contamination of wastewater with antibiotics has emerged as a critical global challenge, with profound implications for environmental integrity and human well-being. Adsorption techniques have been meticulously investigated and developed to mitigate and alleviate their effects. In this study, we have investigated the adsorption behaviour of Erythromycin (ERY), Gentamicin (GEN), Levofloxacin (LEVO), and Metronidazole (MET) antibiotics as pharmaceutical contaminants (PHCs) on amide-functionalized (RC (=O)NH2)/MIL-53 (Al) (AMD/ML53A), using molecular simulations and density functional theory (DFT) calculations. Based on our DFT calculations, it becomes apparent that the adsorption tendencies of antibiotics are predominantly governed by the presence of AMD functional groups on the adsorbent surface. Specifically, hydrogen bonding (HB) and van der Waals (vdW) interactions between antibiotics and AMD groups serve as the primary mechanisms facilitating adsorption. Furthermore, we have observed that the adsorption behaviors of these antibiotics are influenced by their respective functional groups, molecular shapes, and sizes. Our molecular simulations delved into how the AMD/ML53A surfaces interact with antibiotics as PHCs. Moreover, various chemical quantum descriptors based on Frontier Molecular Orbitals (FMO) were explored to elucidate the extent of AMD/ML53A adsorption and to assess potential alterations in their electronic properties throughout the adsorption process. Monte Carlo simulation showed that ERY molecules adsorb stronger to the adsorbent in acidic and basic conditions than other contaminants, with high energies: -404.47 kcal/mol in acidic and -6375.26 kcal/mol in basic environments. Molecular dynamics (MD) simulations revealed parallel orientation for the ERY molecule's adsorption on AMD/ML53A with 80% rejection rate. In conclusion, our study highlighted the importance of modeling in developing practical solutions for removing antibiotics as PHCs from wastewater. The insights gained from our calculations can facilitate the design of more effective adsorption materials, ultimately leading to a more hygienic and sustainable ecosystem.

Enhanced Cataluminescence Sensor Based on SiO2/MIL-53(Al) for Detecting Isobutylaldehyde.

A simple, rapid, and reliable method for detecting harmful gases is urgently required in environmental security fields. In this study, a highly effective cataluminescence sensor based on SiO2/MIL-53(Al) composites was developed to detect trace isobutylaldehyde. The sensor was designed using isobutylaldehyde to generate an interesting cataluminescence phenomenon in SiO2/MIL-53(Al). Under optimized conditions, a positive linear relationship was observed between the signal intensity of the cataluminescence and isobutylaldehyde concentration. The isobutylaldehyde concentration range of 1.55-310 ppm responded well to the sensing test, with an excellent correlation coefficient of 0.9996. The minimum detectable concentration signal-to-noise ratio (S/N = 3) was found to be 0.49 ppm. In addition, the sensor was effectively utilized for analyzing trace isobutylaldehyde; the analysis resulted in recoveries ranging from 83.4% to 105%, with relative standard deviations (RSDs) of 4.8% to 9.4%. Furthermore, the mechanism of cataluminescence between SiO2/MIL-53(Al) and isobutylaldehyde was explored using GC-MS analysis and density functional theory. We expect that this cataluminescence methodology will provide an approach for the environmental monitoring of isobutylaldehyde.

A critical review on the synthesis of NH2-MIL-53(Al) based materials for detection and removal of hazardous pollutants.

