Search results for: heterogenous catalyst

Authors: Paola Leon, Hugo Garcia, Adan Leon, Samuel Munoz

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The enhanced oil recovery by steam injection was considered a process that only generated physical recovery mechanisms. However, there is evidence of the occurrence of a series of chemical reactions, which are called aquathermolysis, which generates hydrogen sulfide, carbon dioxide, methane, and lower molecular weight hydrocarbons. These reactions can be favored by the addition of a catalyst during steam injection; in this way, it is possible to generate the original oil in situ upgrading through the production increase of molecules of lower molecular weight. This additional effect could increase the oil recovery factor and reduce costs in transport and refining stages. Therefore, this research has focused on the experimental evaluation of the catalytic aquathermolysis on a Colombian heavy oil with 12,8°API. The effects of three different catalysts, reaction time, and temperature were evaluated in a batch microreactor. The changes in the Colombian heavy oil were quantified through nuclear magnetic resonance 1H-NMR. The relaxation times interpretation and the absorption intensity allowed to identify the distribution of the functional groups in the base oil and upgraded oils. Additionally, the average number of aliphatic carbons in alkyl chains, the number of substituted rings, and the aromaticity factor were established as average structural parameters in order to simplify the samples' compositional analysis. The first experimental stage proved that each catalyst develops a different reaction mechanism. The aromaticity factor has an increasing order of the salts used: Mo > Fe > Ni. However, the upgraded oil obtained with iron naphthenate tends to form a higher content of mono-aromatic and lower content of poly-aromatic compounds. On the other hand, the results obtained from the second phase of experiments suggest that the upgraded oils have a smaller difference in the length of alkyl chains in the range of 240º to 270°C. This parameter has lower values at 300°C, which indicates that the alkylation or cleavage reactions of alkyl chains govern at higher reaction temperatures. The presence of condensation reactions is supported by the behavior of the aromaticity factor and the bridge carbons production between aromatic rings (RCH₂). Finally, it is observed that there is a greater dispersion in the aliphatic hydrogens, which indicates that the alkyl chains have a greater reactivity compared to the aromatic structures.

Keywords: catalyst, upgrading, aquathermolysis, steam

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Authors: Riffat Iqbal, Sidra Ihsan, Andleeb Batool, Maryam Mukhtar

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Glaucoma is a gathering of optic neuropathies described by dynamic degeneration of retinal ganglionic cells. It is clinically and innately heterogenous illness containing a couple of particular forms each with various causes and severities. Primary open-angle glaucoma (POAG) is the most generally perceived kind of glaucoma. This study investigated the genetic association of single nucleotide polymorphisms (SNPs; rs10483727 and rs33912345) at the SIX1/SIX6 locus with primary open-angle glaucoma (POAG) in the Pakistani population. The SIX6 gene plays an important role in ocular development and has been associated with morphology of the optic nerve. A total of 100 patients clinically diagnosed with glaucoma and 100 control individuals of age over 40 were enrolled in the study. Genomic DNA was extracted by organic extraction method. The SNP genotyping was done by (i) PCR based restriction fragment length polymorphism (RFLP) and sequencing method. Significant genetic associations were observed for rs10483727 (risk allele T) and rs33912345 (risk allele C) with POAG. Hence, it was concluded that Six6 gene is genetically associated with pathogenesis of Glaucoma in Pakistan.

Keywords: genotyping, Pakistani population, primary open-angle glaucoma, SIX6 gene

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Authors: Anıl Dinçer, Dilek Duranoğlu

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Ketones, which are widely used as solvent and chemical intermediates in chemical process industry, are commercially produced by using catalytic dehydrogenation of secondary alcohols at higher temperature (300-500ºC), and pressure (1-5 bar). Although it is possible to obtain high conversion values (60-87%) via gas phase catalytic dehydrogenation, working high temperature and pressure can result in side reactions and shorten the catalyst life. In order to overcome these challenges, catalytic dehydrogenation in the presence of an appropriate liquid solvent has been started to use. Hence, secondary alcohols can be converted to respective ketones at relatively low temperature (150-200ºC) under atmospheric pressure. In this study, methyl ethyl ketone and acetone was produced via catalytic dehydrogenation of appropriate secondary alcohols (isopropyl alcohol and sec-butyl alcohol) in the presence of liquid solvent at 160-190ºC. Obtained methyl ethyl ketone and acetone were analyzed by using FTIR and GC spectrometer. Effects of temperature, amount of catalyst and solvent on conversion and reaction rate were investigated. Optimum process conditions, which gave high conversion and reaction rate, were determined. According to GC results, 70% of secondary butyl alcohol and 42% of isopropyl alcohol was converted to related ketone (methyl ethyl ketone and acetone, respectively) at optimum process conditions. After distillation, 99.13% methyl ethyl ketone and 99.20% acetone was obtained. Consequently, liquid phase dehydrogenation process, which can compete with commercial gas phase process, was developed.

Keywords: dehydrogenation, liquid phase, methyl ethyl ketone, secondary alcohol

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Authors: Xiao-Dong Wang, Wei-Mon Yan

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The flow field design in the bipolar plates affects the performance of the proton exchange membrane (PEM) fuel cell. This work adopted a combined optimization procedure, including a simplified conjugate-gradient method and a completely three-dimensional, two-phase, non-isothermal fuel cell model, to look for optimal flow field design for a single serpentine fuel cell of size 9×9 mm with five channels. For the direct solution, the two-fluid method was adopted to incorporate the heat effects using energy equations for entire cells. The model assumes that the system is steady; the inlet reactants are ideal gases; the flow is laminar; and the porous layers such as the diffusion layer, catalyst layer and PEM are isotropic. The model includes continuity, momentum and species equations for gaseous species, liquid water transport equations in the channels, gas diffusion layers, and catalyst layers, water transport equation in the membrane, electron and proton transport equations. The Bulter-Volumer equation was used to describe electrochemical reactions in the catalyst layers. The cell output power density Pcell is maximized subjected to an optimal set of channel heights, H1-H5, and channel widths, W2-W5. The basic case with all channel heights and widths set at 1 mm yields a Pcell=7260 Wm-2. The optimal design displays a tapered characteristic for channels 1, 3 and 4, and a diverging characteristic in height for channels 2 and 5, producing a Pcell=8894 Wm-2, about 22.5% increment. The reduced channel heights of channels 2-4 significantly increase the sub-rib convection and widths for effectively removing liquid water and oxygen transport in gas diffusion layer. The final diverging channel minimizes the leakage of fuel to outlet via sub-rib convection from channel 4 to channel 5. Near-optimal design without huge loss in cell performance but is easily manufactured is tested. The use of a straight, final channel of 0.1 mm height has led to 7.37% power loss, while the design with all channel widths to be 1 mm with optimal channel heights obtained above yields only 1.68% loss of current density. The presence of a final, diverging channel has greater impact on cell performance than the fine adjustment of channel width at the simulation conditions set herein studied.

