Search results for: recyclable catalysts

Authors: Patrizia Frontera, Anastasia Macario, Sebastiano Candamano, Fortunato Crea, Pierluigi Antonucci

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The increasing of the world energy demand makes today biomass an attractive energy source, based on the minimizing of CO2 emission and on the global warming reduction purposes. Recently, COP-21, the international meeting on global climate change, defined the roadmap for sustainable worldwide development, based on low-carbon containing fuel. Hydrogen is an energy vector able to substitute the conventional fuels from petroleum. Ethanol for hydrogen production represents a valid alternative to the fossil sources due to its low toxicity, low production costs, high biodegradability, high H2 content and renewability. Ethanol conversion to generate hydrogen by a combination of partial oxidation and steam reforming reactions is generally called auto-thermal reforming (ATR). The ATR process is advantageous due to the low energy requirements and to the reduced carbonaceous deposits formation. Catalyst plays a pivotal role in the ATR process, especially towards the process selectivity and the carbonaceous deposits formation. Bimetallic or trimetallic catalysts, as well as catalysts with doped-promoters supports, may exhibit high activity, selectivity and deactivation resistance with respect to the corresponding monometallic ones. In this work, NiMoCo/GDC, NiMoCu/GDC and NiMoRe/GDC (where GDC is Gadolinia Doped Ceria support and the metal composition is 60:30:10 for all catalyst) have been prepared by impregnation method. The support, Gadolinia 0.2 Doped Ceria 0.8, was impregnated by metal precursors solubilized in aqueous ethanol solution (50%) at room temperature for 6 hours. After this, the catalysts were dried at 100°C for 8 hours and, subsequently, calcined at 600°C in order to have the metal oxides. Finally, active catalysts were obtained by reduction procedure (H2 atmosphere at 500°C for 6 hours). All sample were characterized by different analytical techniques (XRD, SEM-EDX, XPS, CHNS, H2-TPR and Raman Spectorscopy). Catalytic experiments (auto-thermal reforming of ethanol) were carried out in the temperature range 500-800°C under atmospheric pressure, using a continuous fixed-bed microreactor. Effluent gases from the reactor were analyzed by two Varian CP4900 chromarographs with a TCD detector. The analytical investigation focused on the preventing of the coke deposition, the metals sintering effect and the sulfur poisoning. Hydrogen productivity, ethanol conversion and products distribution were measured and analyzed. At 600°C, all tri-metallic catalysts show the best performance: H2 + CO reaching almost the 77 vol.% in the final gases. While NiMoCo/GDC catalyst shows the best selectivity to hydrogen whit respect to the other tri-metallic catalysts (41 vol.% at 600°C). On the other hand, NiMoCu/GDC and NiMoRe/GDC demonstrated high sulfur poisoning resistance (up to 200 cc/min) with respect to the NiMoCo/GDC catalyst. The correlation among catalytic results and surface properties of the catalysts will be discussed.

Keywords: catalysts, ceria, ethanol, gadolinia, hydrogen, Nickel

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Authors: Ainouna Bouziane

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The ability of Electron Tomography to recover the 3D structure of catalysts, with spatial resolution in the subnanometer scale, has been widely explored and reviewed in the last decades. A variety of experimental techniques, based either on Transmission Electron Microscopy (TEM) or Scanning Transmission Electron Microscopy (STEM) have been used to reveal different features of nanostructured catalysts in 3D, but High Angle Annular Dark Field imaging in STEM mode (HAADF-STEM) stands out as the most frequently used, given its chemical sensitivity and avoidance of imaging artifacts related to diffraction phenomena when dealing with crystalline materials. In this regard, our group has developed a methodology that combines image denoising by undecimated wavelet transforms (UWT) with automated, advanced segmentation procedures and parameter selection methods using CS-TVM (Compressed Sensing-total variation minimization) algorithms to reveal more reliable quantitative information out of the 3D characterization studies. However, evaluating the accuracy of the magnitudes estimated from the segmented volumes is also an important issue that has not been properly addressed yet, because a perfectly known reference is needed. The problem particularly complicates in the case of multicomponent material systems. To tackle this key question, we have developed a methodology that incorporates volume reconstruction/segmentation methods. In particular, we have established an approach to evaluate, in quantitative terms, the accuracy of TVM reconstructions, which considers the influence of relevant experimental parameters like the range of tilt angles, image noise level or object orientation. The approach is based on the analysis of material-realistic, 3D phantoms, which include the most relevant features of the system under analysis.

Keywords: electron tomography, supported catalysts, nanometrology, error assessment

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Authors: Elitsa Kolentsova, Dimitar Dimitrov, Vasko Idakiev, Tatyana Tabakova, Krasimir Ivanov

