Search results for: inorganic salts
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 678

Search results for: inorganic salts

108 Immobilization of Horseradish Peroxidase onto Bio-Linked Magnetic Particles with Allium Cepa Peel Water Extracts

Authors: Mirjana Petronijević, Sanja Panić, Aleksandra Cvetanović, Branko Kordić, Nenad Grba

Abstract:

Enzyme peroxidases are biological catalysts and play a major role in phenolic wastewater treatments and other environmental applications. The most studied species from the peroxidases family is horseradish peroxidase (HRP). In environmental processes, HRP could be used in its free or immobilized form. Enzyme immobilization onto solid support is performed to improve the enzyme properties, prolong its lifespan and operational stability and allow its reuse in industrial applications. One of the enzyme supports of a newer generation is magnetic particles (MPs). Fe₃O₄ MPs are the most widely pursued immobilization of enzymes owing to their remarkable advantages of biocompatibility and non-toxicity. Also, MPs can be easily separated and recovered from the water by applying an external magnetic field. On the other hand, metals and metal oxides are not suitable for the covalent binding of enzymes, so it is necessary to perform their surface modification. Fe₃O₄ MPs functionalization could be performed during the process of their synthesis if it takes place in the presence of plant extracts. Extracts of plant material, such as wild plants, herbs, even waste materials of the food and agricultural industry (bark, shell, leaves, peel), are rich in various bioactive components such as polyphenols, flavonoids, sugars, etc. When the synthesis of magnetite is performed in the presence of plant extracts, bioactive components are incorporated into the surface of the magnetite, thereby affecting its functionalization. In this paper, the suitability of bio-magnetite as solid support for covalent immobilization of HRP across glutaraldehyde was examined. The activity of immobilized HRP at different pH values (4-9) and temperatures (20-80°C) and reusability were examined. Bio-MP was synthesized by co-precipitation method from Fe(II) and Fe(III) sulfate salts in the presence of water extract of the Allium cepa peel. The water extract showed 81% of antiradical potential (according to DPPH assay), which is connected with the high content of polyphenols. According to the FTIR analysis, the bio-magnetite contains oxygen functional groups (-OH, -COOH, C=O) suitable for binding to glutaraldehyde, after which the enzyme is covalently immobilized. The immobilized enzyme showed high activity at ambient temperature and pH 7 (30 U/g) and retained ≥ 80% of its activity at a wide range of pH (5-8) and temperature (20-50°C). The HRP immobilized onto bio-MPs showed remarkable stability towards temperature and pH variations compared to the free enzyme form. On the other hand, immobilized HRP showed low reusability after the first washing cycle enzyme retains 50% of its activity, while after the third washing cycle retains only 22%.

Keywords: bio-magnetite, enzyme immobilization, water extracts, environmental protection

Procedia PDF Downloads 190
107 Effective Medium Approximations for Modeling Ellipsometric Responses from Zinc Dialkyldithiophosphates (ZDDP) Tribofilms Formed on Sliding Surfaces

Authors: Maria Miranda-Medina, Sara Salopek, Andras Vernes, Martin Jech

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Sliding lubricated surfaces induce the formation of tribofilms that reduce friction, wear and prevent large-scale damage of contact parts. Engine oils and lubricants use antiwear and antioxidant additives such as zinc dialkyldithiophosphate (ZDDP) from where protective tribofilms are formed by degradation. The ZDDP tribofilms are described as a two-layer structure composed of inorganic polymer material. On the top surface, the long chain polyphosphate is a zinc phosphate and in the bulk, the short chain polyphosphate is a mixed Fe/Zn phosphate with a gradient concentration. The polyphosphate chains are partially adherent to steel surface through a sulfide and work as anti-wear pads. In this contribution, ZDDP tribofilms formed on gray cast iron surfaces are studied. The tribofilms were generated in a reciprocating sliding tribometer with a piston ring-cylinder liner configuration. Fully formulated oil of SAE grade 5W-30 was used as lubricant during two tests at 40Hz and 50Hz. For the estimation of the tribofilm thicknesses, spectroscopic ellipsometry was used due to its high accuracy and non-destructive nature. Ellipsometry works under an optical principle where the change in polarisation of light reflected by the surface, is associated with the refractive index of the surface material or to the thickness of the layer deposited on top. Ellipsometrical responses derived from tribofilms are modelled by effective medium approximation (EMA), which includes the refractive index of involved materials, homogeneity of the film and thickness. The materials composition was obtained from x-ray photoelectron spectroscopic studies, where the presence of ZDDP, O and C was confirmed. From EMA models it was concluded that tribofilms formed at 40 Hz are thicker and more homogeneous than the ones formed at 50 Hz. In addition, the refractive index of each material is mixed to derive an effective refractive index that describes the optical composition of the tribofilm and exhibits a maximum response in the UV range, being a characteristic of glassy semitransparent films.

Keywords: effective medium approximation, reciprocating sliding tribometer, spectroscopic ellipsometry, zinc dialkyldithiophosphate

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106 Investigations on Geopolymer Concrete Slabs

Authors: Akhila Jose

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The cement industry is one of the major contributors to the global warming due to the release of greenhouse gases. The primary binder in conventional concrete is Ordinary Portland cement (OPC) and billions of tons are produced annually all over the world. An alternative binding material to OPC is needed to reduce the environmental impact caused during the cement manufacturing process. Geopolymer concrete is an ideal material to substitute cement-based binder. Geopolymer is an inorganic alumino-silicate polymer. Geopolymer Concrete (GPC) is formed by the polymerization of aluminates and silicates formed by the reaction of solid aluminosilicates with alkali hydroxides or alkali silicates. Various Industrial bye- products like Fly Ash (FA), Rice Husk Ash (RHA), Ground granulated Blast Furnace Slag (GGBFS), Silica Fume (SF), Red mud (RM) etc. are rich in aluminates and silicates. Using by-products from other industries reduces the carbon dioxide emission and thus giving a sustainable way of reducing greenhouse gas emissions and also a way to dispose the huge wastes generated from the major industries like thermal plants, steel plants, etc. The earlier research about geopolymer were focused on heat cured fly ash based precast members and this limited its applications. The heat curing mechanism itself is highly cumbersome and costly even though they possess high compressive strength, low drying shrinkage and creep, and good resistance to sulphate and acid environments. GPC having comparable strength and durability characteristics of OPC were able to develop under ambient cured conditions is the solution making it a sustainable alternative in future. In this paper an attempt has been made to review and compare the feasibility of ambient cured GPC over heat cured geopolymer concrete with respect to strength and serviceability characteristics. The variation on the behavior of structural members is also reviewed to identify the research gaps for future development of ambient cured geopolymer concrete. The comparison and analysis of studies showed that GPC most importantly ambient cured type has a comparable behavior with respect to OPC based concrete in terms strength and durability criteria.

Keywords: geopolymer concrete, oven heated, durability properties, mechanical properties

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105 Microbial Activity and Greenhouse Gas (GHG) Emissions in Recovery Process in a Grassland of China

Authors: Qiushi Ning

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The nitrogen (N) is an important limiting factor of various ecosystems, and the N deposition rate is increasing unprecedentedly due to anthropogenic activities. The N deposition altered the microbial growth and activity, and microbial mediated N cycling through changing soil pH, the availability of N and carbon (C). The CO2, CH4 and N2O are important greenhouse gas which threaten the sustainability and function of the ecosystem. With the prolonged and increasing N enrichment, the soil acidification and C limitation will be aggravated, and the microbial biomass will be further declined. The soil acidification and lack of C induced by N addition are argued as two important factors regulating the microbial activity and growth, and the studies combined soil acidification with lack of C on microbial community are scarce. In order to restore the ecosystem affected by chronic N loading, we determined the responses of microbial activity and GHG emssions to lime and glucose (control, 1‰ lime, 2‰ lime, glucose, 1‰ lime×glucose and 2‰ lime×glucose) addition which was used to alleviate the soil acidification and supply C resource into soils with N addition rates 0-50 g N m–2yr–1. The results showed no significant responses of soil respiration and microbial biomass (MBC and MBN) to lime addition, however, the glucose substantially improved the soil respiration and microbial biomass (MBC and MBN); the cumulative CO2 emission and microbial biomass of lime×glucose treatments were not significantly higher than those of only glucose treatment. The glucose and lime×glucose treatments reduced the net mineralization and nitrification rate, due to inspired microbial growth via C supply incorporating more inorganic N to the biomass, and mineralization of organic N was relatively reduced. The glucose addition also increased the CH4 and N2O emissions, CH4 emissions was regulated mainly by C resource as a substrate for methanogen. However, the N2O emissions were regulated by both C resources and soil pH, the C was important energy and the increased soil pH could benefit the nitrifiers and denitrifiers which were primary producers of N2O. The soil respiration and N2O emissions increased with increasing N addition rates in all glucose treatments, as the external C resource improved microbial N utilization. Compared with alleviated soil acidification, the improved availability of C substantially increased microbial activity, therefore, the C should be the main limiting factor in long-term N loading soils. The most important, when we use the organic C fertilization to improve the production of the ecosystems, the GHG emissions and consequent warming potentials should be carefully considered.

