Search results for: heterogeneous catalysts
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 1105

Search results for: heterogeneous catalysts

985 Zinc Oxid Nanotubes Modified by SiO2 as a Recyclable Catalyst for the Synthesis of 2,3-Dihydroquinazolin-4(1H)-Ones

Authors: Rakhshan Hakimelahi

Abstract:

In recent years, zinc oxid nano tubes have attracted much attention. The direct use of zinc oxid nano tubes modified by SiO2 as recoverable catalysts for organic reactions is very rare. The catalysts were characterized by XRD. The average particle size of ZnO catalysts is 57 nm and there are high density defects on nano tubes surfaces. A simple and efficient method for the quinazolin derivatives synthesis from the condensation isatoic anhydride and an aromatic aldehyde with ammonium acetate in the presence of a catalytic amount zinc oxid nano tubes modified by SiO2 is described. The reason proposed for higher catalytic activity of zinc oxid nano tubes modified by SiO2 is a combination effect of the small particle size and high-density surface defects. The practical and simple method led to excellent yields of the 2,3-Di hydro quinazolin-4(1H)-one derivatives under mild conditions and within short times.

Keywords: 2, 3-Dihydroquinazolin-4(1H)-one derivatives, reusable catalyst, SiO2, zinc oxid nanotubes

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984 Reaction Rate Behavior of a Methane-Air Mixture over a Platinum Catalyst in a Single Channel Catalytic Reactor

Authors: Doo Ki Lee, Kumaresh Selvakumar, Man Young Kim

Abstract:

Catalytic combustion is an environmentally friendly technique to combust fuels in gas turbines. In this paper, the behavior of surface reaction rate on catalytic combustion is studied with respect to the heterogeneous oxidation of methane-air mixture in a catalytic reactor. Plug flow reactor (PFR), the simplified single catalytic channel assists in investigating the catalytic combustion phenomenon over the Pt catalyst by promoting the desired chemical reactions. The numerical simulation with multi-step elementary surface reactions is governed by the availability of free surface sites onto the catalytic surface and thereby, the catalytic combustion characteristics are demonstrated by examining the rate of the reaction for lean fuel mixture. Further, two different surface reaction mechanisms are adopted and compared for surface reaction rates to indicate the controlling heterogeneous reaction for better fuel conversion. The performance of platinum catalyst under heterogeneous reaction is analyzed under the same temperature condition, where the catalyst with the higher kinetic rate of reaction would have a maximum catalytic activity for enhanced methane catalytic combustion.

Keywords: catalytic combustion, heterogeneous reaction, plug flow reactor, surface reaction rate

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983 Controlled Synthesis of Pt₃Sn-SnOx/C Electrocatalysts for Polymer Electrolyte Membrane Fuel Cells

Authors: Dorottya Guban, Irina Borbath, Istvan Bakos, Peter Nemeth, Andras Tompos

Abstract:

One of the greatest challenges of the implementation of polymer electrolyte membrane fuel cells (PEMFCs) is to find active and durable electrocatalysts. The cell performance is always limited by the oxygen reduction reaction (ORR) on the cathode since it is at least 6 orders of magnitude slower than the hydrogen oxidation on the anode. Therefore high loading of Pt is required. Catalyst corrosion is also more significant on the cathode, especially in case of mobile applications, where rapid changes of loading have to be tolerated. Pt-Sn bulk alloys and SnO2-decorated Pt3Sn nanostructures are among the most studied bimetallic systems for fuel cell applications. Exclusive formation of supported Sn-Pt alloy phases with different Pt/Sn ratios can be achieved by using controlled surface reactions (CSRs) between hydrogen adsorbed on Pt sites and tetraethyl tin. In this contribution our results for commercial and a home-made 20 wt.% Pt/C catalysts modified by tin anchoring via CSRs are presented. The parent Pt/C catalysts were synthesized by modified NaBH4-assisted ethylene-glycol reduction method using ethanol as a solvent, which resulted either in dispersed and highly stable Pt nanoparticles or evenly distributed raspberry-like agglomerates according to the chosen synthesis parameters. The 20 wt.% Pt/C catalysts prepared that way showed improved electrocatalytic performance in the ORR and stability in comparison to the commercial 20 wt.% Pt/C catalysts. Then, in order to obtain Sn-Pt/C catalysts with Pt/Sn= 3 ratio, the Pt/C catalysts were modified with tetraethyl tin (SnEt4) using three and five consecutive tin anchoring periods. According to in situ XPS studies in case of catalysts with highly dispersed Pt nanoparticles, pre-treatment in hydrogen even at 170°C resulted in complete reduction of the ionic tin to Sn0. No evidence of the presence of SnO2 phase was found by means of the XRD and EDS analysis. These results demonstrate that the method of CSRs is a powerful tool to create Pt-Sn bimetallic nanoparticles exclusively, without tin deposition onto the carbon support. On the contrary, the XPS results revealed that the tin-modified catalysts with raspberry-like Pt agglomerates always contained a fraction of non-reducible tin oxide. At the same time, they showed increased activity and long-term stability in the ORR than Pt/C, which was assigned to the presence of SnO2 in close proximity/contact with Pt-Sn alloy phase. It has been demonstrated that the content and dispersion of the fcc Pt3Sn phase within the electrocatalysts can be controlled by tuning the reaction conditions of CSRs. The bimetallic catalysts displayed an outstanding performance in the ORR. The preparation of a highly dispersed 20Pt/C catalyst permits to decrease the Pt content without relevant decline in the electrocatalytic performance of the catalysts.

