Search results for: ternary metal catalyst
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 3190

Search results for: ternary metal catalyst

1930 Response of Subfossile Diatoms, Cladocera, and Chironomidae in Sediments of Small Ponds to Changes in Wastewater Discharges from a Zn–Pb Mine

Authors: Ewa Szarek-Gwiazda, Agata Z. Wojtal, Agnieszka Pociecha, Andrzej Kownacki, Dariusz Ciszewski

Abstract:

Mining of metal ores is one of the largest sources of heavy metals, which deteriorate aquatic systems. The response of organisms to environmental changes can be well recorded in sediments of the affected water bodies and may be reconstructed based on analyses of organisms' remains. The present study aimed at the response of diatoms (Bacillariophyta), Cladocera, and Chironomidae communities to the impact of Zn-Pb mine water discharge recorded in sediment cores of small subsidence ponds on the Chechło River floodplain (Silesia–Krakow Region, southern Poland). We hypothesize various responses of the above groups to high metal concentrations (Cd, Pb, Zn, and Cu). The investigated ponds were formed either during the peak of the ore exploitation (DOWN) or after mining cessation (UP). Currently, the concentrations of dissolved metals (in µg g⁻¹) in water reached up to 0.53 for Cd, 7.3 for Pb, and up to 47.1 for Zn. All the sediment cores from subsidence ponds were heavily polluted with Cd 6.7–612 μg g⁻¹, Pb 0.1–10.2 mg g⁻¹, and Zn 0.5–23.1 mg g⁻¹. Core sediments varied also in respect to pH 5.8-7.1 and concentrations of organic matter (5.7-39.8%). The impact of high metal concentrations was expressed by the occurrence of metal-tolerant taxa like diatoms – Nitzschia amphibia, Sellaphora nigri, and Surirella brebisonii var. kuetzingii; Cladocera – Chydorus sphaericus (dominated in cores from all ponds), and Chironomidae – Chironomus and Cricotopus especially in the DOWN ponds. Statistical analysis exhibited a negative impact of metals on some taxa of diatoms and Cladocera but only on Polypedilum sp. from Chironomidae. The abundance of such diatoms like Gomphonema utae, Staurosirella pinnata, Eunotia bilunaris, and Cladocera like Alona, Chydorus, Graptoleberis, and Pleuroxus decreased with increasing Pb concentration. However, the occurrence or dominance of more sensitive species of diatoms and Cladocera indicates their adaptation to higher metal loads, which was facilitated by neutral pH and slightly alkaline waters. Diatom assemblages were generally resistant to Zn, Pb, Cu, and Cd pollution, as indicated by their large similarity to populations from non-contaminated waters. Comparison with reference objects clearly indicates the dominance of Achnanthidium minutissimum, Staurosira venter, and Fragilaria gracilis in very diverse assemblages of unpolluted waters. The distribution of the Cladocera and Chironomidae taxa depended on the habitat type. The DOWN ponds with stagnant water and overgrown with macrophytes were more suitable for cladocerans (14 taxa, higher diversity) than the UP ponds with river water flowing through their centre and with a small share of macrophytes (8 taxa). The Chironominae, mainly Chironomus and Microspectra, were abundant in cores from the UP ponds with muddy bottoms. Inversely, the density of Orthocladiinae, especially genus Cricotopus, was related to the organic matter content and dominated in cores from the DOWN ponds. The presence of diatoms like Nitzschia amphibia, Sellaphora nigri, and Surirella brebisonii var. kuetzingii, cladocerans: Bosmina longirostris, Chydorus sphaericus, Alona affinis, and A. rectangularis as well as Chironomidae Chironomus sp. (UP ponds) and Psecrotanypus varius (DOWN ponds) indicate the influence of the water trophy on their distribution.

Keywords: Chironomidae, Cladocera, diatoms, metals, Zn-Pb mine, sediment cores, subsidence ponds

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1929 Optimization of Adsorptive Removal of Common Used Pesticides Water Wastewater Using Golden Activated Charcoal

Authors: Saad Mohamed Elsaid, Nabil Anwar, Mahmoud Rushdi

Abstract:

One of the reasons for the intensive use of pesticides is to protect agricultural crops and orchards from pests or agricultural worms. The period of time that pesticides stay inside the soil is estimated at about (2) to (12) weeks. Perhaps the most important reason that led to groundwater pollution is the easy leakage of these harmful pesticides from the soil into the aquifers. This research aims to find the best ways to use traded activated charcoal with gold nitrate solution; for removing the deadly pesticides from the aqueous solution by adsorption phenomenon. The most used pesticides in Egypt were selected, such as Malathion, Methomyl Abamectin and, Thiamethoxam. Activated charcoal doped with gold ions was prepared by applying chemical and thermal treatments to activated charcoal using gold nitrate solution. Adsorption of studied pesticide onto activated carbon /Au was mainly by chemical adsorption, forming a complex with the gold metal immobilized on activated carbon surfaces. In addition, the gold atom was considered as a catalyst to cracking the pesticide molecule. Gold activated charcoal is a low cost material due to the use of very low concentrations of gold nitrate solution. its notice the great ability of activated charcoal in removing selected pesticides due to the presence of the positive charge of the gold ion, in addition to other active groups such as functional oxygen and lignin cellulose. The presence of pores of different sizes on the surface of activated charcoal is the driving force for the good adsorption efficiency for the removal of the pesticides under study The surface area of the prepared char as well as the active groups, were determined using infrared spectroscopy and scanning electron microscopy. Some factors affecting the ability of activated charcoal were applied in order to reach the highest adsorption capacity of activated charcoal, such as the weight of the charcoal, the concentration of the pesticide solution, the time of the experiment, and the pH. Experiments showed that the maximum limit revealed by the batch adsorption study for the adsorption of selected insecticides was in contact time (80) minutes at pH (7.70). These promising results were confirmed, and by establishing the practical application of the developed system, the effect of various operating factors with equilibrium, kinetic and thermodynamic studies is evident, using the Langmuir application on the effectiveness of the absorbent material with absorption capacities higher than most other adsorbents.

