Search results for: nickel catalysts

Authors: Imran Hanif, Amanda Persdotter, Sedigheh Bigdeli, Jesper Liske, Torbjorn Jonsson

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Renewable fuels such as biomass/waste for power production is an attractive alternative to fossil fuels in order to achieve a CO₂ -neutral power generation. However, the combustion results in the release of corrosive species. This puts high demands on the corrosion resistance of the alloys used in the boiler. Stainless steels containing nickel and/or nickel containing coatings are regarded as suitable corrosion resistance material especially in the superheater regions. However, the corrosive environment in the boiler caused by the presence of water vapour and reactive alkali very rapidly breaks down the primary protection, i.e., the Cr-rich oxide scale formed on stainless steels. The lifetime of the components, therefore, relies on the properties of the oxide scale formed after breakaway, i.e., the secondary protection. The aim of the current study is to investigate the role of varying nickel content (0–82%) on the high-temperature corrosion of model alloys with 18% Cr (Fe in balance) in the laboratory mimicking industrial conditions at 600°C. The influence of nickel is investigated on both the primary protection and especially the secondary protection, i.e., the scale formed after breakaway, during the oxidation/corrosion process in the dry O₂ (primary protection) and more aggressive environment such as H₂O, K₂CO₃ and KCl (secondary protection). All investigated alloys experience a very rapid loss of the primary protection, i.e., the Cr-rich (Cr, Fe)₂O₃, and the formation of secondary protection in the aggressive environments. The microstructural investigation showed that secondary protection of all alloys has a very similar microstructure in all more aggressive environments consisting of an outward growing iron oxide and inward growing spinel-oxide (Fe, Cr, Ni)₃O₄. The oxidation kinetics revealed that it is possible to influence the protectiveness of the scale formed after breakaway (secondary protection) through the amount of nickel in the alloy. The difference in oxidation kinetics of the secondary protection is linked to the microstructure and chemical composition of the complex spinel-oxide. The detailed microstructural investigations were carried out using the extensive analytical techniques such as electron back scattered diffraction (EBSD), energy dispersive X-rays spectroscopy (EDS) via the scanning and transmission electron microscopy techniques and results are compared with the thermodynamic calculations using the Thermo-Calc software.

Keywords: breakaway corrosion, EBSD, high-temperature oxidation, SEM, TEM

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Authors: Ana M. Antolín, Sandra Contreras, Francesc Medina, Didier Tichit

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Introduction: High levels of nitrates (> 50 ppm NO3-) in drinking water are potentially risky to human health. In the recent years, the trend of nitrate concentration in groundwater is rising in the EU and other countries. Conventional catalytic nitrate reduction processes into N2 and H2O lead to some toxic intermediates and by-products, such as NO2-, NH4+, and NOx gases. Alternatively, photocatalytic nitrate removal using solar irradiation and heterogeneous catalysts is a very promising and ecofriendly technique. It has been scarcely performed and more research on highly efficient catalysts is still needed. In this work, different nanocatalysts supported on Aeroxide Titania P25 (P25) have been prepared varying: 0.5-4 % wt. Ag); Pt (2, 4 % wt.); Pt precursor (H2PtCl6/K2PtCl6); and impregnation order of both metals. Pt was chosen in order to increase the selectivity to N2 and decrease that to NO2-. Catalysts were characterized by nitrogen physisorption, X-Ray diffraction, UV-visible spectroscopy, TEM and X Ray-Photoelectron Spectroscopy. The aim was to determine the influence of the composition and the preparation method of the catalysts on the conversion and selectivity in the nitrate reduction, as well as going through an overall and better understanding of the process. Nanocatalysts synthesis: For the mono and bimetallic catalysts preparation, wise-drop wetness impregnation of the precursors (AgNO3, H2PtCl6, K2PtCl6) followed by a reduction step (NaBH4) was used to obtain the metal colloids. Results and conclusions: Denitration experiments were performed in a 350 mL PTFE batch reactor under inert standard operational conditions, ultraviolet irradiations (λ=254 nm (UV-C); λ=365 nm (UV-A)), and presence/absence of hydrogen gas as a reducing agent, contrary to most studies using oxalic or formic acid. Samples were analyzed by Ionic Chromatography. Blank experiments using respectively P25 (dark conditions), hydrogen only and UV irradiations without hydrogen demonstrated a clear influence of the presence of hydrogen on nitrate reduction. Also, they demonstrated that UV irradiation increased the selectivity to N2. Interestingly, the best activity was obtained under ultraviolet lamps, especially at a closer wavelength to visible light irradiation (λ = 365 nm) and H2. 2% Ag/P25 leaded to the highest NO3- conversion among the monometallic catalysts. However, nitrite quantities have to be diminished. On the other hand, practically no nitrate conversion was observed with the monometallics based on Pt/P25. Therefore, the amount of 2% Ag was chosen for the bimetallic catalysts. Regarding the bimetallic catalysts, it is observed that the metal impregnation order, amount and Pt precursor highly affects the results. Higher selectivity to the desirable N2 gas is obtained when Pt was firstly added, especially with K2PtCl6 as Pt precursor. This suggests that when Pt is secondly added, it covers the Ag particles, which are the most active in this reaction. It could be concluded that Ag allows the nitrate reduction step to nitrite, and Pt the nitrite reduction step toward the desirable N2 gas.