Keywords: anode catalyst, cathode catalyst, controlled surface reactions, oxygen reduction reaction, PtSn/C electrocatalyst

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982 UAV’s Enhanced Data Collection for Heterogeneous Wireless Sensor Networks

Authors: Kamel Barka, Lyamine Guezouli, Assem Rezki

Abstract:

In this article, we propose a protocol called DataGA-DRF (a protocol for Data collection using a Genetic Algorithm through Dynamic Reference Points) that collects data from Heterogeneous wireless sensor networks. This protocol is based on DGA (Destination selection according to Genetic Algorithm) to control the movement of the UAV (Unmanned aerial vehicle) between dynamic reference points that virtually represent the sensor node deployment. The dynamics of these points ensure an even distribution of energy consumption among the sensors and also improve network performance. To determine the best points, DataGA-DRF uses a classification algorithm such as K-Means.

Keywords: heterogeneous wireless networks, unmanned aerial vehicles, reference point, collect data, genetic algorithm

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981 Energy Efficient Heterogeneous System for Wireless Sensor Networks (WSN)

Authors: José Anderson Rodrigues de Souza, Teles de Sales Bezerra, Saulo Aislan da Silva Eleuterio, Jeronimo Silva Rocha

Abstract:

Mobile devices are increasingly occupying sectors of society and one of its most important features is mobility. However, the use of mobile devices is subject to the lifetime of the batteries. Thus, the use of energy batteries has become an important issue in the study of wireless network technologies. In this context, new solutions that enable aggregate energy efficiency not only through energy saving, and principally they are evaluated from a more realistic model of energy discharge, if easy adaptation to existing protocols. This paper presents a study on the energy needed and the lifetime for Wireless Sensor Networks (WSN) using a heterogeneous network and applying the LEACH protocol.

Keywords: wireless sensor networks, energy efficiency, heterogeneous, LEACH protocol

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980 Nuclear Characteristics of a Heterogeneous Thorium-Based Fuel Design Aimed at Increasing Fuel Cycle Length of a Typical PWR

Authors: Hendrik Bernard Van Der Walt, Frik Van Niekerk

Abstract:

Heterogeneous thorium-based fuels have been proposed as an alternative for conventional reactor fuels and many studies have shown promising results. Fuel cycle characteristics still have to be explored in detail. This study investigates the use of a novel thorium-based fuel design aimed at increasing fuel cycle length of a typical PWR with an explicit focus on thorium- uranium content, neutron spectrum, flux considerations and neutron economy.As nuclear reactions are highly dependent on reactor flux and material matrix, analytical and numerical calculations have been completed to predict the behaviour of the proposed nuclear fuel. The proposed design utilizes various ratios of thorium oxide and uranium oxide pellets within fuel pins, divided into heterogeneous sections of specified length. This design renders multiple regions with unique characteristics. The goal of this study is to determine and optimally utilize these characteristics. Proliferation considerations result in the need for denaturing of heterogeneous regions, which renders more unique characteristics, these aspects were examined in this study. Finally, the use of fertile thorium to emulate a burnable poison for managing excess BOL reactivity has been investigated, as well as an option for flux shaping in a typical PWR.

Keywords: nuclear fuel, nuclear characteristics, nuclear fuel cycle, thorium-based fuel, heterogeneous design

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979 Preparation of Superparamagnetic Functionalized Magnetite Nanoparticles for Magnetically Separable Catalysis

Authors: Priya Arora, Jaspreet K. Rajput

Abstract:

Superparamagnetism has accelerated the research and use of more economical and ecological magnetically separable catalysts due to their more efficient isolation by response to an applied magnetic field. Magnetite nanomaterials coated by SiO2 shell have received a great deal of focus in the last decades as it provides high stability and also easy further surface functionalization depending upon the application. In this protocol, Fe3O4 magnetic nanoparticles have been synthesized by co-precipitation combined with sonication method. Further, Fe3O4 superparamagnetic nanoparticles have been functionalized by various moieties to serve as efficient catalysts for multicomponent reactions. The functionalized nanoparticles were characterized by techniques like Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) surface area analysis. The as prepared nanocatalysts can be reused for several times without any significant loss in its activity. The utilization of magnetic nanoparticles as catalysts for this reaction is one approach i.e. green, inexpensive, facile and widely applicable.

Keywords: functionalized, magnetite, multicomponent reactions, superparamagnetic

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978 Synthetic Access to Complex Metal Carbonates and Hydroxycarbonates via Sol-Gel Chemistry

Authors: Schirin Hanf, Carlos Lizandara-Pueyo, Timmo P. Emmert, Ivana Jevtovikj, Roger Gläser, Stephan A. Schunk

Abstract:

Metal alkoxides are very versatile precursors for a broad array of complex functional materials. However, metal alkoxides, especially transition metal alkoxides, tend to form oligomeric structures due to the very strong M–O–M binding motif. This fact hinders their facile application in sol-gel-processes and complicates access to complex carbonate or oxidic compounds after hydrolysis of the precursors. Therefore, the development of a synthetic alternative with the aim to grant access to carbonates and hydroxycarbonates from simple metal alkoxide precursors via hydrolysis is key to this project. Our approach involves the reaction of metal alkoxides with unsaturated isoelectronic molecules, such as carbon dioxide. Subsequently, a stoichiometric insertion of the CO₂ into the alkoxide M–O bond takes place and leads to the formation of soluble metal alkyl carbonates. This strategy is a very elegant approach to solubilize metal alkoxide precursors to make them accessible for sol-gel chemistry. After hydrolysis of the metal alkyl carbonates, crystalline metal carbonates, and hydroxycarbonates can be obtained, which were then utilized for the synthesis of Cu/Zn based bulk catalysts for methanol synthesis. Using these catalysts, a comparable catalytic activity to commercially available MeOH catalysts could be reached. Based on these results, a complement for traditional precipitation techniques, which are usually utilized for the synthesis of bulk methanol catalysts, have been found based on an alternative solubilization strategy.

