Search results for: metal organic frameworks(MOFs)

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: V. K. Srivastava

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The chemistry of compounds containing transition metals bound to sulfur containing ligands has been actively studied. Interest in these compounds arises from the identification of the biological importance of iron-sulfur containing proteins as well as the unusual behaviour of several types of synthetic metal-sulfur complexes. Metal complexes (C₆H₅)₄P)₂ Pt(Mos₄)₂, (C₆H₅)₄P)₂ Pd(MoS₄)₂, (C₆H₅)₄P)₂ Ni(MoS₄)₂ of bioinorganic relevance were investigated. The complexes [M(M'S₄)₂]²⁻ were prepared with high yield and purity as salts of the variety of organic cations. The diamagnetism and spectroscopic properties of these complexes confirmed that their structures are essentially equivalent with two bidentate M'S₄²⁻ ligands coordinated to the central d⁸ metal in a square planer geometry. The interaction of the complexes with CT-DNA was studied. Results showed that metal complexes increased DNA's relative viscosity and quench the fluorescence intensity of EB bound to DNA. In antimicrobial activities, all complexes showed good antimicrobial activity higher than ligand against gram positive, gram negative bacteria and fungi. The antitumor properties have been tested in vitro against two tumor human cell lines, Hela (derived from cervical cancer) and MCF-7 (derived from breast cancer) using metabolic activity tests. Result showed that the complexes are promising chemotherapeutic alternatives in the search of anticancer agents.

Keywords: anti cancer, biocidal, DNA binding, spectra

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Authors: Schirin Hanf, Carlos Lizandara-Pueyo, Timmo P. Emmert, Ivana Jevtovikj, Roger Gläser, Stephan A. Schunk

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Metal alkoxides are very versatile precursors for a broad array of complex functional materials. However, metal alkoxides, especially transition metal alkoxides, tend to form oligomeric structures due to the very strong M–O–M binding motif. This fact hinders their facile application in sol-gel-processes and complicates access to complex carbonate or oxidic compounds after hydrolysis of the precursors. Therefore, the development of a synthetic alternative with the aim to grant access to carbonates and hydroxycarbonates from simple metal alkoxide precursors via hydrolysis is key to this project. Our approach involves the reaction of metal alkoxides with unsaturated isoelectronic molecules, such as carbon dioxide. Subsequently, a stoichiometric insertion of the CO₂ into the alkoxide M–O bond takes place and leads to the formation of soluble metal alkyl carbonates. This strategy is a very elegant approach to solubilize metal alkoxide precursors to make them accessible for sol-gel chemistry. After hydrolysis of the metal alkyl carbonates, crystalline metal carbonates, and hydroxycarbonates can be obtained, which were then utilized for the synthesis of Cu/Zn based bulk catalysts for methanol synthesis. Using these catalysts, a comparable catalytic activity to commercially available MeOH catalysts could be reached. Based on these results, a complement for traditional precipitation techniques, which are usually utilized for the synthesis of bulk methanol catalysts, have been found based on an alternative solubilization strategy.

Keywords: metal alkoxides, metal carbonates, metal hydroxycarbonates, CO₂ insertion, solubilization

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Authors: Pawan P. Kalbende, Anil B. Zade

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A novel terpolymer resin has been synthesized by condensation polymerization reaction of 4,4’-biphenol and 4,4’-oxydianiline with formaldehyde in presence of 2M hydrochloric acid as catalyst. Composition of resin was determined on the basis of their elemental analysis and further characterized by UV-Visible, infra-red and nuclear magnetic resonance spectroscopy to confine the most probable structure of synthesized terpolymer. Newly synthesized terpolymer was proved to be a selective chelating ion-exchanger for certain metal ions and were studied for Fe3+, Cu2+, Ni2+, Co2+, Zn2+, Cd2+, Hg2+ and Pb2+ ions using their metal nitrate solutions. A batch equilibrium method was employed to study the selectivity of metal ions uptake involving the measurements of the distribution of a given metal ion between the terpolymer sample and a solution containing the metal ion. The study was carried out over a wide pH range, shaking time and in media of different electrolytes at different ionic strengths. Distribution ratios of metal ions were found to be increased by rising pH of the solutions. Hence, it can be used to recover certain metal ions from waste water for the purpose of purification of water and removal of iron from boiler water.

Keywords: terpolymers, ion-exchangers, distribution ratio, metal ion uptake

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Authors: Berk Kılıç, Ömer Aydın, Kerem Mestani, Defne Uzun

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In agriculture and farming, pesticides are frequently used to kill off or fend off any pests (bugs, bacteria, fungi, etc.). However, traditional pesticides have proven to have harmful effects on both the environment and the human body, such as hazards in the endocrine, neurodevelopmental, and reproductive systems. This experiment aims to test the effectiveness of organic/bio-pesticides (environmentally friendly pesticides) compared to traditional pesticides. Black pepper and garlic will be used as biopesticides in this experiment. The results support that organic farming applying organic pesticides operates through non-toxic mechanisms, offering minimal threats to human well-being and the environment. Consequently, consuming organic produce can significantly diminish the dangers associated with pesticide intake. In this study, method is introduced to reduce pesticide-related risks by promoting organic farming techniques within organic/bio-pesticide usage.

