Search results for: single metal atom catalysts

Authors: Ali Alhajeri, Tarig Makki, Mosa Almutahhar, Mohammed Ahmed, Usman Ali

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Metal powder is the raw material used for laser powder-bed fusion (LPBF) additive manufacturing (AM). There are many metal materials that can be used in LPBF. The properties of these materials are varied between each other, which can affect the building part. The objective of this paper is to do an overview of the titanium powders available in LBPF. Comparison between different literature works will lead us to study the similarities and differences between the powder properties such as size, shape, and chemical composition. Furthermore, the results of this paper will point out the significant titanium powder properties in order to clearly illustrate their effect on the build parts.

Keywords: LPBF, titanium, Ti-6Al-4V, Ti-5553, metal powder, AM

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Authors: Lamla Thungathaa, Conrad Mahlasea, Lisa Ngcebesha

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1,4-Diamino-3,6-dinitropyrazolo[4,3-c]pyrazole (LLM-119) and its structural isomer 3,6-dinitropyrazolo[3,4-c]pyrazole-1,4(6H)-diamine were designed by structural reorientation of the fused pyrazole rings and their respective substituents (-NO2 and -NH2). Structural reorientation involves structural rearrangement which result in different structural isomers, employing this approach, six structural isomers of LLM-119 were achieved. The effect of structural reorientation (isomerisation and derivatives) on the enthalpy of formation, detonation properties, impact sensitivity, and density of these molecules is studied Computationally. The computational method used are detailed in the document and they yielded results that are close to the literature values with a relative error of 2% for enthalpy of formation, 2% for density, 0.05% for detonation velocity, and 4% for detonation pressure. The correlation of the structural reorientation to the calculated thermochemical and detonation properties of the molecules indicated that molecules with a -NO2 group attached to a Carbon atom and -NH2 connected to a Nitrogen atom maximize the enthalpy of formation and detonation velocity. The joining of pyrazole molecules has less effect on these parameters. It was seen that density and detonation pressure improved when both –NO2 or -NH2 functional groups were on the same side of the molecular structure. The structural reorientation gave rise to 3,4-dinitropyrazolo[3,4-c]pyrazole-1,6-diamine which exhibited optimal density and detonation performance compared to other molecules.

Keywords: LLM-119, fused rings, azole, structural isomers, detonation properties

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Authors: Faezeh Aghazadeh

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

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

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Authors: Özgür Öztürk, Cumhur Sipahi, Hande Yeşil

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Implant retained restorations commonly consist of a metal-framework veneered with ceramic or composite facings. The increasing and expanding use of indirect resin composites in dentistry is a result of innovations in materials and processing techniques. Of special interest to the implant restorative field is the possibility that composites present significantly lower peak vertical and transverse forces transmitted at the peri-implant level compared to metal-ceramic supra structures in implant-supported restorations. A 43-year-old male patient referred to the department of prosthodontics for an implant retained fixed prosthesis. The clinical and radiographic examination of the patient demonstrated the presence of an implant in the right mandibular first molar tooth region. A considerable amount of marginal bone loss around the implant was detected in radiographic examinations combined with a remarkable peri-implant soft tissue deficiency. To minimize the chewing loads transmitted to the implant-bone interface it was decided to fabricate an indirect composite resin veneered single metal crown over a screw-retained abutment. At the end of the treatment, the functional and aesthetic deficiencies were fully compensated. After a 6 months clinical and radiographic follow-up period the not any additional pathologic invasion was detected in the implant-bone interface and implant retained restoration did not reveal any vehement complication.

Keywords: dental implant, fixed partial dentures, indirect composite resin, peri-implant defects

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Authors: Yulia Irnidayanti , J. J. Josua, A. Sugianto

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Jakarta Bay with 13 rivers that flow into, the environment has deteriorated and is the most polluted bays in Asia. The entry of waste into the waters of the Bay of Jakarta has caused pollution. Heavy metal contamination has led to pollution levels and may cause toxicity to organisms that live in the sea, down to the cellular level and may affect the ecological balance. Various ways have been conducted to measure the impact of environmental degradation, such as by measuring the levels of contaminants in the environment, including measuring the accumulation of toxic compounds in the tissues of organisms. Biological responses or biomarkers known as a sensitive indicator but need relevant predictions. In heavy metal pollution monitoring, analysis of aquatic biota is very important from the analysis of the water itself. The content of metals in aquatic biota will usually always be increased from time to time due to the nature of metal bioaccumulation, so the aquatic biota is best used as an indicator of metal pollution in aquatic environments. The results of the content analysis results of sea water in coastal estuaries Angke, Kaliadem and Panimbang detected heavy metals cadmium, mercury, lead, but did not find zinc metal. Based on the results of protein electrophoresis methallotionein found heavy metals in the tissues hepatopancreas, gills and muscles, and also the mRNA expression of has detected.

