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Efficient separation of CH4 from N2 is essential for the purification of methane from nitrogen. In order to address this problem, composite materials consisting of rod-shaped SBA-15-based UiO-66-Br2 were synthesized for the purpose of separating a CH4/N2 mixture. The materials were characterized via PXRD, N2 adsorption–desorption, SEM, TEM, FT-IR, and TGA. The adsorption isotherms of CH4 and N2 under standard pressure conditions for the composites were determined and subsequently compared. The study revealed that the composites were formed through the growth of MOF nanocrystals on the surfaces of the SBA-15 matrix. The enhancements in surface area and adsorption capacity of hybrid materials were attributed to the structural modifications resulting from the interactions between surface silanol groups and metal centers. The selectivity of the composites towards a gas mixture of CH4 and N2 was assessed utilizing the Langmuir adsorption equation. The results of the analysis revealed that the U6B2S5/SBA-15 sample exhibited the greatest selectivity for CH4/N2 adsorption compared to the other samples, with an adsorption selectivity parameter (S) of 20.06. Additional research is necessary to enhance the enrichment of methane from CH4/N2 mixtures using SBA-15-based metal-organic framework materials. [ABSTRACT FROM AUTHOR]

JUK-8 ([Zn(oba)(pip)]n, oba2– = 4,4′-oxybis(benzenedicarboxylate), pip = 4-pyridyl-functionalized benzene-1,3-dicarbohydrazide) is a hydrolytically stable flexible metal-organic framework. Owing to its unusual adsorptive properties, JUK-8 can be considered as a promising sensing material for construction of detectors of volatile organic compounds (VOCs) in air. Quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA) is a versatile method dedicated to characterization of porous materials. In this work, QE-TPDA was employed to study co-adsorption of water and selected alcohols in JUK-8. For the first time an infrared detector sensitive to organic compounds was used in the QE-TPDA measurements, allowing the study of the influence of water vapor on sorption of VOCs. The QE-TPDA profiles of the studied alcohols, exhibiting two desorption maxima and two adsorption minima, are consistent with the standard sorption isotherms, revealing a two-step adsorption–desorption mechanism. The profiles recorded in the presence of water are noticeably changed in different ways for different alcohols. While at low relative humidity (RH) (ca. 20%) the low temperature adsorption states of ethanol and 1-propanol were only slightly destabilized, for 2-propanol almost complete suppression of adsorption was observed. The results found for moderate RH levels (ca. 50%) indicated that the opening of the JUK-8 structure, responsible for its breathing behavior, was followed by the filling of the just generated pores with a water–alcohol mixture. [ABSTRACT FROM AUTHOR]

Chemotherapy is one of the most commonly used methods for treating cancer, but its side effects severely limit its application and impair treatment effectiveness. Removing off-target chemotherapy drugs from the serum promptly through adsorption is the most direct approach to minimize their side effects. In this study, we synthesized a series of adsorption materials to remove the chemotherapy drug doxorubicin by modifying MOF nanosheets with sulfonated azocalix[4]arenes. The strong affinity of sulfonated azocalix[4]arenes for doxorubicin results in high adsorption strength (Langmuir adsorption constant = 2.45–5.73 L mg−1) and more complete removal of the drug. The extensive external surface area of the 2D nanosheets facilitates the exposure of a large number of accessible adsorption sites, which capture DOX molecules without internal diffusion, leading to a high adsorption rate (pseudo-second-order rate constant = 0.0058–0.0065 g mg−1 min−1). These adsorbents perform effectively in physiological environments and exhibit low cytotoxicity and good hemocompatibility. These features make them suitable for removing doxorubicin from serum during "drug capture" procedures. The optimal adsorbent can remove 91% of the clinical concentration of doxorubicin within 5 min. [ABSTRACT FROM AUTHOR]

A series of NH2-functionalized nano-sized magnetic metal–organic frameworks (MOFs) were prepared in this study for Cr(VI) removal from wastewater. It was observed that not only the morphological, i.e., orientation growth of N-doped and iron-based metal–organic frameworks, but also the adsorption of magnetic MOFs is largely related to the used amount of ammonium hydroxide in preparation. For example, with increasing amounts of ammonium hydroxide used in preparation, the morphology of magnetic MOFs changed from spherical to cube and triangular cone. Moreover, the maximum adsorption capacity of spherical-magnetic MOFs, cubic-magnetic MOFs and triangular cone-magnetic MOFs could be up to 204.08 mg/g, 232.56 mg/g and 270.27 mg/g, respectively. Under optimal conditions, the adsorption process of magnetic MOFs for Cr(VI) was consistent with the pseudo-second-order rate equation (R2 = 1) and Langmuir isotherm model (R2 > 0.99). Therefore, magnetic MOFs developed in this work offered a viable option for the removal of Cr(VI) from wastewater. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) are regarded as excellent carriers for immobilized enzymes due to their substantial specific surface area, high porosity, and easily tunable pore size. Nevertheless, the use of UIO−66 material is significantly limited in immobilized enzymes due to the absence of active functional groups on its surface. This study comprised the synthesis of UIO−66 and subsequent modification of the proline (Pro) on UIO−66 through post-synthetic modification. UIO−66 and UIO−66/Pro crystals were employed as matrices to immobilize Rhizopus oryzae lipase (ROL). The contact angle demonstrated that the introduction of Pro onto UIO−66 resulted in favorable conformational changes in the structure of ROL. The immobilized enzyme ROL@UIO−66/Pro, produced via the covalent-bonding method, exhibited greater activity (0.064715 U/mg (about 1.73 times that of the free enzyme)) and stability in the ester hydrolysis reaction. The immobilized enzymes ROL@UIO−66 (131.193 mM) and ROL@UIO−66/Pro (121.367 mM), which were synthesized using the covalent-bonding approach, exhibited a lower Km and higher substrate affinity compared to the immobilized enzyme ROL@UIO−66/Pro (24.033 mM) produced via the adsorption method. This lays a solid foundation for the industrialization of immobilized enzymes. [ABSTRACT FROM AUTHOR]

Several types of pollutants have acute adverse effects on living bodies, and the effective removal of these pollutants remains a challenge. Safranin O (a biological dye) and merbromin (a topical mercury-containing antiseptic) are considered organic pollutants, and there are only a few reports on their removal. Synthesized and well-characterized (through PXRD, FTIR, FESEM, and EDS analysis) MOF-5 was used for the first time in the removal of safranin O and merbromin from simulated wastewater and real wastewater. In both cases, MOF-5 effectively removed contaminants. We found that in simulated wastewater, the highest efficiency of removal of safranin O was 53.27% (for 15 mg/L) at pH 10, and for merbromin, it was 41.49% (for 25 mg/L) at pH 6. In the case of real wastewater containing natural ions (Na+, K+, F−, Cl−, SO42−, PO43−, Mg2+, and Ca2+) and other molecules, the removal efficiencies of these two dyes decreased (34.00% and 26.28% for safranin O and merbromin, respectively) because of the presence of other ions and molecules. A plausible mechanism for the removal of these pollutants using MOF-5 was proposed. [ABSTRACT FROM AUTHOR]

