Search results for: catalytic combustor

Authors: Rachna, Uma Shanker

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Aromatic phenols, being priority pollutants, are found in various industrial effluents and seeking the attention of environmentalists worldwide, owing to their life-threatening effects. In the present study, the coupling of zinc oxide with Prussian blue was achieved involving co-precipitation synthesis process using Azadirachta indica plant extract. The fabricated nanocatalyst was employed for the sunlight mediated photodegradation of various phenols (Phenol, 3-Aminophenol, and 2,4-Dinitrophenol). Doping of zinc oxide with Prussian blue caused an increase in the surface area to value 80.109 m²g⁻¹ and also enhanced the semiconducting tendency of the nanocomposite with band gap energy 1.101 eV. The experiment was performed at different parameters of phenols concentration, catalyst amount, pH, time, and exposure of sunlight. The obtained results showed a lower elimination of 2,4-DNP (93%) than 3-AP (97%) and phenol (95%) owing to their molecular weight and basicity differences. In comparison to the starting material (zinc oxide and Prussian blue), nanocomposite was more capable in degrading the phenols and lowered the t1/2 value of phenol (4.405 h), 3-AP (4.04 h) and 2,4-DNP (4.68 h) to a greater extent. Effect of different foreign anions was also studied to check nanocomposite’s liability under natural conditions. The extent of charge recombination being the most limiting factor in the photodegradation of pollutants was determined through the photoluminescence. Sunlight active ZnO@FeHCF nanocomposite was proven to exhibit good catalytic ability up to 10 cycles.

Keywords: nanocomposite, phenols, photodegradation, sunlight, water

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Authors: Osama M. Darwesh, Sahar H. Hassan, Abd El-Raheem R. El-Shanshoury, Shawky Z. Sabae

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Nanotechnology as multidisciplinary technology is growing rapidly with important applications in several sectors. Also, nanobiotechnology is known for the use of microorganisms for the synthesis of targeted nanoparticles. The present study deals with the green synthesis of silver nanoparticles using aquatic bacteria and the development of a biogenic nanocomposite for environmental applications. Twenty morphologically different colonies were isolated from the collected water samples from eight different locations at the Rosetta branch of the Nile Delta, Egypt. The obtained results illustrated that the most effective bacterial isolate (produced the higher amount of AgNPs after 24 h of incubation time) is isolate R3. Bacillus tequilensis was the strongest extracellular bio-manufactory of AgNPs. Biosynthesized nanoparticles had a spherical shape with a mean diameter of 2.74 to 28.4 nm. The antimicrobial activity of silver nanoparticles against many pathogenic microbes indicated that the produced AgNPs had high activity against all tested multi-antibiotic resistant pathogens. Also, the stabilized prepared AgNPs-SA nanocomposite has greater catalytic activity for the decolourization of some dyes like Methylene blue (MB) and Crystal violet. Such results represent a promising stage for producing eco-friendly, cost-effective, and easy-to-handle devices for the bioremediation of contaminated industrial wastewater.

Keywords: bioremediation, AgNPs, AgNPs-SA nanocomposite, Bacillus tequilensis, nanobiotechnology

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Authors: Shah Sufaid, Hussain Shahid, Tianyan You, Liu Guiwu, Qiao Guanjun

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Nickel oxide (NiO) is an optimal material for precise detection of hydrogen (H₂) gas due to its high catalytic activity and low resistivity. However, the gas response kinetics of H₂ gas molecules with the surface of NiO concurrence limitation imposed by its solid structure, leading to a diminished gas response value and slow electron-hole transport. Herein, NiO@CuO NFs with porous sharp-tip and nanospheres morphology were successfully synthesized by using a metal-organic framework (MOFs) as a precursor. The fabricated porous 2 wt% NiO@CuO NFs present outstanding selectivity towards H₂ gas, including a high sensitivity of a response value (170 to 20 ppm at 150 °C) higher than that of porous Ni-MOF (6), low detection limit (300 ppb) with a notable response (21), short response and recovery times at (300 ppb, 40/63 s and 20 ppm, 100/167 s), exceptional long-term stability and repeatability. Furthermore, an understanding of NiO@CuO sensor functioning in an actual environment has been obtained by using the impact of relative humidity as well. The boosted hydrogen sensing properties may be attributed due to synergistic effects of numerous facts including p-p heterojunction at the interface between NiO and CuO nanoflowers. Particularly, a porous Ni-MOF structure combined with the chemical sensitization effect of NiO with the rough surface of CuO nanosphere, are examined. This research presents an effective method for development of Ni-MOF derived metal oxide semiconductor (MOS) heterostructures with rigorous morphology and composition, suitable for gas sensing application.