Keywords: heterogeneous catalysis, hydrogenation, nanocatalyst, nitrate removal, photocatalysis

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Authors: Tahir Ahmad, M. Kamran, R. Ahmad, M. T. Z. Butt

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Hybrid aluminum metal matrix composites with 1, 2, 3 and 4 wt. % of silica sand nanoparticles and electro-less nickel coated carbon fibers were successfully developed using sand casting technique. Epoxy coating of carbon fibers was removed and phosphorous-nickel coating was successfully applied via electro-less route. The developed hybrid composites were characterized using micro hardness tester, tensile testing, and optical microscopy. The gradual increase of reinforcing phases yielded improved mechanical properties such as hardness and tensile strength. The increase in hardness was attributed to the presence of silica sand nanoparticles whereas electro-less nickel coated carbon fibers enhanced the tensile properties of developed hybrid composites. The microstructure of the developed hybrid composites revealed the homogeneous distribution of both carbon fibers and silica sand nanoparticles in aluminum based hybrid composites. The formation of dendrite microstructure is the main cause of improving mechanical properties.

Keywords: aluminum based hybrid composites, mechanical properties, microstructure, microstructure and mechanical properties relationship

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Authors: A. Yönetken, A. Erol, A. Yakar, G. Peşmen

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The microstructure, mechanical properties and metalgraphic characteristics of Ni plated AlN-Astaloy Cr-M powders were investigated using specimens produced by tube furnace sintering at 1000-1400 °C temperature. A uniform nickel layer on AlN powders was deposited prior to sintering using electroless plating technique. A composite consisting of ternary additions, metallic phase, Ni and ceramic phase AlN within a matrix of Astaloy Cr-M had been prepared under Ar shroud and then tube furnace sintered. The experimental results carried out by using XRD (X-Ray Diffraction) and SEM (Scanning Electron Microscope) for composition (10% AlN-Astaloy Cr-M) 10% Ni at 1400 °C suggest that the best properties as 132.45HB and permittivity were obtained at 1400 °C.

Keywords: composite, electroless nickel plating, powder metallurgy, sintering

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Authors: Kalyani Mer

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Hydrogen peroxide (H₂O₂) is one of the most efficient and commonly used oxidants in in-situ chemical oxidation (ISCO) of organic contaminants. In the present study, we investigated the activation of H₂O₂ by heavy metal (nickel and lead metal ions) loaded biochar for phenol degradation in an aqueous solution (concentration = 100 mg/L). It was found that H₂O₂ can be effectively activated by biochar, which produces hydroxyl (•OH) radicals owing to an increase in the formation of persistent free radicals (PFRs) on biochar surface. Ultrasound treated (30s duration) biochar, chemically activated by 30% phosphoric acid and functionalized by diethanolamine (DEA) was used for the adsorption of heavy metal ions from aqueous solutions. It was found that modified biochar could remove almost 60% of nickel in eight hours; however, for lead, the removal efficiency reached up to 95% for the same time duration. The heavy metal loaded biochar was further used for the degradation of phenol in the absence and presence of H₂O₂ (20 mM), within 4 hours of reaction time. The removal efficiency values for phenol in the presence of H₂O₂ were 80.3% and 61.9%, respectively, by modified biochar loaded with nickel and lead metal ions. These results suggested that the biochar loaded with nickel exhibits a better removal capacity towards phenol than the lead loaded biochar when used in H₂O₂ based oxidation systems. Meanwhile, control experiments were set in the absence of any activating biochar, and the removal efficiency was found to be 19.1% when only H₂O₂ was added in the reaction solution. Overall, the proposed approach serves a dual purpose of using biochar for heavy metal ion removal and treatment of organic contaminants by further using the metal loaded biochar for H₂O₂ activation in ISCO processes.

