Simulation study of a practical approach to enhance cadmium removal via biological treatment by controlling the concentration of MLSS.

The fate of cadmium at the Muharram Aisha wastewater treatment plant in Karbala governorate, Iraq was studied using the TOXCHEM model. Cadmium, a known carcinogen, and is considered one of the most dangerous heavy metals and high concentrations, greater than permissible limits, were found in the treated wastewater. The plant operates using an activated sludge system and this was modeled via TOXCHEM with a sensitivity analysis carried out on the extended aeration system. Prior to analysis, the model was calibrated and validated for cadmium, with the adjustments leading to a mean square error (RMSE) and correlation coefficient (R) of 0.0001 and 0.81, respectively. The mass balance of cadmium in the Muharram Aisha treatment plant was found to be 4832.44 g/day (37.1726%) in the treated wastewater and 8164.52 g/day (62.804%) in the sludge, which indicated that the mix liquor suspended solid (MLSS) was the most sensitive factor. The sensitivity to cadmium was analyzed via MLSS in the extended aeration system and the results o indicated that the higher the MLSS concentration (mg/L), the greater the removal of cadmium in the treated wastewater. It was found that increasing the MLSS through a biological treatment method reduced the concentration of cadmium without the need for additional of any (potentially harmful) chemical treatments. The plant was subsequently operated for a period of 5 months with the MLSS increased from 1500 to 4500 mg/L, and this reduced the concentration of cadmium in the wastewater from 0.36 to 0.01 mg/L as a consequence. This research demonstrates how the novel application of TOXCHEM can be a useful tool in the reduction of heavy metal contamination in the environment.

Physiochemical characterization of metal organic framework materials: A mini review.

Metal-organic frameworks (MOFs) are promising materials offering exceptional performance across a myriad of applications, attributable to their remarkable physicochemical properties such as regular porosity, crystalline structure, and tailored functional groups. Despite their potential, there is a lack of dedicated reviews that focus on key physicochemical characterizations of MOFs for the beginners and new researchers in the field. This review is written based on our expertise in the synthesis and characterization of MOFs, specifically to provide a right direction for the researcher who is a beginner in this area. In this way, experimental errors can be reduced, and wastage of time and chemicals can be avoided when new researchers conduct a study. In this article, this topic is critically analyzed, and findings and conclusions are presented. We reviewed three well-known XRD techniques, including PXRD, single crystal XRD, and SAXS, which were used for XRD analysis depending on the crystal size and the quality of crystal morphology. The TGA profile was an effective factor for evaluating the quality of the activation process and for ensuring the successful investigation for other characterizations. The BET and pore size were significantly affected by the activation process and selective benzene chain cross-linkers. FTIR is a prominent method that is used to investigate the functional groups on pore surfaces, and this method is successfully used to evaluate the activation process, characterize functionalized MOFs, and estimate their applications. The most significant methods of characterization include the X-ray diffraction, which is utilized for structural identification, and thermogravimetric analysis (TGA), which is used for exploring thermal decomposition. It is important to note that the thermal stability of MOFs is influenced by two main factors: the metal-ligand interaction and the type of functional groups attached to the organic ligand. The textural properties of the MOFs, on the other hand, can be scrutinized through nitrogen adsorption-desorption isotherms experiments at 77 K. However, for smaller pore size, the Argon adsorption-desorption isotherm at 87.3 K is preferred. Furthermore, the CO2 adsorption isotherm at 273 K can be used to measure ultra-micropore sizes and sizes lower than these, which cannot be measured by using the N2 adsorption-desorption isotherm at 77 K. The highest BET was observed in high-valence MOFs that are constructed based on the metal-oxo cluster, which has an excellent ability to control their textural properties. It was found that the synthesis procedure (including the choice of solvent, cross-linker, secondary metal, surface functional groups, and temperature), activation method, and pressure significantly impact the surface area of the MOF and, by extension, its structural integrity. Additionally, Fourier-transform infrared spectroscopy plays a crucial role in identifying active MOF functional groups. Understanding these physicochemical properties and utilizing relevant characterization techniques will enable more precise MOF selection for specific applications.

Boosting CO2 adsorption and selectivity in metal-organic frameworks of MIL-96(Al) via second metal Ca coordination.

