Search results for: platinum disulfide

Authors: Malihe Moeinin, Robert Hill, Ferranti Wong

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Background: A white spot lesion (WSL) is defined as subsurface enamel porosity from carious demineralisation on the smooth surfaces of the tooth. It appears as a milky white opacity. Lesions shown an apparently intact surface layer, followed underneath by the more porous lesion body. The small pores within the body of the lesion act as diffusion pathway for both acids and minerals, so allowing the demineralisation of enamel to occur at the advancing front of the lesion. Objectives: The objective is to mapthe porosity and its size on WSL with Focused Ion Bean- Scanning Electron Microscopy (FIB-SEM) Method: The basic method used for FIB-SEM consisted of depositing a one micron thick layer of platinum over 25μmx 25μm of the interest region of enamel. Then, making a rough cut (25μmx 5μmx 20μm) with 3nA current and 30Kv was applied with the help of drift suppression (DS), using a standard “cross-sectional” cutting pattern, which ended at the front of the deposited platinum layer. Two adjacent areas (25μmx 5μmx 20μm) on the both sides of the platinum layer were milled under the same conditions. Subsequent, cleaning cross-sections were applied to polish the sub-surface edge of interest running perpendicular to the surface. The "slice and view" was carried out overnight for milling almost 700 slices with 2Kv and 4nA and taking backscattered (BS) images. Then, images were imported into imageJ and analysed. Results: The prism structure is clearly apparent on FIB-SEM slices of WSL with the dissolution of prism boundaries as well as internal porosity within the prism itself. Porosity scales roughly 100-400nm, which is comparable to the light wavelength (500nm). Conclusion: FIB-SEM is useful to characterize the porosity of WSL and it clearly shows the difference between WSL and normal enamel.

Keywords: white spot lesion, FIB-SEM, enamel porosity, porosity

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Authors: Doo Ki Lee, Kumaresh Selvakumar, Man Young Kim

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Catalytic combustion is an environmentally friendly technique to combust fuels in gas turbines. In this paper, the behavior of surface reaction rate on catalytic combustion is studied with respect to the heterogeneous oxidation of methane-air mixture in a catalytic reactor. Plug flow reactor (PFR), the simplified single catalytic channel assists in investigating the catalytic combustion phenomenon over the Pt catalyst by promoting the desired chemical reactions. The numerical simulation with multi-step elementary surface reactions is governed by the availability of free surface sites onto the catalytic surface and thereby, the catalytic combustion characteristics are demonstrated by examining the rate of the reaction for lean fuel mixture. Further, two different surface reaction mechanisms are adopted and compared for surface reaction rates to indicate the controlling heterogeneous reaction for better fuel conversion. The performance of platinum catalyst under heterogeneous reaction is analyzed under the same temperature condition, where the catalyst with the higher kinetic rate of reaction would have a maximum catalytic activity for enhanced methane catalytic combustion.

Keywords: catalytic combustion, heterogeneous reaction, plug flow reactor, surface reaction rate

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Authors: Yingjeng James Li, Chih Chi Hsu, Chiao-Chih Hu

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Membrane electrode assemblies MEAs for proton exchange membrane PEM water electrolyzers were prepared by employing 175um perfluorosulfonic acid PFSA membranes as the PEM, onto which iridium oxide catalyst was coated on one side as the anode and platinum catalyst was coated on the other side as the cathode. The cathode catalyst ink was prepared so that the weight ratio of the catalyst powder to ionomer was 75:25, 70:30, 65:35, 60:40, and 55:45, respectively. Whereas, the ratio of catalyst powder to ionomer of the anode catalyst ink keeps constant at 50:50. All the MEAs have a catalyst coated area of 5cm*5cm. The test cell employs a platinum plated titanium grid as anode gas diffusion media; whereas, carbon paper was employed as the cathode gas diffusion media. The measurements of the MEA gases production rate were carried out by holding the cell voltage ranging from 1.6 to 2.8 volts at room temperature. It was found that the MEA with cathode catalyst to ionomer ratio of 65:35 gives the largest hydrogen production rate which is 2.8mL/cm2*min.

Keywords: electrolyzer, membrane electrode assembly, proton exchange membrane, ionomer, hydrogen

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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: Eleni Poulou-Sidiropoulou, Charalampos N. Bompas, Martina Samiotaki, Alexios Vlamis-Gardikas

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The glutaredoxin (Grx) and thioredoxin (Trx) systems keep the intracellular environment reduced in almost all organisms. In Escherichia coli (E. coli), the Grx system relies on NADPH+ to reduce GSH reductase (GR), the latter reducing oxidized diglutathione to glutathione (GSH) which in turn reduces cytosolic Grxs, the electron donors for different intracellular substrates. In the Trx system, GR and GSH are replaced by Trx reductase (TrxR). Three of the Grxs of E. coli (Grx1, 2, 3) are reduced by GSH, while Grx4 is likely reduced by TrxR. Trx1 and Grx1 from E. coli may reduce ribonucleotide reductase Ia to ensure a constant supply of deoxyribonucleotides for the synthesis of DNA. The role of the other three Grxs is relatively unknown, especially for Grx2 that may amount up to 1 % of total cellular protein in the stationary phase of growth. The protein is known as a potent antioxidant, but no specific functions have been attributed to it. Herein, affinity chromatography of cellular extracts on immobilized Grx2, followed by MS analysis of the resulting eluates, was employed to identify protein ligands that could provide insights into the biological role of Grx2. Ionic, strong non-covalent, and covalent (disulfide) interactions with relevant proteins were detected. As a means of verification, the identified ligands were subjected to in silico docking with monothiol Grx2. In other experiments, protein extracts from E. coli cells lacking the gene for Grx2 (grxB) were compared to those of wild type. Taken together, the two approaches suggest that Grx2 is involved in protein synthesis, nucleotide metabolism, DNA damage repair, stress responses, and various metabolic processes. Grx2 appears as a versatile protein that may participate in a wide range of biological pathways beyond its known general antioxidant function.