Keywords: biochar, ultrasound, heavy metals, in-situ chemical oxidation, chemical activation

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

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

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

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Authors: Ali Noorian

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Crude oil contains various compounds of hydrocarbons but low concentrations of inorganic compounds or metals. Vanadium and Nickel are the most common metals in crude oil. These metals usually exist in solution in the oil and residual fuel oil in the refining process is condensed. Deleterious effects of metals in petroleum have been known for some time. These metals do not only contaminate the product but also cause intoxication and loss of catalyst and corrosion to equipment. In this study, removal of heavy metals and petroleum residues were investigated. These methods include physical, chemical and biological treatment processes. For example, processes such as solvent extraction and hydro-catalytic and catalytic methods are effective and practical methods, but typically often have high costs and cause environmental pollution. Furthermore, biological methods that do not cause environmental pollution have been discussed in recent years, but these methods have not yet been industrialized.

Keywords: removal, metal, heavy oil, nickel, vanadium

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Authors: Shivam Yadav, Neelam Atri

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

Keywords: antioxidative system, arsenic, cyanobacteria, nickel

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

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

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

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Authors: Tomasz Łęga, Marta Sosnowska, Mirosława Panasiuk, Lilit Hovhannisyan, Beata Gromadzka, Marcin Olszewski, Sabina Zoledowska, Dawid Nidzworski

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Toxic heavy metal ion contamination of industrial wastewater has recently become a significant environmental concern in many regions of the world. Although the majority of heavy metals are naturally occurring elements found on the earth's surface, anthropogenic activities such as mining and smelting, industrial production, and agricultural use of metals and metal-containing compounds are responsible for the majority of environmental contamination and human exposure. The permissible limits (ppm) for heavy metals in food, water and soil are frequently exceeded and considered hazardous to humans, other organisms, and the environment as a whole. Human exposure to highly nickel-polluted environments causes a variety of pathologic effects. In 2008, nickel received the shameful name of “Allergen of the Year” (GILLETTE 2008). According to the dermatologist, the frequency of nickel allergy is still growing, and it can’t be explained only by fashionable piercing and nickel devices used in medicine (like coronary stents and endoprostheses). Effective remediation methods for removing heavy metal ions from soil and water are becoming increasingly important. Among others, methods such as chemical precipitation, micro- and nanofiltration, membrane separation, conventional coagulation, electrodialysis, ion exchange, reverse and forward osmosis, photocatalysis and polymer or carbon nanocomposite absorbents have all been investigated so far. The importance of environmentally sustainable industrial production processes and the conservation of dwindling natural resources has highlighted the need for affordable, innovative biosorptive materials capable of recovering specific chemical elements from dilute aqueous solutions. The use of combinatorial phage display techniques for selecting and recognizing material-binding peptides with a selective affinity for any target, particularly inorganic materials, has gained considerable interest in the development of advanced bio- or nano-materials. However, due to the limitations of phage display libraries and the biopanning process, the accuracy of molecular recognition for inorganic materials remains a challenge. This study presents the isolation, identification and characterisation of metal binding phage clones that preferentially recover nickel.

Keywords: Heavy metal recovery, cleaning water, phage display, nickel

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

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

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

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Authors: Rakesh Hajiyani, Chetan Chauhan, Harshkant Jethva, Mihir Joshi

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Metal bis-thiourea type organo-metallic crystals are popular as non-linear optical materials. Bis-thiourea nickel barium chloride was synthesized and crystals were grown by slow aqueous solvent evaporation technique. The transparent and colorless crystals having maximum dimensions of 13 mm x 8 mm x 2.2 mm were obtained. The EDAX was carried out to estimate the content of nickel and barium in the grown crystals. The powder XRD analysis suggested orthorhombic crystal structure with unit cell parameters as: a= 9.70 Å, b= 10.68 Å and c= 17.95 Å. The FTIR spectroscopy study confirmed the presence of various functional groups. The UV-vis spectroscopy study indicated that the crystals were transparent in the visible region with 90% transmittance level further optical parameters were studied. From the TGA it was found that the crystals remained stable up to 170 0C and then decomposed through two decomposition stages. The dielectric study was carried out in the frequency range of applied field from 500 Hz to 1 MHz. The variations of dielectric constant, dielectric loss were studied with frequency. It was found that the dielectric constant and the dielectric loss decreased as the frequency of applied field increased. The results are discussed.

