Search results for: oxygen reduction reaction (ORR)

Authors: Betül Özgenç, Soner Kuşlu, Sabri Çolak, Turan Çalban

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The aim of this study was investigate the leaching kinetics of ulexite in disodium hydrogen phosphate solutions in a mechanical agitation system. Reaction temperature, concentration of disodium hydrogen phosphate solutions, stirring speed, solid/liquid ratio and ulexite particle size were selected as parameters. The experimental results were successfully correlated by linear regression using Statistica program. Dissolution curves were evaluated shrinking core models for solid-fluid systems. It was observed that increase in the reaction temperature and decrease in the solid/liquid ratio causes an increase the dissolution rate of ulexite. The activation energy was found to be 63.4 kJ/mol. The leaching of ulexite was controlled by chemical reaction.

Keywords: ulexite, disodium hydrogen phosphate, leaching kinetics

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Authors: Shyh-Ming Chern, Te-Hsiu Tang

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Hemicellulose is one of the major constituents of all plant cell walls, making up 15-25% of dry wood. It is a biopolymer from many different sugar monomers, including pentoses, like xylose, and hexoses, like mannose. In an effort to gasify real biomass in subcritical and supercritical water in a single process, it is necessary to understand the gasification of hemicellulose, in addition to cellulose and lignin, in subcritical and supercritical water. In the present study, xylose is chosen as the model compound for hemicellulose, since it has the largest amount in most hardwoods. Xylose is gasified in subcritical and supercritical water for the production of higher-valued gaseous products. Experiments were conducted with a 16-ml autoclave batch-type reactor. Hydrogen peroxide is adopted as the oxidant in an attempt to promote the gasification yield. The major operating parameters for the gasification include reaction temperature (400 - 600°C), reaction pressure (5 - 25 MPa), the concentration of xylose (0.05 and 0.30 M), and level of oxidant added (0 and 0.25 chemical oxygen demand). 102 experimental runs were completed out of 46 different set of experimental conditions. Product gases were analyzed with a GC-TCD and determined to be mainly composed of H₂ (10 – 74 mol. %), CO (1 – 56 mol. %), CH₄ (1 – 27 mol. %), CO₂ (10 – 50 mol. %), and C₂H₆ (0 – 8 mol. %). It has been found that the gas yield (amount of gas produced per gram of xylose gasified), higher heating value (HHV) of the dry product gas, and energy yield (energy stored in the product gas divided by the energy stored in xylose) all increase significantly with rising temperature and moderately with reducing pressure. The overall best operating condition occurred at 873 K and 10 MPa, with a gas yield of 54 mmol/g of xylose, a gas HHV of 440 kJ/mol, and an energy yield of 1.3. A seemingly unreasonably energy yield of greater than unity resulted from the external heating employed in the experiments to drive the gasification process. It is concluded that xylose can be completely gasified in subcritical and supercritical water under proper operating conditions. The addition of oxidant does not promote the gasification of xylose.

Keywords: gasification, subcritical water, supercritical water, xylose

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Authors: Hossein Anaraki-Ardakani, Tayebe Heidari-Rakati

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An environmentally benign protocol for the one-pot, three-component synthesis of Triazolo[1,2-a]indazole-1,3,8-trione derivatives by condensation of dimedone, urazole and aromatic aldehydes catalyzed by HClO4/SiO2 NPS as an ecofriendly catalyst with high catalytic activity and reusability at 100 ºC under solvent-free conditions is reported. The reaction proceeds to completion within 20-30 min in 77-86 % yield.

Keywords: one-pot reaction, dimedone, triazoloindazole, urazole

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

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

Keywords: aldol reaction, DFT, organocatalysis, transition structure

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Authors: Sherif Fakher

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Hydrogen has been gaining a lot of global attention as an uprising contributor in the energy sector. Labeled as an energy carrier, hydrogen is used in many industries and can be used to generate electricity via fuel cells. Blue hydrogen involves the production of hydrogen from hydrocarbons using different processes that emit CO₂. However, the CO₂ is captured and stored. Hence, very little environmental damage occurs during the hydrogen production process. This research investigates the ability to use different catalysts for the production of hydrogen from different hydrocarbon sources, including coal, oil, and gas, using a two-step Aquathermolysis reaction. The research presents the results of experiments conducted to evaluate different catalysts and also highlights the main advantages of this process over other blue hydrogen production methods, including methane steam reforming, autothermal reforming, and oxidation. Two methods of hydrogen generation were investigated including partial oxidation and aquathermolysis. For those two reactions, the reaction kinetics, thermodynamics, and medium were all investigated. Following this, experiments were conducted to test the hydrogen generation potential from both methods. The porous media tested were sandstone, ash, and prozzolanic material. The spent oils used were spent motor oil and spent vegetable oil from cooking. Experiments were conducted at temperatures up to 250 C and pressures up to 3000 psi. Based on the experimental results, mathematical models were developed to predict the hydrogen generation potential at higher thermodynamic conditions. Since both partial oxidation and aquathermolysis require relatively high temperatures to undergo, it was important to devise a method by which these high temperatures can be generated at a low cost. This was done by investigating two factors, including the porous media used and the reliance on the spent oil. Of all the porous media used, the ash had the highest thermal conductivity. The second step was the partial combustion of part of the spent oil to generate the heat needed to reach the high temperatures. This reduced the cost of the heat generation significantly. For the partial oxidation reaction, the spent oil was burned in the presence of a limited oxygen concentration to generate carbon monoxide. The main drawback of this process was the need for burning. This resulted in the generation of other harmful and environmentally damaging gases. Aquathermolysis does not rely on burning, which makes it the cleaner alternative. However, it needs much higher temperatures to run the reaction. When comparing the hydrogen generation potential for both using gas chromatography, aquathermolysis generated 23% more hydrogen using the same volume of spent oil compared to partial oxidation. This research introduces the concept of using spent oil for hydrogen production. This can be a very promising method to produce a clean source of energy using a waste product. This can also help reduce the reliance on freshwater for hydrogen generation which can divert the usage of freshwater to other more important applications.