Keywords: optimization, flow field design, simplified conjugate-gradient method, serpentine flow field, sub-rib convection

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Authors: Ashish Bohre, Blaž Likozar, Saikat Dutta, Dionisios G. Vlachos, Basudeb Saha

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Graphene oxide, decorated with surface oxygen functionalities, has emerged as a sustainable alternative to precious metal catalysts for many reactions. Herein, we report for the first time that graphene oxide becomes super active for C-C coupling upon incorporation of multilayer crystalline features, highly oxidized surface, Brønsted acidic functionalities and defect sites on the surface and edges via modified oxidation. The resulting improved graphene oxide (IGO) demonstrates superior activity to commonly used framework zeolites for upgrading of low carbon biomass furanics to long carbon chain aviation fuel precursors. A maximum 95% yield of C15 fuel precursor with high selectivity is obtained at low temperature (60 C) and neat conditions via hydroxyalkylation/alkylation (HAA) of 2-methylfuran (2-MF) and furfural. The coupling of 2-MF with carbonyl molecules ranging from C3 to C6 produced the precursors of carbon numbers 12 to 21. The catalyst becomes inactive in the 4th cycle due to the loss of oxygen functionalities, defect sites and multilayer features; however, regains comparable activity upon regeneration. Extensive microscopic and spectroscopic characterization of the fresh and reused IGO is presented to elucidate high activity of IGO and to establish a correlation between activity and surface and structural properties. Kinetic Monte Carlo (KMC) and density functional theory (DFT) calculations are presented to further illustrate the surface features and the reaction mechanism.

Keywords: methacrylic acid, itaconic acid, biomass, monomer, solid base catalyst

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Authors: Kuan Lun Pan, Moo Been Chang

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Volatile organic compounds (VOCs) are one of major air contaminants, and they can react with nitrogen oxides (NOx) in atmosphere to form ozone (O3) and peroxyacetyl nitrate (PAN) with solar irradiation, leading to environmental hazards. In addition, some VOCs are toxic at low concentration levels and cause adverse effects on human health. How to effectively reduce VOCs emission has become an important issue. Thermal catalysis is regarded as an effective way for VOCs removal because it provides oxidation route to successfully convert VOCs into carbon dioxide (CO2) and water (H2O(g)). Single perovskite-type catalysts are promising for VOC removal, and they are of good potential to replace noble metals due to good activity and high thermal stability. Single perovskites can be generally described as ABO3 or A2BO4, where A-site is often a rare earth element or an alkaline. Typically, the B-site is transition metal cation (Fe, Cu, Ni, Co, or Mn). Catalytic properties of perovskites mainly rely on nature, oxidation states and arrangement of B-site cation. Interestingly, single perovskites could be further synthesized to form double perovskite-type catalysts which can simply be represented by A2B’B”O6. Likewise, A-site stands for an alkaline metal or rare earth element, and the B′ and B′′ are transition metals. Double perovskites possess unique surface properties. In structure, three-dimensional of B-site with ordered arrangement of B’O6 and B”O6 is presented alternately, and they corner-share octahedral along three directions of the crystal lattice, while cations of A-site position between the void of octahedral. It has attracted considerable attention due to specific arrangement of alternating B-site structure. Therefore, double perovskites may have more variations than single perovskites, and this greater variation may promote catalytic performance. It is expected that activity of double perovskites is higher than that of single perovskites toward VOC removal. In this study, double perovskite-type catalyst (La2CoMnO6) is prepared and evaluated for VOC removal. Also, single perovskites including LaCoO3 and LaMnO3 are tested for the comparison purpose. Toluene (C7H8) is one of the important VOCs which are commonly applied in chemical processes. In addition to its wide application, C7H8 has high toxicity at a low concentration. Therefore, C7H8 is selected as the target compound in this study. Experimental results indicate that double perovskite (La2CoMnO6) has better activity if compared with single perovskites. Especially, C7H8 can be completely oxidized to CO2 at 300oC as La2CoMnO6 is applied. Characterization of catalysts indicates that double perovskite has unique surface properties and is of higher amounts of lattice oxygen, leading to higher activity. For durability test, La2CoMnO6 maintains high C7H8 removal efficiency of 100% at 300oC and 30,000 h-1, and it also shows good resistance to CO2 (5%) and H2O(g) (5%) of gas streams tested. For various VOCs including isopropyl alcohol (C3H8O), ethanal (C2H4O), and ethylene (C2H4) tested, as high as 100% efficiency could be achieved with double perovskite-type catalyst operated at 300℃, indicating that double perovskites are promising catalysts for VOCs removal, and possible mechanisms will be elucidated in this paper.

Keywords: volatile organic compounds, Toluene (C7H8), double perovskite-type catalyst, catalysis

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Authors: Hyeonseok Yoo, Kiseok Oh, Jinsub Choi

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Titanium oxide nanotubes have attracted great attention because of its photocatalytic activity and large surface area. For enhancing electrochemical properties, catalysts should be doped into the structure because titanium oxide nanotubes themselves have low electroconductivity and catalytic activity. It has been reported that Ru and Ir doped titanium oxide electrodes exhibit high efficiency and low overpotential in the oxygen evolution reaction (OER) for water splitting. In general, titanium oxide nanotubes with high aspect ratio cannot be easily doped by conventional complex methods. Herein, two types of facile routes, namely single step anodization and potential shock, for Ru doping into high aspect ratio titanium oxide nanotubes are introduced in detail. When single step anodization was carried out, stability of electrodes were increased. However, onset potential was shifted to anodic direction. On the other hand, when high potential shock voltage was applied, a large amount of ruthenium/ruthenium oxides were doped into titanium oxide nanotubes and thick barrier oxide layers were formed simultaneously. Regardless of doping routes, ruthenium/ ruthenium oxides were homogeneously doped into titanium oxide nanotubes. In spite of doping routes, doping in aqueous solution generally led to incorporate high amount of Ru in titanium oxide nanotubes, compared to that in non-aqueous solution. The amounts of doped catalyst were analyzed by X-ray photoelectron spectroscopy (XPS). The optimum condition for water splitting was investigated in terms of the amount of doped Ru and thickness of barrier oxide layer.