Keywords: crystal growth, dielectric study, optical parameters, organo-metallic crystals, powder xrd, slow evaporation technique, TGA

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Authors: Renzhi Qi, Zhaoping Zhong

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Under the dual pressure of the global energy crisis and environmental pollution, avoiding the consumption of non-renewable fossil fuels based on carbon as the energy carrier and developing and utilizing non-carbon energy carriers are the basic requirements for the future new energy economy. Electrocatalyst for water splitting plays an important role in building sustainable and environmentally friendly energy conversion. The oxygen evolution reaction (OER) is essentially limited by the slow kinetics of multi-step proton-electron transfer, which limits the efficiency and cost of water splitting. In this work, CeO₂@NiCo-NRGO/NF hybrid materials were prepared using nickel foam (NF) and nitrogen-doped reduced graphene oxide (NRGO) as conductive substrates by multi-step hydrothermal method and were used as highly efficient catalysts for OER. The well-connected nanosheet array forms a three-dimensional (3D) network on the substrate, providing a large electrochemical surface area with abundant catalytic active sites. The doping of CeO₂ in NiCo-NRGO/NF electrocatalysts promotes the dispersion of substances and its synergistic effect in promoting the activation of reactants, which is crucial for improving its catalytic performance against OER. The results indicate that CeO₂@NiCo-NRGO/NF only requires a lower overpotential of 250 mV to drive the current density of 10 mA cm-2 for an OER reaction of 1 M KOH, and exhibits excellent stability at this current density for more than 10 hours. The double layer capacitance (Cdl) values show that CeO₂@NiCo-NRGO/NF significantly affects the interfacial conductivity and electrochemically active surface area. The hybrid structure could promote the catalytic performance of oxygen evolution reaction, such as low initial potential, high electrical activity, and excellent long-term durability. The strategy for improving the catalytic activity of NiCo-LDH can be used to develop a variety of other electrocatalysts for water splitting.

Keywords: CeO₂, reduced graphene oxide, NiCo-layered double hydroxide, oxygen evolution reaction

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Authors: Naina Deshmukh

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With the wide production, consumption, and disposal of pesticides in the world, the concerns over their human and environmental health impacts are rapidly growing. Among developing treatment technologies, Ultrasonication, as an emerging and promising technology for the removal of pesticides in the aqueous environment, has attracted the attention of many researchers in recent years. The degradation of acephate in aqueous solutions was investigated under the influence of ultrasound irradiation (20 kHz) in the presence of heterogeneous catalysts titanium dioxide (TiO2) and Zinc oxide (ZnO). The influence of various factors such as amount of catalyst (0.25, 0.5, 0.75, 1.0, 1.25 g/l), initial acephate concentration (100, 200, 300, 400 mg/l), and pH (3, 5, 7, 9, 11) were studied. The optimum catalyst dose was found to be 1 g/l of TiO2 and 1.25 g/l of ZnO for acephate at 100 mg/l, respectively. The maximum percentage degradation of acephate was observed at pH 11 for catalysts TiO2 and ZnO, respectively.