Keywords: metal alkoxides, metal carbonates, metal hydroxycarbonates, CO₂ insertion, solubilization

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977 Comparative Catalytic Activity of Some Ferrites for Phenol Degradation in Aqueous Solutions

Authors: Bayan Alqassem, Israa A. Othman, Mohammed Abu Haija, Fawzi Banat

Abstract:

The treatment of wastewater from highly toxic pollutants is one of the most challenging issues for humanity. In this study, the advanced oxidation process (AOP) was employed to study the catalytic degradation of phenol using different ferrite catalysts which are CoFe₂O₄, CrFe₂O₄, CuFe₂O₄, MgFe₂O₄, MnFe₂O₄, NiFe₂O₄ and ZnFe₂O₄. The ferrite catalysts were prepared via sol-gel and co-precipitation methods. Different ferrite composites were also prepared either by varying the metal ratios or incorporating chemically reduced graphene oxide in the ferrite cluster. The effect of phosphoric acid treatment on the copper ferrite activity. All of the prepared catalysts were characterized using infrared spectroscopy (IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The ferrites catalytic activities were tested towards phenol degradation using high performance liquid chromatography (HPLC). The experimental results showed that ferrites prepared through sol-gel route were more active than those of the co-precipitation method towards phenol degradation. In both cases, CuFe₂O₄ exhibited the highest degradation of phenol compared to the other ferrites. The photocatalytic properties of the ferrites were also investigated.

Keywords: ferrite catalyst, ferrite composites, phenol degradation, photocatalysis

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976 NiO-CeO2 Nano-Catalyst for the Removal of Priority Organic Pollutants from Wastewater through Catalytic Wet Air Oxidation at Mild Conditions

Authors: Anushree, Chhaya Sharma, Satish Kumar

Abstract:

Catalytic wet air oxidation (CWAO) is normally carried out at elevated temperature and pressure. This work investigates the potential of NiO-CeO2 nano-catalyst in CWAO of paper industry wastewater under milder operating conditions of 90 °C and 1 atm. The NiO-CeO2 nano-catalysts were synthesized by a simple co-precipitation method and characterized by X-ray diffraction (XRD), before and after use, in order to study any crystallographic change during experiment. The extent of metal-leaching from the catalyst was determined using the inductively coupled plasma optical emission spectrometry (ICP-OES). The catalytic activity of nano-catalysts was studied in terms of total organic carbon (TOC), adsorbable organic halides (AOX) and chlorophenolics (CHPs) removal. Interestingly, mixed oxide catalysts exhibited higher activity than the corresponding single-metal oxides. The maximum removal efficiency was achieved with Ce40Ni60 catalyst. The results indicate that the CWAO process is efficient in removing the priority organic pollutants from wastewater, as it exhibited up to 59% TOC, 55% AOX, and 54 % CHPs removal.

Keywords: catalysis, nano-materials, NiO-CeO2, paper mill, wastewater, wet air oxidation

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975 Influence of Carbon Addition on the Activity of Silica Supported Copper and Cobalt Catalysts in NO Reduction with CO

Authors: N. Stoeva, I. Spassova, R. Nickolov, M. Khristova

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Exhaust gases from stationary and mobile combustion sources contain nitrogen oxides that cause a variety of environmentally harmful effects. The most common approach of their elimination is the catalytic reaction in the exhaust using various reduction agents such as NH3, CO and hydrocarbons. Transition metals (Co, Ni, Cu, etc.) are the most widely used as active components for deposition on various supports. However, since the interaction between different catalyst components have been extensively studied in different types of reaction systems, the possible cooperation between active components and the support material and the underlying mechanisms have not been thoroughly investigated. The support structure may affect how these materials maintain an active phase. The objective is to investigate the addition of carbonaceous materials with different nature and texture characteristics on the properties of the resulting silica-carbon support and how it influences of the catalytic properties of the supported copper and cobalt catalysts for reduction of NO with CO. The versatility of the physico-chemical properties of the composites and the supported copper and cobalt catalysts are discussed with an emphasis on the relationship of the properties with the catalytic performance. The catalysts were prepared by sol-gel process and were characterized by XRD, XPS, AAS and BET analysis. The catalytic experiments were carried out in catalytic flow apparatus with isothermal flow reactor in the temperature range 20–300оС. After the catalytic test temperature-programmed desorption (TPD) was carried out. The transient response method was used to study the interaction of the gas phase with the catalyst surface. The role of the interaction between the support and the active phase on the catalyst’s activity in the studied reaction was discussed. We suppose the carbon particles with small sizes to participate in the formation of the active sites for the reduction of NO with CO along with their effect on the kind of deposited metal oxide phase. The existence of micropore texture for some of composites also influences by mass-transfer limitations.

Keywords: catalysts, no reduction, composites, bet analysis

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974 Catalytic Hydrodesulfurization of Dibenzothiophene Coupled with Ionic Liquids over Low Pd Incorporated Co-Mo@Al₂O₃ and Ni-Mo@Al₂O₃ Catalysts at Mild Operating Conditions

Authors: Yaseen Muhammad, Zhenxia Zhao, Zhangfa Tong

Abstract:

A key problem with hydrodesulfurization (HDS) process of fuel oils is the application of severe operating conditions. In this study, we proposed the catalytic HDS of dibenzothiophene (DBT) integrated with ionic liquids (ILs) application at mild temperature and pressure over low loaded (0.5 wt.%) Pd promoted Co-Mo@Al₂O₃ and Ni-Mo@Al₂O₃ catalysts. Among the thirteen ILs tested, [BMIM]BF₄, [(CH₃)₄N]Cl, [EMIM]AlCl₄, and [(C₈H₁₇)(C₃H₇)₃P]Br enhanced the catalytic HDS efficiency while the latest ranked the top of activity list as confirmed by DFT studies as well. Experimental results revealed that Pd incorporation greatly enhanced the HDS activity of classical Co or Ni based catalysts. At mild optimized experimental conditions of 1 MPa H₂ pressure, 120 oC, IL:oil ratio of 1:3 and 4 h reaction time, the % DBT conversion (21 %) by Ni-Mo@Al₂O₃ was enhanced to 69 % (over Pd-Ni-Mo@ Al₂O₃) using [(C₈H₁₇) (C₃H₇)₃P]Br. The fresh and spent catalysts were characterized for textural properties using XPS, SEM, EDX, XRD and BET surface area techniques. An overall catalytic HDS activity followed the order of: Pd-Ni-Mo@Al₂O₃ > Pd-Co-Mo@Al₂O₃ > Ni-Mo@Al₂O₃ > Co-Mo@Al₂O₃. [(C₈H₁₇) (C₃H₇)₃P]Br.could be recycled four times with minimal decrease in HDS activity. Reaction products were analyzed by GC-MS which helped in proposing reaction mechanism for the IL coupled HDS process. The present approach attributed to its cost-effective nature, ease of operation with less mechanical requirements in terms of mild operating conditions, and high efficiency could be deemed as an alternative approach for the HDS of DBT on industrial level applications.