Keywords: blue hydrogen production, catalytic aquathermolysis, direct carbon dioxide capture, CCUS

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Authors: K. Chethana, A. S. Guru Prasad, S. N. Omkar, B. Vadiraj, S. Asokan

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This paper describes an ab-initio design, development and calibration results of an Optical Sensor Ground Reaction Force Measurement Platform (OSGRFP) for gait and geriatric studies. The developed system employs an array of FBG sensors to measure the respective ground reaction forces from all three axes (X, Y and Z), which are perpendicular to each other. The novelty of this work is two folded. One is in its uniqueness to resolve the tri axial resultant forces during the stance in to the respective pure axis loads and the other is the applicability of inherently advantageous FBG sensors which are most suitable for biomechanical instrumentation. To validate the response of the FBG sensors installed in OSGRFP and to measure the cross sensitivity of the force applied in other directions, load sensors with indicators are used. Further in this work, relevant mathematical formulations are presented for extracting respective ground reaction forces from wavelength shifts/strain of FBG sensors on the OSGRFP. The result of this device has implications in understanding the foot function, identifying issues in gait cycle and measuring discrepancies between left and right foot. The device also provides a method to quantify and compare relative postural stability of different subjects under test, which has implications in post surgical rehabilitation, geriatrics and optimizing training protocols for sports personnel.

Keywords: balance and stability, gait analysis, FBG applications, optical sensor ground reaction force platform

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Authors: Yusuf Ersoy Yildirim, Ismail Tas, Ceren Gorgusen, Tugba Yeter, Aysegul Boyacioglu, K. Mehmet Tugrul, Murat Tugrul, Ayten Namli, H. Sabri Ozturk, M. Onur Akca

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In recent years, a lot of research has been done for the sustainable use of scarce resources in the world. Especially, effective and sustainable use of water resources has been researched for many years. Sub-surface drip irrigation (SDI) is one of the most effective irrigation methods in which efficient and sustainable use of irrigation water can be achieved. When the literature is taken into consideration, it is often emphasized that, besides its numerous advantages, it also allows the application of irrigation water to the plant root zone along with air. It is stated in different studies that the air applied to the plant root zone with irrigation water has a positive effect on the root zone. Plants need sufficient oxygen for root respiration as well as for the metabolic functions of the roots. Decreased root respiration due to low oxygen content reduces transpiration, disrupts the flow of ions, and increases the ingress of salt reaching toxic levels, seriously affecting plant growth. Lack of oxygen (Hypoxia) can affect the survival of plants. The lack of oxygen in the soil is related to the exchange of gases in the soil with the gases in the atmosphere. Soil aeration is an important physical parameter of a soil. It is highly dynamic and is closely related to the amount of water in the soil and its bulk weight. Subsurface drip irrigation; It has higher water use efficiency compared to irrigation methods such as furrow irrigation and sprinkler irrigation. However, in heavy clay soils, subsurface drip irrigation creates continuous wetting fronts that predispose the rhizosphere region to hypoxia or anoxia. With subsurface drip irrigation, the oxygen is limited for root microbial respiration and root development, with the continuous spreading of water to a certain region of the root zone. In this study, the change in sugar beet yield caused by air application in the SDI system will be explained.

Keywords: sugar beet, subsurface drip irrigation, air application, irrigation efficiency

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Authors: Alexandra Tucaliuc, Alexandra C. Blaga, Anca I. Galaction, Lenuta Kloetzer, Dan Cascaval

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Ergosterol (ergosta-5,7,22-trien-3β-ol), also known as provitamin D2, is the precursor of vitamin D2 (ergocalciferol), because it is converted under UV radiation to this vitamin. The natural sources of ergosterol are mainly the yeasts (Saccharomyces sp., Candida sp.), but it can be also found in fungus (Claviceps sp.) or plants (orchids). In the yeasts cells, ergosterol is accumulated in membranes, especially in free form in the plasma membrane, but also as esters with fatty acids in membrane lipids. The chemical synthesis of ergosterol does not represent an efficient method for its production, in these circumstances, the most attractive alternative for producing ergosterol at larger-scale remains the aerobic fermentation using S. cerevisiae on glucose or by-products from agriculture of food industry as substrates, in batch or fed-batch operating systems. The aim of this work is to analyze comparatively the influence of aeration efficiency on ergosterol production by S. cerevisiae in batch and fed-batch fermentations, by considering different levels of mixing intensity, aeration rate, and n-dodecane concentration. The effects of the studied factors are quantitatively described by means of the mathematical correlations proposed for each of the two fermentation systems, valid both for the absence and presence of oxygen-vector inside the broth. The experiments were carried out in a laboratory stirred bioreactor, provided with computer-controlled and recorded parameters. n-Dodecane was used as oxygen-vector and the ergosterol content inside the yeasts cells has been considered at the fermentation moment related to the maximum concentration of ergosterol, 9 hrs for batch process and 20 hrs for fed-batch one. Ergosterol biosynthesis is strongly dependent on the dissolved oxygen concentration. The hydrocarbon concentration exhibits a significant influence on ergosterol production mainly by accelerating the oxygen transfer rate. Regardless of n-dodecane addition, by maintaining the glucose concentration at a constant level in the fed-batch process, the amount of ergosterol accumulated into the yeasts cells has been almost tripled. In the presence of hydrocarbon, the ergosterol concentration increased by over 50%. The value of oxygen-vector concentration corresponding to the maximum level of ergosterol depends mainly on biomass concentration, due to its negative influences on broth viscosity and interfacial phenomena of air bubbles blockage through the adsorption of hydrocarbon droplets–yeast cells associations. Therefore, for the batch process, the maximum ergosterol amount was reached for 5% vol. n-dodecane, while for the fed-batch process for 10% vol. hydrocarbon.

