Search results for: metal organic frameworks (MOFs)

Authors: Yongseok Hong, Kurt Louis Solis

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In the present study, a hybrid sorbent using the metal organic framework (MOF), UiO-66, and powdered activated carbon (pAC) is synthesized to remove cationic and anionic metals simultaneously. UiO-66 is an octahedron-shaped MOF with a Zr₆O₄(OH)₄ metal node and 1,4-benzene dicarboxylic acid (BDC) organic linker. Zr-based MOFs are attractive for trace element remediation in wastewaters, because Zr is relatively non-toxic as compared to other classes of MOF and, therefore, it will not cause secondary pollution. Most remediation studies with UiO-66 target anions such as fluoride, but trace element oxyanions such as arsenic, selenium, and antimony have also been investigated. There have also been studies involving mercury removal by UiO-66 derivatives, however these require post-synthetic modifications or have lower effective surface areas. Activated carbon is known for being a readily available, well-studied, effective adsorbent for metal contaminants. Solvothermal method was employed to prepare hybrid sorbent from UiO66 and activated carbon, which could be used to remove mercury and selenium simultaneously. The hybrid sorbent was characterized using FSEM-EDS, FT-IR, XRD, and TGA. The results showed that UiO66 and activated carbon are successfully composited. From BET studies, the hybrid sorbent has a SBET of 1051 m² g⁻¹. Adsorption studies were performed, where the hybrid showed maximum adsorption of 204.63 mg g⁻¹ and 168 mg g⁻¹ for Hg (II) and selenite, respectively, and follows the Langmuir model for both species. Kinetics studies have revealed that the Hg uptake of the hybrid is pseudo-2nd order and has rate constant of 5.6E-05 g mg⁻¹ min⁻¹ and the selenite uptake follows the simplified Elovich model with α = 2.99 mg g⁻¹ min⁻¹, β = 0.032 g mg⁻¹.

Keywords: adsorption, flue gas wastewater, mercury, selenite, metal organic framework

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Authors: Chun-Wei Yeh, Santhanamoorthi Nachimuthu, Jyh-Chiang Jiang

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Reducing greenhouse gases or converting them into fuels and chemicals with added value is vital for the environment. Given the enhanced techniques for hydrocarbon extraction in this context, the catalytic conversion of methane to methanol is particularly intriguing for future applications as vehicle fuels and/or bulk chemicals. Metal-organic frameworks (MOFs) have received much attention recently for the oxidation of methane to methanol. In addition, biomimetic material, particulate methane monooxygenase (pMMO), has been reported to convert methane using copper oxide clusters as active sites. Inspired by these, in this study, we considered the well-known MIL-53(Al) MOF as support for copper oxide clusters (Cu2Ox, Cu3Ox) to investigate their reactivity towards methane oxidation using Density Functional Theory (DFT) calculations. The copper oxide clusters (Cu2O2, Cu3O2) are modeled by oxidizing copper clusters (Cu2, Cu3) with two oxidizers, O2 and N2O. The initial C-H bond activation barriers on Cu2O2/MIL-53(Al) and Cu3O2/MIL-53(Al) catalysts are 0.70 eV and 0.64 eV, respectively, and are the rate-determining steps in the overall methane conversion to methanol reactions. The desorption energy of the methanol over the Cu2O/MIL-53(Al) and Cu3O/MIL-53(Al) is 0.71eV and 0.75 eV, respectively. Furthermore, to explore the prospect of catalyst reusability, we considered the different oxidants and proposed the different reaction pathways for completing the reaction cycle and regenerating the active copper oxide clusters. To know the reason for the difference between bi-copper and tri-cooper systems, we also did an electronic analysis. Finally, we calculate the Microkinetic Simulation. The result shows that the reaction can happen at room temperature.

Keywords: DFT study, copper oxide cluster, MOFs, methane conversion

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Authors: Youssef R. Hassan, Mohamed S. Hasanin, Reda M. Abdelhameed

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Recently, innovations in packaging security features become more important to see the originality of packaging in industrial application. Luminescent 3d printing materials have been a promising property which can provides a unique opportunity for the design and application of 3D printing. Lack emission of terbium ions, as a source of green emission, in salt form prevent its uses in industrial applications, so searching about stable and highly emitter material become essential. Nowadays, metal organic frameworks (MOFs) play an important role in designing light emitter material. In this work, fluorescent high density polyethylene (FHDPE) composite filament with Tb-benzene 1,3,5-tricarboxylate (Tb-BTC) MOFs for 3D printing have been successfully developed.HDPE pellets were mixed with Tb-BTC and melting extrustion with single screw extruders. It was found that Tb-BTCuniformly dispersed in the HDPE matrix and significantly increased the crystallinity of PE, which not only maintained the good thermal property but also improved the mechanical properties of Tb-BTC@HDPE composites. Notably, the composite filaments emitted ultra-bright green light under UV lamp, and the fluorescence intensity increased as the content of Tb-BTC increased. Finally, several brightly luminescent exquisite articles could be manufactured by fused deposition modeling (FDM) 3D printer with these new fluorescent filaments. In this context, the development of novel fluorescent Tb-BTC@HDPE composites was combined with 3D printing technology to amplified the packaging Security Features.

Keywords: 3D printing, fluorescent, packaging, security

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Authors: M. François, L. Sigot, C. Vallières