Keywords: NiO@CuO NFs, metal organic framework, porous structure, H₂, gas sensing

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Authors: Zhiwen Yang, Jingyuan Li, Zhenkai Xie, Jian Ling, Jiguang Wang, Mengliang Li

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To reflect the effects of different emission control strategies, such as retrofitting after-treatment system and replacing with natural gas-fueled vehicles, on particle number (PN), particle mass (PM) and nitrogen oxides (NOx) emissions emitted by urban bus, a portable emission measurement system (PEMS) was employed herein to conduct real-world driving emission measurements on a diesel oxidation catalytic converter (DOC) and catalyzed diesel particulate filter (CDPF) retrofitting China IV diesel bus, a China IV diesel bus, and a China V natural gas bus. The results show that both tested diesel buses possess markedly advantages in NOx emission control when compared to the lean-burn natural gas bus equipped without any NOx after-treatment system. As to PN and PM, only the DOC+CDPF retrofitting diesel bus exhibits enormous benefits on emission control relate to the natural gas bus, especially the normal diesel bus. Meanwhile, the differences in PM and PN emissions between retrofitted and normal diesel buses generally increase with the increase in vehicle-specific power (VSP). Furthermore, the differences in PM emissions, especially those in the higher VSP ranges, are more significant than those in PN. In addition, the maximum peak PN particle size (32 nm) of the retrofitted diesel bus was significantly lower than that of the normal diesel bus (100 nm). These phenomena indicate that the CDPF retrofitting can effectively reduce diesel bus exhaust particle emissions, especially those with large particle sizes.

Keywords: CDPF, diesel, natural gas, real-world emissions

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Authors: Ge Cui, Mei Fang Chien, Chihiro Inoue

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In this research, enrichment culture using an inorganic liquid medium collected soil contaminated with 1,2-dichlorobenzene (1,2-DCB) in Sendai, Japan, was added 1,2-DCB as the sole carbon source to create a stable consortium. The purpose of this research is to analysis dominant microorganisms in the stable consortium and enzyme system which play a role in the degradation of DCBs. The consortium is now at 30 generation and is still being cultured. By the result of PCR-DGGE and clone library, two bacteria are dominant. The bacteria named sk1 was isolated. 40mg/l of 1,2-DCB and 40mg/l of 1,4-DCB were completely degraded after 32 hours and 50 hours, respectively, but no degradation occurred in the case of 1,3-DCB. By PCR, tecA1 (α-subunit of DCB dioxygenase) gene which plays a role degrading DCB to DCB dihydrodiol, and tecB (dehydrogenase) gene which plays a role degrading DCB dihydrodiol to dichlorocatechol were amplified from strain sk1. Bacteria named sk100 was also isolated. 40mg/l of 1,2-DCB was completely degraded after 32 hours, but no degradation occurred in case of 1,3-DCB and 1,4-DCB. By the result of the catalytic core region of dioxygenase amplified by PCR, gene played a role degrading DCB was analyzed. The results of this study concluded that the isolated strains which have not been reported are able to degrade 1,2-DCB stably, and the characterization of degradation and the genomic analysis which is now in progress is helpful to have an overall view of this microbial degradation.

Keywords: DCB, 1, 2-DCB degrading strains, DCB dioxygenase, enrichment culture

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Authors: Rawaz A. Ahmed, Katherine Huddersman