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Formaldehyde production by selective oxidation of methanol is an important industrial process. The main by-products in the waste gas are CO and dimethyl ether (DME). The idea of this study is to combine the advantages of both Cu-Mn and Cu-Co catalytic systems by obtaining a new mixed Cu-Mn-Co catalyst with high activity and selectivity at the simultaneous oxidation of CO, methanol, and DME. Two basic Cu-Mn samples with high activity were selected for further investigation: (i) manganese-rich Cu-Mn/γ–Al2O3 catalyst with Cu/Mn molar ratio 1:5 and (ii) copper-rich Cu-Mn/γ-Al2O3 catalyst with Cu/Mn molar ratio 2:1. Manganese in these samples was replaced by cobalt in the whole concentration region, and catalytic properties were determined. The results show a general trend of decreasing the activity toward DME oxidation and increasing the activity toward CO and methanol oxidation with the increase of cobalt up to 60% for both groups of catalyst. This general trend, however, contains specific features, depending on the composition of the catalyst and the nature of the oxidized gas. The catalytic activity of the sample with Cu/(Mn+Co) molar ratio of 2:1 is gradually changed with increasing the cobalt content. The activity of the sample with Cu/(Mn+Co) molar ratio of 1: 5 passes through a maximum at 60% manganese replacement by cobalt, probably due to the formation of highly dispersed Co-based spinel structures (Co3O4 and/or MnCo2O4). In conclusion, the present study demonstrates that the Cu-Mn-Co/γ–alumina supported catalysts have enhanced activity toward CO, methanol and DME oxidation. Cu/(Mn+Co) molar ratio 1:5 and Co/Mn molar ratio 1.5 in the active component can ensure successful oxidation of CO, CH3OH and DME. The active component of the mixed Cu-Mn-Co/γ–alumina catalysts consists of at least six compounds - CuO, Co3O4, MnO2, Cu1.5Mn1.5O4, MnCo2O4 and CuCo2O4, depending on the Cu/Mn/Co molar ratio. Chemical composition strongly influences catalytic properties, this effect being quite variable with regards to the different processes.

Keywords: Cu-Mn-Co catalysts, oxidation, carbon oxide, VOCs

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Authors: N. Laosiripojana, P. Tepamatr

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The influence of bismuth on the water gas shift activities of Pt on ceria was studied. The flow reactor was used to study the activity of the catalysts in temperature range 100-400°C. The feed gas composition contains 5%CO, 10% H₂O and balance N₂. The total flow rate was 100 mL/min. The outlet gas was analyzed by on-line gas chromatography with thermal conductivity detector. The catalytic activities of bimetallic 1%Pt1%Bi/CeO₂ catalyst were greatly enhanced when compared with the activities of monometallic 2%Pt/CeO₂ catalyst. The catalysts were characterized by X-ray diffraction (XRD), Temperature-Programmed Reduction (TPR) and surface area analysis. X-ray diffraction pattern of Pt/CeO₂ and PtBi/CeO₂ indicated slightly shift of diffraction angle when compared with pure ceria. This result was due to strong metal-support interaction between platinum and ceria solid solution, causing conversion of Ce⁴⁺ to larger Ce³⁺. The distortions inside ceria lattice structure generated strain into the oxide lattice and facilitated the formation of oxygen vacancies which help to increase water gas shift performance. The H₂-Temperature Programmed Reduction indicated that the reduction peak of surface oxygen of 1%Pt1%Bi/CeO₂ shifts to lower temperature than that of 2%Pt/CeO₂ causing the enhancement of the water gas shift activity of this catalyst. Pt played an important role in catalyzing the surface reduction of ceria and addition of Bi alter the reduction temperature of surface ceria resulting in the improvement of the water gas shift activity of Pt catalyst.

Keywords: bismuth, platinum, water gas shift, ceria

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Authors: Elvis Medina, Alejandro Karelovic, Romel Jiménez

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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: Hossein Bayahia, Mohammed Saad Motlaq Al-Gahmdi

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The gas-phase deoxygenation of propionic acid was investigated in the presence of Co-Mo catalysts in N2 or H2 flow at 200-400 °C. In the presence of N2 the main product was 3-pentanone with other deoxygenates and some light gases: ethane and ethene. Using H2 flow, the catalyst was active for decarboxylation and decarbonylation of acid and the yields of ethane and ethene. The decarboxylation and decarbonylation reactions increased with increasing temperature. Cobalt-molybdenum supported on alumina showed better performance than bulk catalyst, especially at 400 °C in the presence of N2 for the ketonisation of propionic acid to form 3-pentanone as the main product. Bulk and supported catalysts were characterized by surface area porosity (BET), thermogravimetric analysis (TGA) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of pyridine adsorption.

Keywords: deoxygenation, propionic acid, gas-phase, catalyst

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Authors: Sarra Boughaba

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α-aminophosphonates have found a wide range of applications in organic and medicinal chemistry; they are considered as pharmacological agents, anti-inflammatory antitumor agents, and antibiotics. A number of procedures have been developed for their synthesis. However, many of these methods suffer from some disadvantages such as long reaction times, environmental pollution, utilization of organic solvents, and expensive catalysts. In the past few years, heteropolyacids have received great attention as environmentally benign catalysts for organic synthetic processes, they possess unique physicochemical properties, such as super-acidity, high thermal and chemical stability, ability to accept and release electrons and high proton mobility, and the possibility of varying their acidity and oxidizing potential. In this context, an efficient and eco-friendly protocol has been described for the synthesis of α-aminophosphonates via one pot, three component reaction catalyzed by H₆P₂W₁₈O₆₂.14H₂O as reusable catalyst, by condensation of amino acids esters, various aromatic aldehydes and triethylphosphite under solvent-free conditions, the corresponding α-aminophosphonates were formed in good yields as racemic or diastereomericmixture. All the new products were systematically characterized by IR, MS, and ¹H, ¹³C-³¹P-NMR analyses. This method offers advantages such as simplicity workup with the green aspects by avoiding expensive catalysts and toxic solvents, good yields, short reaction times.

