Search results for: Cu-Mn-Cr oxide catalysts
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 1811

Search results for: Cu-Mn-Cr oxide catalysts

911 Pd Supported on Activated Carbon: Effect of Support Texture on the Dispersion of Pd

Authors: Ji Sun Kim, Jae Ho Baek, Kyeong Ho Kim, Ji Hae Ha, Seong Soo Hong, Jung-Wook Park, Man Sig Lee

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Carbon supported palladium catalysts have been used in many industrial reactions, especially for hydrogenation in the fine chemical industry. Porous carbons had been widely used as catalyst supports due to its higher surface area and larger pore volume. The specific surface area, pore structure and surface chemical functional groups of porous carbon affects metal dispersion and particle size. In this paper, we confirm the effect of support texture on the dispersion of Pd. Pd catalyst supported on activated carbon having various specific surface area were characterized by BET, XRD and FE-TEM. Catalyst activity and dispersion of prepared catalyst were evaluated on the basis of the CO adsorption capacity by CO-chemisorption. As concluding remark to this part of our study, let us note that specific area of carbon play important role on the synthesis of Pd/C catalyst/.

Keywords: carbon, dispersion, Pd/C, specific are, support

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910 Comparing Spontaneous Hydrolysis Rates of Activated Models of DNA and RNA

Authors: Mohamed S. Sasi, Adel M. Mlitan, Abdulfattah M. Alkherraz

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This research project aims to investigate difference in relative rates concerning phosphoryl transfer relevant to biological catalysis of DNA and RNA in the pH-independent reactions. Activated Models of DNA and RNA for alkyl-aryl phosphate diesters (with 4-nitrophenyl as a good leaving group) have successfully been prepared to gather kinetic parameters. Eyring plots for the pH–independent hydrolysis of 1 and 2 were established at different temperatures in the range 100–160 °C. These measurements have been used to provide a better estimate for the difference in relative rates between the reactivity of DNA and RNA cleavage. Eyring plot gave an extrapolated rate of kH2O = 1 × 10-10 s -1 for 1 (RNA model) and 2 (DNA model) at 25°C. Comparing the reactivity of RNA model and DNA model shows that the difference in relative rates in the pH-independent reactions is surprisingly very similar at 25°. This allows us to obtain chemical insights into how biological catalysts such as enzymes may have evolved to perform their current functions.

Keywords: DNA and RNA models, relative rates, reactivity, phosphoryl transfe

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909 Zeolite 4A-confined Ni-Co Nanocluster: An Efficient and Durable Electrocatalyst for Alkaline Methanol Oxidation Reaction

Authors: Sarmistha Baruah, Akshai Kumar, Nageswara Rao Peela

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The global energy crisis due to the dependence on fossil fuels and its limited reserves as well as environmental pollution are key concerns to the research communities. However, the implementation of alcohol-based fuel cells such as methanol is anticipated as a reliable source of future energy technology due to their high energy density, environment friendliness, ease of storage, transportation, etc. To drive the anodic methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs), an active and long-lasting catalyst is necessary for efficient energy conversion from methanol. Recently, transition metal-zeolite-based materials have been considered versatile catalysts for a variety of industrial and lab-scale processes. Large specific surface area, well-organized micropores, and adjustable acidity/basicity are characteristics of zeolites that make them excellent supports for immobilizing small-sized and highly dispersed metal species. Significant advancement in the production and characterization of well-defined metal clusters encapsulated within zeolite matrix has substantially expanded the library of materials available, and consequently, their catalytic efficacy. In this context, we developed bimetallic Ni-Co catalysts encapsulated within LTA (also known as 4A) zeolite via a method combined with the in-situ encapsulation of metal species using hydrothermal treatment followed by a chemical reduction process. The prepared catalyst was characterized using advanced characterization techniques, such as X-ray diffraction (XRD), field emission transmission electron microscope (FETEM), field emission scanning electron microscope (FESEM), energy dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of the catalyst for MOR was carried out in an alkaline medium at room temperature using techniques such as cyclic voltammetry (CV), and chronoamperometry (CA). The resulting catalyst exhibited better catalytic activity of 12.1 mA cm-2 at 1.12 V vs Ag/AgCl and retained remarkable stability (~77%) even after 1000 cycles CV test for the electro-oxidation of methanol in alkaline media without any significant microstructural changes. The high surface area, better Ni-Co species integration in the zeolite, and the ample amount of surface hydroxyl groups contribute to highly dispersed active sites and quick analyte diffusion, which provide notable MOR kinetics. Thus, this study will open up new possibilities to develop a noble metal-free zeolite-based electrocatalyst due to its simple synthesis steps, large-scale fabrication, improved stability, and efficient activity for DMFC application.

Keywords: alkaline media, bimetallic, encapsulation, methanol oxidation reaction, LTA zeolite.

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908 Evaluation of Esters Production by Oleic Acid Epoxidation Reaction

Authors: Flavio A. F. Da Ponte, Jackson Q. Malveira, Monica C. G. Albuquerque

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In recent years a worldwide interest in renewable resources from the biomass has spurred the industry. In this work the chemical structure of oleic acid chains was modified by homogeneous and heterogeneous catalysis in order to produce esters. The homogeneous epoxidation was carried out at H2O2 to oleic acid unsaturation molar ratio of 20:1. The reaction temperature was 338 K and reaction time 16 h. Formic acid was used as catalyst. For heterogeneous catalysis reaction temperature was 343 K and reaction time 24 h. The esters production was carried out by heterogeneous catalysis of the epoxidized oleic acid and butanol using Mg/SBA-15 as catalyst. The resulting products were confirmed by NMR (1H and 13C) and FTIR spectroscopy. The products were characterized before and after each reaction. The catalysts were characterized by X-ray diffraction, X-ray fluorescence, thermogravimetric analysis (TGA) and BET surface areas. The results were satisfactory for the bioproducts formed.

Keywords: acid oleic, bioproduct, esters, epoxidation

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907 Physical Characterization of SnO₂ Films Prepared by the Rheotaxial Growth and Thermal Oxidation (RGTO) Method

Authors: A. Kabir, D. Boulainine, I. Bouanane, N. Benslim, B. Boudjema, C. Sedrati

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SnO₂ is an n-type semiconductor with a direct gap of about 3.6 eV. It is largely used in several domains such as nanocrystalline photovoltaic cells. Due to its interesting physic-chemical properties, this material was elaborated in thin film forms using different deposition techniques. It was found that SnO₂ properties were directly affected by the deposition method parameters. In this work, the RGTO method (Rheotaxial Growth and Thermal Oxidation) was used to deposit elaborate SnO₂ thin films. This technique consists on thermal oxidation of the Sn films deposited onto a substrate heated to a temperature close to Sn melting point (232°C). Such process allows the preparation of high porosity tin oxide films which are very suitable for the gas sensing. The films structural, morphological and optical properties pre and post thermal oxidation were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-Visible spectroscopy and Fourier transform infrared spectroscopy (FTIR) respectively. XRD patterns showed a polycrystalline structure of the cassiterite phase of SnO₂. The grain growth was found affected by the oxidation temperature. This grain size evolution was confronted to existing grain growth models in order to understand the growth mechanism. From SEM images, the as deposited Sn film was formed of difference diameter spherical agglomerations. As a function of the oxidation temperature, these spherical agglomerations shape changed due to the introduction of oxygen ions. The deformed spheres started to interconnect by forming bridges between them. The volume porosity, determined from the UV-Visible reflexion spectra, Changes as a function of the oxidation temperature. The variation of the crystalline fraction, determined from FTIR spectra, correlated with the variation of both the grain size and the volume porosity.

