Search results for: cobalt oxides

Authors: A. Guemache, M. Omari

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Oxides with formula Ca1-xSrx MnO3(0≤x≤0.2) were synthesized using co precipitation method. The identification of the obtained phase was carried out using infrared spectroscopy and x-ray diffraction. Thermogravimetric and differential analysis was permitted to characterize different transformations of precursors which take place during one heating cycle. The study of electrochemical behavior was carried out by cyclic voltammetry and impedance spectroscopy. The obtained results show that apparent catalytic activity improved when increasing the concentration of strontium. Anodic current densities varies from 1.3 to 5.9 mA/cm2 at the rate scan of 20 mV.s-1 and a potential 0.8 V for oxides with composition x=0 to 0.2.

Keywords: oxide, co-precipitation, thermal analysis, electrochemical properties

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Authors: Feng Xu, Zhaozhi Liu, Junhua Xu, Xiaolong Tang, Dunwen Zuo

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Chemical vapor deposition (CVD) diamond coated cutting tool has excellent cutting performance, it is the most ideal tool for the processing of nonferrous metals and alloys, composites, nonmetallic materials and other difficult-to-machine materials efficiently and accurately. Depositing CVD diamond coating on the cemented carbide with high cobalt content can improve its toughness and strength, therefore, it is very important to research on the preparation technology and cutting properties of CVD diamond coated cemented carbide cutting tool with high cobalt content. The preparation technology of boron-doped diamond (BDD) coating has been studied and the coated drills were prepared. BDD coating were deposited on the drills by using the optimized parameters and the SEM results show that there are no cracks or collapses in the coating. Cutting tests with the prepared drills against the silumin and aluminum base printed circuit board (PCB) have been studied. The results show that the wear amount of the coated drill is small and the machined surface has a better precision. The coating does not come off during the test, which shows good adhesion and cutting performance of the drill.

Keywords: cemented carbide with high cobalt content, CVD boron-doped diamond, cutting test, drill

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Authors: Dereje Moges Azbite

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Laboratory analysis of igneous rocks is performed with the help of the main oxide plots. The lithology of the two wells was identified using the main oxides obtained using the XRF method. Twenty-four (24) cutting samples with different degrees of alteration were analyzed to determine and identify the rock types by plotting these well samples on special diagrams and correlating with the regional rocks. The results for the analysis of the main oxides and trace elements of 24 samples are presented. Alteration analysis in the two well samples was conducted for 21 samples from two wells for identifying clay minerals. Bulk sample analysis indicated quartz, illite & micas, calcite, cristobalite, smectite, pyrite, epidote, alunite, chlorite, wairakite, diaspore and kaolin minerals present in both wells. Hydrothermal clay minerals such as illite, chlorite, smectite and kaoline minerals were identified in both wells by X-ray diffraction.

Keywords: auto geothermal field, igneous rocks, major oxides, tracer elements, XRF, XRD, alteration minerals

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Authors: Maryam Mirabediny, Tsz Tin Yu, Jun Sun, Matthew Lee, Denis M. O’Carroll, Michael J. Manefield, Björn Akermark, Biswanath Das, Naresh Kumar

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Branched perfluorooctane sulfonic acid (PFOS) is recognized as a threatening environmental pollutant due to its high persistence and bioaccumulation in various environmental matrices as well as for its toxic effects on humans and wildlife, even at very low concentrations. This study reports the first investigation of branched PFOS defluorination catalyzed by metal phthalocyanines. The reaction conditions were optimized using the different reductants and temperatures. Cobalt phthalocyanine, when combined with Ti citrate as a reducing agent, was able to defluorinate 10.9% of technical PFOS within 8 hours. In contrast, vitamin B12 only showed 2.4% defluorination during the same period under similar conditions. The defluorination mediated by cobalt phthalocyanine and Ti citrate system corresponds to 54.5% of all branched PFOS isomers (br-PFOS isomers). Isomer-specific degradation was also investigated via high-resolution LC-orbitrap, followed by their relative rates. The difference in catalytic efficacy of various phthalocyanine complexes is rationalized by their structures and electrochemical response. Lastly, a new defluorination mechanism is proposed based on the newly detected degradation products after the phthalocyanines treatment and the previous studies.

Keywords: branched isomers, catalyst, reductive defluorination, water remediation

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Authors: Ahmed El-Fiqi, Hae-Won Kim

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Incorporation of therapeutic elements such as Sr, Cu and Co into bioglass structure and their release as ions is considered as one of the promising approaches to enhance cellular responses, e.g., osteogenesis and angiogenesis. Here, cobalt as angiogenesis promoter has been incorporated (at 0, 1 and 4 mol%) into sol-gel derived calcium silicate mesoporous bioglass nanoparticles. The composition and structure of cobalt-free (CFN) and cobalt-doped (CDN) mesoporous bioglass nanoparticles have been analyzed by X-ray fluorescence (XRF), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Fourier-Transform Infra-red spectroscopy (FT-IR). The physicochemical properties of CFN and CDN have been investigated using high-resolution transmission electron microscopy (HR-TEM), Selected area electron diffraction (SAED), and Energy-dispersive X-ray (EDX). Furthermore, the textural properties, including specific surface area, pore-volume, and pore size, have been analyzed from N²⁻sorption analyses. Surface charges of CFN and CDN were also determined from surface zeta potential measurements. The release of ions, including Co²⁺, Ca²⁺, and SiO₄⁴⁻ has been analyzed using inductively coupled plasma atomic emission spectrometry (ICP-AES). Loading and release of diclofenac as an anti-inflammatory drug model were explored in vitro using Ultraviolet-visible spectroscopy (UV-Vis). XRD results ensured the amorphous state of CFN and CDN whereas, XRF further confirmed that their chemical compositions are very close to the designed compositions. HR-TEM analyses unveiled nanoparticles with spherical morphologies, highly mesoporous textures, and sizes in the range of 90 - 100 nm. Moreover, N²⁻ sorption analyses revealed that the nanoparticles have pores with sizes of 3.2 - 2.6 nm, pore volumes of 0.41 - 0.35 cc/g and highly surface areas in the range of 716 - 830 m²/g. High-resolution XPS analysis of Co 2p core level provided structural information about Co atomic environment and it confirmed the electronic state of Co in the glass matrix. ICP-AES analysis showed the release of therapeutic doses of Co²⁺ ions from 4% CDN up to 100 ppm within 14 days. Finally, diclofenac loading and release have ensured the drug/ion co-delivery capability of 4% CDN.