Nowadays, emerging hazardous pollutants have caused many harmful effects on the environment and human health, calling for the state of the art methods for detection, qualification, and treatment. Metal-organic frameworks are porous, flexible, and versatile materials with unique structural properties, which can solve such problems. In this work, we reviewed the synthesis, activation, and characterization, and potential applications of NH2-MIL-53(Al). This material exhibited intriguing breathing effects, and obtained very high surface areas (182.3-1934 m2/g) with diverse morphologies. More importantly, NH2-MIL-53(Al) based materials could be used for the detection and removal of various toxic pollutants such as organic dyes, pharmaceuticals, herbicides, insecticides, phenols, heavy metals, and fluorides. We shed light on plausible adsorption mechanisms such as hydrogen bonds, π-π stacking interactions, and electrostatic interactions onto NH2-MIL-53(Al) adsorbents. Interestingly, NH2-MIL-53(Al) based adsorbents could be recycled for many cycles with high stability. This review also recommended that NH2-MIL-53(Al) based materials can be a good platform for the environmental remediation fields.

Facile synthesis of CoFe2O4@MIL-53(Al) nanocomposite for fast dye removal: Adsorption models, optimization and recyclability.

The global occurrence of textile dyes pollution has recently emerged, posing a serious threat to ecological systems. To abate dye contamination, we here developed a novel magnetic porous CoFe2O4@MIL-53(Al) nanocomposite by incorporating magnetic CoFe2O4 nanoparticles with MIL-53(Al) metal-organic framework. This nanocomposite possessed a surface area of 197.144 m2 g-1 and a pore volume of 0.413 cm3 g-1. The effect of contact time (5-120 min), concentration (5-50 mg L-1), dosage (0.1-1.0 g L-1), and pH (2-10) on Congo red adsorption was clarified. CoFe2O4@MIL-53(Al) could remove 95.85% of Cong red dye from water with an accelerated kinetic rate of 0.6544 min-1 within 10 min. The kinetic and isotherm models showed the predominance of Bangham and Temkin. According to Langmuir, the maximum uptake capacities of CoFe2O4@MIL-53(Al), CoFe2O4, and MIL-53(Al) adsorbents were 43.768, 17.982, and 15.295 mg g-1, respectively. CoFe2O4@MIL-53(Al) was selected to optimize Cong red treatment using Box-Behnken experimental design. The outcomes showed that CoFe2O4@MIL-53(Al) achieved the highest experimental uptake capacity of 35.919 mg g-1 at concentration (29.966 mg L-1), time (14.926 min), and dosage (0.486 g L-1). CoFe2O4@MIL-53(Al) could treat dye mixture (methylene blue, methyl orange, Congo red, malachite green, and crystal violet) with an outstanding removal efficiency of 81.24% for 30 min, and could be reused up to five cycles. Therefore, novel recyclable and stable CoFe2O4@MIL-53(Al) is recommended to integrate well with real dye treatments systems.

A membrane solid-phase extraction method based on MIL-53-mixed-matrix membrane for the determination of estrogens and parabens: Polyvinylidene difluoride membrane versus polystyrene-block-polybutadiene membrane.

In this work, MIL-53(Al), as an inorganic "filler" component, was embedded in polyvinylidene difluoride (PVDF) and polystyrene-block-polybutadiene (SBS) matrices to prepare two mixed-matrix membranes (MMMs), using a simpler method than that previously reported. The PVDF and SBS membranes retained much of the properties of PVDF, SBS, and native MIL-53(Al). The prepared MMMs were then placed in a vortex-stirred sample solution to develop a membrane solid-phase extraction method to extract estrogens and parabens, which were determined by high-performance liquid chromatography with fluorescence detection. The extraction efficiencies of the two membranes were compared, with the PVDF membrane exhibiting superior performance. In addition, the PVDF membrane was more freestanding and flexible, and its preparation method was also more facile and simple. The extraction conditions were optimized, and the analytical method showed low limits of detection (0.005-0.18 ng/mL), good linearity, and high accuracy, with recoveries ranging from 90.7% to 102.5%. As a result, this membrane solid-phase extraction method indicated its potential for application in aqueous sample pretreatment. For metal-organic framework-based MMM used in this method, in addition to being durable, freestanding, mechanically stable, and possessing a large area, it should also exhibit high metal-organic framework incorporation, good flexibility, and appropriate thickness and weight.