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High-lipid Fats, Oils and Grease (FOGs) from wastewater are underutilized despite their potential for conversion into valuable fuels; this work describes a surface-functionalized fibrous Polyacrylonitrile (PAN) mesh as a novel heterogeneous acid catalyst for the conversion of free fatty acids (FFAs), via a catalytic esterification process into biodiesel. The esterification of stearic acid (SA) with methanol was studied over an acidified PAN solid acid catalyst. Disappearance of the carboxylic acid (C=O) peak of the stearic acid at 1696 cm-1 in the FT-IR spectrum with the associated appearance of the ester (C=O) peak at 1739 cm-1 confirmed the production of the methyl stearate. This was further supported by 1H NMR spectra with the appearance of the ester (-CH₂OCOR) at 3.60-3.70 ppm. Quantitate analysis by GC-FID showed the catalyst has excellent activity with >95 % yield of methyl stearate (MS) at 90 ◦C after 3 h and a molar ratio of methanol to SA of 35:1. To date, to our best knowledge, there is no research in the literature on the esterification reaction for biodiesel production using a modified PAN mesh as a catalyst. It is noteworthy that this acidified PAN mesh catalyst showed comparable activity to conventional Brönsted acids, namely H₂SO₄ and p-TSA, as well as exhibiting higher activity than various other heterogeneous catalysts such as zeolites, ion-exchange resins and acid clay.

Keywords: fats oil and greases (FOGs), free fatty acid, esterification reaction, methyl ester, PAN

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Authors: Shuafeng Yuan, Bojian Zheng

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The RNA-dependent RNA polymerase of influenza a virus comprises conserved and independently folded subdomains with defined functionalities. The N-terminal domain of the PA subunit (PAN) harbors the endonuclease function so that it can serve as a desired target for drug discovery. To identify a class of anti-influenza inhibitors that impedes PAN endonuclease activity, a screening approach that integrated the fluorescence resonance energy transfer based endonuclease inhibitor assay with the DNA gel-based endonuclease inhibitor assay was conducted, followed by the evaluation of antiviral efficacies and potential cytotoxicity of the primary hits in vitro and in vivo. A small-molecule compound ANA-0 was identified as a potent inhibitor against the replication of multiple subtypes of influenza A virus, including H1N1, H3N2, H5N1, H7N7, H7N9 and H9N2, in cell cultures. Combinational treatment of zanamivir and ANA-0 exerted synergistic anti-influenza effect in vitro. Intranasal administration of ANA-0 protected mice from lethal challenge and reduced lung viral loads in H1N1 virus infected BALB/c mice. Docking analyses predicted ANA-0 bound the endonuclease cavity of PAN by interacting with the metal-binding and catalytic residues. In summary, ANA-0 shows potential to be developed to novel anti-influenza agents.

Keywords: anti-influenza, novel compound, inhibition of endonuclease, PA

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Authors: Sanaa Bardaweel

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Inorganic polyphosphate (poly P) is present in all living forms tested to date, from each of the three kingdoms of life. Studied mainly in prokaryotes, poly P and its associated enzymes are vital in diverse basic metabolism, in at least some structural functions and, notably, in stress responses. These plentiful and unrelated roles for poly P are probably the consequence of its presence in life-forms early in evolution. The genomes of many bacterial species, including pathogens, encode a homologue of a major poly P synthetic enzyme, poly P kinase 1 (PPK1). Genetic deletion of ppk1 results in reduced poly P levels and loss of pathogens virulence towards protozoa and animals. Thus far, no PPK1 homologue has been identified in higher-order eukaryotes and, therefore, PPK1 represents a novel target for chemotherapy. The idea of the current study is to purify the PPK1 from Escherichia coli to homogeneity in order to study the effect of active site point mutations on PPK1 catalysis via the application of site-directed mutagenesis strategy. The knowledge obtained about the active site of PPK1 will be utilized to characterize the catalytic and kinetic mechanism of PPK1 with model substrates. Comprehensive understanding of the enzyme kinetic mechanism and catalysis will be used to design and screen a library of synthetic compounds for potential discovery of selective PPK1-inhibitors.

Keywords: antimicobial, Escherichia coli, inorganic polyphosphate, PPK1-inhibitors

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Authors: N. Laosiripojana, P. Tepamatr

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

Keywords: bismuth, platinum, water gas shift, ceria

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Authors: Wang Zhiwei, Wang Weiwu

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The process of urbanization in China has entered a critical period of transformation from urban expansion and construction to delicate urban design, thus forming a new direction in the field of urban design. So far, catalyst theory has become a prominent guiding strategy in urban planning and design. In this paper, under the background of urban renewal, catalyst theory is taken as the guiding ideology to explore the method of urban design in shouxian county. Firstly, this study briefly introduces and analyzes the catalyst theory. Through field investigation, it is found that the city has a large number of idle Spaces, such as abandoned factories and schools. In the design, the idle Spaces in the county town are utilized and interlinked in space, and functional interaction is carried out from the pattern of the county town. On the one hand, the results showed that the catalyst theory can enhance the vitality of the linear street space with a small amount of monomer construction. On the other hand, the city can also increase the cultural and economic sites of the city without damaging the historical relics and the sense of alterations of the ancient city, to improve the quality of life and quality of life of citizens. The city micro-transformation represented by catalyst theory can help ancient cities like shouxian to realize the activation of the old city and realize the gradual development.

