Search results for: spent catalysts

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: Cristina Opris, Bogdan Cojocaru, Madalina Tudorache, Simona M. Coman, Vasile I. Parvulescu, Camelia Bala, Bahir Duraki, Jeroen A. Van Bokhoven

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The tremendous achievements in the development of the society concretized by more sophisticated materials and systems are merely based on non-renewable resources. Consequently, after more than two centuries of intensive development, among others, we are faced with the decrease of the fossil fuel reserves, an increased impact of the greenhouse gases on the environment, and economic effects caused by the fluctuations in oil and mineral resource prices. The use of biomass may solve part of these problems, and recent analyses demonstrated that from the perspective of the reduction of the emissions of carbon dioxide, its valorization may bring important advantages conditioned by the usage of genetic modified fast growing trees or wastes, as primary sources. In this context, the abundance and complex structure of lignin may offer various possibilities of exploitation. However, its transformation in fuels or chemicals supposes a complex chemistry involving the cleavage of C-O and C-C bonds and altering of the functional groups. Chemistry offered various solutions in this sense. However, despite the intense work, there are still many drawbacks limiting the industrial application. Thus, the proposed technologies considered mainly homogeneous catalysts meaning expensive noble metals based systems that are hard to be recovered at the end of the reaction. Also, the reactions were carried out in organic solvents that are not acceptable today from the environmental point of view. To avoid these problems, the concept of this work was to investigate the synthesis of superparamagnetic core shell catalysts for the fragmentation of lignin directly in the aqueous phase. The magnetic nanoparticles were covered with a nanoshell of an oxide (niobia) with a double role: to protect the magnetic nanoparticles and to generate a proper (acidic) catalytic function and, on this composite, cobalt nanoparticles were deposed in order to catalyze the C-C bond splitting. With this purpose, we developed a protocol to prepare multifunctional and magnetic separable nano-composite Co@Nb2O5@Fe3O4 catalysts. We have also established an analytic protocol for the identification and quantification of the fragments resulted from lignin depolymerization in both liquid and solid phase. The fragmentation of various lignins occurred on the prepared materials in high yields and with very good selectivity in the desired fragments. The optimization of the catalyst composition indicated a cobalt loading of 4wt% as optimal. Working at 180 oC and 10 atm H2 this catalyst allowed a conversion of lignin up to 60% leading to a mixture containing over 96% in C20-C28 and C29-C37 fragments that were then completely fragmented to C12-C16 in a second stage. The investigated catalysts were completely recyclable, and no leaching of the elements included in the composition was determined by inductively coupled plasma optical emission spectrometry (ICP-OES).

Keywords: superparamagnetic core-shell catalysts, environmental production of fuels, renewable lignin, recyclable catalysts

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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: 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: Y. Muto, S. Araki, H. Yamamoto

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The separation of oxygen is one key technology to improve the efficiency and to reduce the cost for the processed of the partial oxidation of the methane and the condensation of the carbon dioxide. Particularly, carbon dioxide at high concentration would be obtained by the combustion using pure oxygen separated from air. However, the oxygen separation process occupied the large part of energy consumption. Therefore, it is considered that the membrane technologies enable to separation at lower cost and lower energy consumption than conventional methods. In this study, it is examined that the separation of oxygen using membranes of mixed conductors. Oxygen permeation through the membrane is occurred by the following three processes. At first, the oxygen molecules dissociate into oxygen ion at feed side of the membrane, subsequently, oxygen ions diffuse in the membrane. Finally, oxygen ions recombine to form the oxygen molecule. Therefore, it is expected that the membrane of thickness and material, or catalysts of the dissociation and recombination affect the membrane performance. However, there is little article about catalysts for the dissociation and recombination. We confirmed the performance of La0.6Sr0.4Co1.0O3-δ (LSC) based catalyst which was commonly used as the dissociation and recombination. It is known that the adsorbed amount of oxygen increase with the increase of doped Fe content in B site of LSC. We prepared the catalysts of La0.1Sr0.9Co0.9Fe0.1O3-δ(C9F1), La0.1Sr0.9Co0.5Fe0.5O3-δ(C5F5) and La0.1Sr0.9Co0.3Fe0.7O3-δ(C7F3). Also, we used Pr2NiO4 type mixed conductor as a membrane material. (Pr0.9La0.1)2(Ni0.74Cu0.21Ga0.05)O4+δ(PLNCG) shows the high oxygen permeability and the stability against carbon dioxide. Oxygen permeation experiments were carried out using a homemade apparatus at 850 -975 °C. The membrane was sealed with Pyrex glass at both end of the outside dense alumina tubes. To measure the oxygen permeation rate, air was fed to the film side at 50 ml min-1, helium as the sweep gas and reference gas was fed at 20 ml min-1. The flow rates of the sweep gas and the gas permeated through the membrane were measured using flow meter and the gas concentrations were determined using a gas chromatograph. Then, the permeance of the oxygen was determined using the flow rate and the concentration of the gas on the permeate side of the membrane. The increase of oxygen permeation was observed with increasing temperature. It is considered that this is due to the catalytic activities are increased with increasing temperature. Another reason is the increase of oxygen diffusivity in the bulk of membrane. The oxygen permeation rate is improved by using catalyst of LSC or LSCF. The oxygen permeation rate of membrane with LSCF showed higher than that of membrane with LSC. Furthermore, in LSCF catalysts, oxygen permeation rate increased with the increase of the doped amount of Fe. It is considered that this is caused by the increased of adsorbed amount of oxygen.