Keywords: ultrasonic degradation, acephate, TiO2, ZnO, heterogeneous catalyst

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Authors: Islam Zeb

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The water of poor quality used for irrigation purposes has the potential to be the direct source of contamination and a vehicle for spreading contamination in the field. A number of wide-ranging review articles have been published that highlight irrigation water as a source of heavy metals toxicity which leads to chronic diseases in the human body. Here a study was planned to determine the microbial and heavy metals status of irrigation water collected from various locations of district Swat in various months. The analyses were carried out at the Environmental Horticulture Laboratory, Department of Horticulture, The University of Agriculture Peshawar, during the year 2018 – 19. The experiment was laid out in Randomized Complete Block Design (RCBD) with two factors and three replicates. Factor A consist of different locations and factor B represent various months. The result of heavy metals concentration in different regions, maximum Lead, Cadmium, Chromium, Nickel and Copper (4.27, 0.56, 0.81, 1.33 and 1.51 mg L-1 respectively) were noted for the irrigation water samples collected from Mingora while minimum Lead, Cadmium, Chromium, Nickel and Copper concentration (2.59, 0.30, 0.27, 0.40 and 0.54 mg L-1 respectively) were noted for the samples of matta. Whereas results of heavy metals content in irrigation water samples for various months maximum content of Lead, Cadmium, Chromium, Nickel and Copper (4.56, 0.63, 1.15, 1.31 and 1.48 mg L-1 respectively) were noted for the samples collected in Jan/Feb while lowest values for Lead, Cadmium, Chromium, Nickel and Copper (2.38, 0.24, 0.21, 0.41 and 0.52 mg L-1 respectively) were noted in the samples of July/August. A significant interaction was found for all the studied parameters. It was concluded that the concentration of heavy metal was maximum in irrigation water samples collected from the Mingora location during the month of Jan/Feb because Mingora is the most polluted area as compared to other studied regions, whereas the water content in winter goes to freeze and mostly contaminated water is used for irrigation purposes.

Keywords: irrigation water, various months, different regions, heavy metals contamination, Swat

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Authors: Shalini Arora, Sri Sivakumar

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

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

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Authors: Payam Rasoulnia, Seyyed Mohammad Mousavi

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Heavy fuel oil firing power plants produce huge amounts of ashes as solid wastes, which seriously need to be managed and processed. Recycling precious metals of V and Ni from these oil-fired ashes which are considered as secondary sources of metals recovery, not only has a great economic importance for use in industry, but also it is noteworthy from the environmental point of view. Vanadium is an important metal that is mainly used in the steel industry because of its physical properties of hardness, tensile strength, and fatigue resistance. It is also utilized in oxidation catalysts, titanium–aluminum alloys and vanadium redox batteries. In the present study bioleaching of vanadium and nickel from an oil-fired ash sample was conducted using Aspergillus niger fungus. The experiments were carried out using spent-medium bioleaching method in both Erlenmeyer flasks and also bubble column bioreactor, in order to compare them together. In spent-medium bioleaching the solid waste is not in direct contact with the fungus and consequently the fungal growth is not retarded and maximum organic acids are produced. In this method the metals are leached through biogenic produced organic acids present in the medium. In shake flask experiments the fungus was cultured for 15 days, where the maximum production of organic acids was observed, while in bubble column bioreactor experiments a 7 days fermentation period was applied. The amount of produced organic acids were measured using high performance liquid chromatography (HPLC) and the results showed that depending on the fermentation period and the scale of experiments, the fungus has different major lixiviants. In flask tests, citric acid was the main produced organic acid by the fungus and the other organic acids including gluconic, oxalic, and malic were excreted in much lower concentrations, while in the bioreactor oxalic acid was the main lixiviant and it was produced considerably. In Erlenmeyer flasks during 15 days fermentation of Aspergillus niger, 8080 ppm citric acid and 1170 ppm oxalic acid was produced, while in bubble column bioreactor over 7 days of fungal growth, 17185 ppm oxalic acid and 1040 ppm citric acid was secreted. The leaching tests using the spent-media obtained from both of fermentation experiments, were performed at the same conditions of leaching duration of 7 days, leaching temperature of 60 °C and pulp density up to 3% (w/v). The results revealed that in Erlenmeyer flask experiments 97% of V and 50% of Ni were extracted while using spent medium produced in bubble column bioreactor, V and Ni recoveries were achieved to 100% and 33%, respectively. These recovery yields indicate that in both scales almost total vanadium can be recovered, while nickel recovery was lower. With help of the bioreactor spent-medium nickel recovery yield was lower than that of obtained from the flask experiments, which it could be due to precipitation of some values of Ni in presence of high levels of oxalic acid existing in its spent medium.

