Search results for: nanodimensional cobalt ferrites

Authors: Sai Snehitha Yadavalli, K. Sruthi, Swati Ghosh Acharyya

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Heavy metal ions are toxic to humans and all living species when exposed in large quantities or for long durations. Though Fe acts as a nutrient, when intake is in large quantities, it becomes toxic. These toxic heavy metal ions, when consumed through water, will cause many disorders and are harmful to all flora and fauna through biomagnification. Specifically, humans are prone to innumerable diseases ranging from skin to gastrointestinal, neurological, etc. In higher quantities, they even cause cancer in humans. Detection of these toxic heavy metal ions in water is thus important. Traditionally, the detection of heavy metal ions in water has been done by techniques like Inductively Coupled Plasma Mass Spectroscopy (ICPMS) and Atomic Absorption Spectroscopy (AAS). Though these methods offer accurate quantitative analysis, they require expensive equipment and cannot be used for on-site measurements. Anodic Stripping Voltammetry is a good alternative as the equipment is affordable, and measurements can be made at the river basins or lakes. In the current study, Square Wave Anodic Stripping Voltammetry (SWASV) was used to detect the heavy metal ions in water. Literature reports various electrodes on which deposition of heavy metal ions was carried out like Bismuth, Polymers, etc. The working electrode used in this study is a polyvinyl chloride (PVC) modified glassy carbon electrode (GCE). Ag/AgCl reference electrode and Platinum counter electrode were used. Biologic Potentiostat SP 300 was used for conducting the experiments. Through this work of simultaneous detection, four heavy metal ions were successfully detected at a time. The influence of modifying GCE with PVC was studied in comparison with unmodified GCE. The simultaneous detection of Cd⁺², Fe⁺², Co⁺², Pb⁺² heavy metal ions was done using PVC modified GCE by drop casting 1 wt.% of PVC dissolved in Tetra Hydro Furan (THF) solvent onto GCE. The concentration of all heavy metal ions was 0.2 mg/L, as shown in the figure. The scan rate was 0.1 V/s. Detection parameters like pH, scan rate, temperature, time of deposition, etc., were optimized. It was clearly understood that PVC helped in increasing the sensitivity and selectivity of detection as the current values are higher for PVC-modified GCE compared to unmodified GCE. The peaks were well defined when PVC-modified GCE was used.

Keywords: cadmium, cobalt, electrochemical sensing, glassy carbon electrodes, heavy metal Ions, Iron, lead, polyvinyl chloride, potentiostat, square wave anodic stripping voltammetry

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Authors: Saud Hamdan Alshammari

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Photocatalytic water splitting to produce hydrogen (H₂) has obtained significant attention as an environmentally friendly technology. This process, which produces hydrogen from water and sunlight, represents a renewable energy source. Titanium dioxide (TiO₂) plays a critical role in photocatalytic hydrogen production due to its chemical stability, availability, and low cost. Nevertheless, TiO₂'s wide band gap (3.2 eV) limits its visible light absorption and might affect the effectiveness of the photocatalytic. Coupling TiO₂ with other semiconductors is a strategy that can enhance TiO₂ by narrowing its band gap and improving visible light absorption. This paper studies the modification of TiO₂ by coupling it with another semiconductor such as CdS nanoparticles using a reflux reactor and autoclave reactor that helps form a core-shell structure. Characterization techniques, including TEM and UV-Vis spectroscopy, confirmed successful coating of TiO₂ on CdS core, reduction of the band gap from 3.28 eV to 3.1 eV, and enhanced light absorption in the visible region. These modifications are attributed to the heterojunction structure between TiO₂ and CdS.The essential goal of this study is to improve TiO₂ for use in photocatalytic water splitting to enhance hydrogen production. The core-shell TiO₂@CdS nanoparticles exhibited promising results, due to band gap narrowing and improved light absorption. Future work will involve adding Pt as a co-catalyst, which is known to increase surface reaction activity by enhancing proton adsorption. Evaluation of the TiO₂@CdS@Pt catalyst will include performance assessments and hydrogen productivity tests, considering factors such as effective shapes and material ratios. Moreover, the study could be enhanced by studying further modifications to the catalyst and displaying additional performance evaluations. For instance, doping TiO₂ with metals such as nickel (Ni), iron (Fe), and cobalt (Co) and non-metals such as nitrogen (N), carbon (C), and sulfur (S) could positively influence the catalyst by reducing the band gap, enhancing the separation of photogenerated electron-hole pairs, and increasing the surface area, respectively. Additionally, to further improve catalytic performance, examining different catalyst morphologies, such as nanorods, nanowires, and nanosheets, in hydrogen production could be highly beneficial. Optimizing photoreactor design for efficient photon delivery and illumination will further enhance the photocatalytic process. These strategies collectively aim to overcome current challenges and improve the efficiency of hydrogen production via photocatalysis.

Keywords: hydrogen production, photocatalytic, water spliiting, semiconductor, nanoparticles

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Authors: L. Sánchez-Abella, I. Loinaz, H-J. Grande, D. Dupin

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Aseptic loosening remains as the principal cause of revision in total hip arthroplasty (THA). For long-term implantations, submicron particles are generated in vivo due to the inherent wear of the prosthesis. When this occurs, macrophages undergo phagocytosis and secretion of bone resorptive cytokines inducing osteolysis, hence loosening of the implanted prosthesis. Therefore, new technologies are required to reduce the wear of the bearing materials and hence increase the life-span of the prosthesis. Our strategy focuses on surface modification of the bearing materials with a hydrophilic coating based on cross-linked water-soluble (meth)acrylic monomers to improve their tribological behavior. These coatings are biocompatible, with high swelling capacity and antifouling properties, mimicking the properties of natural cartilage, i.e. wear resistance with a permanent hydrated layer that prevents prosthesis damage. Cartilage mimicking based coatings may be also used to protect medical device surfaces from damage and scratches that will compromise their integrity and hence their safety. However, there are only a few reports on the mechanical and tribological characteristics of this type of coatings. Clear beneficial advantages of this coating have been demonstrated in different conditions and different materials, such as Ultra-high molecular weight polyethylene (UHMWPE), Polyethylene (XLPE), Carbon-fiber-reinforced polyetheretherketone (CFR-PEEK), cobalt-chromium (CoCr), Stainless steel, Zirconia Toughened Alumina (ZTA) and Alumina. Using routine tribological experiments, the wear for UHMWPE substrate was decreased by 75% against alumina, ZTA and stainless steel. For PEEK-CFR substrate coated, the amount of material lost against ZTA and CrCo was at least 40% lower. Experiments on hip simulator allowed coated ZTA femoral heads and coated UHMWPE cups to be validated with a decrease of 80% of loss material. Further experiments on hip simulator adding abrasive particles (1 micron sized alumina particles) during 3 million cycles, on a total of 6 million, demonstrated a decreased of around 55% of wear compared to uncoated UHMWPE and uncoated XLPE. In conclusion, CIDETEC‘s hydrogel coating technology is versatile and can be adapted to protect a large range of surfaces, even in abrasive conditions.