Keywords: acidification and C limitation, greenhouse gas emission, microbial activity, N deposition

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104 Evaluation of Sugarcane Straw Derived Biochar for the Remediation of Chromium and Nickel Contaminated Soil

Authors: Selam M. Tefera

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Soil constitutes a crucial component of rural and urban environments. This fact is making role of heavy and trace elements in the soil system an issue of global concern. Heavy metals constitute an ill-defined group of inorganic chemical hazards, whose main source is anthropogenic activities mainly related to fabrications. This accumulation of heavy metals soils can prove toxic to the environment. The application of biochar to soil is one way of immobilizing these contaminants through sorption by exploiting the high surface area of this material among its other essential properties. This research examined the ability of sugar cane straw, an organic waste material from sugar farm, derived biochar and ash to remediate soil contaminated with heavy metals mainly Chromium and Zinc from the effluent of electroplating industry. Biochar was produced by varying the temperature from 300 °C to 500 °C and ash at 700 °C. The highest yield (50%) was obtained at the lowest temperature (300 °C). The proximate analysis showed ash content of 42.8%, ultimate analysis with carbon content of 67.18%, the Hydrogen to Carbon ratio of 0.54 and the results from FTIR analysis disclosed the organic nature of biochar. Methylene blue absorption indicated its fine surface area and pore structure, which increases with severity of temperature. Biochar was mixed with soil with at a ration varying from 4% w/w to 10% w/w of soil, and the response variables were determined at a time interval of 150 days, 180 days, and 210 days. As for ash (10% w/w), the characterization was performed at incubation time of 210 days. The results of pH indicated that biochar (9.24) had a notable liming capacity of acidic soil (4.8) by increasing it to 6.89 whereas ash increased it to 7.5. The immobilization capacity of biochar was found to effected mostly by the highest production temperature (500 °C), which was 75.5% for chromium and 80.5% for nickel. In addition, ash was shown to possess an outstanding immobilization capacity of 95.5% and 90.5% for Chromium and Nickel, respectively. All in all, the results from these methods showed that biochar produced from this specific biomass possesses the typical functional groups that enable it to store carbon, the appropriate pH that could remediate acidic soil, a fine amount of macro and micro nutrients that would aid plant growth.

Keywords: biochar, biomass, heavy metal immobalization, soil remediation

Procedia PDF Downloads 122
103 Plasma Technology for Hazardous Biomedical Waste Treatment

Authors: V. E. Messerle, A. L. Mosse, O. A. Lavrichshev, A. N. Nikonchuk, A. B. Ustimenko

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One of the most serious environmental problems today is pollution by biomedical waste (BMW), which in most cases has undesirable properties such as toxicity, carcinogenicity, mutagenicity, fire. Sanitary and hygienic survey of typical solid BMW, made in Belarus, Kazakhstan, Russia and other countries shows that their risk to the environment is significantly higher than that of most chemical wastes. Utilization of toxic BMW requires use of the most universal methods to ensure disinfection and disposal of any of their components. Such technology is a plasma technology of BMW processing. To implement this technology a thermodynamic analysis of the plasma processing of BMW was fulfilled and plasma-box furnace was developed. The studies have been conducted on the example of the processing of bone. To perform thermodynamic calculations software package Terra was used. Calculations were carried out in the temperature range 300 - 3000 K and a pressure of 0.1 MPa. It is shown that the final products do not contain toxic substances. From the organic mass of BMW synthesis gas containing combustible components 77.4-84.6% was basically produced, and mineral part consists mainly of calcium oxide and contains no carbon. Degree of gasification of carbon reaches 100% by the temperature 1250 K. Specific power consumption for BMW processing increases with the temperature throughout its range and reaches 1 kWh/kg. To realize plasma processing of BMW experimental installation with DC plasma torch of 30 kW power was developed. The experiments allowed verifying the thermodynamic calculations. Wastes are packed in boxes weighing 5-7 kg. They are placed in the box furnace. Under the influence of air plasma flame average temperature in the box reaches 1800 OC, the organic part of the waste is gasified and inorganic part of the waste is melted. The resulting synthesis gas is continuously withdrawn from the unit through the cooling and cleaning system. Molten mineral part of the waste is removed from the furnace after it has been stopped. Experimental studies allowed determining operating modes of the plasma box furnace, the exhaust gases was analyzed, samples of condensed products were assembled and their chemical composition was determined. Gas at the outlet of the plasma box furnace has the following composition (vol.%): CO - 63.4, H2 - 6.2, N2 - 29.6, S - 0.8. The total concentration of synthesis gas (CO + H2) is 69.6%, which agrees well with the thermodynamic calculation. Experiments confirmed absence of the toxic substances in the final products.

Keywords: biomedical waste, box furnace, plasma torch, processing, synthesis gas

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102 Synthesis, Characterization and Photocatalytic Applications of Ag-Doped-SnO₂ Nanoparticles by Sol-Gel Method

Authors: M. S. Abd El-Sadek, M. A. Omar, Gharib M. Taha

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In recent years, photocatalytic degradation of various kinds of organic and inorganic pollutants using semiconductor powders as photocatalysts has been extensively studied. Owing to its relatively high photocatalytic activity, biological and chemical stability, low cost, nonpoisonous and long stable life, Tin oxide materials have been widely used as catalysts in chemical reactions, including synthesis of vinyl ketone, oxidation of methanol and so on. Tin oxide (SnO₂), with a rutile-type crystalline structure, is an n-type wide band gap (3.6 eV) semiconductor that presents a proper combination of chemical, electronic and optical properties that make it advantageous in several applications. In the present work, SnO₂ nanoparticles were synthesized at room temperature by the sol-gel process and thermohydrolysis of SnCl₂ in isopropanol by controlling the crystallite size through calculations. The synthesized nanoparticles were identified by using XRD analysis, TEM, FT-IR, and Uv-Visible spectroscopic techniques. The crystalline structure and grain size of the synthesized samples were analyzed by X-Ray diffraction analysis (XRD) and the XRD patterns confirmed the presence of tetragonal phase SnO₂. In this study, Methylene blue degradation was tested by using SnO₂ nanoparticles (at different calculations temperatures) as a photocatalyst under sunlight as a source of irradiation. The results showed that the highest percentage of degradation of Methylene blue dye was obtained by using SnO₂ photocatalyst at calculations temperature 800 ᵒC. The operational parameters were investigated to be optimized to the best conditions which result in complete removal of organic pollutants from aqueous solution. It was found that the degradation of dyes depends on several parameters such as irradiation time, initial dye concentration, the dose of the catalyst and the presence of metals such as silver as a dopant and its concentration. Percent degradation was increased with irradiation time. The degradation efficiency decreased as the initial concentration of the dye increased. The degradation efficiency increased as the dose of the catalyst increased to a certain level and by further increasing the SnO₂ photocatalyst dose, the degradation efficiency is decreased. The best degradation efficiency on which obtained from pure SnO₂ compared with SnO₂ which doped by different percentage of Ag.