Keywords: DFT simulation, GC-MS and reaction mechanism, Ionic liquid coupled HDS of DBT, low Pd loaded catalyst, mild operating condition

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973 Investigation on Fischer-Tropsch Synthesis over Cobalt-Gadolinium Catalyst

Authors: Jian Huang, Weixin Qian, Haitao Zhang, Weiyong Ying

Abstract:

Cobalt-gadolinium catalyst for Fischer-Tropsch synthesis was prepared by impregnation method with commercial silica gel, and its texture properties were characterized by BET, XRD, and TPR. The catalytic performance of the catalyst was tested in a fixed bed reactor. The results showed that the addition of gadolinium to the cobalt catalyst might decrease the size of cobalt particles, and increased the dispersion of catalytic active cobalt phases. The carbon number distributions for the catalysts was calculated by ASF equation.

Keywords: Fischer-Tropsch synthesis, cobalt-based catalysts, gadolinium, carbon number distributions

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972 Ultrafast Ground State Recovery Dynamics of a Cyanine Dye Molecule in Heterogeneous Environment

Authors: Tapas Goswami, Debabrata Goswami

Abstract:

We have studied the changes in ground state recovery dynamics of IR 144 dye using degenerate transient absorption spectroscopy technique when going from homogeneous solution phase to heterogeneous partially miscible liquid/liquid interface. Towards this aim, we set up a partially miscible liquid/liquid interface in which dye is insoluble in one solvent carbon tetrachloride (CCl₄) layer and soluble in other solvent dimethyl sulphoxide (DMSO). A gradual increase in ground state recovery time of the dye molecule is observed from homogenous bulk solution to more heterogeneous environment interface layer. In the bulk solution charge distribution of dye molecule is in equilibrium with polar DMSO solvent molecule. Near the interface micro transportation of non-polar solvent, CCl₄ disturbs the solvent equilibrium in DMSO layer and it relaxes to a new equilibrium state corresponding to a new charge distribution of dye with a heterogeneous mixture of polar and non-polar solvent. In this experiment, we have measured the time required for the dye molecule to relax to the new equilibrium state in different heterogeneous environment. As a result, dye remains longer time in the excited state such that even it can populate more triplet state. The present study of ground state recovery dynamics of a cyanine dye molecule in different solvent environment provides the important characteristics of effect of solvation on excited life time of a dye molecule.

Keywords: excited state, ground state recovery, solvation, transient absorption

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971 Calcined Tertiaries Hydrotalcites as Supports of Cobalt-Molybdenum Based Catalysts for the Hydrodesulfurization Reaction of Dibenzothiophene

Authors: Edwin Oviedo, Carlos Linares, Philippe Ayrault, Sylvette Brunet

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Nowadays, light conventional crude oils are going down. Therefore, the exploitation of heavy crude oils has been increasing. Hence, a major quantity of refractory sulfur compounds such as dibenzothiophene (DBT) should be removed. Many efforts have been carried out to modify hydrotreatment typical supports in order to increase hydrodesulfurization (HDS) reactions. The present work shows the synthesis of tertiaries MgFeAl(0.16), MgFeAl(0.32), CoFeAl, ZnFeAl hydrotalcites, as supports of CoMo based catalysts, where 0.16 and 0.32 are the Fe3+/Al3+ molar ratio. Solids were characterized by different techniques (XRD, CO2-TPD, H2-TPR, FT-IR, BET, Chemical Analysis and HRTEM) and tested in the DBT HDS reaction. The reactions conditions were: Temp=325°C, P=40 Bar, H2/feed=475. Results show that the catalysts CoMo/MgFeAl(0.16) and CoMo/MgFeAl(0.32), which were the most basics, reduced the sulfur content from 500ppm to less than 1 ppm, increasing the cyclohexylbenzene content, i.e. presented a higher selective toward the HYD pathway than reference catalyst CoMo/γ- Al2O3. This is suitable for improving the fuel quality due to the increase of the cetane number. These catalysts were also more active to the HDS reaction increasing the direct desulfurization (DDS) way and presented a good stability. It is advantageous when the gas oil centane number should be improved. Cobalt, iron or zinc species inside support could avoid the Co and Mo dispersion or form spinel species which could be less active to hydrodesulfuration reactions, while hydrotalcites containing Mg increases the HDS activity probably due to improved Co/Mo ratio.