Keywords: waste water, pesticides pollution, adsorption, activated carbon

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1928 Optimisation of Nitrogen as a Protective Gas via the Alternating Shielding Gas Technique in the Gas Metal Arc Welding Process

Authors: M. P. E. E Silva, A. M. Galloway, A. I. Toumpis

Abstract:

An increasing concern exists in the welding industry in terms of faster joining processes. Methods such as the alternation between shielding gases such Ar, CO₂ and He have been able to provide improved penetration of the joint, reduced heat transfer to the workpiece, and increased travel speeds of the welding torch. Nitrogen as a shielding gas is not desirable due to its reactive behavior within the arc plasma, being absorbed by the molten pool during the welding process. Below certain amounts, nitrogen is not harmful. However, the nitrogen threshold is reduced during the solidification of the joint, and if its subsequent desorption is not completed on time, gas entrapment and blowhole formation may occur. The present study expanded the use of the alternating shielding gas method in the gas metal arc welding (GMAW) process by alternately supplying Ar/5%N₂ and He. Improvements were introduced in terms of joint strength and grain refinement. Microstructural characterization findings showed porosity-free welds with reduced inclusion formation while mechanical tests such as tensile and bend tests confirmed the reinforcement of the joint by the addition of nitrogen. Additionally, significant reductions of the final distortion of the workpiece were found after the welding procedure as well as decreased heat affected zones and temperatures of the weld.

Keywords: alternating shielding gas method, GMAW, grain refinement, nitrogen, porosity, mechanical testing

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1927 Chemical Partitioning of Trace Metals in Sub-Surface Sediments of Lake Acigol, Denizli, Turkey

Authors: M. Budakoglu, M. Karaman, D. Kiran, Z. Doner, B. Zeytuncu, B. Tanç, M. Kumral

Abstract:

Lake Acıgöl is one of the large saline lacustrine environment in Turkey. Eleven trace metals (Cr, Mn, Fe, Al, Co, Ni, Cu, Zn, Cd, Pb and As) in 9 surface and subsurface sediment samples from the Lake Acıgöl were analyzed with the bulk and sequential extraction analysis methods by ICP-MS to obtain the metal distribution patterns in this extreme environment. Five stepped sequential extraction technique (1- exchangeable, 2- bond to carbonates, 3- bond to iron and manganese oxides/hydroxides, 4- bond to organic matter and sulphides, and 5- residual fraction incorporated into clay and silicate mineral lattices) was used to characterize the various forms of metals in the <63μ size sediments. The metal contents (ppm) and their percentages for each extraction step were reported and compared with the results obtained from the total digestion. Results indicate that sum of the four fraction are in good agreement with the total digestion results of Ni, Cd, As, Zn, Cu and Fe with the satisfactory recoveries (94.04–109.0%) and the method used is reliable and repeatable for these elements. It was found that there were high correlations between Fe vs. Ni loads in the fraction of F2 and F4 with R2= 0,91 and 0,81, respectively. Comparison of totally 135 chemical analysis results in three sampling location and for 5 fraction between Fe-Co, Co-Ni and Fe-Ni element couples were presented elevated correlations with R2=0,98, 0,92 and 0,91, respectively.

Keywords: Lake Acigol, sequancial extraction, recent lake sediment, geochemical speciation of heavy metals

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1926 A Multi-Scale Study of Potential-Dependent Ammonia Synthesis on IrO₂ (110): DFT, 3D-RISM, and Microkinetic Modeling

Authors: Shih-Huang Pan, Tsuyoshi Miyazaki, Minoru Otani, Santhanamoorthi Nachimuthu, Jyh-Chiang Jiang

Abstract:

Ammonia (NH₃) is crucial in renewable energy and agriculture, yet its traditional production via the Haber-Bosch process faces challenges due to the inherent inertness of nitrogen (N₂) and the need for high temperatures and pressures. The electrocatalytic nitrogen reduction (ENRR) presents a more sustainable option, functioning at ambient conditions. However, its advancement is limited by selectivity and efficiency challenges due to the competing hydrogen evolution reaction (HER). The critical roles of protonation of N-species and HER highlight the necessity of selecting optimal catalysts and solvents to enhance ENRR performance. Notably, transition metal oxides, with their adjustable electronic states and excellent chemical and thermal stability, have shown promising ENRR characteristics. In this study, we use density functional theory (DFT) methods to investigate the ENRR mechanisms on IrO₂ (110), a material known for its tunable electronic properties and exceptional chemical and thermal stability. Employing the constant electrode potential (CEP) model, where the electrode - electrolyte interface is treated as a polarizable continuum with implicit solvation, and adjusting electron counts to equalize work functions in the grand canonical ensemble, we further incorporate the advanced 3D Reference Interaction Site Model (3D-RISM) to accurately determine the ENRR limiting potential across various solvents and pH conditions. Our findings reveal that the limiting potential for ENRR on IrO₂ (110) is significantly more favorable than for HER, highlighting the efficiency of the IrO₂ catalyst for converting N₂ to NH₃. This is supported by the optimal *NH₃ desorption energy on IrO₂, which enhances the overall reaction efficiency. Microkinetic simulations further predict a promising NH₃ production rate, even at the solution's boiling point¸ reinforcing the catalytic viability of IrO₂ (110). This comprehensive approach provides an atomic-level understanding of the electrode-electrolyte interface in ENRR, demonstrating the practical application of IrO₂ in electrochemical catalysis. The findings provide a foundation for developing more efficient and selective catalytic strategies, potentially revolutionizing industrial NH₃ production.

Keywords: density functional theory, electrocatalyst, nitrogen reduction reaction, electrochemistry

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1925 Utilization of Process Mapping Tool to Enhance Production Drilling in Underground Metal Mining Operations

Authors: Sidharth Talan, Sanjay Kumar Sharma, Eoin Joseph Wallace, Nikita Agrawal

