Search results for: catalytic oxidation

Authors: Wei-Shan Wang, Klaus Vogel, Felix Gabler, Maik Wiemer, Thomas Gessner

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Metallic glasses, which are free of grain boundaries, have superior properties including large elastic limits, high strength, and excellent wear and corrosion resistance. Therefore, bulk metallic glasses (BMG) and thin film metallic glasses (TFMG) have been widely developed and investigated. Among various kinds of metallic glasses, Pd-Cu-Si TFMG, which has lower elastic modulus and better resistance of oxidation and corrosions compared to Zr- and Fe-based TFMGs, can be a promising candidate for MEMS applications. However, the study of Pd-TFMG membrane is still limited. This paper presents free-standing Pd-based metallic glass membranes with large area fabricated on wafer level for the first time. Properties of Pd-Cu-Si thin film metallic glass (TFMG) with various deposition parameters are investigated first. When deposited at 25°C, compressive stress occurs in the Pd76Cu6Si18 thin film regardless of Ar pressure. When substrate temperature is increased to 275°C, the stress state changes from compressive to tensile. Thin film stresses are slightly decreased when Ar pressure is higher. To show the influence of temperature on Pd-TFMGs, thin films without and with post annealing below (275°C) and within (370°C) supercooled liquid region are investigated. Results of XRD and TEM analysis indicate that Pd-TFMGs remain amorphous structure with well-controlled parameters. After verification of amorphous structure of the Pd-TFMGs, free-standing Pd-Cu-Si membranes were fabricated by depositing Pd-Cu-Si thin films directly on 200nm-thick silicon nitride membranes, followed by post annealing and dry etching of silicon nitride layer. Post annealing before SiNx removal is used to further release internal stress of Pd-TFMGs. The edge length of the square membrane ranges from 5 to 8mm. The effect of post annealing on Pd-Cu-Si membranes are discussed as well. With annealing at 370°C for 5 min, Pd-MG membranes are fully distortion-free after removal of SiNx layer. Results show that, by introducing annealing process, the stress-relief, distortion-free Pd-TFMG membranes with large area can be a promising candidate for sensing applications such as pressure and gas sensors.

Keywords: amorphous alloy, annealing, metallic glasses, TFMG membrane

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Authors: V. Sai Geethika, Sai Snehitha Yadavalli, Swati Ghosh Acharyya

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This study involves a single element and simultaneous electrochemical detection of heavy metal ions through square wave anodic stripping voltammetry. A glassy carbon electrode was used to detect and quantify heavy metals such as As(III), Hg(II), Cr(VI) ions in water. Under optimized conditions, peak separation was obtained by varying concentrations, scan rates, and temperatures. As (III), Hg (II), Cr (III) were simultaneously detected with GCE. Several analytical methods, such as inductively coupled plasma mass spectroscopy (ICP-MS), atomic absorption spectroscopy (AAS), were used previously to detect heavy metal ions, which are authentic but are not good enough for online monitoring due to the bulkiness of the equipment. The study provides a good alternative that is simple, more efficient, and low-cost, involving a portable potentiostat. Heavy metals having different oxidation states can be detected by anodic stripping voltammetry. This method can be easily integrated with electronics. Square wave Anodic stripping voltammetry is used with a potential range of -2.5 V – 2.5 V for single ion detection by a three-electrode cell consisting of silver/silver chloride(Ag/AgCl) as reference and platinum (Pt) counter and glassy carbon (GCE) working electrodes. All three ions are optimized by varying the parameters like concentration, scan rate, pH, temperature, and all these optimized parameters were used for studying the effects of simultaneous detection. The procedure involves preparing an electrolyte using deionized water, cleaning the surface of GCE, depositing the ions by applying the redox potentials obtained from cyclic voltammetry (CV), and then detecting by applying oxidizing potential, i.e., stripping voltage. So this includes ASV techniques such as open-circuit voltage (OCV), chronoamperometry (CA), and square wave voltammetry (SWV). Firstly, the concentration of the ions varied from 50 ppb to 5000 ppb, and an optimum concentration was determined where the three ions were detected. A concentration of 400 ppb was used while varying the temperatures in the range of 25°C – 45°C. Optimum peak intensity was obtained at a temperature of 30°C with a low scan rate of 0.005 V-s⁻¹. All the parameters were optimized, and several effects have been noticed while three ions As(II), Cr(III), Hg(II) were detected alone and simultaneously.

Keywords: Arsenic(III), Chromium(III), glassy carbon electrode, Mercury (II), square wave anodic stripping voltammetry

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Authors: Wee Tong Liaw, Elaine Wong Yee Sing

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The main objective and focus of this study are to establish the significance of a sustained health promoting workplace on stock and portfolio returns focusing on companies listed on the Singapore stock exchange, using a two-factor model comprising of the single factor CAPM and a 'health promoting workplace' factor. The 'health promoting workplace' factor represents the excess returns derived between two portfolios of component stocks that, when combined, would represent a top tier stock market index in Singapore, namely the STI index. The first portfolio represents companies that are independently assessed by the Singapore’s Health Award, SHA, to have a sustained and comprehensive health promoting workplace (SHA-STI portfolio) and the second portfolio represents companies that had not been independently assessed (Non-SHA STI portfolio). Since 2001, many companies in Singapore have voluntarily participated in the bi-annual Singapore HEALTH Award initiated by the Health Promotion Board of Singapore (HPB). The Singapore HEALTH Award (SHA), is an industry-wide award and assessment process. SHA assesses and recognizes employers in Singapore for implementing a comprehensive and sustainable health promotion programme at their workplaces. When using a ten year holding period instead of a one year holding period, excess returns in the SHA-STI portfolio over Non-SHA STI portfolio were consistently being observed over all test periods, during 2001 to 2013. In addition, when applied to the SHA-STI portfolio, results from the Two Factor Model consistently revealed higher explanatory powers across all test periods for the portfolio as well as all the individual component stocks in SHA-STI portfolio, than the single factor CAPM model. However, with respect to attaining higher level of achievement in the Singapore Health Award, this study did not show any incentive for selecting listed companies that have achieved a higher level of award. Results from this study would give further insights to investors and fund managers alike who intend to consider health promoting workplace as a risk factor in their stock or portfolio selection process, in particular for investors who have a preference for STI’s component stocks and with a longer investment horizon. Key micro factors like management abilities, business development strategies and production capabilities that meet the needs of market would create the demand for a company’s product(s) or service(s) and consequently contribute to its top line and profitability. Thereafter, the existence of a sustainable health promoting workplace would be a key catalytic factor in sustaining a productive workforce needed to support the continued success of a profitable business.

Keywords: asset pricing model, company's performance, stock returns, financial risk factor, sustained health promoting workplace

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Authors: Swati Tomar, Sunil Kumar Gupta

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Anammox is a promising and cost effective alternative to conventional treatment systems that facilitates direct oxidation of ammonium nitrogen under anaerobic conditions with nitrite as an electron acceptor without addition of any external carbon sources. The present study investigates the process kinetics of laboratory scale anammox hybrid reactor (AHR) which combines the dual advantages of attached and suspended growth. The performance & behaviour of AHR was studied under varying hydraulic retention time (HRTs) and nitrogen loading rate (NLRs). The experimental unit consisted of 4 numbers of 5L capacity anammox hybrid reactor inoculated with mixed seed culture containing anoxic and activated sludge. Pseudo steady state (PSS) ammonium and nitrite removal efficiencies of 90.6% and 95.6%, respectively, were achieved during acclimation phase. After establishment of PSS, the performance of AHR was monitored at seven different HRTs of 3.0, 2.5, 2.0, 1.5, 1.0, 0.5 and 0.25 d with increasing NLR from 0.4 to 4.8 kg N/m3d. The results showed that with increase in NLR and decrease in HRT (3.0 to 0.25 d), AHR registered appreciable decline in nitrogen removal efficiency from 92.9% to 67.4 %, respectively. The HRT of 2.0 d was considered optimal to achieve substantial nitrogen removal of 89%, because on further decrease in HRT below 1.5 days, remarkable decline in the values of nitrogen removal efficiency were observed. Analysis of data indicated that attached growth system contributes an additional 15.4 % ammonium removal and reduced the sludge washout rate (additional 29% reduction). This enhanced performance may be attributed to 25% increase in sludge retention time due to the attached growth media. Three kinetic models, namely, first order, Monod and Modified Stover-Kincannon model were applied to assess the substrate removal kinetics of nitrogen removal in AHR. Validation of the models were carried out by comparing experimental set of data with the predicted values obtained from the respective models. For substrate removal kinetics, model validation revealed that Modified Stover-Kincannon is most precise (R2=0.943) and can be suitably applied to predict the kinetics of nitrogen removal in AHR. Lawrence and McCarty model described the kinetics of bacterial growth. The predicted value of yield coefficient and decay constant were in line with the experimentally observed values.

