Search results for: supercritical hydrothermal

Authors: Bartlomiej S. Witkowski, Lukasz Wachnicki, Sylwia Gieraltowska, Rafal Pietruszka, Marek Godlewski

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Zinc oxide is extensively studied II-VI semiconductor with a direct energy gap of about 3.37 eV at room temperature and high transparency in visible light spectral region. Due to these properties, ZnO is an attractive material for applications in photovoltaic, electronic and optoelectronic devices. ZnO nanorods, due to a well-developed surface, have potential of applications in sensor technology and photovoltaics. In this work we present a new inexpensive method of the ultra-fast growth of ZnO nanorods from the aqueous solution. This environment friendly and fully reproducible method allows growth of nanorods in few minutes time on various substrates, without any catalyst or complexing agent. Growth temperature does not exceed 50ºC and growth can be performed at atmospheric pressure. The method is characterized by simplicity and allows regulation of size of the ZnO nanorods in a large extent. Moreover the method is also very safe, it requires organic, non-toxic and low-price precursors. The growth can be performed on almost any type of substrate through the homo-nucleation as well as hetero-nucleation. Moreover, received nanorods are characterized by a very high quality - they are monocrystalline as confirmed by XRD and transmission electron microscopy. Importantly oxygen vacancies are not found in the photoluminescence measurements. First results for obtained by us ZnO nanorods in sensor applications are very promising. Resistance UV sensor, based on ZnO nanorods grown on a quartz substrates shows high sensitivity of 20 mW/m2 (2 μW/cm2) for point contacts, especially that the results are obtained for the nanorods array, not for a single nanorod. UV light (below 400 nm of wavelength) generates electron-hole pairs, which results in a removal from the surfaces of the water vapor and hydroxyl groups. This reduces the depletion layer in nanorods, and thus lowers the resistance of the structure. The so-obtained sensor works at room temperature and does not need the annealing to reset to initial state. Details of the technology and the first sensors results will be presented. The obtained ZnO nanorods are also applied in simple-architecture photovoltaic cells (efficiency over 12%) in conjunction with low-price Si substrates and high-sensitive photoresistors. Details informations about technology and applications will be presented.

Keywords: hydrothermal method, photoresistor, photovoltaic cells, ZnO nanorods

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Authors: Hristina Šalipur, Jasmina Dostanić, Davor Lončarević, Matej Huš

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Photocatalytic water splitting/alcohol photoreforming has been used for the conversion of sunlight energy in the process of hydrogen production due to its sustainability, environmental safety, effectiveness and simplicity. Titanate nanotubes are frequently studied materials since they combine the properties of photo-active semiconductors with the properties of layered titanates, such as the ion-exchange ability. Platinum (Pt) doping into titanate structure has been considered an effective strategy in better separation efficiency of electron-hole pairs and lowering the overpotential for hydrogen production, which results in higher photocatalytic activity. In our work, Pt doped titanate catalysts were synthesized via simple alkaline hydrothermal treatment, incipient wetness impregnation method and temperature-programmed reduction. The structural, morphological and optical properties of the prepared catalysts were investigated using various characterization techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 physisorption, and diffuse reflectance spectroscopy (DRS). The activities of the prepared Pt-doped titanate photocatalysts were tested for hydrogen production via photocatalytic water splitting/alcohol photoreforming process under simulated solar light irradiation. Characterization of synthesized Pt doped titanate catalysts showed crystalline anatase phase, preserved nanotubular structure and high specific surface area. The result showed enhancement of activity in photocatalytic water splitting/alcohol photoreforming in the following order 2-butanol>1-butanol>tert-butanol, with obtained maximal hydrogen production rate of 7.5, 5.3 and 2 mmol g-1 h-1, respectively. Different possible factors influencing the hole scavenging ability, such as hole scavenger redox potential and diffusivity, adsorption and desorption rate of the hole scavenger on the surface and stability of the alcohol radical species generated via hole scavenging, were investigated. The theoretical evaluation using density functional theory (DFT) further elucidated the reaction kinetics and detailed mechanism of photocatalytic water splitting/alcohol photoreforming.

Keywords: hydrogen production, platinum, semiconductor, water splitting, density functional theory

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Authors: Renzhi Qi, Zhaoping Zhong

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Under the dual pressure of the global energy crisis and environmental pollution, avoiding the consumption of non-renewable fossil fuels based on carbon as the energy carrier and developing and utilizing non-carbon energy carriers are the basic requirements for the future new energy economy. Electrocatalyst for water splitting plays an important role in building sustainable and environmentally friendly energy conversion. The oxygen evolution reaction (OER) is essentially limited by the slow kinetics of multi-step proton-electron transfer, which limits the efficiency and cost of water splitting. In this work, CeO₂@NiCo-NRGO/NF hybrid materials were prepared using nickel foam (NF) and nitrogen-doped reduced graphene oxide (NRGO) as conductive substrates by multi-step hydrothermal method and were used as highly efficient catalysts for OER. The well-connected nanosheet array forms a three-dimensional (3D) network on the substrate, providing a large electrochemical surface area with abundant catalytic active sites. The doping of CeO₂ in NiCo-NRGO/NF electrocatalysts promotes the dispersion of substances and its synergistic effect in promoting the activation of reactants, which is crucial for improving its catalytic performance against OER. The results indicate that CeO₂@NiCo-NRGO/NF only requires a lower overpotential of 250 mV to drive the current density of 10 mA cm-2 for an OER reaction of 1 M KOH, and exhibits excellent stability at this current density for more than 10 hours. The double layer capacitance (Cdl) values show that CeO₂@NiCo-NRGO/NF significantly affects the interfacial conductivity and electrochemically active surface area. The hybrid structure could promote the catalytic performance of oxygen evolution reaction, such as low initial potential, high electrical activity, and excellent long-term durability. The strategy for improving the catalytic activity of NiCo-LDH can be used to develop a variety of other electrocatalysts for water splitting.

Keywords: CeO₂, reduced graphene oxide, NiCo-layered double hydroxide, oxygen evolution reaction

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Authors: Niharika Kaushal, Minni Singh

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Fruit crops are widely cultivated throughout the World, with citrus being one of the most common. Mandarins, oranges, grapefruits, lemons, and limes are among the most frequently grown varieties. Citrus cultivars are industrially processed into juice, resulting in approx. 25-40% by wt. of biomass in the form of peels and seeds, generally considered as waste. In consequence, a significant amount of this nutraceutical-enriched biomass goes to waste, which, if utilized wisely, could revolutionize the functional food industry, as this biomass possesses a wide range of bioactive compounds, mainly within the class of polyphenols and terpenoids, making them an abundant source of functional bioactive. Mandarin is a potential source of bioflavonoids with putative antioxidative properties, and its potential application for developing value-added products is obvious. In this study, ‘kinnow’ mandarin (Citrus nobilis X Citrus deliciosa) biomass was studied for its flavonoid profile. For this, dried and pulverized peels were subjected to green and sustainable extraction techniques, namely, supercritical fluid extraction carried out under conditions pressure: 330 bar, temperature: 40 ̊ C and co-solvent: 10% ethanol. The obtained extract was observed to contain 47.3±1.06 mg/ml rutin equivalents as total flavonoids. Mass spectral analysis revealed the prevalence of polymethoxyflavones (PMFs), chiefly tangeretin and nobiletin. Furthermore, the antioxidant potential was analyzed by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) method, which was estimated to be at an IC₅₀ of 0.55μg/ml. The pre-systemic metabolism of flavonoids limits their functionality, as was observed in this study through in vitro gastrointestinal studies where nearly 50.0% of the flavonoids were degraded within 2 hours of gastric exposure. We proposed nanoencapsulation as a means to overcome this problem, and flavonoids-laden polylactic-co-glycolic acid (PLGA) nano encapsulates were bioengineered using solvent evaporation method, and these were furnished to a particle size between 200-250nm, which exhibited protection of flavonoids in the gastric environment, allowing only 20% to be released in 2h. A further step involved impregnating the nano encapsulates within alginate hydrogels which were fabricated by ionic cross-linking, which would act as delivery vehicles within the gastrointestinal (GI) tract. As a result, 100% protection was achieved from the pre-systemic release of bioflavonoids. These alginate hydrogels had key significant features, i.e., less porosity of nearly 20.0%, and Cryo-SEM (Cryo-scanning electron microscopy) images of the composite corroborate the packing ability of the alginate hydrogel. As a result of this work, it is concluded that the waste can be used to develop functional biomaterials while retaining the functionality of the bioactive itself.