Keywords: Escherichia coli, glutaredoxin 2, interactome, thiol-disulfide oxidoreductase

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Authors: Kumaresh Selvakumar, Man Young Kim

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In order to elaborate the main idea of investigating the flow physics inside the catalytic combustor, the characteristics of the catalytic surface reactions are analyzed by employing the CHEMKIN methodology with detailed gas and surface chemistries. The presence of a catalyst inside an engine enables complete combustion at lower temperatures which promotes desired chemical reactions. A single channel from the honeycomb monolith catalytic combustor is preferred to analyze the gas and surface reactions in the catalyst bed considering the fact that every channel in the honeycomb monolith behaves in similar fashion. The simplified approach with single catalyst channel using plug flow reactor can be used to predict the flow behavior inside the catalytic combustor. The hydrogen addition to the combustion reactants offers a way to light-off catalytic combustion of methane on platinum catalyst and aids to reduce the surface ignition temperature. Indeed, the hydrogen adsorption is higher on the uncovered Pt(s) surface sites because the sticking coefficient of hydrogen is larger than that of methane. The location of flame position in the catalyst bed is validated by igniting the methane fuel with the presence of hydrogen for corresponding multistep surface reactions.

Keywords: catalytic combustor, hydrogen adsorption, plug flow reactor, surface ignition temperature

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Authors: A. Gilewska, J. Masternak, K. Kazimierczuk, L. Turlej, J. Wietrzyk, B. Barszcz

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Platinum-based drugs are now widely used as chemotherapeutic agents. However the platinum complexes show the toxic side-effects: i) the development of platinum resistance; ii) the occurrence of severe side effects, such as nephro-, neuro- and ototoxicity; iii) the high toxicity towards human fibroblast. Therefore the development of new anticancer drugs containing different transition-metal ions, for example, ruthenium, rhodium, iridium is a valid strategy in cancer treatment. In this paper, we reported the synthesis, spectroscopic, structural and biological properties of complexes of ruthenium, rhodium, and iridium containing N,N-chelating ligand (2,2’-bisimidazole). These complexes were characterized by elemental analysis, UV-Vis and IR spectroscopy, X-ray diffraction analysis. These complexes exhibit a typical pseudotetrahedral three-legged piano-stool geometry, in which the aromatic arene ring forms the seat of the piano-stool, while the bidentate 2,2’-bisimidazole (ligand) and the one chlorido ligand form the three legs of the stool. The spectroscopy data (IR, UV-Vis) and elemental analysis correlate very well with molecular structures. Moreover, the cytotoxic activity of the complexes was carried out on human cancer cell lines: LoVo (colorectal adenoma), MV-4-11 (myelomonocytic leukaemia), MCF-7 (breast adenocarcinoma) and normal healthy mouse fibroblast BALB/3T3 cell lines. To predict a binding mode, a potential interaction of metal complexes with calf thymus DNA (CT-DNA) and protein (BSA) has been explored using UV absorption and circular dichroism (CD). It is interesting to note that the investigated complexes show no cytotoxic effect towards the normal BALB/3T3 cell line, compared to cisplatin, which IC₅₀ values was determined as 2.20 µM. Importantly, Ru(II) displayed the highest activity against HL-60 (IC₅₀ 4.35 µM). The biological studies (UV-Vis and circular dichroism) suggest that arene-complexes could interact with calf thymus DNA probably via an outside binding mode and interact with protein (BSA).

Keywords: ruthenium(II) complex, rhodium(III) complex, iridium(III) complex, biological activity

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Authors: Elaf Ahmed, Shahid Rasul, Ohoud Alharbi, Peng Wang

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Ultra-Small Nanoparticles of metals (USNPs) have attracted the attention from the perspective of both basic and developmental science in a wide range of fields. These NPs exhibit electrical, optical, magnetic, and catalytic phenomena. In addition, they are considered effective catalysts because of their enormously large surface area. Many chemical methods of synthesising USNPs are reported. However, the drawback of these methods is the use of different capping agents and ligands in the process of the production such as Polyvinylpyrrolidone, Thiol and Ethylene Glycol. In this research ultra-small nanoparticles of gold, palladium and platinum metal have been successfully produced using electrochemically active biofilm (EAB) after optimising the pH of the media. The production of ultra-small nanoparticles has been conducted in a reactor using a simple two steps method. Initially biofilm was grown on the surface of a carbon paper for 7 days using Shewanella Loihica bacteria. Then, biofilm was employed to synthesise platinum, palladium and gold nanoparticles in water using sodium lactate as electron donor without using any toxic chemicals at mild operating conditions. Electrochemically active biofilm oxidise the electron donor and produces electrons in the solution. Since these electrons are a strong reducing agent, they can reduce metal precursors quite effectively and quickly. The As-synthesized ultra-small nanoparticles have a size range between (2-7nm) and showed excellent catalytic activity on the degradation of methyl orange. The growth of metal USNPs is strongly related to the condition of the EAB. Where using low pH for the synthesis was not successful due to the fact that it might affect and destroy the bacterial cells. However, increasing the pH to 7 and 9, led to the successful formation of USNPs. By changing the pH value, we noticed a change in the size range of the produced NPs. The EAB seems to act as a Nano factory for the synthesis of metal nanoparticles by offering a green, sustainable and toxic free synthetic route without the use of any capping agents or ligands and depending only on their respiration pathway.

Keywords: electrochemically active biofilm, electron donor, shewanella loihica, ultra-small nanoparticles

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Authors: N. Laosiripojana, P. Tepamatr

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The influence of bismuth on the water gas shift activities of Pt on ceria was studied. The flow reactor was used to study the activity of the catalysts in temperature range 100-400°C. The feed gas composition contains 5%CO, 10% H₂O and balance N₂. The total flow rate was 100 mL/min. The outlet gas was analyzed by on-line gas chromatography with thermal conductivity detector. The catalytic activities of bimetallic 1%Pt1%Bi/CeO₂ catalyst were greatly enhanced when compared with the activities of monometallic 2%Pt/CeO₂ catalyst. The catalysts were characterized by X-ray diffraction (XRD), Temperature-Programmed Reduction (TPR) and surface area analysis. X-ray diffraction pattern of Pt/CeO₂ and PtBi/CeO₂ indicated slightly shift of diffraction angle when compared with pure ceria. This result was due to strong metal-support interaction between platinum and ceria solid solution, causing conversion of Ce⁴⁺ to larger Ce³⁺. The distortions inside ceria lattice structure generated strain into the oxide lattice and facilitated the formation of oxygen vacancies which help to increase water gas shift performance. The H₂-Temperature Programmed Reduction indicated that the reduction peak of surface oxygen of 1%Pt1%Bi/CeO₂ shifts to lower temperature than that of 2%Pt/CeO₂ causing the enhancement of the water gas shift activity of this catalyst. Pt played an important role in catalyzing the surface reduction of ceria and addition of Bi alter the reduction temperature of surface ceria resulting in the improvement of the water gas shift activity of Pt catalyst.