Keywords: cartilage, hydrogel, hydrophilic coating, joint

Procedia PDF Downloads 119

Authors: Gaweł Magdalena, Lipkowska Anna, Olbert Magdalena, Frąckiewicz Ewelina, Librowski Tadeusz, Nowak Gabriel, Pilc Andrzej

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Heme oxygenase-1 (HO-1), also known as heat shock protein 32 (HSP32), has been shown to be implicated in cytoprotection in various organs. Its activation plays a significant role in acute and chronic inflammation, protecting cells from oxidative injury and apoptosis. This inducible isoform of HO catalyzes the first and rate-limiting step in heme degradation to produce equimolar quantities of biologically active products: carbon monoxide (CO), free iron and biliverdin. CO has been reported to possess anti-apoptotic properties. Moreover, it inhibits the production of proinflammatory cytokines and stimulates the synthesis of the anti-inflammatory interleukin-10 (IL-10), as well as promotes vasodilatation at sites of inflammation. The second product of catalytic HO-1 activity, free cytotoxic iron, is promptly sequestered into the iron storage protein ferritin, which lowers the pro-oxidant state of the cell. The third product, biliverdin, is subsequently converted by biliverdin reductase into the bile pigment bilirubin, the most potent endogenous antioxidant among the constituents of human serum, which modulates immune effector functions and suppresses inflammatory response. Furthermore, being one of the so-called stress proteins, HO-1 adaptively responds to different stressors, such as reactive oxygen species (ROS), inflammatory cytokines and heavy metals and thus protects cells against such conditions as ischemia, hemorrhagic shock, heat shock or hypoxia. It is suggested that pharmacologic modulation of HO-1 may represent an effective strategy for prevention of stress and drug-induced gastrointestinal toxicity. HO-1 is constitutively expressed in normal gastric, intestinal and colonic mucosa and up-regulated during inflammation. It has been proven that HO-1 up-regulated by hemin, heme and cobalt-protoporphyrin ameliorates experimental colitis. In addition, the up-regulation of HO-1 partially explains the mechanism of action of 5-aminosalicylic acid (5-ASA), which is used clinically as an anti-colitis agent. In 2009 Ueda et al. has reported for the first time that mucosal protection by Polaprezinc, a chelate compound of zinc and L-carnosine used as an anti-ulcer drug in Japan, is also attributed to induction of HO-1 in the stomach. Since then, inducers of HO-1 are desired subject of research, as they may constitute therapeutically effective anti-ulcer drugs.

Keywords: heme oxygenase-1, gastric lesions, gastroprotection, Polaprezinc

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Authors: Henry O. Chibudike, Olubamike A. Adeyoju, Bolanle O. Oluwole, Kayode O. Adebowale, Bamidele I. Olu-Owolabi, Chinedum E. Chibudike

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Studies on the Mineral Content of Solojo Flour and Protein Isolates from the two varieties (DAS and BS) of Nigeria cultivated solojo cowpeas were conducted to determine their nutritional value. These inorganic elements or minerals were classified into 3 categories: the ultra-trace minerals, which are the third category; the microelements, also known as the trace minerals, in the second category; while the first category is the macro elements, also known as major minerals. Some of the macro-elements are Ca, P, Na and Cl; the second category, micro-elements include iron, copper, cobalt, potassium, magnesium, iodine, zinc, manganese, molybdenum, F, Cr, Se and S. Results show that the proportion of Sodium (Na) which is ingested into the body in the form of NaCl through food intake maintenance of body pH and to retain water ranged from 728.97 to 253.37 ppm (72.90 to 25.34 mg/100 g); 715.24 to 235.45 ppm; 735.28 to 270.37 ppm; 726.59 to 264.35ppm, for FFDAS, FFBS, DAS and BS respectively with all values of the germinated samples all bellow the control. While FFDAS iron content ranged from 4.25 to 13.50 mg/100 g; FFBS ranged from 3.15 to 12.56 mg/100 g; DAS ranged from 3.81 to 12.90 mg/100g; BS ranged from 3.42 to 9.40 mg/100 g. The values of the germinated flours were all greater than the ungerminated flour. Iron helps to transport oxygen round the body and also helps in red blood cells building and to convert food into needed energy by the body. While Manganese an element that is needed in micro quantity but necessary to convert food into energy, is also crucial for healthy bone and cartilage creation. Results also show that zinc quantity increased as germination proceeded, and the values ranged from 38.80 ppm to 230.00 ppm (3.880 mg/100 g to 23.00 mg/100 g; 0.003880% to 0.0230%); 40.84 to 250.01 ppm; 32.85 to 93.41 ppm; 37.07 to 115.00 ppm, for FFDAS, FFBS, DAS and BS respectively. The Ca content improved significantly (p<0.05) with sprouting; the value extended from 250.56 ppm to 760.03 ppm (25.056 to 76.00 mg/100g or 0.0251 to 0.0760 %); 400.40 to 998.22 ppm; 116.87 to 195.69 ppm; 113.48 to 220.75 ppm, for FFDAS, FFBS, DAS and BS respectively. Zinc element although needed at the micro level in the body, is essential for a strong immune system to keep the body in good health. It is also crucial for the maintenance of a healthy sense of taste and odor, while Calcium is critical for strong bones and teeth, blood coagulation, and muscle tightening and relaxation. Magnesium is needed to build enzymes and antioxidants and also for healthy bones, while Potassium is needed to maintain water balance, muscle movement, and nerve impulses. It functions in conjunction with Na to regulate blood pressure.