The shape and topology of pores have significant impacts on the gas storage properties of nanoporous materials. Metal–organic frameworks (MOFs) are ideal materials with which to tailor to the needs of specific applications, due to properties such as their tunable structure and high specific surface area. It is, therefore, particularly important to develop descriptors that accurately identify the topological features of MOF pores. In this work, a topological data analysis method was used to develop a topological descriptor, based on the pore topology, which was combined with the Extreme Gradient Boosting (XGBoost) algorithm to predict the adsorption performance of MOFs for methane/ethane/propane. The final results show that this descriptor can accurately predict the performance of MOFs, and the introduction of the topological descriptor also significantly improves the accuracy of the model, resulting in an increase of up to 17.55% in the R2 value of the model and a decrease of up to 46.1% in the RMSE, compared to commonly used models that are based on the structural descriptor. The results of this study contribute to a deeper understanding of the relationship between the performance and structure of MOFs and provide useful guidelines and strategies for the design of high-performance separation materials. [ABSTRACT FROM AUTHOR]

In this study, we designed a platform based on a laser-driven approach for fast, efficient, and controllable MOF synthesis. The laser irradiation method was performed for the first time to synthesize Zn-based MOFs in record production time (approximately one hour) compared to all known MOF production methods with comparable morphology. In addition to well-known structural properties, we revealed that the obtained ZnMOFs have a novel optical response, including photoluminescence behavior in the visible range with nanosecond relaxation time, which is also supported by first-principles calculations. Additionally, photocatalytic degradation of methylene blue with ZnMOF was achieved, degrading the 10 ppm methylene blue (MB) solution 83% during 1 min of irradiation time. The application of laser technology can inspire the development of a novel and competent platform for a fast MOF fabrication process and extend the possible applications of MOFs to miniaturized optoelectronic and photonic devices. [ABSTRACT FROM AUTHOR]

The employment of metal-organic frameworks in powder form is undesirable from an industrial perspective due to process and safety issues. This work is devoted to evaluating the impact of compression on the textural and structural properties of CPO-27(Ni). For this purpose, CPO-27(Ni) was synthesized under hydrosolvothermal conditions and characterized. Then, the resulting powder was compressed into binderless pellets using variable compression forces ranging from 5–90 kN (37–678 MPa) and characterized by means of nitrogen adsorption/desorption, thermogravimetric analysis and powder X-ray diffraction to evaluate textural, thermal and structural changes. Both textural and structural properties decreased with increasing compression force. Thermal stability was impacted in pellets compressed at forces over 70 kN. CPO-27(Ni) pelletized at 5, 8 and 10 kN, and retained more than 94% of its initial textural properties, while a loss of about one-third of the textural property was observed for the two most compressed samples (70 and 90 kN) compared to the starting powder. [ABSTRACT FROM AUTHOR]

In this paper, the reported MOF ([Co(bimip)(H2O)0.5]·0.5H2O) was employed in photocatalytic CO2 reduction, antibacterial, and dye adsorption experiments. The photocatalytic activity of the MOF for CO2 reduction was systematically investigated. The high average CO generation rate of 3421.59 μmol·g−1·h−1 after 12 h confirms the efficient photocatalytic CO2 reduction ability of the MOF. At the same time, the MOF can completely inhibit the growth of S. aureus and C. albicans within 24 h when its concentration reaches 400 μg/mL and 500 μg/mL, respectively. The MOF has an adsorption capacity for CR. The adsorption rate was 83.42% at 60 min, and the adsorption capacity of the MOF for CR reached 500.00 mg·g−1. [ABSTRACT FROM AUTHOR]

Fluoride is present in several groundwaters due to natural or anthropogenic origins. Although it is necessary for physiological human functions (in small amounts, i.e., 0.5–1.2 mg/L), it could be very harmful when it exceeds the maximum permissible concentration limit of 1.5 mg/L (according to WHO). Among the numerous technologies for removing fluoride from waters, metal–organic framework (MOF) materials are considered to be promising adsorbents due to their advantages of high porosity, high specific surface area, diverse functions and easy modification. In this study, the synthesis of MOFs and the progress of their application to the removal of fluoride from contaminated water, as published in the recent literature mainly over the past five years, are reviewed. The adsorption mechanism(s) and its main characteristics, such as effect of initial fluoride concentration, adsorbent dosage, solution pH, contact time, adsorption capacity, thermodynamic and regeneration studies, etc., for the removal of fluoride with the addition of different MOFs are compared. According to these comparisons, the hydrothermal/solvothermal synthesis method is most commonly used for the preparation of MOFs, whereas higher BET surface areas are shown by specific MOFs based on aluminum metal ions. The main fluoride adsorption mechanisms were found to be electrostatic attraction and/or complexation. The most common pH for conducting experiments was 7.0, but several examined materials were found to be effective over a wide pH range. Four to six regeneration cycles were successfully applied on average, regarding the MOFs under review, whereas in the majority of these cases, the sorption process was found to be endothermic. [ABSTRACT FROM AUTHOR]

The binary metal organic framework (MOF) is composed of two heterometallic ions bonded to an organic ligand. Compared with monometallic MOFs, bimetallic MOFs have greatly improved in terms of structure, porosity, active site, adsorption, selectivity, and stability, which has attracted wide attention. At present, many effective strategies have been designed for the synthesis of bimetallic MOF-based nanomaterials with specific morphology, structure, and function. The results show that bimetallic MOF-based nanocomposites could achieve multiple synergistic effects, which will greatly improve their research in the fields of adsorption, catalysis, energy storage, sensing, and so on. In this review, the main preparation methods of bimetallic MOFs-based materials are summarized, with emphasis on their applications in adsorption, catalysis, and detection of target pollutants in water environments, and perspectives on the future development of bimetallic MOFs-based nanomaterials in the field of water are presented. [ABSTRACT FROM AUTHOR]

The recovery of precious metals from secondary resources is significant economically and environmentally. However, their separation is still challenging because they often occur in complex metal ion mixtures. The poor selectivity of adsorbents for gold in complicated solutions prevents further application of adsorption technology. In this study, a Zr-based MOF adsorbent, MIL-161, was synthesized using s-tetrazine dicarboxylic acid (H2STz) as an organic ligand. MIL-161 demonstrated a high adsorption capacity of up to 446.49 mg/g and outstanding selectivity for gold(III) in a simulated electronic waste solution as a result of the presence of sulfur- and nitrogen-containing groups. In addition, the MIL-161 adsorbents were characterized using Fourier transform infrared (FT-IR), field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TG), Brunner–Emment–Teller (BET), and X-ray photoelectron spectroscopy (XPS). Additionally, the adsorption kinetics, isotherms, and thermodynamics of the MOF adsorbents were also thoroughly examined. More importantly, the experimental results and DFT calculations indicate that chelation and electrostatic interactions are the main adsorption mechanisms. [ABSTRACT FROM AUTHOR]

