Search results for: ferrite catalysts

Authors: M. Diafi, M. Omari, B. Gasmi

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Perovskite-type La1−xCaxAlO3 were synthesized at 1000◦C by a co- precipitation method. The synthesized oxide powders were characterized by X-ray diffraction (XRD) and the oxide powders were produced in the form of films on pretreated Ni-supports by an oxide-slurry painting technique their electrocatalytic activities towards methanol oxidation in alkaline solutions at 25°C using cyclic voltammetry, chronoamperometry, and anodic Tafel polarization techniques. The oxide catalysts followed the rhombohedral hexagonal crystal geometry. The rate of electro-oxidation of methanol was found to increase with increasing substitution of La by Ca in the oxide matrix. The reaction indicated a Tafel slope of ~2.303RT/F, The electrochemical apparent activation energy (〖∆H〗_el^(°#)) was observed to decrease on increasing Ca content. The results point out the optimum electrode activity and stability of the Ca is x=0.6 of composition.

Keywords: electrocatalysis, oxygen evolution, perovskite-type La1−x Cax AlO3, methanol oxidation

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Authors: Abhishek Sraw, Amit Sobti, Yamini Pandey, R. K. Wanchoo, Amrit Pal Toor

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Monocrotophos (MCP) is a widely used pesticide in India, which belong to an extremely toxic organophosphorus family, is persistent in nature and its toxicity is widely reported in all environmental segments in the country. Advanced Oxidation Process (AOP) is a promising solution to the problem of water pollution. TiO₂ is being widely used as a photocatalyst because of its many advantages, but it has a large band gap, due to which it is modified using metal and nonmetal dopant to make it active under sunlight and visible light. The use of nanosized powdered catalysts makes the recovery process extremely complicated. Hence the aim is to use low cost, easily available, eco-friendly clay material in form of bead as the support for the immobilization of catalyst, to solve the problem of post-separation of suspended catalyst from treated water. A recirculation type photocatalytic reactor (RTPR), using ultraviolet light emitting source (blue black lamp) was designed which work effectively for both suspended catalysts and catalyst coated clay beads. The bare, TiO₂ and W-TiO₂ coated clay beads were characterized by scanning electron microscopy (SEM), electron dispersive spectroscopy (EDS) and N₂ adsorption–desorption measurements techniques (BET) for their structural, textural and electronic properties. The study involved variation of different parameters like light conditions, recirculation rate, light intensity and initial MCP concentration under UV and sunlight for the degradation of MCP. The degradation and mineralization studies of the insecticide solution were performed using UV-Visible spectrophotometer, and COD vario-photometer and GC-MS analysis respectively. The main focus of the work lies in checking the recyclability of the immobilized TiO₂ over clay beads in the developed RTPR up to 30 continuous cycles without reactivation of catalyst. The results demonstrated the economic feasibility of the utilization of developed RTPR for the efficient purification of pesticide polluted water. The prepared TiO₂ clay beads delivered 75.78% degradation of MCP under UV light with negligible catalyst loss. Application of W-TiO₂ coated clay beads filled RTPR for the degradation of MCP under sunlight, however, shows 32% higher degradation of MCP than the same system based on undoped TiO₂. The COD measurements of TiO₂ coated beads led to 73.75% COD reduction while W-TiO₂ resulted in 87.89% COD reduction. The GC-MS analysis confirms the efficient breakdown of complex MCP molecules into simpler hydrocarbons. This supports the promising application of clay beads as a support for the photocatalyst and proves its eco-friendly nature, excellent recyclability, catalyst holding capacity, and economic viability.

Keywords: immobilized clay beads, monocrotophos, recirculation type photocatalytic reactor, TiO₂

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Authors: I. Ben Kaddour, S. Larbaoui

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Since their first synthesis in 1984, silicoaluminophosphates have proven their effectiveness as a good adsorbent and catalyst in several environmental and energy applications. In this work, the photocatalytic reaction of the photo-degradation of a pharmaceutical product in water was carried out in the presence of a series of materials based on titanium oxide, anatase phase, supported on the microporous framework of the SAPO4-5 at different levels, under ultraviolet light. These photo-catalysts were characterized by different physicochemical analysis methods in order to determine their structural, textural, and morphological properties, such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), microscopy scanning electronics (SEM), nitrogen adsorption measurements, UV-visible diffuse reflectance spectroscopy (UV-Vis-DRS). In this study, liquid chromatography coupled with spectroscopy of mass (LC-MS) was used to determine the nature of the intermediate products formed during the photocatalytic degradation of DCF.