17 O solid-state NMR at ultrahigh magnetic field of 35.2 T: Resolution of inequivalent oxygen sites in different phases of MOF MIL-53(Al).

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.

MIL-53(Al)/Fe2O3 nanocomposite for solid-phase microextraction of organophosphorus pesticides followed by GC-MS analysis.

A novel aluminum terephthalate/Fe2O3 nanocomposite was synthesized by the addition of Fe2O3 nanoparticles into a reaction solution containing aluminum terephthalate MOF. The synthesized nanocomposite was successfully used as a fiber coating material for solid-phase microextraction (SPME) of six organophosphorus compounds (OPPs) from river water, grape juice, and tea samples. The effect of different parameters on the efficiency of SPME including desorption temperature and time, extraction temperature and time, salt concentration, pH, and agitation were thoroughly studied. The OPPs were detected and determined using GC-MS. According to the findings, a wide linear range (0.15-800 µg kg-1), low limit of detection (0.04-10 µg kg-1), and high recoveries from spiked samples (87.5-112%) were achieved with low inter-day relative standard deviation (3.2-6.7%, n = 5). The MIL-53(Al)/Fe2O3 nanocomposite showed  a high extraction ability towards OPPs, and hence, it can be considered a promising adsorbent for the extraction of various pesticides in complex matrices like tea and juice.Graphical abstract.

Immobilization of laccase onto meso-MIL-53(Al) via physical adsorption for the catalytic conversion of triclosan.

Due to the abundant binding sites and high stability, a synthesized meso-MIL-53(Al) was selected as the backbone and used for immobilizing laccase (Lac-MIL-53(Al)) to catalytically degrade of TCS. XRD, BET and FTIR analyses proved that the carboxyl groups on PTA of meso-MIL-53(Al) could provide sufficient adsorption sites for physically immobilizing laccase through hydrogen bonds and electrostatic interactions. Although the catalytic efficiency of Vmax/Km slightly decreased from 785 to 607 min-1 due to the mass transfer limitation upon immobilized, Lac-MIL-53(Al) showed high activity recovery (93.8%) and stability. The conformational analysis indicated the laccase could partially enter into the MOF by conformational changes without impairing laccase, although the laccase molecular (6.5 nm × 5.5 nm × 4.5 nm) was larger than the mesopore sizes of the MOF (4 nm). The kinetics indicated that Lac-MIL-53(Al) could remove 99.24% of TCS within 120 min due to the synergy effect of the adsorption of meso-MIL-53(Al) and catalytic degradation of laccase. Meanwhile, Lac-MIL-53(Al) could remain approximately 60% of activity for up to 8 times reuse without desorption. The GC/MS and LC/MS/MS analyses further confirmed that TCS could be transformed to 2, 4-DCP by laccase via the breakage of the ether bond, or to passivated dimers, trimers and tetramers by the self-coupling and oxidization of the phenoxyl radicals, and finally removed by precipitation. In summary, enzyme-MOF composite might be a potential strategy to control the micropollutants in the wastewater.

Amine-functionalized MIL-53(Al)-coated stainless steel fiber for efficient solid-phase microextraction of synthetic musks and organochlorine pesticides in water samples.