Keywords: pesticide, garlic, black pepper, bio-pesticide

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Authors: Olawole Emmanuel Aina, Liziwe Lizbeth Mugivhisa, Joshua Oluwole Olowoyo, Chikwela Lawrence Obi

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In sustained and consistent efforts to improve food security, numerous and different methods are proposed and used in the production of food crops, and farm produce to meet the demands of consumers. However, unregulated and indiscriminate methods of production present another problem that may expose consumers of these food crops to potential health risks. Therefore, it is imperative that a thorough assessment of farm produce is carried out due to the growing trend of health-conscious consumers preference for minimally processed or raw farm produce. This study evaluated the safety and nutritional quality of food crops. The objectives were to compare the nutritional quality of organic and inorganic farm produce in one hand and, on the other, evaluate the safety of farm produce with respect to trace metal and pathogenic contamination. We conducted a broad systematic search of peer-reviewed published literatures from databases and search engines such as science direct, web-of-science, Google scholar, and Scopus. This study concluded that there is no conclusive evidence to support the notion of nutritional superiority of organic food crops over their inorganic counterparts and there are documented reports of pathogenic and metal contaminations of food crops.

Keywords: food crops, fruits and vegetables, pathogens, nutrition, trace metals

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Authors: Rinku Varghese, S. Chandrakaran, K. Rangaswamy

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The standard one-dimensional consolidation test is used to find the consolidation behaviour of artificially consolidated organic soils. Incremental loading tests were conducted on the clay without and with organic matter. The study was conducted with soil having different organic content keeping all other parameters constant. The tests were conducted on clay and artificially prepared organic soil sample at different vertical pressure. The load increment ratio considered for the test is equal to one. Artificial organic soils are used for the test by adding starch to the clay. The percentage of organic content in starch is determined by adding 5% by weight starch into the clay (inorganic soil) sample and corresponding change in organic content of soil was determined. This was expressed as percentage by weight of starch, and it was found that about 95% organic content in the soil sample. Accordingly percentage of organic content fixed and added to the sample for testing to understand the consolidation behaviour clayey soils with organic content. A detailed study of the results obtained from IL test was investigated. The main items investigated were (i) coefficient of consolidation (cv), (ii) coefficient of volume compression (mv), (iii) coefficient of permeability (k). The consolidation parameter obtained from IL test was used for determining the creep strain and creep parameter and also predicting their variation with vertical stress and organic content.

Keywords: consolidation, secondary compression, creep, starch

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Authors: Mohammad Mahdi Mohammadi

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Zinc-coated steel sheets have been joined with aluminum samples in an overlapping as well as in a butt-joint configuration. A bi-metal-wire composed from aluminum and steel was used for additional welding experiments. An advantage of the laser-assisted bi-metal-wire welding is that the welding process is simplified since the primary joint between aluminium and steel exists already and laser welding occurs only between similar materials. FEM-simulations of the process were chosen to determine the ideal dimensions with respect to the formability of the bi-metal-wire. A prototype demonstrated the feasibility of the process.

Keywords: car body, steel sheets, formability of bi-metal-wire, laser-assisted bi-metal-wire

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Authors: Piluntana Panpluem, Monticha Putsakum

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The objectives of this study were to investigate 1) consumers’ behaviors in buying organic products; and 2) the relationships between personal factors, cultural factors, social factors, psychological factors and marketing mix factors, and the behavior in buying organic products of consumers in the greater Bangkok metropolitan area. The sample group was 400 consumers at the age of 15 and older, who bought organic agricultural products from green markets and green shops in Bangkok, including its suburbs. The data were collected by using a questionnaire, which were analyzed by descriptive statistics and chi-square test. The results showed that the consumers bought 3 – 4 types of fresh vegetables with a total expenditure of less than 499 Baht each time. They purchased organic products mainly at a supermarket, 2 – 4 times per month, most frequently on Sundays, which took less than 30 minutes of shopping each time. The purpose of the purchase was for self-consuming. Gaining or retaining good health was the reason for the consumption of the products. Additionally, the first considered factor in the organic product selection was the quality. The decisions in purchasing the products were made directly by consumers, who were influenced mainly by advertising media on television. For the relationships among personal, cultural, social, psychological and marketing mix factors, and consumers’ behavior in buying organic products, the results showed the following: 1) personal factors, which were gender, age and educational level, were related to the behavior in terms of “What”, “Why”, and “Where” the consumers bought organic products (p<0.05); 2) cultural factors were related to “Why” the consumers bought organic products (p<0.05); 3) social factors were related to “Where” and “How” the consumers bought organic products (p<0.05); 4) psychological factors were related to “When” the consumers bought organic products (p<0.05). 5) For the marketing mix factors, “Product” was related to “Who participated” in buying, “What” and “Where” the consumers bought organic products (p<0.05), while “Price” was related to “What” and “When” the consumers bought organic products (p<0.05). “Place” was related to “What” and “How” the consumers bought organic products (p<0.05). Furthermore, “Promotion” was related to “What” and “Where” the consumers bought organic products (p<0.05).