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Volatile Organic Compounds (VOCs) are a real health issue, particularly in domestic indoor environments. Among these VOCs, acetaldehyde is frequently monitored in dwellings ‘air, especially due to smoking and spontaneous emissions from the new wall and soil coverings. It is responsible for respiratory complaints and is classified as possibly carcinogenic to humans. Adsorption processes are commonly used to remove VOCs from the air. Metal-Organic Frameworks (MOFs) are a promising type of material for high adsorption performance. These hybrid porous materials composed of metal inorganic clusters and organic ligands are interesting thanks to their high porosity and surface area. The HKUST-1 (also referred to as MOF-199) is a copper-based MOF with the formula [Cu₃(BTC)₂(H₂O)₃]n (BTC = benzene-1,3,5-tricarboxylate) and exhibits unsaturated metal sites that can be attractive sites for adsorption. The objective of this study is to investigate the impact of HKUST-1 pretreatment on acetaldehyde adsorption. Thus, dynamic adsorption experiments were conducted in 1 cm diameter glass column packed with 2 cm MOF bed height. MOF were sieved to 630 µm - 1 mm. The feed gas (Co = 460 ppmv ± 5 ppmv) was obtained by diluting a 1000 ppmv acetaldehyde gas cylinder in air. The gas flow rate was set to 0.7 L/min (to guarantee a suitable linear velocity). Acetaldehyde concentration was monitored online by gas chromatography coupled with a flame ionization detector (GC-FID). Breakthrough curves must allow to understand the interactions between the MOF and the pollutant as well as the impact of the HKUST-1 humidity in the adsorption process. Consequently, different MOF water content conditions were tested, from a dry material with 7 % water content (dark blue color) to water saturated state with approximately 35 % water content (turquoise color). The rough material – without any pretreatment – containing 30 % water serves as a reference. First, conclusions can be drawn from the comparison of the evolution of the ratio of the column outlet concentration (C) on the inlet concentration (Co) as a function of time for different HKUST-1 pretreatments. The shape of the breakthrough curves is significantly different. The saturation of the rough material is slower (20 h to reach saturation) than that of the dried material (2 h). However, the breakthrough time defined for C/Co = 10 % appears earlier in the case of the rough material (0.75 h) compared to the dried HKUST-1 (1.4 h). Another notable difference is the shape of the curve before the breakthrough at 10 %. An abrupt increase of the outlet concentration is observed for the material with the lower humidity in comparison to a smooth increase for the rough material. Thus, the water content plays a significant role on the breakthrough kinetics. This study aims to understand what can explain the shape of the breakthrough curves associated to the pretreatments of HKUST-1 and which mechanisms take place in the adsorption process between the MOF, the pollutant, and the water.

Keywords: acetaldehyde, dynamic adsorption, HKUST-1, pretreatment influence

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Authors: Aneek Kuila, Yaron Paz

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MIP 177 LT and HT are two-phase transformable metal organic frameworks consisting of a Ti12O15 oxocluster and a tetracarboxylate ligand that exhibits robust chemical stability and improved photoactivity. LT to HT only shows the changes in dimensionality from 0D to 1D without any change in the overall chemical structure. In terms of chemical and photoactivity MIP 177 LT is found to perform better than the MIP 177HT. Step-scan Fourier transform absorption difference time-resolved spectroscopy has been used to collect mid-IR time-resolved infrared spectra of the transient electronic excited states of a nano-porous metal–organic framework MIP 177-LT and HT with 2.5 ns time resolution. Analyzing the time-resolved vibrational data after 355nm LASER excitation reveals the presence of the temporal changes of ν (O-Ti-O) of Ti-O metal cluster and ν (-COO) of the ligand concluding the fact that these moieties are the ultimate acceptors of the excited charges which are localized over those regions on the nanosecond timescale. A direct negative correlation between the differential absorbance (Δ Absorbance) reveals the charge transfer relation among these two moieties. A longer-lived transient signal up to 180ns for MIP 177 LT compared to the 100 ns of MIP 177 HT shows the extended lifetime of the reactive charges over the surface that exerts in their effectivity. An ultrafast change of bidentate to monodentate bridging in the -COO-Ti-O ligand-metal coordination environment was observed after the photoexcitation of MIP 177 LT which remains and lives with for seconds after photoexcitation is halted. This phenomenon is very unique to MIP 177 LT but not observed with HT. This in-situ change in the coordination denticity during the photoexcitation was not observed previously which can rationalize the reason behind the ability of MIP 177 LT to accumulate electrons during continuous photoexcitation leading to a superior photocatalytic activity.

Keywords: time resolved FTIR, metal organic framework, denticity, photoacatalysis

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Authors: Manasi Roy, Raju Mondal

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During last two decades the synthesis and design of MOFs or novel coordination polymers (CPs) has flourished as an emerging area of research due to their role as functional materials. Accordingly, ten new cobalt-based MOFs have been synthesized using a simple bispyrazole ligand, 4,4′-methylene-bispyrazole (H2MBP), and isophthalic acid (H2IPA) and its four 5-substituted derivatives R-H2IPA (R = COOH, OH, tBu, NH2). The major aim of this study was to validate the mutual influence of temperature and substitutions on the final structural self-assembly. Five different isophthalic acid derivatives were used to study the influence of substituents while each reaction was carried out at two different temperatures to assess the temperature effect. A clear correlation was observed between the reaction temperature and the coordination number of the cobalt atoms which consequently changes the self assembly pattern. Another fact that the periodical change in coordination number did bring about some systematic changes in the structural network via secondary building unit selectivity. With the presence of a tunable cavity inside the network, and unsaturated metal centers, MOFs show highly encouraging photocatalytic degradation of toxic dye with a potential application in waste water purification. Another fascinating aspect of this work is the construction of magnetic coordination polymers with the occurrence of a not-so-common MCE behavior of cobalt-based MOF.

Keywords: MOFs, temperature effect, MCE, dye degradation

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Authors: Hassiba Bougueria, Nesrine Benarous, Souheyla Chetioui

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Azo dyes are one of the most widely used compounds in organic chemistry, primarily due to their relatively simple preparation methods. They have therefore been widely used, in particular as colorants for textiles, printing inks, cosmetics, and food additives. In addition to their use as dyes, azo compounds have attracted much attention from chemists as their potential applications are important in coordination chemistry, metal-organic frameworks (MOF) structures, COF (covalent-organic frameworks), and catalysis. Moreover, they have found many applications in different fields, such as nonlinear optics, optical storage, photoluminescence, and magnetism. The compound bis{(E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olato}copper(II) dimethyl sulfoxide monosolvate, the CuII atom is tetracoordinate with a square-planar geometry, surrounded by two bidentate (E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalene-2-olate ligands via two N atoms and two O atoms. The O-Cu-O angles and N-Cu-N are of the order of 177.90(16)° and 177.8(2)°, respectively. The distances Cu-O and Cu- N are 1.892(4) Å and 1.976(4) Å, respectively. The cohesion of the crystal is ensured by hydrogen bonds of the C—H…O type and by π=π staking interactions [centroid–centroid distance = 3.679(4)Å]. The DMSO solvent molecule is disordered at two positions with occupancy rates of 0.70 and 0.30.