Keywords: photocatalysis, titanium dioxide, SAPO-5, diclofenac

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Authors: Anastasiia Maklakova

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The perovskite type oxides formed in the Ln-Me-Me/-O systems (where Ln – rare-earth, Me – alkaline earth metal, Me/ - 3-d metal) have potential applications as gas sensors, catalysts or cathode materials for IT-SOFCs due to the high values of mixed electronic -ionic conductivity and high oxygen diffusivity. Complex oxides in the Sr-(Pr,Gd)-Co-O systems were prepared via the glycerol-nitrate technique The phase composition was determined using a Shimadzu XRD-7000 diffractometer at room temperature in air. Phase identification was performed using the ICDD database. The structure was refined by the full-profile Rietveld method using Fullprof 2008 software. Gradual substitution of strontium by Pr or Gd leads to the decrease of unit cell parameters and unit cell volume that can be explained by the size factor. An introduction of Pr or Gd into the strontium cobaltite increases the oxygen content in samples.

Keywords: phase equilibria, crystal structure, oxygen nonstoichiometry, solid oxide fuel cell

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Authors: Sam Derakhshan Deilami, Iain N. Kings, Lynne E. Macaskie, Brajendra K. Sharma, Anthony V. Bridgwater, Joseph Wood

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This paper reports the application of a bacteria-supported palladium catalyst to the hydrodeoxygenation (HDO) of pyrolysis bio-oil, towards producing an upgraded transport fuel. Biofuels are key to the timely replacement of fossil fuels in order to mitigate the emissions of greenhouse gases and depletion of non-renewable resources. The process is an essential step in the upgrading of bio-oils derived from industrial by-products such as agricultural and forestry wastes, the crude oil from pyrolysis containing a large amount of oxygen that requires to be removed in order to create a fuel resembling fossil-derived hydrocarbons. The bacteria supported catalyst manufacture is a means of utilizing recycled metals and second life bacteria, and the metal can also be easily recovered from the spent catalysts after use. Comparisons are made between bio-Pd, and a conventional activated carbon supported Pd/C catalyst. Bio-oil was produced by fast pyrolysis of beechwood at 500 C at a residence time below 2 seconds, provided by Aston University. 5 wt % BioPd/C was prepared under reducing conditions, exposing cells of E. coli MC4100 to a solution of sodium tetrachloropalladate (Na2PdCl4), followed by rinsing, drying and grinding to form a powder. Pd/C was procured from Sigma-Aldrich. The HDO experiments were carried out in a 100 mL Parr batch autoclave using ~20g bio-crude oil and 0.6 g bio-Pd/C catalyst. Experimental variables investigated for optimization included temperature (160-350C) and reaction times (up to 5 h) at a hydrogen pressure of 100 bar. Most of the experiments resulted in an aqueous phase (~40%) and an organic phase (~50-60%) as well as gas phase (<5%) and coke (<2%). Study of the temperature and time upon the process showed that the degree of deoxygenation increased (from ~20 % up to 60 %) at higher temperatures in the region of 350 C and longer residence times up to 5 h. However minimum viscosity (~0.035 Pa.s) occurred at 250 C and 3 h residence time, indicating that some polymerization of the oil product occurs at the higher temperatures. Bio-Pd showed a similar degree of deoxygenation (~20 %) to Pd/C at lower temperatures of 160 C, but did not rise as steeply with temperature. More coke was formed over bio-Pd/C than Pd/C at temperatures above 250 C, suggesting that bio-Pd/C may be more susceptible to coke formation than Pd/C. Reactions occurring during bio-oil upgrading include catalytic cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation and hydrogenation. In conclusion, it was shown that bio-Pd/C displays an acceptable rate of HDO, which increases with residence time and temperature. However some undesirable reactions also occur, leading to a deleterious increase in viscosity at higher temperatures. Comparisons are also drawn with earlier work on the HDO of Chlorella derived bio-oil manufactured from micro-algae via hydrothermal liquefaction. Future work will analyze the kinetics of the reaction and investigate the effect of bi-metallic catalysts.