Keywords: catalytic theory, urban design, China's ancient city, Renaissance

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Authors: Xin Chen, Xinyong Li, Qidong Zhao, Dong Wang

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A new coupling system was constructed by combining photo-electrochemical cell with electro-fenton cell (PEC-EF). The electrode material in this system was derived from MnyFe₁₋yCo Prussian-Blue-Analog (PBA). Mn₀.₄Fe₀.₆Co₀.₆₇-N@C spin-coated on carbon paper behaved as the gas diffusion cathode and Mn₀.₄Fe₀.₆Co₀.₆₇O₂.₂ spin-coated on fluorine-tin oxide glass (FTO) as anode. The two separated cells could degrade Sulfamethoxazole (SMX) simultaneously and some coupling mechanisms by PEC and EF enhancing the degradation efficiency were investigated. The continuous on-site generation of H₂O₂ at cathode through an oxygen reduction reaction (ORR) was realized over rotating ring-disk electrode (RRDE). The electron transfer number (n) of the ORR with Mn₀.₄Fe₀.₆Co₀.₆₇-N@C was 2.5 in the selected potential and pH range. The photo-electrochemical properties of Mn₀.₄Fe₀.₆Co₀.₆₇O₂.₂ were systematically studied, which displayed good response towards visible light. The photoinduced electrons at anode can transfer to cathode for further use. Efficient photo-electro-catalytic performance was observed in degrading SMX. Almost 100% SMX removal was achieved in 120 min. This work not only provided a highly effective technique for antibiotic treatment but also revealed the synergic effect between PEC and EF.

Keywords: electro-fenton, photo-electrochemical, synergic effect, sulfamethoxazole

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Authors: Krasimir Ivanov, Dimitar Dimitrov, Tatyana Tabakova, Stefka Kirkova, Anna Stoilova, Violina Angelova

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It has been suggested that nicotine, CO and tar in mainstream smoke are the most important substances and have been judged as the most harmful compounds, responsible for the health hazards of smoking. As nicotine is extremely important for smoking qualities of cigarettes and the tar yield in the tobacco smoke is significantly reduced due to the use of filters with various content and design, the main efforts of cigarettes researchers and manufacturers are related to the search of opportunities for CO content reduction. Highly active ceria supported gold catalyst was prepared by the deposition-precipitation method, and the possibilities for CO oxidation in the synthetic gaseous mixture were evaluated using continuous flow equipment with fixed bed glass reactor at atmospheric pressure. The efficiently of the catalyst in CO oxidation in the real cigarette smoke was examined by a single port, puf-by-puff smoking machine. Quality assessment of smoking using cigarette holder containing catalyst was carried out. It was established that the catalytic activity toward CO oxidation in cigarette smoke rapidly decreases from 70% for the first cigarette to nearly zero for the twentieth cigarette. The present study shows that there are two critical factors which do not permit the successful use of catalysts to reduce the CO content in the mainstream cigarette smoke: (i) significant influence of the processes of adsorption and oxidation on the main characteristics of tobacco products and (ii) rapid deactivation of the catalyst due to the covering of the catalyst’s grains with condensate.

Keywords: cigarette smoke, CO oxidation, gold catalyst, mainstream

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Authors: Lifar M. S., Tereshchenko A. A., Bulgakov A. N., Guda S. A., Guda A. A., Soldatov A. V.