Keywords: doping, potential shock, single step anodization, titanium oxide nanotubes

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Authors: Kefale W. Yizengaw, Delele Worku Ayele, Jyh-Chiang Jiang

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The catalytic co-conversion of CO₂ and CH₄ to value-added compounds has become one of the promising approaches to addressing global climate change by having valuable fossil fuels. Thedirect co-conversion of CO₂ and CH₄ to value-added compounds is attractive but tremendously challenging because of both molecules' thermodynamic stability and kinetic inertness. In the present study, a single iridium atom doped and a single oxygen atom defect hematite (110)surface model catalyst, which can comprehend direct C–O coupling based on simultaneous activation of CO2 and CH4 was studied using density functional theory plus U (DFT + U)calculations. The presence of dual active sites on the Ir/Fe₂O₃(110)-OV surface catalyst enablesCO₂ activation on the Ir site and CH₄ activation at the defect site. The electron analysis for the theco-adsorption of CO₂ and CH₄ deals with the electron redistribution on the surface and clearly shows the synergistic effect for simultaneous CO₂ and CH₄ activation on Ir/α- Fe₂O₃(110)-OVsurface. The microkinetic analysis shows that the dissociation of CH4 to CH3 * and H* plays an excellent role in the C–O coupling. The coverage analysis for the intermediate products of the microkinetic simulation results indicates that C–O coupling is the reaction limiting step. Finally, after the CH₃O* intermediate product species is produced, the radical hydrogen species spontaneously diffuse to the CH3O* intermediate product to form methanol at around 490 [K]. The present work provides mechanistic and kinetic insights into the direct C–O coupling of CO₂and CH₄, which could help design more-efficient catalysts.

Keywords: co-conversion, C–O coupling, doping, oxygen vacancy, microkinetic

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Authors: Ipek Gunay, Efe B. Orman, Metin Ozer, Bekir Salih, Ali R. Ozkaya

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Phthalocyanines with macrocyclic ring containing at least three heteroatoms have nine or more membered structures. Metal-free phthalocyanines react with metal salts to obtain chelate complexes. This is one of the most important features of metal-free phthalocyanine as ligand structure. Although phthalocyanines have very similar properties with porphyrins, they have some advantages such as lower cost, easy to prepare, and chemical and thermal stability. It’s known that Pc compounds have shown one-electron metal-and/or ligand-based reversible or quasi-reversible reduction and oxidation processes. The redox properties of phthalocyanines are critically related to the desirable properties of these compounds in their technological applications. Thus, Pc complexes have also been receiving increasing interest in the area of fuel cells due to their high electrocatalytic activity in dioxygen reduction and fuel cell applications. In this study, novel phthalocyanine complexes coordinated with Fe(II) and Co (II) to be used as catalyst were synthesized. Aiming this goal, a new nitrile ligand was synthesized starting from 4-hydroxy-3,5-dimethoxy benzyl alcohol and 4-nitrophthalonitrile in the presence of K2CO3 as catalyst. After the isolation of the new type of nitrile and metal complexes, the characterization of mentioned compounds was achieved by IR, H-NMR and UV-vis methods. In addition, the electrochemical behaviour of Pc complexes was identified by cyclic voltammetry, square wave voltammetry and in situ spectroelectrochemical measurements. Furthermore, the catalytic performances of Pc complexes for oxygen reduction were tested by dynamic voltammetry measurements, carried out by the combined system of rotating ring-disk electrode and potentiostat, in a medium similar to fuel-cell working conditions.

Keywords: phthalocyanine, electrocatalysis, electrochemistry, in-situ spectroelectrochemistry

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Authors: Riad Benelmir, Muhammad Shoaib Ahmed Khan

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The socio-economic importance of the olive oil production is significant in the Mediterranean region, both in terms of wealth and tradition. However, the extraction of olive oil generates huge quantities of wastes that may have a great impact on land and water environment because of their high phytotoxicity. Especially olive mill wastewater (OMWW) is one of the major environmental pollutants in olive oil industry. This work projects to design a smart and sustainable integrated thermochemical catalytic processes of residues from olive mills by hydrothermal carbonization (HTC) of olive mill wastewater (OMWW) and fast pyrolysis of olive mill wastewater sludge (OMWS). The byproducts resulting from OMWW-HTC treatment are a solid phase enriched in carbon, called biochar and a liquid phase (residual water with less dissolved organic and phenolic compounds). HTC biochar can be tested as a fuel in combustion systems and will also be utilized in high-value applications, such as soil bio-fertilizer and as catalyst or/and catalyst support. The HTC residual water is characterized, treated and used in soil irrigation since the organic and the toxic compounds will be reduced under the permitted limits. This project’s concept includes also the conversion of OMWS to a green diesel through a catalytic pyrolysis process. The green diesel is then used as biofuel in an internal combustion engine (IC-Engine) for automotive application to be used for clean transportation. In this work, a theoretical study is considered for the use of heat from the pyrolysis non-condensable gases in a sorption-refrigeration machine for pyrolysis gases cooling and condensation of bio-oil vapors.

Keywords: biomass, olive oil extraction, adsorption cooling, pyrolisis

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Authors: Michael Huber, Maximilian J. Poller, Jens Tochtermann, Wolfgang Korth, Andreas Jess, Jakob Albert

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Aside from the desulfurisation, the denitrogenation of fuels is of great importance to minimize the environmental impact of transport emissions. The oxidative reaction pathway of organic nitrogen in the catalytic oxidative denitrogenation could be successfully elucidated. This is the first time such a pathway could be traced in detail in non-microbial systems. It was found that the organic nitrogen is first oxidized to nitrate, which is subsequently reduced to molecular nitrogen via nitrous oxide. Hereby, the organic substrate serves as a reducing agent. The discovery of this pathway is an important milestone for the further development of fuel denitrogenation technologies. The United Nations aims to counteract global warming with Net Zero Emissions (NZE) commitments; however, it is not yet foreseeable when crude oil-based fuels will become obsolete. In 2021, more than 50 million barrels per day (mb/d) were consumed for the transport sector alone. Above all, heteroatoms such as sulfur or nitrogen produce SO₂ and NOx during combustion in the engines, which is not only harmful to the climate but also to health. Therefore, in refineries, these heteroatoms are removed by hy-drotreating to produce clean fuels. However, this catalytic reaction is inhibited by the basic, nitrogenous reactants (e.g., quinoline) as well as by NH3. The ion pair of the nitrogen atom forms strong pi-bonds to the active sites of the hydrotreating catalyst, which dimin-ishes its activity. To maximize the desulfurization and denitrogenation effectiveness in comparison to just extraction and adsorption, selective oxidation is typically combined with either extraction or selective adsorption. The selective oxidation produces more polar compounds that can be removed from the non-polar oil in a separate step. The extraction step can also be carried out in parallel to the oxidation reaction, as a result of in situ separation of the oxidation products (ECODS; extractive catalytic oxidative desulfurization). In this process, H8PV5Mo7O40 (HPA-5) is employed as a homogeneous polyoxometalate (POM) catalyst in an aqueous phase, whereas the sulfur containing fuel components are oxidized after diffusion from the organic fuel phase into the aqueous catalyst phase, to form highly polar products such as H₂SO₄ and carboxylic acids, which are thereby extracted from the organic fuel phase and accumulate in the aqueous phase. In contrast to the inhibiting properties of the basic nitrogen compounds in hydrotreating, the oxidative desulfurization improves with simultaneous denitrification in this system (ECODN; extractive catalytic oxidative denitrogenation). The reaction pathway of ECODS has already been well studied. In contrast, the oxidation of nitrogen compounds in ECODN is not yet well understood and requires more detailed investigations.