Keywords: bio-oil, catalyst, palladium, upgrading

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Authors: Jenna Metera, Olivia Graeve

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Ceramic capacitor technologies using lead based materials is being phased out for its environmental and handling hazards. Bismuth ferrite (BiFeO₃) is the next best replacement for those lead-based technologies. Unfortunately, the electrical properties in bismuth systems are not as robust as the lead alternatives. The improvement of electrical properties such as charge density, charge anisotropy, relative permittivity, and dielectric loss are the parameters that will make BiFeO₃ a competitive alternative to lead-based ceramic materials. In order to maximize the utility of these properties, we propose the ordering and an evaporation-induced self-assembly of a cubic morphology powder. Evaporation-induced self-assembly is a template-less, bottom-up, self-assembly option. The capillary forces move the particles closer together when the solvent evaporates, promoting organized agglomeration at the particle faces. The assembly of particles into organized structures can lead to enhanced properties compared to unorganized structures or single particles themselves. The interactions between the particles can be controlled based on the long-range order in the organized structure. The cubic particle morphology is produced through a hydrothermal synthesis with changes in the concentration of potassium hydroxide, which changes the morphology of the powder. Once the assembly materializes, the powder is fabricated into workable substrates for electrical testing after consolidation.

Keywords: evaporation, lead-free, morphology, self-assembly

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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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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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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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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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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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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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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

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Authors: Farej Ahmed Emhmmed

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Fracture of duplex stainless steels (DSS) was investigated in air and in 3.5 wt % NaCl solution. Tow sets of fatigued specimens were heat treated at 475ºC for different times and pulled to failure either in air or after kept in 3.5% NaCl with polarization of -900 mV/ SCE. Fracture took place in general by ferrite cleavage and austenite ductile fracture in transgranular mode. Specimens measured stiffness (Ms) was affected by the aging time, with higher values measured for specimens aged for longer times. Microstructural features played a role in "blocking" the crack propagation process leading to lower the CTOD values specially for specimens aged for short times. Unbroken ligaments/ austenite were observed at the crack wake. These features may exerted a bridging stress, blocking effect, at the crack tip giving resistance to the crack propagation process i.e the crack mouth opening was reduced. Higher stress intensity factor Kıc values were observed with increased amounts of crack growth suggesting longer zone of unbroken ligaments in the crack wake. The bridging zone was typically several mm in length. Attempt to model the bridge stress was suggested to understand the role of ligaments/unbroken austenite in increasing the fracture toughness factor.

Keywords: stainless steels, fracture toughness, crack keying effect, ligaments

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Authors: Mohamed K. El-Fawkhry, Ahmed Shash, Ahmed Ismail Zaki Farahat, Sherif Ali Abd El Rahman, Taha Mattar

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High-carbon, silicon-rich steels are commonly suggested to obtain very fine bainitic microstructure at low temperature ranged from 200 to 300°C. Thereby, the resulted microstructure consists of slender of bainitic-ferritic plates interwoven with retained austenite. The advanced strength and ductility package of this steel is much dependent on the fineness of bainitic ferrite, as well as the retained austenite phase. In this article, Aluminum to Silicon ratio, and the isothermal transformation temperature have been adopted to obtain ultra high strength high carbon steel. Optical and SEM investigation of the produced steels have been performed. XRD has been used to track the retained austenite development as a result of the change in the chemical composition of developed steels and heat treatment process. Mechanical properties in terms of hardness and microhardness of obtained phases and structure were investigated. It was observed that the increment of aluminum to silicon ratio has a great effect in promoting the bainitic transformation, in tandem with improving the stability and the fineness of retained austenite. Such advanced structure leads to enhancement in the whole mechanical properties of the high carbon steel.

Keywords: high-carbon steel, silicon-rich steels, fine bainitic microstructure, retained austenite, isothermal transformation

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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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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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Authors: Mehak Munjal, Raj Kishore Sharma, Gurmeet Singh

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Microbial Fuel Cells (MFCs) are an alternative sustainable approach that utilize bacteria present in waste water as a bio-catalyst for the production of energy. It is a promising growing technology with minimal requirement for chemical supplements. Here electrode material plays a vital role in its performance. The present study represents CoFe2O4 spinel as a novel anode material in the MFC. It not only improve the bacterial metabolics but also enhance the power output. Generally, biocompatible conductive carbon paper/cloth, graphite and stainless steel are utilised as anode in MFCs. However, these materials lack electrochemical activity for anodic microbial reaction. Therefore, we developed CoFe2O4 on graphite sheet which enhanced the anodic charge transfer process. Redox pair in CoFe2O4 helped in improvement of extracellular electron transfer, thereby enhancing the performance. The physical characterizations (FT-IR, XRD, Raman) and electrochemical measurements demonstrate the strong interaction with E.coli bacteria and thus providing an excellent power density i.e. 1850 mW/m2 .The maximum anode half -cell potential is measured to be 0.65V. Therefore, use of noble metal free anodic material further decrease the cost and the long term cell stability makes it an effective material for practical applications.