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Metal nanoparticles are widely used as heterogeneous catalysts to activate adsorbed molecules and reduce the energy barrier of the reaction. Reaction product yield depends on the interplay between elementary processes - adsorption, activation, reaction, and desorption. These processes, in turn, depend on the inlet feed concentrations, temperature, and pressure. At stationary conditions, the active surface sites may be poisoned by reaction byproducts or blocked by thermodynamically adsorbed gaseous reagents. Thus, the yield of reaction products can significantly drop. On the contrary, the dynamic control accounts for the changes in the surface properties and adjusts reaction parameters accordingly. Therefore dynamic control may be more efficient than stationary control. In this work, a reinforcement learning algorithm has been applied to control the simulation of CO oxidation on a catalyst. The policy gradient algorithm is learned to maximize the CO₂ production rate based on the CO and O₂ flows at a given time step. Nonstationary solutions were found for the regime with surface deactivation. The maximal product yield was achieved for periodic variations of the gas flows, ensuring a balance between available adsorption sites and the concentration of activated intermediates. This methodology opens a perspective for the optimization of catalytic reactions under nonstationary conditions.

Keywords: artificial intelligence, catalyst, co oxidation, reinforcement learning, dynamic control

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Authors: T. Maruyama, T. Saida, S. Naritsuka, S. Iijima

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Single-walled carbon nanotubes (SWCNTs) are generally synthesized by chemical vapor deposition (CVD) using Fe, Co, and Ni as catalysts. However, due to the Ostwald ripening of metal catalysts, the diameter distribution of the grown SWCNTs is considerably wide (>2 nm), which is not suitable for electronics applications. In addition, reduction in the growth temperature is desirable for fabricating SWCNT devices compatible with the LSI process. Herein, we performed SWCNT growth by alcohol catalytic CVD using platinum-group metal catalysts (Pt, Rh, and Pd) because these metals have high melting points, and the reduction in the Ostwald ripening of catalyst particles is expected. Our results revealed that web-like SWCNTs were obtained from Pt and Rh catalysts at growth temperature between 500 °C and 600 °C by optimizing the ethanol pressure. The SWCNT yield from Pd catalysts was considerably low. By decreasing the growth temperature, the diameter and chirality distribution of SWCNTs from Pt and Rh catalysts became small and narrow. In particular, the diameters of most SWCNTs grown using Pt catalysts were below 1 nm and their diameter distribution was considerably narrow. On the contrary, SWCNTs can grow from Rh catalysts even at 300 °C by optimizing the growth condition, which is the lowest temperature recorded for SWCNT growth. Our results demonstrated that platinum-group metals are useful for the growth of small-diameter SWCNTs and facilitate low-temperature growth.

Keywords: carbon nanotube, chemical vapor deposition, catalyst, platinum, rhodium, palladium

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Authors: Zelalem Bitew, Adane Kassa, Beyene Misgan

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In this study, a sensitive and selective voltammetric method based on poly(diphenylamine-4-sulfonic acid) modified glassy carbon electrode (poly(DPASA)/GCE) was developed for determination of gallic acid. Appearance of an irreversible oxidative peak at both bare GCE and poly(DPASA)/GCE for gallic acid with about three folds current enhancement and much reduced potential at poly(DPASA)/GCE showed catalytic property of the modifier towards oxidation of gallic acid. Under optimized conditions, Adsorptive stripping square wave voltammetric peak current response of the poly(DPASA)/GCE showed linear dependence with gallic acid concentration in the range 5.00 × 10-7 − 3.00 × 10-4 mol L-1 with limit of detection of 4.35 × 10-9. Spike recovery results between 94.62-99.63, 95.00-99.80 and 97.25-103.20% of gallic acid in honey, raw peanut, and commercial peanut butter samples respectively, interference recovery results with less than 4.11% error in the presence of uric acid and ascorbic acid, lower LOD and relatively wider dynamic range than most of the previously reported methods validated the potential applicability of the method based on poly(DPASA)/GCE for determination of gallic acid real samples including in honey and peanut samples.

Keywords: gallic acid, diphenyl amine sulfonic acid, adsorptive anodic striping square wave voltammetry, honey, peanut

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Authors: Waranya Imprasittichai, Patsarawadee Paojinda, Sudaratana R. Krungkrai, Nirianne Marie Q. Palacpac, Toshihiro Horii, Jerapan Krungkrai