Aluminum trimesate-based MOF (MIL-96-(Al)) has attracted intense attention due to its high chemical stability and strong CO2 adsorption capacity. In this study, CO2 capture and selectivity of MIL-96-Al was further improved by the coordination of the second metal Ca. To this end, a series of MIL-96(Al)-Ca were hydrothermally synthesised by a one-pot method, varying the molar ratio of Ca2+/Al3+. It is shown that the variation of Ca2+/Al3+ ratio results in significant changes in crystal shape and size. The shape varies from the hexagonal rods capped in the ends by a hexagonal pyramid in MIL-96(Al) without Ca to the thin hexagonal disks in MIL-96(Al)-Ca4 (the highest Ca content). Adsorption studies reveal that the CO2 adsorption on MIL-96(Al)-Ca1 and MIL-96(Al)-Ca2 at pressures up to 950 kPa is vastly improved due to the enhanced pore volumes compared to MIL-96(Al). The CO2 uptake on these materials measured in the above sequence is 10.22, 9.38 and 8.09 mmol g-1, respectively. However, the CO2 uptake reduces to 5.26 mmol g-1 on MIL-96(Al)-Ca4. Compared with MIL-96(Al)-Ca1, the N2 adsorption in MIL-96(Al)-Ca4 is significantly reduced by 90% at similar operational conditions. At 100 and 28.8 kPa, the selectivity of MIL-96(Al)-Ca4 to CO2/N2 reaches up to 67 and 841.42, respectively, which is equivalent to 5 and 26 times the selectivity of MIL-96(Al). The present findings highlight that MIL-96(Al) with second metal Ca coordination is a potential candidate as an alternative CO2 adsorbent for practical applications.

Multimetal organic frameworks as drug carriers: aceclofenac as a drug candidate.

BACKGROUND: Multimetal organic frameworks (M-MOFs) were synthesized by including a second metal ion with the main base metal in the synthesis process to enhance their applications for drug delivery. Aceclofenac (ACF), a nonsteroidal anti-inflammatory analgesic drug of low aqueous solubility, was selected as a candidate for the drug delivery system. PURPOSE: This study aimed to evaluate the loading capacity (LC) and entrapment efficiency (EE) percentages of multi-Material of Institute Lavoisier (MIL)-100(Fe) (M-MIL-100(Fe)) for ACF. MATERIALS AND METHODS: Hydrothermal synthesis procedure was used to prepare multi-MIL-100(Fe) samples (Zn I-MIL-100(Fe), Zn II-MIL-100(Fe), Ca I-MIL-100(Fe), Ca II-MIL-100-(Fe), Mg I-MIL-100(Fe), Mg II-MIL-100(Fe), Mn I-MIL-100(Fe), and Mn II-MIL-100(Fe)). The characterization of M-MIL-100(Fe) samples was evaluated by X-ray powder diffraction (XRD), Fourier transform infrared spectra, scanning electron microscope (SEM), TGA, and N2 adsorption isotherms. The LC of M-MIL-100(Fe) and EE of ACF were determined. Nuclear magnetic resonance (NMR) and zeta-potential analyses were employed to confirm qualitatively the drug loading within M-MIL-100(Fe). RESULTS: The ACF LC of MIL-100(Fe) was 27%, whereas the LC of M-MIL-100(Fe) was significantly increased and ranged from 37% in Ca I-MIL-100(Fe) to about 57% and 59% in Mn II-MIL-100(Fe) and Zn II-MIL-100(Fe), respectively. The ACF@M-MOFs release profiles showed slow release rates in phosphate buffer solutions at pH 6.8 and 7.4 as compared to the ACF@MIL-100(Fe). CONCLUSION: Therefore, M-MOFs showed a significant potential as a carrier for drug delivery systems.

Removal of monoethylene glycol from wastewater by using Zr-metal organic frameworks.

Mono-ethylene glycol (MEG), used in the oil and gas industries as a gas hydrate inhibitor, is a hazardous chemical present in wastewater from those processes. Metal-organic frameworks (MOFs) (modified UiO-66∗ and UiO-66-2OH) were used for the effective removal of MEG waste from effluents of distillation columns (MEG recovery units). Batch contact adsorption method was used to study the adsorption behavior toward these types of MOFs. Adsorption experiments showed that these MOFs had very high affinity toward MEG. Significant adsorption capacity was demonstrated on UiO-66-2OH and modified UiO-66 at 1000 mg·g-1 and 800 mg·g-1 respectively. The adsorption kinetics were fitted to a pseudo first-order model. UiO-66-2OH showed a higher adsorption capacity due to the presence of hydroxyl groups in its structure. A Langmuir model gave the best fitting for isotherm of experimental data at pH = 7.

Metal organic frameworks as a drug delivery system for flurbiprofen.

BACKGROUND: Metal organic frameworks (MOFs) have attracted more attention in the last decade because of a suitable pore size, large surface area, and high pore volume. Developing biocompatible MOFs such as the MIL family as a drug delivery system is possible. PURPOSE: Flurbiprofen (FBP), a nonsteroidal anti-inflammatory agent, is practically insoluble in aqueous solution, and, therefore, needs suitable drug delivery systems. Different biocompatible MOFs such as Ca-MOF and Fe-MILs (53, 100, and 101) were synthesized and employed for FBP delivery. PATIENTS AND METHODS: A sample of 50 mg of each MOF was mixed and stirred for 24 h with 10 mL of 5 mg FBP in acetonitrile (40%) in a sealed container. The supernatant of the mixture after centrifuging was analyzed by high-performance liquid chromatography to determine the loaded quantity of FBP on the MOF. The overnight-dried solid material after centrifuging the mixture was analyzed for loading percent using X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, nuclear magnetic resonance, and FBP release profile. RESULTS: The loading values of FBP were achieved at 10.0%±1%, 20%±0.8%, 37%±2.3%, and 46%±3.1% on Ca-MOF, Fe-MIL-53, Fe-MIL-101, and Fe-MIL-100, respectively. The FBP release profiles were investigated in a phosphate buffer solution at pH 7.4. The total release of the FBP after 2 days was obtained at 72.9, 75.2, 78.3, and 90.3% for Ca-MOF, Fe-MIL-100, Fe-MIL-53, and Fe-MIL-101, respectively. CONCLUSION: The MOFs are shown to be a promising drug delivery option for FBP with a significant loading percent and relatively prolonged drug release.