Keywords: mesoporous bioactive glass, nanoparticles, cobalt ions, release

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Authors: Navven Desai, Veena Soraganvi

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Heavy metals such as lead, cadmium and mercury do not have biological significance hence they are known to be extremely toxic heavy metals. Water contains various heavy metals like Cadmium (Cd), Chromium (Cr), Copper (Cu), Nickel (Ni), Arsenic (As), Lead (Pb), and Zinc (Zn) etc., when it gets polluted with industrial waste water. These heavy metals cause various health effects even at low concentration when consumed by humans. Most of the heavy metals are poisonous to living organisms. Heavy metals are non-degradable and are preserved in the environment through bioaccumulation. Therefore removal of heavy metals from water is necessary. In recent years, a great deal of attentions has been focused on to the application of nanosized metal oxides to treat heavy metals, especially titanium oxides, ferric oxides, manganese oxides, aluminium oxides and magnesium oxides as adsorbent and photocatalyst. TiO2 based photocatalysts have attracted continuously increasing attention because of the excellent properties such as high light -conversion efficiency, chemical stability, nontoxic nature, low cost. The catalyst displays high photocatalytic activity because of its large surface area. In this study, the photocatalytic degradation of Lead (Pb) from aqueous solution was investigated in natural sunlight by using TiO2 as Nanomaterial. This study was performed at laboratory scale. All the experiments were carried out in the batch process. The concentration of lead was constant (25mg/lit) in the experiment and effect of titanium dioxide dose and pH were varied to study the removal efficiency of the lead by adsorption. Further study was performed on the dependence of photocatalytic reaction on the reaction temperature. The aqueous solution was prepared by Lead metal powder. TiO2 photo catalyst nanopowder used was Sisco-74629 grade. The heavy metal is analyzed with VARIAN AA 240 atomic adsorption spectrophotometer. The study shows, with increasing TiO2 dose and pH the lead removal increases. According to study, it can be concluded that the utilization of titanium dioxide accounted for higher efficiency in the removal of lead from aqueous solution.

Keywords: adsorption, heavy metals, nanomaterial, photocatalysis

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Authors: Hanan. Al Chaghouri, Mohammad Azad Malik, P. John Thomas, Paul O’Brien

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The process of assembling metal nanoparticles at the interface of two liquids has received a great interest over the past few years due to a wide range of important applications and their unusual properties compared to bulk materials. We present a low cost, simple and cheap synthesis of metal nanoparticles, core/shell structures and semiconductors followed by assembly of these particles between immiscible liquids. The aim of this talk is divided to three parts: firstly, to describe the achievement of a closed loop recycling for producing cadmium sulphide as powders and/or nanostructured thin films for solar cells or other optoelectronic devices applications by using a different chain length of commercially available secondary amines of dithiocarbamato complexes. The approach can be extended to other metal sulphides such as those of Zn, Pb, Cu, or Fe and many transition metals and oxides. Secondly, to synthesis significantly cheaper magnetic particles suited for the mass market. Ni/NiO nanoparticles with ferromagnetic properties at room temperature were among the smallest and strongest magnets (5 nm) were made in solution. The applications of this work can be applied to produce viable storage devices and the other possibility is to disperse these nanocrystals in solution and use it to make ferro-fluids which have a number of mature applications. The third part is about preparing and assembling of submicron silver, cobalt and nickel particles by using polyol methods and liquid/liquid interface, respectively. Noble metal like gold, copper and silver are suitable for plasmonic thin film solar cells because of their low resistivity and strong interactions with visible light waves. Silver is the best choice for solar cell application since it has low absorption losses and high radiative efficiency compared to gold and copper. Assembled cobalt and nickel as films are promising for spintronic, magnetic and magneto-electronic and biomedics.

Keywords: assembling nanoparticles, liquid/liquid interface, thin film, core/shell, solar cells, recording media

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Authors: A. T. Zhakiyenova, E. E. Zhatkanbaev, Zh. K. Zhatkanbaeva

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Nickel plays an important role in mechanical engineering and creation of military equipment; practically all steel are alloyed by nickel and other metals for receiving more durable, heat-resistant, corrosion-resistant steel and cast iron. There are many ways of processing of nickel in the world. Generally, it is igneous metallurgy methods. In this article, the review of majority existing ways of technologies of processing silicate nickel - cobalt ores is considered. Leaching of ores of a field Bugetkol is investigated by solution of sulfuric acid. We defined a specific consumption of sulfuric acid in relation to the mass of ore and to the mass of metal.

Keywords: cobalt, degree of extraction, hydrometallurgy, igneous metallurgy, leaching, matte, nickel

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Authors: Manasi Roy, Raju Mondal

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During last two decades the synthesis and design of MOFs or novel coordination polymers (CPs) has flourished as an emerging area of research due to their role as functional materials. Accordingly, ten new cobalt-based MOFs have been synthesized using a simple bispyrazole ligand, 4,4′-methylene-bispyrazole (H2MBP), and isophthalic acid (H2IPA) and its four 5-substituted derivatives R-H2IPA (R = COOH, OH, tBu, NH2). The major aim of this study was to validate the mutual influence of temperature and substitutions on the final structural self-assembly. Five different isophthalic acid derivatives were used to study the influence of substituents while each reaction was carried out at two different temperatures to assess the temperature effect. A clear correlation was observed between the reaction temperature and the coordination number of the cobalt atoms which consequently changes the self assembly pattern. Another fact that the periodical change in coordination number did bring about some systematic changes in the structural network via secondary building unit selectivity. With the presence of a tunable cavity inside the network, and unsaturated metal centers, MOFs show highly encouraging photocatalytic degradation of toxic dye with a potential application in waste water purification. Another fascinating aspect of this work is the construction of magnetic coordination polymers with the occurrence of a not-so-common MCE behavior of cobalt-based MOF.