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Underground mining is at the core of rapidly evolving metals and minerals sector due to the increasing mineral consumption globally. Even though the surface mines are still more abundant on earth, the scales of industry are slowly tipping towards underground mining due to rising depth and complexities of orebodies. Thus, the efficient and productive functioning of underground operations depends significantly on the synchronized performance of key elements such as operating site, mining equipment, manpower and mine services. Production drilling is the process of conducting long hole drilling for the purpose of charging and blasting these holes for the production of ore in underground metal mines. Thus, production drilling is the crucial segment in the underground metal mining value chain. This paper presents the process mapping tool to evaluate the production drilling process in the underground metal mining operation by dividing the given process into three segments namely Input, Process and Output. The three segments are further segregated into factors and sub-factors. As per the study, the major input factors crucial for the efficient functioning of production drilling process are power, drilling water, geotechnical support of the drilling site, skilled drilling operators, services installation crew, oils and drill accessories for drilling machine, survey markings at drill site, proper housekeeping, regular maintenance of drill machine, suitable transportation for reaching the drilling site and finally proper ventilation. The major outputs for the production drilling process are ore, waste as a result of dilution, timely reporting and investigation of unsafe practices, optimized process time and finally well fragmented blasted material within specifications set by the mining company. The paper also exhibits the drilling loss matrix, which is utilized to appraise the loss in planned production meters per day in a mine on account of availability loss in the machine due to breakdowns, underutilization of the machine and productivity loss in the machine measured in drilling meters per unit of percussion hour with respect to its planned productivity for the day. The given three losses would be essential to detect the bottlenecks in the process map of production drilling operation so as to instigate the action plan to suppress or prevent the causes leading to the operational performance deficiency. The given tool is beneficial to mine management to focus on the critical factors negatively impacting the production drilling operation and design necessary operational and maintenance strategies to mitigate them. 

Keywords: process map, drilling loss matrix, SIPOC, productivity, percussion rate

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1924 Use of Vapor Corrosion Inhibitor for Tank Bottom Protection

Authors: Muhammad Arsalan Khan Sherwani

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The use of Volatile Corrosion Inhibitors (VCI) to protect Aboveground Storage Tank (AST) bottom plates against soil-side corrosion is one of the emerging corrosion prevention methods, specifically for tanks constructed on oily sand pad. Oily sand pad and the presence of air gaps underneath the bottom plates lead to severe corrosion and high metal thickness loss. In such cases, the cathodic protection cannot be fully considered as effective due to Cathodic Protection (CP) current shielding. These situations sometimes result in serious failures on multiple fronts, such as; containment losses, system shutdowns, extensive repairs, environmental impact and safety concerns in case of flammable fluids. Recently, East West Pipeline Department (EWPD) of Saudi Aramco has deployed this technology to one of the crude oil storage tanks, which showed high metal thickness loss during its out of service inspection. Soil-side corrosion rustled in major repairs of bottom plates and ultimately caused enormous unplanned activities in term of time as well as cost. This paper mainly focuses on the methodology of VCI installation, corrosion monitoring system and the expected results of protection.

Keywords: Vapor Corrosion Inhibitor, Soil Side Corrosion, External Corrosion, Above Grade Storage Tank

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1923 Engineering Microstructural Evolution during Arc Wire Directed Energy Deposition of Magnesium Alloy (AZ31)

Authors: Nivatha Elangovan, Lakshman Neelakantan, Murugaiyan Amirthalingam

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Magnesium and its alloys are widely used for various lightweight engineering and biomedical applications as they render high strength to low weight ratio and excellent corrosion resistance. These alloys possess good bio-compatibility and similar mechanical properties to natural bone. However, manufacturing magnesium alloy components by conventional formative and subtractive methods is challenging due to their poor castability, oxidation potential, and machinability. Therefore, efforts are made to produce complex-design containing magnesium alloy components by additive manufacturing (AM). Arc-wire directed energy deposition (AW-DED), also known as wire arc additive manufacturing (WAAM), is more attractive to produce large volume components with increased productivity than any other AM technique. In this research work, efforts were made to optimise the deposition parameters to build thick-walled (about 10 mm) AZ31 magnesium alloy components by a gas metal arc (GMA) based AW-DED process. By using controlled dip short-circuiting metal transfer in a GMA process, depositions were carried out without defects and spatter formation. Current and voltage waveforms were suitably modified to achieve stable metal transfer. Moreover, the droplet transfer behaviour was analysed using high-speed image analysis and correlated with arc energy. Optical and scanning electron microscopy analyses were carried out to correlate the influence of deposition parameters with the microstructural evolution during deposition. The investigation reveals that by carefully controlling the current-voltage waveform and droplet transfer behaviour, it is possible to stabilise equiaxed grain microstructures in the deposited AZ31 components. The printed component exhibited an improved mechanical property as equiaxed grains improve the ductility and enhance the toughness. The equiaxed grains in the component improved the corrosion-resistant behaviour of other conventionally manufactured components.

Keywords: arc wire directed energy deposition, AZ31 magnesium alloy, equiaxed grain, corrosion

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1922 The Preparation of High Surface Area Ni/MgAl2O4 Catalysts for Syngas Methanation

Authors: Jingyu Zhou, Hongfang Ma, Haitao Zhang, Weiyong Ying

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High surface area MgAl2O4 supported Nickel catalysts with PVA loadings varying from 0% to 15% were prepared by precipitation and impregnation method. The catalysts were characterized by low temperature N2 adsorption/desorption, X-ray diffraction and H2 temperature programmed reduction. Compared with Ni/γ-Al2O3 catalyst, Ni/MgAl2O4 catalysts exhibited higher activity and selectivity in high temperature. Among the catalysts, Ni/MgAl2O4-5P with 5 wt% PVA showed the best performance, and achieved 95% CO conversion and 96% CH4 selectivity at 600°C, 2.0 MPa, and a WHSV of 12,000 mL·g⁻¹.h⁻¹. It also maintained good stability in 50h life test.

Keywords: methanation, MgAl2O4 support, PVA, high surface area

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1921 Inerting and Upcycling of Foundry Fines

Authors: Chahinez Aissaoui, Cecile Diliberto, Jean-Michel Mechling

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The manufacture of metal foundry products requires the use of sand moulds, which are destroyed, and new ones made each time metal is poured. However, recycled sand requires a regeneration process that produces a polluted fine mineral phase. Particularly rich in heavy metals and organic residues, this foundry co-product is disposed of in hazardous waste landfills and requires an expensive stabilisation process. This paper presents the results of research that valorises this fine fraction of foundry sand by inerting it in a cement phase. The fines are taken from the bag filter suction systems of a foundry. The sample is in the form of filler, with a fraction of less than 140µm, the D50 is 43µm. The Blaine fineness is 3120 cm²/g, and the fines are composed mainly of SiO₂, Al₂O₃ and Fe₂O₃. The loss on ignition at 1000°C of this material is 20%. The chosen inerting technique is to manufacture cement pastes which, once hardened, will be crushed for use as artificial aggregates in new concrete formulations. Different percentages of volume substitutions of Portland cement were tested: 30, 50 and 65%. The substitution rates were chosen to obtain the highest possible recycling rate while satisfying the European discharge limits (these values are assessed by leaching). They were also optimised by adding water-reducing admixtures to increase the compressive strengths of the mixes.