Keywords: oxidative reaction pathway, denitrogenation of fuels, molecular catalysis, polyoxometalate

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Authors: Chinwendu R. Nnabalu, Gioia Falcone, Imma Bortone

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Petroleum refining is a chemical process in which the raw material (crude oil) is converted to finished commercial products for end users. The fluid catalytic cracking (FCC) unit is a key asset in refineries, requiring optimised processes in the context of engineering design. Following the first stage of separation of crude oil in a distillation tower, an additional 40 per cent quantity is attainable in the gasoline pool with further conversion of the downgraded product of crude oil (residue from the distillation tower) using a catalyst in the FCC process. Effective removal of sulphur oxides, nitrogen oxides, carbon and heavy metals from FCC gasoline requires greater separation efficiency and involves an enormous environmental significance. The FCC unit is primarily a reactor and regeneration system which employs cyclone systems for separation.  Catalyst losses in FCC cyclones lead to high particulate matter emission on the regenerator side and fines carryover into the product on the reactor side. This paper aims at demonstrating the importance of FCC unit design criteria in terms of technical performance and compliance with environmental legislation. A systematic review of state-of-the-art FCC technology was carried out, identifying its key technical challenges and sources of emissions.  Case studies of petroleum refineries in Nigeria were assessed against selected global case studies. The review highlights the need for further modelling investigations to help improve FCC design to more effectively meet product specification requirements while complying with stricter environmental legislation.

Keywords: design, emission, fluid catalytic cracking, petroleum refineries

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Authors: Bhairi Lakshminarayana, Surajit Sarker, Ch. Subrahmanyam

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The present study reports the development of noble metal free nano catalysts for low-temperature CO oxidation and water gas shift reaction. Mn-substituted CeO2 solid solution catalysts were synthesized by co-precipitation, combustion and hydrothermal methods. The formation of solid solution was confirmed by XRD with Rietveld refinement and the percentage of carbon and nitrogen doping was ensured by CHNS analyzer. Raman spectroscopic confirmed the oxygen vacancies. The surface area, pore volume and pore size distribution confirmed by N2 physisorption analysis, whereas, UV-visible diffuse reflectance spectroscopy and XPS data confirmed the oxidation state of the Mn ion. The particle size and morphology (spherical shape) of the material was confirmed using FESEM and HRTEM analysis. Ce0.8Mn0.2O2-δ was calcined at 400 °C, 600 °C and 800 °C. Raman spectroscopy confirmed that the catalyst calcined at 400 °C has the best redox properties. The activity of the designed catalysts for CO oxidation (0.2 vol%), carried out with GHSV of 21,000 h-1 and it has been observed that co-precipitation favored the best active catalyst towards CO oxidation and water gas shift reaction, due to the high surface area, improved reducibility, oxygen mobility and highest quantity of surface oxygen species. The activation energy of low temperature CO oxidation on Ce0.8Mn0.2O2- δ (combustion) was 5.5 kcal.K-1.mole-1. The designed catalysts were tested for water gas shift reaction. The present study demonstrates that Mn ion substituted ceria at 400 °C calcination temperature prepared by co-precipitation method promise to revive a green sustainable energy production approach.

Keywords: Ce0.8Mn0.2O2-ð, CO oxidation, physicochemical characterization, water gas shift reaction (WGS)

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Authors: C. Rajalakshmi, Vibin Ipe Thomas

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Sonogashira coupling reactions are widely employed in the synthesis of molecules of biological and pharmaceutical importance. Copper catalyzed Sonogashira coupling reactions are gaining importance owing to the low cost and less toxicity of copper as compared to the palladium catalyst. In the present work, a detailed computational study has been carried out on the Sonogashira coupling reaction between aryl halides and terminal alkynes catalyzed by Copper (I) species with trans-1, 2 Diaminocyclohexane as ligand. All calculations are performed at Density Functional Theory (DFT) level, using the hybrid Becke3LYP functional. Cu and I atoms are described using an effective core potential (LANL2DZ) for the inner electrons and its associated double-ζ basis set for the outer electrons. For all other atoms, 6-311G+* basis set is used. We have identified that the active catalyst species is a neutral 3-coordinate trans-1,2 diaminocyclohexane ligated Cu (I) alkyne complex and found that the oxidative addition and reductive elimination occurs in a single step proceeding through one transition state. This is owing to the ease of reductive elimination involving coupling of Csp2-Csp carbon atoms and the less stable Cu (III) intermediate. This shows the mechanism of copper catalyzed Sonogashira coupling reactions are quite different from those catalyzed by palladium. To gain further insights into the mechanism, substrates containing various functional groups are considered in our study to traverse their effect on the feasibility of the reaction. We have also explored the effect of ligand on the catalytic cycle of the coupling reaction. The theoretical results obtained are in good agreement with the experimental observation. This shows the relevance of a combined theoretical and experimental approach for rationally improving the cross-coupling reaction mechanisms.

Keywords: copper catalysed, density functional theory, reaction mechanism, Sonogashira coupling

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Authors: D. Amaranatha Reddy

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Highly efficient and stable co-catalysts materials is of great important for boosting photo charge carrier’s separation, transportation efficiency, and accelerating the catalytic reactive sites of semiconductor photocatalysts. As a result, it is of decisive importance to fabricate low price noble metal free co-catalysts with high catalytic reactivity, but it remains very challenging. Considering this challenge here, dual metal organic frame work derived N-Doped Fe3C nanocages have been rationally designed and decorated with ultrathin ZnIn2S4 nanosheets for efficient photocatalytic hydrogen generation. The fabrication strategy precisely integrates co-catalyst nanocages with ultrathin two-dimensional (2D) semiconductor nanosheets by providing tightly interconnected nano-junctions and helps to suppress the charge carrier’s recombination rate. Furthermore, constructed highly porous hybrid structures expose ample active sites for catalytic reduction reactions and harvest visible light more effectively by light scattering. As a result, fabricated nanostructures exhibit superior solar driven hydrogen evolution rate (9600 µmol/g/h) with an apparent quantum efficiency of 3.6 %, which is relatively higher than the Pt noble metal co-catalyst systems and earlier reported ZnIn2S4 based nanohybrids. We believe that the present work promotes the application of sulfide based nanostructures in solar driven hydrogen production.