Keywords: MOFs, temperature effect, MCE, dye degradation

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Authors: Marie Kudrnová, Jana Rejková

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The samples of supplied INCONEL 601, 617, 625, and HASTELLOY C-22 alloys and experimental nickel alloy MoNiCr were examined by XPS (X-ray photoelectron spectroscopy) before and after exposure. The experiment was performed in a mixture of LiCl-KCl salt (58.2-41.8 wt. %). The exposure conditions were 440°C, pressure 0.2 MPa, 500 hours in an inert argon atmosphere. The XPS analysis shows that a thin oxide layer composed of metal oxides such as NiO, Cr₂O₃, and Nb₂O₅ was formed. After sputtering the exposed surface with Ar ions, metals were also detected in the elemental state, indicating a very thin protective oxide layer with a thickness in units of up to tens of nanometers.

Keywords: XPS, MSR, nickel alloy, metal oxides

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Authors: Charmaine Lamiel, Van Hoa Nguyen, Marjorie Baynosa, Jae-Jin Shim

Abstract:

The depletion of non-renewable sources had led to the continuous development of various energy storage systems in order to cope with the world’s demand in energy. Supercapacitors have attracted considerable attention because they can store more energy than conventional capacitors and have higher power density than batteries. The combination of carbon-based material and metal chalcogenides are now being considered in response to the search for active electrode materials exhibiting high electrochemical performance. In this study, a hierarchical mesoporous carbon sphere@nickel cobalt sulfide (CS@Ni-Co-S) core-shell was synthesized using a simple hydrothermal method. The CS@Ni-Co-S core-shell microstructures exhibited a high capacitance of 724.4 F g−1 at 2 A g−1 in a 6 M KOH electrolyte. Good specific retention of 86.1% and high Coulombic efficiency of 97.9% was obtained after 2000 charge-discharge cycles. The electrode exhibited a high energy density of 58.0 Wh kg−1 (1440 W kg−1) and high power density of 7200 W kg−1 (34.2 Wh kg−1). The reaction involved green synthesis without further sulfurization or post-heat treatment. Through this study, a cost-effective and facile synthesis of CS@Ni-Co-S as an active electrode showed favorable electrochemical performance.

Keywords: carbon sphere, electrochemical, hydrothermal, nickel cobalt sulfide, supercapacitor

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Authors: Hanan. Al Chaghouri, Mohammad Azad Malik, P. John Thomas, Paul O’Brien

Abstract:

The process of assembling metal nanoparticles at the interface of two liquids has received a great deal of attention over the past few years due to a wide range of important applications and their unusual properties as compared to bulk materials. We present a low cost, simple and cheap synthesis of metal nanoparticles, core/shell structures and semiconductors followed by assembly of these particles between immiscible liquids. The aim of this talk is divided to three parts: Firstly, to describe the achievement of a closed loop recycling for producing cadmium sulfide as powders and/or nanostructured thin films for solar cells or other optoelectronic devices applications by using a different chain length of commercially available secondary amines of dithiocarbamato complexes. The approach can be extended to other metal sulfides such as those of Zn, Pb, Cu, or Fe and many transition metals and oxides. Secondly, to synthesis significantly cheaper magnetic particles suited for the mass market. Ni/NiO nanoparticles with ferromagnetic properties at room temperature were among the smallest and strongest magnets (5 nm) were made in solution. The applications of this work can be to produce viable storage devices and the other possibility is to disperse these nanocrystals in solution and use it to make ferrofluids which have a number of mature applications. The third part is about preparing and assembling of submicron silver, cobalt and nickel particles by using polyol methods and liquid/liquid interface, respectively. Coinage metals like gold, copper and silver are suitable for plasmonic thin film solar cells because of their low resistivity and strong interactions with visible light waves. Silver is the best choice for solar cell application since it has low absorption losses and high radiative efficiency compared to gold and copper. Assembled cobalt and nickel as films are promising for spintronic, magnetic and magneto-electronic and biomedics.

Keywords: metal nanoparticles, core/shell structures and semiconductors, ferromagnetic properties, closed loop recycling, liquid/liquid interface

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Authors: Pauline Bredy, Yves Schuurman, David Farrusseng