Keywords: tin oxide, RGTO, grain growth, volume porosity, crystalline fraction

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906 Increase of the Nanofiber Degradation Rate Using PCL-PEO and PCL-PVP as a Shell in the Electrospun Core-Shell Nanofibers Using the Needleless Blades

Authors: Matej Buzgo, Erico Himawan, Ksenija JašIna, Aiva Simaite

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Electrospinning is a versatile and efficient technology for producing nanofibers for biomedical applications. One of the most common polymers used for the preparation of nanofibers for regenerative medicine and drug delivery applications is polycaprolactone (PCL). PCL is a biocompatible and bioabsorbable material that can be used to stimulate the regeneration of various tissues. It is also a common material used for the development of drug delivery systems by blending the polymer with small active molecules. However, for many drug delivery applications, e.g. cancer immunotherapy, PCL biodegradation rate that may exceed 9 months is too long, and faster nanofiber dissolution is needed. In this paper, we investigate the dissolution and small molecule release rates of PCL blends with two hydrophilic polymers: polyethylene oxide (PEO) or polyvinylpyrrolidone (PVP). We show that adding hydrophilic polymer to the PCL reduces the water contact angle, increases the dissolution rate, and strengthens the interactions between the hydrophilic drug and polymer matrix that further sustain its release. Finally using this method, we were also able to increase the nanofiber degradation rate when PCL-PEO and PCL-PVP were used as a shell in the electrospun core-shell nanofibers and spread up the release of active proteins from their core. Electrospinning can be used for the preparation of the core-shell nanofibers, where active ingredients are encapsulated in the core and their release rate is regulated by the shell. However, such fibers are usually prepared by coaxial electrospinning that is an extremely low-throughput technique. An alternative is emulsion electrospinning that could be upscaled using needleless blades. In this work, we investigate the possibility of using emulsion electrospinning for encapsulation and sustained release of the growth factors for the development of the organotypic skin models. The core-shell nanofibers were prepared using the optimized formulation and the release rate of proteins from the fibers was investigated for 2 weeks – typical cell culture conditions.

Keywords: electrospinning, polycaprolactone (PCL), polyethylene oxide (PEO), polyvinylpyrrolidone (PVP)

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905 The Effect of Zinc Oxide Nanoparticles on Performance Traits, Carcass Quality, Gut Morphology and Haematological Parameters of Broilers Fed Wet Diet

Authors: Farhad Ahmadi, Vafa Pahlavani, Pejman Bidar

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This study was conducted to investigate the effect of zinc oxide nanoparticles (Nano-ZnO) on carcass quality, blood parameters, and gut morphology in broiler chickens feeding wet diets. This research was conducted by total of 300 one-day-old broiler chicks (Ross-308) were distributed into a completely randomized design inclusion of 5 treatments in 4 replicated and 15 birds in each from 1 to 42 d. The experimental diets contain: 1) diet-based on corn-soybean dry (without Nano-ZnO), 2) dry diet whit 25 mg Nano-ZnO, 3) wet diet whit 25 mg Nano-ZnO, 4) dry diet whit 50 mg Nano-ZnO, 5) wet diet whit 50 mg Nano-ZnO to wet diet. The results indicated that trail diets had no significant effect on carcass and fraction cuts in 21 age (P > 0.05). Wet feeding increased (P < 0.05) live, carcass, pancreas, gizzard, proventriculus, breast, wing and SI weight index so that the birds fed wet diet contain 50mg/kg of Nano-ZnO had the highest (P < 0.05) live, carcass, pancreas, proventriculus, gizzard, breast, wing, and gut weights at 42d compared other treatments. The birds fed diet contain 25mg/kg Nano-ZnO had the higher (P < 0.05) leg weight and lowest gizzard and gut weight than others treatment. Wet diet inclusion of 50mg Nano-ZnO increased (P < 0.05) liver weight on d 42. Experimental treatments had no significant effect on blood hematology on 21 and 42. The lymphocyte count had increased (P < 0.05) in dry than wet diet, however, monocyte Percent had significantly (P < 0.05) decreased in dry and increased in wet diets. The birds of height and height: crypts villi ratio had significantly (P < 0.05) increased on d 42, so that the highest and lowest villus height observed in 50 mg Nano-ZnO to form dry and control, respectively. In conclusion, the results of indicated that used of Nano-ZnO and wet feeding had no effect on performance parameters. Wet diet caused increased monocyte percent and 50 mg level Nano-ZnO to form dry caused increased height of villi.

Keywords: broiler, blood, gut, performance, nanoparticles

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904 Carbon, Nitrogen Doped TiO2 Macro/Mesoporous Monoliths with High Visible Light Absorption for Photocatalytic Wastewater Treatment

Authors: Paolo Boscaro, Vasile Hulea, François Fajula, Francis Luck, Anne Galarneau

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TiO2 based monoliths with hierarchical macropores and mesopores have been synthesized following a novel one pot sol-gel synthesis method. Taking advantage of spinodal separation that occurs between titanium isopropoxide and an acidic solution in presence of polyethylene oxide polymer, monoliths with homogeneous interconnected macropres of 3 μm in diameter and mesopores of ca. 6 nm (surface area 150 m2/g) are obtained. Furthermore, these monoliths present some carbon and nitrogen (as shown by XPS and elemental analysis), which considerably reduce titanium oxide energy gap and enable light to be absorbed up to 700 nm wavelength. XRD shows that anatase is the dominant phase with a small amount of brookite. Enhanced light absorption and high porosity of the monoliths are responsible for a remarkable photocatalytic activity. Wastewater treatment has been performed in closed reactor under sunlight using orange G dye as target molecule. Glass reactors guarantee that most of UV radiations (to almost 300 nm) of solar spectrum are excluded. TiO2 nanoparticles P25 (usually used in photocatalysis under UV) and un-doped TiO2 monoliths with similar porosity were used as comparison. C,N-doped TiO2 monolith allowed a complete colorant degradation in less than 1 hour, whereas 10 h are necessary for 40% colorant degradation with P25 and un-doped monolith. Experiment performed in the dark shows that only 3% of molecules have been adsorbed in the C,N-doped TiO2 monolith within 1 hour. The much higher efficiency of C,N-doped TiO2 monolith in comparison to P25 and un-doped monolith, proves that doping TiO2 is an essential issue and that nitrogen and carbon are effective dopants. Monoliths offer multiples advantages in respect to nanometric powders: sample can be easily removed from batch (no needs to filter or to centrifuge). Moreover flow reactions can be set up with cylindrical or flat monoliths by simple sheathing or by locking them with O-rings.

Keywords: C-N doped, sunlight photocatalytic activity, TiO2 monolith, visible absorbance

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903 Influence of Kneading Conditions on the Textural Properties of Alumina Catalysts Supports for Hydrotreating