With the growing population, industrialization, and agriculture, water contamination not only affects people but entire ecosystems. Metal–organic frameworks (MOFs), because of their large surface area and porosity, show great potential as adsorbents for removing pollutants, such as heavy metals, from contaminated water. The current research aims at examining copper (II) benzene-1,3,5-tricarboxylate (Cu-BTC) MOFs and understanding the mechanism for their adsorption of Pb(II) from aqueous solution. The Cu-BTC samples were characterized using FTIR and XRD, and their surface area and porosity were determined based on N2 adsorption isotherms. The concentration of Pb(II) in the solutions was measured using atomic absorption spectroscopy (AAS). Both kinetic and equilibrium adsorption data were collected and then analyzed using numerical models. The analyses led to the findings that the limiting steps in the adsorption of Pb(II) on Cu-BTC are (a) pore diffusion of Pb(II) and (b) the availability of the active sites on Cu-BTC MOFs. It was further revealed that the former step is more dominant in the adsorption of Pb(II) when the lead concentration is low. The latter step, which is directly proportional to the surface areas of the MOFs, affects the adsorption to a greater extent when the lead concentration is high. The results also show that adsorption of Pb(II) ions on Cu-BTC is mainly a multi-layer heterogeneous process. [ABSTRACT FROM AUTHOR]

This research presents the results of the immobilization of Candida Antarctica Lipase B (CALB) on MOF-199 and ZIF-8 and its use in the production of biodiesel through the transesterification reaction using African Palm Oil (APO). The results show that the highest adsorption capacity, the 26.9 mg·g−1 Lipase, was achieved using ZIF-8 at 45 °C and an initial protein concentration of 1.20 mg·mL−1. The results obtained for the adsorption equilibrium studies allow us to infer that CALB was physically adsorbed on ZIF-8 while chemically adsorbed with MOF-199. It was determined that the adsorption between Lipase and the MOFs under study better fit the Sips isotherm model. The results of the kinetic studies show that adsorption kinetics follow the Elovich model for the two synthesized biocatalysts. This research shows that under the experimental conditions in which the studies were carried out, the adsorption processes are a function of the intraparticle and film diffusion models. According to the results, the prepared biocatalysts showed a high efficiency in the transesterification reaction to produce biodiesel, with methanol as a co-solvent medium. In this work, the catalytic studies for the imidazolate, ZIF-8, presented more catalytic activity when used with CALB. This system presented 95% biodiesel conversion, while the biocatalyst formed by MOF-199 and CALB generated a catalytic conversion percentage of 90%. Although both percentages are high, it should be noted that CALB-MOF-199 presented better reusability, which is due to chemical interactions. [ABSTRACT FROM AUTHOR]

Ligands with a purely aliphatic backbone are receiving rising attention in the chemistry of coordination polymers and metal–organic frameworks. Such unique features inherent to the aliphatic bridges as increased conformational freedom, non-polarizable core, and low light absorption provide rare and valuable properties for their derived MOFs. Applications of such compounds in stimuli–responsive materials, gas, and vapor adsorbents with high and unusual selectivity, light-emitting, and optical materials have extensively emerged in recent years. These properties, as well as other specific features of aliphatic-based metal–organic frameworks are summarized and analyzed in this short critical review. Advanced characterization techniques, which have been applied in the reported works to obtain important data on the crystal and molecular structures, dynamics, and functionalities, are also reviewed within a general discussion. In total, 132 references are included. [ABSTRACT FROM AUTHOR]

This work studies the use of Fe/Ni-MOFs for the removal of ciprofloxacin (CIP) in wastewater. Fe/Ni-MOFs are prepared by the solvothermal method and characterized by X-ray diffraction (XRD), a scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), and a thermal gravimetric analyzer (TG). Under the conditions of the concentration of 50 ppm, a mass of 30 mg, and a temperature of 30 °C, the maximum adsorption capacity of ciprofloxacin removal within 5 h was 232.1 mg/g. The maximum removal rate was 94.8% when 40 mg of the Fe/Ni-MOFs was added to the solution of 10 ppm ciprofloxacin. According to the pseudo-second-order (PSO) kinetic model, the R2 values were all greater than 0.99, which proved that the adsorption theory of ciprofloxacin by Fe/Ni-MOFs was consistent with the practice. The adsorption results were mainly affected by solution pH and static electricity, as well as other factors. The Freundlich isotherm model characterized the adsorption of ciprofloxacin by Fe/Ni-MOFs as multilayer adsorption. The above results indicated that Fe/Ni-MOFs were effective in the practical application of ciprofloxacin removal. [ABSTRACT FROM AUTHOR]

Greenhouses with efficient controlled environment offer a promising solution for food security against the impacts of increasing global temperatures and growing water scarcity. However, current technologies used to achieve this controlled environment consume a significant amount of energy, which impacts on operational costs and CO2 emissions. Using advanced metal organic framework materials (MOFs) with superior water adsorption characteristics, this work investigates the development of a new technology for a greenhouse-controlled environment. The system consists of MOF coated heat exchanger, air to air heat exchanger, and evaporative cooler. A three-dimensional computational fluid dynamics (CFD) model was developed using COMSOL software and experimentally validated for the MOF-801/Graphene coated heat exchanger (DCHE) to determine the best cycle time and power input. It was found that using desorption time of 16 min and power input of 1.26 W, the maximum water removal rate was obtained from MOF-801/Graphene of 274.4 g/kgMOF/W.hr. In addition, an overall mathematical model for the greenhouse climate control was developed and used to investigate the effects of air humidity and velocity on the input air conditions to the greenhouse. Results showed that with high relative humidity levels of 90% in the greenhouse can be conditioned to reach the required relative humidity of 50%. [ABSTRACT FROM AUTHOR]

The performance of a Ce(III)-4,4′,4″-((1,3,5-triazine-2,4,6-triyl) tris (azanediyl)) tribenzoic acid–organic framework (Ce-H3TATAB-MOFs) for capturing excess fluoride in aqueous solutions and its subsequent defluoridation was investigated in depth. The optimal sorption capacity was obtained with a metal/organic ligand molar ratio of 1:1. The morphological characteristics, crystalline shape, functional groups, and pore structure of the material were analyzed via SEM, XRD, FTIR, XPS, and N2 adsorption–desorption experiments, and the thermodynamics, kinetics, and adsorption mechanism were elucidated. The influence of pH and co-existing ions for defluoridation performance were also sought. The results show that Ce-H3TATAB-MOFs is a mesoporous material with good crystallinity, and that quasi-second kinetic and Langmuir models can describe the sorption kinetics and thermodynamics well, demonstrating that the entire sorption process is a monolayer-governed chemisorption. The Langmuir maximum sorption capacity was 129.7 mg g−1 at 318 K (pH = 4). The adsorption mechanism involves ligand exchange, electrostatic interaction, and surface complexation. The best removal effect was reached at pH 4, and a removal effectiveness of 76.57% was obtained under strongly alkaline conditions (pH 10), indicating that the adsorbent has a wide range of applications. Ionic interference experiments showed that the presence of PO43− and H2PO4− in water have an inhibitory effect on defluoridation, whereas SO42−, Cl−, CO32−, and NO3− are conducive to the adsorption of fluoride due to the ionic effect. [ABSTRACT FROM AUTHOR]

