Search results for: selective oxidation

Authors: Sanat Kumar, Rahul Kumar Tiwari

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At this time when society is becoming increasingly aware of the declining reserves of fossil, it has become apparent that biodiesel is destined to make a substantial contribution to the future energy demands of the domestic and industrial economies. In this regard, the significance of biodiesel is technically and commercially viable alternative to fossil-diesel. There are different potential feed stocks for biodiesel production. This paper analyses the performance, combustion and emission characteristics of biodiesel from different feed stocks. Biodiesel fuel is considered as offering many benefits like reduction of greenhouse gas emissions and many harmful pollutants (PM, HC, CO etc.). This paper critically reviews the effect of injection timing on combustion and emission characteristics. An attempt has been carried out to discuss the effect of biodiesel in terms of combustion, emission and performance based up on composition and properties. The results of the study show that different chemical composition leads to variation in its combustion, performance and emission characteristics. Biodiesel produced from different aspired feed stocks reduces the pollutant emission and resistive to oxidation but exhibit poor atomization. As a conclusion many research needs to be carried out to understand the relationship between the types of biodiesel feed stock, performance conclusion and emission.

Keywords: atomization, biodiesel, greenhouse gas, oxidation

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Authors: Amarjyoti Das Mahapatra, Umesh Kumar, Bhaskar Datta

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A pseudo peptide can mimic the biological or structural properties of natural peptides. They have become an increasing attention in medicinal chemistry because of their interesting advantages like more bioavailability and less biodegradation than compare to the physiologically active native peptides which increase their therapeutic applications. Many biologically active compounds contain urea as functional groups, and they have improved pharmacokinetic properties because of their bioavailability and metabolic stability. Recently we have reported a single-step synthesis of sulfonyl urea and sulfonyltriuret from sulfonyl chloride and sodium cyanate. But the yield of sulfonyltriuret was less around 40-60% because of the formation of other products like sulfonamide and sulfonylureas. In the present work, we mainly focused on the selective synthesis of sulfonyltriuret using tetrabutylammonium cyanate and sulfonyl chloride. More precisely, we are interested in the controlled synthesis of oligomeric urea mainly sulfonyltriuret as a new class of pseudo peptide and their application as protease modulators. The distinctive architecture of these molecules in the form of their pseudo-peptide backbone offers promise as a potential pharmacophore. The synthesized molecules have been screened on trypsin enzyme, and we observed that these molecules are the efficient modulator of trypsin enzyme.

Keywords: pseudo peptide, pharmacophore, sulfonyltriuret, trypsin

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Authors: J. Franco Macías, E. Montes Alba, A. López Vásquez

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The growing development in the poultry industry has generated a strong and adverse impact on quality and availability of water resources. Inside this industry, is finding out the treatment of by-products such as feathers, viscera and blood demanding highly water consumption, generating contaminant discharges as well. As one of current of treatment of by-products is the effluent of cooking condensate steam that has contaminant organic load; therefore, it is necessary to implement removal treatments before discharging it toward water sources. The photo catalysis appears as a promising alternative of treatment due to the different advantages it has, among others, includes low cost, easily operation, high efficiency and elimination of a wide variety of contaminants in a watery environment. This study has evaluated a heterogeneous photo catalytic treatment for removal contaminant organic load. This process was developed in oxidation and reduction conditions. It was analyzed the effect of factors such as pH, catalyst and sacrifice agent concentration. Finally, good conditions to removal contaminant organic load were achieved to determine percentage of contaminant organic load by means of response surface methodology.

Keywords: poultry industry, advanced oxidation process, photocatalysis, photodegradation, TiO2

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Authors: Samane Maroufi, Rasoul Khayyam Nekouei, Sajjad Sefimofarah, Veena Sahajwalla

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The present work details a three-stage strategy based on selective purification of rare earth oxide (REOs) isolated from end-of-life nickel-metal hydride (Ni-MH) batteries leading to high-yield fabrication of defect-rich Mn1-x-y(CeₓLaᵧ)O2-δ film. In step one, major impurities (Fe and Al) were removed from a REE-rich solution. In step two, the resulting solution with trace content of Mn was further purified through electrodeposition which resulted in the synthesis of a non-stoichiometric Mn₋₁₋ₓ₋ᵧ(CeₓLaₓᵧ)O2-δ ultra-thin film, with controllable thicknesses (5-650 nm) and transmittance (~29-100%)in which Ce4+/3+ and La3+ ions were dissolved in MnO2-x lattice. Due to percolation impacts on the optoelectronic properties of ultrathin films, a representative Mn1-x-y(CexLay)O2-δ film with 86% transmittance exhibited an outstanding areal capacitance of 3.4 mF•cm-2, mainly attributed to the intercalation/de-intercalation of anionic O2- charge carriers through the atomic tunnels of the stratified Mn1-x-y(CexLay)O2-δ crystallites. Furthermore, the Mn1-x-y(CexLay)O2-δ exhibited excellent capacitance retention of ~90% after 16,000 cycles. Such stability was shown to be associated with intervalence charge transfers occurring among interstitial Ce/La cations and Mn oxidation states within the Mn₋₁₋ₓ₋ᵧ(CexLay)O2-δ structure. The energy and power densities of the transparent flexible Mn₋₁₋ₓ₋ᵧ(CexLay)O2-δ full-cell pseudocapacitor device with a solid-state electrolyte was measured to be 0.088 µWh.cm-2 and 843 µW.cm-2, respectively. These values showed insignificant changes under vigorous twisting and bending to 45-180˚, confirming these materials are intriguing alternatives for size-sensitive energy storage devices. In step three, the remaining solution purified further, that led to the formation of REOs (La, Ce, and Nd) nanospheres with ~40-50 nm diameter.