Keywords: amino acids esters, α-aminophosphonates, H₆P₂W₁₈O₆₂.14H₂O catalyst, green chemistry

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Authors: Marius Sebastian Secula, Mihaela Darie, Gabriela Carja

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Persistent organic pollutant discharged by various industries or urban regions into the aquatic ecosystems represent a serious threat to fauna and human health. The endocrine disrupting compounds are known to have toxic effects even at very low values of concentration. The anti-inflammatory agent Ibuprofen is an endocrine disrupting compound and is considered as model pollutant in the present study. The use of light energy to accomplish the latest requirements concerning wastewater discharge demands highly-performant and robust photo-catalysts. Many efforts have been paid to obtain efficient photo-responsive materials. Among the promising photo-catalysts, layered double hydroxides (LDHs) attracted significant consideration especially due to their composition flexibility, high surface area and tailored redox features. This work presents Fe(II) self-supported on ZnMeLDHs (Me =Al3+, Fe3+) as novel efficient photo-catalysts for Fenton-like catalysis. The co-precipitation method was used to prepare ZnAlLDH, ZnFeAlLDH and ZnCrLDH (Zn2+/Me3+ = 2 molar ratio). Fe(II) was self-supported on the LDHs matrices by using the reconstruction method, at two different values of weight concentration. X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG), Fourier transform infrared (FTIR) and transmission electron microscopy (TEM) were used to investigate the structural, textural, and micromorphology of the catalysts. The Fe(II)/ZnMeLDHs nano-hybrids were tested for the degradation of a model pharmaceutical agent, the anti-inflammatory agent ibuprofen, by photocatalysis and photo-Fenton catalysis, respectively. The results point out that the embedment Fe(II) into ZnFeAlLDH and ZnCrLDH lead to a slight enhancement of ibuprofen degradation by light irradiation, whereas in case of ZnAlLDH, the degradation process is relatively low. A remarkable enhancement of ibuprofen degradation was found in the case of Fe(II)/ZnMeLDHs by photo-Fenton process. Acknowledgements: This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS - UEFISCDI, project number PN-II-RU-TE-2014-4-0405.

Keywords: layered double hydroxide, heterogeneous Fenton, micropollutant, photocatalysis

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Authors: O. Eren, L. Zakar

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Recycling steel building components is key to the sustainability of a structure’s end-of-life, as it is the most economical solution. In this paper the effects of usage of recycled steel material in tall buildings aspects are investigated.

Keywords: building, recycled material, steel, structure

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Authors: Timothy Francis Grant

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There are conflicting purposes at play with the design of sustainable packaging which include material reduction, recycling compatibility, use of secondary content and performance of the package in protecting and delivering the product. Life Cycle Assessment (LCA) is able to evaluate these different strategies against environmental metrics such as climate change, land and water use and marine litter pollution. However, LCA has traditionally been too time consuming and expensive to be used effectively in packaging design process. To make LCA practical for packaging technologist and designers a simplified tool is needed to make LCA possible for non-environmental specialists. The Packaging Quick Evaluation Tool (PIQET) is a web-based solution for undertaking LCA of new and existing packaging designs considering the global supply chain and impacts from cradle to grave. PIQET is based on a pre-calculated LCA database covering the materials and processes involved in the packaging lifecycle from cradle to grave. This includes both virgin materials and recycled content, conversion of materials into packaging, and the transportation of packaging to the product filling. In addition, PIQET assesses the impacts once the package is filled looking at storage, transport and product loss through the supply chain. When applied to consumer packaging light weight packages which are note recyclable have lower impacts than more recyclable packages which have a higher mass. Its also apparent that for many products the impacts of product failure and product loss are more important environmentally compared to packaging material efficiency.

Keywords: Climate change, Life Cycle Assessment, Marine litter, Packaging sustainability

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

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

Keywords: aniline, heterogeneous catalyst, methoxycarbonylation, methylphenyl carbamate

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Authors: Srinivas Nerella

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A series of new heterodentate N, O-donor ligands derived from condensing 3-amino Coumarins with hydroxy benzaldehydes and acetophenones were used to afford new mononuclear Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Pd(II) coordination compounds. All the complexes were characterized by IR, 1H-NMR, 13C-NMR, Mass, ESR, Electronic spectra, Conductance, Magnetic and Thermal studies. The ligands show hexa coordination in Mn(II), Co(II), Ni(II), and Pd(II) complexes resulting octahedral geometries, while the ligands in Zn(II) and Cu(II) complexes show tetra coordination resulting tetrahedral and square planar geometries respectively. These mononuclear complexes were investigated as catalysts in the hydrothiolation of aromatic and aliphatic alkynes with thiols. These metal complexes were acted as versatile catalysts and gave good yields.

Keywords: schiff bases, divalent metal complexes of schiff bases, Catalytic activity, hydrothiolation

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Authors: Maksudur Rahman Khan, Kar Min Chan, Huei Ruey Ong, Chin Kui Cheng, Wasikur Rahman

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Microbial fuel cells (MFCs) represent a promising technology for simultaneous bioelectricity generation and wastewater treatment. Catalysts are significant portions of the cost of microbial fuel cell cathodes. Many materials have been tested as aqueous cathodes, but air-cathodes are needed to avoid energy demands for water aeration. The sluggish oxygen reduction reaction (ORR) rate at air cathode necessitates efficient electrocatalyst such as carbon supported platinum catalyst (Pt/C) which is very costly. Manganese oxide (MnO2) was a representative metal oxide which has been studied as a promising alternative electrocatalyst for ORR and has been tested in air-cathode MFCs. However, the single MnO2 has poor electric conductivity and low stability. In the present work, the MnO2 catalyst has been modified by doping Pt nanoparticle. The goal of the work was to improve the performance of the MFC with minimum Pt loading. MnO2 and Pt nanoparticles were prepared by hydrothermal and sol-gel methods, respectively. Wet impregnation method was used to synthesize Pt/MnO2 catalyst. The catalysts were further used as cathode catalysts in air-cathode cubic MFCs, in which anaerobic sludge was inoculated as biocatalysts and palm oil mill effluent (POME) was used as the substrate in the anode chamber. The as-prepared Pt/MnO2 was characterized comprehensively through field emission scanning electron microscope (FESEM), X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) where its surface morphology, crystallinity, oxidation state and electrochemical activity were examined, respectively. XPS revealed Mn (IV) oxidation state and Pt (0) nanoparticle metal, indicating the presence of MnO2 and Pt. Morphology of Pt/MnO2 observed from FESEM shows that the doping of Pt did not cause change in needle-like shape of MnO2 which provides large contacting surface area. The electrochemical active area of the Pt/MnO2 catalysts has been increased from 276 to 617 m2/g with the increase in Pt loading from 0.2 to 0.8 wt%. The CV results in O2 saturated neutral Na2SO4 solution showed that MnO2 and Pt/MnO2 catalysts could catalyze ORR with different catalytic activities. MFC with Pt/MnO2 (0.4 wt% Pt) as air cathode catalyst generates a maximum power density of 165 mW/m3, which is higher than that of MFC with MnO2 catalyst (95 mW/m3). The open circuit voltage (OCV) of the MFC operated with MnO2 cathode gradually decreased during 14 days of operation, whereas the MFC with Pt/MnO2 cathode remained almost constant throughout the operation suggesting the higher stability of the Pt/MnO2 catalyst. Therefore, Pt/MnO2 with 0.4 wt% Pt successfully demonstrated as an efficient and low cost electrocatalyst for ORR in air cathode MFC with higher electrochemical activity, stability and hence enhanced performance.