Keywords: bioflavonoids, gastrointestinal, hydrogels, mandarins

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Authors: Fernando Vega, Esmeralda Portillo, Sara Camino, Benito Navarrete, Elena Montavez

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The European Union aims at strongly reducing their CO₂ emissions from energy and industrial sector by 2030. The energy sector contributes with more than two-thirds of the CO₂ emission share derived from anthropogenic activities. Although efforts are mainly focused on the use of renewables by energy production sector, carbon capture and storage (CCS) remains as a frontline option to reduce CO₂ emissions from industrial process, particularly from fossil-fuel power plants and cement production. Among the most feasible and near-to-market CCS technologies, namely post-combustion and oxy-combustion, partial oxy-combustion is a novel concept that can potentially reduce the overall energy requirements of the CO₂ capture process. This technology consists in the use of higher oxygen content in the oxidizer that should increase the CO₂ concentration of the flue gas once the fuel is burnt. The CO₂ is then separated from the flue gas downstream by means of a conventional CO₂ chemical absorption process. The production of a higher CO₂ concentrated flue gas should enhance the CO₂ absorption into the solvent, leading to further reductions of the CO₂ separation performance in terms of solvent flow-rate, equipment size, and energy penalty related to the solvent regeneration. This work evaluates a portfolio of CCS technologies applied to fossil-fuel power plants. For this purpose, an economic evaluation methodology was developed in detail to determine the main economical parameters for CO₂ emission removal such as the levelized cost of electricity (LCOE) and the CO₂ captured and avoided costs. ASPEN Plus™ software was used to simulate the main units of power plant and solve the energy and mass balance. Capital and investment costs were determined from the purchased cost of equipment, also engineering costs and project and process contingencies. The annual capital cost and operating and maintenance costs were later obtained. A complete energy balance was performed to determine the net power produced in each case. The baseline case consists of a supercritical 500 MWe coal-fired power plant using anthracite as a fuel without any CO₂ capture system. Four cases were proposed: conventional post-combustion capture, oxy-combustion and partial oxy-combustion using two levels of oxygen-enriched air (40%v/v and 75%v/v). CO₂ chemical absorption process using monoethanolamine (MEA) was used as a CO₂ separation process whereas the O₂ requirement was achieved using a conventional air separation unit (ASU) based on Linde's cryogenic process. Results showed a reduction of 15% of the total investment cost of the CO₂ separation process when partial oxy-combustion was used. Oxygen-enriched air production also reduced almost half the investment costs required for ASU in comparison with oxy-combustion cases. Partial oxy-combustion has a significant impact on the performance of both CO₂ separation and O₂ production technologies, and it can lead to further energy reductions using new developments on both CO₂ and O₂ separation processes.

Keywords: carbon capture, cost methodology, economic evaluation, partial oxy-combustion

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Authors: Zulkifli, I. W. Eltara, Anawati

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Understanding the complementary roles of surface energy and roughness on natural nonwetting surfaces has led to the development of a number of biomimetic superhydrophobic surfaces, which exhibit apparent contact angles with water greater than 150 degrees and low contact angle hysteresis. However, superoleophobic surfaces—those that display contact angles greater than 150 degrees with organic liquids having appreciably lower surface tensions than that of water—are extremely rare. In addition to chemical composition and roughened texture, a third parameter is essential to achieve superoleophobicity, namely, re-entrant surface curvature in the form of overhang structures. The overhangs can be realized as fibers. Superoleophobic surfaces are appealing for example, antifouling, since purely superhydrophobic surfaces are easily contaminated by oily substances in practical applications, which in turn will impair the liquid repellency. On the other studied have demonstrate that such aqueous nanofibrillar gels are unexpectedly robust to allow formation of highly porous aerogels by direct water removal by freeze-drying, they are flexible, unlike most aerogels that suffer from brittleness, and they allow flexible hierarchically porous templates for functionalities, e.g. for electrical conductivity. No crosslinking, solvent exchange nor supercritical drying are required to suppress the collapse during the aerogel preparation, unlike in typical aerogel preparations. The aerogel used in current work is an ultralight weight solid material composed of native cellulose nanofibers. The native cellulose nanofibers are cleaved from the self-assembled hierarchy of macroscopic cellulose fibers. They have become highly topical, as they are proposed to show extraordinary mechanical properties due to their parallel and grossly hydrogen bonded polysaccharide chains. We demonstrate that superoleophobic nanocellulose aerogels coating by sol-gel method, the aerogel is capable of supporting a weight nearly 3 orders of magnitude larger than the weight of the aerogel itself. The load support is achieved by surface tension acting at different length scales: at the macroscopic scale along the perimeter of the carrier, and at the microscopic scale along the cellulose nanofibers by preventing soaking of the aerogel thus ensuring buoyancy. Superoleophobic nanocellulose aerogels have recently been achieved using unmodified cellulose nanofibers and using carboxy methylated, negatively charged cellulose nanofibers as starting materials. In this work, the aerogels made from unmodified cellulose nanofibers were subsequently treated with fluorosilanes. To complement previous work on superoleophobic aerogels, we demonstrate their application as cargo carriers on oil, gas permeability, plastrons, and drag reduction, and we show that fluorinated nanocellulose aerogels are high-adhesive superoleophobic surfaces. We foresee applications including buoyant, gas permeable, dirt-repellent coatings for miniature sensors and other devices floating on generic liquid surfaces.

Keywords: superoleophobic, nanocellulose, aerogel, sol-gel

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Authors: Xiang Zheng, Zhaoping Zhong

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In this study, Aspen Plus was used to simulate the whole process of biomass conversion to liquid fuel in different ways, and the main results of material and energy flow were obtained. The process optimization and evaluation were carried out on the four routes of cellulosic biomass pyrolysis gasification low-carbon olefin synthesis olefin oligomerization, biomass water pyrolysis and polymerization to jet fuel, biomass fermentation to ethanol, and biomass pyrolysis to liquid fuel. The environmental impacts of three biomass species (poplar wood, corn stover, and rice husk) were compared by the gasification synthesis pathway. The global warming potential, acidification potential, and eutrophication potential of the three biomasses were the same as those of rice husk > poplar wood > corn stover. In terms of human health hazard potential and solid waste potential, the results were poplar > rice husk > corn stover. In the popular pathway, 100 kg of poplar biomass was input to obtain 11.9 kg of aviation coal fraction and 6.3 kg of gasoline fraction. The energy conversion rate of the system was 31.6% when the output product energy included only the aviation coal product. In the basic process of hydrothermal depolymerization process, 14.41 kg aviation kerosene was produced per 100 kg biomass. The energy conversion rate of the basic process was 33.09%, which can be increased to 38.47% after the optimal utilization of lignin gasification and steam reforming for hydrogen production. The total exergy efficiency of the system increased from 30.48% to 34.43% after optimization, and the exergy loss mainly came from the concentration of precursor dilute solution. Global warming potential in environmental impact is mostly affected by the production process. Poplar wood was used as raw material in the process of ethanol production from cellulosic biomass. The simulation results showed that 827.4 kg of pretreatment mixture, 450.6 kg of fermentation broth, and 24.8 kg of ethanol were produced per 100 kg of biomass. The power output of boiler combustion reached 94.1 MJ, the unit power consumption in the process was 174.9 MJ, and the energy conversion rate was 33.5%. The environmental impact was mainly concentrated in the production process and agricultural processes. On the basis of the original biomass pyrolysis to liquid fuel, the enzymatic hydrolysis lignin residue produced by cellulose fermentation to produce ethanol was used as the pyrolysis raw material, and the fermentation and pyrolysis processes were coupled. In the coupled process, 24.8 kg ethanol and 4.78 kg upgraded liquid fuel were produced per 100 kg biomass with an energy conversion rate of 35.13%.

Keywords: biomass conversion, biofuel, process optimization, life cycle assessment

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Authors: Daniel Manaye Kabtamu, Anteneh Wodaje Bayeh

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With the development and utilization of new energy technology, people’s demand for large-scale energy storage system has become increasingly urgent. Vanadium redox flow battery (VRFB) is one of the most promising technologies for grid-scale energy storage applications because of numerous attractive features, such as long cycle life, high safety, and flexible design. However, the relatively low energy efficiency and high production cost of the VRFB still limit its practical implementations. It is of great attention to enhance its energy efficiency and reduce its cost. One of the main components of VRFB that can impressively impact the efficiency and final cost is the electrode materials, which provide the reactions sites for redox couples (V₂₊/V³⁺ and VO²⁺/VO₂⁺). Graphite felt (GF) is a typical carbon-based material commonly employed as electrode for VRFB due to low-cost, good chemical and mechanical stability. However, pristine GF exhibits insufficient wettability, low specific surface area, and poor kinetics reversibility, leading to low energy efficiency of the battery. Therefore, it is crucial to further modify the GF electrode to improve its electrochemical performance towards VRFB by employing active electrocatalysts, such as less expensive metal oxides. This study successfully fabricates low-cost plate-like bismuth vanadate (BiVO₄) material through a simple one-step hydrothermal route, employed as an electrocatalyst to adorn the GF for use as the negative electrode in VRFB. The experimental results show that BiVO₄-3h exhibits the optimal electrocatalytic activity and reversibility for the vanadium redox couples among all samples. The energy efficiency of the VRFB cell assembled with BiVO₄-decorated GF as the negative electrode is found to be 75.42% at 100 mA cm−2, which is about 10.24% more efficient than that of the cell assembled with heat-treated graphite felt (HT-GF) electrode. The possible reasons for the activity enhancement can be ascribed to the existence of oxygen vacancies in the BiVO₄ lattice structure and the relatively high surface area of BiVO₄, which provide more active sites for facilitating the vanadium redox reactions. Furthermore, the BiVO₄-GF electrode obstructs the competitive irreversible hydrogen evolution reaction on the negative side of the cell, and it also has better wettability. Impressively, BiVO₄-GF as the negative electrode shows good stability over 100 cycles. Thus, BiVO₄-GF is a promising negative electrode candidate for practical VRFB applications.