Keywords: spent Ni-MH batteries, green energy, flexible pseudocapacitor, rare earth elements

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Authors: Vanessa Cho, Janet Hsiao, Nigel King, Robert Anthonappa

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Background: The personal protective equipment (PPE) requirements for health care workers (HCWs) have changed significantly during the COVID-19 pandemic. Aim: To ascertain, using eye-tracking technology, what children notice the most when seeing HCWs in various PPE. Design: A Tobii nano pro-eye-tracking camera tracked 156 children's visual attention while they viewed photographs of HCWs in various PPEs. Eye Movement analysis with Hidden Markov Models (EMHMM) was employed to analyse 624 recordings using two approaches, namely (i) data-driven where children's fixation determined the regions of interest (ROIs), and (ii) fixed ROIs where the investigators predefined the ROIs. Results: Two significant eye movement patterns, namely distributed(85.2%) and selective(14.7%), were identified(P<0.05). Most children fixated primarily on the face regardless of the different PPEs. Children fixated equally on all PPE images in the distributed pattern, while a strong preference for unmasked faces was evident in the selective pattern (P<0.01). Conclusion: Children as young as 2.5 years used a top-down visual search behaviour and demonstrated their face processing ability. Most children did not show a strong visual preference for a specific PPE, while a minority preferred PPE with distinct facial features, namely without masks and loupes.

Keywords: COVID-19, PPE, dentistry, pediatric

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Authors: El-Said I. El-Shafey, Syeda Naheed F. Ali, Saleh S. Al-Busafi, Haider A. J. Al-Lawati

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Date palm leaflets were utilized as a precursor for activated carbon (AC) preparation using KOH activation. AC produced was oxidized using nitric acid producing oxidized activated carbon (OAC). OAC that possesses acidic surface was surface functionalized to produce basic activated carbons using linear diamine compounds (ethylene diamine and propylene diamine). OAC was also functionalized to produce hydrophobic activated carbons using ethylamine (EA) and aniline (AN). Dehydrated carbon was also prepared from date palm leaflets using sulfuric acid dehydration/ oxidation and was surface functionalized in the same way as AC. Nitric acid oxidation was not necessary for DC as it is acidic carbon. The surface area of AC is high (823 m2/g) with microporosity domination, however, after oxidation and surface functionalization, both the surface area and surface microporosity decrease tremendously. DC surface area was low (15 m2/g) with mesoporosity domination. Surface functionalization has decreased the surface area of activated carbons. FTIR spectra show that -COOH group on DC and OAC almost disappeared after surface functionalization. The surface chemistry of all carbons produced was tested for pHzpc, basic sites, boehm titration, thermogravimetric analysis and zeta potential measurement. Scanning electron microscopy and energy dispersive spectroscopy in addition to CHN elemental analysis were also carried out. DC and OAC possess low pHzpc and high surface functionality, however, basic and hydrophobic carbons possess high pHzpc and low surface functionality. The different behavior of carbons is related to their different surface chemistry. Methylene blue adsorption was found to be faster on hydrophobic carbons based on AC and DC. The Larger adsorption capacity of methylene blue was found for hydrophobic carbons. Dominating adsorption forces of methylene blue varies from carbon to another depending on its surface nature. Sorption forces include hydrophobic forces, H-bonding, electrostatic interactions and van der Waals forces.

Keywords: carbon, acidic, basic, hydrophobic

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Authors: T. Häfele, J. Kaspar, M. Vielhaber, W. Calles, J. Griebsch

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The demand for an increasing diversification of the product spectrum associated with the current huge customization desire and subsequently the decreasing unit quantities of each production lot is gaining more and more importance within a great variety of industrial branches, e.g. automotive industry. Nevertheless, traditional product development and production processes (molding, extrusion) are already reaching their limits or fail to address these trends of a flexible and digitized production in view of a product variability up to lot size one. Thus, upcoming innovative production concepts like the additive manufacturing technology basically create new opportunities with regard to extensive potentials in product development (constructive optimization) and manufacturing (economic individualization), but mostly suffer from insufficient strength regarding structural components. Therefore, this contribution presents an innovative technological and procedural conception of a hybrid additive manufacturing process (fiber-reinforced sandwich structures based on selective laser sintering technology) to overcome these current structural weaknesses, and consequently support the design of complex lightweight components.

Keywords: additive manufacturing, fiber-reinforced plastics (FRP), hybrid design, lightweight design

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Authors: A. Mandić, M. Sakač, A. Mišan, B. Šojić, L. Petrović, I. Lončarević, B. Pajin, I. Sedej

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Aldehydes as secondary lipid oxidation products are highly specific to the oxidative degradation of particular polyunsaturated fatty acids present in foods. Gas chromatographic analysis of those volatile compounds has been widely used for monitoring of the deterioration of food products. Developed static headspace gas chromatography method using flame ionization detector (SHS GC FID) was applied to monitor the aldehydes present in processed foods such as bakery, meat and confectionary products. Five selected aldehydes were determined in samples without any sample preparation, except grinding for bakery and meat products. SHS–GC analysis allows the separation of propanal, pentanal, hexanal, heptanal and octanal, within 15min. Aldehydes were quantified in fresh and stored samples, and the obtained range of aldehydes in crackers was 1.62±0.05-9.95±0.05mg/kg, in sausages 6.62±0.46-39.16±0.39mg/kg; and in cocoa spread cream 0.48±0.01-1.13±0.02mg/kg. Referring to the obtained results, the following can be concluded, proposed method is suitable for different types of samples, content of aldehydes varies depending on the type of a sample, and differs in fresh and stored samples of the same type.

Keywords: lipid oxidation, aldehydes, crackers, sausage, cocoa cream spread

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Authors: Samane Maroufi, Rasoul Khayyam Nekouei, Sajjad Mofarah

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Fabrication of the state-of-the-art portable pseudocapacitors with the desired transparency, mechanical flexibility, capacitance, and durability is challenging. In most cases, the fabrication of such devices requires critical elements which are either under the crisis of depletion or their extraction from virgin mineral ores have sever environmental impacts. This urges the use of secondary resources instead of virgin resources in fabrication of advanced devices. In this research, ultrathin films of defect-rich Mn1−x−y(CexLay)O2−δ with controllable thicknesses in the range between 5 nm to 627 nm and transmittance (≈29–100%) have been fabricated via an electrochemical chronoamperometric deposition technique using an aqueous precursor derived during the selective purification of rare earth oxide (REOs) isolated from end-of-life nickel-metal hydride (Ni-MH) batteries. Intercalation/de-intercalation of anionic O2− through the atomic tunnels of the stratified Mn1−x−y(CexLay)O2−δ crystallites was found to be responsible for outstanding areal capacitance of 3.4 mF cm−2 of films with 86% transmittance. The intervalence charge transfer among interstitial Ce/La cations and Mn oxidation states within the Mn1−x−y(CexLay)O2−δ structure resulted in excellent capacitance retention of ≈90% after 16 000 cycles. The synthesised transparent flexible Mn1−x−y(CexLay)O2−δ full-cell pseudocapacitor device possessed the energy and power densities of 0.088 μWh cm⁻² and 843 µW cm⁻², respectively. These values show insignificant changes under vigorous twisting and bending to 45–180° confirming these value-added materials are intriguing alternatives for size-sensitive energy storage devices. This research confirms the feasibility of utilisation of secondary waste resources for the fabrication of high-quality pseudocapacitors with engineered defects with the desired flexibility, transparency, and cycling stability suitable for size-sensitive portable electronic devices.