Keywords: microbial fuel cell, oxygen reduction reaction, Pt/MnO2, palm oil mill effluent, polarization curve

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Authors: Alessio Varotto, Lorenzo Freschi, Umberto Pasqual Laverdura, Anastasia Moschovi, Davide Pumiglia, Iakovos Yakoumis, Marta Feroci, Maria Luisa Grilli

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Dry reforming of Methane (DRM) is considered one of the most valuable technologies for green-house gas valorization thanks to the fact that through this reaction, it is possible to obtain syngas, a mixture of H₂ and CO in an H₂/CO ratio suitable for utilization in the Fischer-Tropsch process of high value-added chemicals and fuels. Challenges of the DRM process are the reduction of costs due to the high temperature of the process and the high cost of precious metals of the catalyst, the metal particles sintering, and carbon deposition on the catalysts’ surface. The aim of this study is to demonstrate the feasibility of the synthesis of catalysts using a leachate solution containing Pt coming directly from the recovery of spent diesel oxidation catalysts (DOCs) without further purification. An unusual perovskite support for DRM, the BaCe₁₋ₓ₋ᵧZrₓGdᵧO₃ (BCZG) perovskite, has been chosen as the catalyst support because of its high thermal stability and capability to produce oxygen vacancies, which suppress the carbon deposition and enhance the catalytic activity of the catalyst. BCZG perovskite has been synthesized by a sol-gel modified Pechini process and calcinated in air at 1100 °C. BCZG supports have been impregnated with a Pt-containing leachate solution of DOC, obtained by a mild hydrometallurgical recovery process, as reported elsewhere by some of the authors of this manuscript. For comparison reasons, a synthetic solution obtained by digesting commercial Pt-black powder in aqua regia was used for BCZG support impregnation. Pt nominal content was 2% in both BCZG-based catalysts formed by real and synthetic solutions. The structure and morphology of catalysts were characterized by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Thermogravimetric Analysis (TGA) was used to study the thermal stability of the catalyst’s samples. Brunauer-Emmett-Teller (BET) analysis provided a high surface area of the catalysts. H₂-TPR (Temperature Programmed Reduction) analysis was used to study the consumption of hydrogen for reducibility, and it was associated with H₂-TPD characterization to study the dispersion of Pt on the surface of the support and calculate the number of active sites used by the precious metal. Dry reforming of methane (DRM) reaction, carried out in a fixed bed reactor, showed a high conversion efficiency of CO₂ and CH4. At 850°C, CO₂ and CH₄ conversion were close to 100% for the catalyst obtained with the aqua regia-based solution of commercial Pt-black, and ~70% (for CH₄) and ~80 % (for CO₂) in the case of real HCl-based leachate solution. H₂/CO ratios were ~0.9 and ~0.70 in the first and latter cases, respectively. As far as we know, this is the first pioneering work in which a BCGZ catalyst and a real Pt-containing leachate solution were successfully employed for DRM reaction.

Keywords: dry reforming of methane, perovskite, PGM, recycled Pt, syngas

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Authors: O. P. Yadav

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Nano-size Ag-N co-doped ZnO/CuO composite photo-catalyst has been synthesized by chemical method and characterized using XRD, TEM, FTIR, AAS and UV-Vis spectroscopic techniques. Photo-catalytic activity of as-synthesized nanomaterial has been studied using degradation of methyl orange as a probe under UV as well as visible radiations. Ag-N co-doped ZnO/CuO composite showed higher photo-catalytic activity than Ag- or N-doped ZnO and undoped ZnO-CuO composite photo-catalysts. The observed highest activity of Ag-N co-doped ZnO-CuO among the studied photo-catalysts is attributed to the cumulative effects of lowering of band-gap energy and decrease of recombination rate of photo-generated electrons and holes owing to doped N and Ag, respectively. Effects of photo-catalyst load, pH and substrate initial concentration on degradation of methyl orange have also been studied. Photo-catalytic degradation of methyl orange follows pseudo first order kinetics.