Keywords: membrane separation, oxygen permeation, K2NiF4-type structure, mixed conductor

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Authors: Sasan Talebnezhad, Saeed Pormahdian, Naghi Assali

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Homogeneous α-diimine nickel (II) catalyst complexes, with and without amino para-aryl position functionality, were synthesized. These complexes were immobilized on carboxyl, hydroxyl, and acyl chloride functionalized multi-walled carbon nanotubes to form five novel heterogeneous α-diiminonickel catalysts. Immobilization was performed by covalent or electrostatic bonding via methylaluminoxane (MAO) linker or amide linkage. Both the nature of α-diimine ligands and the kind of interaction between anchored catalyst complexes and multi-walled carbon nanotube surface influenced the catalytic performance, microstructure, and morphology of obtained polyethylenes. The catalyst prepared by amide bonding showed lowest relative weight loss in thermogravimetry analysis and highest activities up to 5863 gr PE mmol-1Ni.hr-1. This catalyst produced polyethylene with dense botryoidal morphology.

Keywords: α-diimine nickel (II) complexes, immobilization, multi-walled carbon nanotubes, ethylene polymerization

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Authors: Sasan Talebnezhad, Saeed Pourmahdian, Naghi Assali

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Homogeneous α-diimine nickel (II) catalyst complexes, with and without amino para-aryl position functionality, were synthesized. These complexes were immobilized on carboxyl, hydroxyl and acyl chloride functionalized multi-walled carbon nanotubes to form five novel heterogeneous α diiminonickel catalysts. Immobilization was performed by covalent or electrostatic bonding via methylaluminoxane (MAO) linker or amide linkage. Both the nature of α-diimine ligands and the kind of interaction between anchored catalyst complexes and multi-walled carbon nanotube surface influenced the catalytic performance, microstructure, and morphology of obtained polyethylenes. The catalyst prepared by amide bonding showed lowest relative weight loss in thermogravimetry analysis and highest activities up to 5863 gr PE mmol-1Ni.hr-1. This catalyst produced polyethylene with dense botryoidal morphology.

Keywords: α-diimine nickel (II) complexes, immobilization, multi-walled carbon nanotubes, ethylene polymerization

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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: Huanru Wang, Jianzhun Jiang

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At present, the preparation of the catalyst by carbon carrier is one of the improvement directions of the C₂ pre-hydrogenation catalyst. Carbon materials can be prepared from coal direct liquefaction residues, coconut shells, biomass, etc., and the pore structure of carbon carrier materials can be adjusted through the preparation process; at high temperatures, the carbon carrier itself also shows certain catalytic activity. Therefore, this paper mainly selected typical activated carbon and coconut shell carbon as carbon carrier materials, studied their microstructure and surface properties, prepared a series of carbon-based catalysts loaded with Pd, and investigated the effects of the content of promoter Ag and the concentration of reductant on the structure and performance of the catalyst and its catalytic performance for the pre hydrogenation of C₂. In this paper, the carbon supports from two sources and the catalysts prepared by them were characterized in detail. The results showed that the morphology and structure of different supports and the performance of the catalysts prepared were also obviously different. The catalyst supported on coconut shell carbon has a small specific surface area and large pore diameter. The catalyst supported on activated carbon has a large specific surface area and rich pore structure. The active carbon support is mainly a mixture of amorphous graphite and microcrystalline graphite. For the catalyst prepared with coconut shell carbon as the carrier, the sample is very uneven, and its specific surface area and pore volume are irregular. Compared with coconut shell carbon, activated carbon is more suitable as the carrier of the C₂ hydrogenation catalyst. The conversion of acetylene, methyl acetylene, and butadiene decreased, and the ethylene selectivity increased after Ag was added to the supported Pd catalyst. When the amount of promoter Ag is 0.01-0.015%, the catalyst has relatively good catalytic performance. Ag and Pd form an alloying effect, thus reducing the effective demand for Ag. The Pd Ag ratio is the key factor affecting the catalytic performance. When the addition amount of Ag is 0.01-0.015%, the dispersion of Pd on the carbon support surface can be significantly improved, and the size of active particles can be reduced. The Pd Ag ratio is the main factor in improving the selectivity of the catalyst. When the additional amount of sodium formate is 1%, the catalyst prepared has both high acetylene conversion and high ethylene selectivity.

Keywords: C₂ hydrogenation, activated carbon, Ag promoter, Pd catalysts

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Authors: Ahmed I. Osman, Jehad K. Abu-Dahrieh, David W. Rooney, Jillian Thompson

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The effect of loading of copper on the catalytic performance of different alumina support during the dehydration of methanol to dimethyl ether (DME) was performed in a fixed bed reactor. There are two levels of loading; low loading (1, 2, 4 and 6% Cu wt/wt) and high loading (10 and 15% Cu wt/wt) on both AC350 (alumina catalyst calcined at 350) and AC550 (alumina catalyst calcined at 550), to study the effect of loading and the effect of the support during methanol dehydration to DME (MTD). The catalysts were characterized by TGA, XRD, BET, TPD-NH3, TEM and DRIFT-Pyridine. Under reaction conditions where the temperature ranged from 180-300˚C with a WHSV= 12.1 h-1 it was found that all the catalysts calcined at 550˚C showed higher activity than those calcined at 350˚C. In this study, the optimum catalyst was 6% Cu/AC550. This catalyst showed a high degree of stability, had one half activity of the pure catalyst (AC550) and double the activity of the optimum catalyst calcined at 350˚C (6% Cu/AC350). So, we recommended 6% Cu/AC550 for the production of DME from methanol.