Keywords: consumer behavior, organic products, Bangkok Metropolis and Vicinity

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Authors: Yu-Jen Shih, Juan-Zhang Lou

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Nitrogenous compounds, such as NH4+/NH3 and NO3-, have become important contaminants in water resources. Excessive concentration of NH3 leads to eutrophication, which poses a threat to aquatic organisms in the environment. Electrochemical oxidation emerged as a promising water treatment technology, offering advantages such as simplicity, small-scale operation, and minimal reliance on additional chemicals. In this study, a nickel-based metal-organic framework (Ni-MOF) was synthesized using 2-amino terephthalic acid (BDC-NH2) and nickel nitrate. The Ni-MOF was further carbonized as derived nickel oxide and nitrogen-carbon composite, Ni/NiOx/NC. The nickel oxide within the 2D porous carbon texture served as active sites for ammonia oxidation. Results of characterization showed that the Ni-MOF was a hexagonal and flaky nanoparticle. With increasing carbonization temperature, the nickel ions in the organic framework re-crystallized as NiO clusters on the surfaces of the 2D carbon. The electrochemical surface area of Ni/NiOx/NC significantly increased as to improve the efficiency of ammonia oxidation. The phase transition of Ni(OH)2⇌NiOOH at around +0.8 V was the primary mediator of electron transfer. Batch electrolysis was conducted under constant current and constant potential modes. The electrolysis parameters included pyrolysis temperatures, pH, current density, initial feed concentration, and electrode potential. The constant current batch experiments indicated that via carbonization at 800 °C, Ni/NiOx/NC(800) was able to decrease the ammonium nitrogen of 50 mg-N/L to below 1 ppm within 4 hours at a current density of 3 mA/cm2 and pH 11 with negligible oxygenated nitrogen formation. The constant potential experiments confirmed that N2 nitrogen selectivity was enhanced up to 90% at +0.8 V.

Keywords: electrochemical oxidation, nickel oxyhydroxide, metal-organic framework, ammonium, nitrate

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Authors: Satya P. Dubey, Hrushikesh A Abhyankar, Veronica Marchante, James L. Brighton, Björn Bergmann

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Aims: To develop a mathematical model that simulates the ROP of PLA taking into account the effect of alternative energy to be implemented in a continuous reactive extrusion production process of PLA. Introduction: The production of large amount of waste is one of the major challenges at the present time, and polymers represent 70% of global waste. PLA has emerged as a promising polymer as it is compostable, biodegradable thermoplastic polymer made from renewable sources. However, the main limitation for the application of PLA is the traces of toxic metal catalyst in the final product. Thus, a safe and efficient production process needs to be developed to avoid the potential hazards and toxicity. It has been found that alternative energy sources (LASER, ultrasounds, microwaves) could be a prominent option to facilitate the ROP of PLA via continuous reactive extrusion. This process may result in complete extraction of the metal catalysts and facilitate less active organic catalysts. Methodology: Initial investigation were performed using the data available in literature for the reaction mechanism of ROP of PLA based on conventional metal catalyst stannous octoate. A mathematical model has been developed by considering significant parameters such as different initial concentration ratio of catalyst, co-catalyst and impurity. Effects of temperature variation and alternative energies have been implemented in the model. Results: The validation of the mathematical model has been made by using data from literature as well as actual experiments. Validation of the model including alternative energies is in progress based on experimental data for partners of the InnoREX project consortium. Conclusion: The model developed reproduces accurately the polymerisation reaction when applying alternative energy. Alternative energies have a great positive effect to increase the conversion and molecular weight of the PLA. This model could be very useful tool to complement Ludovic® software to predict the large scale production process when using reactive extrusion.

Keywords: polymer, poly-lactic acid (PLA), ring opening polymerization (ROP), metal-catalyst, bio-degradable, renewable source, alternative energy (AE)

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Authors: Ali Moarrefzadeh

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In metalworking, rolling is a metal forming process in which metal stock is passed through a pair of rolls. Rolling is classified according to the temperature of the metal rolled. If the temperature of the metal is above its recrystallization temperature, then the process is termed as hot rolling. If the temperature of the metal is below its recrystallization temperature, the process is termed as cold rolling. In terms of usage, hot rolling processes more tonnage than any other manufacturing process, and cold rolling processes the most tonnage out of all cold working processes. This article describes the use of advanced tubing inspection NDT methods for boiler and heat exchanger equipment in the petrochemical industry to supplement major turnaround inspections. The methods presented include remote field eddy current, magnetic flux leakage, internal rotary inspection system and eddy current.

Keywords: hot forming, cold forming, metal, rolling, simulation

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Authors: Gabriela Wyszogrodzka, Przemyslaw Dorozynski, Barbara Gil, Maciej Strzempek, Bartosz Marszalek, Piotr Kulinowski, Wladyslaw Piotr Weglarz, Elzbieta Menaszek