Keywords: anammox, kinetics, modelling, nitrogen removal, sludge wash out rate, AHR

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Authors: Ying Li, Rui Hu, Shizhen Chen, Xin Zhou, Yunhuang Yang

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Prostate cancer is one of the leading causes of cancer-related death among men. Prostate-specific antigen (PSA), a specific product of prostatic epithelial cells, is an important indicator of prostate cancer. Though PSA is not a specific serum biomarker for the screening of prostate cancer, it is recognized as an indicator for prostate cancer recurrence and response to therapy for patient’s post-prostatectomy. Since radical prostatectomy eliminates the source of PSA production, serum PSA levels fall below 50 pg/mL, and may be below the detection limit of clinical immunoassays (current clinical immunoassay lower limit of detection is around 10 pg/mL). Many clinical studies have shown that intervention at low PSA levels was able to improve patient outcomes significantly. Therefore, ultra-sensitive and precise assays that can accurately quantify extremely low levels of PSA (below 1-10 pg/mL) will facilitate the assessment of patients for the possibility of early adjuvant or salvage treatment. Currently, the commercially available ultra-sensitive ELISA kit (not used clinically) can only reach a detection limit of 3-10 pg/mL. Other platforms developed by different research groups could achieve a detection limit as low as 0.33 pg/mL, but they relied on sophisticated instruments to get the final readout. Herein we report a microfluidic platform for point-of-care (POC) detection of PSA with a detection limit of 0.5 pg/mL and without the assistance of any equipment. This platform is based on a previously reported volumetric-bar-chart chip (V-Chip), which applies platinum nanoparticles (PtNPs) as the ELISA probe to convert the biomarker concentration to the volume of oxygen gas that further pushes the red ink to form a visualized bar-chart. The length of each bar is used to quantify the biomarker concentration of each sample. We devised a long reading channel V-Chip (LV-Chip) in this work to achieve a wide detection window. In addition, LV-Chip employed a unique enzyme-free ELISA probe that enriched PtNPs significantly and owned 500-fold enhanced catalytic ability over that of previous V-Chip, resulting in a significantly improved detection limit. LV-Chip is able to complete a PSA assay for five samples in 20 min. The device was applied to detect PSA in 50 patient serum samples, and the on-chip results demonstrated good correlation with conventional immunoassay. In addition, the PSA levels in finger-prick whole blood samples from healthy volunteers were successfully measured on the device. This completely stand-alone LV-Chip platform enables convenient POC testing for patient follow-up in the physician’s office and is also useful in resource-constrained settings.

Keywords: point-of-care detection, microfluidics, PSA, ultra-sensitive

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Authors: Katerina Zaharieva, Vicente Rives, Martin Tsvetkov, Raquel Trujillano, Boris Kunev, Ivan Mitov, Maria Milanova, Zara Cherkezova-Zheleva

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The nanostructured cobalt ferrite-type materials Sample A - Co0.25Fe2.75O4, Sample B - Co0.5Fe2.5O4, and Sample C - CoFe2O4 were prepared by co-precipitation in our previous investigations. The co-precipitated Sample B and Sample C were mechanochemically activated in order to produce Sample D - Co0.5Fe2.5O4 and Sample E- CoFe2O4. The PXRD, Moessbauer and FTIR spectroscopies, specific surface area determination by the BET method, thermal analysis, element chemical analysis and temperature-programmed reduction were used to investigate the prepared nano-sized samples. The changes of the Malachite green dye concentration during reaction of the photocatalytic decolorization using nanostructured cobalt ferrite-type catalysts with different chemical composition are included. The photocatalytic results show that the increase in the degree of incorporation of cobalt ions in the magnetite host structure for co-precipitated cobalt ferrite-type samples results in an increase of the photocatalytic activity: Sample A (4 х10-3 min-1) < Sample B (5 х10-3 min-1) < Sample C (7 х10-3 min-1). Mechanochemically activated photocatalysts showed a higher activity than the co-precipitated ferrite materials: Sample D (16 х10-3 min-1) > Sample E (14 х10-3 min-1) > Sample C (7 х10-3 min-1) > Sample B (5 х10-3 min-1) > Sample A (4 х10-3 min-1). On decreasing the degree of substitution of iron ions by cobalt ones a higher sorption ability of the dye after the dark period for the co-precipitated cobalt ferrite materials was observed: Sample C (72 %) < Sample B (78 %) < Sample A (80 %). Mechanochemically treated ferrite catalysts and co-precipitated Sample B possess similar sorption capacities, Sample D (78 %) ~ Sample E (78 %) ~ Sample B (78 %). The prepared nano-sized cobalt ferrite-type materials demonstrate good photocatalytic and sorption properties. Mechanochemically activated Sample D - Co0.5Fe2.5O4 (16х10-3 min-1) and Sample E-CoFe2O4 (14х10-3 min-1) possess higher photocatalytic activity than that of the most common used UV-light catalyst Degussa P25 (12х10-3 min-1). The dependence of the photo-catalytic activity and sorption properties on the preparation method and different degree of substitution of iron ions by cobalt ions in synthesized cobalt ferrite samples is established. The mechanochemical activation leads to formation of nano-structured cobalt ferrite-type catalysts (Sample D and Sample E) with higher rate constants than those of the ferrite materials (Sample A, Sample B, and Sample C) prepared by the co-precipitation procedure. The increase in the degree of substitution of iron ions by cobalt ones leads to improved photocatalytic properties and lower sorption capacities of the co-precipitated ferrite samples. The good sorption properties between 72 and 80% of the prepared ferrite-type materials show that they could be used as potential cheap absorbents for purification of polluted waters.

Keywords: nanodimensional cobalt ferrites, photocatalyst, synthesis, mechanochemical activation

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Authors: Emmanuel Billy

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This work is in the CABRISS project (H2020 projects) which aims at developing innovative cost-effective methods for the extraction of materials from the different sources of PV waste: Si based panels, thin film panels or Si water diluted slurries. Aluminum, silicon, indium, and silver will especially be extracted from these wastes in order to constitute materials feedstock which can be used later in a closed-loop process. The extraction of metals from silicon solar cells is often an energy-intensive process. It requires either smelting or leaching at elevated temperature, or the use of large quantities of strong acids or bases that require energy to produce. The energy input equates to a significant cost and an associated CO2 footprint, both of which it would be desirable to reduce. Thus there is a need to develop more energy-efficient and environmentally-compatible processes. Thus, ‘ionometallurgy’ could offer a new set of environmentally-benign process for metallurgy. This work demonstrates that ionic liquids provide one such method since they can be used to dissolve and recover silver. The overall process associates leaching, recovery and the possibility to re-use the solution in closed-loop process. This study aims to evaluate and compare different ionic liquids to leach and recover silver. An electrochemical analysis is first implemented to define the best system for the Ag dissolution. Effects of temperature, concentration and oxidizing agent are evaluated by this approach. Further, a comparative study between conventional approach (nitric acid, thiourea) and the ionic liquids (Cu and Al) focused on the leaching efficiency is conducted. A specific attention has been paid to the selection of the Ionic Liquids. Electrolytes composed of chelating anions are used to facilitate the lixiviation (Cl, Br, I,), avoid problems dealing with solubility issues of metallic species and of classical additional ligands. This approach reduces the cost of the process and facilitates the re-use of the leaching medium. To define the most suitable ionic liquids, electrochemical experiments have been carried out to evaluate the oxidation potential of silver include in the crystalline solar cells. Then, chemical dissolution of metals for crystalline solar cells have been performed for the most promising ionic liquids. After the chemical dissolution, electrodeposition has been performed to recover silver under a metallic form.

Keywords: electrodeposition, ionometallurgy, leaching, recycling, silver

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Authors: Shasha Lv, Zhengcao Li

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Due to the CMOS compatibility, silicon-based field emission (FE) devices as potential electron sources have attracted much attention. The geometrical arrangement and dimensional features of aligned silicon nanowires (SiNWs) have a determining influence on the FE properties. We discuss a multistep template replication process of Ag-assisted chemical etching combined with polystyrene (PS) spheres to fabricate highly periodic and well-aligned silicon nanowires, then their diameter, aspect ratio and density were further controlled via dry oxidation and post chemical treatment. The FE properties related to proximity and aspect ratio were systematically studied. A remarkable improvement of FE propertiy was observed with the average nanowires tip interspace increasing from 80 to 820 nm. On the basis of adjusting SiNWs dimensions and morphology, addition of a secondary material whose properties complement the SiNWs could yield a combined characteristic. Three different nanoheterostructures were fabricated to control the FE performance, they are: NiSi/Si core-shell structures, ZnO/Si nanotrees, and Graphene/SiNWs. We successfully fabricated the high-quality NiSi/Si heterostructured nanowires with excellent conformality. First, nickle nanoparticles were deposited onto SiNWs, then rapid thermal annealing process were utilized to form NiSi shell. In addition, we demonstrate a new and simple method for creating 3D nanotree-like ZnO/Si nanocomposites with a spatially branched hierarchical structure. Compared with the as-prepared SiNRs and ZnO NWs, the high-density ZnO NWs on SiNRs have exhibited predominant FE characteristics, and the FE enhancement factors were attributed to band bending effect and geometrical morphology. The FE efficiency from flat sheet structure of graphene is low. We discussed an effective approach towards full control over the diameter of uniform SiNWs to adjust the protrusions of large-scale graphene sheet deposited on SiNWs. The FE performance regarding the uniformity and dimensional control of graphene protrusions supported on SiNWs was systematically clarified. Therefore, the hybrid SiNWs/graphene structures with protrusions provide a promising class of field emission cathodes.