Keywords: SnO₂ nanoparticles, a sol-gel method, photocatalytic applications, methylene blue, degradation efficiency

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101 Fabrication of Highly Conductive Graphene/ITO Transparent Bi-Film through Chemical Vapor Deposition (CVD) and Organic Additives-Free Sol-Gel Techniques

Authors: Bastian Waduge Naveen Harindu Hemasiri, Jae-Kwan Kim, Ji-Myon Lee

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Indium tin oxide (ITO) remains the industrial standard transparent conducting oxides with better performances. Recently, graphene becomes as a strong material with unique properties to replace the ITO. However, graphene/ITO hybrid composite material is a newly born field in the electronic world. In this study, the graphene/ITO composite bi-film was synthesized by a two steps process. 10 wt.% tin-doped, ITO thin films were produced by an environmentally friendly aqueous sol-gel spin coating technique with economical salts of In(NO3)3.H2O and SnCl4 without using organic additives. The wettability and surface free energy (97.6986 mJ/m2) enhanced oxygen plasma treated glass substrates were used to form voids free continuous ITO film. The spin-coated samples were annealed at 600 0C for 1 hour under low vacuum conditions to obtained crystallized, ITO film. The crystal structure and crystalline phases of ITO thin films were analyzed by X-ray diffraction (XRD) technique. The Scherrer equation was used to determine the crystallite size. Detailed information about chemical composition and elemental composition of the ITO film were determined by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX) coupled with FE-SEM respectively. Graphene synthesis was done under chemical vapor deposition (CVD) method by using Cu foil at 1000 0C for 1 min. The quality of the synthesized graphene was characterized by Raman spectroscopy (532nm excitation laser beam) and data was collected at room temperature and normal atmosphere. The surface and cross-sectional observation were done by using FE-SEM. The optical transmission and sheet resistance were measured by UV-Vis spectroscopy and four point probe head at room temperature respectively. Electrical properties were also measured by using V-I characteristics. XRD patterns reveal that the films contain the In2O3 phase only and exhibit the polycrystalline nature of the cubic structure with the main peak of (222) plane. The peak positions of In3d5/2 (444.28 eV) and Sn3d5/2 (486.7 eV) in XPS results indicated that indium and tin are in the oxide form only. The UV-visible transmittance shows 91.35 % at 550 nm with 5.88 x 10-3 Ωcm specific resistance. The G and 2D band in Raman spectroscopy of graphene appear at 1582.52 cm-1 and 2690.54 cm-1 respectively when the synthesized CVD graphene on SiO2/Si. The determined intensity ratios of 2D to G (I2D/IG) and D to G (ID/IG) were 1.531 and 0.108 respectively. However, the above-mentioned G and 2D peaks appear at 1573.57 cm-1 and 2668.14 cm-1 respectively when the CVD graphene on the ITO coated glass, the positions of G and 2D peaks were red shifted by 8.948 cm-1 and 22.396 cm-1 respectively. This graphene/ITO bi-film shows modified electrical properties when compares with sol-gel derived ITO film. The reduction of sheet resistance in the bi-film was 12.03 % from the ITO film. Further, the fabricated graphene/ITO bi-film shows 88.66 % transmittance at 550 nm wavelength.

Keywords: chemical vapor deposition, graphene, ITO, Raman Spectroscopy, sol-gel

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100 Influence of Initial Curing Time, Water Content and Apparent Water Content on Geopolymer Modified Sludge Generated in Landslide Area

Authors: Minh Chien Vu, Tomoaki Satomi, Hiroshi Takahashi

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As being lack of sufficient strength to support the loading of construction as well as service life cause the clay content and clay mineralogy, soft and highly compressible soils (sludge) constitute a major problem in geotechnical engineering projects. Geopolymer, a kind of inorganic polymer, is a promising material with a wide range of applications and offers a lower level of CO₂ emissions than conventional Portland cement. However, the feasibility of geopolymer in term of modified the soft and highly compressible soil has not been received much attention due to the requirement of heat treatment for activating the fly ash component and the existence of high content of clay-size particles in the composition of sludge that affected on the efficiency of the reaction. On the other hand, the geopolymer modified sludge could be affected by other important factors such as initial curing time, initial water content and apparent water content. Therefore, this paper describes a different potential application of geopolymer: soil stabilization in landslide areas to adapt to the technical properties of sludge so that heavy machines can move on. Sludge condition process is utilized to demonstrate the possibility for stabilizing sludge using fly ash-based geopolymer at ambient curing condition ( ± 20 °C) in term of failure strength, strain and bulk density. Sludge conditioning is a process whereby sludge is treated with chemicals or various other means to improve the dewatering characteristics of sludge before applying in the construction area. The effect of initial curing time, water content and apparent water content on the modification of sludge are the main focus of this study. Test results indicate that the initial curing time has potential for improving failure strain and strength of modified sludge with the specific condition of soft soil. The result further shows that the initial water content over than 50% total mass of sludge could significantly lead to a decrease of strength performance of geopolymer-based modified sludge. The optimum apparent water content of geopolymer modified sludge is strongly influenced by the amount of geopolymer content and initial water content of sludge. The solution to minimize the effect of high initial water content will be considered deeper in the future.

Keywords: landslide, sludge, fly ash, geopolymer, sludge conditioning

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99 Low Energy Technology for Leachate Valorisation

Authors: Jesús M. Martín, Francisco Corona, Dolores Hidalgo

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Landfills present long-term threats to soil, air, groundwater and surface water due to the formation of greenhouse gases (methane gas and carbon dioxide) and leachate from decomposing garbage. The composition of leachate differs from site to site and also within the landfill. The leachates alter with time (from weeks to years) since the landfilled waste is biologically highly active and their composition varies. Mainly, the composition of the leachate depends on factors such as characteristics of the waste, the moisture content, climatic conditions, degree of compaction and the age of the landfill. Therefore, the leachate composition cannot be generalized and the traditional treatment models should be adapted in each case. Although leachate composition is highly variable, what different leachates have in common is hazardous constituents and their potential eco-toxicological effects on human health and on terrestrial ecosystems. Since leachate has distinct compositions, each landfill or dumping site would represent a different type of risk on its environment. Nevertheless, leachates consist always of high organic concentration, conductivity, heavy metals and ammonia nitrogen. Leachate could affect the current and future quality of water bodies due to uncontrolled infiltrations. Therefore, control and treatment of leachate is one of the biggest issues in urban solid waste treatment plants and landfills design and management. This work presents a treatment model that will be carried out "in-situ" using a cost-effective novel technology that combines solar evaporation/condensation plus forward osmosis. The plant is powered by renewable energies (solar energy, biomass and residual heat), which will minimize the carbon footprint of the process. The final effluent quality is very high, allowing reuse (preferred) or discharge into watercourses. In the particular case of this work, the final effluents will be reused for cleaning and gardening purposes. A minority semi-solid residual stream is also generated in the process. Due to its special composition (rich in metals and inorganic elements), this stream will be valorized in ceramic industries to improve the final products characteristics.

Keywords: forward osmosis, landfills, leachate valorization, solar evaporation

Procedia PDF Downloads 178
98 Evaluation of Washing Performance of Household Wastewater Purified by Advanced Oxidation Process

Authors: Nazlı Çetindağ, Pelin Yılmaz Çetiner, Metin Mert İlgün, Emine Birci, Gizemnur Yıldız Uysal, Özcan Hatipoğlu, Ehsan Tuzcuoğlu, Gökhan Sır

Abstract:

Stressing the importance of water conservation, emphasizing the need for efficient management of household water, and underlining the significance of alternative solutions are important. In this context, advanced solutions based on technologies such as the advanced oxidation process have emerged as promising methods for treating household wastewater. Evaluating household water usage holds critical importance for the sustainability of water resources. Researchers and experts are examining various technological approaches to effectively treat and reclaim water for reuse. In this framework, the advanced oxidation process has proven to be an effective method for the removal of various organic and inorganic pollutants in the treatment of household wastewater. In this study, performance will be evaluated by comparing it with the reference case. This international criterion simulates the washing of home textile products, determining various performance parameters. The specially designed stain strips, including sebum, carbon black, blood, cocoa, and red wine, used in experiments, represent various household stains. These stain types were carefully selected to represent challenging stain scenarios, ensuring a realistic assessment of washing performance. Experiments conducted under different temperatures and program conditions successfully demonstrate the practical applicability of the advanced oxidation process for treating household wastewater. It is important to note that both adherence to standards and the use of real-life stain types contribute to the broad applicability of the findings. In conclusion, this study strongly supports the effectiveness of treating household wastewater with the advanced oxidation process in terms of washing performance under both standard and practical application conditions. The study underlines the importance of alternative solutions for sustainable water resource management and highlights the potential of the advanced oxidation process in the treatment of household water, contributing significantly to optimizing water usage and developing sustainable water management solutions.