The fiber coating is the key part of the solid-phase microextraction (SPME) technique, and it determines the sensitivity, selectivity, and repeatability of the analytical method. In this work, amine (NH2)-functionalized material of Institute Lavoisier (MIL)-53(Al) nanoparticles were successfully synthesized, characterized, and applied as the SPME fiber coating for efficient sample pretreatment owing to their unique structures and excellent adsorption properties. Under optimized conditions, the NH2-MIL-53(Al)-coated fiber showed good precision, low limits of detection (LODs) [0.025-0.83 ng L-1 for synthetic musks (SMs) and 0.051-0.97 ng L-1 for organochlorine pesticides (OCPs)], and good linearity. Experimental results showed that the NH2-MIL-53(Al) SPME coating was solvent resistant and thermostable. In addition, the extraction efficiencies of the NH2-MIL-53(Al) coating for SMs and OCPs were higher than those of commercially available SPME fiber coatings such as polydimethylsiloxane, polydimethylsiloxane-divinylbenzene, and polyacrylate. The reasons may be that the analytes are adsorbed on NH2-MIL-53(Al) primarily through π-π interactions, electron donor-electron acceptor interactions, and hydrogen bonds between the analytes and organic linkers of the material. Direct immersion (DI) SPME-gas chromatography-mass spectrometry methods based on NH2-MIL-53(Al) were successfully applied for the analysis of tap and river water samples. The recoveries were 80.3-115% for SMs and 77.4-117% for OCPs. These results indicate that the NH2-MIL-53(Al) coating may be a promising alternative to SPME coatings for the enrichment of SMs and OCPs.

Metal Organic Framework Crystals in Mixed-Matrix Membranes: Impact of the Filler Morphology on the Gas Separation Performance.

Mixed-matrix membranes (MMMs) comprising NH2-MIL-53(Al) and Matrimid® or 6FDA-DAM have been investigated. The MOF loading has been varied between 5 and 20 wt%, while NH2-MIL-53(Al) with three different morphologies: nanoparticles, nanorods and microneedles have been dispersed in Matrimid®. The synthesized membranes have been tested in the separation of CO2 from CH4 in an equimolar mixture. At 3 bar and 298 K for 8 wt% MOF loading, incorporation of NH2-MIL-53(Al) nanoparticles leads to the largest improvement compared to nanorods and microneedles. The incorporation of the best performing filler, i.e. NH2-MIL-53(Al) nanoparticles, to the highly permeable 6FDA-DAM has a larger effect, and the CO2 permeability increased up to 85 % with slightly lower selectivities for 20 wt% MOF loading. Specifically, these membranes have a permeability of 660 Barrer with CO2/CH4 separation factor of 28, leading to a performance very close to the Robeson limit of 2008. Furthermore, a new non-destructive technique based on Raman spectroscopy mapping is introduced to assess the homogeneity of the filler dispersion in the polymer matrix. The MOF contribution can be calculated by modelling the spectra. The determined homogeneity of the MOF filler distribution in the polymer is confirmed by FIB-SEM analysis.

Stimuli-responsive photoluminescent and structural properties of MIL-53(Al) MOF for sensing applications.

Metal-organic frameworks (MOFs) are an intriguing group of porous materials due to their potential influence on the development of indispensable technologies like luminescent sensors and solid-state light devices, luminescent multifunctional nanomaterials. In this research work we explored MIL-53(Al), an exceptional class of MOF that, along with guest adsorption, undergoes structural transitions exhibiting breathing behavior between narrow pore and large pore under temperature and mechanical stress. Therefore, we opted for the time resolved luminescence and FT-Raman spectroscopy to investigate the mechanochromic and thermochromic response of this material under external stimuli. Intriguingly, when subjected to temperature changes, MIL-53(Al) exhibited a ratiometric fluorescence behavior related to the reversible relationship of photoluminescence emission intensity with respect to temperature. Moreover, under higher mechanical stress MIL-53(Al) displayed turn-on behavior in emission intensity, hence offering a thrilling avenue for the application in mechanically deformed-based luminescent sensors and ratiometric fluorescence temperature sensors.

Upcycling of post-consumer polyethylene terephthalate bottles into aluminum-based metal-organic framework adsorbents for efficient orthophosphate removal.