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MOFs (Metal-Organic Frameworks) belong to a new group of porous materials with a hybrid organic-inorganic construction. Their structure is a network consisting of metal cations or clusters (acting as metallic centers, nodes) and the organic linkers between nodes. The interest in MOFs is primarily associated with the use of their well-developed surface and large porous. Possibility to build MOFs of biocompatible components let to use them as potential drug carriers. Furthermore, forming MOFs structure from cations possessing paramagnetic properties (e.g. iron cations) allows to use them as MRI (Magnetic Resonance Imaging) contrast agents. The concept of formation of particles that combine the ability to transfer active substance with imaging properties has been called theranostic (from words combination therapy and diagnostics). By building MOF structure from iron cations it is possible to use them as theranostic agents and monitoring the distribution of the active substance after administration in real time. In the study iron-MOF: Fe-MIL-101-NH2 was chosen, consisting of iron cluster in nodes of the structure and amino-terephthalic acid as a linker. The aim of the study was to investigate the possibility of applying Fe-MIL-101-NH2 as inhalable theranostic particulate system for the first-line anti-tuberculosis antibiotic – isoniazid. The drug content incorporated into Fe-MIL-101-NH2 was evaluated by dissolution study using spectrophotometric method. Results showed isoniazid encapsulation efficiency – ca. 12.5% wt. Possibility of Fe-MIL-101-NH2 application as the MRI contrast agent was demonstrated by magnetic resonance tomography. FeMIL-101-NH2 effectively shortening T1 and T2 relaxation times (increasing R1 and R2 relaxation rates) linearly with the concentrations of suspended material. Images obtained using multi-echo magnetic resonance imaging sequence revealed possibility to use FeMIL-101-NH2 as positive and negative contrasts depending on applied repetition time. MOFs micronization via ultrasound was evaluated by XRD, nitrogen adsorption, FTIR, SEM imaging and did not influence their crystal shape and size. Ultrasonication let to break the aggregates and achieve very homogeneously looking SEM images. MOFs cytotoxicity was evaluated in in vitro test with a highly sensitive resazurin based reagent PrestoBlue™ on L929 fibroblast cell line. After 24h no inhibition of cell proliferation was observed. All results proved potential possibility of application of ironMOFs as an isoniazid carrier and as MRI contrast agent in inhalatory treatment of tuberculosis. Acknowledgments: Authors gratefully acknowledge the National Science Center Poland for providing financial support, grant no 2014/15/B/ST5/04498.

Keywords: imaging agents, metal-organic frameworks, theranostics, tuberculosis

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Authors: Bahaa Eltahawy, Mikko Ylihärsilä, Reino Virrankoski, Esko Petäjä

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Sheet metal processing is automated, but the step from product models to the production machine control still requires human intervention. This may cause time consuming bottlenecks in the production process and increase the risk of human errors. In this paper we present a system, which automatically recognizes features from the CAD-model of the sheet metal product. By using these features, the system produces a complete model of the particular sheet metal product. Then the model is used as an input for the sheet metal processing machine. Currently the system is implemented, capable to recognize more than 11 of the most common sheet metal structural features, and the procedure is fully automated. This provides remarkable savings in the production time, and protects against the human errors. This paper presents the developed system architecture, applied algorithms and system software implementation and testing.

Keywords: feature recognition, automation, sheet metal manufacturing, CAD, CAM

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Authors: P. Charvin, R. Bourrou, F. Lemont, C. Lafon, A. Russello

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For nuclear waste treatment and confinement, a specific IN-CAN melting module based on low-frequency induction heating have been designed. The frequency of 50Hz has been chosen to improve penetration length through metal. In this design, the liquid metal, strongly stirred by electromagnetic effects, presents shape of a dome caused by strong Laplace forces developing in the bulk of bath. Because of a lower density, the glass phase is located above the metal phase and is heated and stirred by metal through interface. Electric parameters (Intensity, frequency) give precious information about metal load and composition (resistivity of alloy) through impedance modification. Then, power supply can be adapted to energy transfer efficiency for suitable process supervision. Modeling of this system allows prediction of metal dome shape (in agreement with experimental measurement with a specific device), glass and metal velocity, heat and motion transfer through interface. MHD modeling is achieved with COMSOL and Fluent. First, a simplified model is used to obtain the shape of the metal dome. Then the shape is fixed to calculate the fluid flow and the thermal part.

Keywords: electromagnetic stirring, induction heating, interface modeling, metal load

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Authors: Sadia Ata, Anila Tabassum, Samina ghafoor, Ijaz ul Mohsin, Azam Muktar

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Heavy metal ions such as Pb2+, Cd2+, Zn2+, Ni2+ and Hg2+, in wastewater are considered as the serious environmental problem. Among these heavy metals, Lead or Pb (II) is the most toxic heavy metal. Exposure to lead causes damage of nervous system, mental retardation, renal kidney disease, anemia and cancer in human beings. Adsorption is the most widely used method to remove metal ions based on the physical interaction between metal ions and sorbents. With the development of nanotechnology, nano-sized materials are proved to be effective sorbents for the removal of heavy metal ions from wastewater due to their unique structural properties. The present work mainly focuses on the synthesis of NiO and ZnO nanoparticles for the removal of Lead ions, their preparation, characterization by XRD, FTIR, SEM, and TEM, adsorption characteristics and mechanism, along with adsorption isotherm model and adsorption kinetics to understand the adsorption procedure.

Keywords: heavy metal, adsorption isotherms, nanoparticles, wastewater

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Authors: Mousaab Alrhmoun, Magali Casellas, Michel Baudu, Christophe Dagot

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The aim of the study is to improve removal of trace organic contaminants dissolved in activated sludge by the process of filtration with membrane bioreactor combined with modified activated carbon, for a maximum removal of organic compounds characterized by low molecular weight. Special treatment was conducted in laboratory on activated carbon. Tow reaction parameters: The pH of aqueous middle and the type of granular activated carbon were very important to improve the removal and to motivate the electrostatic Interactions of organic compounds with modified activated carbon in addition to physical adsorption, ligand exchange or complexation on the surface activated carbon. The results indicate that modified activated carbon has a strong impact in removal 21 of organic contaminants and in percentage of 100% of the process.