Keywords: field emission, silicon nanowires, heterostructures, controllable synthesis

Procedia PDF Downloads 254

Authors: Shian Guan, Marie Bourdin, Isabelle Trenque, Younes Messaddeq, Thierry Cardinal, Nicolas Penin, Issam Mjejri, Aline Rougier, Etienne Duguet, Stephane Mornet, Manuel Gaudon

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At the interface of the studies performed by 3 Ph.D. students: Shian Guan (2017-2020), Marie Bourdin (2016-2019) and Isabelle Trenque (2012-2015), a single synthesis route: polyol-mediated process, was used with success for the preparation of different inorganic oxides. Both of these inorganic oxides were elaborated for their potential application as smart optical compounds. This synthesis route has allowed us to develop nanoparticles of zinc oxide, vanadium oxide or tungsten oxide. This route is with easy implementation, inexpensive and with large-scale production potentialities and leads to materials of high purity. The obtaining by this route of nanometric particles, however perfectly crystalline, has notably led to the possibility of doping these matrix materials with high doping ion concentrations (high solubility limits). Thus, Al3+ or Ga3+ doped-ZnO powder, with high doping rate in comparison with the literature, exhibits remarkable infrared absorption properties thanks to their high free carrier density. Note also that due to the narrow particle size distribution of the as-prepared nanometric doped-ZnO powder, the original correlation between crystallite size and unit-cell parameters have been established. Also, depending on the annealing atmosphere use to treat vanadium precursors, VO2, V2O3 or V2O5 oxides with thermochromic or electrochromic properties can be obtained without any impurity, despite the versatility of the oxidation state of vanadium. This is of more particular interest on vanadium dioxide, a relatively difficult-to-prepare oxide, whose first-order metal-insulator phase transition is widely explored in the literature for its thermochromic behavior (in smart windows with optimal thermal insulation). Finally, the reducing nature of the polyol solvents ensures the production of oxygen-deficient tungsten oxide, thus conferring to the nano-powders exotic colorimetric properties, as well as optimized photochromic and electrochromic behaviors.

Keywords: inorganic oxides, electrochromic, photochromic, thermochromic

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Authors: Massimiliano Condotta, Paolo Ruggeri, Chiara Scanagatta, Giovanni Borga

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Architects and urban planners, when designing and renewing cities, have to face a complex set of problems, including the issues of noise and air pollution which are considered as hot topics (i.e., the Clean Air Act of London and the Soundscape definition). It is usually taken for granted that these problems go by together because the noise pollution present in cities is often linked to traffic and industries, and these produce air pollutants as well. Traffic congestion can create both noise pollution and air pollution, because NO₂ is mostly created from the oxidation of NO, and these two are notoriously produced by processes of combustion at high temperatures (i.e., car engines or thermal power stations). We can see the same process for industrial plants as well. What have to be investigated – and is the topic of this paper – is whether or not there really is a correlation between noise pollution and air pollution (taking into account NO₂) in urban areas. To evaluate if there is a correlation, some low-cost methodologies will be used. For noise measurements, the OpeNoise App will be installed on an Android phone. The smartphone will be positioned inside a waterproof box, to stay outdoor, with an external battery to allow it to collect data continuously. The box will have a small hole to install an external microphone, connected to the smartphone, which will be calibrated to collect the most accurate data. For air, pollution measurements will be used the AirMonitor device, an Arduino board to which the sensors, and all the other components, are plugged. After assembling the sensors, they will be coupled (one noise and one air sensor) and placed in different critical locations in the area of Mestre (Venice) to map the existing situation. The sensors will collect data for a fixed period of time to have an input for both week and weekend days, in this way it will be possible to see the changes of the situation during the week. The novelty is that data will be compared to check if there is a correlation between the two pollutants using graphs that should show the percentage of pollution instead of the values obtained with the sensors. To do so, the data will be converted to fit on a scale that goes up to 100% and will be shown thru a mapping of the measurement using GIS methods. Another relevant aspect is that this comparison can help to choose which are the right mitigation solutions to be applied in the area of the analysis because it will make it possible to solve both the noise and the air pollution problem making only one intervention. The mitigation solutions must consider not only the health aspect but also how to create a more livable space for citizens. The paper will describe in detail the methodology and the technical solution adopted for the realization of the sensors, the data collection, noise and pollution mapping and analysis.

Keywords: air quality, data analysis, data collection, NO₂, noise mapping, noise pollution, particulate matter

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Authors: Kirill M. Dubovikov, Ekaterina S. Marchenko, Gulsharat A. Baigonakova

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NiTi alloys are widely used as implants in medicine due to their unique properties such as superelasticity, shape memory effect and biocompatibility. However, despite these properties, one of the major problems is the release of nickel after prolonged use in the human body under dynamic stress. This occurs due to oxidation and cracking of NiTi implants, which provokes nickel segregation from the matrix to the surface and release into living tissues. As we know, nickel is a toxic element and can cause cancer, allergies, etc. One of the most popular ways to solve this problem is to create a corrosion resistant coating on NiTi. There are many coatings of this type, but not all of them have good biocompatibility, which is very important for medical implants. Coatings based on calcium phosphate phases have excellent biocompatibility because Ca and P are the main constituents of the mineral part of human bone. This fact suggests that a Ca-P coating on NiTi can enhance osteogenesis and accelerate the healing process. Therefore, the aim of this study is to investigate the structure of Ca-P coating on NiTi substrate. Plasma assisted radio frequency (RF) sputtering was used to obtain this film. This method was chosen because it allows the crystallinity and morphology of the Ca-P coating to be controlled by the sputtering parameters. It allows us to obtain three different NiTi samples with Ca-P coating. XRD, AFM, SEM and EDS were used to study the composition, structure and morphology of the coating phase. Scratch tests were carried out to evaluate the adhesion of the coating to the substrate. Wettability tests were used to investigate the hydrophilicity of the different coatings and to suggest which of them had better biocompatibility. XRD showed that the coatings of all samples were hydroxyapatite, but the matrix was represented by TiNi intermetallic compounds such as B2, Ti2Ni and Ni3Ti. The SEM shows that the densest and defect-free coating has only one sample after three hours of sputtering. Wettability tests show that the sample with the densest coating has the lowest contact angle of 40.2° and the largest free surface area of 57.17 mJ/m2, which is mostly disperse. A scratch test was carried out to investigate the adhesion of the coating to the surface and it was shown that all coatings were removed by a cohesive mechanism. However, at a load of 30N, the indenter reached the substrate in two out of three samples, except for the sample with the densest coating. It was concluded that the most promising sputtering mode was the third, which consisted of three hours of deposition. This mode produced a defect-free Ca-P coating with good wettability and adhesion.

Keywords: biocompatibility, calcium phosphate coating, NiTi alloy, radio frequency sputtering.

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Authors: Ahmad Kayvani Fard, Gordon Mckay, Muataz Hussien

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Adsorption/sorption is believed to be one of the optimal processes for the removal of heavy metals from water due to its low operational and capital cost as well as its high removal efficiency. Different materials have been reported in literature as adsorbent for heavy metal removal in waste water such as natural sorbents, organic polymers (synthetic) and mineral materials (inorganic). The selection of adsorbents and development of new functional materials that can achieve good removal of heavy metals from water is an important practice and depends on many factors, such as the availability of the material, cost of material, and material safety and etc. In this study we reported the synthesis of doped Activated carbon and Carbon nanotube (CNT) with different loading of metal oxide nanoparticles such as Fe2O3, Fe3O4, Al2O3, TiO2, SiO2 and Ag nanoparticles and their application in removal of heavy metals, hydrocarbon, and organics from waste water. Commercial AC and CNT with different loadings of mentioned nanoparticle were prepared and effect of pH, adsorbent dosage, sorption kinetic, and concentration effects are studied and optimum condition for removal of heavy metals from water is reported. The prepared composite sorbent is characterized using field emission scanning electron microscopy (FE-SEM), high transmission electron microscopy (HR-TEM), thermogravimetric analysis (TGA), X-ray diffractometer (XRD), the Brunauer, Emmett and Teller (BET) nitrogen adsorption technique, and Zeta potential. The composite materials showed higher removal efficiency and superior adsorption capacity compared to commercially available carbon based adsorbent. The specific surface area of AC increased by 50% reaching up to 2000 m2/g while the CNT specific surface area of CNT increased by more than 8 times reaching value of 890 m2/g. The increased surface area is one of the key parameters along with surface charge of the material determining the removal efficiency and removal efficiency. Moreover, the surface charge density of the impregnated CNT and AC have enhanced significantly where can benefit the adsorption process. The nanoparticles also enhance the catalytic activity of material and reduce the agglomeration and aggregation of material which provides more active site for adsorbing the contaminant from water. Some of the results for treating wastewater includes 100% removal of BTEX, arsenic, strontium, barium, phenolic compounds, and oil from water. The results obtained are promising for the use of AC and CNT loaded with metal oxide nanoparticle in treatment and pretreatment of waste water and produced water before desalination process. Adsorption can be very efficient with low energy consumption and economic feasibility.