2-Phosphonobutane-1,2,4,-tricarboxylic acid (PBTC) is an orthophosphate compound widely used as an antiscalant chemical and corrosion inhibitor in manufacturing. However, PBTC poses persistent environmental concerns due to its stability and resistance to conventional water treatment. In addressing the issues of PBTC in aquatic systems, Al-based metal-organic frameworks (MOFs) have been developed and applied as sustainable adsorbents. The materials are synthesized from terephthalic acid (TPA) linkers derived from upcycling products of post-consumer polyethylene terephthalate (PET) bottles. The PET-derived linker was prepared using alkaline hydrolysis followed by acidification and employed in forming MIL-53 (Al), with a comparative assessment against the corresponding MOFs made from commercial-grade TPA. The structures and properties of the materials were characterized with microscopic and spectroscopic methods. The synthesized adsorbents achieved a phosphate adsorption capacity of 826 mg/g at pH 5, with kinetics fitting a pseudo-second-order model and isotherm patterns aligning with Langmuir, Freundlich, and Sips models, indicative of diverse adsorption on heterogeneous surfaces. The results highlight the role of electrostatic interactions and hydrogen bonding mechanisms in PBTC adsorption. The eco-friendly materials with high adsorption performance offer an innovative route for sustainable waste management and water purification.

Adsorption studies of tetracycline hydrochloride and diclofenac sodium on NH2-MIL-53(Al/Zr) sodium alginate gel spheres.

Metal-organic frameworks are emerging inorganic-organic hybrid materials that can be self-assembled from metal ions and organic ligands via coordination bonds. These materials possess large specific surface area, tunable pore structure, abundant active center, diversity of functional groups as well as high mechanical and thermal stability which promote their applications in adsorption and catalysis studies. In this study, NH2-MIL-53(Al/Zr) was prepared and embedded into sodium alginate gel spheres (NH2-MIL-53(Al/Zr)-SA) and its adsorption properties towards TC and DCF in solution were investigated. According to XRD and FTIR analysis, the structure of the raw material was not changed after making the gel spheres. The maximum adsorption towards TC (pH =3) and DCF (pH =5) reached 98.5 mg·g-1 and 192 mg·g-1, respectively. The process was consistent with Langmuir and Freundlich, suggesting that there was both monolayer and multilayer adsorption which infers the presence of physical adsorption (intra-particle diffusion) and non-homogeneous chemical adsorption. The thermodynamic parameters showed that the adsorption process was a spontaneous entropy increasing reaction. The regeneration rate of spent NH2-MIL-53(Al/Zr)-SA could still reach 99.1 % after three cycles, indicating good regeneration performance. This study can provide a basis for the application of NH2-MIL-53(Al/Zr)-SA in wastewater treatment.

Effect of pyrolysis temperature on characteristics and chloramphenicol adsorption performance of NH2-MIL-53(Al)-derived amine-functionalized porous carbons.

Several activities such as aquaculture, human and feedstock therapies can directly release antibiotics into water. Due to high stability, low hydrolysis and non-biodegradation, they can accumulate in the aqueous environment and transport to aquatic species. Here, we synthesized amine-functionalized porous carbons (ANC) by a direct-pyrolysis process of NH2-MIL-53(Al) as a sacrificial template at between 600 and 900 °C and utilized them to eliminate chloramphenicol antibiotic from water. The NH2-MIL-53(Al)-derived porous carbons obtained high surface areas (304.7-1600 m2 g-1) and chloramphenicol adsorption capacities (148.3-261.5 mg g-1). Several factors such as hydrogen bonding, Yoshida hydrogen bonding, and π-π interaction, hydrophobic interaction possibly controlled adsorption mechanisms. The ANC800 could be reused four cycles along with high stability in structure. As a result, NH2-MIL-53(Al)-derived porous carbons are recommended as recyclable and efficient adsorbents to the treatment of antibiotics in water.

Unveiling the MIL-53(Al) MOF: Tuning Photoluminescence and Structural Properties via Volatile Organic Compounds Interactions.

MIL-53(Al) is a metal-organic framework (MOF) with unique properties, including structural flexibility, thermal stability, and luminescence. Its ability to adsorb volatile organic compounds (VOCs) and water vapor makes it a promising platform for sensing applications. This study investigated the adsorption mechanism of MIL-53(Al) with different VOCs, including ketones, alcohols, aromatics, and water molecules, focusing on structural transformations due to pore size variation and photoluminescence properties. The reported results assess MIL-53(Al) selectivity towards different VOCs and provide insights into their fundamental properties and potential applications in sensing.