Keywords: bioreactors, ergosterol, fermentation, oxygen-vector

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Authors: Fatma A. Mohamed, Hend M. Ahmed

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This research explores the antimicrobial effects of dielectric barrier discharge (DBD) oxygen plasma treatment combined with ZnO NPs on the cotton fabric, focusing on various treatment durations (5, 10, 15, 20, and 30 minutes) and discharge powers (15.5–17.35 watts) at flow rate 0.5 l/min. After treatment with oxygen plasma and ZnO NPs, the fabric was printed with green tea (Camellia sinensis) at five different concentrations. The study evaluated the treatment's effectiveness by analyzing surface wettability, specifically through wet-out time and hydrophilicity, as well as measuring contact angles. To investigate the chemical changes on the fabric's surface, attenuated total reflectance–Fourier transform infrared (ATR-FTIR) spectroscopy was employed to identify the functional groups formed as a result of the plasma treatment. This comprehensive approach aims to understand how DBD oxygen plasma treatment and ZnO nanoparticles change cotton fabric properties and enhance its antimicrobial potential, paving the way for innovative applications in textiles. In addition to the chemical analysis, the surface morphology of the O₂ plasma/ZnO NPs-treated cotton fabric was examined using scanning electron microscopy (SEM). FTIR analysis revealed an increase in polar functional groups (-COOH, -OH, and -C≡O) on the fabric's surface, contributing to enhanced hydrophilicity and functionality. The antimicrobial properties were evaluated using qualitative and quantitative methods, including agar plate assays and modified Hoenstein tests against Staphylococcus aureus and Escherichia coli. The results indicated a significant improvement in antimicrobial effectiveness for the cotton fabric treated with plasma and coated with natural extracts, maintaining this efficacy even after four washing cycles. This research demonstrates that utilizing oxygen DBD plasma/ZnO NPs treatment, combined with the absorption of tea and tulsi leaf extracts, presents a promising strategy for developing natural antimicrobial textiles. This approach is particularly relevant given the increasing medical and healthcare demands for effective antimicrobial materials. Overall, the method not only enhances the absorption of plant extracts but also significantly boosts antimicrobial efficacy, offering valuable insights for future textile applications.

Keywords: cotton, ZnO NPs, green tea leaf, antimicrobial avtivity, DBD oxygen plasma

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Authors: Nhleko Monique Chiloane

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The gold mining industry has predominantly used ammonium nitrate fuel oil (ANFO) explosives for decades, although these are known to be “gassier” and their detonation results in toxic fumes, for example, carbon monoxide (CO), nitrogen oxides (NOx) and ammonia. Re-entry into underground workings too soon after blasting can lead to fatal exposure to toxic fumes. It is, therefore, required that the polluted air be removed from the affected areas within a reasonable period before employees' re-entry into the working area. Post-blast re-entry times have therefore been described as a productivity bottleneck. The known causes of post-blast fumes are water ingress, incorrect fuel to oxygen ratio, confinement, explosive additives etc. To prevent or minimize post-blast fumes, some researchers have used neutralization, re-burning technique and non-explosive products or different oxidizing agents. The use of commercial explosives without nitrate oxidizing agents can also minimize the production of blasting fumes and thereby reduce the time needed for the clearance of these fumes to allow workers to re-enter the underground workings safely. The reduction in non-production time directly contributes to an increase in the available time per shift for productive work, thus leading to continuous mining. However, owing to its low cost and ease of use, ANFO is still widely used in South African underground blasting operations.

Keywords: post-blast fumes, continuous mining, ammonium nitrate explosive, non-explosive blasting, re-entry period

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Authors: Taweesak Janyacharoen, Lalita Pradubgool, Lalita Wongsorn, Pitchayapa Janyacharoen

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Street dance is a form of exercise that is classified as aerobic and is very suitable for teenagers. Street dance is a dance that can create new dance moves all the time. It often incorporates elements from gymnastics and is accompanied by fast-paced music that emphasizes excitement and energy. It is a combination of high-intensity and low-intensity activities. Few studies have looked at the effects of street dance on cardiovascular endurance, and previous studies have long-term effects. However, no research study in Thailand has studied acute effects before. This study was to investigate the acute effect of street dance exercise on blood pressure, heart rate, oxygen saturation and physical fitness in sedentary subjects. Subjects were divided into 2 groups: the control group (n=15) received health education and rest, and the experimental group (n=15) received street dance exercise. Both groups will measure their blood pressure (BP), mean arterial pressure (MAP), heart rate (HR), oxygen saturation (SpO₂) and six-minute walk test (6MWT) before and after completing the program. The results found that both groups had significantly different HR when comparing before and after the program (p<0.05). MAP, HR and SpO₂ had significantly different (p<0.05) when compared between groups. This study concluded that the acute effect of street dance exercise could be increased in HR while the SpO₂ decreased. In clinical, it was seen that the values that were changed are still within the range that is considered normal. Therefore, street dance exercises can be used as one choice of alternative exercise.