Keywords: advanced oxidation process, household water usage, household appliance waste water, modelling, water reuse

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97 Carbon Dioxide Capture and Utilization by Using Seawater-Based Industrial Wastewater and Alkanolamine Absorbents

Authors: Dongwoo Kang, Yunsung Yoo, Injun Kim, Jongin Lee, Jinwon Park

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Since industrial revolution, energy usage by human-beings has been drastically increased resulting in the enormous emissions of carbon dioxide into the atmosphere. High concentration of carbon dioxide is well recognized as the main reason for the climate change by breaking the heat equilibrium of the earth. In order to decrease the amount of carbon dioxide emission, lots of technologies have been developed. One of the methods is to capture carbon dioxide after combustion process using liquid type absorbents. However, for some nations, captured carbon dioxide cannot be treated and stored properly due to their geological structures. Also, captured carbon dioxide can be leaked out when crust activities are active. Hence, the method to convert carbon dioxide as stable and useful products were developed. It is usually called CCU, that is, Carbon Capture and Utilization. There are several ways to convert carbon dioxide into useful substances. For example, carbon dioxide can be converted and used as fuels such as diesel, plastics, and polymers. However, these types of technologies require lots of energy to make stable carbon dioxide into a reactive one. Hence, converting it into metal carbonates salts have been studied widely. When carbon dioxide is captured by alkanolamine-based liquid absorbents, it exists as ionic forms such as carbonate, carbamate, and bicarbonate. When adequate metal ions are added, metal carbonate salt can be produced by ionic reaction with fast reaction kinetics. However, finding metal sources can be one of the problems for this method to be commercialized. If natural resources such as calcium oxide were used to supply calcium ions, it is not thought to have the economic feasibility to use natural resources to treat carbon dioxide. In this research, high concentrated industrial wastewater produced from refined salt production facility have been used as metal supplying source, especially for calcium cations. To ensure purity of final products, calcium ions were selectively separated in the form of gypsum dihydrate. After that, carbon dioxide is captured using alkanolamine-based absorbents making carbon dioxide into reactive ionic form. And then, high purity calcium carbonate salt was produced. The existence of calcium carbonate was confirmed by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) images. Also, carbon dioxide loading curves for absorption, conversion, and desorption were provided. Also, in order to investigate the possibility of the absorbent reuse, reabsorption experiments were performed either. Produced calcium carbonate as final products is seemed to have potential to be used in various industrial fields including cement and paper making industries and pharmaceutical engineering fields.

Keywords: alkanolamine, calcium carbonate, climate change, seawater, industrial wastewater

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96 Properties of Ettringite According to Hydration, Dehydration and Carbonation Process

Authors: Bao Chen, Frederic Kuznik, Matthieu Horgnies, Kevyn Johannes, Vincent Morin, Edouard Gengembre

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The contradiction between energy consumption, environment protection, and social development is increasingly intensified during recent decade years. At the same time, as avoiding fossil-fuels-thirsty, people turn their view on the renewable green energy, such as solar energy, wind power, hydropower, etc. However, due to the unavoidable mismatch on geography and time for production and consumption, energy storage seems to be one of the most reasonable solutions to enlarge the use of renewable energies. Thermal energy storage (TES), a branch of energy storage solution, mainly concerns the capture, storage and consumption of thermal energy for later use in different scales (individual house, apartment, district, and city). In TES research field, sensible heat and latent heat storage have been widely studied and presented at an advanced stage of development. Compared with them, thermochemical energy storage is still at initial phase but provides a relatively higher theoretical energy density and a long shelf life without heat dissipation during storage. Among thermochemical energy storage materials, inorganic pure or composite compounds like micro-porous silica gel, SrBr₂ hydrate and MgSO₄-Zeolithe have been reported as promising to be integrated into thermal energy storage systems. However, the cost of these materials, one of main obstacles, may hinder the wide use of energy storage systems in real application scales (individual house, apartment, district and even city). New studies on ettringite show promising application for thermal energy storage since its high energy density and large resource from cementitious materials. Ettringite, or calcium trisulfoaluminate hydrate, of which chemical formula is 3CaO∙Al₂O₃∙3CaSO₄∙32H₂O, or C₆AS̅₃H₃₂ as known in cement chemistry notation, is one of the most important members of AFt group. As a common compound in hydrated cements, ettringite has been widely studied for its performances in construction but barely known as a thermochemical material. For this study, we summarize available data about the structure and properties of ettringite and its metastable phase (meta-ettringite), including the processes of hydration, thermal conversion and carbonation durability for thermal energy storage.

Keywords: building materials, ettringite, meta-ettringite, thermal energy storage

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95 Study of Chemical State Analysis of Rubidium Compounds in Lα, Lβ₁, Lβ₃,₄ and Lγ₂,₃ X-Ray Emission Lines with Wavelength Dispersive X-Ray Fluorescence Spectrometer

Authors: Harpreet Singh Kainth

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Rubidium salts have been commonly used as an electrolyte to improve the efficiency cycle of Li-ion batteries. In recent years, it has been implemented into the large scale for further technological advances to improve the performance rate and better cyclability in the batteries. X-ray absorption spectroscopy (XAS) is a powerful tool for obtaining the information in the electronic structure which involves the chemical state analysis in the active materials used in the batteries. However, this technique is not well suited for the industrial applications because it needs a synchrotron X-ray source and special sample file for in-situ measurements. In contrast to this, conventional wavelength dispersive X-ray fluorescence (WDXRF) spectrometer is nondestructive technique used to study the chemical shift in all transitions (K, L, M, …) and does not require any special pre-preparation planning. In the present work, the fluorescent Lα, Lβ₁ , Lβ₃,₄ and Lγ₂,₃ X-ray spectra of rubidium in different chemical forms (Rb₂CO₃ , RbCl, RbBr, and RbI) have been measured first time with high resolution wavelength dispersive X-ray fluorescence (WDXRF) spectrometer (Model: S8 TIGER, Bruker, Germany), equipped with an Rh anode X-ray tube (4-kW, 60 kV and 170 mA). In ₃₇Rb compounds, the measured energy shifts are in the range (-0.45 to - 1.71) eV for Lα X-ray peak, (0.02 to 0.21) eV for Lβ₁ , (0.04 to 0.21) eV for Lβ₃ , (0.15 to 0.43) eV for Lβ₄ and (0.22 to 0.75) eV for Lγ₂,₃ X-ray emission lines. The chemical shifts in rubidium compounds have been measured by considering Rb₂CO₃ compounds taking as a standard reference. A Voigt function is used to determine the central peak position of all compounds. Both positive and negative shifts have been observed in L shell emission lines. In Lα X-ray emission lines, all compounds show negative shift while in Lβ₁, Lβ₃,₄, and Lγ₂,₃ X-ray emission lines, all compounds show a positive shift. These positive and negative shifts result increase or decrease in X-ray energy shifts. It looks like that ligands attached with central metal atom attract or repel the electrons towards or away from the parent nucleus. This pulling and pushing character of rubidium affects the central peak position of the compounds which causes a chemical shift. To understand the chemical effect more briefly, factors like electro-negativity, line intensity ratio, effective charge and bond length are responsible for the chemical state analysis in rubidium compounds. The effective charge has been calculated from Suchet and Pauling method while the line intensity ratio has been calculated by calculating the area under the relevant emission peak. In the present work, it has been observed that electro-negativity, effective charge and intensity ratio (Lβ₁/Lα, Lβ₃,₄/Lα and Lγ₂,₃/Lα) are inversely proportional to the chemical shift (RbCl > RbBr > RbI), while bond length has been found directly proportional to the chemical shift (RbI > RbBr > RbCl).

Keywords: chemical shift in L emission lines, bond length, electro-negativity, effective charge, intensity ratio, Rubidium compounds, WDXRF spectrometer

Procedia PDF Downloads 481
94 Predicting Long-Term Performance of Concrete under Sulfate Attack

Authors: Elakneswaran Yogarajah, Toyoharu Nawa, Eiji Owaki

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Cement-based materials have been using in various reinforced concrete structural components as well as in nuclear waste repositories. The sulfate attack has been an environmental issue for cement-based materials exposed to sulfate bearing groundwater or soils, and it plays an important role in the durability of concrete structures. The reaction between penetrating sulfate ions and cement hydrates can result in swelling, spalling and cracking of cement matrix in concrete. These processes induce a reduction of mechanical properties and a decrease of service life of an affected structure. It has been identified that the precipitation of secondary sulfate bearing phases such as ettringite, gypsum, and thaumasite can cause the damage. Furthermore, crystallization of soluble salts such as sodium sulfate crystals induces degradation due to formation and phase changes. Crystallization of mirabilite (Na₂SO₄:10H₂O) and thenardite (Na₂SO₄) or their phase changes (mirabilite to thenardite or vice versa) due to temperature or sodium sulfate concentration do not involve any chemical interaction with cement hydrates. Over the past couple of decades, an intensive work has been carried out on sulfate attack in cement-based materials. However, there are several uncertainties still exist regarding the mechanism for the damage of concrete in sulfate environments. In this study, modelling work has been conducted to investigate the chemical degradation of cementitious materials in various sulfate environments. Both internal and external sulfate attack are considered for the simulation. In the internal sulfate attack, hydrate assemblage and pore solution chemistry of co-hydrating Portland cement (PC) and slag mixing with sodium sulfate solution are calculated to determine the degradation of the PC and slag-blended cementitious materials. Pitzer interactions coefficients were used to calculate the activity coefficients of solution chemistry at high ionic strength. The deterioration mechanism of co-hydrating cementitious materials with 25% of Na₂SO₄ by weight is the formation of mirabilite crystals and ettringite. Their formation strongly depends on sodium sulfate concentration and temperature. For the external sulfate attack, the deterioration of various types of cementitious materials under external sulfate ingress is simulated through reactive transport model. The reactive transport model is verified with experimental data in terms of phase assemblage of various cementitious materials with spatial distribution for different sulfate solution. Finally, the reactive transport model is used to predict the long-term performance of cementitious materials exposed to 10% of Na₂SO₄ for 1000 years. The dissolution of cement hydrates and secondary formation of sulfate-bearing products mainly ettringite are the dominant degradation mechanisms, but not the sodium sulfate crystallization.