Keywords: azo dyes, DRX, structural characterization, biological activity

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Authors: Jin Yue

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Fresh produces especially fruits, vegetables, meats and aquatic products have limited shelf life and are highly susceptible to deterioration. Essential oils (EOs) extracted from plants have excellent antioxidant and broad-spectrum antibacterial activities, and they can play as natural food preservatives. But EOs are volatile, water insoluble, pungent, and easily decomposing under light and heat. Many approaches have been developed to improve the solubility and stability of EOs such as polymeric film, coating, nanoparticles, nano-emulsions and nanofibers. Construction of active packaging film which can incorporate EOs with high loading efficiency and controlled release of EOs has received great attention. It is still difficult to achieve accurate release of antibacterial compounds at specific target locations in active packaging. In this research, a relative humidity-responsive packaging material was designed, employing the electrospinning technique to fabricate a nanofibrous film loaded with a 4-terpineol/β-cyclodextrin inclusion complexes (4-TA/β-CD ICs). Functioning as an innovative food packaging material, the film demonstrated commendable attributes including pleasing appearance, thermal stability, mechanical properties, and effective barrier properties. The incorporation of inclusion complexes greatly enhanced the antioxidant and antibacterial activity of the film, particularly against Shewanella putrefaciens, with an inhibitory efficiency of up to 65%. Crucially, the film realized controlled release of 4-TA under 98% high relative humidity conditions by inducing the plasticization of polymers caused by water molecules, swelling of polymer chains, and destruction of hydrogen bonds within the cyclodextrin inclusion complex. This film with a long-term antimicrobial effect successfully extended the shelf life of Litopenaeus vannamei shrimp to 7 days at 4 °C. To further improve the loading efficiency and long-acting release of EOs, we synthesized the γ-cyclodextrin-metal organic frameworks (γ-CD-MOFs), and then efficiently anchored γ-CD-MOFs on chitosan-cellulose (CS-CEL) composite film by in situ growth method for controlled releasing of carvacrol (CAR). We found that the growth efficiency of γ-CD-MOFs was the highest when the concentration of CEL dispersion was 5%. The anchoring of γ-CD-MOFs on CS-CEL film significantly improved the surface area of CS-CEL film from 1.0294 m2/g to 43.3458 m2/g. The molecular docking and 1H NMR spectra indicated that γ-CD-MOF has better complexing and stabilizing ability for CAR molecules than γ-CD. In addition, the release of CAR reached 99.71±0.22% on the 10th day, while under 22% RH, the release pattern of CAR was a plateau with 14.71 ± 4.46%. The inhibition rate of this film against E. coli, S. aureus and B. cinerea was more than 99%, and extended the shelf life of strawberries to 7 days. By incorporating the merits of natural biopolymers and MOFs, this active packaging offers great potential as a substitute for traditional packaging materials.

Keywords: active packaging, antibacterial activity, controlled release, essential oils, food quality control

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Authors: Rasha Al-Saedi, Anthony Meijer

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The progress of new porous materials has increased rapidly over the past decade for use in applications such as catalysis, gas storage and removal of environmentally unfriendly species due to their high surface area and high thermal stability. In this work, a theoretical study of the zirconium-based metal organic framework (MOFs) were examined in order to determine their potential for gas adsorption of various guest molecules: CO2, N2, CH4 and H2. The zirconium cluster consists of an inner Zr6O4(OH)4 core in which the triangular faces of the Zr6- octahedron are alternatively capped by O and OH groups which bound to nine formate groups and three benzoate groups linkers. General formula is [Zr(μ-O)4(μ-OH)4(HCOO)9((phyO2C)3X))] where X= CH2OH, CH2NH2, CH2CONH2, n(NH2); (n = 1-3). Three types of adsorption sites on the Zr metal center have been studied, named according to capped chemical groups as the ‘−O site’; the H of (μ-OH) site removed and added to (μ-O) site, ‘–OH site’; (μ-OH) site removed, the ‘void site’ where H2O molecule removed; (μ-OH) from one site and H from other (μ-OH) site, in addition to no defect versions. A series of investigations have been performed aiming to address this important issue. First, density functional theory DFT-B3LYP method with 6-311G(d,p) basis set was employed using Gaussian 09 package in order to evaluate the gas adsorption performance of missing-linker defects in zirconium cluster. Next, study the gas adsorption behaviour on different functionalised zirconium clusters. Those functional groups as mentioned above include: amines, alcohol, amide, in comparison with non-substitution clusters. Then, dispersion-corrected density functional theory (DFT-D) calculations were performed to further understand the enhanced gas binding on zirconium clusters. Finally, study the water effect on CO2 and N2 adsorption. The small functionalized Zr clusters were found to result in good CO2 adsorption over N2, CH4, and H2 due to the quadrupole moment of CO2 while N2, CH4 and H2 weakly polar or non-polar. The adsorption efficiency was determined using the dispersion method where the adsorption binding improved as most of the interactions, for example, van der Waals interactions are missing with the conventional DFT method. The calculated gas binding strengths on the no defect site are higher than those on the −O site, −OH site and the void site, this difference is especially notable for CO2. It has been stated that the enhanced affinity of CO2 of no defect versions is most likely due to the electrostatic interactions between the negatively charged O of CO2 and the positively charged H of (μ-OH) metal site. The uptake of the gas molecule does not enhance in presence of water as the latter binds to Zr clusters more strongly than gas species which attributed to the competition on adsorption sites.