Keywords: photocatalysis, water splitting, hydrogen fuel production, solar-driven hydrogen

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Authors: Jasneet Kaur, Swapandeep Singh Chimni

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The unfavorable use of metal-based catalysts that are often extortionate and toxic can be overcome by using small organic molecules known as organocatalysts. A variety of small organic molecules, including Brønsted/Lewis bases and acids, based on sulfonic acids, phosphoric acids, amines, phosphines or carbenes, Cinchona alkaloids, have been used as organocatalysts. One of the key reasons for using organocatalysis is their ability to be effectively removed from the final product in comparison to the metallic counterparts, which are exceedingly difficult to remove. The present investigation seeks to explore the catalytic nature of Cinchona alkaloids as an organocatalyst for enantioselective synthesis of 3-substituted-3-aminooxindole, which is known to exhibit a variety of biological activities and pharmacological activities. In this context, an organocatalytic asymmetric route for the synthesis of 3-aminooxindoles via reaction of isatin imine with α-acetoxy-β-ketoesters has been developed. The bifunctional Cinchona derived thiourea catalyzed the reaction of α-acetoxy-β-ketoesters derivatives with isatin imine to afford 3-substituted-aminooxindole derivatives in up to 93% yield, 95% enantiomeric excess and >20:1 diastereomeric ratio. The reaction was performed at room temperature for two hours using 10 mol% of catalyst, in the presence of 4Å molecular sieves in tetrahydrofuran as a solvent at ambient temperature. After the completion of the reaction, the pure product could be easily separated by using column chromatography using hexane and ethyl acetate as solvents. In conclusion, the catalytic potential of Cinchona derived chiral thiourea-tertiary amine catalyst was explored for an organocatalytic enantioselective Mannich reaction of β-ketoester derivatives with various isatin imine derivatives under mild conditions.

Keywords: asymmetric synthesis, aminooxindoles, enantioselective, isatin imine

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Authors: Sushma Yadav, Anil K. Saroha

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Complex industrial effluent generated from chemical industry is contaminated with toxic and hazardous organic compounds and not amenable to direct biological treatment. To effectively remove many toxic organic pollutants has made it evident that new, compact and more efficient systems are needed. Catalytic Wet Air Oxidation (CWAO) is a promising treatment technology for the abatement of organic pollutants in wastewater. A lot of information is available on using CWAO for the treatment of synthetic solution containing single organic pollutant. But the real industrial effluents containing multi-component mixture of organic compounds were less studied. The main objective of this study is to use the CWAO process for converting the organics into compounds more amenable to biological treatment; complete oxidation may be too expensive. Therefore efforts were made in the present study to explore the potential of alumina based Platinum (Pt) catalyst for the treatment of industrial organic raffinate containing toxic constituents like ammoniacal nitrogen, pyridine etc. The catalysts were prepared by incipient wetness impregnation method and characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and BET (Brunauer, Emmett, and Teller) surface area. CWAO experiments were performed at atmospheric pressure and (30 °C - 70 °C) temperature conditions and the results were evaluated in terms of COD removal efficiency. The biodegradability test was performed by BOD/COD ratio for checking the toxicity of the industrial wastewater as well as for the treated water. The BOD/COD ratio of treated water was significantly increased and signified that the toxicity of the organics was decreased while the biodegradability was increased, indicating the more amenability towards biological treatment.

Keywords: alumina based pt catalyst, BOD/COD ratio, catalytic wet air oxidation, COD removal efficiency, industrial organic raffinate

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Authors: Xiaoling Ren, Guidong Yang

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As one of the largest industrial synthetic chemicals in the world, ammonia has the advantages of high energy density, easy liquefaction, and easy transportation, which is widely used in agriculture, chemical industry, energy storage, and other fields. The industrial Haber-Bosch method process for ammonia synthesis is generally conducted under severe conditions. It is essential to develop a green, sustainable strategy for ammonia production to meet the growing demand. In this direction, photocatalytic nitrogen reduction has huge advantages over the traditional, well-established Haber-Bosch process, such as the utilization of natural sun light as the energy source and significantly lower pressure and temperature to affect the reaction process. However, the high activation energy of nitrogen and the low efficiency of photo-generated electron-hole separation in the photocatalyst result in low ammonia production yield. Many researchers focus on improving the catalyst. In addition to modifying the catalyst, improving the dispersion of the catalyst and making full use of active sites are also means to improve the overall catalytic activity. Few studies have been carried out on this, which is the aim of this work. In this work, by making full use of the nitrogen activation ability of WO3-x with defective sites, small size WO3-x photocatalyst with high dispersibility was constructed, while the growth of WO3-x was restricted by using a high specific surface area mesoporous SBA-15 molecular sieve with the regular pore structure as a template. The morphology of pure SBA-15 and WO3-x/SBA-15 was characterized byscanning electron microscopy (SEM). Compared with pure SBA-15, some small particles can be found in the WO3-x/SBA-15 material, which means that WO3-x grows into small particles under the limitation of SBA-15, which is conducive to the exposure of catalytically active sites. To elucidate the chemical nature of the material, the X-ray diffraction (XRD) analysis was conducted. The observed diffraction pattern inWO3-xis in good agreement with that of the JCPDS file no.71-2450. Compared with WO3-x, no new peaks appeared in WO3-x/SBA-15.It can be concluded that WO3-x/SBA-15 was synthesized successfully. In order to provide more active sites, the mass content of WO3-x was optimized. Then the photocatalytic nitrogen reduction performances of above samples were performed with methanol as a hole scavenger. The results show that the overall ammonia production performance of WO3-x/SBA-15 is improved than pure bulk WO3-x. The above results prove that making full use of active sites is also a means to improve overall catalytic activity.This work provides material basis for the design of high-efficiency photocatalytic nitrogen reduction catalysts.

Keywords: ammonia, photocatalytic, nitrogen reduction, WO3-x, high dispersibility

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Authors: Greg Turner, Bin Lu, Cheer-Sun Yang

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As computing technology advances, smartphone applications can assist in student learning in a pervasive way. For example, the idea of using a mobile apps for the PA Common Trees, Pests, Pathogens, in the field as a reference tool allows middle school students to learn about trees and associated pests/pathogens without bringing a textbook. In the past, some researches study the mobile software Mobile Application Software Development Life Cycle (MADLC) including traditional models such as the waterfall model, or more recent Agile Methods. Others study the issues related to the software development process. Very little research is on the development of three heterogenous mobile systems simultaneously in a small university where the availability of developers is an issue. In this paper, we propose to use a hybride model of Waterfall Model and the Agile Model, known as the Relay Race Methodology (RRM) in practice, to reflect the concept of racing and relaying for scheduling. Based on the development project, we observe that the modeling of the transition between any two phases is manifested naturally. Thus, we claim that the RRM model can provide a de fecto rather than a de jure basis for the core concept in the MADLC. In this paper, the background of the project is introduced first. Then, the challenges are pointed out followed by our solutions. Finally, the experiences learned and the future work are presented.