Keywords: thermodynamic calculations, reactive transport, radioactive waste disposal, PHREEQC

Procedia PDF Downloads 137
93 Application of Recycled Paper Mill Sludge on the Growth of Khaya Senegalensis and Its Effect on Soil Properties, Nutrients and Heavy Metals

Authors: A. Rosazlin Abdullah, I. Che Fauziah, K. Wan Rasidah, A. B. Rosenani

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The paper industry performs an essential role in the global economy of the world. A study was conducted on the paper mill sludge that is applied on the Khaya senegalensis for 1 year planning period at University Agriculture Park, Puchong, Selangor, Malaysia to determine the growth of Khaya senegalensis, soil properties, nutrients concentrations and effects on the status of heavy metals. Paper Mill Sludge (PMS) and composted Recycled Paper Mill Sludge (RPMS) were used with different rates of nitrogen (0, 150, 300 and 600 kg ha-1) at the ratio of 1:1 (Recycled Paper Mill Sludge (RPMS) : Empty Fruit Brunch (EFB). The growth parameters were measured twice a month for 1 year. Plant nutrients and heavy metal uptake were determined. The paper mill sludge has the potential to be a supplementary N fertilizer as well as a soil amendment. The application of RPMS with N, significantly contributed to the improvement in plant growth parameters such as plant height (4.24 m), basal diameter (10.30 cm), total plant biomass and improved soil physical and chemical properties. The pH, EC, available P and total C in soil were varied among the treatments during the planting period. The treatments with raw and RPM compost had higher pH values than those applied with inorganic fertilizer and control. Nevertheless, there was no salinity problem recorded during the planting period and available P in soil treated with raw and RPMS compost was higher than the control plots that reflects the mineralization of organic P from the decomposition of pulp sludge. The weight of the free and occluded light fractions of carbon concentration was significantly higher in the soils treated with raw and RPMS compost. The application of raw and composted RPMS gave significantly higher concentration of the heavy metals, but the total concentrations of heavy metals in the soils were below the critical values. Hence, the paper mill sludge can be successfully used as soil amendment in acidic soil without any serious threat. The use of paper mill sludge for the soil fertility, shows improvement in land application signifies a unique opportunity to recycle sludge back to the land to alleviate the potential waste management problem.

Keywords: growth, heavy metals, nutrients uptake, production, waste management

Procedia PDF Downloads 345
92 Detailed Sensitive Detection of Impurities in Waste Engine Oils Using Laser Induced Breakdown Spectroscopy, Rotating Disk Electrode Optical Emission Spectroscopy and Surface Plasmon Resonance

Authors: Cherry Dhiman, Ayushi Paliwal, Mohd. Shahid Khan, M. N. Reddy, Vinay Gupta, Monika Tomar

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The laser based high resolution spectroscopic experimental techniques such as Laser Induced Breakdown Spectroscopy (LIBS), Rotating Disk Electrode Optical Emission spectroscopy (RDE-OES) and Surface Plasmon Resonance (SPR) have been used for the study of composition and degradation analysis of used engine oils. Engine oils are mainly composed of aliphatic and aromatics compounds and its soot contains hazardous components in the form of fine, coarse and ultrafine particles consisting of wear metal elements. Such coarse particulates matter (PM) and toxic elements are extremely dangerous for human health that can cause respiratory and genetic disorder in humans. The combustible soot from thermal power plants, industry, aircrafts, ships and vehicles can lead to the environmental and climate destabilization. It contributes towards global pollution for land, water, air and global warming for environment. The detection of such toxicants in the form of elemental analysis is a very serious issue for the waste material management of various organic, inorganic hydrocarbons and radioactive waste elements. In view of such important points, the current study on used engine oils was performed. The fundamental characterization of engine oils was conducted by measuring water content and kinematic viscosity test that proves the crude analysis of the degradation of used engine oils samples. The microscopic quantitative and qualitative analysis was presented by RDE-OES technique which confirms the presence of elemental impurities of Pb, Al, Cu, Si, Fe, Cr, Na and Ba lines for used waste engine oil samples in few ppm. The presence of such elemental impurities was confirmed by LIBS spectral analysis at various transition levels of atomic line. The recorded transition line of Pb confirms the maximum degradation which was found in used engine oil sample no. 3 and 4. Apart from the basic tests, the calculations for dielectric constants and refractive index of the engine oils were performed via SPR analysis.

Keywords: surface plasmon resonance, laser-induced breakdown spectroscopy, ICCD spectrometer, engine oil

Procedia PDF Downloads 119
91 Photoinduced Energy and Charge Transfer in InP Quantum Dots-Polymer/Metal Composites for Optoelectronic Devices

Authors: Akanksha Singh, Mahesh Kumar, Shailesh N. Sharma

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Semiconductor quantum dots (QDs) such as CdSe, CdS, InP, etc. have gained significant interest in the recent years due to its application in various fields such as LEDs, solar cells, lasers, biological markers, etc. The interesting feature of the QDs is their tunable band gap. The size of the QDs can be easily varied by varying the synthesis parameters which change the band gap. One of the limitations with II-VI semiconductor QDs is their biological application. The use of cadmium makes them unsuitable for biological applications. III-V QD such as InP overcomes this problem as they are structurally robust because of the covalent bonds which do not allow the ions to leak. Also, InP QDs has large Bohr radii which increase the window for the quantum confinement effect. The synthesis of InP QDs is difficult and time consuming. Authors have synthesized InP using a novel, quick synthesis method which utilizes trioctylphosphine as a source of phosphorus. In this work, authors have made InP composites with P3HT(Poly(3-hexylthiophene-2,5-diyl))polymer(organic-inorganic hybrid material) and gold nanoparticles(metal-semiconductor composites). InP-P3HT shows FRET phenomenon whereas InP-Au shows charge transfer mechanism. The synthesized InP QDs has an absorption band at 397 nm and PL peak position at 491 nm. The band gap of the InP QDs is 2.46 eV as compared to the bulk band gap of InP i.e. 1.35 eV. The average size of the QDs is around 3-4 nm. In order to protect the InP core, a shell of wide band gap material i.e. ZnS is coated on the top of InP core. InP-P3HT composites were made in order to study the charge transfer/energy transfer phenomenon between them. On adding aliquots of P3HT to InP QDs solution, the P3HT PL increases which can be attributed to the dominance of Förster energy transfer between InP QDs (donor) P3HT polymer (acceptor). There is a significant spectral overlap between the PL spectra of InP QDs and absorbance spectra of P3HT. But in the case of InP-Au nanocomposites, significant charge transfer was seen from InP QDs to Au NPs. When aliquots of Au NPs were added to InP QDs, a decrease in the PL of the InP QDs was observed. This is due to the charge transfer from the InP QDs to the Au NPs. In the case of metal semiconductor composites, the enhancement and quenching of QDs depend on the size of the QD and the distance between the QD and the metal NP. These two composites have different phenomenon between donor and acceptor and hence can be utilized for two different applications. The InP-P3HT composite can be utilized for LED devices due to enhancement in the PL emission (FRET). The InP-Au can be utilized efficiently for photovoltaic application owing to the successful charge transfer between InP-Au NPs.