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To fulfill climate objectives, the production of synthetic e-fuels using CO₂ as a raw material appears as part of the solution. In particular, Power-to-Liquid (PtL) concept combines CO₂ with hydrogen supplied from water electrolysis, powered by renewable sources, which is currently gaining interest as it allows the production of sustainable fossil-free liquid fuels. The proposed process discussed here is an upgrading of the well-known Fischer-Tropsch synthesis. The concept deals with two cascade reactions in one pot, with first the conversion of CO₂ into CO via the reverse water gas shift (RWGS) reaction, which is then followed by the Fischer-Tropsch Synthesis (FTS). Instead of using a Fe-based catalyst, which can carry out both reactions, we have chosen the strategy to decouple the two functions (RWGS and FT) on two different catalysts within the same reactor. The FTS shall shift the equilibrium of the RWGS reaction (which alone would be limited to 15-20% of conversion at 250°C) by converting the CO into hydrocarbons. This strategy shall enable optimization of the catalyst pair and thus lower the temperature of the reaction thanks to the equilibrium shift to gain selectivity in the liquid fraction. The challenge lies in maximizing the activity of the RWGS catalyst but also in the ability of the FT catalyst to be highly selective. Methane production is the main concern as the energetic barrier of CH₄ formation is generally lower than that of the RWGS reaction, so the goal will be to minimize methane selectivity. Here we report the study of different combinations of copper-based RWGS catalysts with different cobalt-based FTS catalysts. We investigated their behaviors under mild process conditions by the use of high-throughput experimentation. Our results show that at 250°C and 20 bars, Cobalt catalysts mainly act as methanation catalysts. Indeed, CH₄ selectivity never drops under 80% despite the addition of various protomers (Nb, K, Pt, Cu) on the catalyst and its coupling with active RWGS catalysts. However, we show that the activity of the RWGS catalyst has an impact and can lead to longer hydrocarbons chains selectivities (C₂⁺) of about 10%. We studied the influence of the reduction temperature on the activity and selectivity of the tandem catalyst system. Similar selectivity and conversion were obtained at reduction temperatures between 250-400°C. This leads to the question of the active phase of the cobalt catalysts, which is currently investigated by magnetic measurements and DRIFTS. Thus, in coupling it with a more selective FT catalyst, better results are expected. This was achieved using a cobalt/iron FTS catalyst. The CH₄ selectivity dropped to 62% at 265°C, 20 bars, and a GHSV of 2500ml/h/gcat. We propose that the conditions used for the cobalt catalysts could have generated this methanation because these catalysts are known to have their best performance around 210°C in classical FTS, whereas the iron catalysts are more flexible but are also known to have an RWGS activity.

Keywords: cobalt-copper catalytic systems, CO₂-hydrogenation, Fischer-Tropsch synthesis, hydrocarbons, low-temperature process

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Authors: Jun Sun, Tsz Tin Yu, Maryam Mirabediny, Matthew Lee, Adele Jones, Denis M. O’Carroll, Michael J. Manefield, Björn Åkermark, Biswanath Das, Naresh Kumar

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Reductive defluorination has emerged as a sustainable approach to clean water from Per and polyfluoroalkyl substances (PFASs), also known as forever organic containments. For last few decades, nano zero valent metals (nZVMs) have been intensively applied in the reductive remediation of groundwater contaminated with chlorinated organic compounds due to its low redox potential, easy application, and low production cost. However, there is inadequate information on the effective reductive defluorination of linear or branched PFAS using nZVMs as reductants because of the lack of suitable catalysts. CoII-5,10,15,20-Tetraphenyl-21H,23H-porphyrin (CoTPP) has been recently reported for effective catalyzing reductive defluorination of branched (br-) perfluorooctane sulfonate (PFOS) by using TiIII citrate as reductant. However, the low water solubility of CoTPP limited its applicability. Here, we explored a series of structurally related soluble cobalt porphyrin catalysts based on our previously reported best performing CoTPP. All soluble porphyrins [[meso-tetra(4-carboxyphenyl)porphyrinato]cobalt(III)]Cl·₇H₂O (CoTCPP), [[meso-tetra(4-sulfonatophenyl) porphyrinato]cobalt(III)]·9H2O (CoTPPS), and [[meso-tetra(4-N-methylpyridyl) porphyrinato]cobalt(II)](I)₄·₄H₂O (CoTMpyP) displayed better defluorination efficiencies than CoTPP. Especially, CoTMpyP presented the best defluorination efficiency for br-PFOS (94 %), branched perfluorooctanoic acid (PFOA) (89 %), and 3,7-Perfluorodecanoic acid (PFDA) (60 %) after 1 day at 70 0C. CoTMpyP-nZn0 system showed 88-164 times higher defluorination rate than VB12-nZn0 system in terms of all investigated br-PFASs. The CoTMpyP-nZn0 also performed effectively at room temperature, demonstrating the potential prospect for in-situ reductive systems. Based on the analysis of the intermediate products, the calculated bond dissociation energies (BDEs) and possible first interaction between CoTMpyP and PFAS, degradation pathways of 3,7-PFDA and 6-PFOS are proposed.

Keywords: cationic, soluble porphyrin, cobalt, vitamin b12, pfas, reductive defluorination

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Authors: Khadijat O. Abdulwahab, Mohammad A. Malik, Paul O’Brien, Grigore A. Timco, Floriana Tuna

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The synthesis of spinel ferrite nanoparticles with a narrow size distribution is very crucial in their numerous applications including information storage, hyperthermia treatment, drug delivery, contrast agent in magnetic resonance imaging, catalysis, sensors, and environmental remediation. Ferrites have the general formula MFe2O4 (M = Fe, Co, Mn, Ni, Zn etc.) and possess remarkable electrical and magnetic properties which depend on the cations, method of preparation, size and their site occupancies. To the best of our knowledge, there are no reports on the use of a single source precursor to synthesise quaternary ferrite nanoparticles. Herein, we demonstrated the use of trimetallic iron pivalate cluster [CrCoFeO(O2CtBu)6(HO2CtBu)3] as a single source precursor to synthesise monodisperse cobalt chromium ferrite (FeCoCrO4) nanoparticles by the hot injection thermolysis method. The precursor was thermolysed in oleylamine, oleic acid, with diphenyl ether as solvent at its boiling point (260°C). The effect of concentration on the stoichiometry, phases or morphology of the nanoparticles was studied. The p-XRD patterns of the nanoparticles obtained at both concentrations were matched with cubic iron cobalt chromium ferrite (FeCoCrO4). TEM showed that a more monodispersed spherical ferrite nanoparticles of average diameter 4.0 ± 0.4 nm were obtained at higher precursor concentration. Magnetic measurements revealed that all the ferrite particles are superparamagnetic at room temperature. The nanoparticles were characterised by Powder X-ray Diffraction (p-XRD), Transmission Electron Microscopy (TEM), Inductively Coupled Plasma (ICP), Electron Probe Microanalysis (EPMA), Energy Dispersive Spectroscopy (EDS) and Super Conducting Quantum Interference Device (SQUID).