Authors: Lucie Speyer, Vincent Lecocq, Séverine Humbert, Antoine Hugon

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Mesoporous alumina is commonly used as a catalyst support for the hydrotreating of heavy petroleum cuts. The process of fabrication usually involves: the synthesis of the boehmite AlOOH precursor, a kneading-extrusion step, and a calcination in order to obtain the final alumina extrudates. Alumina is described as a complex porous medium, generally agglomerates constituted of aggregated nanocrystallites. Its porous texture directly influences the active phase deposition and mass transfer, and the catalytic properties. Then, it is easy to figure out that each step of the fabrication of the supports has a role on the building of their porous network, and has to be well understood to optimize the process. The synthesis of boehmite by precipitation of aluminum salts was extensively studied in the literature and the effect of various parameters, such as temperature or pH, are known to influence the size and shape of the crystallites and the specific surface area of the support. The calcination step, through the topotactic transition from boehmite to alumina, determines the final properties of the support and can tune the surface area, pore volume and pore diameters from those of boehmite. However, the kneading extrusion step has been subject to a very few studies. It generally consists in two steps: an acid, then a basic kneading, where the boehmite powder is introduced in a mixer and successively added with an acid and a base solution to form an extrudable paste. During the acid kneading, the induced positive charges on the hydroxyl surface groups of boehmite create an electrostatic repulsion which tends to separate the aggregates and even, following the conditions, the crystallites. The basic kneading, by reducing the surface charges, leads to a flocculation phenomenon and can control the reforming of the overall structure. The separation and reassembling of the particles constituting the boehmite paste have a quite obvious influence on the textural properties of the material. In this work, we are focused on the influence of the kneading step on the alumina catalysts supports. Starting from an industrial boehmite, extrudates are prepared using various kneading conditions. The samples are studied by nitrogen physisorption in order to analyze the evolution of the textural properties, and by synchrotron small-angle X-ray scattering (SAXS), a more original method which brings information about agglomeration and aggregation of the samples. The coupling of physisorption and SAXS enables a precise description of the samples, as same as an accurate monitoring of their evolution as a function of the kneading conditions. These ones are found to have a strong influence of the pore volume and pore size distribution of the supports. A mechanism of evolution of the texture during the kneading step is proposed and could be attractive in order to optimize the texture of the supports and then, their catalytic performances.

Keywords: alumina catalyst support, kneading, nitrogen physisorption, small-angle X-ray scattering

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902 Environmental Catalysts for Refining Technology Application: Reduction of CO Emission and Gasoline Sulphur in Fluid Catalytic Cracking Unit

Authors: Loganathan Kumaresan, Velusamy Chidambaram, Arumugam Velayutham Karthikeyani, Alex Cheru Pulikottil, Madhusudan Sau, Gurpreet Singh Kapur, Sankara Sri Venkata Ramakumar

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Environmentally driven regulations throughout the world stipulate dramatic improvements in the quality of transportation fuels and refining operations. The exhaust gases like CO, NOx, and SOx from stationary sources (e.g., refinery) and motor vehicles contribute to a large extent for air pollution. The refining industry is under constant environmental pressure to achieve more rigorous standards on sulphur content in the fuel used in the transportation sector and other off-gas emissions. Fluid catalytic cracking unit (FCCU) is a major secondary process in refinery for gasoline and diesel production. CO-combustion promoter additive and gasoline sulphur reduction (GSR) additive are catalytic systems used in FCCU to assist the combustion of CO to CO₂ in the regenerator and regulate sulphur in gasoline faction respectively along with main FCC catalyst. Effectiveness of these catalysts is governed by the active metal used, its dispersion, the type of base material employed, and retention characteristics of additive in FCCU such as attrition resistance and density. The challenge is to have a high-density microsphere catalyst support for its retention and high activity of the active metals as these catalyst additives are used in low concentration compare to the main FCC catalyst. The present paper discusses in the first part development of high dense microsphere of nanocrystalline alumina by hydro-thermal method for CO combustion promoter application. Performance evaluation of additive was conducted under simulated regenerator conditions and shows CO combustion efficiency above 90%. The second part discusses the efficacy of a co-precipitation method for the generation of the active crystalline spinels of Zn, Mg, and Cu with aluminium oxides as an additive. The characterization and micro activity test using heavy combined hydrocarbon feedstock at FCC unit conditions for evaluating gasoline sulphur reduction activity are studied. These additives were characterized by X-Ray Diffraction, NH₃-TPD & N₂ sorption analysis, TPR analysis to establish structure-activity relationship. The reaction of sulphur removal mechanisms involving hydrogen transfer reaction, aromatization and alkylation functionalities are established to rank GSR additives for their activity, selectivity, and gasoline sulphur removal efficiency. The sulphur shifting in other liquid products such as heavy naphtha, light cycle oil, and clarified oil were also studied. PIONA analysis of liquid product reveals 20-40% reduction of sulphur in gasoline without compromising research octane number (RON) of gasoline and olefins content.

Keywords: hydrothermal, nanocrystalline, spinel, sulphur reduction

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901 A Comprehensive Study of a Hybrid System Integrated Solid Oxide Fuel cell, Gas Turbine, Organic Rankine Cycle with Compressed air Energy Storage

Authors: Taiheng Zhang, Hongbin Zhao

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Compressed air energy storage become increasingly vital for solving intermittency problem of some renewable energies. In this study, a new hybrid system on a combination of compressed air energy storage (CAES), solid oxide fuel cell (SOFC), gas turbine (GT), and organic Rankine cycle (ORC) is proposed. In the new system, excess electricity during off-peak time is utilized to compress air. Then, the compressed air is stored in compressed air storage tank. During peak time, the compressed air enters the cathode of SOFC directly instead of combustion chamber of traditional CAES. There is no air compressor consumption of SOFC-GT in peak demand, so SOFC- GT can generate power with high-efficiency. In addition, the waste heat of exhaust from GT is recovered by applying an ORC. Three different organic working fluid (R123, R601, R601a) of ORC are chosen to evaluate system performance. Based on Aspen plus and Engineering Equation Solver (EES) software, energy and exergoeconomic analysis are used to access the viability of the combined system. Besides, the effect of two parameters (fuel flow and ORC turbine inlet pressure) on energy efficiency is studied. The effect of low-price electricity at off-peak hours on thermodynamic criteria (total unit exergy cost of products and total cost rate) is also investigated. Furthermore, for three different organic working fluids, the results of round-trip efficiency, exergy efficiency, and exergoeconomic factors are calculated and compared. Based on thermodynamic performance and exergoeconomic performance of different organic working fluids, the best suitable working fluid will be chosen. In conclusion, this study can provide important guidance for system efficiency improvement and viability.

Keywords: CAES, SOFC, ORC, energy and exergoeconomic analysis, organic working fluids

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900 Oxidation Behavior of Ferritic Stainless Steel Interconnects Modified Using Nanoparticles of Rare-Earth Elements under Operating Conditions Specific to Solid Oxide Electrolyzer Cells

Authors: Łukasz Mazur, Kamil Domaradzki, Bartosz Kamecki, Justyna Ignaczak, Sebastian Molin, Aleksander Gil, Tomasz Brylewski

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The rising global power consumption necessitates the development of new energy storage solutions. Prospective technologies include solid oxide electrolyzer cells (SOECs), which convert surplus electrical energy into hydrogen. An electrolyzer cell consists of a porous anode, and cathode, and a dense electrolyte. Power output is increased by connecting cells into stacks using interconnects. Interconnects are currently made from high-chromium ferritic steels – for example, Crofer 22 APU – which exhibit high oxidation resistance and a thermal expansion coefficient that is similar to that of electrode materials. These materials have one disadvantage – their area-specific resistance (ASR) gradually increases due to the formation of a Cr₂O₃ scale on their surface as a result of oxidation. The chromia in the scale also reacts with the water vapor present in the reaction media, forming volatile chromium oxyhydroxides, which in turn react with electrode materials and cause their deterioration. The electrochemical efficiency of SOECs thus decreases. To mitigate this, the interconnect surface can be modified with protective-conducting coatings of spinel or other materials. The high prices of SOEC components -especially the Crofer 22 APU- have prevented their widespread adoption. More inexpensive counterparts, therefore, need to be found, and their properties need to be enhanced to make them viable. Candidates include the Nirosta 4016/1,4016 low-chromium ferritic steel with a chromium content of just 16.3 wt%. This steel's resistance to high-temperature oxidation was improved by depositing Gd₂O₃ nanoparticles on its surface via either dip coating or electrolysis. Modification with CeO₂ or Ce₀.₉Y₀.₁O₂ nanoparticles deposited by means of spray pyrolysis was also tested. These methods were selected because of their low cost and simplicity of application. The aim of this study was to investigate the oxidation kinetics of Nirosta 4016/1,4016 modified using the afore-mentioned methods and to subsequently measure the obtained samples' ASR. The samples were oxidized for 100 h in the air as well as air/H₂O and Ar/H₂/H₂O mixtures at 1073 K. Such conditions reflect those found in the anode and cathode operating space during real-life use of SOECs. Phase and chemical composition and the microstructure of oxidation products were determined using XRD and SEM-EDS. ASR was measured over the range of 623-1073 K using a four-point, two-probe DC technique. The results indicate that the applied nanoparticles improve the oxidation resistance and electrical properties of the studied layered systems. The properties of individual systems varied significantly depending on the applied reaction medium. Gd₂O₃ nanoparticles improved oxidation resistance to a greater degree than either CeO₂ or Ce₀.₉Y₀.₁O₂ nanoparticles. On the other hand, the cerium-containing nanoparticles improved electrical properties regardless of the reaction medium. The ASR values of all surface-modified steel samples were below the 0.1 Ω.cm² threshold set for interconnect materials, which was exceeded in the case of the unmodified reference sample. It can be concluded that the applied modifications increased the oxidation resistance of Nirosta 4016/1.4016 to a level that allows its use as SOEC interconnect material. Acknowledgments: Funding of Research project supported by program "Excellence initiative – research university" for the AGH University of Krakow" is gratefully acknowledged (TB).