Ideal Adsorbed Solution Theory (IAST) is a predictive model that does not require any mixture data. In gas purification and separation processes, IAST is used to predict multicomponent adsorption equilibrium and selectivity based solely on experimental single-component adsorption isotherms. In this work, the mixed gas adsorption isotherms were predicted using IAST calculations with the Python package (pyIAST). The experimental CO2 and CH4 single-component adsorption isotherms of Mg-gallate were first fitted to isotherm models in which the experimental data best fit the Langmuir model. The presence of CH4 in the gas mixture contributed to a lower predicted amount of adsorbed CO2 due to the competitive adsorption among the different components. Nevertheless, CO2 adsorption was more favorable and resulted in a higher predicted adsorbed amount than CH4. Mg-gallate showed a stronger affinity for CO2 molecules and hence contributed to a higher CO2 adsorption capacity even with the coexistence of a CO2/CH4 mixture. Very high IAST selectivity values for CO2/CH4 were obtained which increased as the gas phase mole fraction of CO2 approached unity. Therefore, IAST calculations suggest that Mg-gallate can act as a potential adsorbent for the separation of CO2/CH4 mixed gas. [ABSTRACT FROM AUTHOR]

The synthesis of a Co metal–organic framework assembled from 5,10,15,20-tetrakis((pyridin-4-yl)phenyl)porphyrin; TPhPyP) "Co-MTPhPyP" is reported. The TPhPyP ligand was synthesized via aldehyde condensation in 28% yield and characterized by 1H nuclear magnetic resonance (1H NMR), Fourier-transform infrared (FTIR), high-resolution mass spectrometry (HRMS), and UV-visible spectroscopy (UV-vis). Co-MTPhPyP was prepared by the solvothermal method from TPhPyP and CoCl2·H2O in 55% yield and characterized by X-ray powder diffraction (XRD), FTIR, thermogravimetric analysis (TGA), field-emission scanning electron microscopy with energy-dispersive X-ray (FESEM-EDS), X-ray photoelectron spectroscopy (XPS), and dynamic light scattering (DLS), showing a particle size distribution of 418 ± 58 nm. The sorption properties of the Co-MTPhPyP for the effective removal of Pb(II) and Cu(II) were evaluated in an aqueous medium and Cthe results showed uptake capacities of 383.4 and 168 mg of the metal g−1 after 2 h, respectively. Kinetic studies of Pb(II) adsorption by Co-MTPhPyP were adjusted to the pseudo-second-order model with a maximum adsorption capacity of 458.8 mg g−1 at 30 min of exposition. [ABSTRACT FROM AUTHOR]

As the industry of olive oil continues to grow, the management of olive mill wastewater (OMW) by-products has become an area of great interest. While many strategies for processing OMW have been established, more studies are still required to find an effective adsorbent for total phenolic content uptake. Here, we present a composite of a Cu 1,4-benzene dicarboxylate metal-organic framework (Cu (BDC) MOF) and granular activated carbon (GAC) as an adsorbent for total phenolic content removal from OMW. Experimental results demonstrated that the maximum adsorption capacity was 20 mg/g of total phenolic content (TPC) after 4 h. using 2% wt/wt of GAC/Cu (BDC) MOF composite to OMW at optimum conditions (pH of 4.0 and 25 °C). The adsorption of phenolic content onto the GAC/Cu (BDC) MOF composite was described by the Freundlich adsorption and pseudo-second-order reaction. The adsorption reaction was found to be spontaneous and endothermic at 298 K where ΔS° and ΔH° were found to be 0.105 KJ/mol and 25.7 kJ/mol, respectively. While ΔGº value was −5.74 (kJ/mol). The results of this study provide a potential solution for the local and worldwide olive oil industry. [ABSTRACT FROM AUTHOR]

In the present study, terbium-based metal-organic frameworks (MOFs) based on fcu topology, fcu-Tb- FTZB-MOF, was synthesized using 2-fluoro-4-(1H-tetrazol-5-yl)benzoic acid (FTZB) as a linear ligand, and then was characterized using powder X-ray diffraction (PXRD) and Brunauer-Emmett-Teller (BET) analysis and to study the texture properties of the Tb-FTZB-MOF. The characterization results confirmed the successful synthesis of the high surface area Tb-FTZB-MOF (1220 m2/g). The synthesized Tb-FTZB-MOF was then applied as a catalytic adsorbent to remove direct violet 31 (DV31) dye as an example of organic pollutants, from a model and real solution. The effect of various operational parameters such as adsorbent loading, contact time, initial DV31 dye concentration, initial solution pH, different water matrix, temperature, and ionic strength have also been evaluated. Solution pH and temperature significantly influenced the adsorption of DV31 dye using Tb-FTZB-MOF, and the results should efficiently remove the DV31 dye at ambient temperature, and at pH value of 8.0 using 35 mg Tb-FTZB-MOF, within few minutes. The process was studied kinetically and found to follow the pseudo-second-order kinetic model, and thermodynamically the process was spontaneous, endothermic, with a positive entropy. Finally, the result showed that Tb-FTZB-MOF was able to adsorb a high percentage of DV31 dye and maintained reasonable efficiency even after five cycles, indicating that Tb-FTZB-MOF could be a promising adsorbent in wastewater remediation. [ABSTRACT FROM AUTHOR]

Ciprofloxacin (CIP) is a commonly used antibiotic, however, once in the environment, it is highly toxic with a poor biodegradability. Given these attributes, an effective strategy for the removal of CIP is urgently needed for the protection of water resources. Herein, a novel copper metal-organic framework (CuxO/MOF) multifunctional material has been produced, in this work, by the calcination of Cu-MOF urea at 300 °C, in the presence of a 5% H2 atmosphere. The morphological, structural, and thermal properties of the prepared CuxO/MOF were determined through various techniques, and its photocatalytic behavior was investigated for the degradation of CIP under visible-light irradiation. The prepared CuxO/MOF bifunctional material is presented as a graphitic carbon-layered structure with a particle size of 9.2 ± 2.1 nm. The existence of CuO-Cu2O-C, which was found on the CuxO/MOF surface, enhanced the adsorption efficiency and increased the photosensitivity of CuxO/MOF, towards the degradation of CIP in aqueous solutions. The tailored CuxO/MOF, not only shows an excellent CIP degradation efficiency of up to 92% with a constant kinetic rate (kobs) of 0.048 min−1 under visible light, but it can also retain the stable photodegradation efficiency of >85%, for at least six cycles. In addition, CuxO/MOF has an excellent adsorption capacity at pH 6.0 of the maximum Langmuir adsorption capacity of 34.5 mg g−1 for CIP. The results obtained in this study demonstrate that CuxO/MOF is a reliable integrated material and serves as an adsorbent and photocatalyst, which can open a new pathway for the preparation of visible-light-responsive photocatalysts, for the removal of antibiotics and other emerging pollutants. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) have been broadly applied to numerous domains with a substantial surface area, tunable pore size, and multiple unsaturated metal sites. Recently, hollow MOFs have greatly attracted the scientific community due to their internal cavities and gradient pore structures. Hollow MOFs have a higher tunability, faster mass-transfer rates, and more accessible active sites when compared to traditional, solid MOFs. Hollow MOFs are also considered to be candidates for some functional material carriers. For example, composite materials such as hollow MOFs and metal nanoparticles, metal oxides, and enzymes have been prepared. These composite materials integrate the characteristics of hollow MOFs with functional materials and are broadly used in many aspects. This review describes the preparation strategies of hollow MOFs and their composites as well as their applications in organic catalysis, electrochemical sensing, and adsorption separation. Finally, we hope that this review provides meaningful knowledge about hollow-MOF composites and their derivatives and offers many valuable references to develop hollow-MOF-based applied materials. [ABSTRACT FROM AUTHOR]