Keywords: BiVO₄ electrocatalyst, electrochemical energy storage, graphite felt, vanadium redox flow battery

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Authors: Maksudur Rahman Khan, Kar Min Chan, Huei Ruey Ong, Chin Kui Cheng, Wasikur Rahman

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Microbial fuel cells (MFCs) represent a promising technology for simultaneous bioelectricity generation and wastewater treatment. Catalysts are significant portions of the cost of microbial fuel cell cathodes. Many materials have been tested as aqueous cathodes, but air-cathodes are needed to avoid energy demands for water aeration. The sluggish oxygen reduction reaction (ORR) rate at air cathode necessitates efficient electrocatalyst such as carbon supported platinum catalyst (Pt/C) which is very costly. Manganese oxide (MnO2) was a representative metal oxide which has been studied as a promising alternative electrocatalyst for ORR and has been tested in air-cathode MFCs. However, the single MnO2 has poor electric conductivity and low stability. In the present work, the MnO2 catalyst has been modified by doping Pt nanoparticle. The goal of the work was to improve the performance of the MFC with minimum Pt loading. MnO2 and Pt nanoparticles were prepared by hydrothermal and sol-gel methods, respectively. Wet impregnation method was used to synthesize Pt/MnO2 catalyst. The catalysts were further used as cathode catalysts in air-cathode cubic MFCs, in which anaerobic sludge was inoculated as biocatalysts and palm oil mill effluent (POME) was used as the substrate in the anode chamber. The as-prepared Pt/MnO2 was characterized comprehensively through field emission scanning electron microscope (FESEM), X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) where its surface morphology, crystallinity, oxidation state and electrochemical activity were examined, respectively. XPS revealed Mn (IV) oxidation state and Pt (0) nanoparticle metal, indicating the presence of MnO2 and Pt. Morphology of Pt/MnO2 observed from FESEM shows that the doping of Pt did not cause change in needle-like shape of MnO2 which provides large contacting surface area. The electrochemical active area of the Pt/MnO2 catalysts has been increased from 276 to 617 m2/g with the increase in Pt loading from 0.2 to 0.8 wt%. The CV results in O2 saturated neutral Na2SO4 solution showed that MnO2 and Pt/MnO2 catalysts could catalyze ORR with different catalytic activities. MFC with Pt/MnO2 (0.4 wt% Pt) as air cathode catalyst generates a maximum power density of 165 mW/m3, which is higher than that of MFC with MnO2 catalyst (95 mW/m3). The open circuit voltage (OCV) of the MFC operated with MnO2 cathode gradually decreased during 14 days of operation, whereas the MFC with Pt/MnO2 cathode remained almost constant throughout the operation suggesting the higher stability of the Pt/MnO2 catalyst. Therefore, Pt/MnO2 with 0.4 wt% Pt successfully demonstrated as an efficient and low cost electrocatalyst for ORR in air cathode MFC with higher electrochemical activity, stability and hence enhanced performance.

Keywords: microbial fuel cell, oxygen reduction reaction, Pt/MnO2, palm oil mill effluent, polarization curve

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Authors: Roberta Pecoraro

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The focus of this work was to investigate the potential toxic effect of titanium dioxide-reduced graphene oxide (TiO₂-rGO) nanocomposites on nauplii of microcrustacean Artemia sp. In order to assess the nanocomposite’s toxicity, a short-term test was performed by exposing nauplii to solutions containing TiO₂-rGO. To prepare titanium dioxide-reduced graphene oxide (TiO₂-rGO) nanocomposites, a green procedure based on solar photoreduction was proposed; it allows to obtain the photocatalysts by exploiting the photocatalytic properties of titania activated by the solar irradiation in order to avoid the high temperatures and pressures required for the standard hydrothermal synthesis. Powders of TiO₂-rGO supplied by the Department of Chemical Sciences (University of Catania) are indicated as TiO₂-rGO at 1% and TiO₂-rGO at 2%. Starting from a stock solution (1mg rGO-TiO₂/10 ml ASPM water) of each type, we tested four different concentrations (serial dilutions ranging from 10⁻¹ to 10⁻⁴ mg/ml). All the solutions have been sonicated for 12 min prior to use. Artificial seawater (called ASPM water) was prepared to guarantee the hatching of the cysts and to maintain nauplii; the durable cysts used in this study, marketed by JBL (JBL GmbH & Co. KG, Germany), were hydrated with ASPM water to obtain nauplii (instar II-III larvae). The hatching of the cysts was carried out in the laboratory by immersing them in ASPM water inside a 500 ml beaker and keeping them constantly oxygenated thanks to an aerator for the insufflation of microbubble air: after 24-48 hours, the cysts hatched, and the nauplii appeared. The nauplii in the second and third stages of development were collected one-to-one, using stereomicroscopes, and transferred into 96-well microplates where one nauplius per well was added. The wells quickly have been filled with 300 µl of each specific concentration of the solution used, and control samples were incubated only with ASPM water. Replication was performed for each concentration. Finally, the microplates were placed on an orbital shaker, and the tests were read after 24 and 48 hours from inoculating the solutions to assess the endpoint (immobility/death) for the larvae. Nauplii that appeared motionless were counted as dead, and the percentages of mortality were calculated for each treatment. The results showed a low percentage of immobilization both for TiO₂-rGO at 1% and TiO₂-rGO at 2% for all concentrations tested: for TiO₂-rGO at 1% was below 12% after 24h and below 15% after 48h; for TiO₂-rGO at 2% was below 8% after 24h and below 12% after 48h. According to other studies in the literature, the results have not shown mortality nor toxic effects on the development of larvae after exposure to rGO. Finally, it is important to highlight that the TiO₂-rGO catalysts were tested in the solar photodegradation of a toxic herbicide (2,4-Dichlorophenoxyacetic acid, 2,4-D), obtaining a high percentage of degradation; therefore, this alternative approach could be considered a good strategy to obtain performing photocatalysts.

Keywords: Nauplii, photocatalytic properties, reduced GO, short-term toxicity test, titanium dioxide

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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: Sunil P. Lonkar, Vishnu V. Pillai, Saeed Alhassan

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Design and development of highly efficient, inexpensive, and long-term stable earth-abundant electrocatalysts hold tremendous promise for hydrogen evolution reaction (HER) in water electrolysis. The 2D transition metal dichalcogenides, especially molybdenum disulfide attracted a great deal of interests due to its high electrocatalytic activity. However, due to its poor electrical conductivity and limited exposed active sites, the performance of these catalysts is limited. In this context, a facile and scalable synthesis method for fabrication nanostructured electrocatalysts composed 3D graphene porous aerogels supported with MoS₂ and WS₂ is highly desired. Here we developed a highly active and stable electrocatalyst catalyst for the HER by growing it into a 3D porous architecture on conducting graphene. The resulting nanohybrids were thoroughly investigated by means of several characterization techniques to understand structure and properties. Moreover, the HER performance of these 3D catalysts is expected to greatly improve in compared to other, well-known catalysts which mainly benefits from the improved electrical conductivity of the by graphene and porous structures of the support. This technologically scalable process can afford efficient electrocatalysts for hydrogen evolution reactions (HER) and hydrodesulfurization catalysts for sulfur-rich petroleum fuels. Owing to the lower cost and higher performance, the resulting materials holds high potential for various energy and catalysis applications. In typical hydrothermal method, sonicated GO aqueous dispersion (5 mg mL⁻¹) was mixed with ammonium tetrathiomolybdate (ATTM) and tungsten molybdate was treated in a sealed Teflon autoclave at 200 ◦C for 4h. After cooling, a black solid macroporous hydrogel was recovered washed under running de-ionized water to remove any by products and metal ions. The obtained hydrogels were then freeze-dried for 24 h and was further subjected to thermal annealing driven crystallization at 600 ◦C for 2h to ensure complete thermal reduction of RGO into graphene and formation of highly crystalline MoS₂ and WoS₂ phases. The resulting 3D nanohybrids were characterized to understand the structure and properties. The SEM-EDS clearly reveals the formation of highly porous material with a uniform distribution of MoS₂ and WS₂ phases. In conclusion, a novice strategy for fabrication of 3D nanostructured MoS₂-WS₂/graphene is presented. The characterizations revealed that the in-situ formed promoters uniformly dispersed on to few layered MoS₂¬-WS₂ nanosheets that are well-supported on graphene surface. The resulting 3D hybrids hold high promise as potential electrocatalyst and hydrodesulfurization catalyst.

Keywords: electrocatalysts, graphene, transition metal chalcogenide, 3D assembly

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Authors: Anna Stepien

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The paper presents the results of research on modifications of sand-lime bricks, especially using glass additives (glass fiber and glass sand) and other additives (e.g.:basalt&barite aggregate, lithium silicate and microsilica) as well. The main goal of this paper is to answer the question ‘How to use glass additives in the sand-lime mass and get a better bricks?’ The article contains information on modification of sand-lime bricks using glass fiber, glass sand, microsilica (different structure of silica). It also presents the results of the conducted compression tests, which were focused on compressive strength, water absorption, bulk density, and their microstructure. The Scanning Electron Microscope, spectrum EDS, X-ray diffractometry and DTA analysis helped to define the microstructural changes of modified products. The interpretation of the products structure revealed the existence of diversified phases i.e.the C-S-H and tobermorite. CaO-SiO2-H2O system is the object of intensive research due to its meaning in chemistry and technologies of mineral binding materials. Because the blocks are the autoclaving materials, the temperature of hydrothermal treatment of the products is around 200°C, the pressure - 1,6-1,8 MPa and the time - up to 8hours (it means: 1h heating + 6h autoclaving + 1h cooling). The microstructure of the products consists mostly of hydrated calcium silicates with a different level of structural arrangement. The X-ray diffraction indicated that the type of used sand is an important factor in the manufacturing of sand-lime elements. Quartz sand of a high hardness is also a substrate hardly reacting with other possible modifiers, which may cause deterioration of certain physical and mechanical properties. TG and DTA curves show the changes in the weight loss of the sand-lime bricks specimen against time as well as the endo- and exothermic reactions that took place. The endothermic effect with the maximum at T=573°C is related to isomorphic transformation of quartz. This effect is not accompanied by a change of the specimen weight. The next endothermic effect with the maximum at T=730-760°C is related to the decomposition of the calcium carbonates. The bulk density of the brick it is 1,73kg/dm3, the presence of xonotlite in the microstructure and significant weight loss during DTA and TG tests (around 0,6% after 70 minutes) have been noticed. Silicate elements were assessed on the basis of their compressive property. Orthogonal compositional plan type 3k (with k=2), i.e.full two-factor experiment was applied in order to carry out the experiments both, in the compression strength test and bulk density test. Some modification (e.g.products with barite and basalt aggregate) have improved the compressive strength around 41.3 MPa and water absorption due to capillary raising have been limited to 12%. The next modification was adding glass fiber to sand-lime mass, then glass sand. The results show that the compressive strength was higher than in the case of traditional bricks, while modified bricks were lighter.