Keywords: catalyst, cetane number, dibenzothiophene, diesel, hydrodesulfurization, hydrotreatment, MoS2

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970 Fischer Tropsch Synthesis in Compressed Carbon Dioxide with Integrated Recycle

Authors: Kanchan Mondal, Adam Sims, Madhav Soti, Jitendra Gautam, David Carron

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Fischer-Tropsch (FT) synthesis is a complex series of heterogeneous reactions between CO and H2 molecules (present in the syngas) on the surface of an active catalyst (Co, Fe, Ru, Ni, etc.) to produce gaseous, liquid, and waxy hydrocarbons. This product is composed of paraffins, olefins, and oxygenated compounds. The key challenge in applying the Fischer-Tropsch process to produce transportation fuels is to make the capital and production costs economically feasible relative to the comparative cost of existing petroleum resources. To meet this challenge, it is imperative to enhance the CO conversion while maximizing carbon selectivity towards the desired liquid hydrocarbon ranges (i.e. reduction in CH4 and CO2 selectivities) at high throughputs. At the same time, it is equally essential to increase the catalyst robustness and longevity without sacrificing catalyst activity. This paper focuses on process development to achieve the above. The paper describes the influence of operating parameters on Fischer Tropsch synthesis (FTS) from coal derived syngas in supercritical carbon dioxide (ScCO2). In addition, the unreacted gas and solvent recycle was incorporated and the effect of unreacted feed recycle was evaluated. It was expected that with the recycle, the feed rate can be increased. The increase in conversion and liquid selectivity accompanied by the production of narrower carbon number distribution in the product suggest that higher flow rates can and should be used when incorporating exit gas recycle. It was observed that this process was capable of enhancing the hydrocarbon selectivity (nearly 98 % CO conversion), reducing improving the carbon efficiency from 17 % to 51 % in a once through process and further converting 16 % CO2 to liquid with integrated recycle of the product gas stream and increasing the life of the catalyst. Catalyst robustness enhancement has been attributed to the absorption of heat of reaction by the compressed CO2 which reduced the formation of hotspots and the dissolution of waxes by the CO2 solvent which reduced the blinding of active sites. In addition, the recycling the product gas stream reduced the reactor footprint to one-fourth of the once through size and product fractionation utilizing the solvent effects of supercritical CO2 were realized. In addition to the negative CO2 selectivities, methane production was also inhibited and was limited to less than 1.5%. The effect of the process conditions on the life of the catalysts will also be presented. Fe based catalysts are known to have a high proclivity for producing CO2 during FTS. The data of the product spectrum and selectivity on Co and Fe-Co based catalysts as well as those obtained from commercial sources will also be presented. The measurable decision criteria were the increase in CO conversion at H2:CO ratio of 1:1 (as commonly found in coal gasification product stream) in supercritical phase as compared to gas phase reaction, decrease in CO2 and CH4 selectivity, overall liquid product distribution, and finally an increase in the life of the catalysts.

Keywords: carbon efficiency, Fischer Tropsch synthesis, low GHG, pressure tunable fractionation

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969 Method Validation for Determining Platinum and Palladium in Catalysts Using Inductively Coupled Plasma Optical Emission Spectrometry

Authors: Marin Senila, Oana Cadar, Thorsten Janisch, Patrick Lacroix-Desmazes

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The study presents the analytical capability and validation of a method based on microwave-assisted acid digestion for quantitative determination of platinum and palladium in catalysts using inductively coupled plasma optical emission spectrometry (ICP-OES). In order to validate the method, the main figures of merit such as limit of detection and limit of quantification, precision and accuracy were considered and the measurement uncertainty was estimated based on the bottom-up approach according to the international guidelines of ISO/IEC 17025. Limit of detections, estimated from blank signal using 3 s criterion, were 3.0 mg/kg for Pt and respectively 3.6 mg/kg for Pd, while limits of quantification were 9.0 mg/kg for Pt and respectively 10.8 mg/kg for Pd. Precisions, evaluated as standard deviations of repeatability (n=5 parallel samples), were less than 10% for both precious metals. Accuracies of the method, verified by recovery estimation certified reference material NIST SRM 2557 - pulverized recycled monolith, were 99.4 % for Pt and 101% for Pd. The obtained limit of quantifications and accuracy were satisfactory for the intended purpose. The paper offers all the steps necessary to validate the determination method for Pt and Pd in catalysts using inductively coupled plasma optical emission spectrometry.

Keywords: catalyst analysis, ICP-OES, method validation, platinum, palladium

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968 The Optimization of the Parameters for Eco-Friendly Leaching of Precious Metals from Waste Catalyst

Authors: Silindile Gumede, Amir Hossein Mohammadi, Mbuyu Germain Ntunka

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Goal 12 of the 17 Sustainable Development Goals (SDGs) encourages sustainable consumption and production patterns. This necessitates achieving the environmentally safe management of chemicals and all wastes throughout their life cycle and the proper disposal of pollutants and toxic waste. Fluid catalytic cracking (FCC) catalysts are widely used in the refinery to convert heavy feedstocks to lighter ones. During the refining processes, the catalysts are deactivated and discarded as hazardous toxic solid waste. Spent catalysts (SC) contain high-cost metal, and the recovery of metals from SCs is a tactical plan for supplying part of the demand for these substances and minimizing the environmental impacts. Leaching followed by solvent extraction, has been found to be the most efficient method to recover valuable metals with high purity from spent catalysts. However, the use of inorganic acids during the leaching process causes a secondary environmental issue. Therefore, it is necessary to explore other alternative efficient leaching agents that are economical and environmentally friendly. In this study, the waste catalyst was collected from a domestic refinery and was characterised using XRD, ICP, XRF, and SEM. Response surface methodology (RSM) and Box Behnken design were used to model and optimize the influence of some parameters affecting the acidic leaching process. The parameters selected in this investigation were the acid concentration, temperature, and leaching time. From the characterisation results, it was found that the spent catalyst consists of high concentrations of Vanadium (V) and Nickel (Ni); hence this study focuses on the leaching of Ni and V using a biodegradable acid to eliminate the formation of the secondary pollution.