Keywords: leaching, upcycling, waste, residuals

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1920 Heteroatom Doped Binary Metal Oxide Modified Carbon as a Bifunctional Electrocatalysts for all Vanadium Redox Flow Battery

Authors: Anteneh Wodaje Bayeh, Daniel Manaye Kabtamu, Chen-Hao Wang

Abstract:

As one of the most promising electrochemical energy storage systems, vanadium redox flow batteries (VRFBs) have received increasing attention owing to their attractive features for largescale storage applications. However, their high production cost and relatively low energy efficiency still limit their feasibility. For practical implementation, it is of great interest to improve their efficiency and reduce their cost. One of the key components of VRFBs that can greatly influence the efficiency and final cost is the electrode, which provide the reactions sites for redox couples (VO²⁺/VO₂ + and V²⁺/V³⁺). Carbon-based materials are considered to be the most feasible electrode materials in the VRFB because of their excellent potential in terms of operation range, good permeability, large surface area, and reasonable cost. However, owing to limited electrochemical activity and reversibility and poor wettability due to its hydrophobic properties, the performance of the cell employing carbon-based electrodes remained limited. To address the challenges, we synthesized heteroatom-doped bimetallic oxide grown on the surface of carbon through the one-step approach. When applied to VRFBs, the prepared electrode exhibits significant electrocatalytic effect toward the VO²⁺/VO₂ + and V³⁺/V²⁺ redox reaction compared with that of pristine carbon. It is found that the presence of heteroatom on metal oxide promotes the absorption of vanadium ions. The controlled morphology of bimetallic metal oxide also exposes more active sites for the redox reaction of vanadium ions. Hence, the prepared electrode displays the best electrochemical performance with energy and voltage efficiencies of 74.8% and 78.9%, respectively, which is much higher than those of 59.8% and 63.2% obtained from the pristine carbon at high current density. Moreover, the electrode exhibit durability and stability in an acidic electrolyte during long-term operation for 1000 cycles at the higher current density.

Keywords: VRFB, VO²⁺/VO₂ + and V³⁺/V²⁺ redox couples, graphite felt, heteroatom-doping

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1919 Development of Al Foam by a Low-Cost Salt Replication Method for Industrial Applications

Authors: B. Soni, S. Biswas

Abstract:

Metal foams of Al find diverse applications in several industrial sectors such as in automotive and sports equipment industry as impact, acoustic and vibration absorbers, the aerospace industry as structural components in turbines and spatial cones, in the naval industry as low frequency vibration absorbers, and in construction industry as sound barriers inside tunnels, as fire proof materials and structure protection systems against explosions and even in heat exchangers, orthopedic components, and decorative items. Here, we report on the development of Al foams by a low cost and convenient technique of salt replication method with efficient control over size, geometry and distribution of the pores. Sodium bicarbonate was used as the foaming agent to form the porous refractory salt pattern. The mixed refractory salt slurry was microwave dried followed by sintering for selected time periods. Molten Al was infiltrated into the salt pattern in an inert atmosphere at a pressure of 2 bars. The final products were obtained by leaching out the refractory salt pattern. Mechanical properties of the derived samples were studied with a universal testing machine. The results were analyzed in correlation with their microstructural features evaluated with a scanning electron microscope (SEM).

Keywords: metal foam, Al, salt replication method, mechanical properties, SEM

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1918 Efficiently Dispersed MnOx on Mesoporous 3D Cubic Support for Cyclohexene Epoxidation

Authors: G. Imran, A. Pandurangan

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Epoxides constitute important intermediates for the production of fine and bulk chemicals as well as valuable building blocks for the synthesis of a variety of bioactive molecules. Manganese oxides are used as selective catalyst for various redox type reactions and also effectively used in the field of catalytic disposal of pollutants. Non-toxic, cost efficient factor and more over existence of wide range of oxidation state (+2 to +7) makes catalyst more interesting for both academic research and industrial applications. However, the serious drawback lying is the lower surface area. Exceedingly dispersed manganese oxide grafted over mesoporous solid material KIT-6 through ALD (Atomic Layer Deposition) technique effectively catalyze cyclohexene with H2O2 (30% in water) to corresponding epoxides. Highly selective epoxide >99% with 55.7% conversion of cyclohexene was achieved using huge dispersed active sites of MnOx species containing catalysts. Various weight percent such as (1, 3, 5, 7 & 10 wt %) of manganese (II) acetylacetonate complex was employed as Mn source to post-graft via active silanol groups of KIT-6 and are designated as (Mn-G-KIT-6). XRD, N2 sorption, HR-TEM, DRS-UV-VIS, EPR and H2-TPR were employed for structural and textural properties. Immense Mn species of about 95% proportion on silica matrix obtained was evident from ICP-OES.The resulting materials exhibited Type IV adsorption isotherms indiacting mesopore in nanorange. Si-KIT-6 and Mn-G-KIT-6 materials exhibited surface area of 519-289 m2/g and with decrease in pore volume of 0.96-0.49 cm3/g with pore diameter ranging 7.9- 7.2 with increase in wt%. DRS-UV-VIS spectroscopy and EPR studies reveal that manganese coexists as Mn2+/3+ species as extra-framework sites and frame-work sites that result in dispersion on surface of silica matrix of KIT-6 and incorporated manganese sites with silanol groups along with small sized MnO cluster, evident from HR-TEM which increase with Mn content. Conventional production of epoxides by the intramolecular etherification of chlorohydrins formed by the reaction of alkenes with hypochlorous acid is the major drawbacks obtained recently. The most efficient synthesis of oxiranes (epoxides) is obtained by mesoporous catalysts (Mn-G-KIT-6) are presented here and discussed.

Keywords: ALD, epoxidation, mesoporous, MnOx

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1917 Robotics and Embedded Systems Applied to the Buried Pipeline Inspection

Authors: Robson C. Santos, Julio C. P. Ribeiro, Iorran M. de Castro, Luan C. F. Rodrigues, Sandro R. L. Silva, Diego M. Quesada

Abstract:

The work aims to develop a robot in the form of autonomous vehicle to detect, inspection and mapping of underground pipelines through the ATmega328 Arduino platform. Hardware prototyping very similar to C / C ++ language that facilitates its use in robotics open source, resembles PLC used in large industrial processes. The robot will traverse the surface independently of direct human action, in order to automate the process of detecting buried pipes, guided by electromagnetic induction. The induction comes from coils that sends the signal to the Arduino microcontroller contained in that will make the difference in intensity and the treatment of the information, then this determines actions to electrical components such as relays and motors, allowing the prototype to move on the surface and getting the necessary information. The robot was developed by electrical and electronic assemblies that allowed test your application. The assembly is made up of metal detector coils, circuit boards and microprocessor, which interconnected circuits previously developed can determine, process control and mechanical actions for a robot (autonomous car) that will make the detection and mapping of buried pipelines plates.