Keywords: bricks, fiber, glass, microstructure

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Authors: Sam Derakhshan Deilami, Iain N. Kings, Lynne E. Macaskie, Brajendra K. Sharma, Anthony V. Bridgwater, Joseph Wood

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This paper reports the application of a bacteria-supported palladium catalyst to the hydrodeoxygenation (HDO) of pyrolysis bio-oil, towards producing an upgraded transport fuel. Biofuels are key to the timely replacement of fossil fuels in order to mitigate the emissions of greenhouse gases and depletion of non-renewable resources. The process is an essential step in the upgrading of bio-oils derived from industrial by-products such as agricultural and forestry wastes, the crude oil from pyrolysis containing a large amount of oxygen that requires to be removed in order to create a fuel resembling fossil-derived hydrocarbons. The bacteria supported catalyst manufacture is a means of utilizing recycled metals and second life bacteria, and the metal can also be easily recovered from the spent catalysts after use. Comparisons are made between bio-Pd, and a conventional activated carbon supported Pd/C catalyst. Bio-oil was produced by fast pyrolysis of beechwood at 500 C at a residence time below 2 seconds, provided by Aston University. 5 wt % BioPd/C was prepared under reducing conditions, exposing cells of E. coli MC4100 to a solution of sodium tetrachloropalladate (Na2PdCl4), followed by rinsing, drying and grinding to form a powder. Pd/C was procured from Sigma-Aldrich. The HDO experiments were carried out in a 100 mL Parr batch autoclave using ~20g bio-crude oil and 0.6 g bio-Pd/C catalyst. Experimental variables investigated for optimization included temperature (160-350C) and reaction times (up to 5 h) at a hydrogen pressure of 100 bar. Most of the experiments resulted in an aqueous phase (~40%) and an organic phase (~50-60%) as well as gas phase (<5%) and coke (<2%). Study of the temperature and time upon the process showed that the degree of deoxygenation increased (from ~20 % up to 60 %) at higher temperatures in the region of 350 C and longer residence times up to 5 h. However minimum viscosity (~0.035 Pa.s) occurred at 250 C and 3 h residence time, indicating that some polymerization of the oil product occurs at the higher temperatures. Bio-Pd showed a similar degree of deoxygenation (~20 %) to Pd/C at lower temperatures of 160 C, but did not rise as steeply with temperature. More coke was formed over bio-Pd/C than Pd/C at temperatures above 250 C, suggesting that bio-Pd/C may be more susceptible to coke formation than Pd/C. Reactions occurring during bio-oil upgrading include catalytic cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation and hydrogenation. In conclusion, it was shown that bio-Pd/C displays an acceptable rate of HDO, which increases with residence time and temperature. However some undesirable reactions also occur, leading to a deleterious increase in viscosity at higher temperatures. Comparisons are also drawn with earlier work on the HDO of Chlorella derived bio-oil manufactured from micro-algae via hydrothermal liquefaction. Future work will analyze the kinetics of the reaction and investigate the effect of bi-metallic catalysts.

Keywords: bio-oil, catalyst, palladium, upgrading

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Authors: Sadat Sembatya

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Tantalum metal is used in addressing capacitance challenge in the 21st-century technology growth. Tantalum is rarely found in its elemental form. Hence it’s often found with niobium and the radioactive elements of thorium and uranium. Industrial processes are required to extract pure tantalum. Its deposits are mainly oxide associated and exist in Ta-Nb oxides such as tapiolite, wodginite, ixiolite, rutile and pyrochlore-supergroup minerals are of minor importance. The stability and chemical inertness of tantalum makes it a valuable substance for laboratory equipment and a substitute for platinum. Each period of Tantalum ore formation is characterized by specific mineralogical and geochemical features. Compositions of Columbite-Group Minerals (CGM) are variable: Fe-rich types predominate in the Man Shield (Sierra Leone), the Congo Craton (DR Congo), the Kamativi Belt (Zimbabwe) and the Jos Plateau (Nigeria). Mn-rich columbite-tantalite is typical of the Alto Ligonha Province (Mozambique), the Arabian-Nubian Shield (Egypt, Ethiopia) and the Tantalite Valley pegmatites (southern Namibia). There are large compositional variations through Fe-Mn fractionation, followed by Nb-Ta fractionation. These are typical for pegmatites usually associated with very coarse quartz-feldspar-mica granites. They are young granitic systems of the Kibara Belt of Central Africa and the Older Granites of Nigeria. Unlike ‘simple’ Be-pegmatites, most Ta-Nb rich pegmatites have the most complex zoning. Hence we need systematic exploration tools to find and rapidly assess the potential of different pegmatites. The pegmatites exist as known deposits (e.g., abandoned mines) and the exposed or buried pegmatites. We investigate rocks and minerals to trace for the possibility of the effect of hydrothermal alteration mainly for exposed pegmatites, do mineralogical study to prove evidence of gradual replacement and geochemistry to report the availability of trace elements which are good indicators of mineralisation. Pegmatites are not good geophysical responders resulting to the exclusion of the geophysics option. As for more advanced prospecting, we bulk samples from different zones first to establish their grades and characteristics, then make a pilot test plant because of big samples to aid in the quantitative characterization of zones, and then drill to reveal distribution and extent of different zones but not necessarily grade due to nugget effect. Rapid assessment tools are needed to assess grade and degree of fractionation in order to ‘rule in’ or ‘rule out’ a given pegmatite for future work. Pegmatite exploration is also unique, high risk and expensive hence right traceability system and certification for 3Ts are highly needed.

Keywords: exploration, mineralogy, pegmatites, tantalum

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Authors: Sarmistha Baruah, Akshai Kumar, Nageswara Rao Peela

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The global energy crisis due to the dependence on fossil fuels and its limited reserves as well as environmental pollution are key concerns to the research communities. However, the implementation of alcohol-based fuel cells such as methanol is anticipated as a reliable source of future energy technology due to their high energy density, environment friendliness, ease of storage, transportation, etc. To drive the anodic methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs), an active and long-lasting catalyst is necessary for efficient energy conversion from methanol. Recently, transition metal-zeolite-based materials have been considered versatile catalysts for a variety of industrial and lab-scale processes. Large specific surface area, well-organized micropores, and adjustable acidity/basicity are characteristics of zeolites that make them excellent supports for immobilizing small-sized and highly dispersed metal species. Significant advancement in the production and characterization of well-defined metal clusters encapsulated within zeolite matrix has substantially expanded the library of materials available, and consequently, their catalytic efficacy. In this context, we developed bimetallic Ni-Co catalysts encapsulated within LTA (also known as 4A) zeolite via a method combined with the in-situ encapsulation of metal species using hydrothermal treatment followed by a chemical reduction process. The prepared catalyst was characterized using advanced characterization techniques, such as X-ray diffraction (XRD), field emission transmission electron microscope (FETEM), field emission scanning electron microscope (FESEM), energy dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of the catalyst for MOR was carried out in an alkaline medium at room temperature using techniques such as cyclic voltammetry (CV), and chronoamperometry (CA). The resulting catalyst exhibited better catalytic activity of 12.1 mA cm-2 at 1.12 V vs Ag/AgCl and retained remarkable stability (~77%) even after 1000 cycles CV test for the electro-oxidation of methanol in alkaline media without any significant microstructural changes. The high surface area, better Ni-Co species integration in the zeolite, and the ample amount of surface hydroxyl groups contribute to highly dispersed active sites and quick analyte diffusion, which provide notable MOR kinetics. Thus, this study will open up new possibilities to develop a noble metal-free zeolite-based electrocatalyst due to its simple synthesis steps, large-scale fabrication, improved stability, and efficient activity for DMFC application.

Keywords: alkaline media, bimetallic, encapsulation, methanol oxidation reaction, LTA zeolite.