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Fusion of the last two enzymes in the pyrimidine biosynthetic pathway in the inversed order by having COOH-terminal orotate phosphoribosyltransferase (OPRT) and NH2-terminal orotidine 5'-monophosphate decarboxylase (OMPDC), as OMPDC-OPRT, are described in many organisms. In this study, we constructed gene fusions of Plasmodium falciparum OMPDC-OPRT (1,836 bp) in pTrcHisA vector and expressed as an 6xHis-tag bifunctional protein in three Escherichia coli strains (BL21, Rosetta, TOP10) at 18 °C, 25 °C and 37 °C. The recombinant bifunctional protein was partially purified by Ni-Nitrilotriacetic acid-affinity chromatography. Specific activities of OPRT and OMPDC domains in the bifunctional enzyme expressed in E. coli TOP10 cells were approximately 3-4-fold higher than those in BL21 cells. There were no enzymatic activities when the construct vector expressed in Rosetta cells. Maximal expression of the fused gene was observed at 18 °C and the bifunctional enzyme had specific activities of OPRT and OMPDC domains in a ratio of 1:2. These results provide greater yields and better catalytic activities of the bifunctional OMPDC-OPRT enzyme for further purification and kinetic study.

Keywords: bifunctional enzyme, orotate phosphoribosyltransferase, orotidine 5'-monophosphate decarboxylase, plasmodium falciparum

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Authors: Maryam Kiani

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In order to enhance the efficiency and stability of an electrocatalyst for formic acid electro-oxidation reaction (FAOR), we developed a method to create Pt/Ni nanoparticles with carbon black. These nanoparticles were prepared using a simple impregnation reduction technique. During the observation, it was found that the nanoparticles had a spherical shape. Additionally, the average particle size remained consistent, falling within the range of about 4 nm. This approach aimed to obtain a loaded Pt-based electrocatalyst that would exhibit improved performance and stability when used in FAOR applications. By utilizing the impregnation reduction method and incorporating Ni nanoparticles along with Pt, we sought to enhance the catalytic properties of the material. By incorporating Ni atoms into the Pt structure, the electronic properties of Pt are modified, resulting in a delay in the chemisorption of harmful CO intermediate species. This modification also promotes the dehydrogenation pathway of the formic acid oxidation reaction (FAOR). Through electrochemical analysis, it has been observed that the Pt3Ni-C catalyst exhibits enhanced performance in FAOR compared to traditional Pt catalysts. This means that the addition of Ni atoms improves the efficiency and effectiveness of the Pt3Ni-C catalyst in facilitating the FAOR process. Overall, the utilization of these alloy nanoparticles as electrocatalysts represents a significant advancement in fuel cell technology.

Keywords: electrocatalyst, impregnation reduction method, formic acid electro-oxidation reaction, fuel cells

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Authors: Peikun Zhang, Chunhua Cui

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Photoelectrochemical (PEC) water splitting provides a promising pathway to convert solar energy into renewable fuels. However, the main and seemingly insurmountable obstacle is that the sluggish kinetics of oxygen evolution reaction (OER) severely jeopardizes the overall efficiency, thus exploring highly active, stable, and appreciable catalysts is urgently requested. Herein a competitive coordination strategy was demonstrated to form a reversible hybrid homo-heterogeneous catalyst for efficient OER in alkaline media. The dynamic process involves an in-situ anchoring of soluble nickel–bipyridine pre-catalyst to a conductive substrate under OER and a re-dissolution course under open circuit potential, induced by the competitive coordination between nickel–bipyridine and nickel-hydroxyls. This catalyst allows to elaborately self-modulate a charge-transfer layer thickness upon the catalytic on-off operation, which affords substantially increased active sites, yet remains light transparency, and sustains the stability of over 200 hours of continuous operation. The integration of this catalyst with exemplified state-of-the-art Ni-sputtered Si photoanode can facilitate a ~250 mV cathodic shift at a current density of 20 mA cm-2. This finding helps the understanding of catalyst from a “dynamic” perspective, which represents a viable alternative to address remaining hurdles toward solar-driven water oxidation.

Keywords: molecular catalyst, oxygen evolution reaction, solar energy, transition metal complex, water splitting

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Authors: Cahit Demetgul, Sahin Bayraktar, Neslihan Beyazit