Keywords: density functional theory, gas adsorption, metal- organic frameworks, molecular simulation, porous materials, theoretical chemistry

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Authors: Hoda A. Mohammed, Esraa M. El-Fawal, Howaida M. Abd El-Salam

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Organic sulfurs in fuel oil cause serious environmental pollution and health problems. The important future direction for liquid fuel desulfurization is adsorptive desulfurization technology due to its simplicity, mild operating condition, and low cost. In this work, the well-prepared Nickel NPs were incorporated in a highly porous metal-organic framework MIL-101(Cr)) to produce Ni/Cr-MOF composite. Besides, the synthesis of Ni/Cr-MOF in the presence of Bi₂MoO₆/AC to prepare Bi₂MoO₆/AC@Ni/Cr-MOF. All the prepared composites were synthesized via a facile technique under ambient conditions to remove organosulfur compounds. The XRD, FT-IR, SEM, and BET techniques were used to characterize the prepared composites. The desulfurization performance of real gas oil by Bi₂MoO₆/AC, Ni/Cr-MOF, and Bi₂MoO₆/AC@Ni/Cr-MOF was investigated at different adsorbent doses and contact times. Bi₂MoO₆/AC@Ni/Cr-MOF shows the highest desulfurization performance, with removal efficiency reached to 80% at optimum conditions for a contact time of 4 hours.

Keywords: desulfurization, gas oil, metal-organic framework, sorption characteristics

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Authors: H. Arceo, S. Rincon, C. Ben-Youssef, J. Rivera, A. Zepeda

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Biodiesel has emerged as a material with great potential as a renewable energy replacement to current petroleum-based diesel. Recently, biodiesel production is focused on the development of more efficient, sustainable process with lower costs of production. In this sense, a “green” approach to biodiesel production has stimulated the use of sustainable heterogeneous acid catalysts, that are better alternatives to conventional processes because of their simplicity and the simultaneous promotion of esterification and transesterification reactions from low-grade, highly-acidic and water containing oils without the formation of soap. The focus of this methodology is the development of new heterogeneous catalysts that under ordinary reaction conditions could reach yields similar to homogeneous catalysis. In recent years, metal organic frameworks (MOF) have attracted much interest for their potential as heterogeneous acid catalysts. They are crystalline porous solids formed by association of transition metal ions or metal–oxo clusters and polydentate organic ligands. This hybridization confers MOFs unique features such as high thermal stability, larger pore size, high specific area, high selectivity and recycling potential. Thus, MOF application could be a way to improve the biodiesel production processes. In this work, we evaluated the catalytic activity of MOF [(4,4-bipyridine)2(O₂CCH₃)2Zn]n (MOF Zn-I) for the synthesis of biodiesel from canola oil. The reaction conditions were optimized using the response surface methodology with a compound design central with 24. The variables studied were: Reaction temperature, amount of catalyst, molar ratio oil: MetOH and reaction time. The preparation MOF Zn-I was performed by mixing 5 mmol 4´4 dipyridine dissolved in 25 mL methanol with 10 mmol Zn(O₂CCH₃)₂ ∙ 2H₂O in 25 mL water. The crystals were obtained by slow evaporation of the solvents at 60°C for 18 h. The prepared catalyst was characterized using X-ray diffraction (XRD) and Fourier transform infrared spectrometer (FT-IR). The prepared catalyst was characterized using X-ray diffraction (XRD) and Fourier transform infrared spectrometer (FT-IR). Experiments were performed using commercially available canola oil in ace pressure tube under continuous stirring. The reaction was filtered and vacuum distilled to remove the catalyst and excess alcohol, after which it was centrifuged to separate the obtained biodiesel and glycerol. 1H NMR was used to calculate the process yield. GC-MS was used to quantify the fatty acid methyl ester (FAME). The results of this study show that the acid catalyst MOF Zn-I could be used as catalyst for biodiesel production through heterogeneous transesterification of canola oil with FAME yield 82 %. The optimum operating condition for the catalytic reaction were of 142°C, 0.5% catalyst/oil weight ratio, 1:30 oil:MeOH molar ratio and 5 h reaction time.

Keywords: fatty acid methyl ester, heterogeneous acid catalyst, metal organic framework, transesterification

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Authors: Payam Hayati, Fateme Firoozbakht, Gholamhassan Azimi, Shahram Tangestaninejad

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The synthesis of a photocatalytic adsorbent involved the integration of carbon dots (CD) into a metal-organic framework (MOF) of MIL-88B(Fe) using the solvothermal technique. Characterization of the resulting CD@MIL-88B(Fe) was conducted using various analytical methods, including X-ray-based microscopic and spectroscopic techniques, electrochemical impedance spectroscopy, UV–Vis, FT-IR, DRS, TGA, and photoluminescence (PL) analysis. The adsorbent demonstrated significant photocatalytic activity, achieving up to 92% and 90% removal of amphotericin B (AmB) and naproxen (Nap) from aqueous solutions under visible light, with an RSD value of around 5%. The study explored the factors influencing the degradation of pharmaceuticals and determined the optimal conditions for the process, including pH values of 3 and 4 for AmB and Nap, a photocatalyst concentration of 0.2 g L-1, and an H2O2 concentration ranging from 40 to 50 mM. Reactive oxidative species such as ⋅OH and ⋅O2 were identified through the examination of different scavengers. Additionally, the adsorption isotherm and kinetic studies revealed that the synthesized photocatalyst functions as an effective adsorbent, with maximum adsorption capacities of 42.5 and 121.5 mg g-1 for AmB and Nap, while also serving as a photocatalytic agent for removal purposes.

Keywords: fenton-like degradation, metal-organic frameworks, heterogenous photocatalysts, naproxen

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Authors: Bulent Topcuoglu

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Repeated amendments of organic matter and intensive use of fertilizers, metal-enriched chemicals and biocides may cause soil and environmental pollution in greenhouses. Specially, the impact of heavy metal pollution of soils on food metal content and underground water quality has become a public concern. Due to potential toxicity of heavy metals to human life and environment, determining the chemical form of heavy metals in greenhouse soils is an important approach of chemical characterization and can provide useful information on its mobility and bioavailability. A sequential extraction procedure was used to estimate the availability of heavy metals (Zn, Cd, Ni, Pb and Cr) in greenhouse soils of Antalya Aksu. Zn was predominantly associated with Fe-Mn oxide fraction, major portion of Cd associated with carbonate and organic matter fraction, a major portion of (>65 %) Ni and Cr were largely associated with Fe-Mn oxide and residual fractions and Pb was largely associated with organic matter and Fe-Mn oxide fractions. Results of the present study suggest that the mobility and bioavailability of metals probably increase in the following order: Cr < Pb < Ni < Cd < Zn. Among the elements studied, Zn and Cd appeared to be the most readily soluble and potentially bioavailable metals and these metals may carry a potential risk for metal transfer in food chain and contamination to ground water.