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Authors: Niharika Kaushal, Minni Singh

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Citrus fruits fall into the category of those commercially grown fruits that constitute an excellent repository of phytochemicals with health-promoting properties. Fruits belonging to the citrus family, when processed by industries, produce tons of agriculture by-products in the form of peels, pulp, and seeds, which normally have no further usage and are commonly discarded. In spite of this, such residues are of paramount importance due to their richness in valuable compounds; therefore, agro-waste is considered a valuable bioresource for various purposes in the food sector. A range of biological properties, including anti-oxidative, anti-cancerous, anti-inflammatory, anti-allergenicity, and anti-aging activity, have been reported for these bioactive compounds. Taking advantage of these inexpensive residual sources requires special attention to extract bioactive compounds. Mandarin (Citrus nobilis X Citrus deliciosa) is a potential source of bioflavonoids with antioxidant properties, and it is increasingly regarded as a functional food. Despite these benefits, flavonoids suffer from a barrier of pre-systemic metabolism in gastric fluid, which impedes their effectiveness. Therefore, colloidal delivery systems can completely overcome the barrier in question. This study involved the extraction and identification of key flavonoids from mandarin biomass. Using a green chemistry approach, supercritical fluid extraction at 330 bar, temperature 40C, and co-solvent 10% ethanol was employed for extraction, and the identification of flavonoids was made by mass spectrometry. As flavonoids are concerned with a limitation, the obtained extract was encapsulated in polylactic-co-glycolic acid (PLGA) matrix using a solvent evaporation method. Additionally, the antioxidant potential was evaluated by the 2,2-diphenylpicrylhydrazyl (DPPH) assay. A release pattern of flavonoids was observed over time using simulated gastrointestinal fluids. From the results, it was observed that the total flavonoids extracted from the mandarin biomass were estimated to be 47.3 ±1.06 mg/ml rutin equivalents as total flavonoids. In the extract, significantly, polymethoxyflavones (PMFs), tangeretin and nobiletin were identified, followed by hesperetin and naringin. The designed flavonoid-PLGA nanoparticles exhibited a particle size between 200-250nm. In addition, the bioengineered nanoparticles had a high entrapment efficiency of nearly 80.0% and maintained stability for more than a year. Flavonoid nanoparticles showed excellent antioxidant activity with an IC50 of 0.55μg/ml. Morphological studies revealed the smooth and spherical shape of nanoparticles as visualized by Field emission scanning electron microscopy (FE-SEM). Simulated gastrointestinal studies of free extract and nanoencapsulation revealed the degradation of nearly half of the flavonoids under harsh acidic conditions in the case of free extract. After encapsulation, flavonoids exhibited sustained release properties, suggesting that polymeric encapsulates are efficient carriers of flavonoids. Thus, such technology-driven and biomass-derived products form the basis for their use in the development of functional foods with improved therapeutic potential and antioxidant properties. As a result, citrus processing waste can be considered a new resource that has high value and can be used for promoting its utilization.

Keywords: citrus, agrowaste, flavonoids, nanoparticles

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Authors: Aleksander Ejsmont, Stefan Wuttke, Joanna Goscianska

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Gaining control over particle shape, size and crystallinity is an ongoing challenge for many materials. Especially metalorganic frameworks (MOFs) are recently widely studied. Besides their remarkable porosity and interesting topologies, morphology has proven to be a significant feature. It can affect the further material application. Thus seeking new approaches that enable MOF morphology modulation is important. MOFs are reticular structures, where building blocks are made up of organic linkers and metallic nodes. The most common strategy of ensuring metal source is using salts, which usually exhibit high solubility and hinder morphology control. However, there has been a growing interest in using metal oxides as structure-directing agents towards MOFs due to their very low solubility and shape preservation. Metal oxides can be treated as a metal reservoir during MOF synthesis. Up to now, reports in which receiving MOFs from metal oxides mostly present ZnO conversion to ZIF-8. However, there are other oxides, for instance, Co₃O₄, which often is overlooked due to their structural stability and insolubility in aqueous solutions. Cobalt-based materials are famed for catalytic activity. Therefore the development of their efficient synthesis is worth attention. In the presented work, an optimized Co₃O₄transition to Co-MOFviaa solvothermal approach was proposed. The starting point of the research was the synthesis of Co₃O₄ flower petals and needles under hydrothermal conditions using different cobalt salts (e.g., cobalt(II) chloride and cobalt(II) nitrate), in the presence of urea, and hexadecyltrimethylammonium bromide (CTAB) surfactant as a capping agent. After receiving cobalt hydroxide, the calcination process was performed at various temperatures (300–500 °C). Then cobalt oxides as a source of cobalt cations were subjected to reaction with trimesic acid in solvothermal environment and temperature of 120 °C leading to Co-MOF fabrication. The solution maintained in the system was a mixture of water, dimethylformamide, and ethanol, with the addition of strong acids (HF and HNO₃). To establish how solvents affect metal oxide conversion, several different solvent ratios were also applied. The materials received were characterized with analytical techniques, including X-ray powder diffraction, energy dispersive spectroscopy,low-temperature nitrogen adsorption/desorption, scanning, and transmission electron microscopy. It was confirmed that the synthetic routes have led to the formation of Co₃O₄ and Co-based MOF varied in shape and size of particles. The diffractograms showed receiving crystalline phase for Co₃O₄, and also for Co-MOF. The Co₃O₄ obtained from nitrates and with using low-temperature calcination resulted in smaller particles. The study indicated that cobalt oxide particles of different size influence the efficiency of conversion and morphology of Co-MOF. The highest conversion was achieved using metal oxides with small crystallites.

Keywords: Co-MOF, solvothermal synthesis, morphology control, core-shell

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Authors: Loganathan Kumaresan, Velusamy Chidambaram, Arumugam Velayutham Karthikeyani, Alex Cheru Pulikottil, Madhusudan Sau, Gurpreet Singh Kapur, Sankara Sri Venkata Ramakumar

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Environmentally driven regulations throughout the world stipulate dramatic improvements in the quality of transportation fuels and refining operations. The exhaust gases like CO, NOx, and SOx from stationary sources (e.g., refinery) and motor vehicles contribute to a large extent for air pollution. The refining industry is under constant environmental pressure to achieve more rigorous standards on sulphur content in the fuel used in the transportation sector and other off-gas emissions. Fluid catalytic cracking unit (FCCU) is a major secondary process in refinery for gasoline and diesel production. CO-combustion promoter additive and gasoline sulphur reduction (GSR) additive are catalytic systems used in FCCU to assist the combustion of CO to CO₂ in the regenerator and regulate sulphur in gasoline faction respectively along with main FCC catalyst. Effectiveness of these catalysts is governed by the active metal used, its dispersion, the type of base material employed, and retention characteristics of additive in FCCU such as attrition resistance and density. The challenge is to have a high-density microsphere catalyst support for its retention and high activity of the active metals as these catalyst additives are used in low concentration compare to the main FCC catalyst. The present paper discusses in the first part development of high dense microsphere of nanocrystalline alumina by hydro-thermal method for CO combustion promoter application. Performance evaluation of additive was conducted under simulated regenerator conditions and shows CO combustion efficiency above 90%. The second part discusses the efficacy of a co-precipitation method for the generation of the active crystalline spinels of Zn, Mg, and Cu with aluminium oxides as an additive. The characterization and micro activity test using heavy combined hydrocarbon feedstock at FCC unit conditions for evaluating gasoline sulphur reduction activity are studied. These additives were characterized by X-Ray Diffraction, NH₃-TPD & N₂ sorption analysis, TPR analysis to establish structure-activity relationship. The reaction of sulphur removal mechanisms involving hydrogen transfer reaction, aromatization and alkylation functionalities are established to rank GSR additives for their activity, selectivity, and gasoline sulphur removal efficiency. The sulphur shifting in other liquid products such as heavy naphtha, light cycle oil, and clarified oil were also studied. PIONA analysis of liquid product reveals 20-40% reduction of sulphur in gasoline without compromising research octane number (RON) of gasoline and olefins content.

Keywords: hydrothermal, nanocrystalline, spinel, sulphur reduction

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Authors: Anna Krukowska, Tomasz Klimczuk, Adriana Zaleska-Medynska

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Photoactive materials have attracted attention due to their potential application in the degradation of environmental pollutants to non-hazardous compounds in an eco-friendly route. Among semiconductor photocatalysts, tantalates such as potassium tantalate (KTaO3) is one of the excellent functional photomaterial. However, tantalates-based materials are less active under visible-light irradiation, the enhancement in photoactivity could be improved with the modification of opto-eletronic properties of KTaO3 by doping rare earth metal (Er) and further photodeposition of noble metal nanoparticles (Pt). Inclusion of rare earth element in orthorhombic structure of tantalate can generate one high-energy photon by absorbing two or more incident low-energy photons, which convert visible-light and infrared-light into the ultraviolet-light to satisfy the requirement of KTaO3 photocatalysts. On the other hand, depositions of noble metal nanoparticles on the surface of semiconductor strongly absorb visible-light due to their surface plasmon resonance, in which their conducting electrons undergo a collective oscillation induced by electric field of visible-light. Furthermore, the high dispersion of Pt nanoparticles, which will be obtained by photodeposition process is additional important factor to improve the photocatalytic activity. The present work is aimed to study the effect of photocatalytic process of the prepared Er-doped KTaO3 and further incorporation of Pt nanoparticles by photodeposition. Moreover, the research is also studied correlations between photocatalytic activity and physico-chemical properties of obtained Pt/Er-KTaO3 samples. The Er-doped KTaO3 microcomposites were synthesized by a hydrothermal method. Then photodeposition method was used for Pt loading over Er-KTaO3. The structural and optical properties of Pt/Er-KTaO3 photocatalytic were characterized using scanning electron microscope (SEM), X-ray diffraction (XRD), volumetric adsorption method (BET), UV-Vis absorption measurement, Raman spectroscopy and luminescence spectroscopy. The photocatalytic properties of Pt/Er-KTaO3 microcomposites were investigated by degradation of phenol in aqueous phase as model pollutant under visible and ultraviolet-light irradiation. Results of this work show that all the prepared photocatalysis exhibit low BET surface area, although doping of the bare KTaO3 with rare earth element (Er) presents a slight increase in this value. The crystalline structure of Pt/Er-KTaO3 powders exhibited nearly identical positions for the main peak at about 22,8o and the XRD pattern could be assigned to an orthorhombic distorted perovskite structure. The Raman spectra of obtained semiconductors confirmed demonstrating perovskite-like structure. The optical absorption spectra of Pt nanoparticles exhibited plasmon absorption band for main peaks at about 216 and 264 nm. The addition of Pt nanoparticles increased photoactivity compared to Er-KTaO3 and pure KTaO3. Summary optical properties of KTaO3 change with its doping Er-element and further photodeposition of Pt nanoparticles.