Keywords: microbial fuel cell, cobalt ferrite, E. coli, bioelectricity

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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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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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Authors: Siba Soren, Purnendu Parhi

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Today, the world is facing a severe challenge due to depletion of traditional fossil fuels. Scientists across the globe are working for a solution that involves a dramatic shift to practical and environmentally sustainable energy sources. High-capacity energy systems, such as metal-air batteries, fuel cells, are highly desirable to meet the urgent requirement of sustainable energies. Among the fuel cells, Direct methanol fuel cells (DMFCs) are recognized as an ideal power source for mobile applications and have received considerable attention in recent past. In this advanced electrochemical energy conversion technologies, Oxygen Reduction Reaction (ORR) is of utmost importance. However, the poor kinetics of cathodic ORR in DMFCs significantly hampers their possibilities of commercialization. The oxygen is reduced in alkaline medium either through a 4-electron (equation i) or a 2-electron (equation ii) reduction pathway at the cathode ((i) O₂ + 2H₂O + 4e⁻ → 4OH⁻, (ii) O₂ + H₂O + 2e⁻ → OH⁻ + HO₂⁻ ). Due to sluggish ORR kinetics the ability to control the reduction of molecular oxygen electrocatalytically is still limited. The electrocatalytic ORR starts with adsorption of O₂ on the electrode surface followed by O–O bond activation/cleavage and oxide removal. The reaction further involves transfer of 4 electrons and 4 protons. The sluggish kinetics of ORR, on the one hand, demands high loading of precious metal-containing catalysts (e.g., Pt), which unfavorably increases the cost of these electrochemical energy conversion devices. Therefore, synthesis of active electrocatalyst with an increase in ORR performance is need of the hour. In the recent literature, there are many reports on transition metal oxide (TMO) based ORR catalysts for their high activity TMOs are also having drawbacks like low electrical conductivity, which seriously affects the electron transfer process during ORR. It was found that 2D graphene layer is having high electrical conductivity, large surface area, and excellent chemical stability, appeared to be an ultimate choice as support material to enhance the catalytic performance of bare metal oxide. g-C₃N₄ is also another candidate that has been used by the researcher for improving the ORR performance of metal oxides. This material provides more active reaction sites than other N containing carbon materials. Rare earth oxide like CeO₂ is also a good candidate for studying the ORR activity as the metal oxide not only possess unique electronic properties but also possess catalytically active sites. Here we will discuss the ORR performance (in alkaline medium) of N-rGO/C₃N₄ supported nano Cerium Oxides hybrid synthesized by microwave assisted Solvothermal method. These materials exhibit superior electrochemical stability and methanol tolerance capability to that of commercial Pt/C.

Keywords: oxygen reduction reaction, electrocatalyst, cerium oxide, graphene

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Authors: Tesfay Gebremicheal Reda, K. Samatha, Paul Douglas Sanasi, D. Parajuli

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Nanoparticle technology is fast progressing and is being employed in innumerable medical applications. At this time, the public's health is seriously threatened by the rise of bacterial strains resistant to several medications. Metal nanoparticles are a potential alternate approach for tackling this global concern, and this is the main focus of this study. The citrate precursor sol-gel synthesis method was used to synthesize the Niₓ Co₁₋ₓ Fe₂ O₄, (where x = 0.0:0.2:1.0) nanoparticle. XRD identified the development of the cubic crystal structure to have a preferential orientation along (311), and the average particle size was found to be 29-38 nm. The average crystallizes assessed with ImageJ software and origin 22 of the SEM are nearly identical to the XRD results. In the created NCF NPs, the FT-IR spectroscopy reveals structural examinations and the redistribution of cations between octahedral (505-428 cm⁻¹) and tetrahedral (653-603 cm⁻¹) locales. As the Co²⁺ cation is substituted with Ni²⁺, the coercive fields HC decrease from 2384 Oe to 241.93 Oe. Band gap energy rises as Ni concentration increases, which may be attributed to the fact that the ionic radii of Ni²⁺ ions are smaller than that of Co²⁺ ions, which results in a strong electrostatic interaction. On the contrary, except at x = 0.4, the dielectric constant decreases as the nickel concentration increases. According to the findings of this research work, nanoparticles are composed of Ni₀.₄ Co₀.₆ Fe₂ O₄ have demonstrated a promising value against S. aureus and E. coli, and it suggests a proposed model for their potential use as a source of antibacterial agent.