Keywords: metal speciation, metal mobility, greenhouse soils, biosystems engineering

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Authors: Amina Adala, Nadra Debbache, Tahar Sehili

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Coordination polymers and uniformly {[Zn(II)(BIPY)(Pht)]n} (1), {[Zn (HYD)(Pht)]n} (2) (BIPY = 4,4’ bipyridine, Pht = terephtalic acid, HYD = 8-hydroxyquinoline) have been successfully synthesized by a hydrothermal process using aqueous zinc solution. The as-prepared compounds phases were characterized by X-ray diffraction (XRD), Fourier Transform Infrared spectroscopy, UV-visible spectroscopy, thermogravimetric analysis (TGA), and the electrochemistry study by the voltammetry cyclic. The results showed a crystalline phase for CP1 however, CP2 requires recrystallization; the FTIR showed the presence of characteristic bands of all ligands; besides that, TGA shows thermal stability up to 300°C. The electrochemistry study showed a good charge transfer between the ligands and Zn metal for the two components. UV-Vis measurement showed strong absorption in a wide range from UV to visible light with a band gap of 2.69 eV for CP1 and 2.56 eV for CP2, smaller than that of ZnO. This represents an alternative to using ZnO. The Ibuprofen IBP decomposition kinetics of 5.10⁻⁵ mol.L⁻¹ under solar and artificial light were studied for different irradiation conditions. Good photocatalytic properties were observed due to their high surface area.

Keywords: metal-organic frameworks, photocatalysis, photodegradation, organic pollutant, ibuprofen

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Authors: Sanja O. Podunavac-Kuzmanović, Strahinja Z. Kovačević, Lidija R. Jevrić, Stela Jokić

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The complexes of transition metals with various organic ligands have been extensively studied as models of some important pharmaceutical molecules. It was found that biological properties of different substituted organic molecules are improved when they are complexed by different metals. Therefore, it is of great importance for the development of coordination chemistry to explore the assembly of functional organic ligands with metal ion and to investigate the relationship between the structure and property. In the present work, we have bioassayed the antibacterial potency of benzimidazoles and their metal salts (Cu or Zn) against yeast Sarcina lutea. In order to validate our in vitro study, we performed in silico studies using molecular docking software. The investigated compounds and their metal complexes (Cu, Zn) showed good to moderate inhibitory activity against Sarcina lutea. In silico docking studies of the synthesized compounds suggested that complexed benzimidazoles have a greater binding affinity and improved antibacterial activity in comparison with non-complexed ligands. These results are part of the CMST COST Action No. 1105 "Functional metal complexes that bind to biomolecules".

Keywords: organometallic complexes, benzimidazoles, chemometric design, Sarcina lutea

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Authors: Iltaf Khan, Munzir H. Suliman, Muhammad Usman

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The rapid growth of modern industries has led to increased energy demand and worsened fossil fuel depletion, resulting in global warming, while organic pollutants pose significant threats to aquatic environments due to their stability, insolubleness, and non-biodegradability. So, scientists are investigating high-performance materials to resolve these issues. In this study, we prepared LaFeO₃ nanosheets (LFONS) employing a solvothermal method via a soft template such as polyvinylpyrrolidone (PVP). The LFONS have good performance regarding surface area and charge separation as compared to LaFeO₃ nanoparticles (LFONP). To improve the efficiency of LFONS, it was further modified with Ag and ZIF-67 and utilized for CO₂ conversion. Herein, the results confirm that Ag-doped and ZIF-67 coupled LFONS (ZIF-67/Ag-LFONS) exhibit superior performance compared to pristine LFONP. In addition, the stability tests confirm that our optimal sample is the most active and stable one among various nanocomposites. Ultimately, our studies will open a new pave for cost-effective, eco-friendly, and electroactive nanomaterials for CO₂ conversion.

Keywords: LaFeO₃ nanosheets, Ag incorporation, MOFs coupling, CO₂ conversion

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Authors: Sheng Huang, Xin Zhao, Xiaofeng Gao, Tao Zhou, Shijin Dai, Youcai Zhao

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Adsorption of heavy metal pollutants (Zn, Cd, Pb, Cr, Cu) and organic pesticide (phorate, dithiophosphate diethyl, triethyl phosphorothioate), along with their multi-contamination on the surface of industrial construction & demolition waste (C&D waste) was investigated. Brick powder was selected as the appropriate waste while its maximum equilibrium adsorption amount of heavy metal under single controlled contamination matrix reached 5.41, 0.81, 0.45, 1.13 and 0.97 mg/g, respectively. Effects of pH and spiking dose of ICDW was also investigated. Equilibrium adsorption amount of organic pesticide varied from 0.02 to 0.97 mg/g, which was negatively correlated to the size distribution and hydrophilism. Existence of organic pesticide on surface of ICDW caused various effects on the heavy metal adsorption, mainly due to combination of metal ions and the floccule formation along with wrapping behaviors by pesticide pollutants. Adsorption of Zn was sharply decreased from 7.1 to 0.15 mg/g compared with clean ICDW and phorate contaminated ICDW, while that of Pb, Cr and Cd experienced an increase- then decrease procedure. On the other hand, runoff of pesticide contaminants was investigated under 25 mm/h simulated rainfall. Results showed that the cumulative runoff amount fitted well with curve obtained from a power function, of which r2=0.95 and 0.91 for 1DAA (1 day between contamination and runoff) and 7DAA, respectively. This study helps provide evaluation of industrial construction and demolition waste contamination into aquatic systems.

Keywords: adsorption mechanism, industrial construction waste, metals, pesticide, runoff

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Authors: Yeseul Park

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Biopolymers produced by organisms highly contribute to the production of metal sulfides, both in extracellular and intracellular biomineralization. We discovered a new type of intracellular biomineral composed of copper sulfide in the periplasm of a sulfate-reducing bacterium. We suggest that the structural features of biomineral composed of 1-2 nm subgrains are based on biopolymer-based capping agents and an organic compartment. We further compare with other types of metal sulfide biominerals.