Keywords: eco-friendly leaching, optimization, metal recovery, leaching

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967 Performance Evaluation of Clustered Routing Protocols for Heterogeneous Wireless Sensor Networks

Authors: Awatef Chniguir, Tarek Farah, Zouhair Ben Jemaa, Safya Belguith

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Optimal routing allows minimizing energy consumption in wireless sensor networks (WSN). Clustering has proven its effectiveness in organizing WSN by reducing channel contention and packet collision and enhancing network throughput under heavy load. Therefore, nowadays, with the emergence of the Internet of Things, heterogeneity is essential. Stable election protocol (SEP) that has increased the network stability period and lifetime is the first clustering protocol for heterogeneous WSN. SEP and its descendants, namely SEP, Threshold Sensitive SEP (TSEP), Enhanced TSEP (ETSSEP) and Current Energy Allotted TSEP (CEATSEP), were studied. These algorithms’ performance was evaluated based on different metrics, especially first node death (FND), to compare their stability. Simulations were conducted on the MATLAB tool considering two scenarios: The first one demonstrates the fraction variation of advanced nodes by setting the number of total nodes. The second considers the interpretation of the number of nodes while keeping the number of advanced nodes permanent. CEATSEP outperforms its antecedents by increasing stability and, at the same time, keeping a low throughput. It also operates very well in a large-scale network. Consequently, CEATSEP has a useful lifespan and energy efficiency compared to the other routing protocol for heterogeneous WSN.

Keywords: clustering, heterogeneous, stability, scalability, IoT, WSN

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966 Carbonylative Cross Coupling of 2-Bromopyridine with Different Boronic Acids under Carbon Monoxide Atmosphere

Authors: N. Touj, M. Sauthier, L. Mansour, N. Hamdi

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The palladium NHC complexes are one of the most interesting and widely investigated complexes in different catalytic transformations, especially C–C bond. Thus, the use of N-heterocyclic carbenes associated with palladium has been reported as efficient catalysts for the carbonyl coupling under mild and varied conditions. Herein, we report the synthesis, characterization, and cytotoxic activities of two new families of benzimidazolium salts. Then we studied the use of this class of benzimidazolium salts as a ligand in the carbonylative cross-coupling of 2-bromopyridine with different boronic acids under CO atmosphere to form unsymmetrical arylpyridine ketones.

Keywords: NHC-Pd(II) catalysts, carbonylative Suzuki cross-coupling reaction, arylboronic acids, 2-bromopyridine, unsymmetrical arylpyridine ketones

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965 Effects of Cattaneo-Christov Heat Flux on 3D Magnetohydrodynamic Viscoelastic Fluid Flow with Variable Thermal Conductivity

Authors: Muhammad Ramzan

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A mathematical model has been envisaged to discuss three-dimensional Viscoelastic fluid flow with an effect of Cattaneo-Christov heat flux in attendance of magnetohydrodynamic (MHD). Variable thermal conductivity with the impact of homogeneous-heterogeneous reactions and convective boundary condition is also taken into account. Homotopy analysis method is engaged to obtain series solutions. Graphical illustrations depicting behaviour of sundry parameters on skin friction coefficient and all involved distributions are also given. It is observed that velocity components are decreasing functions of Viscoelastic fluid parameter. Furthermore, strength of homogeneous and heterogeneous reactions have opposite effects on concentration distribution. A comparison with a published paper has also been established and an excellent agreement is obtained; hence reliable results are being presented.

Keywords: Cattaneo Christov heat flux, homogenous-heterogeneous reactions, magnetic field, variable thermal conductivity

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964 One Pot Synthesis of Ultrasmall NiMo Catalysts Supported on Amorphous Alumina with Enhanced type 2 Sites for Hydrodesulfurization Reaction: A Combined Experimental and Theoretical Study

Authors: Shalini Arora, Sri Sivakumar

Abstract:

The deep removal of high molecular weight sulphur compounds (e.g., 4,6, dimethyl dibenzothiophene) is challenging due to their steric hindrance. Hydrogenation desulfurization (HYD) pathway is the main pathway to remove these sulfur compounds, and it is mainly governed by the number of type 2 sites. The formation of type 2 sites can be enhanced by modulating the pore structure and the interaction between the active metal and support. To this end, we report the enhanced HDS catalytic activity of ultrasmall NiMo supported on amorphous alumina (A-Al₂O₃) catalysts by one pot colloidal synthesis method followed by calcination and sulfidation. The amorphous alumina (A-Al₂O₃) was chosen as the support due to its lower surface energy, better physicochemical properties, and enhanced acidic sites (due to the dominance of tetra and penta coordinated [Al] sites) than crystalline alumina phase. At 20% metal oxide composition, NiMo supported on A-Al₂O₃ catalyst showed 1.4 and 1.2 times more reaction rate constant and turn over frequency (TOF) respectively than the conventional catalyst (wet impregnated NiMo catalysts) for HDS reaction of dibenzothiophene reactant molecule. A-Al₂O₃ supported catalysts represented enhanced type 2 sites formation (because this catalystpossesses higher sulfidation degree (80%) and NiMoS sites (19.3 x 10¹⁷ sites/mg) with desired optimum stacking degree (2.5) than wet impregnated catalyst at same metal oxide composition 20%) along with higher active metal dispersion, Mo edge site fraction. The experimental observations were also supported by DFT simulations. Lower heat of adsorption (< 4.2 ev for MoS2 interaction and < 3.15 ev for Ni doped MoS2 interaction) values for A-Al₂O₃ confirmed the presence of weaker metal-support interaction in A-Al₂O₃ in contrast to crystalline ℽ-Al₂O3. The weak metal-support interaction for prepared catalysts clearly suggests the higher formation of type 2 sites which leads to higher catalytic activity for HDS reaction.