Keywords: charge transfer, FRET, gold nanoparticles, InP quantum dots

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90 Hybrid Materials Obtained via Sol-Gel Way, by the Action of Teraethylorthosilicate with 1, 3, 4-Thiadiazole 2,5-Bifunctional Compounds

Authors: Afifa Hafidh, Fathi Touati, Ahmed Hichem Hamzaoui, Sayda Somrani

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The objective of the present study has been to synthesize and to characterize silica hybrid materials using sol-gel technic and to investigate their properties. Silica materials were successfully fabricated using various bi-functional 1,3,4-thiadiazoles and tetraethoxysilane (TEOS) as co-precursors via a facile one-pot sol-gel pathway. TEOS was introduced at room temperature with 1,3,4-thiadiazole 2,5-difunctiunal adducts, in ethanol as solvent and using HCl acid as catalyst. The sol-gel process lead to the formation of monolithic, coloured and transparent gels. TEOS was used as a principal network forming agent. The incorporation of 1,3,4-thiadiazole molecules was realized by attachment of these later onto a silica matrix. This allowed covalent linkage between organic and inorganic phases and lead to the formation of Si-N and Si-S bonds. The prepared hybrid materials were characterized by Fourier transform infrared, NMR ²⁹Si and ¹³C, scanning electron microscopy and nitrogen absorption-desorption measurements. The optic and magnetic properties of hybrids are studied respectively by ultra violet-visible spectroscopy and electron paramagnetic resonance. It was shown in this work, that heterocyclic moieties were successfully attached in the hybrid skeleton. The formation of the Si-network composed of cyclic units (Q3 structures) connected by oxygen bridges (Q4 structures) was proved by ²⁹Si NMR spectroscopy. The Brunauer-Elmet-Teller nitrogen adsorption-desorption method shows that all the prepared xerogels have isotherms type IV and are mesoporous solids. The specific surface area and pore volume of these materials are important. The obtained results show that all materials are paramagnetic semiconductors. The data obtained by Nuclear magnetic resonance ²⁹Si and Fourier transform infrared spectroscopy, show that Si-OH and Si-NH groups existing in silica hybrids can participate in adsorption interactions. The obtained materials containing reactive centers could exhibit adsorption properties of metal ions due to the presence of OH and NH functionality in the mesoporous frame work. Our design of a simple method to prepare hybrid materials may give interest of the development of mesoporous hybrid systems and their use within the domain of environment in the future.

Keywords: hybrid materials, sol-gel process, 1, 3, 4-thiadaizole, TEOS

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89 Risk Assessment on New Bio-Composite Materials Made from Water Resource Recovery

Authors: Arianna Nativio, Zoran Kapelan, Jan Peter van der Hoek

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Bio-composite materials are becoming increasingly popular in various applications, such as the automotive industry. Usually, bio-composite materials are made from natural resources recovered from plants, now, a new type of bio-composite material has begun to be produced in the Netherlands. This material is made from resources recovered from drinking water treatments (calcite), wastewater treatment (cellulose), and material from surface water management (aquatic plants). Surface water, raw drinking water, and wastewater can be contaminated with pathogens and chemical compounds. Therefore, it would be valuable to develop a framework to assess, monitor, and control the potential risks. Indeed, the goal is to define the major risks in terms of human health, quality of materials, and environment associated with the production and application of these new materials. This study describes the general risk assessment framework, starting with a qualitative risk assessment. The qualitative risk analysis was carried out by using the HAZOP methodology for the hazard identification phase. The HAZOP methodology is logical and structured and able to identify the hazards in the first stage of the design when hazards and associated risks are not well known. The identified hazards were analyzed to define the potential associated risks, and then these were evaluated by using the qualitative Event Tree Analysis. ETA is a logical methodology used to define the consequences for a specific hazardous incidents, evaluating the failure modes of safety barriers and dangerous intermediate events that lead to the final scenario (risk). This paper shows the effectiveness of combining of HAZOP and qualitative ETA methodologies for hazard identification and risk mapping. Then, key risks were identified, and a quantitative framework was developed based on the type of risks identified, such as QMRA and QCRA. These two models were applied to assess human health risks due to the presence of pathogens and chemical compounds such as heavy metals into the bio-composite materials. Thus, due to these contaminations, the bio-composite product, during its application, might release toxic substances into the environment leading to a negative environmental impact. Therefore, leaching tests are going to be planned to simulate the application of these materials into the environment and evaluate the potential leaching of inorganic substances, assessing environmental risk.

Keywords: bio-composite, risk assessment, water reuse, resource recovery

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88 Validation of an Impedance-Based Flow Cytometry Technique for High-Throughput Nanotoxicity Screening

Authors: Melanie Ostermann, Eivind Birkeland, Ying Xue, Alexander Sauter, Mihaela R. Cimpan

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Background: New reliable and robust techniques to assess biological effects of nanomaterials (NMs) in vitro are needed to speed up safety analysis and to identify key physicochemical parameters of NMs, which are responsible for their acute cytotoxicity. The central aim of this study was to validate and evaluate the applicability and reliability of an impedance-based flow cytometry (IFC) technique for the high-throughput screening of NMs. Methods: Eight inorganic NMs from the European Commission Joint Research Centre Repository were used: NM-302 and NM-300k (Ag: 200 nm rods and 16.7 nm spheres, respectively), NM-200 and NM- 203 (SiO₂: 18.3 nm and 24.7 nm amorphous, respectively), NM-100 and NM-101 (TiO₂: 100 nm and 6 nm anatase, respectively), and NM-110 and NM-111 (ZnO: 147 nm and 141 nm, respectively). The aim was to assess the biological effects of these materials on human monoblastoid (U937) cells. Dispersions of NMs were prepared as described in the NANOGENOTOX dispersion protocol and cells were exposed to NMs at relevant concentrations (2, 10, 20, 50, and 100 µg/mL) for 24 hrs. The change in electrical impedance was measured at 0.5, 2, 6, and 12 MHz using the IFC AmphaZ30 (Amphasys AG, Switzerland). A traditional toxicity assay, Trypan Blue Dye Exclusion assay, and dark-field microscopy were used to validate the IFC method. Results: Spherical Ag particles (NM-300K) showed the highest toxic effect on U937 cells followed by ZnO (NM-111 ≥ NM-110) particles. Silica particles were moderate to non-toxic at all used concentrations under these conditions. A higher toxic effect was seen with smaller sized TiO2 particles (NM-101) compared to their larger analogues (NM-100). No interferences between the IFC and the used NMs were seen. Uptake and internalization of NMs were observed after 24 hours exposure, confirming actual NM-cell interactions. Conclusion: Results collected with the IFC demonstrate the applicability of this method for rapid nanotoxicity assessment, which proved to be less prone to nano-related interference issues compared to some traditional toxicity assays. Furthermore, this label-free and novel technique shows good potential for up-scaling in directions of an automated high-throughput screening and for future NM toxicity assessment. This work was supported by the EC FP7 NANoREG (Grant Agreement NMP4-LA-2013-310584), the Research Council of Norway, project NorNANoREG (239199/O70), the EuroNanoMed II 'GEMN' project (246672), and the UH-Nett Vest project.

Keywords: cytotoxicity, high-throughput, impedance, nanomaterials

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87 Influence of Kneading Conditions on the Textural Properties of Alumina Catalysts Supports for Hydrotreating

Authors: Lucie Speyer, Vincent Lecocq, Séverine Humbert, Antoine Hugon

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Mesoporous alumina is commonly used as a catalyst support for the hydrotreating of heavy petroleum cuts. The process of fabrication usually involves: the synthesis of the boehmite AlOOH precursor, a kneading-extrusion step, and a calcination in order to obtain the final alumina extrudates. Alumina is described as a complex porous medium, generally agglomerates constituted of aggregated nanocrystallites. Its porous texture directly influences the active phase deposition and mass transfer, and the catalytic properties. Then, it is easy to figure out that each step of the fabrication of the supports has a role on the building of their porous network, and has to be well understood to optimize the process. The synthesis of boehmite by precipitation of aluminum salts was extensively studied in the literature and the effect of various parameters, such as temperature or pH, are known to influence the size and shape of the crystallites and the specific surface area of the support. The calcination step, through the topotactic transition from boehmite to alumina, determines the final properties of the support and can tune the surface area, pore volume and pore diameters from those of boehmite. However, the kneading extrusion step has been subject to a very few studies. It generally consists in two steps: an acid, then a basic kneading, where the boehmite powder is introduced in a mixer and successively added with an acid and a base solution to form an extrudable paste. During the acid kneading, the induced positive charges on the hydroxyl surface groups of boehmite create an electrostatic repulsion which tends to separate the aggregates and even, following the conditions, the crystallites. The basic kneading, by reducing the surface charges, leads to a flocculation phenomenon and can control the reforming of the overall structure. The separation and reassembling of the particles constituting the boehmite paste have a quite obvious influence on the textural properties of the material. In this work, we are focused on the influence of the kneading step on the alumina catalysts supports. Starting from an industrial boehmite, extrudates are prepared using various kneading conditions. The samples are studied by nitrogen physisorption in order to analyze the evolution of the textural properties, and by synchrotron small-angle X-ray scattering (SAXS), a more original method which brings information about agglomeration and aggregation of the samples. The coupling of physisorption and SAXS enables a precise description of the samples, as same as an accurate monitoring of their evolution as a function of the kneading conditions. These ones are found to have a strong influence of the pore volume and pore size distribution of the supports. A mechanism of evolution of the texture during the kneading step is proposed and could be attractive in order to optimize the texture of the supports and then, their catalytic performances.