Keywords: biomineralization, copper sulfide, metal sulfide, biopolymer, capping agent

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Authors: Sanja O. Podunavac-Kuzmanović, Lidija R. Jevrić, Strahinja Z. Kovačević

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In last decade, metal-organic complexes have captured intensive attention because of their wide range of biological activities such as antibacterial, antifungal, anticancerous, antimicrobial and antiHIV. Therefore, it is of great importance for the development of coordination chemistry to explore the assembly of functional organic ligands with metal ion and to investigate the relationship between the structure and property. In view of our studies, we reasoned that benzimidazoles complexed to metal ions could act as a potent antibacterial agents. Thus, we have bioassayed the inhibitory potency of benzimidazoles and their metal salts (Co or Ni) against Gram negative bacteria Escherichia coli. In order to validate our in vitro study, we performed in silico studies using molecular docking software’s. The investigated compounds and their metal complexes (Co, Ni) showed good antibacterial activity against Escherichia coli. In silico docking studies of the synthesized compounds suggested that complexed benzimidazoles have a greater binding affinity and enhanced antibacterial activity in comparison with noncomplexed ligands. In view of their enhanced inhibitory properties we propose that the studied complexes can be used as potential pharmaceuticals. This study is financially supported by COST action CM1306 and the project No. 114-451-347/2015-02, financially supported by the Provincial Secretariat for Science and Technological Development of Vojvodina.

Keywords: benzimidazoles, complexes, antibacterial, Escherichia coli, metal

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Authors: Ahmed Metawea, Rodrigo Soto, Majeida Kharejesh, Gavin Walker, Ahmad B. Albadarin

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In this study, towards a green approach, we have investigated the effect of operating conditions of solvent assessed twin-screw extruder (TSE) for the production of 4, 4-bipyridine (1-dimensional coordinated polymer (1D)) based coordinated polymer using cobalt nitrate as a metal precursor with molar ratio 1:1. Different operating parameters such as solvent percentage, screw speed and feeding rate are considered. The resultant product is characterized using offline characterization methods, namely Powder X-ray diffraction (PXRD), Raman spectroscopy and scanning electron microscope (SEM) in order to investigate the product purity and surface morphology. A lower feeding rate increased the product’s quality as more resident time was provided for the reaction to take place. The most important influencing factor was the amount of liquid added. The addition of water helped in facilitating the reaction inside the TSE by increasing the surface area of the reaction for particles

Keywords: MOFS, multivariate analysis, process optimization, chemometric

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Authors: Kalyani Mer

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Hydrogen peroxide (H₂O₂) is one of the most efficient and commonly used oxidants in in-situ chemical oxidation (ISCO) of organic contaminants. In the present study, we investigated the activation of H₂O₂ by heavy metal (nickel and lead metal ions) loaded biochar for phenol degradation in an aqueous solution (concentration = 100 mg/L). It was found that H₂O₂ can be effectively activated by biochar, which produces hydroxyl (•OH) radicals owing to an increase in the formation of persistent free radicals (PFRs) on biochar surface. Ultrasound treated (30s duration) biochar, chemically activated by 30% phosphoric acid and functionalized by diethanolamine (DEA) was used for the adsorption of heavy metal ions from aqueous solutions. It was found that modified biochar could remove almost 60% of nickel in eight hours; however, for lead, the removal efficiency reached up to 95% for the same time duration. The heavy metal loaded biochar was further used for the degradation of phenol in the absence and presence of H₂O₂ (20 mM), within 4 hours of reaction time. The removal efficiency values for phenol in the presence of H₂O₂ were 80.3% and 61.9%, respectively, by modified biochar loaded with nickel and lead metal ions. These results suggested that the biochar loaded with nickel exhibits a better removal capacity towards phenol than the lead loaded biochar when used in H₂O₂ based oxidation systems. Meanwhile, control experiments were set in the absence of any activating biochar, and the removal efficiency was found to be 19.1% when only H₂O₂ was added in the reaction solution. Overall, the proposed approach serves a dual purpose of using biochar for heavy metal ion removal and treatment of organic contaminants by further using the metal loaded biochar for H₂O₂ activation in ISCO processes.

Keywords: biochar, ultrasound, heavy metals, in-situ chemical oxidation, chemical activation

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Authors: Akanimo Emene, Mark D. Ogden, Robert Edyvean

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Adsorption is a low cost, efficient and economically viable wastewater treatment process. Utilization of this treatment process has not been fully applied due to the complex and not fully understood nature of the adsorption system. To optimize its process is to choose a sufficient adsorbent and to study further the experimental parameters that influence the adsorption design system. Chemically modified adsorbent, Luffa cylindrica, was used to adsorb heavy metal ions and an organic pollutant, methylene blue, from aqueous environmental solution at varying experimental conditions. Experimental factors, adsorption time, initial metal ion or organic pollutant concentration, ionic strength, and pH of solution were studied. The experimental data were analyzed with kinetic and isotherm models. The antagonistic effect of the methylene and some heavy metal ions were recorded. An understanding of the use of this treated Luffa cylindrica for the removal of these toxic substances will establish and improve the commercial application of the adsorption process in treatment of contaminated waters.

Keywords: adsorption, heavy metal ions, Luffa cylindrica, wastewater treatment

Procedia PDF Downloads 165

Authors: Eleni Tsalaporta, Sebastien Vaesen, James M. D. MacElroy, Wolfgang Schmitt

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Carbon dioxide capture has attracted the attention of many governments, industries and scientists over the last few decades, due to the rapid increase in atmospheric CO2 composition, with several studies being conducted in this area over the last few years. In many of these studies, CO2 capture in complex Pressure Swing Adsorption (PSA) cycles has been associated with high energy consumption despite the promising capture performance of such processes. The purpose of this study is the economic capture of atmospheric carbon dioxide for its transformation into a clean type of energy. A single column Temperature /Vacuum Swing Adsorption (TSA/VSA) process is proposed as an alternative option to multi column Pressure Swing Adsorption (PSA) processes. The proposed adsorbent is SIFSIX-3-Ni, a newly developed MOF (Metal Organic Framework), with extended CO2 selectivity and capacity. There are three stages involved in this paper: (i) SIFSIX-3-Ni is synthesized and pelletized and its physical and chemical properties are examined before and after the pelletization process, (ii) experiments are designed and undertaken for the estimation of the diffusion and adsorption parameters and limitations for CO2 undergoing capture from the air; and (iii) the CO2 adsorption capacity and dynamical characteristics of SIFSIX-3-Ni are investigated both experimentally and mathematically by employing a single column TSA/VSA, for the capture of atmospheric CO2. This work is further supported by a technical-economical study for the estimation of the investment cost and the energy consumption of the single column TSA/VSA process. The simulations are performed using gProms.