Keywords: gills, heavy metal, hepatopancreas, metallothionein, muscle

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Authors: Frea Van Steenweghen, Lander Hollevoet, Johan A. Martens

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Compared to other hydrogen (H₂) carriers, ammonia (NH₃) is one of the most promising carriers as it contains 17.6 wt% hydrogen. It is easily liquefied at ≈ 9–10 bar pressure at ambient temperature. More importantly, NH₃ is a carbon-free hydrogen carrier with no CO₂ emission at final decomposition. Ammonia has a well-defined regulatory framework and a good track record regarding safety concerns. Furthermore, the industry already has an existing transport infrastructure consisting of pipelines, tank trucks and shipping technology, as ammonia has been manufactured and distributed around the world for over a century. While NH₃ synthesis and transportation technological solutions are at hand, a missing link in the hydrogen delivery scheme from ammonia is an energy-lean and efficient technology for cracking ammonia into H₂ and N₂. The most explored option for ammonia decomposition is thermo-catalytic cracking which is, by itself, the most energy-efficient approach compared to other technologies, such as plasma and electrolysis, as it is the most energy-lean and robust option. The decomposition reaction is favoured only at high temperatures (> 300°C) and low pressures (1 bar) as the thermocatalytic ammonia cracking process is faced with thermodynamic limitations. At 350°C, the thermodynamic equilibrium at 1 bar pressure limits the conversion to 99%. Gaining additional conversion up to e.g. 99.9% necessitates heating to ca. 530°C. However, reaching thermodynamic equilibrium is infeasible as a sufficient driving force is needed, requiring even higher temperatures. Limiting the conversion below the equilibrium composition is a more economical option. Thermocatalytic ammonia cracking is documented in scientific literature. Among the investigated metal catalysts (Ru, Co, Ni, Fe, …), ruthenium is known to be most active for ammonia decomposition with an onset of cracking activity around 350°C. For establishing > 99% conversion reaction, temperatures close to 600°C are required. Such high temperatures are likely to reduce the round-trip efficiency but also the catalyst lifetime because of the sintering of the supported metal phase. In this research, the first focus was on catalyst bed design, avoiding diffusion limitation. Experiments in our packed bed tubular reactor set-up showed that extragranular diffusion limitations occur at low concentrations of NH₃ when reaching high conversion, a phenomenon often overlooked in experimental work. A second focus was thermocatalyst development for ammonia cracking, avoiding the use of noble metals. To this aim, candidate metals and mixtures were deposited on a range of supports. Sintering resistance at high temperatures and the basicity of the support were found to be crucial catalyst properties. The catalytic activity was promoted by adding alkaline and alkaline earth metals. A third focus was studying the optimum process configuration by process simulations. A trade-off between conversion and favorable operational conditions (i.e. low pressure and high temperature) may lead to different process configurations, each with its own pros and cons. For example, high-pressure cracking would eliminate the need for post-compression but is detrimental for the thermodynamic equilibrium, leading to an optimum in cracking pressure in terms of energy cost.

Keywords: ammonia cracking, catalyst research, kinetics, process simulation, thermodynamic equilibrium

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

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

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

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Authors: Hassiba Bougueria, Nesrine Benarous, Souheyla Chetioui