Keywords: alumina catalyst support, kneading, nitrogen physisorption, small-angle X-ray scattering

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86 Evaluation of Microbial Accumulation of Household Wastewater Purified by Advanced Oxidation Process

Authors: Nazlı Çetindağ, Pelin Yılmaz Çetiner, Metin Mert İlgün, Emine Birci, Gizemnur Yıldız Uysal, Özcan Hatipoğlu, Ehsan Tuzcuoğlu, Gökhan Sır

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Water scarcity is an unavoidable issue impacting an increasing number of individuals daily, representing a global crisis stemming from swift population growth, urbanization, and excessive resource exploitation. Consequently, solutions that involve the reclamation of wastewater are considered essential. In this context, household wastewater, categorized as greywater, plays a significant role in freshwater used for residential purposes and is attributed to washing. This type of wastewater comprises diverse elements, including organic substances, soaps, detergents, solvents, biological components, and inorganic elements such as certain metal ions and particles. The physical characteristics of wastewater vary depending on its source, whether commercial, domestic, or from a hospital setting. Consequently, the treatment strategy for this wastewater type necessitates comprehensive investigation and appropriate handling. The advanced oxidation process (AOP) emerges as a promising technique associated with the generation of reactive hydroxyl radicals highly effective in oxidizing organic pollutants. This method takes precedence over others like coagulation, flocculation, sedimentation, and filtration due to its avoidance of undesirable by-products. In the current study, the focus was on exploring the feasibility of the AOP for treating actual household wastewater. To achieve this, a laboratory-scale device was designed to effectively target the formed radicals toward organic pollutants, resulting in lower organic compounds in wastewater. Then, the number of microorganisms present in treated wastewater, in addition to the chemical content of the water, was analyzed to determine whether the lab-scale device eliminates microbial accumulation with AOP. This was also an important parameter since microbes can indirectly affect human health and machine hygiene. To do this, water samples were taken from treated and untreated conditions and then inoculated on general purpose agar to track down the total plate count. Analysis showed that AOP might be an option to treat household wastewater and lower microorganism growth.

Keywords: usage of household water, advanced oxidation process, water reuse, modelling

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85 The Toxicity of Doxorubicin Connected with Nanotransporters

Authors: Iva Blazkova, Amitava Moulick, Vedran Milosavljevic, Pavel Kopel, Marketa Vaculovicova, Vojtech Adam, Rene Kizek

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Doxorubicin is one of the most commonly used and the most effective chemotherapeutic drugs. This antracycline drug isolated from the bacteria Streptomyces peuceticus var. caesius is sold under the trade name Adriamycin (hydroxydaunomycin, hydroxydaunorubicin). Doxorubicin is used in single therapy to treat hematological malignancies (blood cancers, leukaemia, lymphoma), many types of carcinoma (solid tumors) and soft tissue sarcomas. It has many serious side effects like nausea and vomiting, hair lost, myelosupression, oral mucositis, skin reactions and redness, but the most serious one is the cardiotoxicity. Because of the risk of heart attack and congestive heart failure, the total dose administered to patients has to be accurately monitored. With the aim to lower the side effects and to targeted delivery of doxorubicin into the tumor tissue, the different nanoparticles are studied. The drug can be bound on a surface of nanoparticle, encapsulated in the inner cavity, or incorporated into the structure of nanoparticle. Among others, carbon nanoparticles (graphene, carbon nanotubes, fullerenes) are highly studied. Besides the number of inorganic nanoparticles, a great potential exhibit also organic ones mainly lipid-based and polymeric nanoparticle. The aim of this work was to perform a toxicity study of free doxorubicin compared to doxorubicin conjugated with various nanotransporters. The effect of liposomes, fullerenes, graphene, and carbon nanotubes on the toxicity was analyzed. As a first step, the binding efficacy of between doxorubicin and the nanotransporter was determined. The highest efficacy was detected in case of liposomes (85% of applied drug was encapsulated) followed by graphene, carbon nanotubes and fullerenes. For the toxicological studies, the chicken embryos incubated under controlled conditions (37.5 °C, 45% rH, rotation every 2 hours) were used. In 7th developmental day of chicken embryos doxorubicin or doxorubicin-nanotransporter complex was applied on the chorioallantoic membrane of the eggs and the viability was analyzed every day till the 17th developmental day. Then the embryos were extracted from the shell and the distribution of doxorubicin in the body was analyzed by measurement of organs extracts using laser induce fluorescence detection. The chicken embryo mortality caused by free doxorubicin (30%) was significantly lowered by using the conjugation with nanomaterials. The highest accumulation of doxorubicin and doxorubicin nanotransporter complexes was observed in the liver tissue

Keywords: doxorubicin, chicken embryos, nanotransporters, toxicity

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84 Modification of Carbon-Based Gas Sensors for Boosting Selectivity

Authors: D. Zhao, Y. Wang, G. Chen

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Gas sensors that utilize carbonaceous materials as sensing media offer numerous advantages, making them the preferred choice for constructing chemical sensors over those using other sensing materials. Carbonaceous materials, particularly nano-sized ones like carbon nanotubes (CNTs), provide these sensors with high sensitivity. Additionally, carbon-based sensors possess other advantageous properties that enhance their performance, including high stability, low power consumption for operation, and cost-effectiveness in their construction. These properties make carbon-based sensors ideal for a wide range of applications, especially in miniaturized devices created through MEMS or NEMS technologies. To capitalize on these properties, a group of chemoresistance-type carbon-based gas sensors was developed and tested against various volatile organic compounds (VOCs) and volatile inorganic compounds (VICs). The results demonstrated exceptional sensitivity to both VOCs and VICs, along with the sensor’s long-term stability. However, this broad sensitivity also led to poor selectivity towards specific gases. This project aims at addressing the selectivity issue by modifying the carbon-based sensing materials and enhancing the sensor's specificity to individual gas. Multiple groups of sensors were manufactured and modified using proprietary techniques. To assess their performance, we conducted experiments on representative sensors from each group to detect a range of VOCs and VICs. The VOCs tested included acetone, dimethyl ether, ethanol, formaldehyde, methane, and propane. The VICs comprised carbon monoxide (CO), carbon dioxide (CO2), hydrogen (H2), nitric oxide (NO), and nitrogen dioxide (NO2). The concentrations of the sample gases were all set at 50 parts per million (ppm). Nitrogen (N2) was used as the carrier gas throughout the experiments. The results of the gas sensing experiments are as follows. In Group 1, the sensors exhibited selectivity toward CO2, acetone, NO, and NO2, with NO2 showing the highest response. Group 2 primarily responded to NO2. Group 3 displayed responses to nitrogen oxides, i.e., both NO and NO2, with NO2 slightly surpassing NO in sensitivity. Group 4 demonstrated the highest sensitivity among all the groups toward NO and NO2, with NO2 being more sensitive than NO. In conclusion, by incorporating several modifications using carbon nanotubes (CNTs), sensors can be designed to respond well to NOx gases with great selectivity and without interference from other gases. Because the response levels to NO and NO2 from each group are different, the individual concentration of NO and NO2 can be deduced.

Keywords: gas sensors, carbon, CNT, MEMS/NEMS, VOC, VIC, high selectivity, modification of sensing materials

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83 Dimensionality Control of Li Transport by MOFs Based Quasi-Solid to Solid Electrolyte

Authors: Manuel Salado, Mikel Rincón, Arkaitz Fidalgo, Roberto Fernandez, Senentxu Lanceros-Méndez

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Lithium-ion batteries (LIBs) are a promising technology for energy storage, but they suffer from safety concerns due to the use of flammable organic solvents in their liquid electrolytes. Solid-state electrolytes (SSEs) offer a potential solution to this problem, but they have their own limitations, such as poor ionic conductivity and high interfacial resistance. The aim of this research was to develop a new type of SSE based on metal-organic frameworks (MOFs) and ionic liquids (ILs). MOFs are porous materials with high surface area and tunable electronic properties, making them ideal for use in SSEs. ILs are liquid electrolytes that are non-flammable and have high ionic conductivity. A series of MOFs were synthesized, and their electrochemical properties were evaluated. The MOFs were then infiltrated with ILs to form a quasi-solid gel and solid xerogel SSEs. The ionic conductivity, interfacial resistance, and electrochemical performance of the SSEs were characterized. The results showed that the MOF-IL SSEs had significantly higher ionic conductivity and lower interfacial resistance than conventional SSEs. The SSEs also exhibited excellent electrochemical performance, with high discharge capacity and long cycle life. The development of MOF-IL SSEs represents a significant advance in the field of solid-state electrolytes. The high ionic conductivity and low interfacial resistance of the SSEs make them promising candidates for use in next-generation LIBs. The data for this research was collected using a variety of methods, including X-ray diffraction, scanning electron microscopy, and electrochemical impedance spectroscopy. The data was analyzed using a variety of statistical and computational methods, including principal component analysis, density functional theory, and molecular dynamics simulations. The main question addressed by this research was whether MOF-IL SSEs could be developed that have high ionic conductivity, low interfacial resistance, and excellent electrochemical performance. The results of this research demonstrate that MOF-IL SSEs are a promising new type of solid-state electrolyte for use in LIBs. The SSEs have high ionic conductivity, low interfacial resistance, and excellent electrochemical performance. These properties make them promising candidates for use in next-generation LIBs that are safer and have higher energy densities.