Keywords: degradation, nanocomposite, photocatalyst, spectroscopy, XRD

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Authors: Esther Acha, Jose Cambra, De Chen

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Hydrogen is considered an important energy vector for the 21st century. Nowadays there are some difficulties for hydrogen economy implantation, and one of them is the high purity required for hydrogen. This energy vector is still being mainly produced from fuels, from wich hydrogen is produced as a component of a mixture containing other gases, such as CO, CO2 and H2O. A forthcoming sustainable pathway for hydrogen is steam-reforming of bio-oils derived from biomass, e.g. via fast pyrolysis. Bio-oils are a mixture of acids, alcohols, aldehydes, esters, ketones, sugars phenols, guaiacols, syringols, furans, multi-functional compounds and also up to a 30 wt% of water. The sorption enhanced steam reforming (SESR) process is attracting a great deal of attention due to the fact that it combines both hydrogen production and CO2 separation. In the SESR process, carbon dioxide is captured by an in situ sorbent, which shifts the reversible reforming and water gas shift reactions to the product side, beyond their conventional thermodynamic limits, giving rise to a higher hydrogen production and lower cost. The hydrogen containing mixture has been obtained from the SESR of bio-oil type compounds. Different types of catalysts have been tested. All of them contain Ni at around a 30 wt %. Two samples have been prepared with the wet impregnation technique over conventional (gamma alumina) and non-conventional (olivine) supports. And a third catalysts has been prepared over a hydrotalcite-like material (HT). The employed sorbent is a commercial dolomite. The activity tests were performed in a bench-scale plant (PID Eng&Tech), using a stainless steel fixed bed reactor. The catalysts were reduced in situ in the reactor, before the activity tests. The effluent stream was cooled down, thus condensed liquid was collected and weighed, and the gas phase was analysed online by a microGC. The hydrogen yield, and process behavior was analysed without the sorbent (the traditional SR where a second purification step will be needed but that operates in steady state) and the SESR (where the purification step could be avoided but that operates in batch state). The influence of the support type and preparation method will be observed in the produced hydrogen yield. Additionally, the stability of the catalysts is critical, due to the fact that in SESR process sorption-desorption steps are required. The produced hydrogen yield and hydrogen purity has to be high and also stable, even after several sorption-desorption cycles. The prepared catalysts were characterized employing different techniques to determine the physicochemical properties of the fresh-reduced and used (after the activity tests) materials. The characterization results, together with the activity results show the influence of the catalysts preparation method, calcination temperature, or can even explain the observed yield and conversion.

Keywords: CO2 sorbent, enhanced steam reforming, hydrogen

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Authors: Andrea Dragu, Solen Kinayyigit, Valerie Colliere, Karin Karin Philippot, Camelia Bala, Vasile I. Parvulescu

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The production of transportation fuels from biomass has gained a growing attention due to diminishing fossil fuel reserves, rising petroleum prices and increasing concern about global warming. In recent years, renewable hydrocarbons that are completely fungible with fossil fuels have been suggested to be efficiently produced by catalytic deoxygenation of fatty acids and their derivatives viadecarboxylation / decarbonylation. Several triglycerides (tall oil fatty acids) and saturated/unsaturated fatty acids and their corresponding esters were used as feedstocks. Their impact together with the influence of the reaction conditions and the catalyst composition on the nature of the reaction pathways of the deoxygenation of vegetable oils and their derivatives were recently reviewed. Following this state of the art the aim of the present study was the investigation of Pd NPs deposited onto mesoporous carbon supports as active and stable catalysts for the deoxygenation of oleic acid. The catalysts were prepared by the deposition of Pd NPs synthesised following an organometallic route on mesoporous carbons with different characteristics. Experiments were carried out under both batch and flow conditions. They demonstrated that under batch conditions (200 atm; 573K), the extent of the reaction depended, firstly, on the Pd loading and then on the metal dispersion and the oxidation state of palladium, both influenced by the way the support has been treated before the NPs deposition and by the preparation/stabilization methodology of Pd NPs. No aromatic compounds were detected in the reaction products but octadecanol and octadecane were observed in large extents. Under flow conditions (4 atm; 573 K), the conversion of stearic acid was superior to that observed in batch conditions. The product mixture contained over 20% heptadecane. No octadecanol, octadecane, and aromatic compounds were detected. The maxima in performances are obtained after only 0.5 h. After that, the yields in heptadecane suffer from a severe decrease until 3h reaction time. However, at that time, stopping feeding the reactor with oleic acid and flushing the catalyst only with mesitylene recovered the activity and the selectivity of the catalysts. With the complete removal of H2, the analysis revealed the presence of heptadecene in high excess compared to heptadecane (almost 7 to 1), thus suggesting decarbonylation as the main route. ICP-OES measurements indicated no leaching of palladium and simple washing of catalysts with mesitylene allowed recycling without any change in conversion or product distribution. Noteworthy, mesitylene as solvent exhibited no effect in this reaction. In conclusion, this study demonstrates the feasibility of such catalysts for the green production of fuels from biomass.

Keywords: fuels from biomass, green catalyst, Pd nano-particles , recycble catalyst

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Authors: Hellal Abdelkader, Chafaa Salah, Touafri Lasnouni

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A simple, efficient and general method has been developed for the high diastereoselective synthesis of diethyl α-aminophosphonates in water through “one-pot” three-component reaction of aromatic aldehydes, aminophenols and dialkyl phosphites in the presence of a low catalytic amount (10mol%) of phosphorous acid as highly stable catalyst is described.