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Azo dyes are one of the most widely used compounds in organic chemistry, primarily due to their relatively simple preparation methods. They have therefore been widely used, in particular as colorants for textiles, printing inks, cosmetics, and food additives. In addition to their use as dyes, azo compounds have attracted much attention from chemists as their potential applications are important in coordination chemistry, metal-organic frameworks (MOF) structures, COF (covalent-organic frameworks), and catalysis. Moreover, they have found many applications in different fields, such as nonlinear optics, optical storage, photoluminescence, and magnetism. The compound bis{(E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olato}copper(II) dimethyl sulfoxide monosolvate, the CuII atom is tetracoordinate with a square-planar geometry, surrounded by two bidentate (E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalene-2-olate ligands via two N atoms and two O atoms. The O-Cu-O angles and N-Cu-N are of the order of 177.90(16)° and 177.8(2)°, respectively. The distances Cu-O and Cu- N are 1.892(4) Å and 1.976(4) Å, respectively. The cohesion of the crystal is ensured by hydrogen bonds of the C—H…O type and by π=π staking interactions [centroid–centroid distance = 3.679(4)Å]. The DMSO solvent molecule is disordered at two positions with occupancy rates of 0.70 and 0.30.

Keywords: azo dyes, DRX, structural characterization, biological activity

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Authors: K. Hiro, Y. Imai, M. Tanji, H. Deguchi, K. Hatari

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Negative pressures of liquids have been expected to contribute many kinds of technology. Nevertheless, experiments for subjecting liquids which have not too small volumes to negative pressures are difficult even now. The reason of the difficulties is because the liquids tend to generate cavities easily. In order to remove cavitation nuclei, an apparatus for enclosing water into a metal Berthelot tube under vacuum conditions was developed. By using the apparatus, negative pressures for water rose to ca. -20 MPa. This is the highest value for water in metal Berthelot tubes. Results were explained by a traditional crevice model. Keywords

Keywords: Berthelot method, negative pressure, cavitation nuclei, water

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Authors: Su Jeong Lee, Tae Il Lee, Jung Han Kim, Chul-Hong Kim, Gee Sung Chae, Jae-Min Myoung

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The contact resistance between source/drain electrodes and semiconductor layer is an important parameter affecting electron transporting performance in the thin film transistor (TFT). In this work, we introduced a transparent and the solution prossable single-walled carbon nanotube (SWCNT)/Al-doped ZnO nano particle (AZO NP) bilayer electrodes showing low contact resistance with indium-oxide (In2O3) sol gel thin film. By inserting low work function AZO NPs into the interface between the SWCNTs and the In2O3 which has a high energy barrier, we could obtain an electrical Ohmic contact between them. Finally, with the SWCNT-AZO NP bilayer electrodes, we successfully fabricated a TFT showing a field effect mobility of 5.38 cm2/V∙s at 250 °C.

Keywords: single-walled carbon nanotube (SWCNT), Al-doped ZnO (AZO) nanoparticle, contact resistance, thin-film transistor (TFT)

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Authors: S. A. A. Nabeela Nasreen, S. Sundarrajan, S. A. Syed Nizar, Seeram Ramakrishna

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Metal-organic frameworks (MOFs) have attracted considerable interest due to its diverse pore size tunability, fascinating topologies and extensive uses in fields such as catalysis, membrane separation, chemical sensing, etc. Zeolitic imidazolate frameworks (ZIFs) are a class of MOF with porous crystals containing extended three-dimensional structures of tetrahedral metal ions (e.g., Zn) bridged by Imidazolate (Im). Selected ZIFs are used to separate solvent/solvent mixtures. A layer by layer formation of the nanocomposite of Zinc oxide (ZnO) and ZIF on a ceramic support using a solvothermal method was engaged and tested for target solvent/solvent separation. Metal oxide layer was characterized by XRD, SEM, and TEM to confirm the smooth and continuous coating for the separation process. The chemical composition of ZIF films was studied by using X-Ray absorption near-edge structure (XANES) spectroscopy. The obtained ceramic tube with metal oxide and ZIF layer coating were tested for its packing density, thickness, distribution of seed layers and variation of permeation rate of solvent mixture (isopropyl alcohol (IPA)/methyl isobutyl ketone (MIBK). Pervaporation technique was used for the separation to achieve a high permeation rate with separation ratio of > 99.5% of the solvent mixture.