Keywords: bismuth, platinum, water gas shift, ceria

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Authors: Safa'a M. Rasheed, Saba A. Gheni, Wadood T. Mohamed

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Phenolic compounds are the most carcinogenic pollutants in waste water in effluents of refineries and pulp industry. Catalytic wet air oxidation is an efficient industrial treatment process to oxidize phenolic compounds into unharmful organic compounds. Mode of flow of the fluid to be treated is a dominant factor in determining effectiveness of the catalytic process. The present study aims to obtain a mathematical model describing the conversion of phenolic compounds as a function of the process variables; mode of flow (trickling and pulsing), temperature, pressure, along with a high concentration of phenols and a platinum supported alumina catalyst. The model was validated with the results of experiments obtained in a fixed bed reactor. High pressure and temperature were employed at 8 bar and 140 °C. It has been found that conversion of phenols is highly influenced by mode of flow and the change is caused by changes occurred in hydrodynamic regime at the time of pulsing flow mode, thereby a temporal variation in wetting efficiency of platinum prevails; which in turn increases and/or decreases contact time with phenols in wastewater. The model obtained was validated with experimental results, and it is found that the model is a good agreement with the experimental results.

Keywords: wastewater, phenol, pulsing flow, wet oxidation, high pressure

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Authors: Alka Jakhar, Harmanpreet Kaur Sandhu, Samaresh Das

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The Terahertz (THz) technology-based devices are heightening at an alarming rate on account of the wide range of applications in imaging, security, communication, and spectroscopic field. The various available room operational THz detectors, including Golay cell, pyroelectric detector, field-effect transistors, and photoconductive antennas, have some limitations such as narrow-band response, slow response speed, transit time limits, and complex fabrication process. There is an urgent demand to explore new materials and device structures to accomplish efficient THz detection systems. Recently, TMDs including topological semimetals and topological insulators such as PtSe₂, MoTe₂, WSe₂, and PtTe₂ provide novel feasibility for photonic and optical devices. The peculiar properties of these materials, such as Dirac cone, fermions presence, nonlinear optical response, high conductivity, and ambient stability, make them worthy for the development of the THz devices. Here, the platinum telluride (PtTe₂) based devices have been demonstrated for THz detection in the frequency range of 0.1-1 THz. The PtTe₂ is synthesized by direct selenization of the sputtered platinum film on the high-resistivity silicon substrate by using the chemical vapor deposition (CVD) method. The Raman spectra, XRD, and XPS spectra confirm the formation of the thin PtTe₂ film. The PtTe₂ channel length is 5µm and it is connected with a bow-tie antenna for strong THz electric field confinement in the channel. The characterization of the devices has been carried out in a wide frequency range from 0.1-1 THz. The induced THz photocurrent is measured by using lock-in-amplifier after preamplifier. The maximum responsivity is achieved up to 1 A/W under self-biased mode. Further, this responsivity has been increased by applying biasing voltage. This photo response corresponds to low energy THz photons is mainly due to the photo galvanic effect in PtTe₂. The DC current is induced along the PtTe₂ channel, which is directly proportional to the amplitude of the incident THz electric field. Thus, these new topological semimetal materials provide new pathways for sensitive detection and sensing applications in the THz domain.

Keywords: terahertz, detector, responsivity, topological-semimetals

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Authors: Omoruyi G. Idemudia, Alexander P. Sadimenko

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The need for the development of new sustainable bioactive compounds with unique properties that can become potential replacement for commonly used medicinal drugs has continued to gain tremendous research concerns because of the problems of disease resistant to these medicinal drugs and their toxicity effects. NOS-donor heterocycles are particularly of interest as they have showed good pharmacological activities in the midst of their interesting chelating properties towards metal ions, an important characteristic for transition metal based drugs design. These new compounds have also gained application as dye sensitizers in solar cell panels for the generation of renewable solar energy, as greener water purification polymer for supply and management of clean water and as catalysts which are used to reduce the amount of pollutants from industrial reaction processes amongst others, because of their versatile properties. Di-ketone acylpyrazolones and their azomethine schiff bases have been employed as pharmaceuticals as well as analytical reagents, and their application as transition metal complexes have being well established. In this research work, a new 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one-thiosemicarbazone was synthesized from the reaction of 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one and thiosemicarbazide in methanol. The pure isolate of the thiosemicarbazone was further reacted with aqueous solutions of palladium and platinum salts to obtain their metal complexes, in an effort towards the discovery of transition metal based synthetic drugs. These compounds were characterized by means of analytical, spectroscopic, thermogravimetric analysis TGA, as well as x-ray crystallography. 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one thiosemicarbazone crystallizes in a triclinic crystal system with a P-1 (No. 2) space group according to x-ray crystallography. The tridentate NOS ligand formed a tetrahedral geometry on coordinating with metal ions. Reported compounds showed varying antioxidant free radical scavenging activities against 2, 2-diphenyl-1-picrylhydrazyl DPPH radical at 100, 200, 300, 400 and 500 µg/ml concentrations. The platinum complex have shown a very good antioxidant property against DPPH with an IC50 of 76.03 µg/ml compared with standard ascorbic acid (IC50 of 74.66 µg/ml) and as such have been identified as a potential anticancer candidate.