Keywords: bio-fuel, nano composite catalyst, DME, Cu-Al2O3

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Authors: Marasovic Branka, Aljinovic Zdravka, Poklepovic Tea

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Numerical methods like binomial and trinomial trees and finite difference methods can be used to price a wide range of options contracts for which there are no known analytical solutions. American options are the most famous of that kind of options. Besides numerical methods, American options can be valued with the approximation formulas, like Bjerksund-Stensland formulas from 1993 and 2002. When the value of American option is approximated by Bjerksund-Stensland formulas, the computer time spent to carry out that calculation is very short. The computer time spent using numerical methods can vary from less than one second to several minutes or even hours. However to be able to conduct a comparative analysis of numerical methods and Bjerksund-Stensland formulas, we will limit computer calculation time of numerical method to less than one second. Therefore, we ask the question: Which method will be most accurate at nearly the same computer calculation time?

Keywords: Bjerksund and Stensland approximations, computational analysis, finance, options pricing, numerical methods

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Authors: Ghadeer Jalloul, Nour Hijazi, Cassia Boyadjian, Hussein Awala, Mohammad N. Ahmad, ‎Ahmad Albadarin

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In this study, we applied Fe-sensitized TiO₂ supported over embryonic Beta zeolite (BEA) zeolite ‎for the photocatalytic degradation of Tetracycline (TC) antibiotic under visible light. Four different ‎samples having 20, 40, 60, and 100% w/w as a ratio of TiO₂/BEA were prepared. The ‎immobilization of solgel TiO₂ (33 m²/g) over BEA (390 m²/g) increased its surface area to (227 ‎m²/g) and enhanced its adsorption capacity from 8% to 19%. To expand the activity of TiO₂ ‎photocatalyst towards the visible light region (λ>380 nm), we explored two different metal ‎sensitization techniques with Iron ions (Fe³⁺). In the ion-exchange method, the substitutional cations ‎in the zeolite in TiO₂/BEA were exchanged with (Fe³⁺) in an aqueous solution of FeCl₃. In the ‎doping technique, solgel TiO₂ was doped with (Fe³⁺) from FeCl₃ precursor during its synthesis and ‎before its immobilization over BEA. (Fe-TiO₂/BEA) catalysts were characterized using SEM, XRD, ‎BET, UV-VIS DRS, and FTIR. After testing the performance of the various ion-exchanged catalysts ‎under blue and white lights, only (Fe-TiO₂/BEA 60%) showed better activity as compared to pure ‎TiO₂ under white light with 100 ppm initial catalyst concentration and 20 ppm TC concentration. As ‎compared to ion-exchanged (Fe-TiO₂/BEA), doped (Fe-TiO₂/BEA) resulted in higher photocatalytic ‎efficiencies under blue and white lights. The 3%-Fe-doped TiO₂/BEA removed 92% of TC ‎compared to 54% by TiO₂ under white light. The catalysts were also tested under real solar ‎irradiations. This improvement in the photocatalytic performance of TiO₂ was due to its higher ‎adsorption capacity due to BEA support combined with the presence of Iron ions that enhance the ‎visible light absorption and minimize the recombination effect by the charge carriers. ‎

Keywords: Tetracycline, photocatalytic degradation, immobilized TiO₂, zeolite, iron-doped TiO₂, ion-exchange

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Authors: Talat Baran

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The Suzuki C(sp2)-C(sp2) coupling reaction is considered to be one of the best ways for the synthesis of biaryl compounds. There are many studies reporting the catalytic performance of palladium catalyst in Suzuki coupling reactions. Natural biopolymer (such as zeolite, carbon, silica, and chitosan) supporting catalysts have been lately attracted interest because of their low-cost, nontoxicity, and eco-friendliness. One of the most important natural biopolymer is cellulose, which is widely considered as an eco-friendly biopolymer due to its biodegradable, non-toxic and renewable nature. In this study, (1) cellulose supported Pd(II) catalyst was synthesized (2) its chemical structure was characterized by FT-IR, SEM/EDAX, XRD, TG-DTG, ICP-OES techniques (3) to investigate the performance of the catalyst in Suzuki coupling reactions by using microwave irradiation technique (4) reusability of the catalyst was done under optimum conditions. This cellulose supported Pd(II) catalyst exhibited high selectivity and efficiency in Suzuki coupling reactions under mild conditions (50°C). High TON and TOF values were recorded for the catalyst. Also, the reusability tests showed the catalysts could be used for several times in consequence of reusability tests.