Keywords: pseudocapacitors, energy storage devices, flexible and transparent, sustainability

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Authors: Natalia Lukasik, Ewa Wagner-Wysiecka

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Development of selective, fast-responsive, and economical sensors for diverse ions detection and determination is one of the most extensively studied areas due to its importance in the field of clinical, environmental and industrial analysis. Among chemical sensors, vast popularity has gained ionophore-based optical sensors, where the generated analytical signal is a consequence of the molecular recognition of ion by the ionophore. Change of color occurring during host-guest interactions allows for quantitative analysis and for 'naked-eye' detection without the need of using sophisticated equipment. An example of application of such sensors is colorimetric detection of iron(III) cations. Iron as one of the most significant trace elements plays roles in many biochemical processes. For these reasons, the development of reliable, fast, and selective methods of iron ions determination is highly demanded. Taking all mentioned above into account a chromogenic amide derivative of 3,4-dihydroxybenzoic acid was synthesized, and its ability to iron(III) recognition was tested. To the best of authors knowledge (according to chemical abstracts) the obtained ligand has not been described in the literature so far. The catechol moiety was introduced to the ligand structure in order to mimic the action of naturally occurring siderophores-iron(III)-selective receptors. The ligand–ion interactions were studied using spectroscopic methods: UV-Vis spectrophotometry and infrared spectroscopy. The spectrophotometric measurements revealed that the amide exhibits affinity to iron(III) in dimethyl sulfoxide and fully aqueous solution, what is manifested by the change of color from yellow to green. Incorporation of the tested amide into a polymeric matrix (cellulose triacetate) ensured effective recognition of iron(III) at pH 3 with the detection limit 1.58×10⁻⁵ M. For the obtained sensor material parameters like linear response range, response time, selectivity, and possibility of regeneration were determined. In order to evaluate the effect of the size of the sensing material on iron(III) detection nanospheres (in the form of nanoemulsion) containing the tested amide were also prepared. According to DLS (dynamic light scattering) measurements, the size of the nanospheres is 308.02 ± 0.67 nm. Work parameters of the nanospheres were determined and compared with cellulose triacetate-based material. Additionally, for fast, qualitative experiments the test strips were prepared by adsorption of the amide solution on a glass microfiber material. Visual limit of detection of iron(III) at pH 3 by the test strips was estimated at the level 10⁻⁴ M. In conclusion, reported here amide derived from 3,4- dihydroxybenzoic acid proved to be an effective candidate for optical sensing of iron(III) in fully aqueous solutions. N. L. kindly acknowledges financial support from National Science Centre Poland the grant no. 2017/01/X/ST4/01680. Authors thank for financial support from Gdansk University of Technology grant no. 032406.

Keywords: ion-selective optode, iron(III) recognition, nanospheres, optical sensor

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Authors: W. Kritsarikan, T. Patcharawit, T. Yingnakorn, S. Khumkoa

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Neodymium-iron-boron (NdFeB) magnets classified as high-power magnets are widely used in various applications such as electrical and medical devices and account for 13.5 % of the permanent magnet’s market. Since its typical composition of 29 - 32 % Nd, 64.2 – 68.5 % Fe and 1 – 1.2 % B contains a significant amount of rare earth metals and will be subjected to shortages in the future. Domestic NdFeB magnet waste recycling should therefore be developed in order to reduce social, environmental impacts toward a circular economy. Most research works focus on recycling the magnet wastes, both from the manufacturing process and end of life. Each type of wastes has different characteristics and compositions. As a result, these directly affect recycling efficiency as well as the types and purity of the recyclable products. This research, therefore, focused on the recycling of manufacturing NdFeB magnet waste obtained from the sintering stage of magnet production and the waste contained 23.6% Nd, 60.3% Fe and 0.261% B in order to recover high purity neodymium oxide (Nd₂O₃) using hybrid metallurgical process via oxidative roasting and selective leaching techniques. The sintered NdFeB waste was first ground to under 70 mesh prior to oxidative roasting at 550 - 800 °C to enable selective leaching of neodymium in the subsequent leaching step using H₂SO₄ at 2.5 M over 24 h. The leachate was then subjected to drying and roasting at 700 – 800 °C prior to precipitation by oxalic acid and calcination to obtain neodymium oxide as the recycling product. According to XRD analyses, it was found that increasing oxidative roasting temperature led to an increasing amount of hematite (Fe₂O₃) as the main composition with a smaller amount of magnetite (Fe₃O₄) found. Peaks of neodymium oxide (Nd₂O₃) were also observed in a lesser amount. Furthermore, neodymium iron oxide (NdFeO₃) was present and its XRD peaks were pronounced at higher oxidative roasting temperatures. When proceeded to acid leaching and drying, iron sulfate and neodymium sulfate were mainly obtained. After the roasting step prior to water leaching, iron sulfate was converted to form hematite as the main compound, while neodymium sulfate remained in the ingredient. However, a small amount of magnetite was still detected by XRD. The higher roasting temperature at 800 °C resulted in a greater Fe₂O₃ to Nd₂(SO₄)₃ ratio, indicating a more effective roasting temperature. Iron oxides were subsequently water leached and filtered out while the solution contained mainly neodymium sulfate. Therefore, low oxidative roasting temperature not exceeding 600 °C followed by acid leaching and roasting at 800 °C gave the optimum condition for further steps of precipitation and calcination to finally achieve neodymium oxide.