Keywords: acylpyrazolone, free radical scavenging activities, tridentate ligand, x-ray crystallography

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Authors: Menouar Hanafi

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The original function of the process of platforming is to develop heavy naphtha (HSRN), coming from the atmospheric unit of distillation with a weak octane number (NO=44), to obtain a mixture of fuels â number octane raised by catalytically supporting specific groups of chemical reactions. The installation is divided into two sections: Section hydrobon. Section platforming. The rafinat coming from the bottom of column 12C2 to feed the section platforming, is divided into two parts whose flows are controlled and mixed with gas rich in hydrogen. Bottom of the column, we obtain stabilized reformat which is aspired by there pump to ensure the heating of the column whereas a part is sent towards storage after being cooled by the air cooler and the condenser. In catalytic catalyst of reforming, there is voluntarily associated a hydrogenating function-dehydrogenating, brought by platinum deposited, with an acid function brought by the alumina support (Al 2 0 3). The mechanism of action of this bifunctional catalyst depends on the severity of the operation, of the quality of the load and the type of catalyst. The catalyst used in the catalytic process of reforming is a very elaborate bifunctional catalyst whose performances are constantly improved thanks to the experimental research supported on an increasingly large comprehension of the phenomena. The American company Universel 0i1 petroleum (UOP) marketed several series of bimetallic catalysts such as R16, R20, R30, and R62 consisted Platinum/Rhenium on an acid support consisted the alumina added with a halogenous compound (chlorine).

Keywords: platforming, amelioration, octane number, catalyst

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Authors: Ashima Sharma

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Human Serum Albumin (HSA)- one of the most demanded therapeutic proteins with immense biotechnological applications- is a large multidomain protein containing 17 disulfide bonds. The current source of HSA is human blood plasma which is a limited and unsafe source. Thus, there exists an indispensable need to promote non-animal derived recombinant HSA (rHSA) production. Escherichia coli is one of the most convenient hosts which had contributed to the production of more than 30% of the FDA approved recombinant pharmaceuticals. It grows rapidly and reaches high cell density using inexpensive and simple substrates. E. coli derived recombinant products have more economic potential as fermentation processes are cheaper compared to the other expression hosts. The major bottleneck in exploiting E. coli as a host for a disulfide-rich multidomain protein is the formation of aggregates of overexpressed protein. The majority of the expressed HSA forms inclusion bodies (more than 90% of the total expressed rHSA) in the E. coli cytosol. Recovery of functional rHSA from inclusion bodies is not preferred because it is difficult to obtain a large multidomain disulfide bond rich protein like rHSA in its functional native form. Purification is tedious, time-consuming, laborious and expensive. Because of such limitations, the E. coli host system was neglected for rHSA production for the past few decades despite its numerous advantages. In the present work, we have exploited the capabilities of E. coli as a host for the enhanced functional production of rHSA (~60% of the total expressed rHSA in the soluble fraction). Parameters like intracellular environment, temperature, induction type, duration of induction, cell lysis conditions etc. which play an important role in enhancing the level of production of the desired protein in its native form in vivo have been optimized. We have studied the effect of assistance of different types of exogenously employed chaperone systems on the functional expression of rHSA in the E. coli host system. Different aspects of cell growth parameters during the production of rHSA in presence and absence of molecular chaperones in E. coli have also been studied. Upon overcoming the difficulties to produce functional rHSA in E. coli, it has been possible to produce significant levels of functional protein through engineering the biological system of protein folding in the cell, the E. coli-derived rHSA has been purified to homogeneity. Its detailed physicochemical characterization has been performed by monitoring its conformational properties, secondary and tertiary structure elements, surface properties, ligand binding properties, stability issues etc. These parameters of the recombinant protein have been compared with the naturally occurring protein from the human source. The outcome of the comparison reveals that the recombinant protein resembles exactly the same as the natural one. Hence, we propose that the E. coli-derived rHSA is an ideal biosimilar for human blood plasma-derived serum albumin. Therefore, in the present study, we have introduced and promoted the E. coli- derived rHSA as an alternative to the preparation from a human source, pHSA.

Keywords: recombinant human serum albumin, Escherichia coli, biosimilar, chaperone assisted protein folding

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Authors: Fredrick O. Okumu, Mangaka C. Matoetoe

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Silver-platinum (Ag-Pt) bimetallic nanoparticles (NPs) with varying mole fractions (1:1, 1:3 and 3:1) were prepared by co-reduction of hexachloroplatinate and silver nitrate with sodium citrate. Upon successful formation of both monometallic and bimetallic (BM) core shell nanoparticles, cyclic voltammetry (CV) was used to characterize the NPs. The drop coated nanofilms on the GC substrate showed characteristic peaks of monometallic Ag NPs; Ag+/Ag0 redox couple as well as the Pt NPs; hydrogen adsorption and desorption peaks. These characteristic peaks were confirmed in the bimetallic NPs voltammograms. The following varying current trends were observed in the BM NPs ratios; GCE/Ag-Pt 1:3 > GCE/Ag-Pt 3:1 > GCE/Ag-Pt 1:1. Fundamental electrochemical properties which directly or indirectly affects the applicability of films such as; diffusion coefficient (D), electroactive surface coverage, electrochemical band gap, electron transfer coefficient (α) and charge (Q) were assessed using Randles - Sevcik plot and Laviron’s equations . High charge and surface coverage was observed in GCE/Ag-Pt 1:3 which supports its enhanced current. GCE/Ag-Pt 3:1 showed high diffusion coefficient while GCE/Ag-Pt 1:1 possessed high electron transfer coefficient that is facilitated by its high apparent heterogeneous rate constant relative to other BM NPs ratios. Surface redox reaction was determined as adsorption controlled in all modified GCEs. Surface coverage is inversely proportional to size; therefore the surface coverage data suggests that Ag-Pt 1:1 NPs have a small particle size. Generally, GCE/Ag-Pt 1:3 depicts the best electrochemical properties.