Keywords: carbon nanotube, activated carbon, adsorption, heavy metal, water treatment

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Authors: Elchin Hajiyev, Afet Memmedova Dadash, Sabina Hajiyeva, Aynur Karimova, Ramiz Aliyev

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Although potatoes have a wide distribution range, the yield potential of varieties varies greatly depending on the region. Our country is made up of agricultural regions with very different environmental characteristics.In this case, we cannot expect the introduced varieties to show the same adaptation to the different conditions of our country. For this reason, in our country, varieties with high general adaptability should be used, rather than varieties with special adaptability in certain areas. Soil salinization has become a global problem.Increased salinity has a serious impact on food security by reducing plant productivity. Plants have protective mechanisms of adaptation to salt stress, such as the synthesis of physiologically active substances, resistance to antioxidant stress and oxidation of membrane lipids. One of these substances is free proline. Our study revealed genetic variation in proline accumulation among samples exposed to stress factors.Changes in proline content under stress conditions were studied in 50 samples. There was wide variation across all treatments.The amount of proline varied between 7.2–37.7 μM/g under salinity conditions.The lowest rate was in the SF33 genotype (1.5 times more than the control (2.5 μM/g)).The highest level of proline under the influence of salt stress was in the SF45 genotype (7.25 times higher than the control (32.5 μM/g)). Our studies have found that the protective system reacts differently to the influence of stress factors. According to the results obtained on the amount of proline, adaptation mechanisms must be more actively activated to maintain metabolism and ensure viability in sensitive forms under the influence of stress factors. At high doses of the salt stressor, a tenfold increase in proline compared to the control indicates significant damage to the plant organism as a result of stress.To prevent damage to the body, the antioxidant system needs to quickly mobilize and work at full capacity in adverse conditions. An increase in the dose of the stress factor salt in our study caused a greater increase in the amount of free proline in plant tissues. Considering the functions of proline as an osmoprotector and antioxidant, it was found that increasing its amount is aimed at protecting the plant from the acute effects of stressors.

Keywords: genetic variability, potato, genotypes, proline, stress

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Authors: Laura M. Hovsepyan, Gayane S. Ghazaryan, Hasmik V. Zanginyan

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Hypertension (HD) is the most common cardiovascular pathology that causes disability and mortality in the working population. Most often, heart failure (HF), which is based on myocardial remodeling, leads to death in hypertension. Recently, endothelial dysfunction (EDF) or a violation of the functional state of the vascular endothelium has been assigned a significant role in the structural changes in the myocardium and the occurrence of heart failure in patients with hypertension. It has now been established that tissues affected by inflammation form increased amounts of superoxide radical and NO, which play a significant role in the development and pathogenesis of various pathologies. They mediate inflammation, modify proteins and damage nucleic acids. The aim of this work was to study the processes of oxidative modification of proteins (OMP) and the production of nitric oxide in hypertension. In the experimental work, the blood of 30 donors and 33 patients with hypertension was used. For the quantitative determination of OMP products, the based on the reaction of the interaction of oxidized amino acid residues of proteins and 2,4-dinitrophenylhydrazine (DNPH) with the formation of 2,4-dinitrophenylhydrazones, the amount of which was determined spectrophotometrically. The optical density of the formed carbonyl derivatives of dinitrophenylhydrazones was recorded at different wavelengths: 356 nm - aliphatic ketone dinitrophenylhydrazones (KDNPH) of neutral character; 370 nm - aliphatic aldehyde dinirophenylhydrazones (ADNPH) of neutral character; 430 nm - aliphatic KDNFG of the main character; 530 nm - basic aliphatic ADNPH. Nitric oxide was determined by photometry using Grace's solution. Adsorption was measured on a Thermo Scientific Evolution 201 SF at a wavelength of 546 nm. Thus, the results of the studies showed that in patients with arterial hypertension, an increased level of nitric oxide in the blood serum is observed, and there is also a tendency to an increase in the intensity of oxidative modification of proteins at a wavelength of 270 nm and 363 nm, which indicates a statistically significant increase in aliphatic aldehyde and ketone dinitrophenylhydrazones. The increase in the intensity of oxidative modification of blood plasma proteins in the studied patients, revealed by us, actually reflects the general direction of free radical processes and, in particular, the oxidation of proteins throughout the body. A decrease in the activity of the antioxidant system also leads to a violation of protein metabolism. The most important consequence of the oxidative modification of proteins is the inactivation of enzymes.

Keywords: hypertension (HD), oxidative modification of proteins (OMP), nitric oxide (NO), oxidative stress

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Authors: Luís R. Silva, Fábio Jesus, Catarina Bento, Ana C. Gonçalves

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Over the last few years, the traditional medicine has gained ground at nutritional and pharmacological level. The natural products and their derivatives have great importance in several drugs used in modern therapeutics. Plant-based systems continue to play an essential role in primary healthcare. Additionally, the utilization of their plant parts, such as leaves, stems and flowers as nutraceutical and pharmaceutical products, can add a high value in the natural products market, not just by the nutritional value due to the significant levels of phytochemicals, but also by to the high benefit for the producers and manufacturers business. Stems of Prunus avium L. are a byproduct resulting from the processing of cherry, and have been consumed over the years as infusions and decoctions due to its bioactive properties, being used as sedative, diuretic and draining, to relief of renal stones, edema and hypertension. In this work, we prepared a hydroethanolic and infusion extracts from stems of P. avium collected in Fundão Region (Portugal), and evaluate the phenolic profile by LC/DAD, antioxidant capacity, α-glucosidase inhibitory activity and protection of human erythrocytes against oxidative damage. The LC-DAD analysis allowed to the identification of 19 phenolic compounds, catechin and 3-O-caffolquinic acid were the main ones. In a general way, hydroethanolic extract proved to be more active than infusion. This extract had the best antioxidant activity against DPPH• (IC50=22.37 ± 0.28 µg/mL) and superoxide radical (IC50=13.93 ± 0.30 µg/mL). Furthermore, it was the most active concerning inhibition of hemoglobin oxidation (IC50=13.73 ± 0.67 µg/mL), hemolysis (IC50=1.49 ± 0.18 µg/mL) and lipid peroxidation (IC50=26.20 ± 0.38 µg/mL) on human erythrocytes. On the other hand, infusion revealed to be more efficient towards α-glucosidase inhibitory activity (IC50=3.18 ± 0.23 µg/mL) and against nitric oxide radical (IC50=99.99 ± 1.89 µg/mL). The Sweet cherry sector is very important in Fundão Region (Portugal), and taking profit from the great wastes produced during processing of the cherry to produce added-value products, such as food supplements cannot be ignored. Our results demonstrate that P. avium stems possesses remarkable antioxidant and free radical scavenging properties. It is therefore, suggest, that P. avium stems can be used as a natural antioxidant with high potential to prevent or slow the progress of human diseases mediated by oxidative stress.

Keywords: stems, Prunus avium, phenolic compounds, biological potential

Procedia PDF Downloads 278

Authors: Krupali Mehta, Sandip Bhatt, Umesh Trivedi, Bhavesh Bharatiya, Mukesh Ranjan, Atindra D. Shukla

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Owing to the dominating surface forces and large-scale surface interactions, the nano-scale particles face difficulties in getting suspended in various media. Magnetic nanoparticles of iron oxide offer a great deal of promise due to their ease of preparation, reasonable magnetic properties, low cost and environmental compatibility. We intend to modify the surface of magnetic Fe₂O₃ nanoparticles with selected surface modifying agents using simple and effective single-step chemical reactions in order to enhance dispersibility of magnetic nanoparticles in non-polar media. Magnetic particles were prepared by hydrolysis of Fe²⁺/Fe³⁺ chlorides and their subsequent oxidation in aqueous medium. The dried particles were then treated with Octadecyl quaternary ammonium silane (Terrasil™), stearic acid and gallic acid ester of stearyl alcohol in ethanol separately to yield S-2 to S-4 respectively. The untreated Fe₂O₃ was designated as S-1. The surface modified nanoparticles were then analysed with Dynamic Light Scattering (DLS), Fourier Transform Infrared spectroscopy (FTIR), X-Ray Diffraction (XRD), Thermogravimetric Gravimetric Analysis (TGA) and Scanning Electron Microscopy and Energy dispersive X-Ray analysis (SEM-EDAX). Characterization reveals the particle size averaging 20-50 nm with and without modification. However, the crystallite size in all cases remained ~7.0 nm with the diffractogram matching to Fe₂O₃ crystal structure. FT-IR suggested the presence of surfactants on nanoparticles’ surface, also confirmed by SEM-EDAX where mapping of elements proved their presence. TGA indicated the weight losses in S-2 to S-4 at 300°C onwards suggesting the presence of organic moiety. Hydrophobic character of modified surfaces was confirmed with contact angle analysis, all modified nanoparticles showed super hydrophobic behaviour with average contact angles ~129° for S-2, ~139.5° for S-3 and ~151° for S-4. This indicated that surface modified particles are super hydrophobic and they are easily dispersible in non-polar media. These modified particles could be ideal candidates to be suspended in oil-based fluids, polymer matrices, etc. We are pursuing elaborate suspension/sedimentation studies of these particles in various oils to establish this conjecture.