Keywords: NdFeB magnet waste, oxidative roasting, recycling, selective leaching

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Authors: Woranittha Kritsarikan

Abstract:

Neodymium-iron-boron (NdFeB) magnets classified as high-power magnets are widely used in various applications such as electrical and medical devices and account for 13.5 % of the permanent magnet’s market. Since its typical composition of 29 - 32 % Nd, 64.2 – 68.5 % Fe and 1 – 1.2 % B contains a significant amount of rare earth metals and will be subjected to shortages in the future. Domestic NdFeB magnet waste recycling should therefore be developed in order to reduce social, environmental impacts toward the circular economy. Most research works focus on recycling the magnet wastes, both from the manufacturing process and end of life. Each type of wastes has different characteristics and compositions. As a result, these directly affect recycling efficiency as well as the types and purity of the recyclable products. This research, therefore, focused on the recycling of manufacturing NdFeB magnet waste obtained from the sintering stage of magnet production and the waste contained 23.6% Nd, 60.3% Fe and 0.261% B in order to recover high purity neodymium oxide (Nd₂O₃) using hybrid metallurgical process via oxidative roasting and selective leaching techniques. The sintered NdFeB waste was first ground to under 70 mesh prior to oxidative roasting at 550 - 800 ᵒC to enable selective leaching of neodymium in the subsequent leaching step using H₂SO₄ at 2.5 M over 24 hours. The leachate was then subjected to drying and roasting at 700 – 800 ᵒC prior to precipitation by oxalic acid and calcination to obtain neodymium oxide as the recycling product. According to XRD analyses, it was found that increasing oxidative roasting temperature led to the increasing amount of hematite (Fe₂O₃) as the main composition with a smaller amount of magnetite (Fe3O4) found. Peaks of neodymium oxide (Nd₂O₃) were also observed in a lesser amount. Furthermore, neodymium iron oxide (NdFeO₃) was present and its XRD peaks were pronounced at higher oxidative roasting temperature. When proceeded to acid leaching and drying, iron sulfate and neodymium sulfate were mainly obtained. After the roasting step prior to water leaching, iron sulfate was converted to form hematite as the main compound, while neodymium sulfate remained in the ingredient. However, a small amount of magnetite was still detected by XRD. The higher roasting temperature at 800 ᵒC resulted in a greater Fe2O3 to Nd2(SO4)3 ratio, indicating a more effective roasting temperature. Iron oxides were subsequently water leached and filtered out while the solution contained mainly neodymium sulfate. Therefore, low oxidative roasting temperature not exceeding 600 ᵒC followed by acid leaching and roasting at 800 ᵒC gave the optimum condition for further steps of precipitation and calcination to finally achieve neodymium oxide.

Keywords: NdFeB magnet waste, oxidative roasting, recycling, selective leaching

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Authors: Mabrook Saleh Amera, Prabhakarn Arunachalama, Maged N. Shaddadb, Abdulhadi Al-Qadia

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Global energy crises and water pollution have negatively impacted sustainable development in recent years. It is most promising to use Bismuth vanadate (BiVO4) as an electrode for photoelectrocatalytic (PEC) oxidation of water and pollution degradation. However, BiVO4 anodes suffer from poor charge separation and slow water oxidation. In this paper, a Zr:BiVO4/NiFeOOH heterojunction was successfully prepared by electrodeposition and photoelectrochemical transformation process. The method resulted in a notable 5-fold improvement in photocurrent features (1.27 mAcm−2 at 1.23 VRHE) and a lower onset potential of 0.6 VRHE. Photoanodes with high photocatalytic features and high photocorrosion resistance may be attributed their high conformity and amorphous nature of the coating. In this study, PEC was compared to electrocatalysis (EC), and the effect of bias potential on PEC degradation was discussed for tetracycline (TCH), riboflavin, and streptomycin. In PEC, TCH was degraded in the most efficient way (96 %) by Zr:BiVO4/NiFeOOH, three times larger than Zr:BiVO4 and EC (55 %). Thus, this study offers a potential solution for oxidizing PEC water and treating water pollution.

Keywords: photoelectrochemical, water splitting, pharmaceutical pollutants degradation, photoanodes, cocatalyst

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Authors: María R. Contreras, Diana Endara

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Cyanide leaching is the most used technology for gold mining industry, which produces large amounts of effluents requiring treatment. In Ecuador the development of gold mining industry has increased, causing significant environmental impacts due to the highly use of cyanide, it is estimated that 10 gr of extracted gold generates 7000 liters of water contaminated with 300mg/L of free cyanide. The most common methods used nowadays are the treatment with peroxodisulfuric acid, ozonation, H₂O₂ and other reactants which are expensive and present disadvantages. Several methods have been developed to treat this contaminant such as heterogeneous catalysts. Layered double hydroxides (LDHs) have received much attention due to their wide applications like a catalysis support. Therefore, in this study, Mg-Al/ LDH was synthetized by coprecipitation method and then platinum was impregned on it, in order to enhance its catalytic activity. Two methods of impregnation were used, the first one, called incipient wet impregnation and the second one was developed by continuous agitation of LDH in contact with chloroplatinic acid solution for 24 h. The support impregnated was analyzed by X-ray diffraction, FTIR and SEM. Finally, the oxidation of cyanide ion was performed by preparing synthetic solutions of sodium cyanide (NaCN) with an initial concentration of 500 mg/L at pH 10,5 and air flow of 180 NL/h. After 8 hours of treatment, an 80% of oxidation of ion cyanide was achieved.