Keywords: Aspergillus niger, bubble column bioreactor, oil-fired ash, spent-medium bioleaching

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Authors: Mulatu Kassie Birhanu

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

Keywords: carbondioxide, faradaic efficiency, electrocatalyst, current density

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

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

Keywords: MCM-22, synthesis, transesterification, ZnO

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Authors: Saroj Poudel, Joshua Mancini, Douglas Pike, Jennifer Timm, Alexei Tyryshkin, Vikas Nanda, Paul Falkowski

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On the early Earth, protein-metal complexes likely harvested energy from a reduced environment. These complexes would have been precursors to the metabolic enzymes of ancient organisms. Hydrogenase is an essential enzyme in most anaerobic organisms for the reduction and oxidation of hydrogen in the environment and is likely one of the earliest evolved enzymes. To attempt to reinvent a precursor to modern hydrogenase, we computationally designed a short thirteen amino acid peptide that binds the often-required catalytic transition metal Nickel in hydrogenase. This simple complex can achieve hundreds of hydrogen evolution cycles using light energy in a broad range of temperature and pH. Biophysical and structural investigations strongly indicate the peptide forms a di-nickel active site analogous to Acetyl-CoA synthase, an ancient protein central to carbon reduction in the Wood-Ljungdahl pathway and capable of hydrogen evolution. This work demonstrates that prior to the complex evolution of multidomain enzymes, early peptide-metal complexes could have catalyzed energy transfer from the environment on the early Earth and enabled the evolution of modern metabolism

Keywords: hydrogenase, prebiotic enzyme, metalloenzyme, computational design

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Authors: Bhairi Lakshminarayana, Surajit Sarker, Ch. Subrahmanyam

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

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

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

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

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

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Authors: Shuwen Wu, Zhi LI

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

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

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

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

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

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Authors: Harish Ramesh Babu, Marco Böcker, Mario Raddatz, Sebastian Henkel, Horst Biermann, Uwe Gampe

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Thermal power machines are subjected to cyclic loading conditions under elevated temperatures. At these extreme conditions, the durability of the components has a significant influence. The material mechanical behaviour has to be known in detail for a failsafe construction. For this study a nickel-based alloy is considered, the deformation and fatigue behaviour of the material is analysed under cyclic loading. A viscoplastic model is used for calculating the deformation behaviour as well as to simulate the rate-dependent and cyclic plasticity effects. Finally, the cyclic deformation results of the finite element simulations are compared with low cycle fatigue (LCF) experiments.

Keywords: complex low cycle fatigue, elevated temperature, fe-simulation, viscoplastic

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Authors: R. S. Yadav, J. Havlica, I. Kuřitka, Z. Kozakova, J. Masilko, L. Kalina, M. Hajdúchová, V. Enev, J. Wasserbauer

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Nickel spinel ferrite NiFe2O4 nanoparticles with different particle size at different annealing temperature were synthesized using the starch-assisted sol-gel auto-combustion method. The synthesized nanoparticles were characterized by conventional powder X-ray diffraction (XRD) spectroscopy, Raman Spectroscopy, Fourier Transform Infrared Spectroscopy, Field-Emission Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy and Vibrating Sample Magnetometer. The XRD patterns confirmed the formation of NiFe2O4 spinel ferrite nanoparticles. Field-Emission Scanning Electron Microscopy revealed that particles are of spherical morphology with particle size 5-20 nm at lower annealing temperature. An infrared spectroscopy study showed the presence of two principal absorption bands in the frequency range around 525 cm-1 (ν1) and around 340 cm-1 (ν2); which indicate the presence of tetrahedral and octahedral group complexes, respectively, within the spinel ferrite nanoparticles. Raman spectroscopy study also indicated the change in octahedral and tetrahedral site related Raman modes in nickel ferrite nanoparticles with change of particle size. This change in magnetic behavior with change of particle size of NiFe2O4 nanoparticles was observed.

Keywords: nickel ferrite, nanoparticles, magnetic property, NiFe2O4

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Authors: Yaxin Tang, Mingao Hou, Qian He, Guangfu Luo

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Bimetallic nanoparticles serve as a promising class of catalysts with tunable properties suitable for diverse catalytic reactions, yet a comprehensive understanding of their actual structures under operating conditions and the optimal design principles remains largely elusive. In this study, we unveil a prevalent surface segregation phenomenon in nearly 100 platinum-group-element-based bimetallic nanoparticles through first principles-based molecular dynamics simulations. Our findings highlight that two components in a nanoparticle with relatively lower surface energy tend to segregate to the surface. Motivated by this discovery, we propose a deliberate exploitation of surface segregation in designing bimetallic nanoparticle catalysts, aiming for heightened stability and reduced consumption of precious metals. To validate this strategy, we further investigate 36 platinum-based bimetallic nanoparticles for propane dehydrogenation catalysis. Through a systematic examination of catalytic sites on nanoparticles, we identify several systems as top candidates with Pt-enriched surfaces, remarkable thermal stability, and superior catalytic activity for propane dehydrogenation. The insights gained garnered from this study are anticipated to provide a valuable framework for the optimal design of other bimetallic nanoparticles.