Keywords: characterization, core-shell, electrochemical, nanoparticles

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Authors: Eslam Dabbish, Fortuna Ponte, Stefano Scoditti, Emilia Sicilia, Gloria Mazzone

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The medical techniques based on the use of light for activating the drug are occupying a prominent place in the cancer treatment due to their selectivity that contributes to reduce undesirable side effects of conventional chemotherapy. Among these therapeutic treatments, photodynamic therapy (PDT) and photoactivated chemotherapy (PACT) are emerging as complementary approaches for selective destruction of neoplastic tissue through direct cellular damage. Both techniques rely on the employment of a molecule, photosensitizer (PS), able to absorb within the so-called therapeutic window. Thus, the exposure to light of otherwise inert molecules promotes the population of excited states of the drug, that in PDT are able to produce the cytotoxic species, such as 1O2 and other ROS, in PACT can be responsible of the active species release or formation. Following the success of cisplatin in conventional treatments, many other transition metal complexes were explored as anticancer agents for applications in different medical approaches, including PDT and PACT, in order to improve their chemical, biological and photophysical properties. In this field, several crucial characteristics of candidate PSs can be accurately predicted from first principle calculations, especially in the framework of density functional theory and its time-dependent formulation, contributing to the understanding of the entire photochemical pathways involved which can ultimately help in improving the efficiency of a drug. A brief overview of the outcomes on some platinum and ruthenium-based PSs proposed for the application in the two phototherapies will be provided.

Keywords: TDDFT, metal complexes, PACT, PDT

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Authors: Sarre Nzaba, Bulelwa Ntsendwana, Bekkie Mamba, Alex Kuvarega

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Elimination of toxic organic compounds from wastewater is currently one of the most important subjects in water pollution control. The discharge of azo dyes such as Brilliant black (BB) into the water bodies has carcinogenic and mutagenic effects on humankind and the ecosystem. Conventional water treatment techniques fail to degrade these dyes completely thereby posing more problems. Advanced oxidation processes (AOPs) are promising technologies in solving the problem. Anatase type nitrogen-platinum (N,Pt) co-doped TiO₂ photocatalyts were prepared by a modified sol-gel method using amine terminated polyamidoamine generation 1 (PG1) as a template and source of nitrogen. SEM/ EDX, TEM, XRD, XPS, TGA, FTIR, RS, PL and UV-Vis were used to characterize the prepared nanomaterials. The synthesized photocatalysts exhibited lower band gap energies as compared to the commercial TiO₂ revealing a shift in band gap towards the visible light absorption region. Photocatalytic activity of N,Pt co-doped TiO₂ was measured by the reaction of photocatalytic degradation of BB dye. Enhanced photodegradation efficiency of BB was achieved after 180 min reaction time with initial concentration of 50 ppm BB solution. This was attributed to the rod-like shape of the materials, larger surface area, and enhanced absorption of visible light induced by N,Pt co-doping. The co-doped N,Pt also exhibited pseudo-first order kinetic behaviour with half-life and rate constant of 0.37 min 0.1984 min⁻¹ and respectively. N doped TiO₂ and N,Pt co-doped TiO₂ exhibited enhanced photocatalytic performances for the removal of BB from water.

Keywords: N, Pt co-doped TiO₂, dendrimer, photodegradation, visible-light

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Authors: Livhuwani Muthelo, R. N. Malema, T. M. Mothiba

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Long term exposure to excessive noise in the mining industry increases the risk of noise induced hearing loss, with consequences for employee’s health, productivity and the overall quality of life. Objective: The objective of this study was to investigate the factors that contribute to Noise Induced Hearing Loss amongst employees at the Platinum mine in the Limpopo Province, South Africa. Study method: A qualitative, phenomenological, exploratory, descriptive, contextual design was applied in order to explore and describe the contributory factors. Purposive non-probability sampling was used to select 10 male employees who were diagnosed with NIHL in the year 2014 in four mine shafts, and 10 managers who were involved in a Hearing Conservation Programme. The data were collected using semi-structured one-on-one interviews. A qualitative data analysis of Tesch’s approach was followed. Results: The following themes emerged: Experiences and challenges faced by employees in the work environment, hearing protective device factors and management and leadership factors. Hearing loss was caused by partial application of guidelines, policies, and procedures from the Department of Minerals and Energy. Conclusion: The study results indicate that although there are guidelines, policies, and procedures available, failure in the implementation of one element will affect the development and maintenance of employees hearing mechanism. It is recommended that the mine management should apply the guidelines, policies, and procedures and promptly repair the broken hearing protective devices.

Keywords: employees, factors, noise induced hearing loss, noise exposure

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Authors: Nokubonga G. Zulu, Bongephiwe M. Thethwayo, Mapilane S. Madiba, Peter A. Olubambi

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In South Africa, PGMs’ metallurgy industry is now leaned on the Upper Group 2 (UG2) reef for the beneficiation of 4PGEs (Platinum, Palladium, Rhodium, and Ruthenium). The current effective beneficiation method is direct froth flotation which uses the hydrophobicity of liberated valuables minerals to carefully float them while hydrophilic gangue minerals report to the residue. PGMs are known to be associated with base metal sulphides which are hydrophobic; however, approximately 25% of PGMs from UG2 are associated with hydrophilic silicates, which results in high PGMs grade in the flotation residue. Further, the smallest size in which UG2 PGMs occur is approximately 9 microns which demands high grinding for liberation, imposing energy and cost implications. The use of Bacillus mucilaginosus to liberate PGMs using Bio-leaching of PGMs bearing Silicates is a promising cost-effective, energy-saving, and green solution to liberate PGMs locked in silicates. This is due to the ability of Bacillus mucilaginosus to generate extracellular polysaccharides (EPS) that are responsible for the leaching of silicate minerals. The bioleaching is done at a laboratory beaker using a cultivated Bacillus mucilaginosus as a lixiviant. The bioleaching residue is expected to have a reduced particle size due to silicate consumption, which reduces the need and cost associated with a secondary milling circuit. Moreover, the grade of the bioleaching product is increased since the silicates (gangue minerals) are consumed by Bacillus mucilaginosus; this serves as a pre-concentration step. This paper discusses an alternative liberation and pre-concentrating technique of PGMs that are associated with silicates using Bacillus mucilaginosus leaching to dissolve silicates.