Hexavalent chromium (Cr(VI)) is a highly mobile cancerogenic and teratogenic heavy metal ion. Among the varied technologies applied today to address chromium water pollution, photocatalysis offers a rapid reduction of Cr(VI) to the less toxic Cr(III). In contrast to classic photocatalysts, Metal-Organic frameworks (MOFs) are porous semiconductors that can couple the Cr(VI) to Cr(III) photoreduction to the chromium species immobilization. In this minireview, we wish to discuss and analyze the state-of-the-art of MOFs for Cr(VI) detoxification and contextualizing it to the most recent advances and strategies of MOFs for photocatalysis purposes. The minireview has been structured in three sections: (i) a detailed discussion of the specific experimental techniques employed to characterize MOF photocatalysts, (ii) a description and identification of the key characteristics of MOFs for Cr(VI) photoreduction, and (iii) an outlook and perspective section in order to identify future trends. [ABSTRACT FROM AUTHOR]

Volatile organic compounds (VOCs) are a major threat to human life and health. The technologies currently used to remove VOCs mainly include adsorption and photocatalysis. Adsorption is the most straightforward strategy, but it cannot ultimately eliminate VOCs. Due to the limited binding surface, the formaldehyde adsorption on conventional photocatalysts is limited, and the photocatalytic degradation efficiency is not high enough. By developing novel metal–organic framework (MOF) materials that can catalytically degrade VOCs at room temperature, the organic combination of new MOF materials and traditional purification equipment can be achieved to optimize adsorption and degradation performance. In the present review, based on the research on the adsorption and removal of VOCs by MOF materials in the past 10 years, starting from the structure and characteristics of MOFs, the classification of which was described in detail, the influencing factors and mechanisms in the process of adsorption and removal of VOCs were summarized. In addition, the research progress of MOF materials was summarized, and its future development in this field was prospected. [ABSTRACT FROM AUTHOR]

In this work, the magnetic Zr-based MOF composites with excellent retrievability were prepared using Fe3O4@SiO2 as the core and UiO–66–NH2 as the shell. Fe3O4@SiO2 core could introduce mesopores and result in capillary condensation in MOF composites, which aggravated with the dosage of Fe3O4@SiO2. The as-synthesized MOF composites could be rapidly retrieved from aqueous solution via magnetic separation in 10 seconds. pH imposed an important effect on Au (III) adsorption by governing the ion exchange and electrostatic interaction between Au (III) anions and adsorbents, and the optimal adsorption happened at pH 7. The adsorption process fitted well with the pseudo-second order kinetics model and Langmuir adsorption model. The maximum adsorption capacity of Au (III) by FSUN–10 and FSUN–50 at 298 K were determined to be 611.18 mg∙g−1 and 463.85 mg∙g−1, respectively. Additionally, Au (III) uptakes increased with temperature. Beyond experiments, the adsorption mechanisms were thoroughly studied through systematic characterization, molecular dynamics simulation (MDS) and density functional theory (DFT) study. It was verified that Au (III) was adsorbed via coordination to hydroxyl and amino groups and was reduced to Au (I) and Au (0) by amino groups. The diffusion coefficient of Au (III) along UiO–66–NH2 was calculated to be 5.8 × 10−5 cm2∙s−1. Moreover, the magnetic Zr-based MOF composites exhibit great industrial value in gold recycling with high adsorption selectivity and good recyclability. [ABSTRACT FROM AUTHOR]

Fragrances have been widely used in many customer products to improve the sensory quality and cover flavor defects. The key to the successful application of fragrance is to realize controlled fragrance release, which relies on the use of an appropriate carrier for fragrance. An ideal fragrance carrier helps to achieve the stable storage and controlled release of fragrance. In this work, a novel composite fragrance carrier with MIL-101 (Cr) as the fragrance host and cellulose acetate fiber (CAF) as the protective shell was developed. The encapsulation effect of MIL-101 (Cr) and the protective function of the CAF shell significantly improved the storage stability of L-menthol (LM). Only 5 wt % of LM was lost after 40 days of storage at room temperature. Encapsulated LM could also be effectively released upon heating due to the thermal responsiveness of CAF. In addition, the composite carrier was highly stable with neglectable Cr leaching under different conditions. The results of this work showed that the developed composite carrier could be a promising carrier for the thermally triggered release of fragrance. [ABSTRACT FROM AUTHOR]

The accumulation of toxic heavy metal ions continues to be a global concern due to their adverse effects on the health of human beings and animals. Adsorption technology has always been a preferred method for the removal of these pollutants from wastewater due to its cost-effectiveness and simplicity. Hence, the development of highly efficient adsorbents as a result of the advent of novel materials with interesting structural properties remains to be the ultimate objective to improve the adsorption efficiencies of this method. As such, advanced materials such as metal–organic frameworks (MOFs) that are highly porous crystalline materials have been explored as potential adsorbents for capturing metal ions. However, due to their diverse structures and tuneable surface functionalities, there is a need to find efficient characterization techniques to study their atomic arrangements for a better understanding of their adsorption capabilities on heavy metal ions. Moreover, the existence of various species of heavy metal ions and their ability to form complexes have triggered the need to qualitatively and quantitatively determine their concentrations in the environment. Hence, it is crucial to employ techniques that can provide insight into the structural arrangements in MOF composites as well as their possible interactions with heavy metal ions, to achieve high removal efficiency and adsorption capacities. Thus, this work provides an extensive review and discussion of various techniques such as X-ray diffraction, Brunauer–Emmett–Teller theory, scanning electron microscopy and transmission electron microscopy coupled with energy dispersive spectroscopy, and X-ray photoelectron spectroscopy employed for the characterization of MOF composites before and after their interaction with toxic metal ions. The review further looks into the analytical methods (i.e., inductively coupled plasma mass spectroscopy, ultraviolet-visible spectroscopy, and atomic absorption spectroscopy) used for the quantification of heavy metal ions present in wastewater treatment. [ABSTRACT FROM AUTHOR]

MIL-101(Cr) is one of the most well-studied chromium-based metal–organic frameworks, which consists of metal chromium ion and terephthalic acid ligand. It has an ultra-high specific surface area, large pore size, good thermal/chemical/water stability, and contains unsaturated Lewis acid sites in its structure. Due to the physicochemical properties and structural characteristics, MIL-101(Cr) has a wide range of applications in aqueous phase adsorption, gas storage and separation, and catalysis. In this review, the latest synthesis of MIL-101(Cr) and its research progress in adsorption and catalysis are reviewed. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOF) are a new type of porous materials that have great potential for adsorption of voltaic organic compounds (VOCs). These types of materials composed of metal ions and organic ligands are easy to synthesize, have high surface areas, their surface chemistry can be adjusted to the desired application, and they can also have good chemical and thermal stability. Therefore, this work focuses on the synthesis of a highly hydrophobic MOF material called CIM-80, a porous material that is made up of the Al3+ cation and the mesaconate linker. This MOF has a B.E.T. of approximately 800 m2/g and has potential applications for the adsorption of hydrophobic organic compounds. However, its synthesis is expensive and very dirty. Therefore, we have studied the synthesis conditions necessary to achieve high synthesis yields (85%) and materials with high crystallinity and accessible porosity. To achieve these results, we have used urea as a mild deprotonation reagent and modulator as an alternative to NaOH, which is traditionally used for the synthesis of this MOF. Once the synthesis of this material was controlled, its adsorption/desorption behavior of water and organic compounds such as toluene, cyclohexane and m-xylene was studied by means of vapor adsorption isotherms. The results show the hydrophobic character of the material and the greater affinity the material has toward aliphatic compounds than toward aromatic ones, with toluene being the most adsorbed compound, followed by cyclohexane and m-xylene. [ABSTRACT FROM AUTHOR]