Keywords: bimetallic nanoparticles, platinum-group element, catalysis, surface segregation, first-principles calculations

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Authors: Victor Chinecherem Ejeke, Raphael Eze Nnam

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The main objective of this research is to produce biodiesel from waste vegetable oil using activated eggshell waste as solid catalysts. A transesterification reaction was performed for the conversion to biodiesel. Waste eggshells were calcined at 700°C, 800°C and 900°C for a time period of 3hrs for the preparation of the renewable catalyst. The calcined waste eggshell catalyst was characterized using X-Ray Florescence (XRF) Spectroscopy, which revealed CaO as the major constituent (90.86%); this was further confirmed by X-Ray Diffraction (XRD) and Fourier Transform Infrared (FTIR) analyses. The prepared catalyst was used for transesterification reaction and the effects of calcination temperature (700 to 900°C), Deep Eutectic Solvent DES loading (3 to 18 wt. %), Waste Egg Shell (WES) catalyst loading (6 to 14 wt. %) on the conversion to biodiesel were studied. The yield of biodiesel using a waste eggshell catalyst (91%) is comparable to conventional catalyst like sodium hydroxide with a yield of 80-90%. The maximum biodiesel production yield was obtained at a specific oil-to methanol molar ratio of 1:10, a temperature of 65°C and a catalyst loading of 14g-wt%. The biodiesel produced was characterized as being composed of methyl Tetradecanoate (C₁₄H₂₈O₂) 30.92% using the Gas Chromatographic (GC-MS) analysis. The fuel properties of the biodiesel (Flashpoint 138ᵒC) were comparable to commercial diesel, and hence it can be used in compression-ignition engines. The results indicated that the catalysts derived from waste eggshell had high potential to be used as biodiesel production catalysts in transesterification of waste vegetable oil with the advantage of reusability and also not requiring water washing steps.

Keywords: waste vegetable oil, catalyst , biodiesel , waste egg shell

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Authors: Ram Mohan, Mahendran Samykano, Shyam Aravamudhan

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Metallic nanowires with sub-micron and hundreds of nanometer diameter have a diversity of applications in nano/micro-electromechanical systems (NEMS/MEMS). Characterizing the mechanical properties of such sub-micron and nano-scale metallic nanowires are tedious; require sophisticated and careful experimentation to be performed within high-powered microscopy systems (scanning electron microscope (SEM), atomic force microscope (AFM)). Also, needed are nanoscale devices for placing the nanowires; loading them with the intended conditions; obtaining the data for load–deflection during the deformation within the high-powered microscopy environment poses significant challenges. Even picking the grown nanowires and placing them correctly within a nanoscale loading device is not an easy task. Mechanical characterizations through experimental methods for such nanowires are still very limited. Various techniques at different levels of fidelity, resolution, and induced errors have been attempted by material science and nanomaterial researchers. The methods for determining the load, deflection within the nanoscale devices also pose a significant problem. The state of the art is thus still at its infancy. All these factors result and is seen in the wide differences in the characterization curves and the reported properties in the current literature. In this paper, we discuss and present our experimental method, results, and discussions of uniaxial tensile loading and the development of subsequent stress–strain characteristics curves for Nickel nanowires. Nickel nanowires in the diameter range of 220–270 nm were obtained in our laboratory via an electrodeposition method, which is a solution based, template method followed in our present work for growing 1-D Nickel nanowires. Process variables such as the presence of magnetic field, its intensity; and varying electrical current density during the electrodeposition process were found to influence the morphological and physical characteristics including crystal orientation, size of the grown nanowires1. To further understand the correlation and influence of electrodeposition process variables, associated formed structural features of our grown Nickel nanowires to their mechanical properties, careful experiments within scanning electron microscope (SEM) were conducted. Details of the uniaxial tensile characterization, testing methodology, nanoscale testing device, load–deflection characteristics, microscopy images of failure progression, and the subsequent stress–strain curves are discussed and presented.

Keywords: uniaxial tensile characterization, nanowires, electrodeposition, stress-strain, 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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