Keywords: activated carbon, organic micropolluants, membrane bioreactor, carbon

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Authors: Mohammed Makha, Jakob Heier, Frank Nüesch, Roland Hany

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Organic solar cells (OSCs) have made rapid progress and currently achieve power conversion efficiencies (PCE) of over 10%. OSCs have several merits over other direct light-to-electricity generating cells and can be processed at low cost from solution on flexible substrates over large areas. Moreover, combining organic semiconductors with transparent and conductive electrodes allows for the fabrication of semitransparent OSCs (SM-OSCs). For SM-OSCs the challenge is to achieve a high average visible transmission (AVT) while maintaining a high short circuit current (Jsc). Typically, Jsc of SM-OSCs is smaller than when using an opaque metal top electrode. This is because the non-absorbed light during the first transit through the active layer and the transparent electrode is forward-transmitted out of the device. Recently, OSCs using a ternary blend of organic materials have received attention. This strategy was pursued to extend the light harvesting over the visible range. However, it is a general challenge to manipulate the performance of ternary OSCs in a predictable way, because many key factors affect the charge generation and extraction in ternary solar cells. Consequently, the device performance is affected by the compatibility between the blend components and the resulting film morphology, the energy levels and bandgaps, the concentration of the guest material and its location in the active layer. In this work, we report on a solvent-free lamination process for the fabrication of efficient and semitransparent ternary blend OSCs. The ternary blend was composed of PC70BM and the electron donors PBDTTT-C and an NIR cyanine absorbing dye (Cy7T). Using an opaque metal top electrode, a PCE of 6% was achieved for the optimized binary polymer: fullerene blend (AVT = 56%). However, the PCE dropped to ~2% when decreasing (to 30 nm) the active film thickness to increase the AVT value (75%). Therefore we resorted to the ternary blend and measured for non-transparent cells a PCE of 5.5% when using an active polymer: dye: fullerene (0.7: 0.3: 1.5 wt:wt:wt) film of 95 nm thickness (AVT = 65% when omitting the top electrode). In a second step, the optimized ternary blend was used of the fabrication of SM-OSCs. We used a plastic/metal substrate with a light transmission of over 90% as a transparent electrode that was applied via a lamination process. The interfacial layer between the active layer and the top electrode was optimized in order to improve the charge collection and the contact with the laminated top electrode. We demonstrated a PCE of 3% with AVT of 51%. The parameter space for ternary OSCs is large and it is difficult to find the best concentration ratios by trial and error. A rational approach for device optimization is the construction of a ternary blend phase diagram. We discuss our attempts to construct such a phase diagram for the PBDTTT-C: Cy7T: PC70BM system via a combination of using selective Cy7T selective solvents and atomic force microscopy. From the ternary diagram suitable morphologies for efficient light-to-current conversion can be identified. We compare experimental OSC data with these predictions.

Keywords: organic photovoltaics, ternary phase diagram, ternary organic solar cells, transparent solar cell, lamination

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Authors: Yashfeen Khan, Anees Ahmad

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In the last few decades, nano-composites have been the topic of interest. Presently, the modern era enlightens the synthesis of hybrid nano-composites over their individual counterparts because of higher application potentials and synergism. Recently, CNT hybrids have demonstrated their pronounced capability as effective sorbents for the removal of heavy metal ions (the root trouble) and organic contaminants due to their high specific surface area, enhanced reactivity, and sequestration characteristics. The present abstract discusses removal efficiencies of organic, inorganic pollutants through CNT/PANI/ composites. It also represents the widespread applications of CNT like monitoring biological systems, biosensors, as heat resources for treating cancer, fire retardant applications of polymer/CNT composites etc. And considering the same, this article aims to brief the scenario of CNT-PANI nano-composites.

Keywords: biosensors, CNT, hybrids, polyaniline, synergism

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Authors: Artur Saraiva, Moritz von Schwedler, Emília Fernandes

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In recent years, the organic sector has increased significantly. However, with the ‘conventionalization’ of these products, it has been questioned whether these products have been losing their original vision. Accordingly, this research based on 31 phenomenological interviews with committed organic consumers in urban and rural areas of Portugal, aims to analyse how ethical motivations and ecological awareness are related to organic food consumption. The content thematic analysis highlights aspects related to society and environmental concerns. On an individual level, the importance of internal coherence, peace of mind and balance that these consumers find in the consumption of local organic products was stressed. For these consumers, local organic products consumption made for significant changes in their lives, aiding in the establishment of a green identity, and involves a certain philosophy of life. This vision of an organic lifestyle is grounded in a political and ecological perspective, beyond the usual organic definition, as a ‘post-organic era’. The paper contributes to better understand how an ideological environmental discourse allows highlighting the relationship between consumers’ environmental concerns and the politics of food, resulting in a possible transition to new sustainable consumption practices.