Keywords: palladium, cellulose, Schiff base, reusability

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Authors: Karolina Wieczorek, Zofia Przypaśniak

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Climate change is a rapidly growing threat to global health, and part of the responsibility to combat it lies within the healthcare sector itself, including adequate education of future medical professionals. To mitigate the consequences, the General Medical Council (GMC) has equipped medical schools with a list of outcomes regarding sustainability teaching. Students are expected to analyze the impact of the healthcare sector’s emissions on climate change. The delivery of the related teaching content is, however, often inadequate and insufficient time is devoted for exploration of the topics. Teaching curricula lack in-depth exploration of the learning objectives. This study aims to assess the extent and characteristics of climate change and sustainability subjects teaching in the curriculum of a chosen UK medical school (Barts and The London School of Medicine and Dentistry). It compares the data to the national average scores from the Climate Change and Sustainability Teaching (C.A.S.T.) in Medical Education Audit to draw conclusions about teaching on a regional level. This is a single-center audit of the timetabled sessions of teaching in the medical course. The study looked at the academic year 2020/2021 which included a review of all non-elective, core curriculum teaching materials including tutorials, lectures, written resources, and assignments in all five years of the undergraduate and graduate degrees, focusing only on mandatory teaching attended by all students (excluding elective modules). The topics covered were crosschecked with GMC Outcomes for graduates: “Educating for Sustainable Healthcare – Priority Learning Outcomes” as gold standard to look for coverage of the outcomes and gaps in teaching. Quantitative data was collected in form of time allocated for teaching as proxy of time spent per individual outcomes. The data was collected independently by two students (KW and ZP) who have received prior training and assessed two separate data sets to increase interrater reliability. In terms of coverage of learning outcomes, 12 out of 13 were taught (with the national average being 9.7). The school ranked sixth in the UK for time spent per topic and second in terms of overall coverage, meaning the school has a broad range of topics taught with some being explored in more detail than others. For the first outcome 4 out of 4 objectives covered (average 3.5) with 47 minutes spent per outcome (average 84 min), for the second objective 5 out of 5 covered (average 3.5) with 46 minutes spent (average 20), for the third 3 out of 4 (average 2.5) with 10 mins pent (average 19 min). A disproportionately large amount of time is spent delivering teaching regarding air pollution (respiratory illnesses), which resulted in the topic of sustainability in other specialties being excluded from teaching (musculoskeletal, ophthalmology, pediatrics, renal). Conclusions: Currently, there is no coherent strategy on national teaching of climate change topics and as a result an unstandardized amount of time spent on teaching and coverage of objectives can be observed.

Keywords: audit, climate change, sustainability, education

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Authors: Chengyu Dong, Shao-Yuan Leu

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Cellulosic ethanol production from lignocellulosic biomass can reduce our reliance on fossil fuel, mitigate climate change, and stimulate rural economic development. The relative low ethanol production (60 g/L) limits the economic viable of lignocellulose-based biorefinery. The ethanol production can be increased up to 80 g/L by removing nearly all the non-cellulosic materials, while the capital of the pretreatment process increased significantly. In this study, a fed-batch prehydrolysis simultaneously saccharification and fermentation process (PSSF) was designed to converse the sulfite pretreated softwood (~30% residual lignin) to high concentrations of ethanol (80 g/L). The liquefaction time of hydrolysis process was shortened down to 24 h by employing the fed-batch strategy. Washing out the spent liquor with water could eliminate the inhibition of the pretreatment spent liquor. However, the ethanol yield of lignocellulose was reduced as the fermentable sugars were also lost during the process. Fed-batch prehydrolyzing the while slurry (i.e. liquid plus solid fraction) pretreated softwood for 24 h followed by simultaneously saccharification and fermentation process at 28 °C can generate 80 g/L ethanol production. Fed-batch strategy is very effectively to eliminate the “solid effect” of the high gravity saccharification, so concentrating the cellulose to nearly 90% by the pretreatment process is not a necessary step to get high ethanol production. Detoxification of the pretreatment spent liquor caused the loss of sugar and reduced the ethanol yield consequently. The tolerance of yeast to inhibitors was better at 28 °C, therefore, reducing the temperature of the following fermentation process is a simple and valid method to produce high ethanol production.

Keywords: cellulosic ethanol, sulfite pretreatment, Fed batch PSSF, temperature

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Authors: Alvaro Ramírez, Martín Muñoz-Morales, Ester López- Fernández, Javier Llanos, C. Ania

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Carbon blacks are value-added materials typically produced through the incomplete combustion or thermal decomposition of hydrocarbons. Traditionally, they have been used as catalysts in many different applications, but in the last decade, their potential in green chemistry has gained significant attention. Among them, the electrochemical production of H₂O₂ has attracted interest because of their properties as high oxidant capacity or their industrial interest as a bleaching agent. Carbon blacks are commonly used in this application in a catalytic ink that is drop-casted on supporting electrodes and acts as catalysts for the electrochemical production of H₂O₂ through oxygen reduction reaction (ORR). However, the different structural and electrochemical behaviors of each type of carbon black influence their applications. In this line, the term ‘carbon black’, has to be considered as a generic name that does not guarantee any physicochemical properties if any further description is mentioned. In fact, different specific surface area (SSA), surface functional groups, porous structure, and electro catalysts effect seem very important for electrochemical applications, and considerable differences were found during the analysis of four types of carbon blacks. Thus, the aim of this work is to evaluate the influence of SSA, porous structure, oxygen functional groups, and structural defects to differentiate among these carbon blacks (e.g. Vulcan XC72, Superior Graphite Co, Printex XE2, and Prolabo) for H₂O₂ production via ORR, using carbon paper as electrode support with improved selectivity and efficiency. Results indicate that the number and size of pores, along with surface functional groups, are key parameters that significantly affect the overall process efficiency.