Keywords: agile methods, mobile apps, software process model, waterfall model

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Authors: Adamantini Loukodimou, David Weston, Shiladitya Paul

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Offshore structures are subjected to harsh environments. It is documented that carbon steel needs protection from corrosion. The combined effect of UV radiation, seawater splash, and fluctuating temperatures diminish the integrity of these structures. In addition, the possibility of damage caused by floating ice, seaborne debris, and maintenance boats make them even more vulnerable. Their inspection and maintenance when far out in the sea are difficult, risky, and expensive. The most known method of mitigating corrosion of offshore structures is the use of cathodic protection. There are several zones in an offshore wind turbine. In the atmospheric zone, due to the lack of a continuous electrolyte (seawater) layer between the structure and the anode at all times, this method proves inefficient. Thus, the use of protective coatings becomes indispensable. This research focuses on the atmospheric zone. The conversion of commercially available and conventional paint (epoxy) system to an autonomous self-healing paint system via the addition of suitable encapsulated healing agents and catalyst is investigated in this work. These coating systems, which can self-heal when damaged, can provide a cost-effective engineering solution to corrosion and related problems. When the damage of the paint coating occurs, the microcapsules are designed to rupture and release the self-healing liquid (monomer), which then will react in the presence of the catalyst and solidify (polymerization), resulting in healing. The catalyst should be compatible with the system because otherwise, the self-healing process will not occur. The carbon steel substrate will be exposed to a corrosive environment, so the use of a sacrificial layer of Zn is also investigated. More specifically, the first layer of this new coating system will be TSZA (Thermally Sprayed Zn85/Al15) and will be applied on carbon steel samples with dimensions 100 x 150 mm after being blasted with alumina (size F24) as part of the surface preparation. Based on the literature, it corrodes readily, so one additional paint layer enriched with microcapsules will be added. Also, the reaction and the curing time are of high importance in order for this bilayer system of coating to work successfully. For the first experiments, polystyrene microcapsules loaded with 3-octanoyltio-1-propyltriethoxysilane were conducted. Electrochemical experiments such as Electrochemical Impedance Spectroscopy (EIS) confirmed the corrosion inhibiting properties of the silane. The diameter of the microcapsules was about 150-200 microns. Further experiments were conducted with different reagents and methods in order to obtain diameters of about 50 microns, and their self-healing properties were tested in synthetic seawater using electrochemical techniques. The use of combined paint/electrodeposited coatings allows for further novel development of composite coating systems. The potential for the application of these coatings in offshore structures will be discussed.

Keywords: corrosion mitigation, microcapsules, offshore wind turbines, self-healing

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Authors: Vidula Shevade, B. J. Nagare, Sajeev Chacko

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First principles simulation, meaning density functional theory (DFT) calculations with plane waves and pseudopotential, has become a prized technique in condensed matter theory. Nanoparticles (NP) have been known to possess good catalytic activities, especially for molecules such as CO, O₂, etc. Among the metal NPs, Aluminium based NPs are also widely known for their catalytic properties. Aluminium metal is a lightweight, excellent electrical, and thermal abundant chemical element in the earth’s crust. Aluminium NPs, when added to solid rocket fuel, help improve the combustion speed and considerably increase combustion heat and combustion stability. Adding aluminium NPs into normal Al/Al₂O₃ powder improves the sintering processes of the ceramics, with high heat transfer performance, increased density, and enhanced thermal conductivity of the sinter. We used VASP and Gaussian 0₃ package to compute the geometries, electronic structure, and bonding properties of Al₁₂Ni as well as its interaction with O₂ and CO molecules. Several MD simulations were carried out using VASP at various temperatures from which hundreds of structures were optimized, leading to 24 unique structures. These structures were then further optimized through a Gaussian package. The lowest energy structure of Al₁₂Ni has been reported to be a singlet. However, through our extensive search, we found a triplet state to be lower in energy. In our structure, the Ni atom is found to be on the surface, which gives the non-zero magnetic moment. Incidentally, O2 and CO molecules are also triplet in nature, due to which the Al₁₂-Ni cluster is likely to facilitate the oxidation process of the CO molecule. Our results show that the most favourable site for the CO molecule is the Ni atom and that for the O₂ molecule is the Al atom that is nearest to the Ni atom. Al₁₂Ni-O₂ and Al₁₂-Ni-CO structures we extracted using VMD. Al₁₂Ni nanocluster, due to in triplet electronic structure configuration, indicates it to be a potential candidate as a catalyst for oxidation of CO molecules.

Keywords: catalyst, gaussian, nanoparticles, oxidation

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Authors: Bolysbek Utelbayev, Tasmagambetova Aigerim, Toktasyn Raila, Markayev Yergali, Myrzakhanov Maxat

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Intensive development of secondary processes of destructive processing of crude oil has led to the occurrence of oil refining factories resources of C2-C4 hydrocarbons. Except for oil gases also contain basically C2-C4 hydrocarbon gases where some of the amounts are burned. All these data has induced interest to the study of producing alkylate from hydrocarbons С2-С4 which being as components of motor fuels. The purpose of this work was studying transformation propane-propene, butane-butene fractions at the presence of the ruthenium-chromic support catalyst whereas the carrier is served pillar - structural montmorillonite containing in native bentonite clay. In this work is considered condition and structure of the bentonite clay from the South-Kazakhstan area of the Republic Kazakhstan. For preparation rhodium support catalyst (0,5-1,0 mass. % Rh) was used chloride of rhodium-RhCl3∙3H2O, as a carrier was used modified bentonite clay. For modifying natural clay to pillar structural form were used polyhydroxy complexes of chromium. To aqueous solution of chloride chromium gradually flowed the solution of sodium hydroxide at gradual hashing up to pH~3-4. The concentration of chloride chromium was paid off proceeding from calculation 5-30 mmole Cr3+ per gram clay. Suspension bentonite (~1,0 mass. %) received by intensive washing it in water during 4 h, pH-water extract of clay makes -8-9. The acidity of environment supervised by means of digital pH meter OP-208/1. In order to prevent coagulation of a solution polyhydroxy complexes of chromium, it was slowly added to a suspension of clay. "Reserve of basicity" Cr3+:/OH-allowing to prevent coagulation chloride of rhodium made 1/3. After endurance processed suspensions of clay during 24 h, a deposit was washed by water and condensed. The sample, after separate from a liquid phase, dried at first at the room temperature, and then at 110°C (2h) with the subsequent rise the temperature up to 180°C (4h). After cooling the firm mass was pounded to a powder, it was shifted infractions with the certain sizes of particles. Fractions of particles modifying clay in the further were impregnated with an aqueous solution with rhodium-RhCl3∙3H2O (0,5-1,0 mаss % Rh ). Obtained pillar structural bentonite approaches heat resistance and its porous structure above the 773K. Pillar structural bentonite was used for preparation 1.0% Ru/Carrier (modifying bentonite) support catalysts where is realised alkylation of C2-C4 hydrocarbons. The process of alkylation is carried out at a partial pressure of hydrogen 0.5-1.0MPa. Outcome 2.2.4 three methyl pentane and 2.2.3 trimethylpentane achieved 40%. At alkylation butane-butene mixture outcome of the isooctane is achieved 60%. In this condition of studying the ethene is not undergoing to alkylation.