Keywords: catalysis, cyanide, LDHs, mining

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Authors: Shamima Akhter, Samira Bagheri, M. Shalauddin, Wan Jefrey Basirun

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In the present study, a nanocomposite of f-MWCNTs-Chitosan was prepared by the immobilization of Co(II) transition metal through self-assembly method and used for the simultaneous voltammetric determination of paracetamol (PA). The composite material was characterized by field emission scanning electron microscopy (FESEM) and energy dispersive X-Ray analysis (EDX). The electroactivity of cobalt immobilized f-MWCNTs with excellent adsorptive polymer chitosan was assessed during the electro-oxidation of paracetamol. The resulting GCE modified f-MWCNTs/CTS-Co showed electrocatalytic activity towards the oxidation of PA. The electrochemical performances were investigated using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV) methods. Under favorable experimental conditions, differential pulse voltammetry showed a linear dynamic range for paracetamol solution in the range of 0.1 to 400µmol L⁻¹ with a detection limit of 0.01 µmol L⁻¹. The proposed sensor exhibited significant selectivity for the paracetamol detection. The proposed method was successfully applied for the determination of paracetamol in commercial tablets and human serum sample.

Keywords: nanomaterials, paracetamol, electrochemical technique, multi-wall carbon nanotube

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Authors: Olumayede Emmanuel Gbenga, Adeniyi Azeez Adebayo

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Carbonyls are the first-generation products from tropospheric degradation reactions of volatile organic compounds (VOCs). This computational study examined the mechanism of removal of carbonyls from the atmosphere via hydroxyl radical. The kinetics of the reactions were computed from the activation energy (using enthalpy (ΔH**) and Gibbs free energy (ΔG**). The minimum energy path (MEP) analysis reveals that in all the molecules, the products have more stable energy than the reactants, which implies that the forward reaction is more thermodynamically favorable. The hydrogen abstraction of the aromatic aldehyde, especially without methyl substituents, is more kinetically favorable compared with the other aldehydes in the order of aromatic (without methyl or meta methyl) > alkene (short chain) > diene > long-chain aldehydes. The activation energy is much lower for the forward reaction than the backward, indicating that the forward reactions are more kinetically stable than their backward reaction. In terms of thermodynamic stability, the aromatic compounds are found to be less favorable in comparison to the aliphatic. The study concludes that the chemistry of the carbonyl bond of the aldehyde changed significantly from the reactants to the products.

Keywords: atmospheric carbonyls, oxidation, mechanism, kinetic, thermodynamic

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Authors: Mahdi Almaky, Reda Hassanin, Benjamin Horrocks, Andrew Houlton

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DNA-templated poly(N-substituted pyrrole)bipyridinium nanowires were synthesised at room temperature using the chemical oxidation method. The resulting CPs/DNA hybrids have been characterised using electronic and vibrational spectroscopic methods especially Ultraviolet-Visible (UV-Vis) spectroscopy and FTIR spectroscpy. The nanowires morphology was characterised using Atomic Force Microscopy (AFM). The electrical properties of the prepared nanowires were characterised using Electrostatic Force Microscopy (EFM), and measured using conductive AFM (c-AFM) and two terminal I/V technique, where the temperature dependence of the conductivity was probed. The conductivities of the prepared CPs/DNA nanowires are generally lower than PPy/DNA nanowires showingthe large effect on N-alkylation in decreasing the conductivity of the polymer, butthese are higher than the conductivity of their corresponding bulk films.This enhancement in conductivity could be attributed to the ordering of the polymer chains on DNA during the templating process. The prepared CPs/DNA nanowires were used as templates for the growth of copper nanowires at room temperature using aqueous solution of Cu(NO3)2as a source of Cu2+ and ascorbic acid as reducing agent. AFM images showed that these nanowires were uniform and continuous compared to copper nanowires prepared using the templating method directly onto DNA. Electrical characterization of the nanowires by c AFM revealed slight improvement in conductivity of these nanowires (Cu-CPs/DNA) compared to CPs/DNA nanowires before metallisation.

Keywords: templating, copper nanowires, polymer/DNA hybrid, chemical oxidation method

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Authors: Silviya Todorova, Anton Naydenov, Ralitsa Velinova, Alexander Larin

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Catalytic combustion of methane has been extensively investigated for emission control and power generation during the last decades. The alumina-supported palladium catalyst is widely accepted as the most active catalysts for catalytic combustion of methane. The activity of Pd/Al₂O₃ decreases during the time on stream, especially underwater vapor. The following order of activity in the reaction of complete oxidation of methane was established: Co₃O₄> CuO>NiO> Mn₂O₃> Cr₂O₃. It may be expected that the combination between Pd and these oxides could lead to the promising catalysts in the reaction of complete methane. In the present work, we investigate the activity of Pd/Al₂O₃ catalysts promoted with other metal oxides (MOx; M= Ni, Co, Ce). The Pd-based catalysts modified by metal oxide were prepared by sequential impregnation of Al₂O₃ with aqueous solutions of Me(NO₃)₂.6H₂O and Pd(NO₃)₂H₂O. All samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS). An improvement of activity was observed after modification with different oxides. The results demonstrate that the Pd/Al₂O₃ catalysts modified with Co and Ce by impregnation with a common solution of respective salts, exhibit the most promising catalytic activity for methane oxidation. Most probably, the presence of Co₃O₄ and CeO₂ on catalytic surface increases surface oxygen and therefore leads to the better reactivity in methane combustion.

Keywords: methane combustion, palladium, Co-Ce, Ni-Ce

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Authors: J. Martin, A. Nominé, T. Czerwiec, G. Henrion, T. Belmonte