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Metalloenzymes are enzyme proteins containing metal ions, which are directly bound to the protein or to enzyme-bound nonprotein components. One of the major metalloenzymes that play a key role in oxidation reactions is catechol oxidase, which shows catecholase activity i.e. oxidation of a broad range of catechols to quinones through the four-electron reduction of molecular oxygen to water. Studies on the model compounds mimicking the catecholase activity are very useful and promising for the development of new, more efficient bioinspired catalysts, for in vitro oxidation reactions. In this study, a new tetradentate asymmetrical Schiff-base and its Cu(II) complex were synthesized by condensation of 4-nitro-1,2-phenylenediamine with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one and by using an appropriate Cu(II) salt, respectively. The prepared compounds were characterized by elemental analysis, FT-IR, NMR, UV-Vis and magnetic susceptibility. The catecholase-mimicking activity of the new Schiff Base Cu(II) complex was performed for the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) in methanol at 25 °C, where the electronic spectra were recorded at different time intervals. The yield of the quinone (3,5-DTBQ) was determined from the measured absorbance at 400 nm of the resulting solution. The compatibility of catalytic reaction with Michaelis-Menten kinetics was also investigated. In conclusion, we have found that our new Schiff Base Cu(II) complex presents a significant capacity to catalyze the oxidation reaction of the catechol to o-quinone.

Keywords: catecholase activity, Michaelis-Menten kinetics, Schiff base, transition metals

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Authors: Mohamed H. El-Newehy, Badr M. Thamer, Nasser A. M. Barakat, Mohammad A.Abdelkareem, Salem S. Al-Deyab, Hak Y. Kim

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In this study, the influence of nitrogen doping on the electrocatalytic activity of carbon nanofibers with nickel nanoparticles toward methanol oxidation is introduced. The modified carbon nanofibers have been synthesized from calcination of electrospun nanofiber mats composed of nickel acetate tetrahydrate, poly(vinyl alcohol) and urea in argon atmosphere at 750oC. The utilized physicochemical characterizations indicated that the proposed strategy leads to form carbon nanofibers having nickel nanoparticles and doped by nitrogen. Moreover, due to the high-applied voltage during the electrospinning process, the utilized urea chemically bonds with the polymer matrix, which leads to form nitrogen-doped CNFs after the calcination process. Investigation of the electrocatalytic activity indicated that nitrogen doping NiCNFs strongly enhances the oxidation process of methanol as the current density increases from 52.5 to 198.5 mA/cm2 when the urea content in the original electrospun solution was 4 wt% urea. Moreover, the nanofibrous morphology exhibits distinct impact on the electrocatalytic activity. Also, nitrogen-doping enhanced the stability of the introduced Ni-based electrocatalyst. Overall, the present study introduces effective and simple strategy to modify the electrocatalytic activity of the nickel-based materials.

Keywords: electrospinning, methanol electrooxidation, fuel cells, nitrogen-doping, nickel

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Authors: Jiang Xu, Daoping Wang, Qun Li, Yinghong Pan

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2,4-Epibrassinolide (EBR), which is a kind of plant hormone Brassinosteroids (BRs), is widely studied and applied in the global scale but the proteomic characteristics of EBR alleviating low temperature stress in rice seedling leaves are still not clear. In this study, seeding rice of Nipponbare were treated with EBR and distilled water, then stressed at 4℃ or 26 ℃, and analyzed by mass spectrometry analysis, verified by parallel reaction monitoring technique (PRM). The results showed that 5778 proteins were identified in total and 4834 proteins were identified with quantitative information. Among them, 401 up-regulated and 220 down-regulated proteins may be related to EBR alleviating low temperature stress in rice seedling leaves. The molecular functions of most of up-regulated proteins are RNA binding and hydrolase activity and are mainly enriched in the pathways of carbon metabolism, folic acid synthesis, and amino acid biosynthesis. The down-regulated proteins are mainly related to catalytic activity and oxidoreductase activity and are mainly enriched in the pathways of limonene and pinene degradation, riboflavin metabolism, porphyrin and chlorophyll metabolism, and other metabolic pathways. PRM validation and literature analysis showed that NADP-malic acidase, peroxidase, 3-phosphoglycerate dehydrogenase, enolase, glyceraldehyde-3- phosphate dehydrogenase and pyruvate kinase are closely related to the effect of EBR on low temperature stress. These results also suggested that BRs could relieve the effect of low temperature stress on rice seed germination in many ways.