Keywords: cerium oxide, ferritic stainless steel, gadolinium oxide, interconnect, SOEC

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899 Biomedical Application of Green Biosynthesis Magnetic Iron Oxide (Fe3O4) Nanoparticles Using Seaweed (Sargassum muticum) Aqueous Extract

Authors: Farideh Namvar, Rosfarizan Mohamed

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In the field of nanotechnology, the use of various biological units instead of toxic chemicals for the reduction and stabilization of nanoparticles, has received extensive attention. This use of biological entities to create nanoparticles has designated as “Green” synthesis and it is considered to be far more beneficial due to being economical, eco-friendly and applicable for large-scale synthesis as it operates on low pressure, less input of energy and low temperatures. The lack of toxic byproducts and consequent decrease in degradation of the product renders this technique more preferable over physical and classical chemical methods. The variety of biomass having reduction properties to produce nanoparticles makes them an ideal candidate for fabrication. Metal oxide nanoparticles have been said to represent a "fundamental cornerstone of nanoscience and nanotechnology" due to their variety of properties and potential applications. However, this also provides evidence of the fact that metal oxides include many diverse types of nanoparticles with large differences in chemical composition and behaviour. In this study, iron oxide nanoparticles (Fe3O4-NPs) were synthesized using a rapid, single step and completely green biosynthetic method by reduction of ferric chloride solution with brown seaweed (Sargassum muticum) water extract containing polysaccharides as a main factor which acts as reducing agent and efficient stabilizer. Antimicrobial activity against six microorganisms was tested using well diffusion method. The resulting S-IONPs are crystalline in nature, with a cubic shape. The average particle diameter, as determined by TEM, was found to be 18.01 nm. The S-IONPs were efficiently inhibited the growth of Listeria monocytogenes, Escherichia coli and Candida species. Our favorable results suggest that S-IONPs could be a promising candidate for development of future antimicrobial therapies. The nature of biosynthesis and the therapeutic potential by S-IONPs could pave the way for further research on design of green synthesis therapeutic agents, particularly nanomedicine, to deal with treatment of infections. Further studies are needed to fully characterize the toxicity and the mechanisms involved with the antimicrobial activity of these particles. Antioxidant activity of S-IONPs synthesized by green method was measured by ABTS (2, 2'-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) (IC50= 1000µg) radical scavenging activity. Also, with the increasing concentration of S-IONPs, catalase gene expression compared to control gene GAPDH increased. For anti-angiogenesis study the Ross fertilized eggs were divided into four groups; the control and three experimental groups. The gelatin sponges containing albumin were placed on the chorioalantoic membrane and soaked with different concentrations of S-IONPs. All the cases were photographed using a photo stereomicroscope. The number and the lengths of the vessels were measured using Image J software. The crown rump (CR) and weight of the embryo were also recorded. According to the data analysis, the number and length of the blood vessels, as well as the CR and weight of the embryos reduced significantly compared to the control (p < 0.05), dose dependently. The total hemoglobin was quantified as an indicator of the blood vessel formation, and in the treated samples decreased, which showed its inhibitory effect on angiogenesis.

Keywords: anti-angiogenesis, antimicrobial, antioxidant, biosynthesis, iron oxide (fe3o4) nanoparticles, sargassum muticum, seaweed

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898 Sustainable Membranes Based on 2D Materials for H₂ Separation and Purification

Authors: Juan A. G. Carrio, Prasad Talluri, Sergio G. Echeverrigaray, Antonio H. Castro Neto

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Hydrogen as a fuel and environmentally pleasant energy carrier is part of this transition towards low-carbon systems. The extensive deployment of hydrogen production, purification and transport infrastructures still represents significant challenges. Independent of the production process, the hydrogen generally is mixed with light hydrocarbons and other undesirable gases that need to be removed to obtain H₂ with the required purity for end applications. In this context, membranes are one of the simplest, most attractive, sustainable, and performant technologies enabling hydrogen separation and purification. They demonstrate high separation efficiencies and low energy consumption levels in operation, which is a significant leap compared to current energy-intensive options technologies. The unique characteristics of 2D laminates have given rise to a diversity of research on their potential applications in separation systems. Specifically, it is already known in the scientific literature that graphene oxide-based membranes present the highest reported selectivity of H₂ over other gases. This work explores the potential of a new type of 2D materials-based membranes in separating H₂ from CO₂ and CH₄. We have developed nanostructured composites based on 2D materials that have been applied in the fabrication of membranes to maximise H₂ selectivity and permeability, for different gas mixtures, by adjusting the membranes' characteristics. Our proprietary technology does not depend on specific porous substrates, which allows its integration in diverse separation modules with different geometries and configurations, looking to address the technical performance required for industrial applications and economic viability. The tuning and precise control of the processing parameters allowed us to control the thicknesses of the membranes below 100 nanometres to provide high permeabilities. Our results for the selectivity of new nanostructured 2D materials-based membranes are in the range of the performance reported in the available literature around 2D materials (such as graphene oxide) applied to hydrogen purification, which validates their use as one of the most promising next-generation hydrogen separation and purification solutions.

Keywords: membranes, 2D materials, hydrogen purification, nanocomposites

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897 Role of SiOx Interlayer on Lead Oxide Electrodeposited on Stainless Steel for Promoting Electrochemical Treatment of Wastewater Containing Textile Dye

Authors: Hanene Akrout, Ines Elaissaoui, Sabrina Grassini, Daniele Fulginiti, Latifa Bousselmi

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The main objective of this work is to investigate the efficiency of depollution power related to PbO₂ layer deposited onto a stainless steel (SS) substrate with SiOx as interlayer. The elaborated electrode was used as anode for anodic oxidation of wastewater containing Amaranth dye, as recalcitrant organic pollutant model. SiOx interlayer was performed using Plasma Enhanced Chemical Vapor Deposition ‘PECVD’ in plasma fed with argon, oxygen, and tetraethoxysilane (TEOS, Si precursor) in different ratios, onto the SS substrate. PbO₂ layer was produced by pulsed electrodeposition on SS/SiOx. The morphological of different surfaces are depicted with Field Emission Scanning Electron Microscope (FESEM) and the composition of the lead oxide layer was investigated by X-Ray Diffractometry (XRD). The results showed that the SiOx interlayer with more rich oxygen content improved better the nucleation of β-PbO₂ form. Electrochemical Impedance Spectroscopy (EIS) measurements undertaken on different interfaces (at optimized conditions) revealed a decrease of Rfilm while CPE film increases for SiOx interlayer, characterized by a more inorganic nature and deposited in a plasma fed by higher O2-to-TEOS ratios. Quantitative determinations of the Amaranth dye degradation rate were performed in terms of colour and COD removals, reaching a 95% and an 80% respectively removal at pH = 2 in 300 min. Results proved the improvement of the degradation wastewater containing the amaranth dye. During the electrolysis, the Amaranth dye solution was sampled at 30 min intervals and analyzed by ‘High-performance Liquid Chromatography’ HPLC. The gradual degradation of the Amaranth dye confirmed by the decrease in UV absorption using the SS/SiOx(20:20:1)/PbO₂ anode, the reaction exhibited an apparent first-order kinetic for electrolysis time of 5 hours, with an initial rate constant of about 0.02 min⁻¹.