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The plasma electrolytic oxidation (PEO) is a particular electrochemical process to produce protective oxide ceramic coatings on light-weight metals (Al, Mg, Ti). When applied to aluminum alloys, the resulting PEO coating exhibit improved wear and corrosion resistance because thick, hard, compact and adherent crystalline alumina layers can be achieved. Several investigations have been carried out to improve the efficiency of the PEO process and one particular way consists in tuning the suitable electrical regime. Despite the considerable interest in this process, there is still no clear understanding of the underlying discharge mechanisms that make possible metal oxidation up to hundreds of µm through the ceramic layer. A key parameter that governs the PEO process is the numerous short-lived micro-discharges (micro-plasma in liquid) that occur continuously over the processed surface when the high applied voltage exceeds the critical dielectric breakdown value of the growing ceramic layer. By using a bipolar pulsed current to supply the electrodes, we previously observed that micro-discharges are delayed with respect to the rising edge of the anodic current. Nevertheless, explanation of the origin of such phenomena is still not clear and needs more systematic investigations. The aim of the present communication is to identify the relationship that exists between this delay and the mechanisms responsible of the oxide growth. For this purpose, the delay of micro-discharges ignition is investigated as the function of various electrical parameters such as the current density (J), the current pulse frequency (F) and the anodic to cathodic charge quantity ratio (R = Qp/Qn) delivered to the electrodes. The PEO process was conducted on Al2214 aluminum alloy substrates in a solution containing potassium hydroxide [KOH] and sodium silicate diluted in deionized water. The light emitted from micro-discharges was detected by a photomultiplier and the micro-discharge parameters (number, size, life-time) were measured during the process by means of ultra-fast video imaging (125 kfr./s). SEM observations and roughness measurements were performed to characterize the morphology of the elaborated oxide coatings while XRD was carried out to evaluate the amount of corundum -Al203 phase. Results show that whatever the applied current waveform, the delay of micro-discharge appearance increases as the process goes on. Moreover, the delay is shorter when the current density J (A/dm2), the current pulse frequency F (Hz) and the ratio of charge quantity R are high. It also appears that shorter delays are associated to stronger micro-discharges (localized, long and large micro-discharges) which have a detrimental effect on the elaborated oxide layers (thin and porous). On the basis of the results, a model for the growth of the PEO oxide layers will be presented and discussed. Experimental results support that a mechanism of electrical charge accumulation at the oxide surface / electrolyte interface takes place until the dielectric breakdown occurs and thus until micro-discharges appear.

Keywords: aluminium, micro-discharges, oxidation mechanisms, plasma electrolytic oxidation

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Authors: J. Bolobajev, M. Trapido, A. Goi

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The practical application of the Fenton-based treatment method for organic compounds-contaminated water purification is limited mainly because of the large amount of ferric sludge formed during the treatment, where ferrous iron (Fe(II)) is used as the activator of the hydrogen peroxide oxidation processes. Reuse of ferric sludge collected from clarifiers to substitute Fe(II) salts allows reducing the total cost of Fenton-type treatment technologies and minimizing the accumulation of hazardous ferric waste. Dissolution of ferric iron (Fe(III)) from the sludge to liquid phase at acidic pH and autocatalytic transformation of Fe(III) to Fe(II) by phenolic compounds (tannic acid, lignin, phenol, catechol, pyrogallol and hydroquinone) added or present as water/wastewater constituents were found to be essentially involved in the Fenton-based oxidation mechanism. Observed enhanced formation of highly reactive species, hydroxyl radicals, resulted in a substantial organic contaminant degradation increase. Sludge reuse at acidic pH and in the presence of ferric iron reductants is a novel strategy in the Fenton-based treatment application for organic compounds-contaminated water purification.

Keywords: ferric sludge recycling, ferric iron reductant, water treatment, organic pollutant

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Authors: Usha N. Murthy, H. B. Rekha, Mahaveer Devoor

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The introduction of more stringent pollution regulations, in relation to financial and social pressures for sustainable development, has pressed toward limiting the volumes of industrial and domestic effluents discharged into the environment-as well as to increase the efforts within research and development of new or more efficient wastewater treatment technologies. Considering both discharge volume and effluent composition, wastewater generated by the textile industry is rated as the most polluting among all industrial sectors. The pollution load is mainly due to spent dye baths, which are composed of unreacted dyes, dispersing agents, surfactants, salts and organics. In the present investigation, the textile dye wastewater was characterized by high colour, chemical oxygen demand (COD), total dissolved solids (TDS) and pH. Electrochemical oxidation process for four plate electrodes was carried out at five different current intensities, out of which 0.14A has achieved maximum percentage removal of COD with 75% and 83% of colour. The COD removal rate in kg COD/h/m2 decreases with increase in the current intensity. The energy consumption increases with increase in the current intensity. Hence, textile dye wastewater can be effectively pre-treated by electrochemical oxidation method where the process limits objectionable colour while leaving the COD associated with organics left for natural degradation thus causing a sustainable reduction in pollution load.

Keywords: electrochemical treatment, COD, colour, environmental engineering

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Authors: Gaddafi Sani Shehu, Tankut Yalcınoz, Abdullahi Bala Kunya

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Multilevel inverters such as flying capacitor, diode-clamped, and cascaded H-bridge inverters are very popular particularly in medium and high power applications. This paper focuses on a cascaded H-bridge module using a single direct current (DC) source in order to generate an 11-level output voltage. The noble approach reduces the number of switches and gate drivers, in comparison with a conventional method. The anticipated topology produces more accurate result with an isolation transformer at high switching frequency. Different modulation techniques can be used for the multilevel inverter, but this work features modulation techniques known as selective harmonic elimination (SHE).This modulation approach reduces the number of carriers with reduction in Switching Losses, Total Harmonic Distortion (THD), and thereby increasing Power Quality (PQ). Based on the simulation result obtained, it appears SHE has the ability to eliminate selected harmonics by chopping off the fundamental output component. The performance evaluation of the proposed cascaded multilevel inverter is performed using PSIM simulation package and THD of 0.94% is obtained.

Keywords: cascaded H-bridge multilevel inverter, power quality, selective harmonic elimination

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Authors: Eugene Ivanov, Eduardo del-Rio, Igor Kapchenko, Maija Nystrӧm, Juha Kotila

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Series of low modulus beta Ti alloy billets and powders can be produced in commercial quantities using a combination of electron beam melting (EBM) and EIGA atomization processes. In the present study, TNZT alloy powder was produced and processed in the EOSINT M290 laser sintering system to produce parts for mechanical testing. Post heat treatments such as diffusion annealing to reduce internal stresses or hot isostatic pressing to remove closed pores were not applied. The density can visually be estimated to be > 99,9 %. According to EDS study Nb, Zr, and Ta are distributed homogeneously throughout the printed sample. There are no indications for any segregation or chemical inhomogeneity, i.e. variation of the element distribution. These points to the fact that under the applied experimental conditions the melt generated by the laser rapidly cools down in the SLM (Selective Laser Melting) process. The selective laser sintering yielded dense structures with relatively good surface quality. The mechanical properties, especially the elongation (24%) along with tensile strength ( > 500MPa) and modulus of elasticity (~60GPa), were found to be promising compared to titanium alloys in general.