Residual antibiotics in wastewater have gained widespread attention because of their toxicity to humans and the environment. In this work, Cu-doped ZIF-8s (Cu-ZIF-8s) were successfully synthesized by the impregnation of Cu2+ in ZIF-8 and applied in the removal of ofloxacin (OFX) from water. Remarkably, excellent adsorption performance was obtained in Cu-ZIF-8s, especially for Cu-ZIF-8-1, in which the adsorption capacity (599.96 mg·g−1) was 4.2 times higher than that of ZIF-8 and superior to various adsorbents reported previously. The adsorption kinetics and adsorption isotherm follow the pseudo-second-order model and the Langmuir model, respectively. Furthermore, the removal efficiencies of OFX in Cu-ZIF-8-1 reached over 90% at low concentrations. It was revealed that electrostatic interaction and complexation play important roles in the adsorption process. In addition, the material can be regenerated by simple methods. Therefore, the obtained Cu-doped MOFs may have a promising application in the treatment of antibiotic-containing wastewater. [ABSTRACT FROM AUTHOR]

Wastewater treatment plants (WWTPs) are one of the most energy-intensive industries. Every stage of wastewater treatment consumes energy, which is the primary contributor to WWTP costs. Adsorbents and process optimization are critical for energy savings. The removal of dyes from industrial wastewater by adsorption using commercially available adsorbents is inefficient. Metal–organic frameworks (MOFs) have outstanding properties that can improve separation performance over current commercial adsorbents, and thus, these materials represent a milestone in improving dye removal in water treatment methods. In this work, three types of metal–organic frameworks (Fe-BTC, Cu-BTC, and ZIF-8) have been investigated as prospective adsorbents for methyl orange removal from water in batch setups. The results showed that at 15 mg/L MO initial concentration and 100 mg dosage, Fe-BTC had the highest removal efficiency of 91%, followed by ZIF-8 (63%), and finally Cu-BTC (35%), which exhibited structural damage due to its instability in water. Fe-BTC maintained consistent adsorption capacity over a wide range of pH values. Furthermore, a 23 full factorial design analysis was implemented to evaluate the conditions for maximum MO-removal efficiency. The main effects, interaction effects, analysis of variance (ANOVA), and the Pareto chart were reported. The statistical analysis demonstrated that the MOF type was the most significant factor, followed by dosage and initial concentration. The analysis indicated that the type of MOF and dosage had a positive effect on the removal efficiency, while the initial concentration had a negative effect. The two-way and three-way interactions were also found to be significant. [ABSTRACT FROM AUTHOR]

Water covers about 70% of the Earth's surface, but the amount of freshwater available for human use is only 2.5% and, although it is continuously replenished via the water cycle, freshwater is a finite and limited resource. The Earth's water is affected by pollution and while water quality is an issue of global concern, the specific regulations on contaminants of emerging concern (CECs) are limited. In order to achieve the goals set by EU regulations, the treatment of wastewater is a scientifically and technologically challenging issue. Metal–organic frameworks (MOFs) are promising materials used for the removal of priority and emerging contaminants from wastewater, since they can mitigate those contaminants via both adsorption as well as catalysis processes. MOFs can offer selective adsorption of CECs by various adsorption mechanisms. The catalytic removal of priority and emerging organic contaminants from wastewater using MOFs implies Fenton, electro-Fenton, and photo-Fenton processes. Overall, MOFs can be considered as promising materials for the elimination of priority and emerging organic contaminants from various wastewater types, but the involved processes must be studied in detail for a larger number of compounds. [ABSTRACT FROM AUTHOR]

The interaction strength of nitrogen dioxide (NO2) with a set of 43 functionalized benzene molecules was investigated by performing density functional theory (DFT) calculations. The functional groups under study were strategically selected as potential modifications of the organic linker of existing metal–organic frameworks (MOFs) in order to enhance their uptake of NO2 molecules. Among the functional groups considered, the highest interaction energy with NO2 (5.4 kcal/mol) was found for phenyl hydrogen sulfate (-OSO3H) at the RI-DSD-BLYP/def2-TZVPP level of theory—an interaction almost three times larger than the corresponding binding energy for non-functionalized benzene (2.0 kcal/mol). The groups with the strongest NO2 interactions (-OSO3H, -PO3H2, -OPO3H2) were selected for functionalizing the linker of IRMOF-8 and investigating the trend in their NO2 uptake capacities with grand canonical Monte Carlo (GCMC) simulations at ambient temperature for a wide pressure range. The predicted isotherms show a profound enhancement of the NO2 uptake with the introduction of the strongly-binding functional groups in the framework, rendering them promising modification candidates for improving the NO2 uptake performance not only in MOFs but also in various other porous materials. [ABSTRACT FROM AUTHOR]

A magnetic metal–organic framework nanocomposite (magnetic MIL-68(Ga)) was synthesized through a "one pot" reaction and used for heavy metal ion removal. The morphology and elemental properties of the nanocomposite were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), X-ray powder diffraction (XRD), as well as zeta potential. Moreover, the factors affecting the adsorption capacity of the nanocomposite, including time, pH, metal ion type and concentration, were studied. It was found that the adsorption capacity of magnetic MIL-68(Ga) for Pb2+ and Cu2+ was 220 and 130 mg/g, respectively. Notably, the magnetic adsorbents could be separated easily using an external magnetic field, regenerated by ethylenediaminetetraacetic acid disodium salt (EDTA-Na2) and reused three times, in favor of practical application. This study provides a reference for the rapid separation and purification of heavy metal ions from wastewater. [ABSTRACT FROM AUTHOR]

Composite materials have been used based on coordination polymers or microporous metal-organic frameworks (MOFs) combined with mesoporous matrices for adsorption-related techniques, which enable outflanking some adverse phenomena manifested during pristine components operation and enhance the performance and selectivity of the resulting materials. In this work, for the first time, the novel HKUST-1@BPS composites synthesized by the microwave-assisted (MW) technique starting from microporous HKUST-1 (Cu3(btc)2) MOF and biporous silica matrix (BPS) with bimodal mesopore size distribution were comparatively studied as materials for liquid-phase adsorption techniques utilizing the high-performance liquid chromatography (HPLC) method and benzene as a model adsorbate. It was established that the studied HKUST-1@BPS composites can function as stationary phases for HPLC, unlike the pristine HKUST-1 and bare BPS materials, due to the synergetic effect of both components based on the preliminary enhanced adsorbate mass transfer throughout the silica mesopores and, subsequently, its penetrating into HKUST-1 micropores. The suggested mechanism involves the initial deactivation of open metal Cu2+ sites in the HKUST-1 framework structure by isopropanol molecules upon adding this polar component into the mobile phase in the region of the isopropanol concentration of 0.0 to 0.2 vol.%. Thereafter, at the medium range of varying the isopropanol concentration in the eluent of 0.2 to 0.3 vol.%, there is an expansion of the previously inaccessible adsorption centers in the HKUST-1@BPS composites. Subsequently, while further increasing the isopropanol volume fraction in the eluent in the region of 0.3 to 5.0 vol.%, the observed behavior of the studied chromatographic systems is similar to the quasi-normal-phase HPLC pattern. According to the obtained thermodynamic data, benzene adsorption into HKUST-1 micropores from solutions with a vol.% of isopropanol in the range of 0.4 to 5.0 follows the unique entropy-driven mechanism previously described for the MIL-53(Al) framework. It was found that HKUST-1 loading in the composites and their preparation conditions have pronounced effects on their physicochemical properties and adsorption performance, including the adsorption mechanism. [ABSTRACT FROM AUTHOR]