Keywords: electrochemical treatment, PbO₂ anodes, COD removal, plasma

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896 The Application of New Ligands including Different Atoms and Evaluation of Their Nucleophile Effects against Various Metals

Authors: Saman Hajmohamadi, Sohrab Hajmohamadi

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The objectives of this experiment were to investigate the application of new ligands including different atoms and evaluation of their nucleophile effects against various metals. Chemistry researchers are really interested in this field. From among various ligands, there are some ligands with different coordinating ligands as well. There are great number of intermediate complexes and major elements of organic compositions with various atoms. There is a regular adding of new compositions. Complexes are the most important chemical combinations with various catalysts and biological, medicinal and other applications. Those complexes with ligands including different atom givers are really important and their synthesis could solve most of chemical problems. Supplying of new ligands is an important and key part of coordination chemistry which may cause some varieties and different properties in complexes with equal central nucleus. As a result, this research has evaluated new ligands including different coordination atoms, such as oxygen, nitrogen etc. along with their behavior against various metals like copper, nickel, iron etc.

Keywords: ligands, nucleophile, iron, cobalt, copper

Procedia PDF Downloads 203
895 Iron Oxide Reduction Using Solar Concentration and Carbon-Free Reducers

Authors: Bastien Sanglard, Simon Cayez, Guillaume Viau, Thomas Blon, Julian Carrey, Sébastien Lachaize

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The need to develop clean production processes is a key challenge of any industry. Steel and iron industries are particularly concerned since they emit 6.8% of global anthropogenic greenhouse gas emissions. One key step of the process is the high-temperature reduction of iron ore using coke, leading to large amounts of CO2 emissions. One route to decrease impacts is to get rid of fossil fuels by changing both the heat source and the reducer. The present work aims at investigating experimentally the possibility to use concentrated solar energy and carbon-free reducing agents. Two sets of experimentations were realized. First, in situ X-ray diffraction on pure and industrial powder of hematite was realized to study the phase evolution as a function of temperature during reduction under hydrogen and ammonia. Secondly, experiments were performed on industrial iron ore pellets, which were reduced by NH3 or H2 into a “solar furnace” composed of a controllable 1600W Xenon lamp to simulate and control the solar concentrated irradiation of a glass reactor and of a diaphragm to control light flux. Temperature and pressure were recorded during each experiment via thermocouples and pressure sensors. The percentage of iron oxide converted to iron (called thereafter “reduction ratio”) was found through Rietveld refinement. The power of the light source and the reduction time were varied. Results obtained in the diffractometer reaction chamber show that iron begins to form at 300°C with pure Fe2O3 powder and 400°C with industrial iron ore when maintained at this temperature for 60 minutes and 80 minutes, respectively. Magnetite and wuestite are detected on both powders during the reduction under hydrogen; under ammonia, iron nitride is also detected for temperatures between400°C and 600°C. All the iron oxide was converted to iron for a reaction of 60 min at 500°C, whereas a conversion ratio of 96% was reached with industrial powder for a reaction of 240 min at 600°C under hydrogen. Under ammonia, full conversion was also reached after 240 min of reduction at 600 °C. For experimentations into the solar furnace with iron ore pellets, the lamp power and the shutter opening were varied. An 83.2% conversion ratio was obtained with a light power of 67 W/cm2 without turning over the pellets. Nevertheless, under the same conditions, turning over the pellets in the middle of the experiment permits to reach a conversion ratio of 86.4%. A reduction ratio of 95% was reached with an exposure of 16 min by turning over pellets at half time with a flux of 169W/cm2. Similar or slightly better results were obtained under an ammonia reducing atmosphere. Under the same flux, the highest reduction yield of 97.3% was obtained under ammonia after 28 minutes of exposure. The chemical reaction itself, including the solar heat source, does not produce any greenhouse gases, so solar metallurgy represents a serious way to reduce greenhouse gas emission of metallurgy industry. Nevertheless, the ecological impact of the reducers must be investigated, which will be done in future work.

Keywords: solar concentration, metallurgy, ammonia, hydrogen, sustainability

Procedia PDF Downloads 138
894 Electrochemical Performance of Femtosecond Laser Structured Commercial Solid Oxide Fuel Cells Electrolyte

Authors: Mohamed A. Baba, Gazy Rodowan, Brigita Abakevičienė, Sigitas Tamulevičius, Bartlomiej Lemieszek, Sebastian Molin, Tomas Tamulevičius

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Solid oxide fuel cells (SOFC) efficiently convert hydrogen to energy without producing any disturbances or contaminants. The core of the cell is electrolyte. For improving the performance of electrolyte-supported cells, it is desirable to extend the available exchange surface area by micro-structuring of the electrolyte with laser-based micromachining. This study investigated the electrochemical performance of cells micro machined using a femtosecond laser. Commercial ceramic SOFC (Elcogen, AS) with a total thickness of 400 μm was structured by 1030 nm wavelength Yb: KGW fs-laser Pharos (Light Conversion) using 100 kHz repetition frequency and 290 fs pulse length light by scanning with the galvanometer scanner (ScanLab) and focused with a f-Theta telecentric lens (SillOptics). The sample height was positioned using a motorized z-stage. The microstructures were formed using a laser spiral trepanning in Ni/YSZ anode supported membrane at the central part of the ceramic piece of 5.5 mm diameter at active area of the cell. All surface was drilled with 275 µm diameter holes spaced by 275 µm. The machining processes were carried out under ambient conditions. The microstructural effects of the femtosecond laser treatment on the electrolyte surface were investigated prior to the electrochemical characterisation using a scanning electron microscope (SEM) Quanta 200 FEG (FEI). The Novo control Alpha-A was used for electrochemical impedance spectroscopy on a symmetrical cell configuration with an excitation amplitude of 25 mV and a frequency range of 1 MHz to 0.1 Hz. The fuel cell characterization of the cell was examined on open flanges test setup by Fiaxell. Using nickel mesh on the anode side and au mesh on the cathode side, the cell was electrically linked. The cell was placed in a Kittec furnace with a Process IDentifier temperature controller. The wires were connected to a Solartron 1260/1287 frequency analyzer for the impedance and current-voltage characterization. In order to determine the impact of the anode's microstructure on the performance of the commercial cells, the acquired results were compared to cells with unstructured anode. Geometrical studies verified that the depth of the -holes increased linearly according to laser energy and scanning times. On the other hand, it reduced as the scanning speed increased. The electrochemical analysis demonstrates that the open circuit voltage OCV values of the two cells are equal. Further, the modified cell's initial slope reduces to 0.209 from 0.253 of the unmodified cell, revealing that the surface modification considerably decreases energy loss. Plus, the maximum power density for the cell with the microstructure and the reference cell respectively, are 1.45 and 1.16 Wcm⁻².