Keywords: metal oxide, membrane, pervaporation, solvothermal, ZIF

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Authors: P. V. Krupakara

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This paper deals with the high corrosion resistance developed by the hybrid metal matrix composites when compared with that of matrix alloy. Matrix selected is Al6061. Reinforcements selected are graphite and red mud particulates. The composites are prepared using liquid melt metallurgy technique using vortex method. Metal matrix composites containing 2 percent graphite and 2 percent red mud, 2 percent graphite and 4 percent red mud, 2 percent graphite and 6 percent of red mud are prepared. Bar castings are cut into cylindrical discs of 20mm diameter and 20mm thickness. Corrosion tests were conducted at room temperature (230 °C) using conventional weight loss method according to ASTM G69-80. The corrodents used for the test were hydrochloric acid solution of different concentrations. Specimens were tested for every 24 hours interval up to 96 hours. Four specimens for each condition and time were immersed in corrodent. In each case the corrosion rate decreases with increase in exposure time for matrix and metal matrix composites whatever may be the concentration of hydrochloric acid. This may be due to aluminium, which may induce passivation due to development of non-porous layer. As red mud content increases the composites become corrosion resistant due to insulating nature of ceramic material red mud and less exposure of matrix alloy in those metal matrix composites.

Keywords: Al6061, graphite, passivation, red mud, vortex

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Authors: Li Li, Lei Wang, Chenglin Du, Mengxin Ren, Xinzheng Zhang, Wei Cai, Jingjun Xu

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Strong coupling between excitons of quantum dots and plasmons in nanocavites can be realized at room temperature due to the strong confinement of the plasmon fields, which offers building blocks for quantum information systems or ultralow-power switches and lasers. In this work, by using cathodoluminescence, ultrastrong coupling with Rabi splitting above 1 eV between breathing plasmons in Aluminum metal-insulator-metal (MIM) cavity and excited state of CdZnS/ZnS quantum dots was reported in near-UV spectrum. Analytic analysis and full-wave electromagnetic simulations provide the evidence for the strong coupling and confirm the hybridization of the QDs exciton and LSP breathing mode. This study opens the way for new emerging applications based on strongly coupled light-matter states all over the visible region down to ultra-violet frequencies.

Keywords: breathing mode, plasmonics, quantum dot, strong coupling, ultraviolet

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Authors: Zhenqiu Liu

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Visualizing the heterogeneity within cell-populations for single-cell RNA-seq data is crucial for studying the functional diversity of a cell. However, because of the high level of noises, outlier, and dropouts, it is very challenging to measure the cell-to-cell similarity (distance), visualize and cluster the data in a low-dimension. Minimum volume embedding (MVE) projects the data into a lower-dimensional space and is a promising tool for data visualization. However, it is computationally inefficient to solve a semi-definite programming (SDP) when the sample size is large. Therefore, it is not applicable to single-cell RNA-seq data with thousands of samples. In this paper, we develop an efficient algorithm with an accelerated proximal gradient method and visualize the single-cell RNA-seq data efficiently. We demonstrate that the proposed approach separates known subpopulations more accurately in single-cell data sets than other existing dimension reduction methods.

Keywords: single-cell RNA-seq, minimum volume embedding, visualization, accelerated proximal gradient method

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Authors: Lotanna Ezeonu, Jason P. Robbins, Ziyu Tang, Xiaofang Yang, Bruce E. Koel, Simon G. Podkolzin

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The interaction of organic molecules with metal surfaces is of interest in numerous technological applications, such as catalysis, bone replacement, and biosensors. Acetic acid is one of the main products of bio-oils produced from the pyrolysis of hemicellulosic feedstocks. However, their high oxygen content makes them unsuitable for use as fuels. Hydrodeoxygenation is a proven technique for catalytic deoxygenation of bio-oils. An understanding of the energetics and control of the bond-breaking sequences of biomass-derived oxygenates on metal surfaces will enable a guided optimization of existing catalysts and the development of more active/selective processes for biomass transformations to fuels. Such investigations have been carried out with the aid of ultrahigh vacuum and its concomitant techniques. The high catalytic activity of platinum in biomass-derived oxygenate transformations has sparked a lot of interest. We herein exploit infrared reflection absorption spectroscopy(IRAS), temperature-programmed desorption(TPD), and density functional theory(DFT) to study the adsorption and decomposition of acetic acid on a Pt(111) surface, which was then compared with Ni(111), a model non-noble metal. We found that acetic acid adsorbs molecularly on the Pt(111) surface, interacting through the lone pair of electrons of one oxygen atomat 90 K. At 140 K, the molecular form is still predominant, with some dissociative adsorption (in the form of acetate and hydrogen). Annealing to 193 K led to complete dehydrogenation of molecular acetic acid species leaving adsorbed acetate. At 440 K, decomposition of the acetate species occurs via decarbonylation and decarboxylation as evidenced by desorption peaks for H₂,CO, CO₂ and CHX fragments (x=1, 2) in theTPD.The assignments for the experimental IR peaks were made using visualization of the DFT-calculated vibrational modes. The results showed that acetate adsorbs in a bridged bidentate (μ²η²(O,O)) configuration. The coexistence of linear and bridge bonded CO was also predicted by the DFT results. Similar molecular acid adsorption energy was predicted in the case of Ni(111) whereas a significant difference was found for acetate adsorption.