Keywords: street dance, exercise, blood pressure, heart rate, oxygen saturation

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Authors: D. Kuvshinov, A. Siswanto, J. Lozano-Parada, W. Zimmerman

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Ozone is well known as a powerful fast reaction rate oxidant. The ozone based processes produce no by-product left as a non-reacted ozone returns back to the original oxygen molecule. Therefore an application of ozone is widely accepted as one of the main directions for a sustainable and clean technologies development. There are number of technologies require ozone to be delivered to specific points of a production network or reactors construction. Due to space constrains, high reactivity and short life time of ozone the use of ozone generators even of a bench top scale is practically limited. This requires development of mini/micro scale ozone generator which can be directly incorporated into production units. Our report presents a feasibility study of a new micro scale rector for ozone generation (MROG). Data on MROG calibration and indigo decomposition at different operation conditions are presented. At selected operation conditions with residence time of 0.25 s the process of ozone generation is not limited by reaction rate and the amount of ozone produced is a function of power applied. It was shown that the MROG is capable to produce ozone at voltage level starting from 3.5kV with ozone concentration of 5.28E-6 (mol/L) at 5kV. This is in line with data presented on numerical investigation for a MROG. It was shown that in compare to a conventional ozone generator, MROG has lower power consumption at low voltages and atmospheric pressure. The MROG construction makes it applicable for emerged and dry systems. With a robust compact design MROG can be used as incorporated unit for production lines of high complexity.

Keywords: dielectric barrier discharge (DBD), micro reactor, ozone, plasma

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Authors: Wen Po Cheng, Chen Zhao Feng, Ruey Fang Yu, Lin Jia Jun, Lin Ji Ye, Chen Yuan Wei

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Humic acid was used as the removal target for evaluating the coagulation efficiency in this study. When the coagulant ions mix with a humic acid solution, a Fluorescence quenching effect may be observed conditionally. This effect can be described by Stern-Volmer linear equation which can be used for quantifying the quenching value (Kq) of the Fluorescence quenching effect. In addition, a Complex-Formation Titration (CFT) theory was conducted and the result was used to explain the electron-neutralization capability of the coagulant (AlCl₃) at different pH. The results indicated that when pH of the ACl₃ solution was between 6 and 8, fluorescence quenching effect obviously occurred. The maximum Kq value was found to be 102,524 at pH 6. It means that the higher the Kq value is, the better complex reaction between a humic acid and aluminum salts will be. Through the Kq value study, the optimum pH can be quantified when the humic acid solution is coagulated with aluminum ions.

Keywords: humic acid, fluorescence quenching effect, complex reaction, titration

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Authors: Sarai Alvarado Pineda, Ricardo Maldonado Soto

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The acquisition of Verb Particle Constructions is a challenge for Spanish speakers learning English. The acquisition is particularly difficult for speakers of languages with no verb particle constructions. The purpose of the current study is to define the procedural steps in the acquisition of constructions with the particle on. There are three outstanding meanings for the particle on; Surface: The movie is based on a true story, Activation: John turn on the light, Continuity: The band played on all night. The central aim of this study is to measure how Mexican Spanish participants respond to both the three meanings mentioned above and the degree of meaning transparency/opacity of on verb particle constructions. Forty Mexican Spanish learners of English (20 basic and 20 advanced) are compared against a control group of 20 American native English speakers through a reaction time test (PsychoPy2 2015). The participants were asked to discriminate 90 items based on their knowledge of these constructions. There are 30 items per meaning divided into two groups of transparent and opaque meaning. Results revealed three major findings: Advanced students have a reaction time similar to that of native speakers (advanced 4.5s versus native 3.7s), while students with a lower level of English proficiency, show a high reaction time (7s). Likewise, there is a shorter reaction time in constructions with lower opacity in the three groups of participants, with differences between each level (basic 6.7s, advanced 4.3s, and native 3.4s). Finally, a difference in reaction time can be identified according to the meaning provided by the construction. The reaction time for the activation category (5.27s) is greater than continuity (5.04s), and this category is also slower than the surface (4.94s). The study shows that the level of sensitivity of English learners increases significantly aiming towards native speaker patterns as determined by the level of transparency of meaning of each construction as well as the degree of entrenchment of each constructional meaning.

Keywords: meaning of the particle, opacity, reaction time, verb particle constructions

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Authors: Rafael Zhindon Almeida

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Surface water quality is an important concern for the evaluation and prediction of water quality conditions. The objective of this study is to develop a statistical model that can accurately predict the water quality of the El Macho estuary in the city of Machala, El Oro province. The methodology employed in this study is of a basic type that involves a thorough search for theoretical foundations to improve the understanding of statistical modeling for water quality analysis. The research design is correlational, using a multivariate statistical model involving multiple linear regression and principal component analysis. The results indicate that water quality parameters such as fecal coliforms, biochemical oxygen demand, chemical oxygen demand, iron and dissolved oxygen exceed the allowable limits. The water of the El Macho estuary is determined to be below the required water quality criteria. The multiple linear regression model, based on chemical oxygen demand and total dissolved solids, explains 99.9% of the variance of the dependent variable. In addition, principal component analysis shows that the model has an explanatory power of 86.242%. The study successfully developed a statistical model to evaluate the water quality of the El Macho estuary. The estuary did not meet the water quality criteria, with several parameters exceeding the allowable limits. The multiple linear regression model and principal component analysis provide valuable information on the relationship between the various water quality parameters. The findings of the study emphasize the need for immediate action to improve the water quality of the El Macho estuary to ensure the preservation and protection of this valuable natural resource.