Magnetic nitrogen-doped porous carbon (MNPC) has been prepared via self-catalytic pyrolysis of bimetallic metal-organic frameworks (MOFs). The as-obtainedMNPC showed favorable features for antibiotics adsorption such as high specific surface area (871 m2 g-1), high pore volume (0.75 cm3 g-1), porous structure, good graphitization degree, and rich N-doping. Moreover, theMNPC has magnetic properties due to the Co species, which is embedded with a high dispersion, so the absorbent can be easily separated. Based on the above excellent characteristics, the MNPC was used as the absorbent for norfloxacin (NOR) removal. The experimental maximum NOR adsorption capacity ofMNPC was 55.12 mg g-1 at 298.15 K and a pH of 6.0 with an initial NOR concentration of 50 mg L-1. The data analysis of the kinetics revealed that the experimental data of NOR uptakes versus time agreed with the pseudo-second order model. The isotherm data analysis revealed the favorable application of the Freundlich model. Based on the adsorption results over a wide range of conditions, the dominant adsorption mechanisms were found to be pore-filling, electrostatic interaction, and the H-bond. [ABSTRACT FROM AUTHOR]

Isostructural zirconium-based metal-organic frameworks (Zr-MOFs) have attracted the attention of researchers because of their remarkable stability at high temperatures and high pressures and their chemical stabilities against acids and bases. Due to this stability, Zr-MOFs can be utilized in adsorption research, and the adsorption performance of a Zr-MOF depends on the pore size and the surroundings of the MOF. In this study, as the dimensions changed and the adsorption was carried out, the Zr-MOF material remained stable, and the adsorption of the best state was achieved at 235 mg/g. Through the simulation of theoretical kinetic models of Zr-MOFs, we initially postulated that the adsorption capacity is proportional to the pore size and that acid orange 7 (AO7) was adsorbed by the MOFs. Afterwards, we verified our hypotheses through a series of Brunauer-Emmett-Teller (BET) data analysis; non-local density function theory (NLDFT) was mainly used to analyze the data. Moreover, we determined that physical adsorption occurs on the surface of the MOFs during the adsorption process, while chemisorption occurs in the form of dye molecules combining with active sites. Ultimately, we concluded that the larger the pore size, the stronger the adsorption capacity, and this contribution casts a new light on the issue of wastewater treatment. [ABSTRACT FROM AUTHOR]

We herein selected a 3D metal-organic framework decorated with carboxylate groups as an adsorbent to remove the pharmaceutical molecules of diclofenac sodium and chlorpromazine hydrochloride from water. The experiment aimed at exploring the effect factors of initial concentration, equilibrium time, temperature, pH and adsorbent dosage on the adsorption process. The adsorption uptake rate of the diclofenac sodium is much higher than that of the chlorpromazine hydrochloride. This paper presents the high adsorption capacity of diclofenac sodium, in which porous MOFs are used for the removal of drug contaminants from water. According to linear fitting with adsorption isotherm equation and kinetic equations, diclofenac sodium conforms to the Langmuir model and pseudo-first-order kinetic equation, while chlorpromazine hydrochloride accords with the Temkin model and pseudo-second-order kinetic equation. The results of the study indicate that the title compound could be a promising hybrid material for removing diclofenac sodium and chlorpromazine hydrochloride from wastewater. [ABSTRACT FROM AUTHOR]

A cationic porous framework with mobile anions (MIL-101(Cr)-Cl) was easily and successfully synthesized by utilizing the stronger affinity of F- to Al3+ than Cr3+ in the chargebalanced framework of MIL-101(Cr). The structure, morphology and porosity of MIL-101(Cr)-Cl were characterized. The obtained new materials retain the high surface area, good thermostability, and structure topology of MIL-101(Cr). With the mobile Cl- anion, MIL-101(Cr)-Cl can be used as an ion-exchange material for anionic organic pollutions. In this work, 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model to test the absorption performance of this new material. This new material exhibited improved adsorbability compared to that of the original metal-organic frameworks (MOFs). At the same time, this material also shows high anti-interference performance with changing solution pH. [ABSTRACT FROM AUTHOR]

Y(btc) (btc = 1,3,5-benzenetricarboxylate) is a metal-organic framework that exhibits significant adsorption of industrially-relevant gases such as H2, CH4, and O2. Previous studies have noted a surprising lack of close interactions between the adsorbed guest molecules and Y, despite the apparent availability of a "bare-metal" binding site. We have extended our previous work in a detailed investigation of the adsorption behaviours of CO2, CD4, and O2 in Y(btc) over a range of concentrations using in situ neutron powder diffraction methods. The O-Y-O bond angles enclosing the bare-metal site are found to change considerably depending on the type and quantity of guest molecules present. Multiple binding sites are found for each guest species, and the largest changes in O-Y-O angles are accompanied by changes in the filling sequences of the binding sites, pointing to an important interplay between guest-induced framework distortions and binding site accessibility. These results suggest the potential for coordinatively flexible rare-earth metal centres to promote guest-selective binding in metal-organic frameworks. [ABSTRACT FROM AUTHOR]

Zirconia-carbon (ZC) composites were prepared via calcination of Zr-based metal organic frameworks, UiO-66 and amino-functionalized UiO-66, under N2 atmosphere. The prepared composites were characterized using a series of instrumental analyses. The surface area of the ZC composites increased with the increase of calcination temperature, with the formation of a graphite oxide phase observed at 900 °C. The composites were used for adsorptive removal of a dye (crystal violet, CV) and a pharmaceutical and personal care product (salicylic acid, SA). The increase of the calcination temperature resulted in enhanced adsorption capability of the composites toward CV. The composite calcined at 900 °C exhibited a maximum uptake of 243 mg ⋅ g-1, which was much greater than that by a commercial activated carbon. The composite was also effective in SA adsorption (102 mg ⋅ g-1), and N-functionalization of the composite further enhanced its adsorption capability (109 mg ⋅ g-1). CV adsorption was weakly influenced by solution pH, but was more dependent on the surface area and pore volume of the ZC composite. Meanwhile, SA adsorption showed strong pH dependence, which implies an active role of electrostatic interactions in the adsorption process. Base-base repulsion and hydrogen bonding are also suggested to influence the adsorption of CV and SA, especially for the N-functionalized composite. [ABSTRACT FROM AUTHOR]