Keywords: Solojo cowpea, underutilized legumes, protein isolates, BS, DAS, ungerminated

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Authors: Suchhanda Ghosh, A. K. Paul

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Nickel, an industrially important metal is not mined in India, due to the lack of its primary mining resources. But, the chromite deposits occurring in the Sukinda and Baula-Nuasahi region of Odhisa, India, is reported to contain around 0.99% of nickel entrapped in the goethite matrix of the lateritic iron rich ore. Weathering of the dumped chromite mining overburden often leads to the contamination of the ground as well as the surface water with toxic nickel. Microbes inherent to this metal contaminated environment are reported to be capable of removal as well as detoxification of various metals including nickel. Nickel resistant fungal isolates obtained in pure form from the metal rich overburden were evaluated for their potential to biosorb nickel by using their dried biomass. Penicillium simplicissimum SAU203 was the best nickel biosorbant among the 20 fungi tested and was capable to sorbing 16.85 mg Ni/g biomass from a solution containing 50 mg/l of Ni. The identity of the isolate was confirmed using 18S rRNA gene analysis. The sorption capacity of the isolate was further standardized following Langmuir and Freundlich adsorption isotherm models and the results reflected energy efficient sorption. Fourier-transform infrared spectroscopy studies of the nickel loaded and control biomass in a comparative basis revealed the involvement of hydroxyl, amine and carboxylic groups in Ni binding. The sorption process was also optimized for several standard parameters like initial metal ion concentration, initial sorbet concentration, incubation temperature and pH, presence of additional cations and pre-treatment of the biomass by different chemicals. Optimisation leads to significant improvements in the process of nickel biosorption on to the fungal biomass. P. simplicissimum SAU203 could sorb 54.73 mg Ni/g biomass with an initial Ni concentration of 200 mg/l in solution and 21.8 mg Ni/g biomass with an initial biomass concentration of 1g/l solution. Optimum temperature and pH for biosorption was recorded to be 30°C and pH 6.5 respectively. Presence of Zn and Fe ions improved the sorption of Ni(II), whereas, cobalt had a negative impact. Pre-treatment of biomass with various chemical and physical agents has affected the proficiency of Ni sorption by P. simplicissimum SAU203 biomass, autoclaving as well as treatment of biomass with 0.5 M sulfuric acid and acetic acid reduced the sorption as compared to the untreated biomass, whereas, NaOH and Na₂CO₃ and Twin 80 (0.5 M) treated biomass resulted in augmented metal sorption. Hence, on the basis of the present study, it can be concluded that P. simplicissimum SAU203 has the potential for the removal as well as detoxification of nickel from contaminated environments in general and particularly from the chromite mining areas of Odhisa, India.

Keywords: nickel, fungal biosorption, Penicillium simplicissimum SAU203, Indian chromite mines, mining overburden

Procedia PDF Downloads 191

Authors: L. C. Nwosu, C. O. Adedire, M. O. Ashamo, E. O. Ogunwolu

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The maize weevil, Sitophilus zeamais Motschulsky is a notorious pest of stored maize (Zea mays L.). The development of resistant maize varieties to manage weevils is a major breeding objective. The study investigated the parameters and mechanisms that confer resistance on a maize variety to S. zeamais infestation using twenty elite maize varieties. Detailed morphological, physical and chemical studies were conducted on whole-maize grain and the grain pericarp. Resistance was assessed at 33, 56, and 90 days post infestation using weevil mortality rate, weevil survival rate, percent grain damage, percent grain weight loss, weight of grain powder, oviposition rate and index of susceptibility as indices rated on a scale developed by the present study and on Dobie’s modified scale. Linear regression models that can predict maize grain damage in relation to the duration of storage were developed and applied. The resistant varieties identified particularly 2000 SYNEE-WSTR and TZBRELD3C5 with very high degree of resistance should be used singly or best in an integrated pest management system for the control of S. zeamais infestation in stored maize. Though increases in the physical properties of grain hardness, weight, length, and width increased varietal resistance, it was found that the bases of resistance were increased chemical attributes of phenolic acid, trypsin inhibitor and crude fibre while the bases of susceptibility were increased protein, starch, magnesium, calcium, sodium, phosphorus, manganese, iron, cobalt and zinc, the role of potassium requiring further investigation. Characters that conferred resistance on the test varieties were found distributed in the pericarp and the endosperm of the grains. Increases in grain phenolic acid, crude fibre, and trypsin inhibitor adversely and significantly affected the bionomics of the weevil on further assessment. The flat side of a maize grain at the point of penetration was significantly preferred by the weevil. Why the south area of the flattened side of a maize grain was significantly preferred by the weevil is clearly unknown, even though grain-face-type seemed to be a contributor in the study. The preference shown to the south area of the grain flat side has implications for seed viability. The study identified antibiosis, preference, antixenosis, and host evasion as the mechanisms of maize post harvest resistance to Sitophilus zeamais infestation.