One-pot synthesis of binary metal organic frameworks (HKUST-1 and UiO-66) for enhanced adsorptive removal of water contaminants.

In this study, binary metal organic frameworks (MOFs) with HKUST-1 and UiO-66 have been synthesized in a one-pot process. The synthesized MOFs were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption, and thermogravimetric analysis (TGA). The meso-porosity and thermal stability of the binary MOFs were higher than those of single HKUST-1 or UiO-66. The synthesized MOF hybrids were then tested for adsorptive removal of methylene blue (MB) from wastewater in terms of kinetic and isothermal adsorption as compared to a commercially available activated carbon (AC). All the synthesized MOFs showed significant removal of MB under a wide range of pH. The adsorption capacities of HKUST-1 are higher than UiO-66 and commercial AC while the binary MOFs presented an even higher adsorption capacity than single MOFs. This is the first time that binary HKUST-1 and UiO-66 MOFs have been successfully synthesized and demonstrated enhanced adsorptive removal of contaminants.

Excellent performance of copper based metal organic framework in adsorptive removal of toxic sulfonamide antibiotics from wastewater.

The increasing concerns on toxicity of sulfonamide antibiotics in water require a prompt action to establish efficient wastewater treatment processes for their removal. In this study, adsorptive removal of a model sulfonamide antibiotic, sulfachloropyridazine (SCP), from wastewater is presented for the first time using a metal organic framework (MOF). A high surface area and thermally stable MOF, HKUST-1, was synthesized by a facile method. Batch adsorption studies were systematically carried out using HKUST-1. The high surface area and unsaturated metal sites resulted in a significant adsorption capacity with faster kinetics. Most of the SCP was removed in 15min and the kinetic data were best fitted with the pseudo second order model. Moreover, isothermal data were best fitted with the Langmuir model. The thermodynamic results showed that the adsorption is a spontaneous and endothermic process. The adsorption capacity of HKUST-1 is 384mg/g at 298K which is the highest compared to most of the materials for the antibiotics. The high adsorption capacity is attributed mainly to π-π stacking, hydrogen bonding and electrostatic interactions.

Effects of ammonium hydroxide on the structure and gas adsorption of nanosized Zr-MOFs (UiO-66).

Several zirconium-based metal-organic frameworks (Zr-MOFs) have been synthesized using ammonium hydroxide as an additive in the synthesis process. Their physicochemical properties have been characterized by N(2) adsorption/desorption, XRD, SEM, FTIR, and TGA, and their application in CO(2) adsorption was evaluated. It was found that addition of ammonium hydroxide produced some effects on the structure and adsorption behavior of Zr-MOFs. The pore size and pore volume of Zr-MOFs were enhanced with the additive, however, specific surface area of Zr-MOFs was reduced. Using an ammonium hydroxide additive, the crystal size of Zr-MOF was reduced with increasing amount of the additive. All the samples presented strong thermal stability. Adsorption tests showed that capacity of CO(2) adsorption on the Zr-MOFs under standard conditions was reduced due to decreased micropore fractions. However, modified Zr-MOFs had significantly lower adsorption heat. The adsorption capacity of carbon dioxide was increased at high pressure, reaching 8.63 mmol g(-1) at 987 kPa for Zr-MOF-NH(4)-2.

Adsorption of CH4 and CO2 on Zr-metal organic frameworks.

Zirconium-metal organic frameworks (Zr-MOFs) were synthesized with or without ammonium hydroxide as an additive in the synthesis process. It was found that addition of ammonium hydroxide would change the textural structure of Zr-MOF. The BET surface area, pore volume, and crystal size of Zr-MOF were reduced after addition of ammonium hydroxide. However, the crystalline structure and thermal stability were maintained and no functional groups were formed. Adsorption tests showed that Zr-MOF presented much higher CO(2) adsorption than CH(4). Zr-MOF exhibited CO(2) and CH(4) adsorption of 8.1 and 3.6 mmol/g, respectively, at 273 K, 988 kPa. The addition of ammonium hydroxide resulted in the Zr-MOF with a slight lower adsorption of CO(2) and CH(4), however, the selectivity of CO(2)/CH(4) is significantly enhanced.