Keywords: Bacillus mucilaginosus, bio-leaching of PGMs bearing silicates, liberation of PGMs, pre-concentration of PGMs

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Authors: Yingjeng James Li, Yun Jyun Ou, Chih Chi Hsu, Chiao-Chih Hu

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A fuel cell is a device that produces electric power by reacting fuel and oxidant electrochemically. There is no pollution produced from a fuel cell if hydrogen is employed as the fuel. Therefore, a fuel cell is considered as a zero emission device and is a source of green power. A membrane electrode assembly (MEA) is the key component of a fuel cell. It is, therefore, beneficial to develop MEAs with high performance. In this study, an MEA for proton exchange membrane fuel cell (PEMFC) was prepared from a 15-micron thick reinforced PEM. The active area of such MEA is 25 cm2. Carbon supported platinum (Pt/C) was employed as the catalyst for both anode and cathode. The platinum loading is 0.6 mg/cm2 based on the sum of anode and cathode. Commercially available carbon papers coated with a micro porous layer (MPL) serve as gas diffusion layers (GDLs). The original thickness of the GDL is 250 μm. It was compressed down to 163 μm when assembled into the single cell test fixture. Polarization curves were taken by using eight different test conditions. At our standard test condition (cell: 70 °C; anode: pure hydrogen, 100%RH, 1.2 stoic, ambient pressure; cathode: air, 100%RH, 3.0 stoic, ambient pressure), the cell current density is 1250 mA/cm2 at 0.6 V, and 2400 mA/cm2 at 0.4 V. At self-humidified condition and cell temperature of 55 °C, the cell current density is 1050 mA/cm2 at 0.6 V, and 2250 mA/cm2 at 0.4 V. Hydrogen crossover rate of the MEA is 0.0108 mL/min*cm2 according to linear sweep voltammetry experiments. According to the MEA’s Pt loading and the cyclic voltammetry experiments, the Pt electrochemical surface area is 60 m2/g. The ohmic part of the impedance spectroscopy results shows that the membrane resistance is about 60 mΩ*cm2 when the MEA is operated at 0.6 V.

Keywords: fuel cell, membrane electrode assembly, proton exchange membrane, reinforced

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Authors: Merve Yünlü, Nihat Kandemir, Aylin Ersoy

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Temperature sensors are used in home appliances not only to monitor the basic functions of the machine but also to minimize energy consumption and ensure safe operation. In parallel with the development of smart home applications and IoT algorithms, these sensors produce important data such as the frequency of use of the machine, user preferences, and the compilation of critical data in terms of diagnostic processes for fault detection throughout an appliance's operational lifespan. Commercially available thin-film resistive temperature sensors have a well-established manufacturing procedure that allows them to operate over a wide temperature range. However, these sensors are over-designed for white goods applications. The operating temperature range of these sensors is between -70°C and 850°C, while the temperature range requirement in home appliance applications is between 23°C and 500°C. To ensure the operation of commercial sensors in this wide temperature range, usually, a platinum coating of approximately 1-micron thickness is applied to the wafer. However, the use of platinum in coating and the high coating thickness extends the sensor production process time and therefore increases sensor costs. In this study, an attempt was made to develop a low-cost temperature sensor design and production method that meets the technical requirements of white goods applications. For this purpose, a custom design was made, and design parameters (length, width, trim points, and thin film deposition thickness) were optimized by using statistical methods to achieve the desired resistivity value. To develop thin film resistive temperature sensors, one side polished sapphire wafer was used. To enhance adhesion and insulation 100 nm silicon dioxide was coated by inductively coupled plasma chemical vapor deposition technique. The lithography process was performed by a direct laser writer. The lift-off process was performed after the e-beam evaporation of 10 nm titanium and 280 nm platinum layers. Standard four-point probe sheet resistance measurements were done at room temperature. The annealing process was performed. Resistivity measurements were done with a probe station before and after annealing at 600°C by using a rapid thermal processing machine. Temperature dependence between 25-300 °C was also tested. As a result of this study, a temperature sensor has been developed that has a lower coating thickness than commercial sensors but can produce reliable data in the white goods application temperature range. A relatively simplified but optimized production method has also been developed to produce this sensor.

Keywords: thin film resistive sensor, temperature sensor, household appliance, sustainability, energy efficiency

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Authors: Omoruyi Gold Idemudia, Alexander P. Sadimenko

Abstract:

The synthesis of N-heterocycles with novel properties, having broad spectrum biological activities that may become alternative medicinal drugs, have been attracting a lot of research attention due to the emergence of medicinal drug’s limitations such as disease resistance and their toxicity effects among others. Acylpyrazolones have been employed as pharmaceuticals as well as analytical reagent and their application as coordination complexes with transition metal ions have been well established. By way of a condensation reaction with amines acylpyrazolone ketones form a more chelating and superior group of compounds known as azomethines. 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one was reacted with phenylhydrazine to get a new phenylhydrazone which was further reacted with aqueous solutions of palladium and platinum salts, in an effort towards the discovery of transition metal based synthetic drugs. The compounds were characterized by means of analytical, spectroscopic, thermogravimetric analysis TGA, as well as x-ray crystallography. 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one phenylhydrazone crystallizes in a triclinic crystal system with a P-1 (No. 2) space group based on x-ray crystallography. The bidentate ON ligand formed a square planar geometry on coordinating with metal ions based on FTIR, electronic and NMR spectra as well as magnetic moments. Reported compounds showed antibacterial activities against the nominated bacterial isolates using the disc diffusion technique at 20 mg/ml in triplicates. The metal complexes exhibited a better antibacterial activity with platinum complex having an MIC value of 0.63 mg/ml. Similarly, ligand and complexes also showed antioxidant scavenging properties against 2, 2-diphenyl-1-picrylhydrazyl DPPH radical at 0.5mg/ml relative to ascorbic acid (standard drug).

Keywords: acylpyrazolone, antibacterial studies, metal complexes, phenylhydrazone, spectroscopy

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Authors: A. Attaf, I. Bouhaf Kharkhachi

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Hexagonal tin disulfide (SnS2) films were deposited by spray ultrasonic technique on glass substrates at different experimental conditions. The effect of deposition time (2, 4, 6, and 7 min) on different properties of SnS2 thin films was investigated by XRD and UV spectroscopy visible spectrum. X-ray diffraction study detected the preferential orientation growth of SnS2 compound having structure along (001) plane increased with the deposition time. The results of UV spectroscopy visible spectrum showed that films deposited at 4 min have high transmittance, up to 60%, in the visible region.