Keywords: statistical modeling, water quality, multiple linear regression, principal components, statistical models

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Authors: Hanene Akrout, Ines Elaissaoui, Sabrina Grassini, Daniele Fulginiti, Latifa Bousselmi

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The main objective of this work is to investigate the efficiency of depollution power related to PbO₂ layer deposited onto a stainless steel (SS) substrate with SiOx as interlayer. The elaborated electrode was used as anode for anodic oxidation of wastewater containing Amaranth dye, as recalcitrant organic pollutant model. SiOx interlayer was performed using Plasma Enhanced Chemical Vapor Deposition ‘PECVD’ in plasma fed with argon, oxygen, and tetraethoxysilane (TEOS, Si precursor) in different ratios, onto the SS substrate. PbO₂ layer was produced by pulsed electrodeposition on SS/SiOx. The morphological of different surfaces are depicted with Field Emission Scanning Electron Microscope (FESEM) and the composition of the lead oxide layer was investigated by X-Ray Diffractometry (XRD). The results showed that the SiOx interlayer with more rich oxygen content improved better the nucleation of β-PbO₂ form. Electrochemical Impedance Spectroscopy (EIS) measurements undertaken on different interfaces (at optimized conditions) revealed a decrease of Rfilm while CPE film increases for SiOx interlayer, characterized by a more inorganic nature and deposited in a plasma fed by higher O2-to-TEOS ratios. Quantitative determinations of the Amaranth dye degradation rate were performed in terms of colour and COD removals, reaching a 95% and an 80% respectively removal at pH = 2 in 300 min. Results proved the improvement of the degradation wastewater containing the amaranth dye. During the electrolysis, the Amaranth dye solution was sampled at 30 min intervals and analyzed by ‘High-performance Liquid Chromatography’ HPLC. The gradual degradation of the Amaranth dye confirmed by the decrease in UV absorption using the SS/SiOx(20:20:1)/PbO₂ anode, the reaction exhibited an apparent first-order kinetic for electrolysis time of 5 hours, with an initial rate constant of about 0.02 min⁻¹.

Keywords: electrochemical treatment, PbO₂ anodes, COD removal, plasma

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Authors: Abhishek Chandra, Man Singh

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Highly stable and homogeneously dispersed amino acid coated silver nanoparticles (ANP) of ≈ 10 nm diameter, ranging from 420 to 430 nm are prepared on AgNO3 solution addition to gum of Azadirachta indica solution at 373.15 K. The amino acids were selected based on their polarity. The synthesized nanoparticles were characterized by UV-Vis, FTIR spectroscopy, HR-TEM, XRD, SEM and 1H-NMR. The coated nanoparticles were used as catalyst for the reduction of methylene blue dye in presence of Sn(II) in aqueous, anionic and cationic micellar media. The rate of reduction of dye was determined by measuring the absorbance at 660 nm, spectrophotometrically and followed the order: Kcationic > Kanionic > Kwater. After 12 min and in absence of the ANP, only 2%, 3% and 6% of the dye reduction was completed in aqueous, anionic and cationic micellar media respectively while, in presence of ANP coated by polar neutral amino acid with non-polar -R group, the reduction completed to 84%, 95% and 98% respectively. The ANP coated with polar neutral amino acid having non-polar -R group, increased the rate of reduction of the dye by 94, 3205 and 6370 folds in aqueous, anionic and cationic micellar media respectively. Also, the rate of reduction of the dye increased by three folds when the micellar media was changed from anionic to cationic when the ANP is coated by a polar neutral amino acid having a non-polar -R group.

Keywords: silver nanoparticle, surfactant, methylene blue, amino acid

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Authors: C. Rajalakshmi, Vibin Ipe Thomas

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Sonogashira coupling reactions are widely employed in the synthesis of molecules of biological and pharmaceutical importance. Copper catalyzed Sonogashira coupling reactions are gaining importance owing to the low cost and less toxicity of copper as compared to the palladium catalyst. In the present work, a detailed computational study has been carried out on the Sonogashira coupling reaction between aryl halides and terminal alkynes catalyzed by Copper (I) species with trans-1, 2 Diaminocyclohexane as ligand. All calculations are performed at Density Functional Theory (DFT) level, using the hybrid Becke3LYP functional. Cu and I atoms are described using an effective core potential (LANL2DZ) for the inner electrons and its associated double-ζ basis set for the outer electrons. For all other atoms, 6-311G+* basis set is used. We have identified that the active catalyst species is a neutral 3-coordinate trans-1,2 diaminocyclohexane ligated Cu (I) alkyne complex and found that the oxidative addition and reductive elimination occurs in a single step proceeding through one transition state. This is owing to the ease of reductive elimination involving coupling of Csp2-Csp carbon atoms and the less stable Cu (III) intermediate. This shows the mechanism of copper catalyzed Sonogashira coupling reactions are quite different from those catalyzed by palladium. To gain further insights into the mechanism, substrates containing various functional groups are considered in our study to traverse their effect on the feasibility of the reaction. We have also explored the effect of ligand on the catalytic cycle of the coupling reaction. The theoretical results obtained are in good agreement with the experimental observation. This shows the relevance of a combined theoretical and experimental approach for rationally improving the cross-coupling reaction mechanisms.