Keywords: quaternary ferrite nanoparticles, single source precursor, monodisperse, cobalt chromium ferrite, colloidal, hot injection thermolysis

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Authors: Saleem Rao, Mohammed Al-Ghadeer, Archan Banerjee, Hossein Fariborzi

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Materials imperfection, particularly two-level-system (TLS) defects in planer superconducting quantum circuits, contributes significantly to decoherence, ultimately limiting the performance of quantum computation and sensing. Oxides at air interfaces are among the host of TLS, and different material has been used to reduce TLS losses. Passivation with an inorganic layer is not an option to reduce these interface oxides; however, they can be etched away, but their regrowth remains a problem. Here, we report the chemisorption of molecular self-assembled monolayers (SAMs) at air interfaces of superconducting co-planer waveguide (CPW) resonators that suppress the regrowth of oxides and also modify the dielectric constant of the interface. With SAMs, we observed sustained order of magnitude improvement in quality factor -better than oxide etched interfaces. Quality factor measurements at millikelvin temperature and at single photon, XPS data, and TEM images of SAM passivated air interface sustenance our claim. Compatibility of SAM with micro-/nano-fabrication processes opens new ways to improve the coherence time in cQED.

Keywords: superconducting circuits, quality-factor, self-assembled monolayer, coherence

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Authors: Uzaira Rafique, Kousar Parveen

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The discharge volume and composition of Textile effluents gains scientific concern due to its hazards and biotoxcity of azo dyes. Azo dyes are non-biodegradable due to its complex molecular structure and recalcitrant nature. Serious attempts have been made to synthesize and develop new materials to combat the environmental problems. The present study is designed for removal of a range of azo dyes (Methyl orange, Congo red and Basic fuchsine) from synthetic aqueous solutions and real textile effluents. For this purpose, Metal (cobalt) doped alumina hybrids are synthesized and applied as adsorbents in the batch experiment. Two different aluminium precursor (aluminium nitrate and spent aluminium foil) and glucose are mixed following sol gel method to get hybrids. The synthesized materials are characterized for surface and bulk properties using FTIR, SEM-EDX and XRD techniques. The characterization of materials under FTIR revealed that –OH (3487-3504 cm-1), C-H (2935-2985 cm-1), Al-O (~ 800 cm-1), Al-O-C (~1380 cm-1), Al-O-Al (659-669 cm-1) groups participates in the binding of dyes onto the surface of hybrids. Amorphous shaped particles and elemental composition of carbon (23%-44%), aluminium (29%-395%), and oxygen (11%-20%) is demonstrated in SEM-EDX micrograph. Time-dependent batch-experiments under identical experimental parameters showed 74% congo red, 68% methyl orange and 85% maximum removal of basic fuchsine onto the surface of cobalt doped alumina hybrids probably through the ion-exchange mechanism. The experimental data when treated with adsorption models is found to have good agreement with pseudo second order kinetic and freundlich isotherm for adsorption process. The present study concludes the successful synthesis of novel and efficient cobalt doped alumina hybrids providing environmental friendly and economical alternative to the commercial adsorbents for the treatment of industrial effluents.

Keywords: alumina hybrid, adsorption, dopant, isotherm, kinetic

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Authors: I. Yordanova, H. Kolev, S. Todorova, Z. Cherkezova-Zheleva

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Catalysis plays a key role in solving many environmental problems by establishing efficient catalytic systems for environmental protection and reducing emissions of greenhouse gases from industry. Volatile organic compounds are major air pollutants. There are several ways to dispose of emissions like - adsorption, condensation, absorption, bio-filtration, thermal, catalytic, plasma and ultraviolet oxidation. The catalytic oxidation has more advantages over other methods. For example - lower energy consumption; the concentration of the organic contaminant may be low or may vary within wide limits. Catalysts for complete oxidation of VOCs can be classified into three categories: noble metal, metal oxides or supported metal oxides and mixture of noble metals and metal oxides. Most of the catalysts for the complete catalytic oxidation are based on Pt, Pd, Rh or a combination thereof. The oxides of the transition metal are one of the alternatives to noble metal catalysts for these reactions. They are less active at low temperatures, but at higher - their activity is similar. The properties of the catalyst depend on the distribution of the active phase, the medium type of the pre-treatment, the interaction between the active phase and the support and the interaction between the active phase and the reaction medium. Supported mono-component Mn and bi-component Mn-Co systems are examined in present study. The samples are prepared using co-precipitation method. SiO2 (Aerosil) is used as a support. The studied samples were precipitated by NH4OH. The synthesized samples were characterized by XRD, XPS, TPR and tested in the catalytic reaction of complete oxidation of n-hexane, propane, methanol, ethanol and propanol.

Keywords: catalytic oxidation, Co-Mn oxide, oxidation of hydrocarbons and alcohols, environmental protection

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Authors: Vera Varazashvili, Murman Tsarakhov, Tamar Mirianashvili, Teimuraz Pavlenishvili, Tengiz Machaladze, Mzia Khundadze

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Standard Gibbs energy of formation ΔGfor(298.15) of lanthanide-iron double oxides of garnet-type crystal structure R3Fe5O12 - RIG (R – are rare earth ions) from initial oxides are evaluated. The calculation is based on the data of standard entropies S298.15 and standard enthalpies ΔH298.15 of formation of compounds which are involved in the process of garnets synthesis. Gibbs energy of formation is presented as temperature function ΔGfor(T) for the range 300-1600K. The necessary starting thermodynamic data were obtained from calorimetric study of heat capacity – temperature functions and by using the semi-empirical method for calculation of ΔH298.15 of formation. Thermodynamic functions for standard temperature – enthalpy, entropy and Gibbs energy - are recommended as reference data for technological evaluations. Through the isostructural series of rare earth-iron garnets the correlation between thermodynamic properties and characteristics of lanthanide ions are elucidated.