Keywords: carbon blacks, oxygen reduction reaction, hydrogen peroxide, porosity, surface functional groups

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Authors: Sam Derakhshan Deilami, Iain N. Kings, Lynne E. Macaskie, Brajendra K. Sharma, Anthony V. Bridgwater, Joseph Wood

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This paper reports the application of a bacteria-supported palladium catalyst to the hydrodeoxygenation (HDO) of pyrolysis bio-oil, towards producing an upgraded transport fuel. Biofuels are key to the timely replacement of fossil fuels in order to mitigate the emissions of greenhouse gases and depletion of non-renewable resources. The process is an essential step in the upgrading of bio-oils derived from industrial by-products such as agricultural and forestry wastes, the crude oil from pyrolysis containing a large amount of oxygen that requires to be removed in order to create a fuel resembling fossil-derived hydrocarbons. The bacteria supported catalyst manufacture is a means of utilizing recycled metals and second life bacteria, and the metal can also be easily recovered from the spent catalysts after use. Comparisons are made between bio-Pd, and a conventional activated carbon supported Pd/C catalyst. Bio-oil was produced by fast pyrolysis of beechwood at 500 C at a residence time below 2 seconds, provided by Aston University. 5 wt % BioPd/C was prepared under reducing conditions, exposing cells of E. coli MC4100 to a solution of sodium tetrachloropalladate (Na2PdCl4), followed by rinsing, drying and grinding to form a powder. Pd/C was procured from Sigma-Aldrich. The HDO experiments were carried out in a 100 mL Parr batch autoclave using ~20g bio-crude oil and 0.6 g bio-Pd/C catalyst. Experimental variables investigated for optimization included temperature (160-350C) and reaction times (up to 5 h) at a hydrogen pressure of 100 bar. Most of the experiments resulted in an aqueous phase (~40%) and an organic phase (~50-60%) as well as gas phase (<5%) and coke (<2%). Study of the temperature and time upon the process showed that the degree of deoxygenation increased (from ~20 % up to 60 %) at higher temperatures in the region of 350 C and longer residence times up to 5 h. However minimum viscosity (~0.035 Pa.s) occurred at 250 C and 3 h residence time, indicating that some polymerization of the oil product occurs at the higher temperatures. Bio-Pd showed a similar degree of deoxygenation (~20 %) to Pd/C at lower temperatures of 160 C, but did not rise as steeply with temperature. More coke was formed over bio-Pd/C than Pd/C at temperatures above 250 C, suggesting that bio-Pd/C may be more susceptible to coke formation than Pd/C. Reactions occurring during bio-oil upgrading include catalytic cracking, decarbonylation, decarboxylation, hydrocracking, hydrodeoxygenation and hydrogenation. In conclusion, it was shown that bio-Pd/C displays an acceptable rate of HDO, which increases with residence time and temperature. However some undesirable reactions also occur, leading to a deleterious increase in viscosity at higher temperatures. Comparisons are also drawn with earlier work on the HDO of Chlorella derived bio-oil manufactured from micro-algae via hydrothermal liquefaction. Future work will analyze the kinetics of the reaction and investigate the effect of bi-metallic catalysts.

Keywords: bio-oil, catalyst, palladium, upgrading

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Authors: S. F. H. Tasfy, N. A. M. Zabidi, M. S. Shaharun

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Carbon dioxide is highly thermochemical stable molecules where it is very difficult to activate the molecule and achieve higher catalytic conversion into alcohols or other hydrocarbon compounds. In this paper, series of the bimetallic Cu/ZnO-based catalyst supported by SBA-15 were systematically prepared via impregnation technique with different Cu: Zn ratio for hydrogenation of CO₂ to methanol. The synthesized catalysts were characterized by transmission electron microscopy (TEM), temperature programmed desorption, reduction, oxidation and pulse chemisorption (TPDRO), and surface area determination was also performed. All catalysts were tested with respect to the hydrogenation of CO₂ to methanol in microactivity fixed-bed reactor at 250^oC, 2.25 MPa, and H₂/CO₂ ratio of 3. The results demonstrate that the catalytic structure, activity, and methanol selectivity was strongly affected by the ratio between Cu: Zn, Where higher catalytic activity of 14 % and methanol selectivity of 92 % was obtained over Cu/ZnO-SBA-15 catalyst with Cu:Zn ratio of 7:3 wt. %. Comparing with the single catalyst, the synergetic between Cu and Zn provides additional active sites to adsorb more H₂ and CO₂ and accelerate the CO₂ conversion, resulting in higher methanol production under mild reaction conditions.

Keywords: hydrogenation of carbon dioxide, methanol synthesis, Cu/ZnO-based catalyst, mesoporous silica (SBA-15), metal ratio

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Authors: Selen Demirtas-Zorbaz

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This study aimed to determine if there is any relation between child–parent relationships and parental self-efficacy. The participants of this study are 208 parents, and 82,5% of them are mothers. The children’s age range are differed from 4 to 13 (x̄=7,8). The results showed that there is a significant positive correlation between positive relationship with parents and parental self-efficacy (r=0.52, p < .01); and significant negative correlation between conflict with parents and parental self-efficacy (r=-0.28, p < .01). Also, findings reveal that there was no significant correlation between the time spent with the child and conflict with parents (r=-0.08, p>.05). It was also found that there was no significant correlation between the time spends with the child and positive relationship with parents (r=0.08, p > 0.5). In addition to this; regression analysis’ results indicated that parental self-efficacy is significant predictors of conflict (β=-.268, t=-4.002, p < .001) and positive relationship with parents (β =.519, t= 8.733, p < .001) whereas time spent with children is not (β =-.070, t=-1,045, p > .05 for conflict; β =.061, t=1.023, p > .05 for positive relationship with parents).