Keywords: robotic, metal detector, embedded system, pipeline inspection

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1916 Cu Nanoparticle Embedded-Zno Nanoplate Thin Films for Highly Efficient Photocatalytic Hydrogen Production

Authors: Premrudee Promdet, Fan Cui, Gi Byoung Hwang, Ka Chuen To, Sanjayan Sathasivam, Claire J. Carmalt, Ivan P. Parkin

Abstract:

A novel single-step fabrication of Cu nanoparticle embedded ZnO (Cu.ZnO) thin films was developed by aerosol-assisted chemical vapor deposition for stable and efficient hydrogen production in Photoelectrochemical (PEC) cell. In this approach, the Cu.ZnO nanoplate thin films were grown by using acetic acid to promote preferential growth and enhance surface active sites, where Cu nanoparticles can be formed under chemical deposition by reduction of Cu salt. Studies using photoluminescence spectroscopy indicate the enhanced photocatalytic performance is attributed to hot electron generated from SPR. The Cu metal in the composite material is functioning as a sensitizer to supply electrons to the semiconductor resulting in enhanced electron density for redox reaction. This work not only describes a way to obtain photoanodes with high photocatalytic activity but also suggests a low-cost route towards production of photocatalysts for hydrogen production. This work also supports a vital need to understand electron transfer between photoexcited semiconductor materials and metals, a requirement for tailoring the properties of semiconductor/metal composites.

Keywords: photocatalysis, photoelectrochemical cell (PEC), aerosol-assisted chemical vapor deposition (AACVD), surface plasmon resonance (SPR)

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1915 Mechanical Characterization and Metallography of Sintered Aluminium-Titanium Diboride Metal Matrix Composite

Authors: Sai Harshini Irigineni, Suresh Kumar Reddy Narala

Abstract:

The industrial applicability of aluminium metal matrix composites (AMMCs) has been rapidly growing due to their exceptional materials traits such as low weight, high strength, excellent thermal performance, and corrosion resistance. The increasing demand for AMMCs in automobile, aviation, aerospace and defence ventures has opened up windows of opportunity for the development of processing methods that facilitate low-cost production of AMMCs with superior properties. In the present work, owing to its economy, efficiency, and suitability, powder metallurgy (P/M) technique was employed to develop AMMCs with pure aluminium as matrix material and titanium diboride (TiB₂) as reinforcement. AMMC samples with different weight compositions (Al-0.1%TiB₂, Al-5%TiB₂, Al-10%TiB₂, and Al-15% TiB₂) were prepared through hot press compacting followed by traditional sintering. The developed AMMC was subjected to metallographic studies and mechanical characterization. Experimental evidences show significant improvement in mechanical properties such as tensile strength, hardness with increasing reinforcement content. The current study demonstrates the superiority of AMMCs over conventional metals and alloys and the results obtained may be of immense in material selection for different structural applications.

Keywords: AMMCs, mechanical characterization, powder metallurgy, TiB₂

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1914 Nutritional Quality Assessment and Safety Evaluation of Food Crops

Authors: Olawole Emmanuel Aina, Liziwe Lizbeth Mugivhisa, Joshua Oluwole Olowoyo, Chikwela Lawrence Obi

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In sustained and consistent efforts to improve food security, numerous and different methods are proposed and used in the production of food crops, and farm produce to meet the demands of consumers. However, unregulated and indiscriminate methods of production present another problem that may expose consumers of these food crops to potential health risks. Therefore, it is imperative that a thorough assessment of farm produce is carried out due to the growing trend of health-conscious consumers preference for minimally processed or raw farm produce. This study evaluated the safety and nutritional quality of food crops. The objectives were to compare the nutritional quality of organic and inorganic farm produce in one hand and, on the other, evaluate the safety of farm produce with respect to trace metal and pathogenic contamination. We conducted a broad systematic search of peer-reviewed published literatures from databases and search engines such as science direct, web-of-science, Google scholar, and Scopus. This study concluded that there is no conclusive evidence to support the notion of nutritional superiority of organic food crops over their inorganic counterparts and there are documented reports of pathogenic and metal contaminations of food crops.

Keywords: food crops, fruits and vegetables, pathogens, nutrition, trace metals

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1913 Comparative Analysis of Photosynthetic and Antioxidative Responses of Two Species of Anabaena under Ni and As(III) Stress

Authors: Shivam Yadav, Neelam Atri

Abstract:

Cyanobacteria, the photosynthetic prokaryotes are indispensable components of paddy soil contribute substantially to the nitrogen economy however often appended with metal load. They are well known to play crucial roles in maintenance of soil fertility and rice productivity. Nickel is one such metal that plays a vital role in the cellular physiology, however at higher concentrations it exerts adverse effects. Arsenic is another toxic metalloid that negatively affects the cyanobacterial proliferation. However species-specific comparative responses under As and Ni is largely unknown. The present study focuses on the comparative effects of nickel (Ni2+) and arsenite (As(III)) on two diazotrophic cyanobacterial species (Anabaena doliolum and Anabaena sp. PCC7120) in terms of antioxidative aspects. Oxidative damage measured in terms of lipid peroxidation and peroxide content was significantly higher after As(III) than Ni treatment as compared to control. Similarly, all the studied enzymatic and non-enzymatic parameters of antioxidative defense system except glutathione reductase (GR) showed greater induction against As(III) than Ni. Moreover, integrating comparative analysis of all studied parameters also demonstrated interspecies variation in terms of stress adaptive strategies reflected through higher sensitivity of Anabaena doliolum over Anabaena PCC7120.