A large volume of produced water (PW) has been produced as a result of extensive industrialization and rising energy demands. PW comprises organic and inorganic pollutants, such as oil, heavy metals, aliphatic hydrocarbons, and radioactive materials. The increase in PW volume globally may result in irreversible environmental damage due to the pollutants' complex nature. Several conventional treatment methods, including physical, chemical, and biological methods, are available for produced water treatment that can reduce the environmental damages. Studies have shown that adsorption is a useful technique for PW treatment and may be more effective than conventional techniques. However, the application of adsorption when treating PW is not well recorded. In the current review, the removal efficiencies of adsorbents in PW treatment are critically analyzed. An overview is provided on the merits and demerits of the adsorption techniques, focusing on overall water composition, regulatory discharge limits, and the hazardous effects of the pollutants. Moreover, this review highlights a potential alternative to conventional technologies, namely, porous adsorbent materials known as metal–organic frameworks (MOFs), demonstrating their significance and efficiency in removing contaminants. This study suggests ways to overcome the existing limitations of conventional adsorbents, which include low surface area and issues with reuse and regeneration. Moreover, it is concluded that there is a need to develop highly porous, efficient, eco-friendly, cost-effective, mechanically stable, and sustainable MOF hybrids for produced water treatment. [ABSTRACT FROM AUTHOR]

This paper reports on the comparison of three zirconium-based metal organic frameworks (MOFs) for the capture of carbon dioxide and ethanol vapour at ambient conditions. In terms of efficiency, two parameters were evaluated by experimental and modeling means, namely the nature of the ligands and the size of the cavities. We demonstrated that amongst three Zr-based MOFs, MIP-202 has the highest affinity for CO2 (−50 kJ·mol−1 at low coverage against around −20 kJ·mol−1 for MOF-801 and Muc Zr MOF), which could be related to the presence of amino functions borne by its aspartic acid ligands as well as the presence of extra-framework anions. On the other side, regardless of the ligand size, these three materials were able to adsorb similar amounts of carbon dioxide at 1 atm (between 2 and 2.5 µmol·m−2 at 298 K). These experimental findings were consistent with modeling studies, despite chemisorption effects, which could not be taken into consideration by classical Monte Carlo simulations. Ethanol adsorption confirmed these results, higher enthalpies being found at low coverage for the three materials because of stronger van der Waals interactions. Two distinct sorption processes were proposed in the case of MIP-202 to explain the shape of the enthalpic profiles. [ABSTRACT FROM AUTHOR]

A simple not solvent and time consuming Fe3O4@MIL-100(Fe), synthesized in the presence of a small amount of magnetite (Fe3O4) nanoparticles (27.3 wt%), is here presented and discussed. Layer-by-layer alone (20 shell), and combined layer-by-layer (5 shell)/reflux or /hydrothermal synthetic procedures were compared. The last approach (Fe3O4@MIL-100_H sample) is suitable (i) to obtain rounded-shaped nanoparticles (200–400 nm diameter) of magnetite core and MIL-100(Fe) shell; (ii) to reduce the solvent and time consumption (the layer-by-layer procedure is applied only 5 times); (iii) to give the highest MIL-100(Fe) amount in the composite (72.7 vs. 18.5 wt% in the layer-by-layer alone); (iv) to obtain a high surface area of 3546 m2 g−1. The MIL-100(Fe) sample was also synthesized and both materials were tested for the absorption of Ofloxacin antibiotic (OFL). Langmuir model well describes OFL adsorption on Fe3O4@MIL-100_H, indicating an even higher adsorption capacity (218 ± 7 mg g−1) with respect to MIL-100 (123 ± 5 mg g−1). Chemisorption regulates the kinetic process on both the composite materials. Fe3O4@MIL-100_H performance was then verified for OFL removal at µg per liter in tap and river waters, and compared with MIL-100. Its relevant and higher adsorption efficiency and the magnetic behavior make it an excellent candidate for environmental depollution. [ABSTRACT FROM AUTHOR]

New kinds of inorganic–organic hybrid porous materials, metal–organic frameworks (MOFs), have shown great application potential in various fields, but their powdery nature limits their application to a certain extent. As a green and renewable biomass material in nature, cellulose fiber (CelF) has the advantages of biodegradability, recyclability and easy processing, and can be used as an excellent flexible substrate for MOFs. However, the efficient deposition of MOFs on CelF is still a great challenge for the development of this new material. Herein, polyaniline (PANI) and de-doped PANI (DPANI) with rich functional groups as a mediating layer was proposed to promote the in-situ growth and immobilization of some MOFs on CelF. The PANI (especially DPANI) layer greatly promoted the deposition of the four MOFs, and more encouragingly, significantly promoted the in-situ growth and nanocrystallization of MIL-100(Fe). MIL-100(Fe)@DPANI@CelF was selected as an adsorbent-photocatalyst to be used for the adsorptive-photocatalytic removal of ciprofloxacin (CIP) in water. The removal efficiency of CIP by MIL-100(Fe)@DPANI@CelF reached 82.78%, and the removal capacity of CIP was as high as 105.96 mg g−1. The study found that DPANI had a synergistic effect on both the in-situ growth of MIL-100(Fe) on CelF and the adsorption-photocatalysis of CIP in water. The universal platform of PANI-mediated in-situ growth and immobilization of MOFs on CelF constructed in this study widens the road for the development of MOF@CelF composites. [ABSTRACT FROM AUTHOR]

Adsorption-based processes using metal-organic frameworks (MOFs) are a promising option for carbon dioxide (CO2) capture from flue gases and biogas upgrading to biomethane. Here, the adsorption of CO2, methane (CH4), and nitrogen (N2) on Zn(dcpa) MOF (dcpa (2,6-dichlorophenylacetate)) is reported. The characterization of the MOF by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), and N2 physisorption at 77 K shows that it is stable up to 650 K, and confirms previous observations suggesting framework flexibility upon exposure to guest molecules. The adsorption equilibrium isotherms of the pure components (CO2, CH4, and N2), measured at 273–323 K, and up to 35 bar, are Langmuirian, except for that of CO2 at 273 K, which exhibits a stepwise shape with hysteresis. The latter is accurately interpreted in terms of the osmotic thermodynamic theory, with further refinement by assuming that the free energy difference between the two metastable structures of Zn(dcpa) is a normally distributed variable due to the existence of different crystal sizes and defects in a real sample. The ideal selectivities of the equimolar mixtures of CO2/N2 and CO2/CH4 at 1 bar and 303 K are 12.8 and 2.9, respectively, which are large enough for Zn(dcpa) to be usable in pressure swing adsorption. [ABSTRACT FROM AUTHOR]

The accumulation of pollutants in water is dangerous for the environment and human lives. Some of them are considered as persistent organic pollutants (POPs) that cannot be eliminated from wastewater effluent. Thus, many researchers have devoted their efforts to improving the existing technology or providing an alternative strategy to solve this environmental problem. One of the attractive materials for this purpose are metal-organic frameworks (MOFs) due to their superior high surface area, high porosity, and the tunable features of their structures and function. This review provides an up-to-date and comprehensive description of MOFs and their crucial role as adsorbent, catalyst, and membrane in wastewater treatment. This study also highlighted several strategies to improve their capability to remove pollutants from water effluent. [ABSTRACT FROM AUTHOR]