Keywords: DFT, HOMO-LUMO, phosphonic acid, aminophenols

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Authors: Richard Krijnen, Alan Wang

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As the world is aiming to reach net zero around 2050, structural engineers must begin finding solutions to contribute to this global initiative. Approximately 40% of global energy-related emissions are due to buildings and construction, and a building’s structure accounts for 50% of its embodied carbon, which indicates that structural engineers are key contributors to finding solutions to reach carbon neutrality. However, this task presents a multifaceted challenge as structural engineers must navigate technical, safety and economic considerations while striving to reduce emissions. This study reviews several options and considerations to reduce carbon emissions that structural engineers can use in their future designs without compromising the structural integrity of their proposed design. Low-carbon structures should adhere to several guiding principles. Firstly, prioritize the selection of materials with low carbon footprints, such as recyclable or alternative materials. Optimization of design and engineering methods is crucial to minimize material usage. Encouraging the use of recyclable and renewable materials reduces dependency on natural resources. Energy efficiency is another key consideration involving the design of structures to minimize energy consumption across various systems. Choosing local materials and minimizing transportation distances help in reducing carbon emissions during transport. Innovation, such as pre-fabrication and modular design or low-carbon concrete, can further cut down carbon emissions during manufacturing and construction. Collaboration among stakeholders and sharing experiences and resources are essential for advancing the development and application of low-carbon structures. This paper identifies current available tools and solutions to reduce embodied carbon in structures, which can be used as part of daily structural engineering practice.

Keywords: efficient structural design, embodied carbon, low-carbon material, sustainable structural design

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Authors: Faezeh Aghazadeh

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The catalytic activity of Pt/γ-Al₂O₃ and Pt-Fe/γ-Al₂O₃ catalysts was investigated to bring about the complete oxidation of 2-Propanol. Among them, Pt-Fe/γ-Al₂O₃ was found to be the most promising catalyst based on activity. The catalysts were characterized by (XRD), (SEM), (TEM) and ICP-AES techniques. Iron loadings on Pt/γ-Al₂O₃ had a great effect on catalytic activity, and Pt-Fe/γ-Al₂O₃ (1.75 wt% Fe) catalyst at calcination temperature 300°C was observed to be the most active, which might be contributed to the favorable synergetic effects between Pt and Fe, high activity and the well-dispersed bimetallic phase. The combustion of 2-Propanol in the vapor phase was carried out in a conventional flow U-shape glass reactor used in the differential mode at atmospheric pressure. 2-Propanol was analyzed by a gas chromatograph VARIAN 3800 CX equipped with an FID. As observed, better performance and activity were observed for Pt-Fe/Al₂O₃ bimetallic catalyst. These results indicate that the high dispersion on support gives a positive effect on catalytic activity.

Keywords: volatile organic compounds, bimetallic catalyst, catalytic activity, low temperature

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Authors: Abrar Hussain, Kuen-Song Lin, Sayed Maeen Badshah, Jamshid Hussain

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The conversion of CO₂ into versatile, useful compounds such as fuels and other chemicals remains a challenging frontier in research, demanding the innovation of increasingly effective catalysts. In the present work, a catalyst-incorporating zirconium (Zr) modification within CuO–ZnO–Al₂O₃ (CZA) was synthesized via a co-precipitation method to convert CO₂ into methanol. Furthermore, bio-HZSM-5 was used to promote methanol dehydration to produce dimethyl ether (DME). We prepared the porous hierarchy bio-HZSM-5 with remarkable pore connectivity by utilizing an economical loofah sponge and rice husks as biotemplates. The synthesized catalysts were characterized using Field Emission Scanning Electron Microscopy (FE-SEM), X–ray diffraction (XRD), N₂ adsorption (BET), temperature-programmed desorption (NH₃-TPD) and thermogravimetric analysis (TGA). The Zr addition improved the performance of the CZZA catalyst as a structural promoter, leading to increased DME selectivity and total carbon conversion by enhancing active sites, surface area, and the synergistic interfaces between CuO and ZnO. The presence of silicon in the biomass, notably from the loofah sponge (0.016 wt %) and rice husks (8.3 wt %), also performed a pivotal role in the preparation of bio-HZSM-5. Furthermore, contrasted to the CZZA/com-ZSM-5 catalyst, the integration of CZZA with bio-HZSM-5-L bifunctional catalyst achieved the highest DME yield (12.1 %), DME selectivity (58.6%), CO₂ conversion (22.5%) at 280 °C and 30 bar. The payback time for 5 and 10-tons per day (5 and10-TPD) DME formation using the catalytic process of CO₂ from petrochemical refinery plant waste gas emissions was 2.98 and 2.44 years, respectively.

Keywords: Cost assessment, Dimethyl ether, low-cost bio-HZSM-5, CZZA catalyst, CO₂ hydrogenation

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Authors: Hamza Hafidi Alaoui, Damien Leduc, Mounsif Ech Cherif El Kettani

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This study is dedicated to the evaluation of the ageing of turbine blades in sea conditions, based on ultrasonic Non Destructive Testing (NDT) methods. This study is being developed within the framework of the European Interreg TIGER project. The Tidal Stream Industry Energiser Project, known as TIGER, is the biggest ever Interreg project driving collaboration and cost reductionthrough tidal turbine installations in the UK and France. The TIGER project will drive the growth of tidal stream energy to become a greater part of the energy mix, with significant benefits for coastal communities. In the bay of Paimpol-Bréhat (Brittany), different samples of composite material and bonded composite/composite structures have been immersed at the same time near a turbine. The studied samples are either conventional carbon-epoxy composite samples or composite samples based on a recyclable resin (called recyclamine). One of the objectives of the study is to compare the ageing of the two types of structure. A sample of each structure is picked up every 3 to 6 months and analyzed using ultrasonic guided waves and bulk waves and compared to reference samples. In order to classify the damage level as a function of time spent under the sea, the measure have been compared to a rheological model based on the Finite Elements Method (FEM). Ageing of the composite material, as well as that of the adhesive, is identified. The aim is to improve the quality of the turbine blade structure in terms of longevity and reduced maintenance needs.