Metal-organic frame material encapsulated Rhodamine 6G: A highly sensitive fluorescence sensing platform for the detection of picric acid contaminants in water.

As a water pollutant with excellent solubility, 2,4,6-trinitrophenol (also known as picric acid, PA) poses a potential threat to the natural environment and human health, so it is crucial important to detect PA in water. In this study, a novel composite material (MIL-53(Al)@R6G) was successfully synthesized by encapsulating Rhodamine 6G into a metal-organic frame material, which was used for fluorescence detection of picric acid (PA) in water. The composite exhibits bright yellow fluorescence emission with a fluorescence quantum yield of 58.23 %. In the process of PA detection, the composite has excellent selectivity and anti-interference performance, and PA can significantly quench the fluorescence intensity of MIL-53(Al)@R6G. MIL-53(Al)@R6G has the advantages of fast detection time (20 s), wide linear range (1-100 µM) and low detection limit (4.8 nM). In addition, MIL-53(Al)@R6G has demonstrated its potential for the detection of PA in environmental water samples with satisfactory results.

Composite poly(ethylene oxide)-based solid electrolyte with consecutive and fast ion transport channels constructed by upper-dimensional MIL-53(Al) nanofibers.

Novel structural designs for metal organic frameworks (MOFs) are expected to improve ion-transport behavior in composite solid electrolytes. Herein, upper-dimensional MIL-53(Al) nanofibers (MNFs, MIL-53 belongs to the MIL (Material Institute Lavoisier) group) with flower-like nanoflake structures have been designed and constructed via modified hydrothermal coordination. The optimized MNFs with high surface area and porosity can form abundant interfaces with poly(ethylene oxide) (PEO) matrix. The plasticization of MNFs to the PEO matrix will facilitate segmental movement of PEO chains to facilitate Li+ conduction. The unsaturated open metal centers of MNFs can effectively capture bis(trifluoromethanesulfonyl)imide anions (TFSI-) to deliver more free lithium ions for transfer. Moreover, the upper-dimensional nanofiber structure endows lithium ions with a long-range and consecutive transport pathway. The obtained composite solid electrolyte (MNFs@PEO) presents a high ionic conductivity of 4.1 × 10-4 S cm-1 and a great Li+ transference number of 0.4 at 60 °C. The electrolyte also exhibits a stable Li plating/stripping behavior over 1000 h at 0.1 mA cm-1 with inhibited Li dendrite growth. Furthermore, the Li/LiFePO4 and Li/LiNi0.8Mn0.1Co0.1O2 batteries with MNFs@PEO as electrolytes both display great cycling stabilities with high-capacity retention, indicating their potential applications in lithium metal batteries. The study will put forward new inspirations for designing advanced MOF-based composite solid electrolytes.

Dispersive micro-solid phase extraction based on two MOFs as highly effective adsorbents for analysis of nilotinib in plasma and wastewater.