Keywords: antimicrobial, band gap, citrate precursor, dielectric, nanoparticle

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Authors: Brenda Cecilia Ledesma, Andrea Beltramone

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This work deals with the bio-waste valorization approach for catalyst development, the use of products derived from biomass as raw material and the obtaining of biofuels. In this research, activated carbons were synthesized from the orange peel using different synthesis conditions. With the activated carbons obtained with the best structure and texture, PtIr bimetallic catalysts were prepared. Carbon activation was carried out through a chemical process with phosphoric acid as an activating agent, varying the acid concentration, the ratio substrate/activating agent and time of contact between them. The best support was obtained using a carbonization time of 1 h, the temperature of carbonization of 470oC, the phosphoric acid concentration of 50 wt.% and a BET area of 1429 m2/g. Subsequently, the metallic nanoparticles were deposited in the activated carbon to use the solid as a catalytic material for the hydrogenation of HMF to 2,5-DMF. The catalyst presented an excellent performance for biofuels generation.

Keywords: orange peel, bio-waste valorization, platinum, iridium, 5-hydroxymethylfurfural

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Authors: Joanna Drzeżdżon

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Polyvinyl alcohol and its derivatives such as 2-chloro-2-propen-1-ol have found application in many industries. They are mainly used for the production of adhesives, thickeners and stabilizers of emulsion paints, and surgical threads. Moreover, polyvinyl alcohol derivatives are indispensable reagents in the synthesis of hemiacetals. Polyolefins derived from polyvinyl alcohol are obtained by using catalysts belonging to complex compounds of transition metal ions. The aim of the studies is to the synthesis of a new complex, i.e. dipicolinate oxovanadium(IV) complex with 4,4’-dimethoxy-2,2’-bipyridyl, and to determine its catalytic activities. Moreover, the another aim of the studies was to set conditions for 2-chloro-2-propen-1-ol oligomerization. The catalytic system has been based on the dipicolinate complex of oxovanadium(IV) with 4,4’-dimethoxy-2,2’-bipyridyl and MMAO-12. The results of the studies showed that how a new oxovanadium(IV) complex compound effects on the 2-chloro-2-propen-1-ol oligomerization. Moreover, the results revealed that new catalytic material is a highly active catalyst for the investigated oligomerization.

Keywords: 2-chloro-2-propen-1-ol, oligomerization, dipicolinate, vanadium, methylaluminoxane

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Authors: Angelika-Ioanna Gialleli, Gousi Mantha, Maria Kanellaki, Bekatorou Argyro, Athanasios Koutinas

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In this study, a new brewing technology with dry raw materials is proposed with potential application in home brewing. Bio catalysts were prepared by immobilization of the psychrotolerant yeast strain Saccharomyces cerevisiae AXAZ-1 on tubular cellulose. Both the word and the biocatalysts were freeze-dried without any cryoprotectants and used for low temperature brewing. The combination of immobilization and freeze-drying techniques was applied successfully, giving a potential for supplying breweries with preserved and ready-to-use immobilized cells. The effect of wort sugar concentration (7°, 8.5°, 10°Be), temperature (2, 5, 7° C) and carrier concentration (5, 10, 20 g/L) on fermentation kinetics and final product quality (volatiles, colour, polyphenols, bitterness) was assessed. The same procedure was repeated with free cells for comparison of the results. The results for immobilized cells were better compared to free cells regarding fermentation kinetics and organoleptic characteristics.