Keywords: organic consumption, localism, content thematic analysis, pro-environmental discourse, political consumption, Portugal

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Authors: Sam Bahreini, Payam Hayati

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Metal-organic coordination [Cu(L)₄(SCN)₂] was synthesized applying ultrasonic irradiation, and its photocatalytic performance for the degradation of Remdesivir (RS) under sunlight irradiation was systematically explored for the first time in this study. The physicochemical properties of the synthesized photocatalyst were investigated using Fourier-transform infrared (FT-IR), field emission scanning electron microscopy (FE-SEM), powder x-ray diffraction (PXRD), energy-dispersive x-ray (EDX), thermal gravimetric analysis (TGA), diffuse reflectance spectroscopy (DRS) techniques. Systematic examinations were carried out by changing irradiation time, temperature, solution pH value, contact time, RS concentration, and catalyst dosage. The photodegradation kinetic profiles were modeled in pseudo-first order, pseudo-second-order, and intraparticle diffusion models reflected that photodegradation onto [Cu(L)₄(SCN)₂] catalyst follows pseudo-first order kinetic model. The fabricated [Cu(L)₄(SCN)₂] nanostructure bandgap was determined as 2.60 eV utilizing the Kubelka-Munk formula from the diffuse reflectance spectroscopy method. Decreasing chemical oxygen demand (COD) (from 70.5 mgL-1 to 36.4 mgL-1) under optimal conditions well confirmed mineralizing of the RS drug. The values of ΔH° and ΔS° was negative, implying the process of adsorption is spontaneous and more favorable in lower temperatures.

Keywords: Photocatalytic degradation, COVID-19, density functional theory (DFT), molecular electrostatic potential (MEP)

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Authors: Arpan Kumar Nayak, Debabrata Pradhan

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A simple, single-step and one-pot hydrothermal method was employed to synthesize WO₃-SnO₂ mixed nanostructured metal oxides at 200°C in 12h. The SnO₂ nanoparticles were found to be uniformly decorated on the WO₃ nanoplates. Though it is widely known that noble metals such as Pt, Pd doping or decoration on metal oxides improve the sensing response and sensitivity, we varied the SnO₂ concentration in the WO₃-SnO₂ mixed oxide and demonstrated their performance in ammonia, ethanol and acetone sensing. The sensing performance of WO₃-(x)SnO₂ [x = 0.27, 0.54, 1.08] mixed nanostructured oxides was found to be not only superior to that of pristine oxides but also higher/better than that of reported noble metal-based sensors. The sensing properties (selectivity, limit of detection, response and recovery times) are measured as a function of operating temperature (150-350°C). In particular, the gas selectivity is found to be highly temperature-dependent with optimum performance obtained at 200°C, 300°C and 350°C for ammonia, ethanol, and acetone, respectively. The present results on cost effective WO₃-SnO₂ sensors can find potential application in human breath analysis by noninvasive detection.

Keywords: gas sensing, mixed oxides, nanoplates, ammonia, ethanol, acetone

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Authors: Sitti Nurani Sirajuddin, Ikrar Moh. Saleh, Kasmiyati Kasim

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The aim of this study was to know the perception of livestock farmers on the use of liquid organic fertilizer from urine of cattle at Sinjai Regency, South Sulawesi Province. The choice of location for a farmer group manufactures and markets liquid organic fertilizer from cattle urine. This research was conducted in May to July 2013.The population were all livestock farmers who use organic liquid fertilizer from cattle urine samples while livestock farmers who are directly involved in the manufacture of liquid organic fertilizer totaled 42 people. Data were collected through observation and interview. Data were analyzed descriptively. The results showed that the perception of livestock farmers of using liquid organic fertilizer from cattle urine provide additional revenue benefits, cost minimization farming, reducing environmental pollution which not contrary to the customs.

Keywords: liquid organic fertilizer, perceptions, farmers, beef cattle

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Authors: Noor Us Saher

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Oceans and Marine areas have a great importance, mainly regarding food resources, fishery products and reliance of livelihood. Aquatic pollution is common due to the incorporation of various chemicals mainly entering from urbanization, industrial and commercial facilities, such as oil and chemical spills. Many hazardous wastes and industrial effluents contaminate the nearby areas and initiate to affect the marine environment. These contaminated conditions may become worse in those aquatic environments situated besides the world’s largest cities, which are hubs of various commercial activities. Heavy metal contamination is one of the most important predicaments for marine environments and during past decades this problem has intensified due to an increase in urbanization and industrialization. Coastal regions of Pakistan are facing severe threats from various organic and inorganic pollutants, especially the estuarine and coastal areas of Karachi city, the most populated and industrialized city situated along the coastline. Metal contamination causes severe toxicity in biota resulting the degradation of Marine environments and depletion of fishery resources and sustainability. There are several abiotic (air, water and sediment) and biotic (fauna and flora) indicators that indicate metal contamination. However, all these indicators have certain limitations and complexities, which delay their implementation for rehabilitation and conservation in the marine environment. The inadequate evidences have presented on this significant topic till the time and this study discussed metal pollution and its consequences along the marine environment of Pakistan. This study further helps in identification of possible hazards for the ecological system and allied resources for management strategies and decision making for sustainable approaches.