Keywords: alkylation, butene, pillar structure, ruthenium catalyst

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Authors: Hanan Azzam1, Nashwa Abousamra1, Amany Mansour1, Yaser Abd El-dayem2, , Solafa Elsharawy1

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Background: Inherited thrombophilias are a heterogenous group of conditions which have been implicated in a variety of pregnancy complications. More recently, deficiency of protein Z (PZ) has been liked to pregnancy complications, including preterm delivery. Aim: We designed this study to evaluate the association of inherited thrombophilias including [Protein C (PC), Protein S (PS), Anti thrombin III (ATIII) deficiency and activated protein C (APC) resistance] and protein Z deficiency with a variety of pregnancy complications. Patients and Methods: 60 women with different pregnancy complications, including 20 patients with preeclampsia, 20 patients with intrauterine growth resistance (IUGR), and 20 patients with intrauterine fetal death (IUFD), in addition to 30 healthy pregnant women were recruited for the present study. PC and free PS antigen, ATIII activity, modified functional APC-resistance, and PZ levels were determined. Results: There was no significant association between inherited thrombophilias and complicated pregnancies as regards PC deficiency (p=1.0), AT III and PS deficiency (p=0.312), and APC-resistance (P=0.083). PZ was significantly associated with complicated pregnancies (p=0.012). Patients with protein Z levels below 1.5 µg/ml were considered deficient. Accordingly, we demonstrated protein Z deficiency in 30% of complicated pregnancies (RR 6.0, 95% CI 1.29-27.90;p=0.022), 20% of preeclampsia (RR 3.5, 95% CI 0.57 – 21.28; P = 0.174), 40% of IUGR (RR 9.3 95% CI 1.72-50.61; P = 0.010) and 30% of IUFD (RR 6, 95% CI 1.07 – 33.64; P = 0.042). Conclusions: These findings indicate the absence of association of inherited thrombophilias, including PC, PS, AT III deficiency, and APC resistance with pregnancy complications. However, PZ deficiency is associated with increased risk of pregnancy complications, especially intrauterine growth restriction and intrauterine fetal death.

Keywords: protein C, protein S, thrombophelia, pregnancy, protein Z

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Authors: Zubi Sadiq, Ghazala Yaqub, Almas Hamid

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We wish to report herein a very stimulating variation in Fischer indole reaction by adopting solvent and catalyst free conditions. A concise synthesis of dinitro tetrahydrocarbazole derivative 3 was introduced without the use of any accelerating agent at ambient temperature with fairly good yield. Product was fully corroborated by UV, FTIR, 1H NMR, 13C NMR, MS, and CHN analysis.

Keywords: fischer indole reaction, neutral medium, solvent free synthesis, tetrahydrocarbazole

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Authors: Ruchi Jain, Chinnakonda S. Gopinath

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The CO oxidation is a primary reaction in heterogeneous catalysis due to its potential to overcome the air pollution caused by various reasons. Indeed, in the study of sustainable catalysis, the role played by water is very important. The present work is focused on studying the effect of moisture on the sustainability of Co3O4 NR catalyst for CO oxidation reaction at ambient temperature. The catalytic activity, electronic structure and the mechanistic aspects of spinel Co3O4 nanorod surfaces have been explored in dry and wet atmosphere by near-ambient pressure photoelectron spectroscopic techniques (NAP-PES) with conventional x-ray (Al kα) and ultraviolet sources (He-I).Comparative NAPPES studies have been employed to understand the elucidation of the catalytic reaction pathway and the evolution of various surface species. The presence of water with CO+O2 plummet the catalytic activity due to the change in electronic nature from predominantly oxidic (without water in the feed) to few intermediates covered Co3O4 surface. However, ≥ 375 K Co3O4 surface recovers and regain oxidation activity, at least partially, even in the presence of water. Above mentioned observations are fully supported by the changes observed in the work function of Co3O4 in the presence of wet (H2O+CO+O2) compared to dry (CO+O2) conditions. Various type of surface species, such as CO(ads), carbonate, formate, are found to be on the catalyst surface depending on the reaction conditions. Under dry condition, CO couples with labile O atoms to form CO2, however under wet conditions it also interacts with surface OH groups results in the formation carbonate and formate intermediate. The carbonate acts at reaction inhibitor at room temperature, however proves as active intermediate at temperature 375 K or above. On the other hand, formate has proved to be reaction spectator due to its high stability. The intrinsic role of these species to suppress the oxidation has been demonstrated through a possible reaction mechanism under different reaction conditions.

Keywords: heterogeneous catalysis, surface chemistry, photoelectron spectroscopy, ambient oxidation

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Authors: Ramzi Farra, Detre Teschner, Marc Willinger, Robert Schlögl

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Introduction: The conventional approach of characterizing solid catalysts under static conditions, i.e., before and after reaction, does not provide sufficient knowledge on the physicochemical processes occurring under dynamic conditions at the molecular level. Hence, the necessity of improving new in situ characterizing techniques with the potential of being used under real catalytic reaction conditions is highly desirable. In situ Prompt Gamma Activation Analysis (PGAA) is a rapidly developing chemical analytical technique that enables us experimentally to assess the coverage of surface species under catalytic turnover and correlate these with the reactivity. The catalytic HCl oxidation (Deacon reaction) over bulk ceria will serve as our example. Furthermore, the in situ Transmission Electron Microscopy is a powerful technique that can contribute to the study of atmosphere and temperature induced morphological or compositional changes of a catalyst at atomic resolution. The application of such techniques (PGAA and TEM) will pave the way to a greater and deeper understanding of the dynamic nature of active catalysts. Experimental/Methodology: In situ Prompt Gamma Activation Analysis (PGAA) experiments were carried out to determine the Cl uptake and the degree of surface chlorination under reaction conditions by varying p(O2), p(HCl), p(Cl2), and the reaction temperature. The abundance and dynamic evolution of OH groups on working catalyst under various steady-state conditions were studied by means of in situ FTIR with a specially designed homemade transmission cell. For real in situ TEM we use a commercial in situ holder with a home built gas feeding system and gas analytics. Conclusions: Two complimentary in situ techniques, namely in situ PGAA and in situ FTIR were utilities to investigate the surface coverage of the two most abundant species (Cl and OH). The OH density and Cl uptake were followed under multiple steady-state conditions as a function of p(O2), p(HCl), p(Cl2), and temperature. These experiments have shown that, the OH density positively correlates with the reactivity whereas Cl negatively. The p(HCl) experiments give rise to increased activity accompanied by Cl-coverage increase (opposite trend to p(O2) and T). Cl2 strongly inhibits the reaction, but no measurable increase of the Cl uptake was found. After considering all previous observations we conclude that only a minority of the available adsorption sites contribute to the reactivity. In addition, the mechanism of the catalysed reaction was proposed. The chlorine-oxygen competition for the available active sites renders re-oxidation as the rate-determining step of the catalysed reaction. Further investigations using in situ TEM are planned and will be conducted in the near future. Such experiments allow us to monitor active catalysts at the atomic scale under the most realistic conditions of temperature and pressure. The talk will shed a light on the potential and limitations of in situ PGAA and in situ TEM in the study of catalyst dynamics.