Keywords: maize weevil, resistant, parameters, mechanisms, preference

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Authors: Kali Prasad Sarma, Sanghita Dutta

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Deepor Beel (DB), the lone Ramsar site and an important wetland of the Brahmaputra valley in the state of Assam. The local people from fourteen peripheral villages traditionally utilize the wetland for harvesting vegetables, flowers, aquatic seeds, medicinal plants, fish, molluscs, fodder for domestic cattle etc. Therefore, it is of great importance to understand the concentration and distribution of trace metals in water-sediment system of the beel in order to protect its ecological environment. DB lies between26°05′26′′N to 26°09′26′′N latitudes and 90°36′39′′E to 91°41′25′′E longitudes. Water samples from the surface layer of water up to 40cm deep and sediment samples from the top 5cm layer of surface sediments were collected. The trace metals in waters and sediments were analysed using ICP-OES. The organic Carbon was analysed using the TOC analyser. The different mineral present in the sediments were confirmed by X-ray diffraction method (XRD). SEM images were recorded for the samples using SEM, attached with energy dispersive X-ray unit, with an accelerating voltage of 20 kv. All the statistical analyses were performed using SPSS20.0 for windows. In the present research, distribution, source apportionment, temporal and spatial variability, extent of pollution and the ecological risk of eight toxic trace metals in sediments and water of DB were investigated. The average concentrations of chromium(Cr) (both the seasons), copper(Cu) and lead(Pb) (pre-monsoon) and zinc(Zn) and cadmium(Cd) (post-monsoon) in sediments were higher than the consensus based threshold concentration(TEC). The persistent exposure of toxic trace metals in sediments pose a potential threat, especially to sediment dwelling organisms. The degree of pollution in DB sediments for Pb, Cobalt (Co) Zn, Cd, Cr, Cu and arsenic (As) was assessed using Enrichment Factor (EF), Geo-accumulation index (Igeo) and Pollution Load Index (PLI). The results indicated that contamination of surface sediments in DB is dominated by Pb and Cd and to a lesser extent by Co, Fe, Cu, Cr, As and Zn. A significant positive correlation among the pairs of element Co/Fe, Zn/As in water, and Cr/Zn, Fe/As in sediments indicates similar source of origin of these metals. The effects of interaction among trace metals between water and sediments shows significant variations (F =94.02, P < 0.001), suggesting maximum mobility of trace metals in DB sediments and water. The source apportionment of the heavy metals was carried out using Principal Component Analysis (PCA). SEM-EDS detects the presence of Cd, Cu, Cr, Zn, Pb, As and Fe in the sediment sample. The average concentration of Cd, Zn, Pb and As in the bed sediments of DB are found to be higher than the crustal abundance. The EF values indicate that Cd and Pb are significantly enriched. From source apportionment studies of the eight metals using PCA revealed that Cd was anthropogenic in origin; Pb, As, Cr, and Zn had mixed sources; whereas Co, Cu and Fe were natural in origin.

Keywords: Deepor Beel, enrichment factor, principal component analysis, trace metals

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Authors: Remy Mpulumba Badiambile, Paul Musa Obadia, Malick Useni Mutayo, Jeef Numbi Mukanya, Patient Nkulu Banza, Tony Kayembe Kitenge, Erik Smolders, Jean-François Picron, Vincent Haufroid, Célestin Banza Lubaba Nkulu, Benoit Nemery

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Background: In July 2021, the Tshikapa river became heavily polluted by mining wastes from a diamond mine in neighboring Angola, leading to massive killing of fish, as well as disease and even deaths among residents living along the Tshikapa and Kasai rivers, a major contributory of the Congo river. The exact nature of the pollutants was unknown. Methods: In a cross-sectional study conducted in the city of Tshikapa in August 2021, we enrolled by opportunistic sampling 65 residents (11 children < 16y) living alongside the polluted rivers and 65 control residents (5 children) living alongside a non-affected portion of the Kasai river (upstream from the Tshikapa-Kasai confluence). We administered a questionnaire and obtained spot urine samples for measurements of thiocyanate (a metabolite of cyanide) and 26 trace metals (by ICP-MS). Metals (and pH) were also measured in samples of river water. Results: Participants from both groups consumed river water. In the area affected by the pollution, most participants had eaten dead fish. Prevalences of reported health symptoms were higher in the exposed group than among controls: skin rashes (52% vs 0%), diarrhea (40% vs 8%), abdominal pain (8% vs 3%), nausea (3% vs 0%). In polluted water, concentrations [median (range)] were only higher for nickel [(2.2(1.4–3.5)µg/L] and uranium [78(71–91)ng/L] than in non-polluted water [0.8(0.6–1.9)µg/L; 9(7–19)ng/L]. In urine, concentrations [µg/g creatinine, median(IQR)] were significantly higher in the exposed group than in controls for lithium [19.5(12.4–27.3) vs 6.9(5.9–12.1)], thallium [0.41(0.31–0.57) vs 0.19(0.16–0.39)], and uranium [0.026(0.013–0.037)] vs 0.012(0.006–0.024)]. Other elements did not differ between the groups, but levels were higher than reference values for several metals (including manganese, cobalt, nickel, and lead). Urinary thiocyanate concentrations did not differ. Conclusion: This study, after an ecological disaster in the DRC, has documented contamination of river water by nickel and uranium and high urinary levels of some trace metals among affected riverine populations. However, the exact cause of the massive fish kill and disease among residents remains elusive. The capacity to rapidly investigate toxic pollution events must be increased in the area.

Keywords: metal contaminants, river water and human urine, pollution by mining wastes, DR Congo

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Authors: Adeleke G. E., Bello M. A., Abdulateef R. B., Olasinde T. T., Oriaje K. O., AransiI A., Elaigwu K. O., Omidoyin O. S., Shoyinka E. D., Awoyomi M. B., Akano M., Adaramoye O. A.