Keywords: amorphous alumina, colloidal, desulfurization, metal-support interaction

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963 Electrochemical Reduction of Carbon-dioxide Using Metal Nano-particles Supported on Nano-Materials

Authors: Mulatu Kassie Birhanu

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Electrochemical reduction of CO₂ is an emerging and current issue for its conversion in to valuable product upon minimization of its atmospheric level for contribution of maintaining within the range of permissible limit. Among plenty of electro-catalysts gold and copper are efficient and effective catalysts, which are synthesized and applicable for this research work. The two metal catalysts were prepared in inert environment with different compositions through co-reduction process from their corresponding precursors and then by adding multi-walled carbon nano-tube as a supporter and enhanced the conductivity. The catalytic performance of CO₂ reduction for each composition was performed and resulted an outstanding catalytic activity with generation of high current density (70 mA/cm² at 0.91V vs. RHE) and relatively small onset potential. The catalytic performance, compositions, morphologies, structure and geometric arrangements were evaluated by electrochemical analysis (LSV, impedance, chronoamperometry & tafel plot), EDS, SEM and XAS respectively. The composite metals showed better selectivity of products and faradaic efficiencies due to the synergetic effects of the combined nano-particles in addition to the impact of grain size in reduction of CO₂. Carbon monoxide, hydrogen, formate and ethanol are the reduction products, which are detected and quantifiable by chromatographic techniques considering their physical state of each product.

Keywords: carbondioxide, faradaic efficiency, electrocatalyst, current density

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962 Preparation and Characterization of Modified ZnO Incorporated into Mesoporous MCM-22 Catalysts and Their Catalytic Performances of Crude Jatropha Oil to Biodiesel

Authors: Bashir Abubakar Abdulkadir, Anita Ramli, Lim Jun Wei, Yoshimitsu Uemura

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In this study, the ZnO/MCM-22 catalyst with different ZnO loading were prepared using conventional wet impregnation process and the catalyst activity was tested for biodiesel production from Jatropha oil. The effects of reaction parameters with regards to catalyst activity were investigated. The synthesized catalysts samples were then characterized by X-ray diffraction (XRD) for crystal phase, Brunauer–Emmett–Teller (BET) for surface area, pore volume and pore size, Field Emission Scanning electron microscope attached to energy dispersive x-ray (FESEM/EDX) for morphology and elemental composition and TPD (NH3 and CO2) for basic and acidic properties of the catalyst. The XRD spectra couple with the EDX result shows the presence of ZnO in the catalyst confirming the positive intercalation of the metal oxide into the mesoporous MCM-22. The synthesized catalyst was confirmed to be mesoporous according to BET findings. Also, the catalysts can be considered as a bifunctional catalyst based on TPD outcomes. Transesterification results showed that the synthesized catalyst was highly efficient and effective to be used for biodiesel production from low grade oil such as Jatropha oil and other industrial application where the high fatty acid methyl ester (FAMEs) yield was achieved at moderate reaction conditions. It was also discovered that the catalyst can be used more than five (5) runs with little deactivation confirming the catalyst to be highly active and stable to the heat of reaction.

Keywords: MCM-22, synthesis, transesterification, ZnO

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961 Improved Performance of Mn Substituted Ceria Nanospheres for Water Gas Shift Reaction: Influence of Preparation Conditions

Authors: Bhairi Lakshminarayana, Surajit Sarker, Ch. Subrahmanyam

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The present study reports the development of noble metal free nano catalysts for low-temperature CO oxidation and water gas shift reaction. Mn-substituted CeO2 solid solution catalysts were synthesized by co-precipitation, combustion and hydrothermal methods. The formation of solid solution was confirmed by XRD with Rietveld refinement and the percentage of carbon and nitrogen doping was ensured by CHNS analyzer. Raman spectroscopic confirmed the oxygen vacancies. The surface area, pore volume and pore size distribution confirmed by N2 physisorption analysis, whereas, UV-visible diffuse reflectance spectroscopy and XPS data confirmed the oxidation state of the Mn ion. The particle size and morphology (spherical shape) of the material was confirmed using FESEM and HRTEM analysis. Ce0.8Mn0.2O2-δ was calcined at 400 °C, 600 °C and 800 °C. Raman spectroscopy confirmed that the catalyst calcined at 400 °C has the best redox properties. The activity of the designed catalysts for CO oxidation (0.2 vol%), carried out with GHSV of 21,000 h-1 and it has been observed that co-precipitation favored the best active catalyst towards CO oxidation and water gas shift reaction, due to the high surface area, improved reducibility, oxygen mobility and highest quantity of surface oxygen species. The activation energy of low temperature CO oxidation on Ce0.8Mn0.2O2- δ (combustion) was 5.5 kcal.K-1.mole-1. The designed catalysts were tested for water gas shift reaction. The present study demonstrates that Mn ion substituted ceria at 400 °C calcination temperature prepared by co-precipitation method promise to revive a green sustainable energy production approach.

Keywords: Ce0.8Mn0.2O2-ð, CO oxidation, physicochemical characterization, water gas shift reaction (WGS)

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960 Evaluation of Ensemble Classifiers for Intrusion Detection

Authors: M. Govindarajan

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One of the major developments in machine learning in the past decade is the ensemble method, which finds highly accurate classifier by combining many moderately accurate component classifiers. In this research work, new ensemble classification methods are proposed with homogeneous ensemble classifier using bagging and heterogeneous ensemble classifier using arcing and their performances are analyzed in terms of accuracy. A Classifier ensemble is designed using Radial Basis Function (RBF) and Support Vector Machine (SVM) as base classifiers. The feasibility and the benefits of the proposed approaches are demonstrated by the means of standard datasets of intrusion detection. The main originality of the proposed approach is based on three main parts: preprocessing phase, classification phase, and combining phase. A wide range of comparative experiments is conducted for standard datasets of intrusion detection. The performance of the proposed homogeneous and heterogeneous ensemble classifiers are compared to the performance of other standard homogeneous and heterogeneous ensemble methods. The standard homogeneous ensemble methods include Error correcting output codes, Dagging and heterogeneous ensemble methods include majority voting, stacking. The proposed ensemble methods provide significant improvement of accuracy compared to individual classifiers and the proposed bagged RBF and SVM performs significantly better than ECOC and Dagging and the proposed hybrid RBF-SVM performs significantly better than voting and stacking. Also heterogeneous models exhibit better results than homogeneous models for standard datasets of intrusion detection. 