Keywords: calorimetry, entropy, enthalpy, heat capacity, gibbs energy of formation, rare earth iron garnets

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Authors: Vera Varazashvili, Murman Tsarakhov, Tamar Mirianashvili, Teimuraz Pavlenishvili, Tengiz Machaladze, Mzia Khundadze

Abstract:

Standard Gibbs energy of formation ΔGfor(298.15) of lanthanide-iron double oxides of garnet-type crystal structure R3Fe5O12 - RIG (R – are rare earth ions) from initial oxides are evaluated. The calculation is based on the data of standard entropies S298.15 and standard enthalpies ΔH298.15 of formation of compounds which are involved in the process of garnets synthesis. Gibbs energy of formation is presented as temperature function ΔGfor(T) for the range 300-1600K. The necessary starting thermodynamic data were obtained from calorimetric study of heat capacity and by using the semi-empirical method for calculation of ΔH298.15 (formation). Thermodynamic functions for standard temperature – enthalpy, entropy and Gibbs energy - are recommended as reference data for technological evaluations. Through the isostructural series of rare earth-iron garnets the correlation between thermodynamic properties and characteristics of lanthanide ions are elucidated.

Keywords: calorimetry, entropy, heat capacity, Gibbs energy of formation, rare earth iron garnets

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Authors: Silviya Todorova, Anton Naydenov, Ralitsa Velinova, Alexander Larin

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Catalytic combustion of methane has been extensively investigated for emission control and power generation during the last decades. The alumina-supported palladium catalyst is widely accepted as the most active catalysts for catalytic combustion of methane. The activity of Pd/Al₂O₃ decreases during the time on stream, especially underwater vapor. The following order of activity in the reaction of complete oxidation of methane was established: Co₃O₄> CuO>NiO> Mn₂O₃> Cr₂O₃. It may be expected that the combination between Pd and these oxides could lead to the promising catalysts in the reaction of complete methane. In the present work, we investigate the activity of Pd/Al₂O₃ catalysts promoted with other metal oxides (MOx; M= Ni, Co, Ce). The Pd-based catalysts modified by metal oxide were prepared by sequential impregnation of Al₂O₃ with aqueous solutions of Me(NO₃)₂.6H₂O and Pd(NO₃)₂H₂O. All samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS). An improvement of activity was observed after modification with different oxides. The results demonstrate that the Pd/Al₂O₃ catalysts modified with Co and Ce by impregnation with a common solution of respective salts, exhibit the most promising catalytic activity for methane oxidation. Most probably, the presence of Co₃O₄ and CeO₂ on catalytic surface increases surface oxygen and therefore leads to the better reactivity in methane combustion.

Keywords: methane combustion, palladium, Co-Ce, Ni-Ce

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Authors: Tatyana T. Tabakova, Elitsa N. Kolentsova, Dimitar Y. Dimitrov, Krasimir I. Ivanov, Yordanka G. Karakirova, Petya Cv. Petrova, Georgi V. Avdeev

Abstract:

The catalytic oxidation of CO and volatile organic compounds (VOCs) is considered as one of the most efficient ways to reduce harmful emissions from various chemical industries. The effectiveness of gold-based catalysts for many reactions of environmental significance was proven during the past three decades. The aim of this work was to combine the favorable features of Au and Cu-Ce mixed oxides in the design of new catalytic materials of improved efficiency and economic viability for removal of air pollutants in waste gases from formaldehyde production. Supported oxides of copper and cerium with Cu: Ce molar ratio 2:1 and 1:5 were prepared by wet impregnation of g-alumina. Gold (2 wt.%) catalysts were synthesized by a deposition-precipitation method. Catalysts characterization was carried out by texture measurements, powder X-ray diffraction, temperature programmed reduction and electron paramagnetic resonance spectroscopy. The catalytic activity in the oxidation of CO, CH₃OH and (CH₃)₂O was measured using continuous flow equipment with fixed bed reactor. Both Cu-Ce/alumina samples demonstrated similar catalytic behavior. The addition of gold caused significant enhancement of CO and methanol oxidation activity (100 % degree of CO and CH₃OH conversion at about 60 and 140 ^oC, respectively). The composition of Cu-Ce mixed oxides affected the performance of gold-based samples considerably. Gold catalyst on Cu-Ce/γ-Al₂O₃ 1:5 exhibited higher activity for CO and CH₃OH oxidation in comparison with Au on Cu-Ce/γ-Al₂O₃ 2:1. The better performance of Au/Cu-Ce 1:5 was related to the availability of highly dispersed gold particles and copper oxide clusters in close contact with ceria.

Keywords: CO and VOCs oxidation, copper oxide, Ceria, gold catalysts

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Authors: Dhuha Albusalih, David Weston, Simon Gill

Abstract:

Nanocomposites Co-SiC with well dispersed nanoparticles and Co nano grain size has produced using Pulse Reverse Plating (PRP) and using anionic surfactant. Different particle contents of nanocomposites were produced by altering the plating parameters. The method allows great control over the level of nanoparticles in the coating, without changing bath chemistry. Examination by Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDX), TEM and X-Ray Diffraction (XRD) analysis was performed to characterize and study the strengthening mechanisms of these nanocomposites. The primary strengthening mechanisms were shown to be grain refinement and dispersion strengthening. Tribological performances of the produced electroplated nanocomposite Co-SiC coatings were examined. Results showed that the coating with the higher volume fraction (vol. %) of SiC and the smallest grain size has the higher hardness and low wear rate.