Keywords: beta titanium alloys, additive manufacturing, powder, implants

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Authors: Gerrit Ter Haar, Thorsten Becker, Deborah Blaine

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The Additive Manufacturing (AM) process of Selective Laser Melting (SLM) has seen an exponential growth in sales and development in the past fifteen years. Whereas the capability of SLM was initially limited to rapid prototyping, progress in research and development (R&D) has allowed SLM to be capable of fully functional parts. This technology is still at a primitive stage and technical knowledge of the vast number of variables influencing final part quality is limited. Ongoing research and development of the sensitive printing process and post processes is of utmost importance in order to qualify SLM parts to meet international standards. Quality concerns in Ti-6Al-4V manufactured through SLM has been identified, which include: high residual stresses, part porosity, low ductility and anisotropic mechanical properties. Whereas significant quality improvements have been made through optimising printing parameters, research indicates as-produced part ductility to be a major limiting factor when compared to its wrought counterpart. This study aims at achieving an in-depth understanding of the underlining links between SLM produced Ti-6Al-4V microstructure and its mechanical properties. Knowledge of microstructural transformation kinetics of Ti-6Al-4V allows for the optimisation of post-process heat treatments thereby achieving the required process route to manufacture high quality SLM produced Ti-6Al-4V parts. Experimental methods used to evaluate the kinematics of microstructural transformation of SLM Ti-6Al-4V are: optical microscopy and electron backscatter diffraction. Results show that a low-temperature heat treatment is capable of transforming the as-produced, martensitic microstructure into a duel-phase microstructure exhibiting both a high strength and improved ductility. Furthermore, isotropy of mechanical properties can be achieved through certain annealing routes. Mechanical properties identical to that of wrought Ti-6Al-4V can, therefore, be achieved through an optimised process route.

Keywords: EBSD analysis, heat treatments, microstructural characterisation, selective laser melting, tensile behaviour, Ti-6Al-4V

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Authors: Didem Ildırar, Serap Fındık

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Baker’s yeast industry uses molasses as a raw material. Molasses wastewater contains high molecular weight polymers called melanoidins. Melanoidins are obtained after the reactions between the amino acids and carbonyl groups in molasses. The molasses wastewater has high biochemical and chemical oxygen demand and dark brown color. If it is discharged to receiving bodies without any treatment, it prevents light penetration and dissolved oxygen level of the surface water decreases. Melanoidin compounds are toxic effect to the microorganism in water and there is a resistance to microbial degradation. Before discharging molasses wastewater, adequate treatment is necessary. In addition to changing environmental regulations, properties of treated wastewater must be improved. Advanced oxidation processes can be used to improve existing properties of wastewater. Sonochemical oxidation is one of the alternative methods. Sonochemical oxidation employs the use of ultrasound resulting in cavitation phenomena. In this study, decolorization and chemical oxygen demand removal (COD) of baker’s yeast effluent was investigated by using ultrasound. Baker’s yeast effluent was supplied from a factory which is located in the north of Turkey. An ultrasonic homogenizator was used for this study. Its operating frequency is 20kHz. SnO2/TiO2 catalyst has been used as sonocatalyst. The effects of the composite preparation method, mixing time while composite prepared, the molar ratio of SnO2/TiO2, the calcination temperature, and time, the catalyst amount were investigated on the treatment of baker’s yeast effluent. . According to the results, the prepared composite SnO2/TiO2 by using ultrasonic probe gave a better result than prepared composite by using an ultrasonic bath. Prepared composite by using an ultrasonic probe with a 4:1 molar ratio treated at 800°C for 60min gave a better result. By using this composite, optimum catalyst amount was 0.2g/l. At these conditions 26.6% decolorization was obtained. There was no COD removal at the studied conditions.

Keywords: baker’s yeast effluent, COD, decolorization, sonocatalyst, ultrasonic irradiation

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Authors: Nanxi Miao, Junjie Wang

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The discovery of 2D materials with distinct compositions and properties has been a research aim since the report of graphene. One of the latest members of the 2D material family is MXene, which is produced from the topochemical deintercalation of the A layer from a laminate MAX phase. Recently, analogous 2D MBenes (transitional metal borides) have been predicted by theoretical calculations as excellent alternatives in applications such as metal-ion batteries, magnetic devices, and catalysts. However, the practical applications of two-dimensional (2D) transition-metal borides (MBenes) have been severely hindered by the lack of accessible MBenes because of the difficulties in the selective etching of traditional ternary MAB phases with orthorhombic symmetry (ort-MAB). Here, we discover a family of ternary hexagonal MAB (h-MAB) phases and 2D hexagonal MBenes (h-MBenes) by ab initio predictions and experiments. Calculations suggest that the ternary h-MAB phases are more suitable precursors for MBenes than the ort-MAB phases. Based on the prediction, we report the experimental synthesis of h-MBene HfBO by selective removal of in from h-MAB Hf2InB2. The synthesized 2D HfBO delivered a specific capacity of 420 mAh g-1 as an anode material in lithium-ion batteries, demonstrating the potential for energy-storage applications. The discovery of this h-MBene HfBO added a new member to the growing family of 2D materials and provided opportunities for a wide range of novel applications.

Keywords: 2D materials, DFT calculations, high-throughput screening, lithium-ion batteries

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Authors: Davyd Urbanas, Pranas Baltrenas

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It is well-known that, despite the constant increase of alternative energy sources usage, today combustible fuels are still widely used in power engineering. As a result of fuel combustion, significant amounts of nitrogen oxides (NOx) and carbon monoxide (CO is a product of incomplete combustion) are supplied to the atmosphere. Also, these pollutants are formed in industry (chemical production, refining, and metal production). In this work, the investigation of nitrogen oxides CO-selective catalytic reduction using new grain load-type catalysts was carried out. The catalysts containing the substrate and a thin active coating made of transition metal (Mn, Cu, and Nb) oxides were prepared with the use of electroless chemical deposition method. Chemical composition, chemical state, and morphology of the formed active coating were investigated using ICP-OES, EDX, SEM, and XPS techniques. The obtained results revealed that the prepared catalysts (Cu-Mn-oxide and Cu-Mn-Nb-oxide) have rough and developed surface and can be successfully used for the flue gas catalytic purification. The significant advantage of prepared catalysts is their suitability from technological application point of view, which differs this work from others dedicated to gas purification by SCR.