Keywords: CeO2, deacon process, in situ PGAA, in situ TEM, in situ FTIR

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Authors: Ali Gharib, Leila Vojdanifard, Nader Noroozi Pesyan

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Different Pyrazoline derivatives were synthesized by cyclization of substituted chalcone derivatives in presence of hydrazine hydrate. A series of novel 1,3,5-triaryl pyrazoline derivatives has been synthesized by the reaction of chalcone and phenylhydrazine in the presence of the Fe3O4 NPs, in high yields. The structures of compounds obtained were determined by IR and 1H NMR spectra. Fe3O4 NPs was recycled and no appreciable change in activity was noticed after three cycles.

Keywords: pyrazoline, chalcone, nanoparticles, Fe3O4, catalyst, synthesis

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Authors: C. Patrascioiu, V. Matei, N. Nicolae

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The paper describes the experiments and the kinetic parameters calculus of the gasoil hydrofining. They are presented experimental results of gasoil hidrofining using Mo and promoted with Ni on aluminum support catalyst. The authors have adapted a kinetic model gasoil hydrofining. Using this proposed kinetic model and the experimental data they have calculated the parameters of the model. The numerical calculus is based on minimizing the difference between the experimental sulf concentration and kinetic model estimation.

Keywords: hydrofining, kinetic, modeling, optimization

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Authors: Biswaranjan D. Mohapatra, Ipsha Hota, Swarna P. Mantry, Nibedita Behera, Kumar S. K. Varadwaj

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Designing highly active and low-cost oxygen evolution (2H₂O → 4H⁺ + 4e⁻ + O₂) electrocatalyst is one of the most active areas of advanced energy research. Some precious metal-based electrocatalysts, such as IrO₂ and RuO₂, have shown excellent performance for oxygen evolution reaction (OER); however, they suffer from high-cost and low abundance which limits their applications. Recently, layered double hydroxides (LDHs), composed of layers of divalent and trivalent transition metal cations coordinated to hydroxide anions, have gathered attention as an alternative OER catalyst. However, LDHs are insulators and coupled with carbon materials for the electrocatalytic applications. Graphene covalently doped with nitrogen has been demonstrated to be an excellent electrocatalyst for energy conversion technologies such as; oxygen reduction reaction (ORR), oxygen evolution reaction (OER) & hydrogen evolution reaction (HER). However, they operate at high overpotentials, significantly above the thermodynamic standard potentials. Recently, we reported remarkably enhanced catalytic activity of benzoate or 1-pyrenebutyrate functionalized N-doped graphene towards the ORR in alkaline medium. The molecular and heteroatom co-doping on graphene is expected to tune the electronic structure of graphene. Therefore, an innovative catalyst architecture, in which LDHs are anchored on aromatic acid functionalized ‘N’ doped graphene may presumably boost the OER activity to a new benchmark. Herein, we report fabrication of Co₂Fe-LDH on aromatic acid (AA) functionalized ‘N’ doped reduced graphene oxide (NG) and studied their OER activities in alkaline medium. In the first step, a novel polyol method is applied for synthesis of AA functionalized NG, which is well dispersed in aqueous medium. In the second step, Co₂Fe LDH were grown on AA functionalized NG by co-precipitation method. The hybrid samples are abbreviated as Co₂Fe LDH/AA-NG, where AA is either Benzoic acid or 1, 3-Benzene dicarboxylic acid (BDA) or 1, 3, 5 Benzene tricarboxylic acid (BTA). The crystal structure and morphology of the samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). These studies confirmed the growth of layered single phase LDH. The electrocatalytic OER activity of these hybrid materials was investigated by rotating disc electrode (RDE) technique on a glassy carbon electrode. The linear sweep voltammetry (LSV) on these catalyst samples were taken at 1600rpm. We observed significant OER performance enhancement in terms of onset potential and current density on Co₂Fe LDH/BTA-NG hybrid, indicating the synergic effect. This exploration of molecular functionalization effect in doped graphene and LDH system may provide an excellent platform for innovative design of OER catalysts.

Keywords: π-π functionalization, layered double hydroxide, oxygen evolution reaction, reduced graphene oxide

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Authors: Mahshid Davoodpoor, Zahra Shamohammadi Ghahsareh, Saeid Razfar, Alaleh Dabbaghi

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Nowadays, air pollution has become a topic of great concern all over the world. One of the main sources of air pollution is automobile exhaust gas, which introduces a large number of toxic gases, including CO, unburned hydrocarbons (HCs), NOx, and non-methane hydrocarbons (NMHCs), into the air. The application of three-way catalysts (TWCs) is still the most effective strategy to mitigate the emission of these pollutants. Due to the stringent environmental regulations which continuously become stricter, studies on the TWCs are ongoing despite several years of research and development. This arises from the washcoat complexity and the several numbers of parameters involved in the redox reactions. The main objectives of these studies are the optimization of washcoat formulation and the investigation of different coating modes. Perovskite (ABO₃), as a promising class of materials, has unique features that make it versatile to use as an alternative to commonly mixed oxides in washcoats. High catalytic activity for oxidation reactions and its relatively high oxygen storage capacity are important properties of perovskites in catalytic applications. Herein, La₀.₈Ba₀.₂FeO₃ perovskite material was synthesized using the co-precipitation method and characterized by XRD, ICP, and BET analysis. The effect of synthesis conditions, including B site metal (Fe and Co), metal precursor concentration, and dopant (Ba), were examined on the phase purity of the products. The selected perovskite sample was used as one of the components in the TWC formulation to evaluate its catalytic performance through Light-off, oxygen storage capacity, and emission analysis. Results showed a remarkable increment in oxygen storage capacity and also revealed that T50 and emission of CO, HC, and NOx reduced in the presence of perovskite structure which approves the enhancement of catalytic performance for the new washcoat formulation. This study shows the brilliant future of advanced oxide structures in the TWCs.

Keywords: Perovskite, three-way catalyst, PGMs, PGMs reduction

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