Keywords: nanocomposites, pulse reverse plating, tribological performance of cobalt nanocomposites

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Authors: A. Mekroud, A. Khemis, M. S. Mecibah

Abstract:

The tribological behavior of a pin of paramagnetic material (aluminum), rolling on a rotating disk made of ferromagnetic material (steel XC48) in the presence of an externally applied alternating magnetic field, with the passage of electric current were studied. All tests were performed using a conventional tribometer pin- disk. Structural characterization of the surfaces in contact, oxides and wear debris, by X-ray diffraction (θ-2θ angle), showed the significant effect of magnetic field on the activation of the contact surface of the pin in no ferromagnetic material. The absence of the magnetic field causes a change of wear mode.

Keywords: structural characterization of the surfaces, oxides and wear debris, X-ray diffraction

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Authors: Elvis Medina, Alejandro Karelovic, Romel Jiménez

Abstract:

Catalytic ammonia decomposition represents an attractive alternative due to its high H₂ content (17.8% w/w), a product stream free of COₓ, among others; however, challenges need to be addressed for its consolidation as an H₂ chemical storage technology, especially, those focused on the synthesis of efficient bimetallic catalytic systems, as an alternative to the price and scarcity of ruthenium, the most active catalyst reported. In this sense, from the perspective of rational catalyst design, adjusting the main catalytic activity descriptor, a screening of supported catalysts with different compositional settings of cobalt-molybdenum metals is presented to evaluate their effect on the catalytic decomposition rate of ammonia. Subsequently, a kinetic study on the supported monometallic Co and Mo catalysts, as well as on the bimetallic CoMo catalyst with the highest activity is shown. The synthesis of catalysts supported on γ-alumina was carried out using the Charge Enhanced Dry Impregnation (CEDI) method, all with a 5% w/w loading metal. Seeking to maintain uniform dispersion, the catalysts were oxidized and activated (In-situ activation) using a flow of anhydrous air and hydrogen, respectively, under the same conditions: 40 ml min⁻¹ and 5 °C min⁻¹ from room temperature to 600 °C. Catalytic tests were carried out in a fixed-bed reactor, confirming the absence of transport limitations, as well as an Approach to equilibrium (< 1 x 10⁻⁴). The reaction rate on all catalysts was measured between 400 and 500 ºC at 53.09 kPa NH3. The synergy theoretically (DFT) reported for bimetallic catalysts was confirmed experimentally. Specifically, it was observed that the catalyst composed mainly of 75 mol% cobalt proved to be the most active in the experiments, followed by the monometallic cobalt and molybdenum catalysts, in this order of activity as referred to in the literature. A kinetic study was performed at 10.13 – 101.32 kPa NH3 and at four equidistant temperatures between 437 and 475 °C the data were adjusted to an LHHW-type model, which considered the desorption of nitrogen atoms from the active phase surface as the rate determining step (RDS). The regression analysis were carried out under an integral regime, using a minimization algorithm based on SLSQP. The physical meaning of the parameters adjusted in the kinetic model, such as the RDS rate constant (k₅) and the lumped adsorption constant of the quasi-equilibrated steps (α) was confirmed through their Arrhenius and Van't Hoff-type behavior (R² > 0.98), respectively. From an energetic perspective, the activation energy for cobalt, cobalt-molybdenum, and molybdenum was 115.2, 106.8, and 177.5 kJ mol⁻¹, respectively. With this evidence and considering the volcano shape described by the ammonia decomposition rate in relation to the metal composition ratio, the synergistic behavior of the system is clearly observed. However, since characterizations by XRD and TEM were inconclusive, the formation of intermetallic compounds should be still verified using HRTEM-EDS. From this point onwards, our objective is to incorporate parameters into the kinetic expressions that consider both compositional and structural elements and explore how these can maximize or influence H₂ production.

Keywords: CEDI, hydrogen carrier, LHHW, RDS

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Authors: Muhammad Shoaib, Hassan M. Al-Swaidan

Abstract:

Air pollution has been a major challenge for the scientists today, due to the release of toxic emissions from various industries like power plants, desalination plants, industrial processes and transportation vehicles. Harmful emissions into the air represent an environmental pressure that reflects negatively on human health and productivity, thus leading to a real loss in the national economy. Variety of air pollutants in the form of carbon oxides, hydrocarbons, nitrogen oxides, sulfur oxides, suspended particulate material etc. are present in air due to the combustion of different types of fuels like crude oil, diesel oil and natural gas. Among various pollutants, NOx and SOx emissions are considered as highly toxic due to its carcinogenicity and its relation with various health disorders. In Kingdom of Saudi Arabia electricity is generated by burning of crude, diesel or natural gas in the turbines of electricity stations. Out of these three, crude oil is used extensively for electricity generation. Due to the burning of the crude oil there are heavy contents of gaseous pollutants like sulfur dioxides (SOx) and nitrogen oxides (NOx), gases which are ultimately discharged in to the environment and is a serious environmental threat. The breakthrough point in case of lab studies using 1 gm of sliced activated carbon adsorbant comes after 20 and 30 minutes for NOx and SOx, respectively, whereas in case of PP8 plant breakthrough point comes in seconds. The saturation point in case of lab studies comes after 100 and 120 minutes and for actual PP8 plant it comes after 60 and 90 minutes for NOx and SOx adsorption, respectively. Surface characterization of NOx and SOx adsorption on SAC confirms the presence of peaks in the FT-IR spectrum. CHNS study verifies that the SAC is suitable for NOx and SOx along with some other C and H containing compounds coming out from stack emission stream from the turbines of a power plant.