Keywords: electrochemical performance, electrolyte-supported cells, laser micro-structuring, solid oxide fuel cells

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893 Exploring Tree Growth Variables Influencing Carbon Sequestration in the Face of Climate Change

Authors: Funmilayo Sarah Eguakun, Peter Oluremi Adesoye

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One of the major problems being faced by human society is that the global temperature is believed to be rising due to human activity that releases carbon IV oxide (CO2) to the atmosphere. Carbon IV oxide is the most important greenhouse gas influencing global warming and possible climate change. With climate change becoming alarming, reducing CO2 in our atmosphere has become a primary goal of international efforts. Forest landsare major sink and could absorb large quantities of carbon if the trees are judiciously managed. The study aims at estimating the carbon sequestration capacity of Pinus caribaea (pine)and Tectona grandis (Teak) under the prevailing environmental conditions and exploring tree growth variables that influencesthe carbon sequestration capacity in Omo Forest Reserve, Ogun State, Nigeria. Improving forest management by manipulating growth characteristics that influences carbon sequestration could be an adaptive strategy of forestry to climate change. Random sampling was used to select Temporary Sample Plots (TSPs) in the study area from where complete enumeration of growth variables was carried out within the plots. The data collected were subjected to descriptive and correlational analyses. The results showed that average carbon stored by Pine and Teak are 994.4±188.3 Kg and 1350.7±180.6 Kg respectively. The difference in carbon stored in the species is significant enough to consider choice of species relevant in climate change adaptation strategy. Tree growth variables influence the capacity of the tree to sequester carbon. Height, diameter, volume, wood density and age are positively correlated to carbon sequestration. These tree growth variables could be manipulated by the forest manager as an adaptive strategy for climate change while plantations of high wood density speciescould be relevant for management strategy to increase carbon storage.

Keywords: adaptation, carbon sequestration, climate change, growth variables, wood density

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892 Application of Host Factors as Biomarker in Early Diagnosis of Pulmonary Tuberculosis

Authors: Ambrish Tiwari, Sudhasini Panda, Archana Singh, Kalpana Luthra, S. K. Sharma

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Introduction: On the basis of available literature we know that various host factors play a role in outcome of Tuberculosis (TB) infection by modulating innate immunity. One such factor is Inducible Nitric Oxide Synthase enzyme (iNOS) which help in the production of Nitric Oxide (NO), an antimicrobial agent. Expression of iNOS is in control of various host factors in which Vitamin D along with its nuclear receptor Vitamin D receptor (VDR) is one of them. Vitamin D along with its receptor also produces cathelicidin (antimicrobicidal agent). With this background, we attempted to investigate the levels of Vitamin D and NO along with their associated molecules in tuberculosis patients and household contacts as compared to healthy controls and assess the implication of these findings in susceptibility to tuberculosis (TB). Study subjects and methods: 100 active TB patients, 75 household contacts, and 70 healthy controls were taken. VDR and iNOS mRNA levels were studied using real-time PCR. Serum VDR, cathelicidin, iNOS levels were measured using ELISA. Serum Vitamin D levels were measured in serum samples using chemiluminescence based immunoassay. NO was measured using colorimetry based kit. Results: VDR and iNOS mRNA levels were found to be lower in active TB group compared to household contacts and healthy controls (P=0.0001 and 0.005 respectively). The serum levels of Vitamin D were also found to be lower in active TB group as compared to healthy controls (P =0.001). Levels of cathelicidin and NO was higher in patient group as compared to other groups (p=0.01 and 0.5 respectively). However, the expression of VDR and iNOS and levels of vitamin D was significantly (P < 0.05) higher in household contacts compared to both active TB and healthy control groups. Inference: Higher levels of Vitamin D along with VDR and iNOS expression in household contacts as compared to patients suggest that vitamin D might have a protective role against TB which prevents activation of the disease. From our data, we can conclude that decreased vitamin D levels could be implicated in disease progression and we can use cathelicidin and NO as a biomarker for early diagnosis of pulmonary tuberculosis.

Keywords: vitamin D, VDR, iNOS, tuberculosis

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891 Magnetic Properties of Nickel Oxide Nanoparticles in Superparamagnetic State

Authors: Navneet Kaur, S. D. Tiwari

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Superparamagnetism is an interesting phenomenon and observed in small particles of magnetic materials. It arises due to a reduction in particle size. In the superparamagnetic state, as the thermal energy overcomes magnetic anisotropy energy, the magnetic moment vector of particles flip their magnetization direction between states of minimum energy. Superparamagnetic nanoparticles have been attracting the researchers due to many applications such as information storage, magnetic resonance imaging, biomedical applications, and sensors. For information storage, thermal fluctuations lead to loss of data. So that nanoparticles should have high blocking temperature. And to achieve this, nanoparticles should have a higher magnetic moment and magnetic anisotropy constant. In this work, the magnetic anisotropy constant of the antiferromagnetic nanoparticles system is determined. Magnetic studies on nanoparticles of NiO (nickel oxide) are reported well. This antiferromagnetic nanoparticle system has high blocking temperature and magnetic anisotropy constant of order 105 J/m3. The magnetic study of NiO nanoparticles in the superparamagnetic region is presented. NiO particles of two different sizes, i.e., 6 and 8 nm, are synthesized using the chemical route. These particles are characterized by an x-ray diffractometer, transmission electron microscope, and superconducting quantum interference device magnetometry. The magnetization vs. applied magnetic field and temperature data for both samples confirm their superparamagnetic nature. The blocking temperature for 6 and 8 nm particles is found to be 200 and 172 K, respectively. Magnetization vs. applied magnetic field data of NiO is fitted to an appropriate magnetic expression using a non-linear least square fit method. The role of particle size distribution and magnetic anisotropy is taken in to account in magnetization expression. The source code is written in Python programming language. This fitting provides us the magnetic anisotropy constant for NiO and other magnetic fit parameters. The particle size distribution estimated matches well with the transmission electron micrograph. The value of magnetic anisotropy constants for 6 and 8 nm particles is found to be 1.42 X 105 and 1.20 X 105 J/m3, respectively. The obtained magnetic fit parameters are verified using the Neel model. It is concluded that the effect of magnetic anisotropy should not be ignored while studying the magnetization process of nanoparticles.

Keywords: anisotropy, superparamagnetic, nanoparticle, magnetization

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890 Studies on Structural and Electrical Properties of Lanthanum Doped Sr₂CoMoO₆₋δ System

Authors: Pravin Kumar, Rajendra K. Singh, Prabhakar Singh

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A widespread research work on Mo-based double perovskite systems has been reported as a potential application for electrode materials of solid oxide fuel cells. Mo-based double perovskites studied in form of B-site ordered double perovskite materials, with general formula A₂B′B″O₆ structured by alkaline earth element (A = Sr, Ca, Ba) and heterovalent transition metals (B′ = Fe, Co, Ni, Cr, etc. and B″ = Mo, W, etc.), are raising a significant interest as potential mixed ionic-electronic conductors in the temperature range of 500-800 °C. Such systems reveal higher electrical conductivity, particularly those assigned in form of Sr₂CoMoO₆₋δ (M = Mg, Mn, Fe, Co, Ni, Zn etc.) which were studied in different environments (air/H₂/H₂-Ar/CH₄) at an intermediate temperature. Among them, the Sr₂CoMoO₆₋δ system is a potential candidate as an anode material for solid oxide fuel cells (SOFCs) due to its better electrical conductivity. Therefore, Sr₂CoMoO₆₋δ (SCM) system with La-doped on Sr site has been studied to discover the structural and electrical properties. The double perovskite system Sr₂CoMoO₆₋δ (SCM) and doped system Sr₂-ₓLaₓCoMoO₆₋δ (SLCM, x=0.04) were synthesized by the citrate-nitrate combustion synthesis route. Thermal studies were carried out by thermo-gravimetric analysis. Phase justification was confirmed by powder X-ray diffraction (XRD) as a tetragonal structure with space group I4/m. A minor phase of SrMoO₄ (s.g. I41/a) was identified as a secondary phase using JCPDS card no. 85-0586. Micro-structural investigations revealed the formation of uniform grains. The average grain size of undoped (SCM) and doped (SLCM) compositions was calculated by a linear intercept method and found to be ⁓3.8 μm and 2.7 μm, respectively. The electrical conductivity of SLCM is found higher than SCM in the air within the temperature range of 200-600 °C. SLCM system was also measured in reducing atmosphere (pure H₂) in the temperature range 300-600 °C. SLCM has been showed the higher conductivity in the reducing atmosphere (H₂) than in air and therefore it could be a promising anode material for SOFCs.