Keywords: heterogeneous photocatalytic, KTaO3 photocatalysts, Er3+ ion doping, Pt photodeposition

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Authors: Totsaporn Suwannaruang, Kitirote Wantala

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The purposes of this research were to synthesize titanium dioxide photocatalyst doped with nitrogen (N-doped TiO₂) by hydrothermal method and to test the photocatalytic degradation of paraquat under UV and visible light illumination. The effect of calcination treatment temperature on their physical and chemical properties and photocatalytic efficiencies were also investigated. The characterizations of calcined N-doped TiO₂ photocatalysts such as specific surface area, textural properties, bandgap energy, surface morphology, crystallinity, phase structure, elements and state of charges were investigated by Brunauer, Emmett, Teller (BET) and Barrett, Joyner, Halenda (BJH) equations, UV-Visible diffuse reflectance spectroscopy (UV-Vis-DRS) by using the Kubelka-Munk theory, Wide-angle X-ray scattering (WAXS), Focussed ion beam scanning electron microscopy (FIB-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS), respectively. The results showed that the effect of calcination temperature was significant on surface morphology, crystallinity, specific surface area, pore size diameter, bandgap energy and nitrogen content level, but insignificant on phase structure and oxidation state of titanium (Ti) atom. The N-doped TiO₂ samples illustrated only anatase crystalline phase due to nitrogen dopant in TiO₂ restrained the phase transformation from anatase to rutile. The samples presented the nanorice-like morphology. The expansion on the particle was found at 650 and 700°C of calcination temperature, resulting in increased pore size diameter. The bandgap energy was determined by Kubelka-Munk theory to be in the range 3.07-3.18 eV, which appeared slightly lower than anatase standard (3.20 eV), resulting in the nitrogen dopant could modify the optical absorption edge of TiO₂ from UV to visible light region. The nitrogen content was observed at 100, 300 and 400°C only. Also, the nitrogen element disappeared at 500°C onwards. The nitrogen (N) atom can be incorporated in TiO₂ structure with the interstitial site. The uncalcined (100°C) sample displayed the highest percent paraquat degradation under UV and visible light irradiation due to this sample revealed both the highest specific surface area and nitrogen content level. Moreover, percent paraquat removal significantly decreased with increasing calcination treatment temperature. The nitrogen content level in TiO₂ accelerated the rate of reaction with combining the effect of the specific surface area that generated the electrons and holes during illuminated with light. Therefore, the specific surface area and nitrogen content level demonstrated the important roles in the photocatalytic activity of paraquat under UV and visible light illumination.

Keywords: restraining phase transformation, interstitial site, chemical charge state, photocatalysis, paraquat degradation

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Authors: Quentin C.P. Bourgogne, Vanessa Bouchart, Pierre Chevrier, Emmanuel Dattoli

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This study presents an experimental and theoretical work conducted on a PolyPhenylene Sulfide reinforced with 40%wt of short glass fibers (PPS GF40) and its matrix. Thermoplastics are widely used in the automotive industry to lightweight automotive parts. The replacement of metallic parts by thermoplastics is reaching under-the-hood parts, near the engine. In this area, the parts are subjected to high temperatures and are immersed in cooling liquid. This liquid is composed of water and glycol and can affect the mechanical properties of the composite. The aim of this work was thus to quantify the evolution of mechanical properties of the thermoplastic composite, as a function of temperature and liquid aging effects, in order to develop a reliable design of parts. An experimental campaign in the tensile mode was carried out at different temperatures and for various glycol proportions in the cooling liquid, for monotonic and cyclic loadings on a neat and a reinforced PPS. The results of these tests allowed to highlight some of the main physical phenomena occurring during these solicitations under tough hydro-thermal conditions. Indeed, the performed tests showed that temperature and liquid cooling aging can affect the mechanical behavior of the material in several ways. The more the cooling liquid contains water, the more the mechanical behavior is affected. It was observed that PPS showed a higher sensitivity to absorption than to chemical aggressiveness of the cooling liquid, explaining this dominant sensitivity. Two kinds of behaviors were noted: an elasto-plastic type under the glass transition temperature and a visco-pseudo-plastic one above it. It was also shown that viscosity is the leading phenomenon above the glass transition temperature for the PPS and could also be important under this temperature, mostly under cyclic conditions and when the stress rate is low. Finally, it was observed that soliciting this composite at high temperatures is decreasing the advantages of the presence of fibers. A new phenomenological model was then built to take into account these experimental observations. This new model allowed the prediction of the evolution of mechanical properties as a function of the loading environment, with a reduced number of parameters compared to precedent studies. It was also shown that the presented approach enables the description and the prediction of the mechanical response with very good accuracy (2% of average error at worst), over a wide range of hydrothermal conditions. A temperature-humidity equivalence principle was underlined for the PPS, allowing the consideration of aging effects within the proposed model. Then, a limit of improvement of the reachable accuracy was determinate for all models using this set of data by the application of an artificial intelligence-based model allowing a comparison between artificial intelligence-based models and phenomenological based ones.

Keywords: aging, analytical modeling, mechanical testing, polymer matrix composites, sequential model, thermomechanical

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Authors: Ghodsieh Isapour Toutizad, Aiyong Wang, Joonsoo Han, Derek Creaser, Louise Olsson, Magnus Skoglundh, Hanna HaRelind

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Nitrous oxide (N2O), which is generally formed as a byproduct of industrial chemical processes and fossil fuel combustion, has attracted considerable attention due to its destructive role in global warming and ozone layer depletion. From various developed technologies used for lean NOx reduction, the selective catalytic reduction (SCR) of NOx with ammonia is presently the most applied method. Therefore, the development of catalysts for efficient lean NOx reduction without forming N2O in the process, or only forming it to a very small extent from the exhaust gases is of crucial significance. One type of catalysts that nowadays are used for this aim are zeolite-based catalysts. It is owing to their remarkable catalytic performance under practical reaction conditions such as high thermal stability and high N2 selectivity. Among all zeolites, copper ion-exchanged zeolites, with CHA, MFI, and BEA framework structure (like SSZ-13, ZSM-5 and Beta, respectively), represent higher hydrothermal stability, high activity and N2 selectivity. This work aims at investigating the effect of the zeolite framework structure on the formation of N2O during NH3-SCR reaction conditions over three Cu-based zeolites ranging from small-pore to large-pore framework structure. In the zeolite framework, Cu exists in two cationic forms, that can catalyze the SCR reaction by activating NO to form NO+ and/or surface nitrate species. The nitrate species can thereafter react with NH3 to form another intermediate, ammonium nitrate, which seems to be one source for N2O formation at low temperatures. The results from in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) indicate that during the NO oxidation step, mainly NO+ and nitrate species are formed on the surface of the catalysts. The intensity of the absorption peak attributed to NO+ species is higher for the Cu-CHA sample compared to the other two samples, indicating a higher stability of this species in small cages. Furthermore, upon the addition of NH3, through the standard SCR reaction conditions, absorption peaks assigned to N-H stretching and bending vibrations are building up. At the same time, negative peaks are evolving in the O-H stretching region, indicating blocking/replacement of surface OH-groups by NH3 and NH4+. By removing NH3 and adding NO2 to the inlet gas composition, the peaks in the N-H stretching and bending vibration regions show a decreasing trend in intensity, with the decrease being more pronounced for increasing pore size. It can probably be owing to the higher accumulation of ammonia species in the small-pore size zeolite compared to the other two samples. Furthermore, it is worth noting that the ammonia surface species are strongly bonded to the CHA zeolite structure, which makes it more difficult to react with NO2. To conclude, the framework structure of the zeolite seems to play an important role in the formation and reactivity of surface species relevant for the SCR process. Here we intend to discuss the connection between the zeolite structure, the surface species, and the formation of N2O during ammonia-SCR.