Keywords: acetic acid, platinum, nickel, infared-absorption spectrocopy, temperature programmed desorption, density functional theory

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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: I. Made Gatot Karohika, Shigeyuki Haruyama, Ken Kaminishi, Oke Oktavianty, Didik Nurhadiyanto

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Contact width and contact stress are important parameters related to the leakage behavior of corrugated metal gasket. In this study, contact width and contact stress of three-layer corrugated metal gasket are investigated due to the modulus of elasticity and thickness of surface layer for 2 type gasket (0-MPa and 400-MPa mode). A finite element method was employed to develop simulation solution to analysis the effect of each parameter. The result indicated that lowering the modulus of elasticity ratio of surface layer will result in better contact width but the average contact stresses are smaller. When the modulus of elasticity ratio is held constant with thickness ratio increase, its contact width has an increscent trend otherwise the average contact stress has decreased trend.

Keywords: contact width, contact stress, layer, metal gasket, corrugated, simulation

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Authors: Jiwoo Park, Junseok Yoon, Jeong Kim, Beomsoo Kang

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Multi-Point Stretch Forming (MPSF) process is suitable for flexible manufacturing, and it has several advantages including that it could be applied to various forming such as sheet metal forming, single curved surface forming and double curved one. In this study, a systematic numerical simulation was carried out for atypical double curved surface forming using the multiple die stretch forming process. In this simulation, urethane pads were defined based on hyper-elastic material model as a cushion for the smooth forming surface. The deformation behaviour on elastic recovery was also investigated to consider the exact result after the last forming process, and then the experiment was also carried out to confirm the formability of this forming process. By comparing the simulation and experiment results, the suitability of the multiple die stretch forming process for the atypical double curved surface was verified. Consequently, it is confirmed that the multi-point stretch forming process has the capability and feasibility of being used to manufacture the double curved surfaces of sheet metal.

Keywords: multi-point stretch forming, double curved surface, numerical simulation, manufacturing

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Authors: Akanimo Emene, Mark D. Ogden, Robert Edyvean

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Adsorption is a low cost, efficient and economically viable wastewater treatment process. Utilization of this treatment process has not been fully applied due to the complex and not fully understood nature of the adsorption system. To optimize its process is to choose a sufficient adsorbent and to study further the experimental parameters that influence the adsorption design system. Chemically modified adsorbent, Luffa cylindrica, was used to adsorb heavy metal ions and an organic pollutant, methylene blue, from aqueous environmental solution at varying experimental conditions. Experimental factors, adsorption time, initial metal ion or organic pollutant concentration, ionic strength, and pH of solution were studied. The experimental data were analyzed with kinetic and isotherm models. The antagonistic effect of the methylene and some heavy metal ions were recorded. An understanding of the use of this treated Luffa cylindrica for the removal of these toxic substances will establish and improve the commercial application of the adsorption process in treatment of contaminated waters.

Keywords: adsorption, heavy metal ions, Luffa cylindrica, wastewater treatment

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Authors: Dong-Cheol Jeong, Jookyung Lee, Yu Hyeon Ro, Changsik Song