Keywords: iron nanoparticles, modification, hydrophobic, dispersion

Procedia PDF Downloads 124

Authors: Ketsada Sutthiumporn, Sittichot Thongkaw, Malee Santikunaporn

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In Thailand, biodiesel has been utilized as an attractive substitute of petroleum diesel and the government imposes a mandatory biodiesel blending requirement in transport sector to improve energy security, support agricultural sector and reduce emissions. Though biodiesel blend has many advantages over diesel fuel such as improved lubricity, low sulfur content and higher flash point, there are still some technical problems such as oxidative stability, poor cold- flow properties and impurity. Such problems were related to the fatty acid composition in feedstock. Moreover, Thailand has announced the use of low sulfur diesel as a base diesel and will be continually upgrading to EURO 5 in 2023. With ultra low sulfur content, it may affect the diesel fuel properties especially lubricity as well. Therefore, in this study, the physical and chemical properties of palm oil-based biodiesel in low sulfur diesel blends from different producers will be investigated by standard methods per ASTM and EN. Also, its economic benefits based on diesel price structure in Thailand will be highlighted. The appropriate biodiesel blend ratio can affect the physico-chemical properties and reasonable price in the country. Properties of biodiesel, including specific gravity, kinematic viscosity, FAME composition, flash point, sulfur, water, oxidation stability and lubricity were measured by standard methods of ASTM and EN. The results show that the FAME composition of biodiesel has the fatty acid of C12:0 to C20:1, mostly in C16:0, C18:0, C18:1, and C18:2, which were main characteristic compositions of palm biodiesel. The physical and chemical properties of biodiesel blended diesel was found to be increases with an increasing amount of biodiesel such as specific gravity, flash point and kinematic viscosity while sulfur value was decreased. Moreover, in this study, the various properties of each biodiesel blends were plotted to determine the appropriate proportional range of biodiesel-blended diesel with an optimum fuel price.It can be seen that the amount of B100 can be filled from 1% up to 7% in which the quality was in accordance with Notification of the department of Energy business.The understanding of relation between physico-chemical properties of palm oil-based biodiesel and pricing is beneficial to guide the better development of desired feedstock in Thailand and to implement biodiesel blends with comparative price and diesel engine performance.

Keywords: fatty acid methyl ester, biodiesel, fuel price structure, palm oil in Thailand

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Authors: Kuheli Chakrabarty, Animesh Ghosh, Atanu Roy, Gourab Kanti Das

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Aldol reaction is an important class of carbon-carbon bond forming reactions. One of the popular ways to impose asymmetry in aldol reaction is the introduction of chiral auxiliary that binds the approaching reactants and create dissymmetry in the reaction environment, which finally evolves to enantiomeric excess in the aldol products. The last decade witnesses the usage of natural amino acids as chiral auxiliary to control the stereoselectivity in various carbon-carbon bond forming processes. In this context, L-proline was found to be an effective organocatalyst in asymmetric aldol additions. In last few decades the use of water as solvent or co-solvent in asymmetric organocatalytic reaction is increased sharply. Simple amino acids like L-proline does not catalyze asymmetric aldol reaction in aqueous medium not only that, In organic solvent medium high catalytic loading (~30 mol%) is required to achieve moderate to high asymmetric induction. In this context, huge efforts have been made to modify L-proline and 4-hydroxy-L-proline to prepare organocatalyst for aqueous medium asymmetric aldol reaction. Here, we report the result of our DFT calculations on asymmetric aldol reaction of benzaldehyde, p-NO2 benzaldehyde and t-butyraldehyde with a number of ketones using L-proline hydrazide as organocatalyst in wet solvent free condition. Gaussian 09 program package and Gauss View program were used for the present work. Geometry optimizations were performed using B3LYP hybrid functional and 6-31G(d,p) basis set. Transition structures were confirmed by hessian calculation and IRC calculation. As the reactions were carried out in solvent free condition, No solvent effect were studied theoretically. Present study has revealed for the first time, the direct involvement of two water molecules in the aldol transition structures. In the TS, the enamine and the aldehyde is connected through hydrogen bonding by the assistance of two intervening water molecules forming a supramolecular network. Formation of this type of supramolecular assembly is possible due to the presence of protonated -NH2 group in the L-proline hydrazide moiety, which is responsible for the favorable entropy contribution to the aldol reaction. It is also revealed from the present study that, water assisted TS is energetically more favorable than the TS without involving any water molecule. It can be concluded from this study that, insertion of polar group capable of hydrogen bond formation in the L-proline skeleton can lead to a favorable aldol reaction with significantly high enantiomeric excess in wet solvent free condition by reducing the activation barrier of this reaction.

Keywords: aldol reaction, DFT, organocatalysis, transition structure

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Authors: H. Minor-Pérez, A. M. Mota-Silva, S. Ortiz-Barrios

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Substances of vegetable origin with antioxidant capacity have a high potential for application on the conservation of some foods, can prevent or reduce for example oxidation of lipids. However a food is a complex system whose wide variety of components wich can reduce or eliminate this antioxidant capacity. The antioxidant activity can be determined with the ABTS technique. The radical ABTS+ is generated from the acid 2, 2´ - Azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS). This radical is a composite color bluish-green, stable and with a spectrum of absorption into the UV-visible. The addition of antioxidants causes discoloration, value that can be reported as a percentage of inhibition of the cation radical ABTS+. The objective of this study was evaluated the effect of the combination of the pH and the essential oil of cinnamon (EOC) on inhibition of the radical ABTS+, using statistical design of central point (Design Expert) to obtain mathematical models that describe this phenomenon. Were evaluated 17 treatments with combinations of pH 5, 6 and 7 (citrate-phosphate buffer) and the concentration of essential oil of cinnamon (C): 0 µg/mL, 100 µg/mL and 200 µg/mL. The samples were analyzed using the ABTS technique. The reagent was dissolved in methanol 80% to standardized the absorbance to 0.7 +/- 0.1 at 754 nm. Then samples were mixed with reagent standardized ABTS and after 1 min and 7 min absorbance was read for each treatment at 754 nm. Was used a curve pattern with vitamin C and reported the values as inhibition (%) of radical ABTS+. The statistical analysis shows the experimental results were adjusted to a quadratic model, to the times of 1 min and 7 min. This model describes the influence of the factors investigated independently: pH and cinnamon essential oil (µg/mL) and the effect of the interaction between pH*C, as well as the square of the pH2 and C2. The model obtained was Y = 10.33684 - 3.98118*pH + 1.17031*C + 0.62745*pH2 - 3.26675*10-3*C2 - 0.013112*pH*C, where Y is the response variable. The coefficient of determination was 0.9949 for 1 min. The equation was obtained at 7 min and = - 10.89710 + 1.52341*pH + 1.32892*C + 0.47953*pH2 - 3.56605*10- *C2 - 0.034687*pH*C. The coefficient of determination was 0.9970. This means that only 1% of the total variation is not explained by the developed models. At 100 µg/mL of EOC was obtained an inhibition percentage of 80%, 84% and 97% for the pH values of 5,6 and 7 respectively, while a value of 200 µg/mL the inhibition (%) was very similar for the treatments. In these values of pH was obtained an inhibition close 97%. In conclusion the pH does not have a significant effect on the antioxidant capacity, while the concentration of EOC was decisive for the antioxidant capacity. The authors acknowledge the funding provided by the CONACYT for the project 131998.