Keywords: fast SCR, nitrous oxide, NOx, standard SCR, zeolites

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Authors: Mayoorika Shukla, Pramila Jakhar, Tejendra Dixit, I. A. Palani, Vipul Singh

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Biosensors are analytical devices with wide range of applications in biological, chemical, environmental and clinical analysis. It comprises of bio-recognition layer which has biomolecules (enzymes, antibodies, DNA, etc.) immobilized over it for detection of analyte and transducer which converts the biological signal into the electrical signal. The performance of biosensor primarily the depends on the bio-recognition layer and therefore it has to be chosen wisely. In this regard, nanostructures of metal oxides such as ZnO, SnO2, V2O5, and TiO2, etc. have been explored extensively as bio-recognition layer. Recently, ZnO has the attracted attention of researchers due to its unique properties like high iso-electric point, biocompatibility, stability, high electron mobility and high electron binding energy, etc. Although there have been many reports on usage of ZnO as bio-recognition layer but to the authors’ knowledge, none has ever observed correlation between optical properties like defect suppression and biosensing capability of the sensor. Here, ZnO nanorods (ZNR) have been synthesized by a low cost, simple and low-temperature hydrothermal growth process, over Platinum (Pt) coated glass substrate. The ZNR have been synthesized in two steps viz. initially a seed layer was coated over substrate (Pt coated glass) followed by immersion of it into nutrient solution of Zinc nitrate and Hexamethylenetetramine (HMTA) with in situ addition of KMnO4. The addition of KMnO4 was observed to have a profound effect over the growth rate anisotropy of ZnO nanostructures. Clustered and powdery growth of ZnO was observed without addition of KMnO4, although by addition of it during the growth, uniform and crystalline ZNR were found to be grown over the substrate. Moreover, the same has resulted in suppression of defects as observed by Normalized Photoluminescence (PL) spectra since KMnO4 is a strong oxidizing agent which provides an oxygen rich growth environment. Further, to explore the correlation between defect suppression and biosensing capability of the ZNR Glucose oxidase (Gox) was immobilized over it, using physical adsorption technique followed by drop casting of nafion. Here the main objective of the work was to analyze effect of defect suppression over biosensing capability, and therefore Gox has been chosen as model enzyme, and electrochemical amperometric glucose detection was performed. The incorporation of KMnO4 during growth has resulted in variation of optical and charge transfer properties of ZNR which in turn were observed to have deep impact on biosensor figure of merits. The sensitivity of biosensor was found to increase by 12-18 times, due to variations introduced by addition of KMnO4 during growth. The amperometric detection of glucose in continuously stirred buffer solution was performed. Interestingly, defect suppression has been observed to contribute towards the improvement of biosensor performance. The detailed mechanism of growth of ZNR along with the overall influence of defect suppression on the sensing capabilities of the resulting enzymatic electrochemical biosensor and different figure of merits of the biosensor (Glass/Pt/ZNR/Gox/Nafion) will be discussed during the conference.

Keywords: biosensors, defects, KMnO4, ZnO nanorods

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Authors: Fang Lian, Zefang Chenli, Laijun Ma, Lei Mao

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Up to now, electrolytic process is a popular way to prepare Mn and MnO2 (EMD) with high purity. However, the conventional preparation process of manganese oxide such as Mn3O4 with high purity from electrolytic manganese metal is characterized by long production-cycle, high-pollution discharge and high energy consumption especially initially from low-grade rhodochrosite, the main resources for exploitation and applications in China. Moreover, Mn3O4 prepared from electrolytic manganese shows large particles, single morphology beyond the control and weak chemical activity. On the other hand, hydrometallurgical method combined with thermal decomposition, hydrothermal synthesis and sol-gel processes has been widely studied because of its high efficiency, low consumption and low cost. But the key problem in direct preparation of manganese oxide series from low-grade rhodochrosite is to remove completely the multiple impurities such as iron, silicon, calcium and magnesium. It is urgent to develop a sustainable approach to high pure manganese oxide series with character of short process, high efficiency, environmentally friendly and economical benefit. In our work, the preparation technique of high pure Mn3O4 directly from low-grade rhodochrosite ore (13.86%) was studied and improved intensively, including the effective leaching process and the short purifying process. Based on the same ion effect, the repeated leaching of rhodochrosite with sulfuric acid is proposed to improve the solubility of Mn2+ and inhibit the dissolution of the impurities Ca2+ and Mg2+. Moreover, the repeated leaching process could make full use of sulfuric acid and lower the cost of the raw material. With the aid of theoretical calculation, Ba(OH)2 was chosen to adjust the pH value of manganese sulfate solution and BaF2 to remove Ca2+ and Mg2+ completely in the process of purifying. Herein, the recovery ratio of manganese and removal ratio of the impurity were evaluated via chemical titration and ICP analysis, respectively. Comparison between conventional preparation technique from electrolytic manganese and a sustainable approach directly from low-grade rhodochrosite have also been done herein. The results demonstrate that the extraction ratio and the recovery ratio of manganese reached 94.3% and 92.7%, respectively. The heavy metal impurities has been decreased to less than 1ppm, and the content of calcium, magnesium and sodium has been decreased to less than 20ppm, which meet standards of high pure reagent for energy and electronic materials. In compare with conventional technique from electrolytic manganese, the power consumption has been reduced to ≤2000 kWh/t(product) in our short-process approach. Moreover, comprehensive recovery rate of manganese increases significantly, and the wastewater generated from our short-process approach contains low content of ammonia/ nitrogen about 500 mg/t(product) and no toxic emissions. Our study contributes to the sustainable application of low-grade manganese ore. Acknowledgements: The authors are grateful to the National Science and Technology Support Program of China (No.2015BAB01B02) for financial support to the work.

Keywords: leaching, high purity, low-grade rhodochrosite, manganese oxide, purifying process, recovery ratio

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Authors: Mostafa Feiz, Mohammad Safari, Hossein Hadizadeh

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The Chalpo copper area is located in northeastern Iran, which is part of the structural zone of central Iran and the back-arc basin of Sabzevar. This sedimentary basin accumulated in destructive-oligomiocene sediments is named the Nasr-Chalpo-Sangerd (NCS) basin. The sedimentary layers in this basin originated mainly from Upper Cretaceous ophiolitic rocks and intermediate to mafic-post ophiolitic volcanic rocks, deposited as a nonconformity. The mineralized sandstone layers in the Chalpo area include leached zones (with a thickness of 5 to 8 meters) and mineralized lenses with a thickness of 0.5 to 0.7 meters. Ore minerals include primary sulfide minerals, such as chalcocite, chalcopyrite, and pyrite, as well as secondary minerals, such as covellite, digenite, malachite, and azurite, formed in three stages that comprise primary, simultaneously, and supergene stage. The best agents that control the mineralization in this area include the permeability of host rocks, the presence of fault zones as the conduits for copper oxide solutions, and significant amounts of plant fossils, which create a reducing environment for the deposition of mineralized layers. The calculations of mass changes on copper-bearing layers and primary sandstone layers indicate that Pb, As, Cd, Te, and Mo are enriched in the mineralized zones, whereas SiO₂, TiO₂, Fe₂O₃, V, Sr, and Ba are depleted. The combination of geological, stratigraphic, and geochemical studies suggests that the origin of copper may have been the underlying red strata that contained hornblende, plagioclase, biotite, alkaline feldspar, and labile minerals. Dehydration and hydrolysis of these minerals during the diagenetic process caused the leaching of copper and associated elements by circling fluids, which formed an oxidant-hydrothermal solution. Copper and silver in this oxidant solution might have moved upwards through the basin-fault zones and deposited in the reducing environments in the sandstone layers that have had abundant organic matter. Copper in these solutions was probably carried by chloride complexes. The collision of oxidant and reduced solutions caused the deposition of Cu and Ag, whereas some s elements in oxidant environments (e.g., Fe₂O₃, TiO₂, SiO₂, REEs) become uns in the reduced condition. Therefore, the copper-bearing sandstones in the study area are depleted from these elements resulting from the leaching process. The results indicate that during the mineralization stage, LREEs and MREEs were depleted, but Cu, Ag, and S were enriched. Based on field evidence, it seems that the circulation of connate fluids in the reb-bed strata, produced by diagenetic processes, encountered to reduced facies, which formed earlier by abundant fossil-plant debris in the sandstones, is the best model for precipitating sulfide-copper minerals.

Keywords: Chalpo, Oligo-Miocene red beds, sandstone-hosted copper mineralization, mass change, LREEs and MREEs

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Authors: Demetrio L. Valle Jr., Juliana Janet M. Puzon, Windell L. Rivera

Abstract:

From the various medicinal plants available in the Philippines, crude ethanol extracts of twelve (12) Philippine medicinal plants, namely: Senna alata L. Roxb. (akapulko), Psidium guajava L. (bayabas), Piper betle L. (ikmo), Vitex negundo L. (lagundi), Mitrephora lanotan (Blanco) Merr. (Lanotan), Zingiber officinale Roscoe (luya), Curcuma longa L. (Luyang dilaw), Tinospora rumphii Boerl (Makabuhay), Moringga oleifera Lam. (malunggay), Phyllanthus niruri L. (sampa-sampalukan), Centella asiatica (L.) Urban (takip kuhol), and Carmona retusa (Vahl) Masam (tsaang gubat) were studied. In vitro methods of evaluation against selected Gram-positive and Gram-negative multidrug-resistant (MDR), bacteria were performed on the plant extracts. Although five of the plants showed varying antagonistic activities against the test organisms, only Piper betle L. exhibited significant activities against both Gram-negative and Gram-positive multidrug-resistant bacteria, exhibiting wide zones of growth inhibition in the disk diffusion assay, and with the lowest concentrations of the extract required to inhibit the growth of the bacteria, as supported by the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) assays. Further antibacterial studies of the Piper betle L. leaf, obtained by three extraction methods (ethanol, methanol, supercritical CO2), revealed similar inhibitory activities against a multitude of Gram-positive and Gram-negative MDR bacteria. Thin layer chromatography (TLC) assay of the leaf extract revealed a maximum of eight compounds with Rf values of 0.92, 0.86, 0.76, 0.53, 0.40, 0.25, 0.13, and 0.013, best visualized when inspected under UV-366 nm. TLC- agar overlay bioautography of the isolated compounds showed the compounds with Rf values of 0.86 and 0.13 having inhibitory activities against Gram-positive MDR bacteria (MRSA and VRE). The compound with an Rf value of 0.86 also possesses inhibitory activity against Gram-negative MDR bacteria (CRE Klebsiella pneumoniae and MBL Acinetobacter baumannii). Gas Chromatography-Mass Spectrometry (GC-MS) was able to identify six volatile compounds, four of which are new compounds that have not been mentioned in the medical literature. The chemical compounds isolated include 4-(2-propenyl)phenol and eugenol; and the new four compounds were ethyl diazoacetate, tris(trifluoromethyl)phosphine, heptafluorobutyrate, and 3-fluoro-2-propynenitrite. Phytochemical screening and investigation of its antioxidant, cytotoxic, possible hemolytic activities, and mechanisms of antibacterial activity were also done. The results showed that the local variant of Piper betle leaf extract possesses significant antioxidant, anti-cancer and antimicrobial properties, attributed to the presence of bioactive compounds, particularly of flavonoids (condensed tannin, leucoanthocyanin, gamma benzopyrone), anthraquinones, steroids/triterpenes and 2-deoxysugars. Piper betle L. is also traditionally known to enhance wound healing, which could be primarily due to its antioxidant, anti-inflammatory and antimicrobial activities. In vivo studies on mice using 2.5% and 5% of the ethanol leaf extract cream formulations in the excised wound models significantly increased the process of wound healing in the mice subjects, the results and values of which are at par with the current antibacterial cream (Mupirocin). From the results of the series of studies, we have definitely proven the value of Piper betle L. as a source of bioactive compounds that could be developed into therapeutic agents against MDR bacteria.