Keywords: energy storage, solid-electrolyte, ionic liquid, metal-organic-framework, electrochemistry, organic inorganic plastic crystal

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82 Integration of the Electro-Activation Technology for Soy Meal Valorization

Authors: Natela Gerliani, Mohammed Aider

Abstract:

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

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

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81 The Influence of Morphology and Interface Treatment on Organic 6,13-bis (triisopropylsilylethynyl)-Pentacene Field-Effect Transistors

Authors: Daniel Bülz, Franziska Lüttich, Sreetama Banerjee, Georgeta Salvan, Dietrich R. T. Zahn

Abstract:

For the development of electronics, organic semiconductors are of great interest due to their adjustable optical and electrical properties. Especially for spintronic applications they are interesting because of their weak spin scattering, which leads to longer spin life times compared to inorganic semiconductors. It was shown that some organic materials change their resistance if an external magnetic field is applied. Pentacene is one of the materials which exhibit the so called photoinduced magnetoresistance which results in a modulation of photocurrent when varying the external magnetic field. Also the soluble derivate of pentacene, the 6,13-bis (triisopropylsilylethynyl)-pentacene (TIPS-pentacene) exhibits the same negative magnetoresistance. Aiming for simpler fabrication processes, in this work, we compare TIPS-pentacene organic field effect transistors (OFETs) made from solution with those fabricated by thermal evaporation. Because of the different processing, the TIPS-pentacene thin films exhibit different morphologies in terms of crystal size and homogeneity of the substrate coverage. On the other hand, the interface treatment is known to have a high influence on the threshold voltage, eliminating trap states of silicon oxide at the gate electrode and thereby changing the electrical switching response of the transistors. Therefore, we investigate the influence of interface treatment using octadecyltrichlorosilane (OTS) or using a simple cleaning procedure with acetone, ethanol, and deionized water. The transistors consist of a prestructured OFET substrates including gate, source, and drain electrodes, on top of which TIPS-pentacene dissolved in a mixture of tetralin and toluene is deposited by drop-, spray-, and spin-coating. Thereafter we keep the sample for one hour at a temperature of 60 °C. For the transistor fabrication by thermal evaporation the prestructured OFET substrates are also kept at a temperature of 60 °C during deposition with a rate of 0.3 nm/min and at a pressure below 10-6 mbar. The OFETs are characterized by means of optical microscopy in order to determine the overall quality of the sample, i.e. crystal size and coverage of the channel region. The output and transfer characteristics are measured in the dark and under illumination provided by a white light LED in the spectral range from 450 nm to 650 nm with a power density of (8±2) mW/cm2.

Keywords: organic field effect transistors, solution processed, surface treatment, TIPS-pentacene

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80 Study of Bis(Trifluoromethylsulfonyl)Imide Based Ionic Liquids by Gas Chromatography

Authors: F. Mutelet, L. Cesari

Abstract:

Development of safer and environmentally friendly processes and products is needed to achieve sustainable production and consumption patterns. Ionic liquids, which are of great interest to the chemical and related industries because of their attractive properties as solvents, should be considered. Ionic liquids are comprised of an asymmetric, bulky organic cation and a weakly coordinating organic or inorganic anion. A large number of possible combinations allows for the ability to ‘fine tune’ the solvent properties for a specific purpose. Physical and chemical properties of ionic liquids are not only influenced by the nature of the cation and the nature of cation substituents but also by the polarity and the size of the anion. These features infer to ionic liquids numerous applications, in organic synthesis, separation processes, and electrochemistry. Separation processes required a good knowledge of the behavior of organic compounds with ionic liquids. Gas chromatography is a useful tool to estimate the interactions between organic compounds and ionic liquids. Indeed, retention data may be used to determine infinite dilution thermodynamic properties of volatile organic compounds in ionic liquids. Among others, the activity coefficient at infinite dilution is a direct measure of solute-ionic liquid interaction. In this work, infinite dilution thermodynamic properties of volatile organic compounds in specific bis(trifluoromethylsulfonyl)imide based ionic liquids measured by gas chromatography is presented. It was found that apolar compounds are not miscible in this family of ionic liquids. As expected, the solubility of organic compounds is related to their polarity and hydrogen-bond. Through activity coefficients data, the performance of these ionic liquids was evaluated for different separation processes (benzene/heptane, thiophene/heptane and pyridine/heptane). Results indicate that ionic liquids may be used for the extraction of polar compounds (aromatics, alcohols, pyridine, thiophene, tetrahydrofuran) from aliphatic media. For example, 1-benzylpyridinium bis(trifluoromethylsulfonyl) imide and 1-cyclohexylmethyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide are more efficient for the extraction of aromatics or pyridine from aliphatics than classical solvents. Ionic liquids with long alkyl chain length present important capacity values but their selectivity values are low. In conclusion, we have demonstrated that specific bis(trifluoromethylsulfonyl)imide based ILs containing polar chain grafted on the cation (for example benzyl or cyclohexyl) increases considerably their performance in separation processes.

Keywords: interaction organic solvent-ionic liquid, gas chromatography, solvation model, COSMO-RS

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79 Highly Selective Phosgene Free Synthesis of Methylphenylcarbamate from Aniline and Dimethyl Carbonate over Heterogeneous Catalyst

Authors: Nayana T. Nivangune, Vivek V. Ranade, Ashutosh A. Kelkar

Abstract:

Organic carbamates are versatile compounds widely employed as pesticides, fungicides, herbicides, dyes, pharmaceuticals, cosmetics and in the synthesis of polyurethanes. Carbamates can be easily transformed into isocyanates by thermal cracking. Isocyantes are used as precursors for manufacturing agrochemicals, adhesives and polyurethane elastomers. Manufacture of polyurethane foams is a major application of aromatic ioscyanates and in 2007 the global consumption of polyurethane was about 12 million metric tons/year and the average annual growth rate was about 5%. Presently Isocyanates/carbamates are manufactured by phosgene based process. However, because of high toxicity of phoegene and formation of waste products in large quantity; there is a need to develop alternative and safer process for the synthesis of isocyanates/carbamates. Recently many alternative processes have been investigated and carbamate synthesis by methoxycarbonylation of aromatic amines using dimethyl carbonate (DMC) as a green reagent has emerged as promising alternative route. In this reaction methanol is formed as a by-product, which can be converted to DMC either by oxidative carbonylation of methanol or by reacting with urea. Thus, the route based on DMC has a potential to provide atom efficient and safer route for the synthesis of carbamates from DMC and amines. Lot of work is being carried out on the development of catalysts for this reaction and homogeneous zinc salts were found to be good catalysts for the reaction. However, catalyst/product separation is challenging with these catalysts. There are few reports on the use of supported Zn catalysts; however, deactivation of the catalyst is the major problem with these catalysts. We wish to report here methoxycarbonylation of aniline to methylphenylcarbamate (MPC) using amino acid complexes of Zn as highly active and selective catalysts. The catalysts were characterized by XRD, IR, solid state NMR and XPS analysis. Methoxycarbonylation of aniline was carried out at 170 °C using 2.5 wt% of the catalyst to achieve >98% conversion of aniline with 97-99% selectivity to MPC as the product. Formation of N-methylated products in small quantity (1-2%) was also observed. Optimization of the reaction conditions was carried out using zinc-proline complex as the catalyst. Selectivity was strongly dependent on the temperature and aniline:DMC ratio used. At lower aniline:DMC ratio and at higher temperature, selectivity to MPC decreased (85-89% respectively) with the formation of N-methylaniline (NMA), N-methyl methylphenylcarbamate (MMPC) and N,N-dimethyl aniline (NNDMA) as by-products. Best results (98% aniline conversion with 99% selectivity to MPC in 4 h) were observed at 170oC and aniline:DMC ratio of 1:20. Catalyst stability was verified by carrying out recycle experiment. Methoxycarbonylation preceded smoothly with various amine derivatives indicating versatility of the catalyst. The catalyst is inexpensive and can be easily prepared from zinc salt and naturally occurring amino acids. The results are important and provide environmentally benign route for MPC synthesis with high activity and selectivity.

Keywords: aniline, heterogeneous catalyst, methoxycarbonylation, methylphenyl carbamate

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