BACKGROUND: Nilotinib (NIL) is a prescription medication employed in the treatment of specific types of leukemia, namely chronic myelogenous leukemia (CML). The determination of NIL levels in patients undergoing treatment for CML is of paramount importance for effective management of treatment and toxicity. Also, monitoring and controlling its level in wastewater sources could help scientists to identify potential hotspots of contamination and take appropriate measures to mitigate their impact on the environment and public health. OBJECTIVES: This study presents a D-µ-SPE technique utilizing two MOFs as adsorbents for the efficient detection of nilotinib in plasma and wastewater samples for the first time. METHODS: Two highly effective MOFs, MIL-101(Fe) and MIL-53(Al), were synthesized and applied as dispersive micro-solid phase extraction (D-µ-SPE) adsorbents for the extraction of nilotinib coupled with HPLC-UV in a short time of analysis. Experimental parameters affecting extraction efficacy such as adsorbent amount, ionic strength, pH value, adsorption-desorption time and type of elution solvent, were optimized. RESULTS: Under optimal experimental conditions, the linear dynamic was achieved in the range of 0.25-5.00 µg/mL in human plasma and 0.01-0.20 µg/mL in wastewater. The extraction recovery was in the range of 89.18-91.53% and 94.39-99.60% for nilotinib and MIL-101(Fe) and also 91.22-97.35% and 98.14-100.78% for nilotinib and MIL-53(Al) from human plasma and wastewater respectively. CONCLUSION: HPLC-UV determination of nilotinib after the D-µ-SPE method showed acceptable accuracy and precision in both plasma and wastewater. In comparison between the two adsorbents, the extraction procedure was easier and faster with MIL-53(Al) as the adsorbent.

Application of a novel hybrid MIL-53(Al)@rice husk for the adsorption of glyphosate in water: Characteristics and mechanism of the process.

The development of new materials that have a high capacity to remove pollutants in water-based media is becoming increasingly important because of the serious contamination of water and the negative impact on biodiversity and public health. The presence of glyphosate in water, the most widely used herbicide worldwide, has triggered alerts owing to the collateral effects it may cause on human health. The main objective of the present study was to investigate the potential of the hybrid material MIL-53(Al)@RH for the adsorption of glyphosate in aqueous solution. The material was obtained following the methodology of MIL-53(Al) synthesis in the presence of hydrolyzed rice husk assisted by microwave. Batch adsorption experiments were carried out to evaluate the adsorbent dosage, pH0 solution effect, contact time, adsorbate concentration, and temperature effect. The results demonstrated that a maximum adsorption capacity of 296.95 mg g-1, at pH0 4 with a ratio of 0.04 g MIL-53(Al)@RH/50 mL of solution, was achieved in 30 min. The Avrami and pseudo-second order models appropriately described the adsorption kinetics and the equilibrium by Langmuir and Sips models. The enthalpy changes (ΔH°) determined propose an endothermic reaction governed by chemisorption, corroborating the kinetic and equilibrium settings. Hydrogen bonds, π*-π interactions, and complexation between the metal centers of MIL-53(Al) and the anionic groups of glyphosate were postulated to be involved as adsorption mechanisms. Finally, for practical application, MIL-53(Al)@RH was packed in a column for a fixed-bed test which revealed that the hybrid can remove glyphosate with an adsorption capacity of 76.304 mg L-1, utilizing 90% of the bed.

MIL-53(Al) assisted in upcycling plastic bottle waste into nitrogen-doped hierarchical porous carbon for high-performance supercapacitors.

Disposable aluminum cans and plastic bottles are common wastes found in modern societies. This article shows that they can be upcycled into functional materials, such as metal-organic frameworks and hierarchical porous carbon nanomaterials for high-value applications. Through a solvothermal method, used poly(ethylene terephthalate) bottles and aluminum cans are converted into MIL-53(Al). Subsequently, the as-prepared MIL-53(Al) can be further carbonized into a nitrogen-doped (4.52 at%) hierarchical porous carbon framework. With an optical amount of urea present during the carbonization process, the carbon nanomaterial of a high specific surface area of 1324 m2 g-1 with well-defined porosity can be achieved. These features allow the nitrogen-doped hierarchical porous carbon to perform impressively as the working electrode of supercapacitors, delivering a high specific capacitance of 355 F g-1 at 0.5 A g-1 in a three-electrode cell and exhibiting a high energy density of 20.1 Wh kg-1 at a power density of 225 W kg-1, while simultaneously maintaining 88.2% capacitance retention over 10,000 cycles in two-electrode system. This work demonstrates the possibility of upcycling wastes to obtain carbon-based high-performance supercapacitors.