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Hymenocardia acidatul belongs to the genus, Hymenocardiaceae, which is widely distributed in Africa. Both the leaf and stem bark of the plant have been used in the treatment of several diseases. The present study examined the chemical constituents of the H. acida stem bark extract (HASBE) and its effects on some antioxidant indices and esterase enzymes in female Wistar rats. The HASBE was obtained by Soxhlet extraction using methanol and then subjected to Atomic Absorption Spectroscopy (AAS) for elemental analysis, and Fourier-Transform Infrared (FT-IR) spectroscopy, ultraviolet (UV) spectroscopy, for functional group analysis, while High-performance liquid chromatography (HPLC), and Gas Chromatography-Flame ionization detection (GC-FID) were carried out for compound identification. Forty-eight female Wistar rats were assigned into eight groups of six rats each and separately administered orally with normal saline (Control), 50, 100, 150, 200, 250, 300, 350 mg/kg of HASBE twice per week for eight weeks. The rats were sacrificed under chloroform anesthesia, and kidneys and heart were excised and processed to obtain homogenates. The levels of superoxide dismutase (SOD), catalase, Malondialdehyde (MDA), glutathione peroxidase (GPx), acetylcholinesterase (AChE), and carboxylesterase (CE) were determined spectrophotometrically. The AAS of HASBE shows the presence of eight elements, including Cobalt (0.303), Copper (0.222), Zinc (0.137), Iron (2.027), Nickel (1.304), Chromium (0.313), Manganese (0.213), and Magnesium (0.337 ppm). The FT-IR result of HASBE shows four peaks at 2961.4, 2926.0, 1056.7, and 1034.3 cm-1, while UV analysis shows a maximum absorbance (0.522) at 205 nm. The HPLC spectrum of HASBE indicates the presence of four major compounds, including orientin (77%), β-sitosterol (6.58%), rutin (5.02%), and betulinic acid (3.33%), while GC-FID result shows five major compounds, including rutin (53.27%), orientin (13.06%) and stigmasterol (11.73%), hymenocardine (6.43%) and homopterocarpin (5.29%). The SOD activity was significantly (p < 0.05) lowered in the kidney but elevated in the heart, while catalase was elevated in both organs relative to control rats. The GPx activity was significantly elevated only in the kidney, while MDA was not significantly (p > 0.05) affected in the two organs compared with controls. The activity of AChE was significantly elevated in both organs, while CE activity was elevated only in the kidney relative to control rats. The present study reveals that Hymenocardia acida stem bark extract majorly contains orientin, rutin, stigmasterol, hymenocardine, β-sitosterol, homopterocarpin, and betulinic acid. In addition, these compounds could possibly enhance redox status and esterase activities in the kidney and heart of Wistar rats.

Keywords: hymenocardia acida, elemental analysis, compounds identification, redox status, organs

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Authors: Katerina Zaharieva, Katya Milenova, Zara Cherkezova-Zheleva, Alexander Eliyas, Boris Kunev, Ivan Mitov

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The synthesized nanosized manganese ferrite-type of samples have been tested as photocatalysts in the reaction of oxidative degradation of model contaminant Reactive Black 5 (RB5) dye in aqueous solutions under UV irradiation. As it is known this azo dye is applied in the textile-coloring industry and it is discharged into the waterways causing pollution. The co-precipitation procedure has been used for the synthesis of manganese ferrite-type of materials: Sample 1 - Mn0.25Fe2.75O4, Sample 2 - Mn0.5Fe2.5O4 and Sample 3 - MnFe2O4 from 0.03M aqueous solutions of MnCl2•4H2O, FeCl2•4H2O and/or FeCl3•6H2O and 0.3M NaOH in appropriate amounts. The mechanochemical activation of co-precipitated ferrite-type of samples has been performed in argon (Samples 1 and 2) or in air atmosphere (Sample 3) for 2 hours at a milling speed of 500 rpm. The mechano-chemical treatment has been carried out in a high energy planetary ball mill type PM 100, Retsch, Germany. The mass ratio between balls and powder was 30:1. As a result mechanochemically activated Sample 4 - Mn0.25Fe2.75O4, Sample 5 - Mn0.5Fe2.5O4 and Sample 6 - MnFe2O4 have been obtained. The synthesized manganese ferrite-type photocatalysts have been characterized by X-ray diffraction method and Moessbauer spectroscopy. The registered X-ray diffraction patterns and Moessbauer spectra of co-precipitated ferrite-type of materials show the presence of manganese ferrite and additional akaganeite phase. The presence of manganese ferrite and small amounts of iron phases is established in the mechanochemically treated samples. The calculated average crystallite size of manganese ferrites varies within the range 7 – 13 nm. This result is confirmed by Moessbauer study. The registered spectra show superparamagnetic behavior of the prepared materials at room temperature. The photocatalytic investigations have been made using polychromatic UV-A light lamp (Sylvania BLB, 18 W) illumination with wavelength maximum at 365 nm. The intensity of light irradiation upon the manganese ferrite-type photocatalysts was 0.66 mW.cm-2. The photocatalytic reaction of oxidative degradation of RB5 dye was carried out in a semi-batch slurry photocatalytic reactor with 0.15 g of ferrite-type powder, 150 ml of 20 ppm dye aqueous solution under magnetic stirring at rate 400 rpm and continuously feeding air flow. The samples achieved adsorption-desorption equilibrium in the dark period for 30 min and then the UV-light was turned on. After regular time intervals aliquot parts from the suspension were taken out and centrifuged to separate the powder from solution. The residual concentrations of dye were established by a UV-Vis absorbance single beam spectrophotometer CamSpec M501 (UK) measuring in the wavelength region from 190 to 800 nm. The photocatalytic measurements determined that the apparent pseudo-first-order rate constants calculated by linear slopes approximating to first order kinetic equation, increase in following order: Sample 3 (1.1х10-3 min-1) < Sample 1 (2.2х10-3 min-1) < Sample 2 (3.3 х10-3 min-1) < Sample 4 (3.8х10-3 min-1) < Sample 6 (11х10-3 min-1) < Sample 5 (15.2х10-3 min-1). The mechanochemically activated manganese ferrite-type of photocatalyst samples show significantly higher degree of oxidative degradation of RB5 dye after 120 minutes of UV light illumination in comparison with co-precipitated ferrite-type samples: Sample 5 (92%) > Sample 6 (91%) > Sample 4 (63%) > Sample 2 (53%) > Sample 1 (42%) > Sample 3 (15%). Summarizing the obtained results we conclude that the mechanochemical activation leads to a significant enhancement of the degree of oxidative degradation of the RB5 dye and photocatalytic activity of tested manganese ferrite-type of catalyst samples under our experimental conditions. The mechanochemically activated Mn0.5Fe2.5O4 ferrite-type of material displays the highest photocatalytic activity (15.2х10-3 min-1) and degree of oxidative degradation of the RB5 dye (92%) compared to the other synthesized samples. Especially a significant improvement in the degree of oxidative degradation of RB5 dye (91%) has been determined for mechanochemically treated MnFe2O4 ferrite-type of sample with the highest extent of substitution of iron ions by manganese ions than in the case of the co-precipitated MnFe2O4 sample (15%). The mechanochemically activated manganese ferrite-type of samples show good photocatalytic properties in the reaction of oxidative degradation of RB5 azo dye in aqueous solutions and it could find potential application for dye removal from wastewaters originating from textile industry.