Keywords: non-destructive testing, ultrasound, composites, guides waves

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Authors: Yijin Kang

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Chemical-electrical energy conversion and storage are greatly attractive for the development of sustainable energy. Catalytic processes are heavily involved in such energy conversion and storage. Development of high-performance catalyst nanomaterials relies on tuning material structures at nanoscale. This is in particular manifested in the design of catalysts demanding both high activity and durability. Here, a research system will be presented that connects fundamental investigation on well-defined extended surfaces (e.g. single crystal surfaces), extrapolation onto nanocrystals with highly controlled shape and size, exploration of interfacial interaction using novel nanocrystal superlattices as platform, and finally design of high performance catalysts in which all the possible beneficial properties from complex functional structures are implemented. Using recently published results, it will be demonstrated that optimal and fine balanced activity and durability, as well as tunable functionality, can be achieved by carefully tailoring the nanostructure of catalytic nanomaterials.

Keywords: energy, nanomaterials, catalysis, electrocatalysis

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Authors: K. Mondal, S. Talapatra, M. Terrones, S. Pokhrel, C. Frizzel, B. Sumpter, V. Meunier, A. L. Elias

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Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H₂) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H₂, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.

Keywords: CNT, CO Hydrodeoxygenation, DFT, liquid fuels, XPS, XTL

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Authors: Issam A. Al-Khatib

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In order to achieve a significant reduction of waste amount flowing into landfills, it is important to first understand the composition of the solid municipal waste generated. Hence a detailed analysis of municipal solid waste composition has been conducted in Nablus city. The aim is to provide data on the potential recyclable fractions in the actual waste stream, with a focus on the plastic fraction. Hence, waste-sorting campaigns were conducted on mixed waste containers from five districts in Nablus city. The districts vary in terms of infrastructure and average income. The target is to obtain representative data about the potential quantity and quality of household plastic waste. The study has measured the composition of municipal solid waste collected/ transported by Nablus municipality. The analysis was done by categorizing the samples into eight primary fractions (organic and food waste, paper and cardboard, glass, metals, textiles, plastic, a fine fraction (<10 mm), and others). The study results reveal that the MSW stream in Nablus city has a significant bio- and organic waste fraction (about 68% of the total MSW). The second largest fraction is paper and cardboard (13.6%), followed by plastics (10.1%), textiles (3.2%), glass (1.9%), metals (1.8%), a fine fraction (0.5%), and other waste (0.3%). After this complete and detailed characterization of MSW collected in Nablus and taking into account the content of biodegradable organic matter, the composting could be a solution for the city of Nablus where the surrounding areas of Nablus city have agricultural activities and could be a natural outlet to the compost product. Different waste management options could be practiced in the future in addition to composting, such as energy recovery and recycling, which result in a greater possibility of reducing substantial amounts that are disposed of at landfills.

Keywords: developing countries, composition, management, recyclable, waste.

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Authors: Gabi N. Nehme, Saeed Ghalambor

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The use of titanium fluoride and iron fluoride (TiF3/FeF3) catalysts in combination with polutetrafluoroethylene (PTFE) in plain zinc dialkyldithiophosphate (ZDDP) oil is important for the study of engine tribocomponents and is increasingly a strategy to improve the formation of tribofilm and to provide low friction and excellent wear protection in reduced phosphorus plain ZDDP oil. The influence of surface roughness and the concentration of TiF3/FeF3/PTFE were investigated using bearing steel samples dipped in lubricant solution @100°C for two different heating time durations. This paper addresses the effects of water drop contact angle using different surface finishes after treating them with different lubricant combination. The calculated water drop contact angles were analyzed using Design of Experiment software (DOE) and it was determined that a 0.05 μm Ra surface roughness would provide an excellent TiF3/FeF3/PTFE coating for antiwear resistance as reflected in the scanning electron microscopy (SEM) images and the tribological testing under extreme pressure conditions. Both friction and wear performance depend greatly on the PTFE/and catalysts in plain ZDDP oil with 0.05% phosphorous and on the surface finish of bearing steel. The friction and wear reducing effects, which was observed in the tribological tests, indicated a better micro lubrication effect of the 0.05 μm Ra surface roughness treated at 100°C for 24 hours when compared to the 0.1 μm Ra surface roughness with the same treatment.

Keywords: scanning electron microscopy, ZDDP, catalysts, PTFE, friction, wear

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Authors: Anahita Mortazavi Manesh, Mojtaba Bagherzadeh

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Metalloporphyrins are well known to mimic the activity of monooxygenase enzymes. In this regard, metalloporphyrin complexes have been largely employed as valuable biomimetic catalysts, owing to the critical roles they play in oxygen transfer processes in catalytic oxidation reactions. Investigating in this area is based on different strategies to design selective, stable and high turnover catalytic systems. Immobilization of expensive metalloporphyrin catalysts onto supports appears to be a good way to improve their stability, selectivity and the catalytic performance because of the support environment and other advantages with respect to recovery, reuse. In other words, supporting metalloporphyrins provides a physical separation of active sites, thus minimizing catalyst self-destruction and dimerization of unhindered metalloporphyrins. Furthermore, heterogeneous catalytic oxidations have become an important target since their process are used in industry, helping to minimize the problems of industrial waste treatment. Hence, the immobilization of these biomimetic catalysts is much desired. An attractive approach is the preparation of the heterogeneous catalyst involves immobilization of complexes on silica coated magnetic nano-particles. Fe3O4@SiO2 magnetic nanoparticles have been studied extensively due to their superparamagnetism property, large surface area to volume ratio and easy functionalization. Using heterogenized homogeneous catalysts is an attractive option to facile separation of catalyst, simplified product work-up and continuity of catalytic system. Homogeneous catalysts immobilized on magnetic nanoparticles (MNPs) surface occupy a unique position due to combining the advantages of both homogeneous and heterogeneous catalysts. In addition, superparamagnetic nature of MNPs enable very simple separation of the immobilized catalysts from the reaction mixture using an external magnet. In the present work, an efficient heterogeneous catalyst was prepared by immobilizing manganese porphyrin on functionalized magnetic nanoparticles through the amino propyl linkage. The prepared catalyst was characterized by elemental analysis, FT-IR spectroscopy, X-ray powder diffraction, atomic absorption spectroscopy, UV-Vis spectroscopy, and scanning electron microscopy. Application of immobilized metalloporphyrin in the oxidation of various organic substrates was explored using Gas chromatographic (GC) analyses. The results showed that the supported Mn-porphyrin catalyst (Fe3O4@SiO2-NH2@MnPor) is an efficient and reusable catalyst in oxidation reactions. Our catalytic system exhibits high catalytic activity in terms of turnover number (TON) and reaction conditions. Leaching and recycling experiments revealed that nanocatalyst can be recovered several times without loss of activity and magnetic properties. The most important advantage of this heterogenized catalytic system is the simplicity of the catalyst separation in which the catalyst can be separated from the reaction mixture by applying a magnet. Furthermore, the separation and reuse of the magnetic Fe3O4 nanoparticles were very effective and economical.