Keywords: Philippine herbal medicine, multidrug-resistant bacteria, Piper betle, TLC-bioautography

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Authors: Hanna Abbo, Siyasanga Noganta, Salam Titinchi

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The global lack of clean water for human sanitation and other purposes has become an emerging dilemma for human beings. The presence of organic pollutants in wastewater produced by textile industries, leather manufacturing and chemical industries is an alarming matter for a safe environment and human health. For the last decades, conventional methods have been applied for the purification of water but due to industrialization these methods fall short. Advanced oxidation processes and their reliable application in degradation of many contaminants have been reported as a potential method to reduce and/or alleviate this problem. Lately it has been assumed that incorporation of some metal nanoparticles such as magnetite nanoparticles as photocatalyst for Fenton reaction which could improve the degradation efficiency of contaminants. Core/shell nanoparticles, are extensively studied because of their wide applications in the biomedical, drug delivery, electronics fields and water treatment. The current study is centred on the synthesis of silver-doped Fe3O4/SiO2/TiO2 photocatalyst. Magnetically separable Fe3O4@SiO2@TiO2 composite with core–shell structure were synthesized by the deposition of uniform anatase TiO2 NPs on Fe3O4@SiO2 by using titanium butoxide (TBOT) as titanium source. Then, the silver is doped on SiO2 layer by hydrothermal method. Integration of magnetic nanoparticles was suggested to avoid the post separation difficulties associated with the powder form of the TiO2 catalyst, increase of the surface area and adsorption properties. The morphology, structure, composition, and magnetism of the resulting composites were characterized and their photocatalytic activities were also evaluated. The results demonstrate that TiO2 NPs were uniformly deposited on the Fe3O4@SiO2 surface. The silver nanoparticles were also uniformly distributed on the surface of TiO2 nanoparticles. The aim of this work is to study the suitability of photocatalysis for the treatment of aqueous streams containing organic pollutants such as methylene blue which is selected as a model compound to represent one of the pollutants existing in wastewaters. Various factors such as initial pollutant concentration, photocatalyst dose and wastewater matrix were studied for their effect on the photocatalytic degradation of the organic model pollutants using the as synthesized catalysts and compared with the commercial titanium dioxide (Aeroxide P25). Photocatalysis was found to be a potential purification method for the studied pollutant also in an industrial wastewater matrix with the removal percentages of over 81 % within 15 minutes. Methylene blue was removed most efficiently and its removal consumed the least of energy in terms of the specific applied energy. The magnetic Ag/SiO2/TiO2 composites show high photocatalytic performance and can be recycled three times by magnetic separation without major loss of activity, which meant that they can be used as efficient and conveniently renewable photocatalyst.

Keywords: Magnetite nanoparticles, Titanium, Photocatalyst, Organic pollutant, Water treatment

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Authors: Marta Paszkiewicz, Justyna Łuczak, Martyna Marchelek, Adriana Zaleska-Medynska

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In recent years, photocatalytical processes have been intensively investigated for destruction of pollutants, hydrogen evolution, disinfection of water, air and surfaces, for the construction of self-cleaning materials (tiles, glass, fibres, etc.). Titanium dioxide (TiO2) is the most popular material used in heterogeneous photocatalysis due to its excellent properties, such as high stability, chemical inertness, non-toxicity and low cost. It is well known that morphology and microstructure of TiO2 significantly influence the photocatalytic activity. This characteristics as well as other physical and structural properties of photocatalysts, i.e., specific surface area or density of crystalline defects, could be controlled by preparation route. In this regard, TiO2 particles can be obtained by sol-gel, hydrothermal, sonochemical methods, chemical vapour deposition and alternatively, by ionothermal synthesis using ionic liquids (ILs). In the TiO2 particles synthesis ILs may play a role of a solvent, soft template, reagent, agent promoting reduction of the precursor or particles stabilizer during synthesis of inorganic materials. In this work, the effect of the ILs anion type on morphology and photoactivity of TiO2 is presented. The preparation of TiO2 microparticles with spherical structure was successfully achieved by solvothermal method, using tetra-tert-butyl orthotitatane (TBOT) as the precursor. The reaction process was assisted by an ionic liquids 1-butyl-3-methylimidazolium bromide [BMIM][Br], 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] and 1-butyl-3-methylimidazolium haxafluorophosphate [BMIM][PF6]. Various molar ratios of all ILs to TBOT (IL:TBOT) were chosen. For comparison, reference TiO2 was prepared using the same method without IL addition. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Brenauer-Emmett-Teller surface area (BET), NCHS analysis, and FTIR spectroscopy were used to characterize the surface properties of the samples. The photocatalytic activity was investigated by means of phenol photodegradation in the aqueous phase as a model pollutant, as well as formation of hydroxyl radicals based on detection of fluorescent product of coumarine hydroxylation. The analysis results showed that the TiO2 microspheres had spherical structure with the diameters ranging from 1 to 6 µm. The TEM micrographs gave a bright observation of the samples in which the particles were comprised of inter-aggregated crystals. It could be also observed that the IL-assisted TiO2 microspheres are not hollow, which provides additional information about possible formation mechanism. Application of the ILs results in rise of the photocatalytic activity as well as BET surface area of TiO2 as compared to pure TiO2. The results of the formation of 7-hydroxycoumarin indicated that the increased amount of ·OH produced at the surface of excited TiO2 for samples TiO2_ILs well correlated with more efficient degradation of phenol. NCHS analysis showed that ionic liquids remained on the TiO2 surface confirming structure directing role of that compounds.

Keywords: heterogeneous photocatalysis, IL-assisted synthesis, ionic liquids, TiO2

Procedia PDF Downloads 267

Authors: Elodie Niemiec, Philippe Champagne, Jean-Francois Blach, Philippe Moreau, Anthony Thuault, Arnaud Tricoteaux

Abstract:

Hygiene of equipment in contact with users is an important issue in the railroad industry. The numerous cleanings to eliminate bacteria and dirt cost a lot. Besides, mechanical solicitations on contact parts are observed daily. It should be interesting to elaborate on a self-cleaning and antibacterial coating with sufficient adhesion and good resistance against mechanical and chemical solicitations. Thus, a Hauts-de-France and Maubeuge Val-de-Sambre conurbation authority co-financed Ph.D. thesis has been set up since October 2017 based on anterior studies carried by the Laboratory of Ceramic Materials and Processing. To accomplish this task, a soft chemical route has been implemented to bring a lotus effect on metallic substrates. It involves nanometric liquid zinc oxide synthesis under 100°C. The originality here consists in a variation of surface texturing by modification of the synthesis time of the species in solution. This helps to adjust wettability. Nanostructured zinc oxide has been chosen because of the inherent photocatalytic effect, which can activate organic substance degradation. Two methods of heating have been compared: conventional and microwave assistance. Tested subtracts are made of stainless steel to conform to transport uses. Substrate preparation was the first step of this protocol: a meticulous cleaning of the samples is applied. The main goal of the elaboration protocol is to fix enough zinc-based seeds to make them grow during the next step as desired (nanorod shaped). To improve this adhesion, a silica gel has been formulated and optimized to ensure chemical bonding between substrate and zinc seeds. The last step consists of deposing a wide carbonated organosilane to improve the superhydrophobic property of the coating. The quasi-proportionality between the reaction time and the nanorod length will be demonstrated. Water Contact (superior to 150°) and Roll-off Angle at different steps of the process will be presented. The antibacterial effect has been proved with Escherichia Coli, Staphylococcus Aureus, and Bacillus Subtilis. The mortality rate is found to be four times superior to a non-treated substrate. Photocatalytic experiences were carried out from different dyed solutions in contact with treated samples under UV irradiation. Spectroscopic measurements allow to determinate times of degradation according to the zinc quantity available on the surface. The final coating obtained is, therefore, not a monolayer but rather a set of amorphous/crystalline/amorphous layers that have been characterized by spectroscopic ellipsometry. We will show that the thickness of the nanostructured oxide layer depends essentially on the synthesis time set in the hydrothermal growth step. A green, easy-to-process and control coating with self-cleaning and antibacterial properties has been synthesized with a satisfying surface structuration.

Keywords: antibacterial, biomimetism, soft-chemistry, zinc oxide

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