Keywords: double perovskite, electrical conductivity, SEM, XRD

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889 Electrochemical Study of Ni and/or Fe Based Mono- And Bi- Hydroxides

Authors: H. Benaldjia, N. Habib, F. Djefaflia, A. Nait-Merzoug, A. Harat, J. El-Haskouri, O. Guellati

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Currently, the technology has attracted knowledge of energy storage sources similar to batteries, capacitors and super-capacitors because of its very different applications in many fields with major social and economic challenges. Moreover, hydroxides have attracted much attention as a promising and active material choice in large-scale applications such as molecular adsorption/storage and separation for the environment, ion exchange, nanotechnology, supercapacitor for energy storage and conversion, electro-biosensing, and catalysts, due to their unique properties which are strongly influenced by their composition, microstructure, and synthesis method. In this context, we report in this study the synthesis of hydroxide-based nanomaterials precisely based on Ni and Fe using a simple hydrothermal method with mono and bi precursors at optimized growth conditions (6h-120°C). The obtained products were characterized using different techniques, such as XRD, FTIR, FESEM and BET, as well as electrochemical measurements.

Keywords: energy storage, Supercapacitors, nanocomposites, nanohybride, electro-active materials.

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888 Microwave-Assisted Fabrication of Visible-Light Activated BiOBr-Nanoplate Photocatalyst

Authors: Meichen Lee, Michael K. H. Leung

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In recent years, visible-light activated photocatalysis has become a major field of intense researches for the higher efficiency of solar energy utilizations. Many attempts have been made on the modification of wide band gap semiconductors, while more and more efforts emphasize on cost-effective synthesis of visible-light activated catalysts. In this work, BiOBr nanoplates with band gap of visible-light range are synthesized through a promising microwave solvothermal method. The treatment time period and temperature dependent BiOBr nanosheets of various particle sizes are investigated through SEM. BiOBr synthesized under the condition of 160°C for 60 mins shows the most uniform particle sizes around 311 nm and the highest surface-to-volume ratio on account of its smallest average particle sizes compared with others. It exhibits the best photocatalytic behavior among all samples in RhB degradation.

Keywords: microwave solvothermal process, nanoplates, solar energy, visible-light photocatalysis

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887 Li2o Loss of Lithium Niobate Nanocrystals during High-Energy Ball-Milling

Authors: Laura Kocsor, Laszlo Peter, Laszlo Kovacs, Zsolt Kis

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The aim of our research is to prepare rare-earth-doped lithium niobate (LiNbO3) nanocrystals, having only a few dopant ions in the focal point of an exciting laser beam. These samples will be used to achieve individual addressing of the dopant ions by light beams in a confocal microscope setup. One method for the preparation of nanocrystalline materials is to reduce the particle size by mechanical grinding. High-energy ball-milling was used in several works to produce nano lithium niobate. Previously, it was reported that dry high-energy ball-milling of lithium niobate in a shaker mill results in the partial reduction of the material, which leads to a balanced formation of bipolarons and polarons yielding gray color together with oxygen release and Li2O segregation on the open surfaces. In the present work we focus on preparing LiNbO3 nanocrystals by high-energy ball-milling using a Fritsch Pulverisette 7 planetary mill. Every ball-milling process was carried out in zirconia vial with zirconia balls of different sizes (from 3 mm to 0.1 mm), wet grinding with water, and the grinding time being less than an hour. Gradually decreasing the ball size to 0.1 mm, an average particle size of about 10 nm could be obtained determined by dynamic light scattering and verified by scanning electron microscopy. High-energy ball-milling resulted in sample darkening evidenced by optical absorption spectroscopy measurements indicating that the material underwent partial reduction. The unwanted lithium oxide loss decreases the Li/Nb ratio in the crystal, strongly influencing the spectroscopic properties of lithium niobate. Zirconia contamination was found in ground samples proved by energy-dispersive X-ray spectroscopy measurements; however, it cannot be explained based on the hardness properties of the materials involved in the ball-milling process. It can be understood taking into account the presence of lithium hydroxide formed the segregated lithium oxide and water during the ball-milling process, through chemically induced abrasion. The quantity of the segregated Li2O was measured by coulometric titration. During the wet milling process in the planetary mill, it was found that the lithium oxide loss increases linearly in the early phase of the milling process, then a saturation of the Li2O loss can be seen. This change goes along with the disappearance of the relatively large particles until a relatively narrow size distribution is achieved in accord with the dynamic light scattering measurements. With the 3 mm ball size and 1100 rpm rotation rate, the mean particle size achieved is 100 nm, and the total Li2O loss is about 1.2 wt.% of the original LiNbO3. Further investigations have been done to minimize the Li2O segregation during the ball-milling process. Since the Li2O loss was observed to increase with the growing total surface of the particles, the influence of ball-milling parameters on its quantity has also been studied.

Keywords: high-energy ball-milling, lithium niobate, mechanochemical reaction, nanocrystals

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886 Charge Transport of Individual Thermoelectric Bi₂Te₃ Core-Poly(3,4-Ethylenedioxythiophene):Polystyrenesulfonate Shell Nanowires Determined Using Conductive Atomic Force Microscopy and Spectroscopy

Authors: W. Thongkham, K. Sinthiptharakoon, K. Tantisantisom, A. Klamchuen, P. Khanchaitit, K. Jiramitmongkon, C. Lertsatitthanakorn, M. Liangruksa

Abstract:

Due to demands of sustainable energy, thermoelectricity converting waste heat into electrical energy has become one of the intensive fields of worldwide research. However, such harvesting technology has shown low device performance in the temperature range below 150℃. In this work, a hybrid nanowire of inorganic bismuth telluride (Bi₂Te₃) and organic poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) synthesized using a simple in-situ one-pot synthesis, enhancing efficiency of the nanowire-incorporated PEDOT:PSS-based thermoelectric converter is highlighted. Since the improvement is ascribed to the increased electrical conductivity of the thermoelectric host material, the individual hybrid nanowires are investigated using voltage-dependent conductive atomic force microscopy (CAFM) and spectroscopy (CAFS) considering that the electrical transport measurement can be performed either on insulating or conducting areas of the sample. Correlated with detailed chemical information on the crystalline structure and compositional profile of the nanowire core-shell structure, an electrical transporting pathway through the nanowire and the corresponding electronic-band structure have been determined, in which the native oxide layer on the Bi₂Te₃ surface is not considered, and charge conduction on the topological surface states of Bi₂Te₃ is suggested. Analyzing the core-shell nanowire synthesized using the conventional mixing of as-prepared Bi₂Te₃ nanowire with PEDOT:PSS for comparison, the oxide-removal effect of the in-situ encapsulating polymeric layer is further supported. The finding not only provides a structural information for mechanistic determination of the thermoelectricity, but it also encourages new approach toward more appropriate encapsulation and consequently higher efficiency of the nanowire-based thermoelectric generation.