Keywords: antioxidant activity, ABTS technique, essential oil of cinnamon, mathematical models

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Authors: Nafees Ahmed, Nur Izyani Kamaruzman, Saralla Nathan, Mohd Ezharul Hoque Chowdhury, Anuar Zaini Md Zain, Iekhsan Othman, Sharifah Binti Syed Hassan

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Meat quality is always subject to consumer scrutiny when purchasing from retail markets on mislabeling as fresh meat. Various physiological and biochemical changes influence the quality of meat. As a major component of muscle tissue, proteins play a major role in muscle foods. In meat industry, freezing is the most common form of storage of meat products. Repeated cycles of freezing and thawing are common in restaurants, kitchen, and retail outlets and can also occur during transportation or storage. Temperature fluctuation is responsible for physical, chemical, and biochemical changes. Repeated cycles of ‘freeze-thaw’ degrade the quality of meat by stimulating the lipid oxidation and surface discoloration. The shelf life of meat is usually determined by its appearance, texture, color, flavor, microbial activity, and nutritive value and is influenced by frozen storage and subsequent thawing. The main deterioration of frozen meat during storage is due to protein. Due to the large price differences between fresh and frozen–thawed meat, it is of great interest to consumer to know whether a meat product is truly fresh or not. Researchers have mainly focused on the reduction of moisture loss due to freezing and thawing cycles of meat. The water holding capacity (WHC) of muscle proteins and reduced water content are key quality parameters of meat that ultimately changes color and texture. However, there has been limited progress towards understanding the actual mechanisms behind the meat quality changes under the freeze–thaw cycles. Furthermore, effect of freeze-thaw process on integrity of proteins is ignored. In this paper, we have studied the effect of ‘freeze-thawing’ on physicochemical changes of chicken meat protein. We have assessed the quality of meat by pH, spectroscopic measurements, Western Blot. Our results showed that increase in freeze-thaw cycles causes changes in pH. Measurements of absorbance (UV-visible and IR) indicated the degradation of proteins. The expression of various proteins (CREB, AKT, MAPK, GAPDH, and phosphorylated forms) were performed using Western Blot. These results indicated the repeated cycles of freeze-thaw is responsible for deterioration of protein, thus causing decrease in nutritious value of meat. It damges the use of these products in Islamic Sharia.

Keywords: chicken meat, freeze-thaw, halal, protein, western blot

Procedia PDF Downloads 387

Authors: Augustus K. Lebechi, Kenneth I. Ozoemena

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Rechargeable zinc-air batteries (RZABs) have been described as one of the most viable next-generation ‘beyond-the-lithium-ion’ battery technologies with great potential for renewable energy storage. It is safe, with a high specific energy density (1086 Wh/kg), environmentally benign, and low-cost, especially in resource-limited African countries. For widespread commercialization, the sluggish oxygen reaction kinetics pose a major challenge that impedes the reversibility of the system. Hence, there is a need for low-cost and highly active bifunctional electrocatalysts. Manganese oxide catalysts on carbon conducting additives remain the best couple for the realization of such low-cost RZABs. In this work, hausmannite Mn₃O₄ nanoparticles were synthesized through the annealing method from commercial electrolytic manganese dioxide (EMD), multi-walled carbon nanotubes (MWCNTs) were synthesized via the chemical vapor deposition (CVD) method and carbon nanofibers (CNFs) were synthesized via the electrospinning process with subsequent carbonization. Both Mn₃O₄ catalysts and the carbon conducting additives (MWCNT and CNF) were thoroughly characterized using X-ray powder diffraction spectroscopy (XRD), scanning electron microscopy (SEM), thermogravimetry analysis (TGA) and X-ray photoelectron spectroscopy (XPS). Composite electrocatalysts (Mn₃O₄/CNT and Mn₃O₄/CNF) were investigated for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in an alkaline medium. Using the established electrocatalytic modalities for evaluating the electrocatalytic performance of materials (including double layer, electrochemical active surface area, roughness factor, specific current density, and catalytic stability), CNFs proved to be the most efficient conducting additive material for the Mn₃O₄ catalyst. From the DFT calculations, the higher performance of the CNFs over the MWCNTs is related to the ability of the CNFs to allow for a more favorable distribution of the d-electrons of the manganese (Mn) and enhanced synergistic effect with Mn₃O₄ for weaker adsorption energies of the oxygen intermediates (O*, OH* and OOH*). In a proof-of-concept, Mn₃O₄/CNF was investigated as the air cathode for rechargeable zinc-air battery (RZAB) in a micro-3D-printed cell configuration. The RZAB showed good performance in terms of open circuit voltage (1.77 V), maximum power density (177.5 mW cm-2), areal-discharge energy and cycling stability comparable to Pt/C (20 wt%) + IrO2. The findings here provide fresh physicochemical perspectives on the future design and utility of CNFs for developing manganese-based RZABs.

Keywords: bifunctional electrocatalyst, oxygen evolution reaction, oxygen reduction reactions, rechargeable zinc-air batteries.

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Authors: Natela Gerliani, Mohammed Aider

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Nowadays, the interest of using sustainable technologies for protein extraction from underutilized oilseeds is growing. Currently, a major disposal problem for the oil industry is by-products of plant food processing such as soybean meal. That is why valorization of soybean meal is important for the oil industry since it contains high-quality proteins and other valuable components. Generally, soybean meal is used in livestock and poultry feed but is rarely used in human feed. Though chemical composition of this meal compensate nutritional deficiency and can be used to balance protein in human food. Regarding the efficiency of soybean meal valorization, extraction is a key process for obtaining enriched protein ingredient, which can be incorporated into the food matrix. However, most of the food components such as proteins extracted from oilseeds by-products imply the utilization of organic and inorganic chemicals (e.g. acids, bases, TCA-acetone) having a significant environmental impact. In a context of sustainable production, the use of an electro-activation technology seems to be a good alternative. Indeed, the electro-activation technology requires only water, food grade salt and electricity as main materials. Moreover, this innovative technology helps to avoid special equipment and trainings for workers safety as well as transport and storage of hazardous materials. Electro-activation is a technology based on applied electrochemistry for the generation of acidic and alkaline solutions on the basis of the oxidation-reduction reactions that occur at the vicinity electrode/solution interfaces. It is an eco-friendly process that can be used to replace the conventional acidic and alkaline extraction. In this research, the electro-activation technology for protein extraction from soybean meal was carried out in the electro-activation reactor. This reactor consists of three compartments separated by cation and anion exchange membranes that allow creating non-contacting acidic and basic solutions. Different current intensities (150 mA, 300 mA and 450 mA) and treatment durations (10 min, 30 min and 50 min) were tested. The results showed that the extracts obtained by the electro-activation method have good quality in comparison to conventional extracts. For instance, extractability obtained with electro-activation method was 55% whereas with the conventional method it was only 36%. Moreover, a maximum protein quantity of 48 % in the extract was obtained with the electro-activation technology comparing to the maximum amount of protein obtained by conventional extraction of 41 %. Hence, the environmentally sustainable electro-activation technology seems to be a promising type of protein extraction that can replace conventional extraction technology.

Keywords: by-products, eco-friendly technology, electro-activation, soybean meal

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Authors: Ana M. Antolín, Sandra Contreras, Francesc Medina, Didier Tichit

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Introduction: High levels of nitrates (> 50 ppm NO3-) in drinking water are potentially risky to human health. In the recent years, the trend of nitrate concentration in groundwater is rising in the EU and other countries. Conventional catalytic nitrate reduction processes into N2 and H2O lead to some toxic intermediates and by-products, such as NO2-, NH4+, and NOx gases. Alternatively, photocatalytic nitrate removal using solar irradiation and heterogeneous catalysts is a very promising and ecofriendly technique. It has been scarcely performed and more research on highly efficient catalysts is still needed. In this work, different nanocatalysts supported on Aeroxide Titania P25 (P25) have been prepared varying: 0.5-4 % wt. Ag); Pt (2, 4 % wt.); Pt precursor (H2PtCl6/K2PtCl6); and impregnation order of both metals. Pt was chosen in order to increase the selectivity to N2 and decrease that to NO2-. Catalysts were characterized by nitrogen physisorption, X-Ray diffraction, UV-visible spectroscopy, TEM and X Ray-Photoelectron Spectroscopy. The aim was to determine the influence of the composition and the preparation method of the catalysts on the conversion and selectivity in the nitrate reduction, as well as going through an overall and better understanding of the process. Nanocatalysts synthesis: For the mono and bimetallic catalysts preparation, wise-drop wetness impregnation of the precursors (AgNO3, H2PtCl6, K2PtCl6) followed by a reduction step (NaBH4) was used to obtain the metal colloids. Results and conclusions: Denitration experiments were performed in a 350 mL PTFE batch reactor under inert standard operational conditions, ultraviolet irradiations (λ=254 nm (UV-C); λ=365 nm (UV-A)), and presence/absence of hydrogen gas as a reducing agent, contrary to most studies using oxalic or formic acid. Samples were analyzed by Ionic Chromatography. Blank experiments using respectively P25 (dark conditions), hydrogen only and UV irradiations without hydrogen demonstrated a clear influence of the presence of hydrogen on nitrate reduction. Also, they demonstrated that UV irradiation increased the selectivity to N2. Interestingly, the best activity was obtained under ultraviolet lamps, especially at a closer wavelength to visible light irradiation (λ = 365 nm) and H2. 2% Ag/P25 leaded to the highest NO3- conversion among the monometallic catalysts. However, nitrite quantities have to be diminished. On the other hand, practically no nitrate conversion was observed with the monometallics based on Pt/P25. Therefore, the amount of 2% Ag was chosen for the bimetallic catalysts. Regarding the bimetallic catalysts, it is observed that the metal impregnation order, amount and Pt precursor highly affects the results. Higher selectivity to the desirable N2 gas is obtained when Pt was firstly added, especially with K2PtCl6 as Pt precursor. This suggests that when Pt is secondly added, it covers the Ag particles, which are the most active in this reaction. It could be concluded that Ag allows the nitrate reduction step to nitrite, and Pt the nitrite reduction step toward the desirable N2 gas.