Keywords: copper catalysed, density functional theory, reaction mechanism, Sonogashira coupling

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Authors: M. A. Motin, M. A. Aziz, M. Hafiz Mia, M. A. Hasem

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The redox behavior of catechol in the presence of nicotinamide as nucleophiles has been studied in aqueous solution with various pH values and different concentration of nicotinamide using cyclic voltammetry and differential pulse voltammetry. Cyclic voltammetry of catechol in buffer solution (3.00 < pH < 9.00) shows one anodic and corresponding cathodic peak which relates to the transformation of catechol to corresponding o-benzoquinone and vice versa within a quasi reversible two electron transfer process. Cyclic voltammogram of catechol in the presence of nicotinamide in buffer solution of pH 7, show one anodic peak in the first cycle of potential and on the reverse scan the corresponding cathodic peak slowly decreases and new peak is observed at less positive potential. In the second cycle of potential a new anodic peak is observed at less positive potential. This indicates that nicotinamide attached with catechol and formed adduct after first cycle of oxidation. The effect of pH of catechol in presence of nicotinamide was studied by varying pH from 3 to 11. The substitution reaction of catechol with nicotimamide is facilitated at pH 7. In buffer solution of higher pH (>9), the CV shows different pattern. The effect of concentration of nicotinamide was studied by 2mM to 100 mM. The maximum substitution reaction has been found for 50 mM of nicotinamide and of pH 7. The proportionality of the first scan anodic and cathodic peak currents with square root of scan rate suggests that the peak current of the species at each redox reaction is controlled by diffusion process. The current functions (1/v-1/2) of the anodic peak decreased with the increasing of scan rate demonstrated that the behavior of the substitution reaction is of ECE type.

Keywords: redox interaction, catechol, nicotinamide, substituion reaction, pH effect

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Authors: Ayesha Sohail, Khadija Maqbool, Anila Asif, Haroon Ahmad

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The field of tissue engineering is an active area of research. Bone tissue engineering helps to resolve the clinical problems of critical size and non-healing defects by the creation of man-made bone tissue. We will design and validate an efficient numerical model, which will simulate the effective diffusivity in bone tissue engineering. Our numerical model will be based on the finite element analysis of the diffusion-reaction equations. It will have the ability to optimize the diffusivity, even at multi-scale, with the variation of time. It will also have a special feature, with which we will not only be able to predict the oxygen, glucose and cell density dynamics, more accurately, but will also sort the issues arising due to anisotropy. We will fix these problems with the help of modifying the governing equations, by selecting appropriate spatio-temporal finite element schemes, by adaptive grid refinement strategy and by transient analysis.

Keywords: scaffolds, porosity, diffusion, transient analysis

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Authors: K. R. Guna, Aldin Justin Sundararaj, B. C. Pillai, A. N. Subash

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A systematic study has been made for ignition delay times measurement behind a reflected shock wave for the low molecular weight hydrocarbon fuel in argon simulated gas mixtures. The low molecular hydrocarbon fuel–oxygen was diluted with argon for desired concentration is taken for the study. The suitability of the shock tube for measuring the ignition delay time is demonstrated by measuring the ignition delay for the liquefied petroleum gas for equivalence ratios (ф=0.5 & 1) in the temperature range 1150-1650 K. The pressure range was fixed from 5-15 bar. The ignition delay was measured by recording the ignition-induced pressure jump and emission from CH radical simultaneously. From conducting experiments, it was found that the ignition delay time for liquefied petroleum gas reduces with increase in temperature. The shock tube was calibrated for ethane-oxygen gas mixture and the results obtained from this study is compared with the earlier reported values and found to be comparably well suited for the measurement of ignition delay times. The above work was carried out using the shock tube facility at propulsion and high enthalpy laboratory, Karunya University.

Keywords: ignition delay, LPG, reflected shock, shock wave

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Authors: Marisa Chrysochoou, James Mahoney, Kay Wille

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Pyrrhotite is an iron-sulfide mineral which releases sulfuric acid when exposed to water and oxygen. The presence of this mineral in concrete foundations across Connecticut and Massachusetts in the US is causing in some cases premature failure. This has resulted in a devastating crisis for all parties affected by this type of failure which can take up to 15-25 years before internal damage becomes visible on the surface. This study shares laboratory results aimed to investigate the fundamental mechanisms of pyrrhotite reaction and to further the understanding of its deterioration kinetics within concrete. This includes the following analyses: total sulfur, wavelength dispersive X-ray fluorescence, expansion, reaction rate combined with ion-chromatography, as well as damage evolution using electro-chemical acceleration. This information is coupled to a statistical analysis of over 150 analyzed concrete foundations. Those samples were obtained and process using a developed and validated sampling method that is minimally invasive to the foundation in use, provides representative samples of the concrete matrix across the entire foundation, and is time and cost-efficient. The processed samples were then analyzed using a developed modular testing method based on total sulfur and wavelength dispersive X-ray fluorescence analysis to quantify the amount of pyrrhotite. As part of the statistical analysis the results were grouped into the following three categories: no damage observed and no pyrrhotite detected, no damage observed and pyrrhotite detected and damaged observed and pyrrhotite detected. As expected, a strong correlation between amount of pyrrhotite, age of the concrete and damage is observed. Information from the laboratory investigation and from the statistical analysis of field samples will aid in forming a scientific basis to support the decision process towards sustainable financial and administrative solutions by state and local stakeholders.

Keywords: concrete, pyrrhotite, risk of failure, statistical analysis

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Authors: Zubi Sadiq, Ghazala Yaqub, Almas Hamid

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We wish to report herein a very stimulating variation in Fischer indole reaction by adopting solvent and catalyst free conditions. A concise synthesis of dinitro tetrahydrocarbazole derivative 3 was introduced without the use of any accelerating agent at ambient temperature with fairly good yield. Product was fully corroborated by UV, FTIR, 1H NMR, 13C NMR, MS, and CHN analysis.