Keywords: Fe3O4 nanoparticle, immobilized metalloporphyrin, magnetically separable nanocatalyst, oxidation reactions

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Authors: M. Al Zallouha, Y. Landkocz, J. Brunet, R. Cousin, J. M. Halket, E. Genty, P. J. Martin, A. Verdin, D. Courcot, S. Siffert, P. Shirali, S. Billet

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Toluene is one of the most used Volatile Organic Compounds (VOCs) in the industry. Amongst VOCs, Benzene, Toluene, Ethylbenzene and Xylenes (BTEX) emitted into the atmosphere have a major and direct impact on human health. It is, therefore, necessary to minimize emissions directly at source. Catalytic oxidation is an industrial technique which provides remediation efficiency in the treatment of these organic compounds. However, during operation, the catalysts can release some compounds, called byproducts, more toxic than the original VOCs. The catalytic oxidation of a gas stream containing 1000ppm of toluene on Pd/α-Al2O3 can release a few ppm of benzene, according to the operating temperature of the catalyst. The development of new catalysts must, therefore, include chemical and toxicological validation phases. In this project, A549 human lung cells were exposed in air/liquid interface (Vitrocell®) to gas mixtures derived from the oxidation of toluene with a catalyst of Pd/α-Al2O3. Both exposure concentrations (i.e. 10 and 100% of catalytic emission) resulted in increased gene expression of Xenobiotics Metabolising Enzymes (XME) (CYP2E1 CYP2S1, CYP1A1, CYP1B1, EPHX1, and NQO1). Some of these XMEs are known to be induced by polycyclic organic compounds conventionally not searched during the development of catalysts for VOCs degradation. The increase in gene expression suggests the presence of undetected compounds whose toxicity must be assessed before the adoption of new catalyst. This enhances the relevance of toxicological validation of such systems before scaling-up and marketing.

Keywords: BTEX toxicity, air/liquid interface cell exposure, Vitrocell®, catalytic oxidation

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Authors: M. P. Joshi, F. Deganello, L. F. Liotta, V. La Parola, G. Pantaleo

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For the first time, commercial iron nitrate was replaced by rust wastes, as a source of Iron for the preparation of LaFeO₃ powders by solution combustion synthesis (SCS). A detailed comparison with a reference powder obtained by SCS, starting from a commercial iron nitrate, was also performed. Several techniques such as X-ray diffraction combined with Rietveld refinement, mass plasma atomic emission spectroscopy, nitrogen adsorption measurements, temperature programmed reduction, X-ray photoelectron spectroscopy, Fourier transform analysis and scanning electron microscopy were used for the characterization of the rust wastes as well as of the perovskite powders. The performance of this ecofriendly material was evaluated by testing the activity and selectivity in the propylene oxidation, in order to use it for the benefit of the environment. Characterization and performance results clearly evidenced limitations and peculiarities of this new approach.

Keywords: perovskite type catalysts, solution combustion synthesis, X-ray diffraction, rust wastes

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Authors: Arnold S. Freitas Neto, Rodrigo E. Coelho, Erick S. Mendonça

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The study aims to assess if high-purity iron powder in iron-aluminum alloys can be replaced by SAE 1020 steel chips with an atomicity proportion of 50% for each element. Chips of SAE 1020 are rejected in industrial processes. Thus, the use of SAE 1020 as a replaceable composite for iron increase the sustainability of ferrous alloys by recycling industrial waste. The alloys were processed by high energy milling, of which the main advantage is the minimal loss of raw material. The raw material for three of the six samples were high purity iron powder and recyclable aluminum cans. For the other three samples, the high purity iron powder has been replaced with chips of SAE 1020 steel. The process started with the separate milling of chips of aluminum and SAE 1020 steel to obtain the powder. Subsequently, the raw material was mixed in the pre-defined proportions, milled together for five hours and then underwent a closed-die hot compaction at the temperature of 500 °C. Thereafter, the compacted samples underwent heat treatments known as sintering and solubilization. All samples were sintered one hour, and 4 samples were solubilized for either 4 or 10 hours under well-controlled atmosphere conditions. Lastly, the composition and the mechanical properties of their hardness were analyzed. The samples were analyzed by optical microscopy, scanning electron microscopy and hardness testing. The results of the analysis showed a similar chemical composition and interesting hardness levels with low standard deviations. This verified that the use of SAE 1020 steel chips can be a low-cost alternative for high-purity iron powder and could possibly replace high-purity Iron in industrial applications.

Keywords: Fe-Al alloys, high energy milling, iron-aluminum alloys, metallography characterization, powder metallurgy, recycling ferrous alloy, SAE 1020 steel recycling

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