Keywords: heterogeneous catalysis, hydrogenation, nanocatalyst, nitrate removal, photocatalysis

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Authors: Sankha Chakrabortty, Biswajit Ruj, Parimal Pal

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Methanol is one of the most important chemical products and intermediates. It can be used as a solvent, intermediate or raw material for a number of higher valued products, fuels or additives. From the last one decay, the total global demand of methanol has increased drastically which forces the scientists to produce a large amount of methanol from a renewable source to meet the global demand with a sustainable way. Different types of non-renewable based raw materials have been used for the synthesis of methanol on a large scale which makes the process unsustainable. In this circumstances, photocatalytic conversion of CO₂ into methanol under solar/UV excitation becomes a viable approach to give a sustainable production approach which not only meets the environmental crisis by recycling CO₂ to fuels but also reduces CO₂ amount from the atmosphere. Development of such sustainable production approach for CO₂ conversion into methanol still remains a major challenge in the current research comparing with conventional energy expensive processes. In this backdrop, the development of environmentally friendly materials, like photocatalyst has taken a great perspective for methanol synthesis. Scientists in this field are always concerned about finding an improved photocatalyst to enhance the photocatalytic performance. Graphene-based hybrid and composite materials with improved properties could be a better nanomaterial for the selective conversion of CO₂ to methanol under visible light (solar energy) or UV light. The present invention relates to synthesis an improved heterogeneous graphene-based photocatalyst with improved catalytic activity and surface area. Graphene with enhanced surface area is used as coupled material of copper-loaded titanium oxide to improve the electron capture and transport properties which substantially increase the photoinduced charge transfer and extend the lifetime of photogenerated charge carriers. A fast reduction method through H₂ purging has been adopted to synthesis improved graphene whereas ultrasonication based sol-gel method has been applied for the preparation of graphene coupled copper loaded titanium oxide with some enhanced properties. Prepared photocatalysts were exhaustively characterized using different characterization techniques. Effects of catalyst dose, CO₂ flow rate, reaction temperature and stirring time on the efficacy of the system in terms of methanol yield and productivity have been studied in the present study. The study shown that the newly synthesized photocatalyst with an enhanced surface resulting in a sustained productivity and yield of methanol 0.14 g/Lh, and 0.04 g/gcat respectively, after 3 h of illumination under UV (250W) at an optimum catalyst dosage of 10 g/L having 1:2:3 (Graphene: TiO₂: Cu) weight ratio.

Keywords: renewable energy, CO₂ capture, photocatalytic conversion, methanol

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Authors: Piotr J. Skusiewicz, Johnathan Saul, Ijhar Rusli, Svetlana Aleksandrova, Stephen. F. Benjamin, Miroslaw Gall, Steve Pierson, Carol A. Roberts

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The application of turbocharging in automotive engines leads to swirling flow entering the catalyst. The behaviour of this type of flow within the catalyst has yet to be adequately documented. This work discusses the effect of swirling flow on the flow distribution in automotive exhaust catalysts. Compressed air supplied to a moving-block swirl generator allowed for swirling flow with variable intensities to be generated. Swirl intensities were measured at the swirl generator outlet using single-sensor hot-wire probes. The swirling flow was fed into diffusers with total angles of 10°, 30° and 180°. Downstream of the diffusers, a wash-coated diesel oxidation catalyst (DOC) of length 143.8 mm, diameter 76.2 mm and nominal cell density of 400 cpsi was fitted. Velocity profiles were measured at the outlet sleeve about 30 mm downstream of the monolith outlet using single-sensor hot-wire probes. Wall static pressure was recorded using a multi-tube manometer connected to pressure taps positioned along the diffuser walls. The results show that as swirl is increased, more of the flow is directed towards the diffuser walls. The velocity decreases around the centre-line and maximum velocities are observed close to the outer radius of the monolith for all flow rates. At the maximum swirl intensity, reversed flow was recorded near the centre of the monolith. Wall static pressure measurements in the 180° diffuser indicated no pressure recovery as the flow enters the diffuser. This is indicative of flow separation at the inlet to the diffuser. To gain insight into the flow structure, CFD simulations have been performed for the 180° diffuser for a flow rate of 63 g/s. The geometry of the model consists of the complete assembly from the upstream swirl generator to the outlet sleeve. Modelling of the flow in the monolith was achieved using the porous medium approach, where the monolith with parallel flow channels is modelled as a porous medium that resists the flow. A reasonably good agreement was achieved between the experimental and CFD results downstream of the monolith. The CFD simulations allowed visualisation of the separation zones and central toroidal recirculation zones that occur within the expansion region at certain swirl intensities which are highlighted.

Keywords: catalyst, computational fluid dynamics, diffuser, hot-wire anemometry, swirling flow

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Authors: Tobias Schnabel

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Naphthalene and naphthalene similar compounds are a common problem in the indoor air of buildings from the 1960s and 1970s in Germany. Often tar containing roof felt was used under the concrete floor to prevent humidity to come through the floor. This tar containing roof felt has high concentrations of PAH (Polycyclic aromatic hydrocarbon) and naphthalene. Naphthalene easily evaporates and contaminates the indoor air. Especially after renovations and energetically modernization of the buildings, the naphthalene concentration rises because no forced air exchange can happen. Because of this problem, it is often necessary to change the floors after renovation of the buildings. The MFPA Weimar (Material research and testing facility) developed in cooperation a project with LEJ GmbH and Reichmann Gebäudetechnik GmbH. It is a technical solution for the disintegration of naphthalene in naphthalene, similar compounds in indoor air with photocatalytic reforming. Photocatalytic systems produce active oxygen species (hydroxyl radicals) through trading semiconductors on a wavelength of their bandgap. The light energy separates the charges in the semiconductor and produces free electrons in the line tape and defect electrons. The defect electrons can react with hydroxide ions to hydroxyl radicals. The produced hydroxyl radicals are a strong oxidation agent, and can oxidate organic matter to carbon dioxide and water. During the research, new titanium oxide catalysator surface coatings were developed. This coating technology allows the production of very porous titan oxide layer on temperature stable carrier materials. The porosity allows the naphthalene to get easily absorbed by the surface coating, what accelerates the reaction of the heterogeneous photocatalysis. The photocatalytic reaction is induced by high power and high efficient UV-A (ultra violet light) Leds with a wavelength of 365nm. Various tests in emission chambers and on the reformer itself show that a reduction of naphthalene in important concentrations between 2 and 250 µg/m³ is possible. The disintegration rate was at least 80%. To reduce the concentration of naphthalene from 30 µg/m³ to a level below 5 µg/m³ in a usual 50 ² classroom, an energy of 6 kWh is needed. The benefits of the photocatalytic indoor air treatment are that every organic compound in the air can be disintegrated and reduced. The use of new photocatalytic materials in combination with highly efficient UV leds make a safe and energy efficient reduction of organic compounds in indoor air possible. At the moment the air cleaning systems take the step from prototype stage into the usage in real buildings.

Keywords: naphthalene, titandioxide, indoor air, photocatalysis

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Authors: Prateek Goyal, Archini Paruthi, Superb K. Misra

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Contamination of water resources has been a major concern, which has drawn attention to the need to develop new material models for treatment of effluents. Existing conventional waste water treatment methods remain ineffective sometimes and uneconomical in terms of remediating contaminants like heavy metal ions (mercury, arsenic, lead, cadmium and chromium); organic matter (dyes, chlorinated solvents) and high salt concentration, which makes water unfit for consumption. We believe that nanotechnology based strategy, where we use nanoparticles as a tool to remediate a class of pollutants would prove to be effective due to its property of high surface area to volume ratio, higher selectivity, sensitivity and affinity. In recent years, scientific advancement has been made to study the application of photocatalytic (ZnO, TiO2 etc.) nanomaterials and magnetic nanomaterials in remediating contaminants (like heavy metals and organic dyes) from water/wastewater. Our study focuses on the synthesis and monitoring remediation efficiency of ZnO, Fe3O4 and Fe3O4 coated ZnO nanoparticulate system for the removal of heavy metals and dyes simultaneously. Multitude of ZnO nanostructures (spheres, rods and flowers) using multiple routes (microwave & hydrothermal approach) offers a wide range of light active photo catalytic property. The phase purity, morphology, size distribution, zeta potential, surface area and porosity in addition to the magnetic susceptibility of the particles were characterized by XRD, TEM, CPS, DLS, BET and VSM measurements respectively. Further on, the introduction of crystalline defects into ZnO nanostructures can also assist in light activation for improved dye degradation. Band gap of a material and its absorbance is a concrete indicator for photocatalytic activity of the material. Due to high surface area, high porosity and affinity towards metal ions and availability of active surface sites, iron oxide nanoparticles show promising application in adsorption of heavy metal ions. An additional advantage of having magnetic based nanocomposite is, it offers magnetic field responsive separation and recovery of the catalyst. Therefore, we believe that ZnO linked Fe3O4 nanosystem would be efficient and reusable. Improved photocatalytic efficiency in addition to adsorption for environmental remediation has been a long standing challenge, and the nano-composite system offers the best of features which the two individual metal oxides provide for nanoremediation.