Keywords: carbon dioxide capture, temperature/vacuum swing adsorption, metal organic frameworks, SIFSIX-3-Ni

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Authors: Anushree, Chhaya Sharma, Satish Kumar

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Catalytic wet air oxidation (CWAO) is normally carried out at elevated temperature and pressure. This work investigates the potential of NiO-CeO₂ nano-catalyst in CWAO of paper industry wastewater under milder operating conditions of 90 °C and 1 atm. The NiO-CeO₂ nano-catalysts were synthesized by a simple co-precipitation method and characterized by X-ray diffraction (XRD), before and after use, in order to study any crystallographic change during experiment. The extent of metal-leaching from the catalyst was determined using the inductively coupled plasma optical emission spectrometry (ICP-OES). The catalytic activity of nano-catalysts was studied in terms of total organic carbon (TOC), adsorbable organic halides (AOX) and chlorophenolics (CHPs) removal. Interestingly, mixed oxide catalysts exhibited higher activity than the corresponding single-metal oxides. The maximum removal efficiency was achieved with Ce₄₀Ni₆₀ catalyst. The results indicate that the CWAO process is efficient in removing the priority organic pollutants from wastewater, as it exhibited up to 59% TOC, 55% AOX, and 54 % CHPs removal.

Keywords: catalysis, nano-materials, NiO-CeO2, paper mill, wastewater, wet air oxidation

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Authors: Yuri A. Kalvachev, Totka D. Todorova

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Zeolite mordenite has been investigated as a transition metal support for the preparation of efficient catalysts in the oxidation of volatile organic compounds (VOCs). The highly crystalline mordenite samples were treated with hydrofluoric acid and ammonium fluoride to get hierarchical material with secondary porosity. The obtained supports by this method have a high active surface area, good diffusion properties and prevent the extraction of metal components during catalytic reactions. The active metal phases platinum and copper were loaded by impregnation on both mordenite materials (parent and acid treated counterparts). Monometalic Pt and Cu, and bimetallic Pt/Cu catalysts were obtained. The metal phases were fine dispersed as nanoparticles on the functional porous materials. The catalysts synthesized in this way were investigated in the reaction of complete oxidation of propane and benzene. Platinum, copper and platinum/copper were loaded and there catalytic activity was investigated and compared. All samples are characterized by X-ray diffraction analysis, nitrogen adsorption, scanning electron microscopy (SEM), X-ray photoelectron measurements (XPS) and temperature programed reduction (TPR). The catalytic activity of the samples obtained is investigated in the reaction of complete oxidation of propane and benzene by using of Gas Chromatography (GC). The oxidation of three organic molecules was investigated—methane, propane and benzene. The activity of metal loaded mordenite catalysts for methane oxidation is almost the same for parent and treated mordenite as a support. For bigger molecules as propane and benzene, the activity of catalysts based on treated mordenite is higher than those based on parent zeolite.

Keywords: metal loaded catalysts, mordenite, VOCs oxidation, zeolites

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Authors: Muhammad Umair Mushtaq, Ameena Iqbal, Muhammad Aqib Hassan Ali Khan, Ismat Nawaz, Sohail Yousaf, Mazhar Iqbal

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Heavy metals are one of the priority pollutants as they pose serious health and environmental threats. They can be removed by various physiochemical methods but are costly and responsible for additional environmental problems. Bioremediation that exploits plants and their associated microbes have been referred as cost effective and environmental friendly technique. In this study, a pot experiment was conducted in a greenhouse to evaluate the potential of Celosia cristata and effects of bacteria, Pseudomonas japonica, and organic amendment moss/compost on tolerating/accumulating heavy metals. Two weeks old seedlings were transferred to soil in pots, and after four weeks they were inoculated with bacterial strain, while after growth of six weeks they were watered with a metal containing synthetic wastewater and were harvested after a growth period of nine weeks. After harvesting, morphological and physiological parameters and metal content of plants were measured. The results showed highest plant growth and biomass production in case of organic amendments while highest metal uptake has been found in non-amended pots. Positive controls have shown highest Pb uptake of 2900 mg/kg DW, while P. japonica amended pots have shown highest Cd, Cr, Ni and Cu uptake of 963.53, 1481.17, 1022.01 and 602.17 mg/kg DW, respectively. In conclusion organic amendments have strong impacts on growth enhancement while P. japonica enhances metal translocation and accumulation to aerial parts with little significant involvement in plant growth.