Keywords: antioxidative system, arsenic, cyanobacteria, nickel

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1912 Development and Characterization of Cathode Materials for Sodium-Metal Chloride Batteries

Authors: C. D’Urso, L. Frusteri, M. Samperi, G. Leonardi

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Solid metal halides are used as active cathode ingredients in the case of Na-NiCl2 batteries that require a fused secondary electrolyte, sodium tetrachloraluminate (NaAlCl4), to facilitate the movement of the Na+ ion into the cathode. The sodium-nickel chloride (Na - NiCl2) battery has been extensively investigated as a promising system for large-scale energy storage applications. The growth of Ni and NaCl particles in the cathodes is one of the most important factors that degrade the performance of the Na-NiCl2 battery. The larger the particles of active ingredients contained in the cathode, the smaller the active surface available for the electrochemical reaction. Therefore, the growth of Ni and NaCl particles can lead to an increase in cell polarization resulting from the reduced active area. A higher current density, a higher state of charge (SOC) at the end of the charge (EOC) and a lower Ni / NaCl ratio are the main parameters that result in the rapid growth of Ni particles. In light of these problems, cathode and chemistry Nano-materials with recognized and well-documented electrochemical functions have been studied and manufactured to simultaneously improve battery performance and develop less expensive and more performing, sustainable and environmentally friendly materials. Starting from the well-known cathodic material (Na-NiCl2), the new electrolytic materials have been prepared on the replacement of nickel with iron (10-90%substitution of Nichel with Iron), to obtain a new material with potential advantages compared to current battery technologies; for example,, (1) lower cost of cathode material compared to state of the art as well as (2) choices of cheaper materials (stainless steels could be used for cell components, including cathode current collectors and cell housings). The study on the particle size of the cathode and the physicochemical characterization of the cathode was carried out in the test cell using, where possible, the GITT method (galvanostatic technique of intermittent titration). Furthermore, the impact of temperature on the different cathode compositions of the positive electrode was studied. Especially the optimum operating temperature is an important parameter of the active material.

Keywords: critical raw materials, energy storage, sodium metal halide, battery

Procedia PDF Downloads 115
1911 3-D Strain Imaging of Nanostructures Synthesized via CVD

Authors: Sohini Manna, Jong Woo Kim, Oleg Shpyrko, Eric E. Fullerton

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CVD techniques have emerged as a promising approach in the formation of a broad range of nanostructured materials. The realization of many practical applications will require efficient and economical synthesis techniques that preferably avoid the need for templates or costly single-crystal substrates and also afford process adaptability. Towards this end, we have developed a single-step route for the reduction-type synthesis of nanostructured Ni materials using a thermal CVD method. By tuning the CVD growth parameters, we can synthesize morphologically dissimilar nanostructures including single-crystal cubes and Au nanostructures which form atop untreated amorphous SiO2||Si substrates. An understanding of the new properties that emerge in these nanostructures materials and their relationship to function will lead to for a broad range of magnetostrictive devices as well as other catalysis, fuel cell, sensor, and battery applications based on high-surface-area transition-metal nanostructures. We use coherent X-ray diffraction imaging technique to obtain 3-D image and strain maps of individual nanocrystals. Coherent x-ray diffractive imaging (CXDI) is a technique that provides the overall shape of a nanostructure and the lattice distortion based on the combination of highly brilliant coherent x-ray sources and phase retrieval algorithm. We observe a fine interplay of reduction of surface energy vs internal stress, which plays an important role in the morphology of nano-crystals. The strain distribution is influenced by the metal-substrate interface and metal-air interface, which arise due to differences in their thermal expansion. We find the lattice strain at the surface of the octahedral gold nanocrystal agrees well with the predictions of the Young-Laplace equation quantitatively, but exhibits a discrepancy near the nanocrystal-substrate interface resulting from the interface. The strain in the bottom side of the Ni nanocube, which is contacted on the substrate surface is compressive. This is caused by dissimilar thermal expansion coefficients between Ni nanocube and Si substrate. Research at UCSD support by NSF DMR Award # 1411335.

Keywords: CVD, nanostructures, strain, CXRD

Procedia PDF Downloads 394
1910 Supramolecular Approach towards Novel Applications: Battery, Band Gap and Gas Separation

Authors: Sudhakara Naidu Neppalli, Tejas S. Bhosale

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It is well known that the block copolymer (BCP) can form a complex molecule, through non-covalent bonds such as hydrogen bond, ionic bond and co-ordination bond, with low molecular weight compound as well as with macromolecules, which provide vast applications, includes the alteration of morphology and properties of polymers. Hence we covered the research that, the importance of non-covalent bonds in increasing the non-favourable segmental interactions of the blocks was well examined by attaching and detaching the bonds between the BCP and additive. We also monitored the phase transition of block copolymer and effective interaction parameter (χeff) for Li-doped polymers using small angle x-ray scattering and transmission electron microscopy. The effective interaction parameter (χeff) between two block components was evaluated using Leibler theory based on the incompressible random phase approximation (RPA) for ionized BCP in a disordered state. Furthermore, conductivity experiments demonstrate that the ionic conductivity in the samples quenched from the different structures is morphology-independent, while it increases with increasing ion salt concentration. Morphological transitions, interaction parameter, and thermal stability also examined in quarternized block copolymer. D-spacing was used to estimate effective interaction parameter (χeff) of block components in weak and strong segregation regimes of ordered phase. Metal-containing polymer has been the topic of great attention in recent years due to their wide range of potential application. Similarly, metal- ligand complex is used as a supramolecular linker between the polymers giving rise to a ‘Metallo-Supramolecule assembly. More precisely, functionalized polymer end capped with 2, 2’:6’, 2”- terpyridine ligand can be selectively complexed with wide range of transition metal ions and then subsequently attached to other terpyridine terminated polymer block. In compare to other supramolecular assembly, BCP involved metallo-supramolecule assembly offers vast applications such as optical activity, electrical conductivity, luminescence and photo refractivity.