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The design and synthesis of photo-active polymeric systems are important in regard to solar energy harvesting and utilization. In this study, we synthesized photo-active polymer, thin films, and polymer gel via iterative self-assembly using reversible metal-terpyridine (M-tpy) interactions. The photocurrent generated in the polymeric thin films with Zn(II) was much higher than those of other films. Apparent diffusion rate constant (kapp) was measured for the electron hopping process via potential-step chronoamperometry. As a result, the kapp for the polymeric thin films with Zn(II) was almost two times larger than those with other metal ions. We found that the anodic photocurrents increased with the inclusion of the multi-walled carbon nanotube (MWNT) layer. Inclusion of MWNTs can provide efficient electron transfer pathways. In addition, polymer gel based on interactions between terpyridine and metal ions was shown the photocatalytic activity. Interestingly, in the Mg-terpyridine gel, the reaction rate of benzylamine to imine photo-oxidative coupling was faster than Fe-terpyridine gel because the Mg-terpyridine gel has two steps electron transfer pathway but Fe-terpyridine gel has three steps electron transfer pathway.

Keywords: terpyridine, photocatalyst, self-assebly, metal-ligand

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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

Abstract:

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: Hamsasew Hankebo Lemago, Dóra Hessz, Tamás Igricz, Zoltán Erdélyi, , Imre Miklós Szilágyi

Abstract:

Metal oxide inverse opals are a promising class of photocatalysts with a unique hierarchical structure. Atomic layer deposition (ALD) is a versatile technique for the synthesis of high-precision metal oxide thin films, including inverse opals. In this study, we report the synthesis of TiO₂, ZnO, and Al₂O₃ inverse opal and their composites photocatalysts using thermal or plasma-enhanced ALD. The synthesized photocatalysts were characterized using a variety of techniques, including scanning electron microscopy (SEM)-energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Raman spectroscopy, photoluminescence (PL), ellipsometry, and UV-visible spectroscopy. The results showed that the ALD-synthesized metal oxide inverse opals had a highly ordered structure and a tunable pore size. The PL spectroscopy results showed low recombination rates of photogenerated electron-hole pairs, while the ellipsometry and UV-visible spectroscopy results showed tunable optical properties and band gap energies. The photocatalytic activity of the samples was evaluated by the degradation of methylene blue under visible light irradiation. The results showed that the ALD-synthesized metal oxide inverse opals exhibited high photocatalytic activity, even under visible light irradiation. The composites photocatalysts showed even higher activity than the individual metal oxide inverse opals. The enhanced photocatalytic activity of the composites can be attributed to the synergistic effect between the different metal oxides. For example, Al₂O₃ can act as a charge carrier scavenger, which can reduce the recombination of photogenerated electron-hole pairs. The ALD-synthesized metal oxide inverse opals and their composites are promising photocatalysts for a variety of applications, such as wastewater treatment, air purification, and energy production. The ALD-synthesized metal oxide inverse opals and their composites are promising photocatalysts for a variety of applications, such as wastewater treatment, air purification, and energy production.

Keywords: ALD, metal oxide inverse opals, photocatalysis, composites

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

Abstract:

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: Charn Loong Ng, Mamun Bin Ibne Reaz

Abstract:

As elderly population grows globally, the percentage of people diagnosed with musculoskeletal disorder (MSD) increase proportionally. Electromyography (EMG) is an important biosignal that contributes to MSD’s clinical diagnose and recovery process. Conventional conductive electrode has many disadvantages in the continuous EMG measurement application. This research has design a new surface EMG biosensor based on the parallel-plate capacitive coupling principle. The biosensor is developed by using a double-sided PCB with having one side of the PCB use to construct high input impedance circuitry while the other side of the copper (CU) plate function as biosignal sensing metal plate. The metal plate is insulated using kapton tape for contactless application. The result implicates that capacitive biosensor is capable to constantly capture EMG signal without having galvanic contact to human skin surface. However, there are noticeable noise couple into the measured signal. Post signal processing is needed in order to present a clean and significant EMG signal. A complete design of single ended, non-contact, high input impedance, front end EMG biosensor is presented in this paper.

Keywords: contactless, capacitive, biosensor, electromyography

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Authors: E. Moroydor Derun, N. Tugrul, N. Baran Acarali, A. S. Kipcak, S. Piskin

Abstract:

Fly ash is a waste material of coal firing thermal plants that is released from thermal power plants. It was defined as very fine particles that are drifted upward which are taken up by the flue gases. The emerging amount of fly ash in the world is approximately 600 million tons per year. In our country, it is expected that will be occurred 50 million tons of waste ash per year until 2020. The fly ashes can be evaluated by using as adsorbent material. The purpose of this study is to investigate the possibility of use of various fly ashes (Tuncbilek, Catalagzi, Orhaneli) like low-cost adsorbents for heavy metal adsorption. First of all, fly ashes were characterized. For this purpose; analyses such as XRD, XRF, SEM and FT-IR were performed.