Keywords: coastal and estuarine environment, heavy metals pollution, pollution indicators, Pakistan

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Authors: Dimitra Das, Anuradha Mitra, Kalyan Kumar Chattopadhyay

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Organic polymers, constructed from light elements like carbon, hydrogen, nitrogen, oxygen, sulphur, and boron atoms, are the emergent class of non-toxic, metal-free, environmental benign advanced materials. Covalent triazine-based polymers with a functional triazine group are significant class of organic materials due to their remarkable stability arising out of strong covalent bonds. They can conventionally form hydrogen bonds, favour π–π contacts, and they were recently revealed to be involved in interesting anion–π interactions. The present work mainly focuses upon the development of a single-crystalline, highly cross-linked triazine-based nitrogen-rich organic polymer with nanodendritic morphology and significant thermal stability. The polymer has been synthesized through hydrothermal treatment of melamine and ethylene glycol resulting in cross-polymerization via condensation-polymerization reaction. The crystal structure of the polymer has been evaluated by employing Rietveld whole profile fitting method. The polymer has been found to be composed of monoclinic melamine having space group P21/a. A detailed insight into the chemical structure of the as synthesized polymer has been elucidated by Fourier Transform Infrared Spectroscopy (FTIR) and Raman spectroscopic analysis. X-Ray Photoelectron Spectroscopic (XPS) analysis has also been carried out for further understanding of the different types of linkages required to create the backbone of the polymer. The unique rod-like morphology of the triazine based polymer has been revealed from the images obtained from Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). Interestingly, this polymer has been found to selectively detect mercury (Hg²⁺) ions at an extremely low concentration through fluorescent quenching with detection limit as low as 0.03 ppb. The high toxicity of mercury ions (Hg²⁺) arise from its strong affinity towards the sulphur atoms of biological building blocks. Even a trace quantity of this metal is dangerous for human health. Furthermore, owing to its small ionic radius and high solvation energy, Hg²⁺ ions remain encapsulated by water molecules making its detection a challenging task. There are some existing reports on fluorescent-based heavy metal ion sensors using covalent organic frameworks (COFs) but reports on mercury sensing using triazine based polymers are rather undeveloped. Thus, the importance of ultra-trace detection of Hg²⁺ ions with high level of selectivity and sensitivity has contemporary significance. A plausible sensing phenomenon by the polymer has been proposed to understand the applicability of the material as a potential sensor. The impressive sensitivity of the polymer sample towards Hg²⁺ is the very first report in the field of highly crystalline triazine based polymers (without the introduction of any sulphur groups or functionalization) towards mercury ion detection through photoluminescence quenching technique. This crystalline metal-free organic polymer being cheap, non-toxic and scalable has current relevance and could be a promising candidate for Hg²⁺ ion sensing at commercial level.

Keywords: fluorescence quenching , mercury ion sensing, single-crystalline, triazine-based polymer

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Authors: D. Geringswald, B. Hintze

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The miniaturization of circuits is advancing. During chip manufacturing, structures are filled for example by metal organic chemical vapor deposition (MOCVD). Since this process reaches its limits in case of very high aspect ratios, the use of alternatives such as the atomic layer deposition (ALD) is possible, requiring the extension of existing coating systems. However, it is an unsolved question to what extent MOCVD can achieve results similar as an ALD process. In this context, this work addresses the characterization of a metal organic vapor deposition of titanium nitride. Based on the current state of the art, the film properties coating thickness, sheet resistance, resistivity, stress and chemical composition are considered. The used setting parameters are temperature, plasma gas ratio, plasma power, plasma treatment time, deposition time, deposition pressure, number of cycles and TDMAT flow. The derived process instructions for unstructured wafers and inside a structure with high aspect ratio include lowering the process temperature and increasing the number of cycles, the deposition and the plasma treatment time as well as the plasma gas ratio of hydrogen to nitrogen (H₂:N₂). In contrast to the current process configuration, the deposited titanium nitride (TiN) layer is more uniform inside the entire test structure. Consequently, this paper provides approaches to employ the MOCVD for structures with increasing aspect ratios.

Keywords: ALD, high aspect ratio, PE-MOCVD, TiN

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Authors: I. Nitoi, P. Oancea, M. Raileanu, M. Crisan, L. Constantin, I. Cristea

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Hazardous organic compounds like nitroaromatics are frequently found in chemical and petroleum industries discharged effluents. Due to their bio-refractory character and high chemical stability cannot be efficiently removed by classical biological or physical-chemical treatment processes. In the past decades, semiconductor photocatalysis has been frequently applied for the advanced degradation of toxic pollutants. Among various semiconductors titania was a widely studied photocatalyst, due to its chemical inertness, low cost, photostability and nontoxicity. In order to improve optical absorption and photocatalytic activity of TiO2 many attempts have been made, one feasible approach consists of doping oxide semiconductor with metal. The degradation of dinitrobenzene (DNB) and dinitrotoluene (DNT) from aqueous solution under UVA-VIS irradiation using heavy metal (0.5% Fe, 1%Co, 1%Ni ) doped titania was investigated. The photodegradation experiments were carried out using a Heraeus laboratory scale UV-VIS reactor equipped with a medium-pressure mercury lamp which emits in the range: 320-500 nm. Solutions with (0.34-3.14) x 10-4 M pollutant content were photo-oxidized in the following working conditions: pH = 5-9; photocatalyst dose = 200 mg/L; irradiation time = 30 – 240 minutes. Prior to irradiation, the photocatalyst powder was added to the samples, and solutions were bubbled with air (50 L/hour), in the dark, for 30 min. Dopant type, pH, structure and initial pollutant concentration influence on the degradation efficiency were evaluated in order to set up the optimal working conditions which assure substrate advanced degradation. The kinetics of nitroaromatics degradation and organic nitrogen mineralization was assessed and pseudo-first order rate constants were calculated. Fe doped photocatalyst with lowest metal content (0.5 wt.%) showed a considerable better behaviour in respect to pollutant degradation than Co and Ni (1wt.%) doped titania catalysts. For the same working conditions, degradation efficiency was higher for DNT than DNB in accordance with their calculated adsobance constants (Kad), taking into account that degradation process occurs on catalyst surface following a Langmuir-Hinshalwood model. The presence of methyl group in the structure of DNT allows its degradation by oxidative and reductive pathways, while DNB is converted only by reductive route, which also explain the highest DNT degradation efficiency. For highest pollutant concentration tested (3 x 10-4 M), optimum working conditions (0.5 wt.% Fe doped –TiO2 loading of 200 mg/L, pH=7 and 240 min. irradiation time) assures advanced nitroaromatics degradation (ηDNB=89%, ηDNT=94%) and organic nitrogen mineralization (ηDNB=44%, ηDNT=47%).