Keywords: data mining, ensemble, radial basis function, support vector machine, accuracy

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959 Butene Catalytic Cracking to Propylene over Iron and Phosphorus Modified HZSM-5

Authors: Jianwen Li, Hongfang Ma, Haitao Zhang, Qiwen Sun, Weiyong Ying

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HZSM-5 zeolites modified by iron and phosphorus were applied in catalytic cracking of butene. N2 adsorption and NH3-TPD were employed to measure the structure and acidity of catalysts. The results indicate that increasing phosphorus loading decreased surface area, pore volume and strong acidity of catalysts. The introduction of phosphorus significantly decreased butene conversion and promoted propylene selectivity. The catalytic performance of catalyst was strongly dependent on the reaction conditions. Appropriate reaction conditions could suppress side reactions and enhance propylene selectivity.

Keywords: butene catalytic cracking, HZSM-5, modification, reaction conditions

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958 Single Cu‒N₄ Sites Enable Atomic Fe Clusters with High-Performance Oxygen Reduction Reaction

Authors: Shuwen Wu, Zhi LI

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Atomically dispersed Fe‒N₄ catalysts are proven as promising alternatives to commercial Pt/C for the oxygen reduction reaction. Most reported Fe‒N₄ catalysts suffer from inferior O‒O bond-breaking capability due to superoxo-like O₂ adsorption, though the isolated dual-atomic metal sites strategy is extensively adopted. Atomic Fe clusters hold greater promise for promoting O‒O bond cleavage by forming peroxo-like O₂ adsorption. However, the excessively strong binding strength between Fe clusters and oxygenated intermediates sacrifices the activity. Here, we first report a Fex/Cu‒N@CF catalyst with atomic Fe clusters functionalized by adjacent single Cu‒N₄ sites anchoring on a porous carbon nanofiber membrane. The theoretical calculation indicates that the single Cu‒N₄ sites can modulate the electronic configuration of Fe clusters to reduce O₂* protonation reaction free energy, which ultimately enhances the electrocatalytic performance. Particularly, the Cu‒N₄ sites can increase the overlaps between the d orbitals of Fe and p orbitals of O to accelerate O‒O cleavage in OOH*. As a result, this unique atomic catalyst exhibits a half potential (E1/2) of 0.944 V in an alkaline medium exceeding that of commercial Pt/C, whereas acidic performance E1/2 = 0.815 V is comparable to Pt/C. This work shows the great potential of single atoms for improvements in atomic cluster catalysts.

Keywords: Hierarchical porous fibers, atomic Fe clusters, Cu single atoms, oxygen reduction reaction; O-O bond cleavage

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957 Carbon-Foam Supported Electrocatalysts for Polymer Electrolyte Membrane Fuel Cells

Authors: Albert Mufundirwa, Satoru Yoshioka, K. Ogi, Takeharu Sugiyama, George F. Harrington, Bretislav Smid, Benjamin Cunning, Kazunari Sasaki, Akari Hayashi, Stephen M. Lyth

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Polymer electrolyte membrane fuel cells (PEMFCs) are electrochemical energy conversion devices used for portable, residential and vehicular applications due to their low emissions, high efficiency, and quick start-up characteristics. However, PEMFCs generally use expensive, Pt-based electrocatalysts as electrode catalysts. Due to the high cost and limited availability of platinum, research and development to either drastically reduce platinum loading, or replace platinum with alternative catalysts is of paramount importance. A combination of high surface area supports and nano-structured active sites is essential for effective operation of catalysts. We synthesize carbon foam supports by thermal decomposition of sodium ethoxide, using a template-free, gram scale, cheap, and scalable pyrolysis method. This carbon foam has a high surface area, highly porous, three-dimensional framework which is ideal for electrochemical applications. These carbon foams can have surface area larger than 2500 m²/g, and electron microscopy reveals that they have micron-scale cells, separated by few-layer graphene-like carbon walls. We applied this carbon foam as a platinum catalyst support, resulting in the improved electrochemical surface area and mass activity for the oxygen reduction reaction (ORR), compared to carbon black. Similarly, silver-decorated carbon foams showed higher activity and efficiency for electrochemical carbon dioxide conversion than silver-decorated carbon black. A promising alternative to Pt-catalysts for the ORR is iron-impregnated nitrogen-doped carbon catalysts (Fe-N-C). Doping carbon with nitrogen alters the chemical structure and modulates the electronic properties, allowing a degree of control over the catalytic properties. We have adapted our synthesis method to produce nitrogen-doped carbon foams with large surface area, using triethanolamine as a nitrogen feedstock, in a novel bottom-up protocol. These foams are then infiltrated with iron acetate (FeAc) and pyrolysed to form Fe-N-C foams. The resulting Fe-N-C foam catalysts have high initial activity (half-wave potential of 0.68 VRHE), comparable to that of commercially available Pt-free catalysts (e.g., NPC-2000, Pajarito Powder) in acid solution. In alkaline solution, the Fe-N-C carbon foam catalysts have a half-wave potential of 0.89 VRHE, which is higher than that of NPC-2000 by almost 10 mVRHE, and far out-performing platinum. However, the durability is still a problem at present. The lessons learned from X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements will be used to carefully design Fe-N-C catalysts for higher performance PEMFCs.

Keywords: carbon-foam, polymer electrolyte membrane fuel cells, platinum, Pt-free, Fe-N-C, ORR

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956 Adaptive Routing in NoC-Based Heterogeneous MPSoCs

Authors: M. K. Benhaoua, A. E. H. Benyamina, T. Djeradi, P. Boulet

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In this paper, we propose adaptive routing that considers the routing of communications in order to optimize the overall performance. The routing technique uses a newly proposed Algorithm to route communications between the tasks. The routing we propose of the communications leads to a better optimization of several performance metrics (time and energy consumption). Experimental results show that the proposed routing approach provides significant performance improvements when compared to those using static routing.

Keywords: multi-processor systems-on-chip (mpsocs), network-on-chip (noc), heterogeneous architectures, adaptive routin

Procedia PDF Downloads 348