Keywords: fischer indole reaction, neutral medium, solvent free synthesis, tetrahydrocarbazole

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Authors: Seung Ho Park, Young Su Moon, Nam Ik Cho

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We propose a convolution neural network (CNN) for quality adaptive compression artifact reduction named QCARNet. The proposed method is different from the existing discriminative models that learn a specific model at a certain quality level. The method is composed of a quality estimation CNN (QECNN) and a compression artifact reduction CNN (CARCNN), which are two functionally separate CNNs. By connecting the QECNN and CARCNN, each CARCNN layer is able to adaptively reduce compression artifacts and preserve details depending on the estimated quality level map generated by the QECNN. We experimentally demonstrate that the proposed method achieves better performance compared to other state-of-the-art blind compression artifact reduction methods.

Keywords: compression artifact reduction, deblocking, image denoising, image restoration

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Authors: Ivanor Zardo, Fernanda Walper Da Cunha, Júlia Sarkis, Ligia Damasceno Ferreira Marczak

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Lipid oxidation is one of the most important deteriorating processes in oil industry, resulting in the losses of nutritional value of oils as well as changes in color, flavor and other physiological properties. Autoxidation of lipids occurs naturally between molecular oxygen and the unsaturation of fatty acids, forming fat-free radicals, peroxide free radicals and hydroperoxides. In order to avoid the lipid oxidation in vegetable oils, synthetic antioxidants such as butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and tertiary butyl hydro-quinone (TBHQ) are commonly used. However, the use of synthetic antioxidants has been associated with several health side effects and toxicity. The use of natural antioxidants as stabilizers of vegetable oils is being suggested as a sustainable alternative to synthetic antioxidants. The alternative that has been studied is the use of natural extracts obtained mainly from fruits, vegetables and seeds, which have a well-known antioxidant activity related mainly to the presence of phenolic compounds. The sunflower seed cake is rich in phenolic compounds (1 4% of the total mass), being the chlorogenic acid the major constituent. The aim of this study was to evaluate the in vitro application of the phenolic extract obtained from the sunflower seed cake as a retarder of the lipid oxidation reaction in soybean oil and to compare the results with a synthetic antioxidant. For this, the soybean oil, provided from the industry without any addition of antioxidants, was subjected to an accelerated storage test for 17 days at 65 °C. Six samples with different treatments were submitted to the test: control sample, without any addition of antioxidants; 100 ppm of synthetic antioxidant BHT; mixture of 50 ppm of BHT and 50 ppm of phenolic compounds; and 100, 500 and 1200 ppm of phenolic compounds. The phenolic compounds concentration in the extract was expressed in gallic acid equivalents. To evaluate the oxidative changes of the samples, aliquots were collected after 0, 3, 6, 10 and 17 days and analyzed for the peroxide, diene and triene conjugate values. The soybean oil sample initially had a peroxide content of 2.01 ± 0.27 meq of oxygen/kg of oil. On the third day of the treatment, only the samples treated with 100, 500 and 1200 ppm of phenolic compounds showed a considerable oxidation retard compared to the control sample. On the sixth day of the treatment, the samples presented a considerable increase in the peroxide value (higher than 13.57 meq/kg), and the higher the concentration of phenolic compounds, the lower the peroxide value verified. From the tenth day on, the samples had a very high peroxide value (higher than 55.39 meq/kg), where only the sample containing 1200 ppm of phenolic compounds presented significant oxidation retard. The samples containing the phenolic extract were more efficient to avoid the formation of the primary oxidation products, indicating effectiveness to retard the reaction. Similar results were observed for dienes and trienes. Based on the results, phenolic compounds, especially chlorogenic acid (the major phenolic compound of sunflower seed cake), can be considered as a potential partial or even total substitute for synthetic antioxidants.

Keywords: chlorogenic acid, natural antioxidant, vegetables oil deterioration, waste valorization

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Authors: F. A. F. da Ponte, J. Q. Malveira, I. A. Maciel, M. C. G. Albuquerque

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In this work aviation, biofuel production was studied by fatty acids (C6 to C16) esterification. The process variables in heterogeneous catalysis were evaluated using an experimental design. Temperature and reaction time were the studied parameters, and the methyl esters content was the response of the experimental design. An ion exchange resin was used as a heterogeneous catalyst. The process optimization was carried out using response surface methodology (RSM) and polynomial model of second order. Results show that the most influential variables on the linear coefficient of each effect studied were temperature and reaction time. The best result of methyl esters conversion in the experimental design was under the conditions: 10% wt of catalyst; 100 °C and 4 hours of reaction. The best-achieved conversion was 96.5% wt of biofuel.

Keywords: esterification, ion-exchange resins, response surface methodology, biofuel

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Authors: Sudheer Kumar J., Sudhanshu Sharma

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Stone columns are extensively used as constructive and environmentally sustainable improvement methods for improving stiffness, modulus of subgrade reaction, and maximum lateral displacement in the multilayer soil system. The advantage of using stone columns in improving the single-layer soft soil as a ground reinforcement element for supporting various structures up to shallow depth is well researched, but the understanding of strengthening the multiplayer soil system for a deeper level requires further studies. In this paper, a series of cases have been conducted to study the behaviour of ordinary stone columns (OSC), geosynthetic encased stone columns (GESC) over various objectives for strengthening multilayer soil system up to deep level. A finite element analyses were carried out using the software package PLAXIS to study further correlate the results. The study aims to find the stiffness of composite soil, modulus of subgrade reaction, which is generally required for designing of various foundations, and also discusses the maximum horizontal displacement location, which is the major failure criteria seen after the installation of stone columns.