Keywords: hazardous organic compounds, irradiation, nitroaromatics, photocatalysis

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Authors: Deniz Sahin

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This study provides a literature review of the special issue on wastewater treatment technologies, especially membrane technologies. Currently, wastewater is a serious and increasing worldwide problem with an adverse effect on the environment and living organisms. For this reason, many technologies have been developed to treat wastewater before discharging it to water bodies. We have been discussed membrane technologies to remove contaminants from wastewater such as heavy metals, dyes, pesticides, etc., which represent the main pollutants in wastewater. All the properties of these technologies including performance, economics, simplicity, and operability are also compared with other wastewater treatment technologies. The conventional water treatment technologies have the disadvantages of low separation efficiency, high energy consumption, and strict operating temperature. To overcome these difficulties, membrane technologies have been developed and used in wastewater treatment. Membrane technology uses a selectively permeable membrane to remove suspended and dissolved solids from water. This membrane is a very thin film of synthetic organic or inorganic materials, that can allow a very selective separation between a mixture and its components. Examples of membrane technologies include microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), reverse osmosis (RO), electrodialysis (ED), gas separation, etc. Most of these technologies have been used extensively for the treatment of heavy metal wastewater. For instance, wastewater that contains Cu²⁺, Cd²⁺, Pb²⁺, Zn²⁺ was treated by ultrafiltration technology. It was shown that complete removal of metal ions could be achieved.

Keywords: industrial pollution, membrane technologies, metal ions, wastewater

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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: A. Hamza, H. Kathyayini, N. Nagaraju

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Aluminophosphates, both amorphous and crystalline materials find applications as adsorbents, ceramics, and pigments and as catalysts/catalyst supports in organic fine chemical synthesis. Most of the applications are varied depending on the type of metal incorporated, particle size, surface area, porosity and morphology of aluminophosphate. The porous and surface properties of these materials are normally fine-tuned by adopting various preparation methodologies. Numerous crystalline microporous and mesoporous aluminophosphates and metal-aluminophosphates have been reported in literature, in which the synthesis has been carried out by using structure directing organic molecules/surfactants. In present work, amorphous aluminophosphate (AlP) and metal-aluminophosphates MAlP (M = Cu, Zn, Cr, Fe, Ce and Zr) and their mixed forms M-1M2AlP are prepared under a typical precipitation condition, i.e. at low temperature in order to keep the Von-Weirmann relative super saturation of the precipitating medium and obtain small size precipitate particles. These materials are prepared without using any surfactants. All materials are thoroughly characterised for surface and bulk properties by N2 adsorption-desorption technique, XRD, FT-IR, TG and SEM. The materials are also analysed for the amount and the strength of their surface acid sites, by NH3-TPD and CO2-TPD techniques respectively. All the materials prepared in the work are investigated for their catalytic activity in following applications in the synthesis of industrially important Jasminaldehyde via, aldol condensation of n-heptanal and benzaldehyde, in the synthesis of biologically important chalcones by Claisen-shmidth condensation of benzaldehyde and substituted chalcones. The effect of the amount of the catalysts, duration of the reaction, temperature of the reaction, molar ratio of the reactants has been studied. The porosity of pure aluminophosphate is found to be changed significantly by the incorporation of transition metals during preparation of aluminophosphate. The pore size increased from microporous to mesoporous and finally to macroporous by following order of metals Cu = Zn < Cr < Ce < Fe = Zr. The change in surface area and porosity of double metal-aluminophosphates depended on the concentration of both the metals. The acidity of aluminophosphate is either increased or decreased which depended on the type and valence of metals loaded. A good number of basic sites are created in metal-aluminophosphates irrespective of the metals used. A maximum catalytic activity for synthesis of both jasminaldehyde and chalcone is obtained by FeAlP as catalysts; these materials are characterized by decreased strength and concentration of acidic sites with optimum level basic sites.

Keywords: amorphous metal-aluminophosphates, surface properties, acidic-basic properties, Aldol, Claisen-Shmidth condensation, jasminaldehyde, chalcone

Procedia PDF Downloads 276