Keywords: adsorption, nanocomposite, nanoremediation, photocatalysis

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Authors: Harish Kuruva, Vedasri Bai Khavala, Tiju Thomas, K. Murugan, B. S. Murty

Abstract:

Industries are growing day to day to increase the economy of the country. The biggest problem with industries is wastewater treatment. Releasing these wastewater directly into the river is more harmful to human life and a threat to aquatic life. These industrial effluents contain many dissolved solids, organic/inorganic compounds, salts, toxic metals, etc. Phenols, pesticides, dioxins, herbicides, pharmaceuticals, and textile dyes were the types of industrial effluents and more challenging to degrade eco-friendly. So many advanced techniques like electrochemical, oxidation process, and valorization have been applied for industrial wastewater treatment, but these are not cost-effective. Industrial effluent degradation is complicated compared to commercially available pollutants (dyes) like methylene blue, methylene orange, rhodamine B, etc. TiO₂ is one of the widely used photocatalysts which can degrade organic compounds using solar light and moisture available in the environment (organic compounds converted to CO₂ and H₂O). TiO₂ is widely studied in photocatalysis because of its low cost, non-toxic, high availability, and chemically and physically stable in the atmosphere. This study mainly focused on valorizing the mineralogical product TiO₂ (IREL, India). This mineralogical graded TiO₂ was characterized and compared with its structural and photocatalytic properties (industrial effluent degradation) with the commercially available Degussa P-25 TiO₂. It was testified that this mineralogical TiO₂ has the best photocatalytic properties (particle shape - spherical, size - 30±5 nm, surface area - 98.19 m²/g, bandgap - 3.2 eV, phase - 95% anatase, and 5% rutile). The industrial effluent was characterized by TDS (total dissolved solids), ICP-OES (inductively coupled plasma – optical emission spectroscopy), CHNS (Carbon, Hydrogen, Nitrogen, and sulfur) analyzer, and FT-IR (fourier-transform infrared spectroscopy). It was observed that it contains high sulfur (S=11.37±0.15%), organic compounds (C=4±0.1%, H=70.25±0.1%, N=10±0.1%), heavy metals, and other dissolved solids (60 g/L). However, the organo-sulfur industrial effluent was degraded by photocatalysis with the industrial mineralogical product TiO₂. In this study, the industrial effluent pH value (2.5 to 10), catalyst concentration (50 to 150 mg) were varied, and effluent concentration (0.5 Abs) and light exposure time (2 h) were maintained constant. The best degradation is about 80% of industrial effluent was achieved at pH 5 with a concentration of 150 mg - TiO₂. The FT-IR results and CHNS analyzer confirmed that the sulfur and organic compounds were degraded.

Keywords: wastewater treatment, industrial mineralogical product TiO₂, photocatalysis, organo-sulfur industrial effluent

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Authors: Michelle Belinda S. Weerawardana, Gobika Thiripuranathar, Priyani A. Paranagama

Abstract:

Most of fresh vegetables and fruits available in the retail markets undergo a physiological disorder in its appearance and coloration, which indeed discourages consumer purchase. A loss of millions of dollars yearly to the food industry had been due to this pronounced color reaction called Enzymatic Browning which is driven due to the catalytic activity by an oxidoreductase enzyme, polyphenol oxidase (PPO). The enzyme oxidizes the phenolic compounds which are abundantly available in fruits and vegetables as substrates into quinones, which could react with proteins in its surrounding to generate black pigments, called melanins, which are highly UV-active compounds. Annona muricata (Katu anoda) and Musa acuminata (Ash plantains) is a fruit and a vegetable consumed by Sri Lankans widely due to their high nutritional values, medicinal properties and economical importance. The objective of the present study was to evaluate and determine the effective natural anti-browning inhibitors that could prevent PPO activity in the selected fruit and vegetable. Enzyme extracts from Annona muricata (Katu anoda) and Musa acuminata (Ash plantains), were prepared by homogenizing with analytical grade acetone, and pH of each enzyme extract was maintained at 7.0 using a phosphate buffer. The extracts of inhibitors were prepared using powdered ginger rhizomes and essential oil from the bark of Cinnamomum zeylanicum. Water extracts of ginger were prepared and the essential oil from Ceylon cinnamon bark was extracted using steam distillation method. Since the essential oil is not soluble in water, 0.1µl of cinnamon bark oil was mixed with 0.1µl of Triton X-100 emulsifier and 5.00 ml of water. The effect of each inhibitor on the PPO activity was investigated using catechol (0.1 mol dm-3) as the substrate and two samples of enzyme extracts prepared. The dosages of the prepared Cinnamon bark oil, and ginger (2 samples) which were used to measure the activity were 0.0035 g/ml, 0.091 g/ml and 0.087 g/ml respectively. The measurements of the inhibitory activity were obtained at a wavelength of 525 nm using the UV-visible spectrophotometer. The results evaluated thus revealed that % inhibition observed with cinnamon bark oil, and ginger for Annona muricata was 51.97%, and 60.90% respectively. The effects of cinnamon bark oil, and ginger extract on PPO activity of Musa acuminata were 49.51%, and 48.10%. The experimental findings thus revealed that Cinnamomum zeylanicum bark oil was a more effective inhibitor for PPO enzyme present in Musa acuminata and ginger was effective for PPO enzyme present in Annona muricata. Overall both the inhibitors were proven to be more effective towards the activities of PPO enzyme present in both samples. These inhibitors can thus be corroborated as effective, natural, non-toxic, anti-browning extracts, which when added to the above fruit and vegetable will increase the shelf life and also the acceptance of the product by the consumers.

Keywords: anti-browning agent, enzymatic browning, inhibitory activity, polyphenol oxidase

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Authors: Andrea M. Rivas-Castillo, Marlenne Gómez-Ramirez, Isela Rodríguez-Pozos, Norma G. Rojas-Avelizapa

Abstract:

Spent catalysts are considered as hazardous residues of major concern, mainly due to the simultaneous presence of several metals in elevated concentrations. Although hydrometallurgical, pyrometallurgical and chelating agent methods are available to remove and recover some metals contained in spent catalysts; these procedures generate potentially hazardous wastes and the emission of harmful gases. Thus, biotechnological treatments are currently gaining importance to avoid the negative impacts of chemical technologies. To this end, diverse microorganisms have been used to assess the removal of metals from spent catalysts, comprising bacteria, archaea and fungi, whose resistance and metal uptake capabilities differ depending on the microorganism tested. Acidophilic sulfur oxidizing bacteria have been used to investigate the biotreatment and extraction of valuable metals from spent catalysts, namely Acidithiobacillus thiooxidans and Acidithiobacillus ferroxidans, as they present the ability to produce leaching agents such as sulfuric acid and sulfur oxidation intermediates. In the present work, the ability of A. thiooxidans DSM 26636 for the bioleaching of metals contained in five different spent catalysts was assessed by growing the culture in modified Starkey mineral medium (with elemental sulfur at 1%, w/v), and 1% (w/v) pulp density of each residue for up to 21 days at 30 °C and 150 rpm. Sulfur-oxidizing activity was periodically evaluated by determining sulfate concentration in the supernatants according to the NMX-k-436-1977 method. The production of sulfuric acid was assessed in the supernatants as well, by a titration procedure using NaOH 0.5 M with bromothymol blue as acid-base indicator, and by measuring pH using a digital potentiometer. On the other hand, Inductively Coupled Plasma - Optical Emission Spectrometry was used to analyze metal removal from the five different spent catalysts by A. thiooxidans DSM 26636. Results obtained show that, as could be expected, sulfuric acid production is directly related to the diminish of pH, and also to highest metal removal efficiencies. It was observed that Al and Fe are recurrently removed from refinery spent catalysts regardless of their origin and previous usage, although these removals may vary from 9.5 ± 2.2 to 439 ± 3.9 mg/kg for Al, and from 7.13 ± 0.31 to 368.4 ± 47.8 mg/kg for Fe, depending on the spent catalyst proven. Besides, bioleaching of metals like Mg, Ni, and Si was also obtained from automotive spent catalysts, which removals were of up to 66 ± 2.2, 6.2±0.07, and 100±2.4, respectively. Hence, the data presented here exhibit the potential of A. thiooxidans DSM 26636 for the simultaneous bioleaching of metals contained in spent catalysts from diverse provenance.

Keywords: bioleaching, metal removal, spent catalysts, Acidithiobacillus thiooxidans

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