Keywords: nanostructured manganese ferrite-type materials, photocatalytic activity, Reactive Black 5, water treatment

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Authors: Francisco Vidal Vázquez, Pekka Simell, Christian Frilund, Matti Reinikainen, Ilkka Hiltunen, Tim Böltken, Benjamin Andris, Paolo Piermartini

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Carbon capture and utilization (CCU) are one of the key topics in mitigation of CO2 emissions. There are many different technologies that are applied for the production of diverse chemicals from CO2 such as synthetic natural gas, Fischer-Tropsch products, methanol and polymers. Power-to-Gas and Power-to-Liquids concepts arise as a synergetic solution for storing energy and producing value added products from the intermittent renewable energy sources and CCU. VTT is a research and technology development company having energy in transition as one of the key focus areas. VTT has extensive experience in piloting and upscaling of new energy and chemical processes. Recently, VTT has developed and commissioned a Mobile Synthesis Unit (MOBSU) in close collaboration with INERATEC, a spin-off company of Karlsruhe Institute of Technology (KIT, Germany). The MOBSU is a multipurpose synthesis unit for CO2 upgrading to energy carriers and chemicals, which can be transported on-site where CO2 emission and renewable energy are available. The MOBSU is initially used for production of fuel compounds and chemical intermediates by combination of two consecutive processes: reverse Water-Gas Shift (rWGS) and Fischer-Tropsch synthesis (FT). First, CO2 is converted to CO by high-pressure rWGS and then, the CO and H2 rich effluent is used as feed for FT using an intensified reactor technology developed and designed by INERATEC. Chemical equilibrium of rWGS reaction is not affected by pressure. Nevertheless, compression would be required in between rWGS and FT in the case when rWGS is operated at atmospheric pressure. This would also require cooling of rWGS effluent, water removal and reheating. For that reason, rWGS is operated using precious metal catalyst in the MOBSU at similar pressure as FT to simplify the process. However, operating rWGS at high pressures has also some disadvantages such as methane and carbon formation, and more demanding specifications for materials. The main parts of FT module are an intensified reactor, a hot trap to condense the FT wax products, and a cold trap to condense the FT liquid products. The FT synthesis is performed using cobalt catalyst in a novel compact reactor technology with integrated highly-efficient water evaporation cooling cycle. The MOBSU started operation in November 2016. First, the FT module is tested using as feedstock H2 and CO. Subsequently, rWGS and FT modules are operated together using CO2 and H2 as feedstock of ca. 5 Nm3/hr total flowrate. On spring 2017, The MOBSU unit will be integrated together with a direct air capture (DAC) of CO2 unit, and a PEM electrolyser unit at Lappeenranta University of Technology (LUT) premises for demonstration of the SoletAir concept. This would be the first time when synthetic fuels are produced by combination of DAC unit and electrolyser unit which uses solar power for H2 production.

Keywords: CO2 utilization, demonstration, Fischer-Tropsch synthesis, intensified reactors, reverse water-gas shift

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Authors: Anupama Singh, Papia Raj

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Though Municipal Solid Waste (MSW) is a worldwide problem, yet its implications are enormous in developing countries, as they are unable to provide proper Municipal Solid Waste Management (MSWM) for the large volume of MSW. As a result, the collected wastes are dumped in open dumping at landfilling sites while the uncollected wastes remain strewn on the roadside, many-a-time clogging drainage. Such unsafe and inadequate management of MSW causes various public health hazards. For example, MSW directly on contact or by leachate contaminate the soil, surface water, and ground water; open burning causes air pollution; anaerobic digestion between the piles of MSW enhance the greenhouse gases i.e., carbon dioxide and methane (CO2 and CH4) into the atmosphere. Moreover, open dumping can cause spread of vector borne disease like cholera, typhoid, dysentery, and so on. Patna, the capital city of Bihar, one of the most underdeveloped provinces in India, is a unique representation of this situation. Patna has been identified as the ‘garbage city’. Over the last decade there has been an exponential increase in the quantity of MSW generation in Patna. Though a large proportion of such MSW is recyclable in nature, only a negligible portion is recycled. Plastic constitutes the major chunk of the recyclable waste. The chemical composition of plastic is versatile consisting of toxic compounds, such as, plasticizers, like adipates and phthalates. Pigmented plastic is highly toxic and it contains harmful metals such as copper, lead, chromium, cobalt, selenium, and cadmium. Human population becomes vulnerable to an array of health problems as they are exposed to these toxic chemicals multiple times a day through air, water, dust, and food. Based on analysis of health data it can be emphasized that in Patna there has been an increase in the incidence of specific diseases, such as, diarrhoea, dysentry, acute respiratory infection (ARI), asthma, and other chronic respiratory diseases (CRD). This trend can be attributed to improper MSWM. The results were reiterated through a survey (N=127) conducted during 2014-15 in selected areas of Patna. Random sampling method of data collection was used to better understand the relationship between different variables affecting public health due to exposure to MSW and lack of MSWM. The results derived through bivariate and logistic regression analysis of the survey data indicate that segregation of wastes at source, segregation behavior, collection bins in the area, distance of collection bins from residential area, and transportation of MSW are the major determinants of public health issues. Sustainable recycling is a robust method for MSWM with its pioneer concerns being environment, society, and economy. It thus ensures minimal threat to environment and ecology consequently improving public health conditions. Hence, this paper concludes that sustainable recycling would be the most viable approach to manage MSW in Patna and would eventually reduce public health hazards.