Keywords: structural and optical properties, tin sulfide, thin films, ultrasonic spray

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Authors: Bernd Sauer, Michel Werner, Stefan Emrich, Michael Kopnarski, Oliver Koch

Abstract:

Friction reduction is an important aspect in the context of sustainability and energy transition. Rolling bearings are therefore used in many applications in which components move relative to each other. Conventionally lubricated rolling bearings are used in a wide range of applications, but are not suitable under certain conditions. Conventional lubricants such as grease or oil cannot be used at very high or very low temperatures. In addition, these lubricants evaporate at very low ambient pressure, e.g. in a high vacuum environment, making the use of solid lubricated bearings unavoidable. With the use of solid-lubricated bearings, predicting the service life becomes more complex. While the end of the service life of bearings with conventional lubrication is mainly caused by the failure of the bearing components due to material fatigue, solid-lubricated bearings fail at the moment when the lubrication layer is worn and the rolling elements come into direct contact with the raceway during operation. In order to extend the service life of these bearings beyond the service life of the initial coating, the use of transfer lubrication is recommended, in which pockets or sacrificial cages are used in which the balls run and can thus absorb the lubricant, which is then available for lubrication in tribological contact. This contribution presents the results of wear and service life tests on solid-lubricated rolling bearings with sacrificial cage pockets. The cage of the bearing consists of a polyimide (PI) matrix with 15% molybdenum disulfide (MoS2) and serves as a lubrication depot alongside the silver-coated balls. The bearings are tested under high vacuum (pE < 10-2 Pa) at a temperature of 300 °C on a four-bearing test rig. First, investigations of the bearing system within the bearing service life are presented and the torque curve, the wear mass and surface analyses are discussed. With regard to wear, it can be seen that the bearing rings tend to increase in mass over the service life of the bearing, while the balls and the cage tend to lose mass. With regard to the elementary surface properties, the surfaces of the bearing rings and balls are examined in terms of the mass of the elements on them. Furthermore, service life investigations with different material pairings are presented, whereby the focus here is on the service life achieved in addition to the torque curve, wear development and surface analysis. It was shown that MoS2 in the cage leads to a longer service life, while a silver (Ag) coating on the balls has no positive influence on the service life and even appears to reduce it in combination with MoS2.

Keywords: ball bearings, molybdenum disulfide, solid lubricated bearings, solid lubrication mechanisms

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Authors: J. Tomilla Ajayi, Werner E. Van Zyl

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This work presents an overview of the reaction of 2, 4-diferrocenyl-1, 3-dithiadiphosphetane-2, 4-disulfide (Ferrocenyl Lawesson’s reagent) with water to produce the non-symmetric, ferocenyl dithiophosphonic acid respectively in high yields. These acids were readily deprotonated by anhydrous Ammonia to yield the corresponding ammonium salt NH4S2PFcOH. These were complex to Ni (II) in molar ratio 1:1 and 1:2. The resulting complex from the reaction formed same compound with different isomers (Cis and Trans) and also compound with multimetallic coordination. Quality X-ray crystals were formed from THF/Ether. The compounds were characterized by 1H, 31P NMR, and FTIR. Bulk purity were confirmed by either ESI-MS or elemental analysis and The XRD images were obtained using single crystal X-ray crystallographic studies. The electrochemical investigation of the Compounds were carried out using cyclic voltammetry.

Keywords: ferrocenyl, dithiophosphonate, isomer, coordination

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Authors: Amgad A. Farghal, Dina I. El Desouki

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Energy consumption and users’ satisfaction were compared in three LEED certified office buildings in turkey and an office building in Egypt. The field studies were conducted in summer 2012. The measured environmental parameters in the four buildings were indoor air temperature, relative humidity, CO2 percentage and light intensity. The traditional building is located in Smart Village in Abu Rawash, Cairo, Egypt. The building was studied for 7 days resulting in 84 responds. The three rated buildings are in Istanbul; Turkey. A Platinum LEED certified office building is owned by BASF and gained a platinum certificate for new construction and major renovation. The building was studied for 3 days resulting in 13 responds. A Gold LEED certified office building is owned by BASF and gained a gold certificate for new construction and major renovation. The building was studied for 2 days resulting in 10 responds. A silver LEED certified office building is owned by Unilever and gained a silver certificate for commercial interiors. The building was studied for 7 days resulting in 84 responds. The results showed that all buildings had no significant difference regarding occupants’ satisfaction with the amount of lighting, noise level, odor and access to the outdoor view. There was significant difference between occupants’ satisfaction in LEED certified buildings and the traditional building regarding the thermal environment and the perception of the general environment (colors, carpet and decoration. The findings suggest that careful design could lead to a certified building that enhances the thermal environment and the perception of the indoor environment leading to energy consumption without scarifying occupants’ satisfaction.

Keywords: energy consumption, occupants’ satisfaction, rating systems, office buildings

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Authors: Vishnu S. Prasad, Preeti Aghalayam

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The major harmful automobile exhausts are nitric oxide (NO) and unburned hydrocarbon (HC). Reduction of NO using unburned fuel HC as a reductant is the technique used in hydrocarbon-selective catalytic reduction (HC-SCR). In this work, we study the microkinetic modelling of NO reduction using propene as a reductant on Pt catalysts. The selectivity of NO reduction to N₂O is detected in some ranges of operating conditions, whereas the effect of inlet O₂% causes a number of changes in the feasible regimes of operation.