Keywords: flue gas, nitrogen oxides, selective catalytic reduction, transition metal oxides

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Authors: Tae Hyun Ahn, Gyo Woo Lee, Man Young Kim

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Because of high thermal efficiency and low CO2 emission, diesel engines are being used widely in many industrial fields although it makes many PM and NOx which give both human health and environment a negative effect. NOx regulations for diesel engines, however, are being strengthened and it is impossible to meet the emission standard without NOx reduction devices such as SCR (Selective Catalytic Reduction), LNC (Lean NOx Catalyst), and LNT (Lean NOx Trap). Among the NOx reduction devices, urea-SCR system is known as the most stable and efficient method to solve the problem of NOx emission. But this device has some issues associated with the ammonia slip phenomenon which is occurred by shortage of evaporation and thermolysis time, and that makes it difficult to achieve uniform distribution of the injected urea in front of monolith. Therefore, this study has focused on the mixing enhancement between urea and exhaust gases to enhance the efficiency of the SCR catalyst equipped in catalytic muffler by changing inlet gas temperature and spray conditions to improve the spray uniformity of the urea water solution. Finally, it can be found that various parameters such as inlet gas temperature and injector and injection angles significantly affect the evaporation and mixing of the urea water solution with exhaust gases, and therefore, optimization of these parameters are required.

Keywords: UWS (Urea-Water-Solution), selective catalytic reduction (SCR), evaporation, thermolysis, injection

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Authors: Smita Mondal, Dinesh Kumar Pandey, Prakash Biswas

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During past two decades, considerable attention has been given to the value addition of biodiesel derived glycerol (~10wt.%) to make the biodiesel industry economically viable. Among the various glycerol value-addition methods, hydrogenolysis of glycerol to 1,2-propanediol is one of the attractive and promising routes. In this study, highly active and selective γ-Al₂O₃ supported bimetallic Cu-Ni catalyst was developed for selective hydrogenolysis of glycerol to 1,2-propanediol in the liquid phase. The catalytic performance was evaluated in a high-pressure autoclave reactor. The formation of mixed oxide indicated the strong interaction of Cu, Ni with the alumina support. Experimental results demonstrated that bimetallic copper-nickel catalyst was more active and selective to 1,2-PDO as compared to monometallic catalysts due to bifunctional behavior. To verify the effect of calcination temperature on the formation of Cu-Ni mixed oxide phase, the calcination temperature of 20wt.% Cu:Ni(1:1)/Al₂O₃ catalyst was varied from 300°C-550°C. The physicochemical properties of the catalysts were characterized by various techniques such as specific surface area (BET), X-ray diffraction study (XRD), temperature programmed reduction (TPR), and temperature programmed desorption (TPD). The BET surface area and pore volume of the catalysts were in the range of 71-78 m²g⁻¹, and 0.12-0.15 cm³g⁻¹, respectively. The peaks at the 2θ range of 43.3°-45.5° and 50.4°-52°, was corresponded to the copper-nickel mixed oxidephase [JCPDS: 78-1602]. The formation of mixed oxide indicated the strong interaction of Cu, Ni with the alumina support. The crystallite size decreased with increasing the calcination temperature up to 450°C. Further, the crystallite size was increased due to agglomeration. Smaller crystallite size of 16.5 nm was obtained for the catalyst calcined at 400°C. Total acidic sites of the catalysts were determined by NH₃-TPD, and the maximum total acidic of 0.609 mmol NH₃ gcat⁻¹ was obtained over the catalyst calcined at 400°C. TPR data suggested the maximum of 75% degree of reduction of catalyst calcined at 400°C among all others. Further, 20wt.%Cu:Ni(1:1)/γ-Al₂O₃ catalyst calcined at 400°C exhibited highest catalytic activity ( > 70%) and 1,2-PDO selectivity ( > 85%) at mild reaction condition due to highest acidity, highest degree of reduction, smallest crystallite size. Further, the modified Power law kinetic model was developed to understand the true kinetic behaviour of hydrogenolysis of glycerol over 20wt.%Cu:Ni(1:1)/γ-Al₂O₃ catalyst. Rate equations obtained from the model was solved by ode23 using MATLAB coupled with Genetic Algorithm. Results demonstrated that the model predicted data were very well fitted with the experimental data. The activation energy of the formation of 1,2-PDO was found to be 45 kJ mol⁻¹.

Keywords: glycerol, 1, 2-PDO, calcination, kinetic

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Authors: Sri Rahayu, M. Dwi Susan, Aris Soewondo, W. M. Agung Pramana

Abstract:

Semen is an organic fluid (seminal plasma) that contain spermatozoa. Proteins are one of the major seminal plasma components that modulate sperm functionality, influence sperm capacitation and maintaining the stability of the membrane. Semen freezing is a procedure to preserve sperm cells. The process causes decrease in sperm viability due to temperature shock and oxidation stress. Oxidation stress is a disturbance on phosphorylation that increases ROS concentration, and it produces lipid peroxide in spermatozoa membrane resulted in high MDA (malondialdehyde) concentration. The objective of this study was to examine the effect of freezing on protein and MDA profile of bovine sperm cell and seminal plasma after freezing. Protein and MDA of sperm cell and seminal plasma were isolated from 10 sample. Protein profiles was analyzed by SDS PAGE with separating gel 12,5 %. The concentration of MDA was measured by spectrophotometer. The results of the research indicated that freezing of semen cause lost of the seminal plasma proteins with molecular with 20, 10, and 9 kDa. In addition, the result research showed that protein of the sperm (26, 10, 9, 7, and 6 kDa) had been lost. There were difference MDA concentration of seminal plasma and sperm cell were increase after freezing. MDA concentration of seminal plasma before and after freezing were 2.2 and 2.4 nmol, respectively. MDA concentration of sperm cell before and after freezing were 1,5 and 1.8 nmol, respectively. In conclusion, there were differences protein profiles of spermatozoa before and after semen freezing and freezing cause increasing of the MDA concentration.

Keywords: MDA, semen freezing, SDS PAGE, protein profile

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