Keywords: child-parent relationship, conflict with parents, positive relationship with parents, parental efficacy

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Authors: A. Goma Amira, U. E. Mahrous

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Measuring the effect of perinatal lead exposure on learning ability of offspring is considered as a sensitive and selective index for providing an early marker for central nervous system damage produced by this toxic metal. A total of 35 Sprague-Dawley adult rats were used to investigate the effect of lead acetate toxicity on behavioral patterns of adult female rats and learning ability of offspring. Rats were allotted into 4 groups, group one received 1g/l lead acetate (n=10), group two received 1.5g/l lead acetate (n=10), group three received 2g/l lead acetate in drinking water (n=10), and control group did not receive lead acetate (n=5) from 8th day of pregnancy till weaning of pups. The obtained results revealed a dose-dependent increase in the feeding time, drinking frequency, licking frequency, scratching frequency, licking litters, nest building, and retrieving frequencies, while standing time increased significantly in rats treated with 1.5g/l lead acetate than other treated groups and control. On the contrary, lying time decreased gradually in a dose-dependent manner. Moreover, movement activities were higher in rats treated with 1g/l lead acetate than other treated groups and control. Furthermore, time spent in closed arms was significantly lower in rats given 2g/l lead acetate than other treated groups, while they spent significantly much time spent in open arms than other treated groups which could be attributed to occurrence of adaptation. Furthermore, number of entries in open arms was-dose dependent. However, the ratio between open/closed arms revealed a significant decrease in rats treated with 2g/l lead acetate than the control group.

Keywords: lead toxicity, rats, learning ability, behavior

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Authors: Shady S. Hassan, Brijesh K. Tiwari, Gwilym A. Williams, Amit K. Jaiswal

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EU is known as the destination with the highest rate of the coffee consumption per capita in the world. Spent coffee grounds (SCG) are the main by-product of coffee brewing. SCG is either disposed as a solid waste or employed as compost, although the polysaccharides from such lignocellulosic biomass might be used as feedstock for fermentation processes. However, SCG as a lignocellulose have a complex structure and pretreatment process is required to facilitate an efficient enzymatic hydrolysis of carbohydrates. However, commonly used pretreatment methods, such as chemical, physico-chemical and biological techniques are still insufficient to meet optimal industrial production requirements in a sustainable way. Ultrasound is a promising candidate as a sustainable green pretreatment solution for lignocellulosic biomass utilization in a large scale biorefinery. Thus, ultrasound pretreatment of SCG without adding harsh chemicals investigated as a green technology to enhance enzyme hydrolysis. In the present work, ultrasound pretreatment experiments were conducted on SCG using different ultrasound frequencies (25, 35, 45, 130, and 950 kHz) for 60 min. Regardless of ultrasound power, low ultrasound frequency is more effective than high ultrasound frequency in pretreatment of biomass. Ultrasound pretreatment of SCG (at ultrasound frequency of 25 kHz for 60 min) followed by enzymatic hydrolysis resulted in total reducing sugars of 56.1 ± 2.8 mg/g of biomass. Fourier transform Infrared Spectroscopy (FTIR) was employed to investigate changes in functional groups of biomass after pretreatment, while high-performance liquid chromatography (HPLC) was employed for determination of glucose. Pretreatment of lignocellulose by low frequency ultrasound in water only was found to be an effective green approach for SCG to improve saccharification and glucose yield compared to native biomass. Pretreatment conditions will be optimized, and the enzyme hydrolysate will be used as media component substitute for the production of ethanol.

Keywords: lignocellulose, ultrasound, pretreatment, spent coffee grounds

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Authors: M. Shopska, D. Paneva, G. Kadinov, Z. Cherkezova-Zheleva, I. Mitov