Keywords: adsorbent, fly ash, heavy metal, waste

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Authors: Anaam H. Al-ShaikhAli, Mansour A. Al-Herz

Abstract:

The research leverages the proven HS-FCC technology to directly crack crude oils into petrochemical building blocks. Crude oils were subjected to an optimized hydro-processing process where metal contaminants and sulfur were reduced to an acceptable level for feeding the crudes into the HS-FCC technology. The hydro-processing is achieved through a fixed-bed reactor which is composed of 3 layers of catalysts. The crude oil is passed through a dementalization catalyst followed by a desulfurization catalyst and finally a de-aromatization catalyst. The hydroprocessing was conducted at an optimized liquid hourly space velocity (LHSV), temperature, and pressure for an optimal reduction of metals and sulfur from the crudes. The hydro-processed crudes were then fed into a micro activity testing (MAT) unit to simulate the HS-FCC technology. The catalytic cracking of crude oils was conducted over tailored catalyst formulations under an optimized catalyst/oil ratio and cracking temperature for optimal production of total light olefins.

Keywords: petrochemical, catalytic cracking, catalyst synthesis, HS-FCC technology

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

Abstract:

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: Biswaranjan D. Mohapatra, Ipsha Hota, Swarna P. Mantry, Nibedita Behera, Kumar S. K. Varadwaj

Abstract:

Designing highly active and low-cost oxygen evolution (2H₂O → 4H⁺ + 4e⁻ + O₂) electrocatalyst is one of the most active areas of advanced energy research. Some precious metal-based electrocatalysts, such as IrO₂ and RuO₂, have shown excellent performance for oxygen evolution reaction (OER); however, they suffer from high-cost and low abundance which limits their applications. Recently, layered double hydroxides (LDHs), composed of layers of divalent and trivalent transition metal cations coordinated to hydroxide anions, have gathered attention as an alternative OER catalyst. However, LDHs are insulators and coupled with carbon materials for the electrocatalytic applications. Graphene covalently doped with nitrogen has been demonstrated to be an excellent electrocatalyst for energy conversion technologies such as; oxygen reduction reaction (ORR), oxygen evolution reaction (OER) & hydrogen evolution reaction (HER). However, they operate at high overpotentials, significantly above the thermodynamic standard potentials. Recently, we reported remarkably enhanced catalytic activity of benzoate or 1-pyrenebutyrate functionalized N-doped graphene towards the ORR in alkaline medium. The molecular and heteroatom co-doping on graphene is expected to tune the electronic structure of graphene. Therefore, an innovative catalyst architecture, in which LDHs are anchored on aromatic acid functionalized ‘N’ doped graphene may presumably boost the OER activity to a new benchmark. Herein, we report fabrication of Co₂Fe-LDH on aromatic acid (AA) functionalized ‘N’ doped reduced graphene oxide (NG) and studied their OER activities in alkaline medium. In the first step, a novel polyol method is applied for synthesis of AA functionalized NG, which is well dispersed in aqueous medium. In the second step, Co₂Fe LDH were grown on AA functionalized NG by co-precipitation method. The hybrid samples are abbreviated as Co₂Fe LDH/AA-NG, where AA is either Benzoic acid or 1, 3-Benzene dicarboxylic acid (BDA) or 1, 3, 5 Benzene tricarboxylic acid (BTA). The crystal structure and morphology of the samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). These studies confirmed the growth of layered single phase LDH. The electrocatalytic OER activity of these hybrid materials was investigated by rotating disc electrode (RDE) technique on a glassy carbon electrode. The linear sweep voltammetry (LSV) on these catalyst samples were taken at 1600rpm. We observed significant OER performance enhancement in terms of onset potential and current density on Co₂Fe LDH/BTA-NG hybrid, indicating the synergic effect. This exploration of molecular functionalization effect in doped graphene and LDH system may provide an excellent platform for innovative design of OER catalysts.

Keywords: π-π functionalization, layered double hydroxide, oxygen evolution reaction, reduced graphene oxide

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