Keywords: electrical transport measurement, hybrid Bi₂Te₃-PEDOT:PSS nanowire, nanoencapsulation, thermoelectricity, topological insulator

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885 Refining Waste Spent Hydroprocessing Catalyst and Their Metal Recovery

Authors: Meena Marafi, Mohan S. Rana

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Catalysts play an important role in producing valuable fuel products in petroleum refining; but, due to feedstock’s impurities catalyst gets deactivated with carbon and metal deposition. The disposal of spent catalyst falls under the category of hazardous industrial waste that requires strict agreement with environmental regulations. The spent hydroprocessing catalyst contains Mo, V and Ni at high concentrations that have been found to be economically significant for recovery. Metal recovery process includes deoiling, decoking, grinding, dissolving and treatment with complexing leaching agent such as ethylene diamine tetra acetic acid (EDTA). The process conditions have been optimized as a function of time, temperature and EDTA concentration in presence of ultrasonic agitation. The results indicated that optimum condition established through this approach could recover 97%, 94% and 95% of the extracted Mo, V and Ni, respectively, while 95% EDTA was recovered after acid treatment.

Keywords: atmospheric residue desulfurization (ARDS), deactivation, hydrotreating, spent catalyst

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884 Non-Steroidal Anti-inflammatory Drugs, Plant Extracts, and Characterized Microparticles to Modulate Antimicrobial Resistance of Epidemic Meca Positive S. Aureus of Dairy Origin

Authors: Amjad I. Aqib, Shanza R. Khan, Tanveer Ahmad, Syed A. R. Shah, Muhammad A. Naseer, Muhammad Shoaib, Iqra Sarwar, Muhammad F. A. Kulyar, Zeeshan A. Bhutta, Mumtaz A. Khan, Mahboob Ali, Khadija Yasmeen

Abstract:

The current study focused on resistance modulation of dairy linked epidemic mec A positive S. aureus for resistance modulation by plant extract (Eucalyptus globolus, Calotropis procera), NSAIDs, and star like microparticles. Zinc oxide {ZnO}c and {Zn (OH)₂} microparticles were synthesized by solvothermal method and characterized by calcination, X-ray diffraction (XRD), and scanning electron microscope (SEM). Plant extracts were prepared by the Soxhlet extraction method. The study found 34% of subclinical samples (n=200) positive for S. aureus from dairy milk having significant (p < 0.05) association of assumed risk factors with pathogen. The antimicrobial assay showed 55, 42, 41, and 41% of S. aureus resistant to oxacillin, ciprofloxacin, streptomycin, and enoxacin. Amoxicillin showed the highest percentage of increase in zone of inhibitions (ZOI) at 100mg of Calotropis procera extract (31.29%) followed by 1mg/mL (28.91%) and 10mg/mL (21.68%) of Eucalyptus globolus. Amoxicillin increased ZOI by 42.85, 37.32, 29.05, and 22.78% in combination with 500 ug/ml with each of diclofenac, aspirin, ibuprofen, and meloxicam, respectively. Fractional inhibitory concentration indices (FICIs) showed synergism of amoxicillin with diclofenac and aspirin and indifferent synergy with ibuprofen and meloxicam. The preliminary in vitro finding of combination of microparticles with amoxicillin proved to be synergistic, giving rise to 26.74% and 14.85% increase in ZOI of amoxicillin in combination with zinc oxide and zinc hydroxide, respectively. The modulated antimicrobial resistance incurred by NSAIDs, plant extracts, and microparticles against pathogenic S. aureus invite immediate attention to probe alternative antimicrobial sources.

Keywords: antimicrobial resistance, dairy milk, nanoparticles, NSIDs, plant extracts, resistance modulation, S. aureus

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883 Precise Electrochemical Metal Recovery from Emerging Waste Streams

Authors: Wei Jin

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Efficient and selective metal recovery from emerging solid waste, such as spent lithium batteries, electronic waste and SCR catalysts, is of great importance from both environmental and resource considerations. In order to overcome the bottlenecks of long flow-sheet and severe secondary pollution in conventional processes, the rational design of 2-electron oxygen reduction reaction (ORR) and capacitive deionization (CDI) nanomaterials were developed for the precise electrochemical metal recovery. It has been demonstrated that the modified carbon nanomaterials can be employed as 2e ORR to produce H2O2 in aqueous solution, in which the metal can be leached out from the solid waste as ions. Moreover, the multi-component metallic solution can be electrochemically extracted with good efficiency and selectivity with the nanoporous aerogel. Each system presents stable performance for long-term operation and can be used in industrial solid waste treatment. This study provides a materials-oriented, cleaner metal recovery approach for strategic metal resources sustainability.

Keywords: electrochemistry, metal recovery, waste steams, nanomaterials

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882 Allylation of Active Methylene Compounds with Cyclic Baylis-Hillman Alcohols: Why Is It Direct and Not Conjugate?

Authors: Karim Hrratha, Khaled Essalahb, Christophe Morellc, Henry Chermettec, Salima Boughdiria

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Among the carbon-carbon bond formation types, allylation of active methylene compounds with cyclic Baylis-Hillman (BH) alcohols is a reliable and widely used method. This reaction is a very attractive tool in organic synthesis of biological and biodiesel compounds. Thus, in view of an insistent and peremptory request for an efficient and straightly method for synthesizing the desired product, a thorough analysis of various aspects of the reaction processes is an important task. The product afforded by the reaction of active methylene with BH alcohols depends largely on the experimental conditions, notably on the catalyst properties. All experiments reported that catalysis is needed for this reaction type because of the poor ability of alcohol hydroxyl group to be as a suitable leaving group. Within the catalysts, several transition- metal based have been used such as palladium in the presence of acid or base and have been considered as reliable methods. Furthemore, acid catalysts such as BF3.OEt2, BiX3 (X= Cl, Br, I, (OTf)3), InCl3, Yb(OTf)3, FeCl3, p-TsOH and H-montmorillonite have been employed to activate the C-C bond formation through the alkylation of active methylene compounds. Interestingly a report of a smoothly process for the ability of 4-imethyaminopyridine(DMAP) to catalyze the allylation reaction of active methylene compounds with cyclic Baylis-Hillman (BH) alcohol appeared recently. However, the reaction mechanism remains ambiguous, since the C- allylation process leads to an unexpected product (noted P1), corresponding to a direct allylation instead of conjugate allylation, which involves the most electrophilic center according to the electron withdrawing group CO effect. The main objective of the present theoretical study is to better understand the role of the DMAP catalytic activity as well as the process leading to the end- product (P1) for the catalytic reaction of a cyclic BH alcohol with active methylene compounds. For that purpose, we have carried out computations of a set of active methylene compounds varying by R1 and R2 toward the same alcohol, and we have attempted to rationalize the mechanisms thanks to the acid–base approach, and conceptual DFT tools such as chemical potential, hardness, Fukui functions, electrophilicity index and dual descriptor, as these approaches have shown a good prediction of reactions products.The present work is then organized as follows: In a first part some computational details will be given, introducing the reactivity indexes used in the present work, then Section 3 is dedicated to the discussion of the prediction of the selectivity and regioselectivity. The paper ends with some concluding remarks. In this work, we have shown, through DFT method at the B3LYP/6-311++G(d,p) level of theory that: The allylation of active methylene compounds with cyclic BH alcohol is governed by orbital control character. Hence the end- product denoted P1 is generated by direct allylation.

Keywords: DFT calculation, gas phase pKa, theoretical mechanism, orbital control, charge control, Fukui function, transition state

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