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The iron containing materials are used as catalysts in different processes. The chemical methods of their synthesis use toxic and expensive chemicals; sophisticated devices; energy consumption processes that raise their cost. Besides, dangerous waste products are formed. At present time such syntheses are out of date and wasteless technologies are indispensable. The bioinspired technologies are consistent with the ecological requirements. Different microorganisms participate in the biomineralization of the iron and some phytochemicals are involved, too. The methods for biogenic production of iron containing materials are clean, simple, nontoxic, realized at ambient temperature and pressure, cheaper. The biogenic iron materials embrace different iron compounds. Due to their origin these substances are nanosized, amorphous or poorly crystalline, porous and have number of useful properties like SPM, high magnetism, low toxicity, biocompatibility, absorption of microwaves, high surface area/volume ratio, active sites on the surface with unusual coordination that distinguish them from the bulk materials. The biogenic iron materials are applied in the heterogeneous catalysis in different roles - precursor, active component, support, immobilizer. The application of biogenic iron oxide materials gives rise to increased catalytic activity in comparison with those of abiotic origin. In our study we investigated the catalytic behavior of biomasses obtained by cultivation of Leptothrix bacteria in three nutrition media – Adler, Fedorov, and Lieske. The biomass composition was studied by Moessbauer spectroscopy and transmission IRS. Catalytic experiments on CO oxidation were carried out using in situ DRIFTS. Our results showed that: i) the used biomasses contain α-FeOOH, γ-FeOOH, γ-Fe2O3 in different ratios; ii) the biomass formed in Adler medium contains γ-FeOOH as main phase. The CO conversion was about 50% as evaluated by decreased integrated band intensity in the gas mixture spectra during the reaction. The main phase in the spent sample is γ-Fe2O3; iii) the biomass formed in Lieske medium contains α-FeOOH. The CO conversion was about 20%. The main phase in the spent sample is α-Fe2O3; iv) the biomass formed in Fedorov medium contains γ-Fe2O3 as main phase. CO conversion in the test reaction was about 19%. The results showed that the catalytic activity up to 200°C resulted predominantly from α-FeOOH and γ-FeOOH. The catalytic activity at temperatures higher than 200°C was due to the formation of γ-Fe2O3. The oxyhydroxides, which are the principal compounds in the biomass, have low catalytic activity in the used reaction; the maghemite has relatively good catalytic activity; the hematite has activity commensurate with that of the oxyhydroxides. Moreover it can be affirmed that catalytic activity is inherent in maghemite, which is obtained by transformation of the biogenic lepidocrocite, i.e. it has biogenic precursor.

Keywords: nanosized biogenic iron compounds, catalytic behavior in reaction of CO oxidation, in situ DRIFTS, Moessbauer spectroscopy

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Authors: M. T. Asadollahzadeh, A. Ghasemian, A. R. Saraeian, H. Resalati, P. R. Lennartsson, M. J. Taherzadeh

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Since filamentous fungi are capable of assimilating several types of sugars (hexoses and pentoses), they are potential candidates for bioconversion of spent sulfite liquor (SSL). Three filamentous fungi such as Aspergillus oryzae, Mucor indicus, and Rhizopus oryzae were investigated in this work. The SSL was diluted in order to obtain concentrations of 50, 60, 70, 80, and 90% and supplemented with two types of nutrients. The results from cultivations in shake flask showed that A. oryzae and M. indicus were not able to grow in pure SSL and SSL90% while R. oryzae could grow only in SSL50% and SSL60%. Cultivation with A. oryzae resulted in the highest yield of produced fungal biomass, while R. oryzae cultivation resulted in the lowest fungal biomass yield. Although, the mediums containing yeast extract, (NH₄)₂SO₄, KH₂PO₄, CaCl₂∙2H₂O, and MgSO₄∙7H₂O as nutrients supplementations produced higher fungal biomass compared to the mediums containing NH₄H₂PO₄ and ammonia, but there was no significant difference between two types of nutrients in terms of sugars and acetic acid consumption rate. The sugars consumption in M. indicus cultivation was faster than A. oryzae and R. oryzae cultivation. Acetic acid present in SSL was completely consumed during cultivation of all fungi. M. indicus was the best and fastest ethanol producer from SSL among the fungi examined, when yeast extract and salts were used as nutrients supplementations. Furthermore, no further improvement in ethanol concentration and rate of sugars consumption was obtained in medium supplemented with NH₄H₂PO₄ and ammonia compared to medium containing yeast extract, (NH₄)₂SO₄, KH₂PO₄, CaCl₂∙2H₂O, and MgSO₄∙7H₂O. On the other hand, the higher dilution of SSL resulted in a better fermentability, and better consumption of sugars and acetic acid.

Keywords: ethanol, filamentous fungi, fungal biomass, spent sulfite liquor

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Authors: Bhavna Malik

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The study is build on a theoretical framework that links characteristics of job, key attitudes and intention to leave, why faculty may be disengaging from institutional service. The literature indicates that job characteristics, key attitudes and intention to leave are very important for effective organizational functioning. In general, the literature showed that some job characteristics might be the antecedents of job satisfaction and the aggregate variable job scope was positively associated with organizational commitment, and these key attitudes predicted intention to leave negatively. The present study attempted to propose a new integrative model of the relationships among job characteristics, key attitudes, and intention to leave. The main purpose of the present study is to examine the effects of job characteristics on intention to leave. While examining the role of job characteristics, the mediating roles of key attitudes were taken into account in order to better understand how job characteristics affect the exhibition of intention to leave. The secondary purpose is to investigate the effects of job characteristics on key attitudes, and the effects of key attitudes on intention to leave. Job characteristics of remuneration, resource for professional activities, career opportunities were positively associated with the work attitude of job satisfaction. The aggregate job scope was positively associated with the work attitude of organizational commitment although no single job characteristic was significantly associated with organizational commitment. Commitment, however, did not significantly affect time spent on institutional service. Two job characteristics—time spent on research and time spent on teaching—were negatively associated with this behavior. In general, the literature showed that some job characteristics might be the antecedents of job satisfaction and the aggregate variable job scope was positively associated with organizational commitment, and these key attiudes predicted intention to leave negatively. In turn, job satisfaction and organizational commitment were negatively associated with the intention to leave. In addition to these, organizational commitment was negatively associated with the intention to leave. However, no significant direct association was found between job characteristics and intention to leave.