Keywords: band gap, block copolymer, conductivity, interaction parameter, phase transition

Procedia PDF Downloads 171
1909 Optimized Parameters for Simultaneous Detection of Cd²⁺, Pb²⁺ and CO²⁺ Ions in Water Using Square Wave Voltammetry on the Unmodified Glassy Carbon Electrode

Authors: K. Sruthi, Sai Snehitha Yadavalli, Swathi Gosh Acharyya

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Water is the most crucial element for sustaining life on earth. Increasing water pollution directly or indirectly leads to harmful effects on human life. Most of the heavy metal ions are harmful in their cationic form. These heavy metal ions are released by various activities like disposing of batteries, industrial wastes, automobile emissions, and soil contamination. Ions like (Pb, Co, Cd) are carcinogenic and show many harmful effects when consumed more than certain limits proposed by WHO. The simultaneous detection of the heavy metal ions (Pb, Co, Cd), which are highly toxic, is reported in this study. There are many analytical methods for quantifying, but electrochemical techniques are given high priority because of their sensitivity and ability to detect and recognize lower concentrations. Square wave voltammetry was preferred in electrochemical methods due to the absence of background currents which is interference. Square wave voltammetry was performed on GCE for the quantitative detection of ions. Three electrode system consisting of a glassy carbon electrode as the working electrode (3 mm diameter), Ag/Agcl electrode as the reference electrode, and a platinum wire as the counter electrode was chosen for experimentation. The mechanism of detection was done by optimizing the experimental parameters, namely pH, scan rate, and temperature. Under the optimized conditions, square wave voltammetry was performed for simultaneous detection. Scan rates were varied from 5 mV/s to 100 mV/s and found that at 25 mV/s all the three ions were detected simultaneously with proper peaks at particular stripping potential. The variation of pH from 3 to 8 was done where the optimized pH was taken as pH 5 which holds good for three ions. There was a decreasing trend at starting because of hydrogen gas evolution, and after pH 5 again there was a decreasing trend that is because of hydroxide formation on the surface of the working electrode (GCE). The temperature variation from 25˚C to 45˚C was done where the optimum temperature concerning three ions was taken as 35˚C. Deposition and stripping potentials were given as +1.5 V and -1.5 V, and the resting time of 150 seconds was given. Three ions were detected at stripping potentials of Cd²⁺ at -0.84 V, Pb²⁺ at -0.54 V, and Co²⁺ at -0.44 V. The parameters of detection were optimized on a glassy carbon electrode for simultaneous detection of the ions at lower concentrations by square wave voltammetry.

Keywords: cadmium, cobalt, lead, glassy carbon electrode, square wave anodic stripping voltammetry

Procedia PDF Downloads 117
1908 3D Simulation and Modeling of Magnetic-Sensitive on n-type Double-Gate Metal-Oxide-Semiconductor Field-Effect Transistor (DGMOSFET)

Authors: M. Kessi

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We investigated the effect of the magnetic field on carrier transport phenomena in the transistor channel region of Double-Gate Metal-Oxide-Semiconductor Field-Effect Transistor (MOSFET). This explores the Lorentz force and basic physical properties of solids exposed to a constant external magnetic field. The magnetic field modulates the electrons and potential distribution in the case of silicon Tunnel FETs. This modulation shows up in the device's external electrical characteristics such as ON current (ION), subthreshold leakage current (IOF), the threshold voltage (VTH), the magneto-transconductance (gm) and the output magneto-conductance (gDS) of Tunnel FET. Moreover, the channel doping concentration and potential distribution are obtained using the numerical method by solving Poisson’s transport equation in 3D modules semiconductor magnetic sensors available in Silvaco TCAD tools. The numerical simulations of the magnetic nano-sensors are relatively new. In this work, we present the results of numerical simulations based on 3D magnetic sensors. The results show excellent accuracy comportment and good agreement compared with that obtained in the experimental study of MOSFETs technology.

Keywords: single-gate MOSFET, magnetic field, hall field, Lorentz force

Procedia PDF Downloads 182
1907 Synthesis of Bimetallic Ti-Fe-SBA-15 Using Silatrane

Authors: Ratchadaporn Kaewmuang, Hussaya Maneesuwan, Thanyalak Chaisuwan, Sujitra Wongkasemjit

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Mesoporous materials have been used in many applications, such as adsorbent and catalyst. SBA-15, a 2D hexagonal ordered mesoporous silica material, has not only high specific surface area, but also thicker wall, larger pore size, better hydrothermal stability, and mechanical properties than M41s. However, pure SBA-15 still lacks of redox properties. Therefore, bimetallic incorporation into framework is of interest since it can create new active sites. In this work, Ti-Fe-SBA-15 is studied and successfully synthesized via sol-gel process, using silatrane, FeCl3, and titanium (VI) isopropoxide as silica, iron, and titanium sources, respectively. The products are characterized by SAXD, FE-SEM, and N2 adsorption/desorption, DR-UV, and XRF.

Keywords: SBA-15, mesoporous silica, bimetallic, titanium, iron, silatrane

Procedia PDF Downloads 380
1906 Treatment and Characterization of Cadmium Metal From Textile Factory Wastewater by Electrochemical Process Using Aluminum Plate Electrode

Authors: Dessie Tibebe, Yeshifana Ayenew, Marye Mulugeta, Yezbie Kassa, Zerubabel Moges, Dereje Yenealem, Tarekegn Fentie, Agmas Amare, Hailu Sheferaw Ayele

Abstract:

Electrochemical treatment technology is a technique used for wastewater treatment due to its ability to eliminate impurities that are not easily removed by chemical processes. The objective of the study is the treatment and characterization of textile wastewater by an electrochemical process. The results obtained at various operational parameters indicated that at 20 minutes of electrochemical process at ( pH =7), initial concentration 10 mg/L, current density 37.5 mA/cm², voltage 9 v and temperature 25⁰C the highest removal efficiency was achieved. The kinetics of removal of selected metal by electrochemical treatment has been successfully described by the first-order rate equation. The results of microscopic techniques using SEM for the scarified electrode before treatment were uniform and smooth, but after the electrochemical process, the morphology was completely changed. This is due to the detection of the adsorbed aluminum hydroxide coming from adsorption of the conducting electrolyte, chemicals used in the experiments, alloying and the scrap impurities of the anode and cathode. The FTIR spectroscopic analysis broad bands at 3450 cm-¹ representing O-H functional groups, while the presence of H-O-H and Al-H groups are indicated by the bands at 2850-2750 cm-¹ and 1099 representing C-H functional groups.