Keywords: municipal solid waste, Patna, public health, sustainable recycling

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Authors: Kyoungrean Kim

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Importance of deep-sea mineral resources is dramatically increasing due to the depletion of land mineral resources corresponding to increasing human’s economic activities. Korea has acquired exclusive exploration licenses at four areas which are the Clarion-Clipperton Fracture Zone in the Pacific Ocean (2002), Tonga (2008), Fiji (2011) and Indian Ocean (2014). The preparation for commercial mining of Nautilus minerals (Canada) and Lockheed martin minerals (USA) is expected by 2020. The London Protocol 1996 (LP) under International Maritime Organization (IMO) and International Seabed Authority (ISA) will set environmental guidelines for deep-sea mining until 2020, to protect marine environment. In this research, the applicability of washing/extraction treatment for the remediation of deep-sea mining tailings was mainly evaluated in order to present preliminary data to develop practical remediation technology in near future. Polymetallic nodule samples were collected at the Clarion-Clipperton Fracture Zone in the Pacific Ocean, then stored at room temperature. Samples were pulverized by using jaw crusher and ball mill then, classified into 3 particle sizes (> 63 µm, 63-20 µm, < 20 µm) by using vibratory sieve shakers (Analysette 3 Pro, Fritsch, Germany) with 63 µm and 20 µm sieve. Only the particle size 63-20 µm was used as the samples for investigation considering the lower limit of ore dressing process which is tens to 100 µm. Rhamnolipid and sodium alginate as biosurfactant and aluminum sulfate which are mainly used as flocculant were used as environmentally friendly additives. Samples were adjusted to 2% liquid with deionized water then mixed with various concentrations of additives. The mixture was stirred with a magnetic bar during specific reaction times and then the liquid phase was separated by a centrifugal separator (Thermo Fisher Scientific, USA) under 4,000 rpm for 1 h. The separated liquid was filtered with a syringe and acrylic-based filter (0.45 µm). The extracted heavy metals in the filtered liquid were then determined using a UV-Vis spectrometer (DR-5000, Hach, USA) and a heat block (DBR 200, Hach, USA) followed by US EPA methods (8506, 8009, 10217 and 10220). Polymetallic nodule was mainly composed of manganese (27%), iron (8%), nickel (1.4%), cupper (1.3 %), cobalt (1.3%) and molybdenum (0.04%). Based on remediation standards of various countries, Nickel (Ni), Copper (Cu), Cadmium (Cd) and Zinc (Zn) were selected as primary target materials. Throughout this research, the use of rhamnolipid was shown to be an effective approach for removing heavy metals in samples originated from manganese nodules. Sodium alginate might also be one of the effective additives for the remediation of deep-sea mining tailings such as polymetallic nodules. Compare to the use of rhamnolipid and sodium alginate, aluminum sulfate was more effective additive at short reaction time within 4 h. Based on these results, sequencing particle separation, selective extraction/washing, advanced filtration of liquid phase, water treatment without dewatering and solidification/stabilization may be considered as candidate technologies for the remediation of deep-sea mining tailings.

Keywords: deep-sea mining tailings, heavy metals, remediation, extraction, additives

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Authors: Reyna Singh, David Lokhat, Milan Carsky

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The world crude oil demand is projected to rise to 108.5 million bbl/d by the year 2035. With reserves estimated at 869 billion tonnes worldwide, coal is an abundant resource. This work was aimed at producing a high value hydrocarbon liquid product from the Direct Coal Liquefaction (DCL) process at, comparatively, mild operating conditions. Via hydrogenation, the temperature-staged approach was investigated. In a two reactor lab-scale pilot plant facility, the objectives included maximising thermal dissolution of the coal in the presence of a hydrogen donor solvent in the first stage, subsequently promoting hydrogen saturation and hydrodesulphurization (HDS) performance in the second. The feed slurry consisted of high grade, pulverized bituminous coal on a moisture-free basis with a size fraction of < 100μm; and Tetralin mixed in 2:1 and 3:1 solvent/coal ratios. Magnetite (Fe3O4) at 0.25wt% of the dry coal feed was added for the catalysed runs. For both stages, hydrogen gas was used to maintain a system pressure of 100barg. In the first stage, temperatures of 250℃ and 300℃, reaction times of 30 and 60 minutes were investigated in an agitated batch reactor. The first stage liquid product was pumped into the second stage vertical reactor, which was designed to counter-currently contact the hydrogen rich gas stream and incoming liquid flow in the fixed catalyst bed. Two commercial hydrotreating catalysts; Cobalt-Molybdenum (CoMo) and Nickel-Molybdenum (NiMo); were compared in terms of their conversion, selectivity and HDS performance at temperatures 50℃ higher than the respective first stage tests. The catalysts were activated at 300°C with a hydrogen flowrate of approximately 10 ml/min prior to the testing. A gas-liquid separator at the outlet of the reactor ensured that the gas was exhausted to the online VARIOplus gas analyser. The liquid was collected and sampled for analysis using Gas Chromatography-Mass Spectrometry (GC-MS). Internal standard quantification methods for the sulphur content, the BTX (benzene, toluene, and xylene) and alkene quality; alkanes and polycyclic aromatic hydrocarbon (PAH) compounds in the liquid products were guided by ASTM standards of practice for hydrocarbon analysis. In the first stage, using a 2:1 solvent/coal ratio, an increased coal to liquid conversion was favoured by a lower operating temperature of 250℃, 60 minutes and a system catalysed by magnetite. Tetralin functioned effectively as the hydrogen donor solvent. A 3:1 ratio favoured increased concentrations of the long chain alkanes undecane and dodecane, unsaturated alkenes octene and nonene and PAH compounds such as indene. The second stage product distribution showed an increase in the BTX quality of the liquid product, branched chain alkanes and a reduction in the sulphur concentration. As an HDS performer and selectivity to the production of long and branched chain alkanes, NiMo performed better than CoMo. CoMo is selective to a higher concentration of cyclohexane. For 16 days on stream each, NiMo had a higher activity than CoMo. The potential to cover the demand for low–sulphur, crude diesel and solvents from the production of high value hydrocarbon liquid in the said process, is thus demonstrated.