Keywords: brewing, tubular cellulose, low temperature, biocatalyst

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Authors: Zoubida Lounis, Naouel Boumesla, Abd El Kader Bengueddach

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The main objective of this study is to synthesize a composite materials by direct synthesis at atmospheric pression having the MFI structure and MCM-41 by using double structuring. In the first part of this work we are interested in the study of the synthesis parameters, in addition to temperature, the crystallization time and pH. The second part of this work is to vary the ratio of the concentrations of both structuring C9 [C9H19(CH3)3NBr] and C16 [C16H33(CH3)3NBr] and determining the area of formation of the two materials (microporous and mesoporous at same time), for this reason we performed a battery of experiments ranging from 0 to 100% for both structural. To enhance the economic purposes of this study, the experiments were carried out by using very cheap and simple process, the pyrex tubes were used instead of the reactors, and the synthesis were done at atmospheric pressure and moderate temperature. The final products (composite materials) were obtained at high and pure quality.

Keywords: composite materials, syntheisis, catalysts, mesoporous materials, microporous materials

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Authors: Leila Samiee, Amir Yadegari, Saeedeh Tasharrofi

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In the work presented here, nitrogen-doped graphene materials were synthesized and used as metal-free electrocatalysts for oxygen reduction reaction (ORR) under alkaline conditions. Paraphenylenediamine was used as N precursor. The N-doped graphene was synthesized under hydrothermal treatment at 200°C. All the materials have been characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS). Moreover, for electrochemical evaluation of samples, Rotating Disk electrode (RDE) and Cyclic Voltammetry techniques (CV) were employed. The resulting material exhibits an outstanding catalytic activity for the oxygen reduction reaction (ORR) as well as excellent resistance towards methanol crossover effects, indicating their promising potential as ORR electrocatalysts for alkaline fuel cells.

Keywords: alkaline fuel cell, graphene, metal-free catalyst, paraphenylen diamine

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Authors: Kevin Mark Banks, Dannis Rorisang Nkarapa Maubane, Carel Coetzee

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The influence of aluminium content, reheating temperature, and sizing (final) strain on the as-rolled microstructure was systematically investigated in vanadium-microalloyed and C-Mn plate steels. Reheating, followed by hot rolling and air cooling simulations were performed on steels containing a range of aluminium and nitrogen contents. Natural air cooling profiles, corresponding to 6 and 20mm thick plates, were applied. The austenite and ferrite/pearlite microstructures were examined using light optical microscopy. Precipitate species and volume fraction were determined on selected specimens. No influence of aluminium content was found below 0.08% on the as-rolled grain size in all steels studied. A low Al-V-steel produced the coarsest initial austenite grain size due to AlN dissolution at low temperatures leading to abnormal grain growth. An Al-free V-N steel had the finest initial microstructure. Although the as-rolled grain size for 20mm plate was similar in all steels tested, the grain distribution was relatively mixed. The final grain size in 6mm plate was similar for most compositions; the exception was an as-cast V low N steel, where the size of the second phase was inversely proportional to the sizing strain. This was attributed to both segregation and a low VN volume fraction available for effective pinning of austenite grain boundaries during cooling. Increasing the sizing strain refined the microstructure significantly in all steels.

Keywords: aluminium, grain size, nitrogen, reheating, sizing strain, steel, vanadium

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Authors: Frea Van Steenweghen, Lander Hollevoet, Johan A. Martens