Keywords: Job Characteristics Model, job satisfaction, organizational commitment, intention to leave

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Authors: Peter Kus, Anna Ostroverkh, Yurii Yakovlev, Yevheniia Lobko, Roman Fiala, Ivan Khalakhan, Vladimir Matolin

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Hydrogen economy is a concept of low-emission society which harvests most of its energy from renewable sources (e.g., wind and solar) and in case of overproduction, electrochemically turns the excess amount into hydrogen, which serves as an energy carrier. Proton exchange membrane water electrolyzers (PEMWE) are the backbone of this concept. By fast-response electricity to hydrogen conversion, the PEMWEs will not only stabilize the electrical grid but also provide high-purity hydrogen for variety of fuel cell powered devices, ranging from consumer electronics to vehicles. Wider commercialization of PEMWE technology is however hindered by high prices of noble metals which are necessary for catalyzing the redox reactions within the cell. Namely, platinum for hydrogen evolution reaction (HER), running on cathode, and iridium for oxygen evolution reaction (OER) on anode. Possible way of how to lower the loading of Pt and Ir is by using conductive high-surface nanostructures as catalyst supports in conjunction with thin-film catalyst deposition. The presented study discusses unconventional technique of membrane electron assembly (MEA) preparation. Noble metal catalysts (Pt and Ir) were magnetron sputtered in very low loadings onto the surface of porous sublayers (located on gas diffusion layer or directly on membrane), forming so to say localized three-phase boundary. Ultrasonically sprayed corrosion resistant TiC-based sublayer was used as a support material on anode, whereas magnetron sputtered nanostructured etched nitrogenated carbon (CNx) served the same role on cathode. By using this configuration, we were able to significantly decrease the amount of noble metals (to thickness of just tens of nanometers), while keeping the performance comparable to that of average state-of-the-art catalysts. Complex characterization of prepared supported catalysts includes in-cell performance and durability tests, electrochemical impedance spectroscopy (EIS) as well as scanning electron microscopy (SEM) imaging and X-ray photoelectron spectroscopy (XPS) analysis. Our research proves that magnetron sputtering is a suitable method for thin-film deposition of electrocatalysts. Tested set-up of thin-film supported anode and cathode catalysts with combined loading of just 120 ug.cm⁻² yields remarkable values of specific current. Described approach of thin-film low-loading catalyst deposition might be relevant when noble metal reduction is the topmost priority.

Keywords: hydrogen economy, low-loading catalyst, magnetron sputtering, proton exchange membrane water electrolyzer

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Authors: Thabelo Nelushi, Michael Scurrell, Tumelo Seadira

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Global warming is one of the most important environmental issues which arise from occurrence of gases such as carbon dioxide (CO2) and methane (CH4) in the atmosphere. Exposure to these greenhouse gases results in health risk. Hydrogen is regarded as an alternative energy source which is a clean energy carrier for the future. There are different methods to produce hydrogen such as steam reforming, coal gasification etc., however the challenge with these processes is that they emit CO and CO2 gases and are costly. Photocatalytic reforming is a substitute process which is fascinating due to the combination of solar energy and renewable sources and the use of semiconductor materials such as catalysts. TiO2 is regarded as the most promising catalysts. TiO2 nanoparticles prepared by hydrothermal method and Ag/TiO2 are being investigated for photocatalytic production of hydrogen from butanol. The samples were characterized by raman spectroscopy, TEM/SEM, XRD, XPS, EDAX, DRS and BET surface area. 2 wt% Ag-doped TiO2 nanoparticle showed enhanced hydrogen production compared to a non-doped TiO2. The results of characterization and photoactivity shows that TiO2 nanoparticles play a very important role in producing high hydrogen by utilizing solar irradiation.

Keywords: butanol, hydrogen production, silver particles, TiO2 nanoparticles

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Authors: Alexandre Chagnes

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Lithium-ion battery is the technology of choice in the development of electric vehicles. This technology is now mature, although there are still many challenges to increase their energy density while ensuring an irreproachable safety of use. For this goal, it is necessary to develop new cathodic materials that can be cycled at higher voltages and electrolytes compatible with these materials. But the challenge does not only concern the production of efficient batteries for the electrochemical storage of energy since lithium-ion battery technology relies on the use of critical and/or strategic value resources. It is, therefore, crucial to include Lithium-ion batteries development in a circular economy approach very early. In particular, optimized recycling and reuse of battery components must both minimize their impact on the environment and limit geopolitical issues related to tensions on the mineral resources necessary for lithium-ion battery production. Although recycling will never replace mining, it reduces resource dependence by ensuring the presence of exploitable resources in the territory, which is particularly important for countries like France, where exploited or exploitable resources are limited. This conference addresses the development of a new hydrometallurgical process combining leaching of cathodic material from spent lithium-ion battery in acidic chloride media and solvent extraction process. Most of recycling processes reported in the literature rely on the sulphate route, and a few studies investigate the potentialities of the chloride route despite many advantages and the possibility to develop new chemistry, which could get easier the metal separation. The leaching mechanisms and the solvent extraction equilibria will be presented in this conference. Based on the comprehension of the physicochemistry of leaching and solvent extraction, the present study will introduce a new hydrometallurgical process for the production of cobalt, nickel, manganese and lithium from spent cathodic materials.

Keywords: lithium-ion battery, recycling, hydrometallurgy, leaching, solvent extraction

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