Keywords: stone columns, geotextile, finite element method, stiffness, modulus of subgrade reaction, maximum lateral displacement point

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Authors: Aicha Assal, El Mostapha Lotfi

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According to data from the Directorate General of Meteorology (DGM), the average amount of precipitation recorded nationwide between September 1, 2021, and January 31, 2022, is 38.8 millimeters. This is well below the climatological normal of 106.8 millimeters for the same period between 1981 and 2010. This situation is becoming increasingly worrying, particularly for farmers who are finding it difficult to irrigate their land and feed their livestock. Drought is greatly influenced by the effects of climate change, mainly caused by pollution and greenhouse gases (GHGs). The aim of this work is to contribute to the purification of wastewater (considered as polluting) in order to reuse it for irrigation in agricultural areas or for livestock watering. This will be achieved once physico-chemical treatment tests on these waters have been carried out and validated. The main parameters analyzed in this study, after carrying out discoloration tests on domestic wastewater, include COD (chemical oxygen demand), BOD5 (biochemical oxygen demand), pH, conductivity, dissolved oxygen, suspended solids (SS), phosphate, nitrate, nitrite and ammonium ions, faecal and total coliforms, as well as monitoring heavy metal concentrations. This work is also aimed at reclaiming the sludge produced by the decantation process, which will enable the waste to be transformed and reused as compost in agriculture and gardening.

Keywords: wastewater, irrigation, COD, COB, SS

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Authors: Eko S. Kunarti, Akhmad Syoufian, Indriana Kartini, Agnes

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Fe₃O₄/SiO₂/TiO₂ nanoparticles have been synthesized and applied as a photocatalyst for the recovery of gold from the mixture of Au(III) and Cu(II) ions. The synthesis was started by the preparation of magnetite (Fe₃O₄) using coprecipitation and sonication methods, followed by SiO₂ coating on magnetite using sol-gel reactions, and then TiO₂ coating using sol-gel process. Characterization was performed by using infrared spectroscopy, X-ray diffraction, transmission electron microscopy methods. Activity of Fe₃O₄/SiO₂/TiO₂ nanoparticles was evaluated as a photocatalyst for recovery of gold through photoreduction of Au(III) ions in Au(III) and Cu(II) ions mixture with a ratio of 1:1, in a closed reactor equipped with UV lamp. The photoreduction yield was represented as a percentage (%) of reduced Au(III) which was calculated by substraction of initial Au(III) concentration by the unreduced one. The unreduced Au(III) was determined by atomic absorption spectrometry. Results showed that the Fe₃O₄/SiO₂/TiO₂ nanoparticles were successfully synthesised with excellent magnetic and photocatalytic properties. The nanoparticles present optimum activity at a pH of 5 under UV irradiation for 120 minutes. At the optimum condition, the Fe₃O₄/SiO₂/TiO₂ nanoparticles could reduce Au³⁺ to Au⁰ 97.24%. In the mixture of Au(III) and Cu(II) ions, the Au(III) ions are more easily reducible than Cu(II) ions with the reduction results of 96.9% and 45.80% for Au(III) and Cu(II) ions, respectively. In addition, the presence of Cu(II) ions has no significant effect on the amount of gold recovered and its reduction reaction rate.

Keywords: Fe₃O₄/SiO₂/TiO₂, photocatalyst, recovery, gold, Au(III) and Cu(II) mixture

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Authors: Nhan N. T. Ton, Anh T. N. Dao, Kouichirou Katou, Toshiaki Taniike

Abstract:

Facile electron-hole recombination and the broad band gap are two major drawbacks of titanium dioxide (TiO₂) when applied in visible-light photocatalysis. Hybridization of TiO₂ with graphene is a promising strategy to lessen these pitfalls. Recently, there have been many reports on the synthesis of TiO₂/graphene nanocomposites, in most of which graphene oxide (GO) was used as a starting material. However, the reduction of GO introduced a large number of defects on the graphene framework. In addition, the sensitivity of titanium alkoxide to water (GO usually contains) significantly obstructs the uniform and controlled growth of TiO₂ on graphene. Here, we demonstrate a novel technique to synthesize TiO₂/graphene nanocomposites without the use of GO. Graphene dispersion was obtained through the chemical exfoliation of graphite in titanium tetra-n-butoxide with the aid of ultrasonication. The dispersion was directly used for the sol-gel reaction in the presence of different catalysts. A TiO₂/reduced graphene oxide (TiO₂/rGO) nanocomposite, which was prepared by a solvothermal method from GO, and the commercial TiO₂-P25 were used as references. It was found that titanium alkoxide afforded the graphene dispersion of a high quality in terms of a trace amount of defects and a few layers of dispersed graphene. Moreover, the sol-gel reaction from this dispersion led to TiO₂/graphene nanocomposites featured with promising characteristics for visible-light photocatalysts including: (I) the formation of a TiO₂ nano layer (thickness ranging from 1 nm to 5 nm) that uniformly and thinly covered graphene sheets, (II) a trace amount of defects on the graphene framework (low ID/IG ratio: 0.21), (III) a significant extension of the absorption edge into the visible light region (a remarkable extension of the absorption edge to 578 nm beside the usual edge at 360 nm), and (IV) a dramatic suppression of electron-hole recombination (the lowest photoluminescence intensity compared to reference samples). These advantages were successfully demonstrated in the photocatalytic decomposition of methylene blue under visible light irradiation. The TiO₂/graphene nanocomposites exhibited 15 and 5 times higher activity than TiO₂-P25 and the TiO₂/rGO nanocomposite, respectively.

Keywords: chemical exfoliation, photocatalyst, TiO₂/graphene, sol-gel reaction

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