Keywords: activated carbon, flue gases, NOx and SOx adsorption, physical activation, power plants

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Authors: Ehsan Gholami, Vincent Demers

Abstract:

Low-pressure powder injection molding is an emerging technology for cost-effectively producing complex shape metallic parts with the proper dimensional tolerances, either in high or in low production volumes. In this study, the molding properties of cobalt-chrome-based feedstocks were evaluated for use in a low-pressure powder injection molding process. The rheological properties of feedstock formulations were obtained by mixing metallic powder with a proprietary wax-based binder system. Rheological parameters such as reference viscosity, shear rate sensitivity index, and activation energy for viscous flow, were extracted from the viscosity profiles and introduced into the Weir model to calculate the moldability index. Feedstocks were experimentally injected into a spiral mold cavity to validate the injection performance calculated with the model.

Keywords: binder, feedstock, moldability, powder injection molding, viscosity

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Authors: Bedarnia Ishak

Abstract:

In the recent years, the dry reforming of methane has received considerable attention from an environmental view point because it consumes and eliminates two gases (CH4 and CO2) responsible for global warming by greenhouse effect. Many catalysts containing noble metal (Rh, Ru, Pd, Pt and Ir) or transition metal (Ni, Co and Fe) have been reported to be active in this reaction. Compared to noble metals, Ni-materials are cheap but very easily deactivated by coking. Ni-based mixed oxides structurally well-defined like perovskites and spinels are being studied because they possibly make solid solutions and allow to vary the composition and thus the performances properties. In this work, nano-sized nickel ferrite oxides are synthesized using three different methods: Co-precipitation (CP), hydrothermal (HT) and sol gel (SG) methods and characterized by XRD, Raman, XPS, BET, TPR, SEM-EDX and TEM-EDX. XRD patterns of all synthesized oxides showed the presence of NiFe2O4 spinel, confirmed by Raman spectroscopy. Hematite was present only in CP sample. Depending on the synthesis method, the surface area, particle size, as well as the surface Ni/Fe atomic ratio (XPS) and the behavior upon reduction varied. The materials were tested in methane dry reforming with CO2 at 1 atm and 650-800 °C. The catalytic activity of the spinel samples was not very high (XCH4 = 5-20 mol% and XCO2 = 25-40 mol %) when no pre-reduction step was carried out. A significant contribution of RWGS explained the low values of H2/CO ratio obtained. The reoxidation step of the catalyst carried out after reaction showed little amounts of coke deposition. The reducing pretreatment was particularly efficient in the case of SG (XCH4 = 80 mol% and XCO2 = 92 mol%, at 800 °C), with H2/CO > 1. In conclusion, the influence of preparation was strong for most samples and the catalytic behavior could be interpreted by considering the distribution of cations among octahedral (Oh) and tetrahedral (Td) sites as in (Ni2+1-xFe3+x) Td (Ni2+xFe3+2-x) OhO2-4 influenced the reducibility of materials and thus their catalytic performance.

Keywords: NiFe2O4, dry reforming of methane, spinel oxide, oxide zenc

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Authors: Abdelaziz Ghrib, Samir Hattali, Mouloud Ghrib, Mohamed Lamine Aouissia, David Ruch

Abstract:

In the present study, the solid solutions with a chemical composition of Zr0.8Y0.2-xLaxO2 (x=0, 0.1, 0.2) were synthesized via two routes, by hydrothermal method using NaOH as precipitating agent at 230°C for 15h and by the sol–gel process using citric acid as complexing agent. Compounds have been characterized by powder X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Thermo gravimetric Analysis (TGA) and Differential Thermal Analysis (DTA) techniques for appropriate characterization of the distinct thermal events occurring during synthesis. All the compounds crystallize in cubic fluorite structure, as indicated by X-ray diffraction studie. The microstructure of oxides synthesized by sol-gel showed porosity that increased with the lanthanum La3+ contents compared to hydrothermal method which gives a single crystal oxide.

Keywords: oxide, hydrothermal, rare earth, solubility, sol-gel, ternary mixture

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Authors: Bouhenni Mohamed Saif El Islam

Abstract:

In the recent years, the dry reforming of methane has received considerable attention from an environmental view point because it consumes and eliminates two gases (CH4 and CO2) responsible for global warming by greenhouse effect. Many catalysts containing noble metal (Rh, Ru, Pd, Pt and Ir) or transition metal (Ni, Co and Fe) have been reported to be active in this reaction. Compared to noble metals, Ni-materials are cheap but very easily deactivated by coking. Ni-based mixed oxides structurally well-defined like perovskites and spinels are being studied because they possibly make solid solutions and allow to vary the composition and thus the performances properties. In this work, nano-sized nickel ferrite oxides are synthesized using three different methods: Co-precipitation (CP), hydrothermal (HT) and sol gel (SG) methods and characterized by XRD, Raman, XPS, BET, TPR, SEM-EDX and TEM-EDX. XRD patterns of all synthesized oxides showed the presence of NiFe2O4 spinel, confirmed by Raman spectroscopy. Hematite was present only in CP sample. Depending on the synthesis method, the surface area, particle size, as well as the surface Ni/Fe atomic ratio (XPS) and the behavior upon reduction varied. The materials were tested in methane dry reforming with CO2 at 1 atm and 650-800 °C. The catalytic activity of the spinel samples was not very high (XCH4 = 5-20 mol% and XCO2 = 25-40 mol %) when no pre-reduction step was carried out. A significant contribution of RWGS explained the low values of H2/CO ratio obtained. The reoxidation step of the catalyst carried out after reaction showed little amounts of coke deposition. The reducing pretreatment was particularly efficient in the case of SG (XCH4 = 80 mol% and XCO2 = 92 mol%, at 800 °C), with H2/CO > 1. In conclusion, the influence of preparation was strong for most samples and the catalytic behavior could be interpreted by considering the distribution of cations among octahedral (Oh) and tetrahedral (Td) sites as in (Ni2+1-xFe3+x)Td (Ni2+xFe3+2-x)OhO2-4 influenced the reducibility of materials and thus their catalytic performance.

Keywords: NiFe2O4, dry reforming of methane, spinel oxide, XCO2

Procedia PDF Downloads 347