Keywords: electrochemical, treatment, textile wastewater, kinetics, removal efficiency

Procedia PDF Downloads 99
1905 The Effect of Supercritical Fluid on the Extraction Efficiency of Heavy Metal from Soil

Authors: Haifa El-Sadi, Maria Elektorowicz, Reed Rushing, Ammar Badawieh, Asif Chaudry

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Clay soils have particular properties that affect the assessment and remediation of contaminated sites. In clay soils, electro-kinetic transport of heavy metals has been carried out. The transport of these metals is predicated on maintaining a low pH throughout the cell, which, in turn, keeps the metals in the pore water phase where they are accessible to electro-kinetic transport. Supercritical fluid extraction and acid digestion were used for the analysis of heavy metals concentrations after the completion of electro-kinetic experimentation. Supercritical fluid (carbon dioxide) extraction is a new technique used to extract the heavy metal (lead, nickel, calcium and potassium) from clayey soil. The comparison between supercritical extraction and acid digestion of different metals was carried out. Supercritical fluid extraction, using ethylenediaminetetraacetic acid (EDTA) as a modifier, proved to be efficient and a safer technique than acid digestion technique in extracting metals from clayey soil. Mixing time of soil with EDTA before extracting heavy metals from clayey soil was investigated. The optimum and most practical shaking time for the extraction of lead, nickel, calcium and potassium was two hours.

Keywords: clay soil, heavy metals, supercritical fluid extraction, acid digestion

Procedia PDF Downloads 470
1904 Electronic/Optoelectronic Property Tuning in Two-Dimensional Transition Metal Dichalcogenides via High Pressure

Authors: Juan Xia, Jiaxu Yan, Ze Xiang Shen

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The tuneable interlayer interactions in two-dimensional (2D) transition metal dichlcogenides (TMDs) offer an exciting platform for exploring new physics and applications by material variety, thickness, stacking sequence, electromagnetic filed, and stress/strain. Compared with the five methods mentioned above, high pressure is a clean and powerful tool to induce dramatic changes in lattice parameters and physical properties for 2D TMD materials. For instance, high pressure can strengthen the van der Waals interactions along c-axis and shorten the covalent bonds in atomic plane, leading to the typical first-order structural transition (2Hc to 2Ha for MoS2), or metallization. In particular, in the case of WTe₂, its unique symmetry endows the significant anisotropy and the corresponding unexpected properties including the giant magnetoresistance, pressure-induced superconductivity and Weyl semimetal states. Upon increasing pressure, the Raman peaks for WTe₂ at ~120 cm⁻¹, are gradually red-shifted and totally suppressed above 10 GPa, attributed to the possible structural instability of orthorhombic Td phase under high pressure and phase transition to a new monoclinic T' phase with inversion symmetry. Distinct electronic structures near Fermi level between the Td and T' phases may pave a feasible way to achieve the Weyl state tuning in one material without doping.

Keywords: 2D TMDs, electronic property, high pressure, first-principles calculations

Procedia PDF Downloads 233
1903 Advanced Nanomaterials in Catalysis: Bridging the Gap Between Pollution Control and Renewable Energy

Authors: Abonyi Matthew Ndubuisi, Christopher Chiedozie Obi, Joseph Tagbo Nwabanne

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This review focuses on the application of advanced nanomaterials in catalysis for pollution control and renewable energy solutions. This review provides a comprehensive examination of the latest developments in nanocatalysts, highlighting their role in addressing environmental challenges and facilitating sustainable energy solutions. The unique properties of nanomaterials, including high surface area, tunable electronic properties, and enhanced reactivity, make them ideal candidates for catalytic applications. This review explores various types of nanomaterials, such as metal nanoparticles, carbon-based nanostructures, and metal-organic frameworks, and their effectiveness in processes like photocatalysis, electrocatalysis, and hydrogen production. Additionally, the review discusses the environmental benefits of using nanocatalysts in pollution control, focusing on the degradation of pollutants in water and air. The potential of these materials to bridge the gap between environmental remediation and clean energy production is emphasized, showcasing their dual role in mitigating pollution and advancing renewable energy technologies. In conclusion, the review analyzes the current challenges and future directions in the field, highlighting the need for continued research to improve the design and application of nanocatalysts for a sustainable future.

Keywords: nanomaterials, catalysis, pollution control, renewable energy, sustainable technology

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1902 Synthesis, Characterization and Biological Activites of Azomethine Derivatives

Authors: Lynda Golea, Rachid Chebaki

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Schiff bases contain heterocyclic structural units with N and O donor atoms which plays an important role in coordination chemistry. Azomethine groups are a broad class of widely used compounds with applications in many fields, including analytical, inorganic chemistry and biological. Schiff's base is of promising research interest due to the widespread antibacterial resistance in medical science. In addition, the research is essential to generate Schiff base metal complexes with various applications. Schiff complexes have been used as drugs and have antibacterial, antifungal, antiviral, and anti-inflammatory properties. The various donor atoms they contain offer a special ability for metal binding. In this research on the physicochemical properties of azomethine groups, we synthesized and studied the Schiff base compounds by a condensation reaction of tryptamines and acetophenone in ethanol. The structure of the prepared compound was interpreted using 1H NMR, 13C NMR, UV-vis and FT-IR. A computational analysis at the level of DFT with functional B3LYP in conjunction with the base 6-311+G (d, p) was conducted to study its electronic and molecular structure. The biological study was performed on three bacterial strains usually causing infection, including Gram-positive and Gram-negative, for antibacterial activity. Results showed moderate biological activity and proportional activity with increasing concentration.

Keywords: azomethine, HOMO, LUMO, RMN, molecular docking

Procedia PDF Downloads 64
1901 Finite Element Method for Modal Analysis of FGM

Authors: S. J. Shahidzadeh Tabatabaei, A. M. Fattahi

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Modal analysis of a FGM plate containing the ceramic phase of Al2O3 and metal phase of stainless steel 304 was performed using ABAQUS, with the assumptions that the material has an elastic mechanical behavior and its Young modulus and density are varying in thickness direction. For this purpose, a subroutine was written in FOTRAN and linked with ABAQUS. First, a simulation was performed in accordance to other researcher’s model, and then after comparing the obtained results, the accuracy of the present study was verified. The obtained results for natural frequency and mode shapes indicate good performance of user-written subroutine as well as FEM model used in present study. After verification of obtained results, the effect of clamping condition and the material type (i.e. the parameter n) was investigated. In this respect, finite element analysis was carried out in fully clamped condition for different values of n. The results indicate that the natural frequency decreases with increase of n, since with increase of n, the amount of ceramic phase in FGM plate decreases, while the amount of metal phase increases, leading to decrease of the plate stiffness and hence, natural frequency, as the Young modulus of Al2O3 is equal to 380 GPa and the Young modulus of stainless steel 304 is equal to 207 GPa.

Keywords: FGM plates, modal analysis, natural frequency, finite element method

Procedia PDF Downloads 317