Keywords: catalyst, coal, liquefaction, temperature-staged

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Authors: Łukasz Mazur, Kamil Domaradzki, Maciej Bik, Tomasz Brylewski, Aleksander Gil

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Interconnects used in solid oxide fuel and electrolyzer cells (SOFCₛ/SOECs) serve several important functions, and therefore interconnect materials must exhibit certain properties. Their thermal expansion coefficient needs to match that of the ceramic components of these devices – the electrolyte, anode and cathode. Interconnects also provide structural rigidity to the entire device, which is why interconnect materials must exhibit sufficient mechanical strength at high temperatures. Gas-tightness is also a prerequisite since they separate gas reagents, and they also must provide very good electrical contact between neighboring cells over the entire operating time. High-chromium ferritic steels meets these requirements to a high degree but are affected by the formation of a Cr₂O₃ scale, which leads to increased electrical resistance. The final criterion for interconnect materials is chemical inertness in relation to the remaining cell components. In the case of ferritic steels, this has proved difficult due to the formation of volatile and reactive oxyhydroxides observed when Cr₂O3 is exposed to oxygen and water vapor. This process is particularly harmful on the cathode side in SOFCs and the anode side in SOECs. To mitigate this, protective-conducting ceramic coatings can be deposited on an interconnect's surface. The area-specific resistance (ASR) of a single interconnect cannot exceed 0.1 m-2 at any point of the device's operation. The rate at which the CrO₃ scale grows on ferritic steels can be reduced significantly via the so-called reactive element effect (REE). Research has shown that the deposition of Gd₂O₃ nanoparticles on the surface of the Crofer 22 APU, already modified using a protective-conducting spinel layer, further improves the oxidation resistance of this steel. However, the deposition of the manganese-cobalt spinel layer is a rather complex process and is performed at high temperatures in reducing and oxidizing atmospheres. There was thus reason to believe that this process may reduce the effectiveness of Gd₂O₃ nanoparticles added as an active element source. The objective of the present study was, therefore, to determine any potential impact by introducing a preoxidation stage after the nanoparticle deposition and before the steel is coated with the spinel. This should have allowed the nanoparticles to incorporate into the interior of the scale formed on the steel. Different samples were oxidized for 7000 h in air at 1073 K under quasi-isothermal conditions. The phase composition, chemical composition, and microstructure of the oxidation products formed on the samples were determined using X-ray diffraction, Raman spectroscopy, and scanning electron microscopy combined with energy-dispersive X-ray spectroscopy. A four-point, two-probe DC method was applied to measure ASR. It was found that coating deposition does indeed reduce the beneficial effect of Gd₂O₃ addition, since the smallest mass gain and the lowest ASR value were determined for the sample for which the additional preoxidation stage had been performed. It can be assumed that during this stage, gadolinium incorporates into and segregates at grain boundaries in the thin Cr₂O₃ that is forming. This allows the Gd₂O₃ nanoparticles to be a more effective source of the active element.

Keywords: interconnects, oxide nanoparticles, reactive element effect, SOEC, SOFC

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Authors: Glauco M. M. M. Lustosa, João Paulo C. Costa, Sonia M. Zanetti, Mario Cilense, Leinig Antônio Perazolli, Maria Aparecida Zaghete

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The contamination of the environment has been one of the biggest problems of our time, mostly due to developments of many industries. SnO2 is an n-type semiconductor with band gap about 3.5 eV and has its electrical conductivity dependent of type and amount of modifiers agents added into matrix ceramic during synthesis process, allowing applications as sensing of gaseous pollutants on ambient. The chemical synthesis by polymeric precursor method consists in a complexation reaction between tin ion and citric acid at 90 °C/2 hours and subsequently addition of ethyleneglycol for polymerization at 130 °C/2 hours. It also prepared polymeric resin of zinc, cobalt and niobium ions. Stoichiometric amounts of the solutions were mixed to obtain the systems (Zn, Nb)-SnO2 and (Co, Nb) SnO2 . The metal immobilization reduces its segregation during the calcination resulting in a crystalline oxide with high chemical homogeneity. The resin was pre-calcined at 300 °C/1 hour, milled in Atritor Mill at 500 rpm/1 hour, and then calcined at 600 °C/2 hours. X-Ray Diffraction (XDR) indicated formation of SnO2 -rutile phase (JCPDS card nº 41-1445). The characterization by Scanning Electron Microscope of High Resolution showed spherical ceramic powder nanostructured with 10-20 nm of diameter. 20 mg of SnO2 -based powder was kept in 20 ml of isopropyl alcohol and then taken to an electrophoretic deposition (EPD) system. The EPD method allows control the thickness films through the voltage or current applied in the electrophoretic cell and by the time used for deposition of ceramics particles. This procedure obtains films in a short time with low costs, bringing prospects for a new generation of smaller size devices with easy integration technology. In this research, films were obtained in an alumina substrate with interdigital electrodes after applying 2 kV during 5 and 10 minutes in cells containing alcoholic suspension of (Zn, Nb)-SnO2 and (Co, Nb) SnO2 of powders, forming a sensing layer. The substrate has designed integrated micro hotplates that provide an instantaneous and precise temperature control capability when a voltage is applied. The films were sintered at 900 and 1000 °C in a microwave oven of 770 W, adapted by the research group itself with a temperature controller. This sintering is a fast process with homogeneous heating rate which promotes controlled growth of grain size and also the diffusion of modifiers agents, inducing the creation of intrinsic defects which will change the electrical characteristics of SnO2 -based powders. This study has successfully demonstrated a microfabricated system with an integrated micro-hotplate for detection of CO and NO2 gas at different concentrations and temperature, with self-heating SnO2 - based nanoparticles films, being suitable for both industrial process monitoring and detection of low concentrations in buildings/residences in order to safeguard human health. The results indicate the possibility for development of gas sensors devices with low power consumption for integration in portable electronic equipment with fast analysis. Acknowledgments The authors thanks to the LMA-IQ for providing the FEG-SEM images, and the financial support of this project by the Brazilian research funding agencies CNPq, FAPESP 2014/11314-9 and CEPID/CDMF- FAPESP 2013/07296-2.

Keywords: chemical synthesis, electrophoretic deposition, self-heating, gas sensor

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