Keywords: ornamental plants, plant microbe interaction, amendments, bacteria

Procedia PDF Downloads 254

Authors: Tiantian Min, Chuanxiang Cheng, Jin Yue

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The growth and reproduction of microorganisms in food packaging can cause food decay and foodborne diseases, which pose a serious threat to the health of consumers and even cause serious economic losses. Active food packaging containing antibacterial bioactive compounds is a promising strategy for extending the shelf life of products and maintaining the food quality, as well as reducing the food waste. However, most active packaging can only act as slow-release effect for antimicrobials, which causes the release rate of antimicrobials not match the growth rate of microorganisms. Stimuli-responsive active packaging materials based on biopolymeric substrates and bioactive substances that respond to some biological and non-biological trigger factors provide more opportunities for fresh food preservation. The biological stimuli factors such as relative humidity, pH and enzyme existed in the exudate secreted by microorganisms have been expected to design food packaging materials. These stimuli-responsive materials achieved accurate release or delivery of bioactive substances at specific time and appropriate dose. Recently, metal-organic-frameworks (MOFs) nanoparticles become attractive carriers to enhance the efficiency of bioactive compounds or drugs. Cellulose nanofibrils have been widely applied for film substrates due to their biodegradability and biocompatibility. The abundant hydroxyl groups in cellulose can be oxidized to carboxyl groups by TEMPO, making it easier to anchoring MOFs and to be further modification. In this study, a pH and enzyme dual-responsive CAR@ZIF-8/TOCNF/PE film was fabricated by in-situ growth of ZIF-8 nanoparticles onto TEMPO-oxidized cellulose (TOCNF) film and further coated with pectin (PE) for stabilization and controlled release of carvacrol (CAR). The enzyme triggered release of CAR was achieved owing to the degradation of pectin by pectinase secreted by microorganisms. Similarly, the pH-responsive release of CAR was attributed to the unique skeleton degradation of ZIF-8, further accelerating the release of CAR from the topological structure of ZIF-8. The composite film performed excellent crystallinity and adsorb ability confirmed by X-ray diffraction and BET analysis, and the inhibition efficiency against Escherichia coli, Staphylococcus aureus and Aspergillus niger reached more than 99%. The composite film was capable of releasing CAR when exposure to dose-dependent enzyme (0.1, 0.2, and 0.3 mg/mL) and acidic condition (pH = 5). When inoculated 10 μL of Aspergillus niger spore suspension on the equatorial position of mango and raspberries, this composite film acted as packaging pads effectively inhibited the mycelial growth and prolonged the shelf life of mango and raspberries to 7 days. Such MOF-TOCNF based film provided a targeted, controlled and sustained release of bioactive compounds for long-term antibacterial activity and preservation effect, which can also avoid the cross-contamination of fruits.

Keywords: active food packaging, controlled release, fruit preservation, in-situ growth, stimuli-responsive

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Authors: A. Giwa, S. M. Jung, W. Fang, J. Kong, S. W. Hasan

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MnO₂ nanowires were developed as filtration media for wastewater treatment that uniquely combines several advantages. The resulting material demonstrated strong capability to remove the pollution of heavy metal ions and organic contents in water. In addition, the manufacture process of such material is practical and economical. In this work, MnO₂ nanowires were integrated with the state-of-art bio-electrochemical system for wastewater treatment, to overcome problems currently encountered with organic, inorganic, heavy metal, and microbe removal, and to minimize the unit footprint (land/space occupation) at low cost. Results showed that coupling the bio-electrochemical with MnO₂ resulted in very encouraging results with higher removal efficiencies of such pollutants.

Keywords: bio-electrochemical, nanowires, novel, wastewater

Procedia PDF Downloads 351

Authors: E. Gil, A. Zepeda, J. Rivera, C. Ben-Youssef, S. Rincón

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Water pollution has become one of the most serious environmental problems. Multiple methods have been proposed for the removal of Pb(II) from contaminated water. Among these, adsorption processes have shown to be more efficient, cheaper and easier to handle with respect to other treatment methods. However, research for adsorbents with high adsorption capacities is still necessary. For this purpose, we proposed in this work the study of metal-organic Framework [Co2(btec)(bipy)(DMF)2]n (MOF-Co) as adsorbent material of Pb (II) in aqueous media. MOF-Co was synthesized by a simple method. Firstly 4, 4’ dipyridyl, 1,2,4,5 benzenetetracarboxylic acid, cobalt (II) and nitrate hexahydrate were first mixed each one in N,N dimethylformamide (DMF) and then, mixed in a reactor altogether. The obtained solution was heated at 363 K in a muffle during 68 h to complete the synthesis. It was washed and dried, obtaining MOF-Co as the final product. MOF-Co was characterized before and after the adsorption process by Fourier transforms infrared spectra (FTIR) and X-ray photoelectron spectroscopy (XPS). The Pb(II) in aqueous media was detected by Absorption Atomic Spectroscopy (AA). In order to evaluate the adsorption process in the presence of Pb(II) in aqueous media, the experiments were realized in flask of 100 ml the work volume at 200 rpm, with different MOF-Co quantities (0.0125 and 0.025 g), pH (2-6), contact time (0.5-6 h) and temperature (298,308 and 318 K). The kinetic adsorption was represented by pseudo-second order model, which suggests that the adsorption took place through chemisorption or chemical adsorption. The best adsorption results were obtained at pH 5. Langmuir, Freundlich and BET equilibrium isotherms models were used to study the adsorption of Pb(II) with 0.0125 g of MOF-Co, in the presence of different concentration of Pb(II) (20-200 mg/L, 100 mL, pH 5) with 4 h of reaction. The correlation coefficients (R2) of the different models show that the Langmuir model is better than Freundlich and BET model with R2=0.97 and a maximum adsorption capacity of 833 mg/g. Therefore, the Langmuir model can be used to best describe the Pb(II) adsorption in monolayer behavior on the MOF-Co. This value is the highest when compared to other materials such as the graphene/activated carbon composite (217 mg/g), biomass fly ashes (96.8 mg/g), PVA/PAA gel (194.99 mg/g) and MOF with Ag12 nanoparticles (120 mg/g).

Keywords: adsorption, heavy metals, metal-organic frameworks, Pb(II)

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Authors: Sachin Saxena, Manju Srivastava

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The present study describes a stable, highly sensitive and selective analytical sensor. Fe-BTC was synthesized at room temperature using the noble Iron-trimesate system. The high surface area of as synthesized Fe-BTC proved MOFs as ideal modifiers for glassy carbon electrode. The characterization techniques such as TGA, XRD, FT-IR, BET (BET surface area= 1125 m2/gm) analysis explained the electrocatalytic behaviour of Fe-BTC towards these two drugs. The material formed is cost effective and exhibit higher catalytic behaviour towards analyte systems. The synergism between synthesized Fe-BTC and electroanalytical techniques helped in developing a highly sensitive analytical method for studying the redox fate of ARP and RZ, respectively. Cyclic voltammetry of ferricyanide system proved Fe-BTC/GCE with an increase in 132% enhancement in peak current value as compared to that of GCE. The response characteristics of cyclic voltammetry (CV) and square wave voltammetry (SWV) revealed that the ARP and RZ could be effectively accumulated at Fe-BTC/GCE. On the basis of the electrochemical measurements, electrode dynamics parameters have been evaluated. Present study opens up new field of applications of MOFs modified GCE for drug sensing.

Keywords: MOFs, anti-psychotic, electrochemical sensor, anti-migraine drugs

Procedia PDF Downloads 135