Keywords: microkinetic modelling, NOx, platinum on alumina catalysts, selective catalytic reduction

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Authors: Thirupathi Thippani, Kothandaraman Ramanujam

Abstract:

Current research on energy storage has been paid to metal-air batteries, because of attractive alternate energy source for the future. Metal – air batteries have the probability to significantly increase the power density, decrease the cost of energy storage and also used for a long time due to its high energy density, low-level pollution, light weight. The performance of these batteries mostly restricted by the slow kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on cathode during battery discharge and charge. The ORR and OER are conventionally carried out with precious metals (such as Pt) and metal oxides (such as RuO₂ and IrO₂) as catalysts separately. However, these metal-based catalysts are regularly undergoing some difficulties, including high cost, low selectivity, poor stability and unfavorable to environmental effects. So, in order to develop the active, stable, corrosion resistance and inexpensive bi-functional catalyst material is mandatory for the commercialization of zinc-air rechargeable battery technology. We have attempted and synthesized non-precious metal (NPM) catalysts comprising cobalt and N-doped multiwalled carbon nanotubes (N-MWCNTs-Co) were synthesized by the solid-state pyrolysis (SSP) of melamine with Co₃O₄. N-MWCNTs-Co acts as an excellent electrocatalyst for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), and hence can be used in secondary metal-air batteries and in unitized regenerative fuel cells. It is important to study the OER and ORR at high concentrations of KOH as most of the metal-air batteries employ KOH concentrations > 4M. In the first 16 cycles of the zinc-air battery while using N-MWCNTs-Co, 20 wt.% Pt/C or 20 wt.% IrO₂/C as air electrodes. In the ORR regime (the discharge profile of the zinc-air battery), the cell voltage exhibited by N-MWCNTs-Co was 44 and 83 mV higher (based on 5th cycle) in comparison to of 20 wt.% Pt/C and 20 wt.% IrO₂/C respectively. To demonstrate this promise, a zinc-air battery was assembled and tested at a current density of 0.5 Ag⁻¹ for charge-discharge 100 cycles.

Keywords: oxygen reduction reaction (ORR), oxygen evolution reaction(OER), non-platinum, zinc air battery

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Authors: Guillaume Soubeyran, Fabrice Micoud, Benoit Morin, Jean-Philippe Poirot-Crouvezier, Magali Reytier

Abstract:

Proton Exchange Membrane Fuel Cell (PEMFC) technology is considered as a solution for the reduction of CO2 emissions. However, this technology still meets several challenges for high-scale industrialization. In this context, the increase of durability remains a critical aspect for competitiveness of this technology. Fortunately, performance degradations in nominal operating conditions is partially reversible, meaning that if specific conditions are applied, a partial recovery of fuel cell performance can be achieved, while irreversible degradations can only be mitigated. Thus, it is worth studying the optimal conditions to rejuvenate these reversible degradations and assessing the long-term impact of such procedures on the performance of the cell. Reversible degradations consist mainly of anode Pt active sites poisoning by carbon monoxide at the anode, heterogeneities in water management during use, and oxidation/deactivation of Pt active sites at the cathode. The latter is identified as a major source of reversible performance loss caused by the presence oxygen, high temperature and high cathode potential that favor platinum oxidation, especially in high efficiency operating points. Hence, we studied here a recovery procedure aiming at reducing the platinum oxides by decreasing cathode potential during operation. Indeed, the application of short air starvation phase leads to a drop of cathode potential. Cell performances are temporarily increased afterwards. Nevertheless, local temperature and current heterogeneities within the cells are favored and shall be minimized. The consumption of fuel during the recovery phase shall also be considered to evaluate the global efficiency. Consequently, the purpose of this work is to find an optimal compromise between the recovery of reversible degradations by air starvation, the increase of global cell efficiency and the mitigation of irreversible degradations effects. Different operating parameters have first been studied such as cell voltage, temperature and humidity in single cell set-up. Considering the global PEMFC system efficiency, tests showed that reducing duration of recovery phase and reducing cell voltage was the key to ensure an efficient recovery. Recovery phase frequency was a major factor as well. A specific method was established to find the optimal frequency depending on the duration and voltage of the recovery phase. Then, long-term degradations have also been studied by applying FC-DLC cycles based on NEDC cycles on a 4-cell short stack by alternating test sequences with and without recovery phases. Depending on recovery phase timing, cell efficiency during the cycle was increased up to 2% thanks to a mean voltage increase of 10 mV during test sequences with recovery phases. However, cyclic voltammetry tests results suggest that the implementation of recovery phases causes an acceleration of the decrease of platinum active areas that could be due to the high potential variations applied to the cathode electrode during operation.

Keywords: durability, PEMFC, recovery procedure, reversible degradation

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Authors: Abidullah, Basharat Hussain, Jong Seok Kim

Abstract:

Polymer electrolyte membrane fuel cell (PEMFC) is an electrochemical cell, which undergoes an oxygen reduction reaction to produce electrical energy. Platinum (Pt) metal has been used as a catalyst since its inception, but expensiveness is the major obstacle in the commercialization of fuel cells. Herein a non-precious group metal (NPGM) is employed instead of Pt to reduce the cost of PEMFCs. Manganese dioxide impregnated carbon nanotubes (MnO₂-CNTs composite) is a catalyst having excellent electrochemical properties and offers a better alternative to the Platinum-based PEMFC. The catalyst is synthesized by impregnating the transition metal on large surface carbonaceous CNTs by hydrothermal synthesis techniques. To enhance the catalytic activity and increase the volumetric current density, the sample was pyrolyzed at 800ᵒC under a nitrogen atmosphere. During pyrolysis, the nitrogen was doped in the framework of CNTs. Then the material was treated with acid for removing the unreacted metals and adding oxygen functional group to the CNT framework. This process ameliorates the catalytic activity of the manganese-based catalyst. The catalyst has been characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), and the catalyst activity has been examined by rotating disc electrode (RDE) experiment. The catalyst was strong enough to withstand an austere alkaline environment in experimental conditions and had a high electrocatalytic activity for oxygen reduction reaction (ORR). Linear Sweep Voltammetry (LSV) depicts an excellent current density of -4.0 mA/cm² and an overpotential of -0.3V vs. standard calomel electrode (SCE) in 0.1M KOH electrolyte. Rotating disk electrode (RDE) was conducted at 400, 800, 1200, and 1600 rpm. The catalyst exhibited a higher methanol tolerance and long term durability with respect to commercial Pt/C. The results for MnO₂-CNT show that the low-cost catalyst will supplant the expensive Pt/C catalyst in the fuel cell.

Keywords: carbon nanotubes, methanol fuel cell, oxygen reduction reaction, MnO₂-CNTs

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