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Compared to other hydrogen (H₂) carriers, ammonia (NH₃) is one of the most promising carriers as it contains 17.6 wt% hydrogen. It is easily liquefied at ≈ 9–10 bar pressure at ambient temperature. More importantly, NH₃ is a carbon-free hydrogen carrier with no CO₂ emission at final decomposition. Ammonia has a well-defined regulatory framework and a good track record regarding safety concerns. Furthermore, the industry already has an existing transport infrastructure consisting of pipelines, tank trucks and shipping technology, as ammonia has been manufactured and distributed around the world for over a century. While NH₃ synthesis and transportation technological solutions are at hand, a missing link in the hydrogen delivery scheme from ammonia is an energy-lean and efficient technology for cracking ammonia into H₂ and N₂. The most explored option for ammonia decomposition is thermo-catalytic cracking which is, by itself, the most energy-efficient approach compared to other technologies, such as plasma and electrolysis, as it is the most energy-lean and robust option. The decomposition reaction is favoured only at high temperatures (> 300°C) and low pressures (1 bar) as the thermocatalytic ammonia cracking process is faced with thermodynamic limitations. At 350°C, the thermodynamic equilibrium at 1 bar pressure limits the conversion to 99%. Gaining additional conversion up to e.g. 99.9% necessitates heating to ca. 530°C. However, reaching thermodynamic equilibrium is infeasible as a sufficient driving force is needed, requiring even higher temperatures. Limiting the conversion below the equilibrium composition is a more economical option. Thermocatalytic ammonia cracking is documented in scientific literature. Among the investigated metal catalysts (Ru, Co, Ni, Fe, …), ruthenium is known to be most active for ammonia decomposition with an onset of cracking activity around 350°C. For establishing > 99% conversion reaction, temperatures close to 600°C are required. Such high temperatures are likely to reduce the round-trip efficiency but also the catalyst lifetime because of the sintering of the supported metal phase. In this research, the first focus was on catalyst bed design, avoiding diffusion limitation. Experiments in our packed bed tubular reactor set-up showed that extragranular diffusion limitations occur at low concentrations of NH₃ when reaching high conversion, a phenomenon often overlooked in experimental work. A second focus was thermocatalyst development for ammonia cracking, avoiding the use of noble metals. To this aim, candidate metals and mixtures were deposited on a range of supports. Sintering resistance at high temperatures and the basicity of the support were found to be crucial catalyst properties. The catalytic activity was promoted by adding alkaline and alkaline earth metals. A third focus was studying the optimum process configuration by process simulations. A trade-off between conversion and favorable operational conditions (i.e. low pressure and high temperature) may lead to different process configurations, each with its own pros and cons. For example, high-pressure cracking would eliminate the need for post-compression but is detrimental for the thermodynamic equilibrium, leading to an optimum in cracking pressure in terms of energy cost.

Keywords: ammonia cracking, catalyst research, kinetics, process simulation, thermodynamic equilibrium

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Authors: A. Volperts, G. Dobele, A. Zhurinsh, I. Kruusenberg, A. Plavniece, J. Locs

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Nowadays energy consumption constantly increases and development of effective and cheap electrochemical sources of power, such as fuel cells and electrochemical capacitors, is topical. Due to their high specific power, charge and discharge rates, working lifetime supercapacitor based energy accumulation systems are more and more extensively being used in mobile and stationary devices. Lignocellulosic materials are widely used as precursors and account for around 45% of the total raw materials used for the manufacture of activated carbon which is the most suitable material for supercapacitors. First part of our research is devoted to study of influence of main stages of wood thermochemical activation parameters on activated carbons porous structure formation. It was found that the main factors governing the properties of carbon materials are specific surface area, volume and pore size distribution, particles dispersity, ash content and oxygen containing groups content. Influence of activated carbons attributes on capacitance and working properties of supercapacitor are demonstrated. The correlation between activated carbons porous structure indices and electrochemical specifications of supercapacitors with electrodes made from these materials has been determined. It is shown that if synthesized activated carbons are used in supercapacitors then high specific capacitances can be reached – more than 380 F/g in 4.9M sulfuric acid based electrolytes and more than 170 F/g in 1 M tetraethylammonium tetrafluoroborate in acetonitrile electrolyte. Power specifications and minimal price of H₂-O₂ fuel cells are limited by the expensive platinum-based catalysts. The main direction in development of non-platinum catalysts for the oxygen reduction is the study of cheap porous carbonaceous materials which can be obtained by the pyrolysis of polymers including renewable biomass. It is known that nitrogen atoms in carbon materials to a high degree determine properties of the doped activated carbons, such as high electrochemical stability, hardness, electric resistance, etc. The lack of sufficient knowledge on the doping of the carbon materials calls for the ongoing researches of properties and structure of modified carbon matrix. In the second part of this study, highly porous activated carbons were synthesized using alkali thermochemical activation from wood, cellulose and cellulose production residues – craft lignin and sewage sludge. Activated carbon samples were doped with dicyandiamide and melamine for the application as fuel cell cathodes. Conditions of nitrogen introduction (solvent, treatment temperature) and its content in the carbonaceous material, as well as porous structure characteristics, such as specific surface and pore size distribution, were studied. It was found that efficiency of doping reaction depends on the elemental oxygen content in the activated carbon. Relationships between nitrogen content, porous structure characteristics and electrodes electrochemical properties are demonstrated.

Keywords: activated carbons, low-temperature fuel cells, nitrogen doping, porous structure, supercapacitors

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