Keywords: 2, 4-Epibrassinolid, low temperature stress, proteomic analysis, rice

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Authors: Olga A. Krysiak, Grzegorz Cichowicz, Wojciech Hyk, Michal Cyranski, Jan Augustynski

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Metal oxides are known electrocatalyst in water oxidation reaction. Due to the fact that it is desirable for efficient oxygen evolution catalyst to contain numerous redox-active metal ions to guard four electron water oxidation reaction, mixed metal oxides exhibit enhanced catalytic activity towards oxygen evolution reaction compared to single metal oxide systems. On the surface of fluorine doped tin oxide coated glass slide (FTO) deposited (doctor blade technique) mixed metal oxide layer composed of nickel, iron, and chromium. Oxide coating was acquired by heat treatment of the aqueous precursors' solutions of the corresponding salts. As-prepared electrodes were photosensitive and acted as an efficient oxygen evolution catalyst. Our results showed that obtained by this method electrodes can be activated which leads to achieving of higher current densities. The recorded current and photocurrent associated with oxygen evolution process were at least two orders of magnitude higher in the presence of oxide layer compared to bare FTO electrode. The overpotential of the process is low (ca. 0,2 V). We have also checked the activity of the catalyst at different known photoanodes used in sun-driven water splitting. Herein, we demonstrate that we were able to achieve efficient oxygen evolution catalysts using relatively cheap precursor consisting of earth abundant metals and simple method of preparation.

Keywords: chromium, electrocatalysis, iron, metal oxides, nickel, oxygen evolution

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Authors: Elmineh Tsegahun Gedif

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Zinc oxide nanoparticles (ZnO NPs) have attracted huge attention due to catalytic, optical, photonic, and antibacterial activity. Zinc oxide nanoparticles were successfully synthesized via a fast, non-toxic, cost-effective, and eco-friendly method by biologically reducing Zn(NO3)2.6H2O solution with Neem (Azadirachta indica) leaf extract under optimum conditions (pH = 9). The presence of active flavonoids, phenolic groups, alkaloids, terpenoids, and tannins, which were in the biomass of the Neem leaf extract before and after reduction, was identified using qualitative screening methods (observing the color changes) and FT-IR Spectroscopy. The formation of ZnO NPs was visually indicated by the color changes from colorless to light yellow color. Biosynthesized nanoparticles were also characterized by UV-visible, FT-IR, and XRD spectroscopies. The reduction process was simple and convenient to handle and was monitored by UV-visible spectroscopy that showed surface plasmon resonance (SPR) of the ZnO NPs at 321 nm. This result clearly revealed the formation of ZnO NPs. X-ray diffraction was used to investigate the crystal structure. The average particle size of ZnO powder and around 20 nm using the line width of the plane, and the refraction peak using Scherrer’s equation. The synthesized zinc oxide nanoparticles were evaluated for antimicrobial activities against Gram-positive and Gram-negative bacteria. Zinc nanoparticles exhibited the maximum zone of inhibition against Escherichia coli (15 mm), while the least activity was seen against Staphylococcus aureus.

Keywords: antimicrobial activity, azadirachta indica, green synthesis, ZnO NPs

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Authors: Schirin Hanf, Carlos Lizandara-Pueyo, Timmo P. Emmert, Ivana Jevtovikj, Roger Gläser, Stephan A. Schunk

Abstract:

Metal alkoxides are very versatile precursors for a broad array of complex functional materials. However, metal alkoxides, especially transition metal alkoxides, tend to form oligomeric structures due to the very strong M–O–M binding motif. This fact hinders their facile application in sol-gel-processes and complicates access to complex carbonate or oxidic compounds after hydrolysis of the precursors. Therefore, the development of a synthetic alternative with the aim to grant access to carbonates and hydroxycarbonates from simple metal alkoxide precursors via hydrolysis is key to this project. Our approach involves the reaction of metal alkoxides with unsaturated isoelectronic molecules, such as carbon dioxide. Subsequently, a stoichiometric insertion of the CO₂ into the alkoxide M–O bond takes place and leads to the formation of soluble metal alkyl carbonates. This strategy is a very elegant approach to solubilize metal alkoxide precursors to make them accessible for sol-gel chemistry. After hydrolysis of the metal alkyl carbonates, crystalline metal carbonates, and hydroxycarbonates can be obtained, which were then utilized for the synthesis of Cu/Zn based bulk catalysts for methanol synthesis. Using these catalysts, a comparable catalytic activity to commercially available MeOH catalysts could be reached. Based on these results, a complement for traditional precipitation techniques, which are usually utilized for the synthesis of bulk methanol catalysts, have been found based on an alternative solubilization strategy.

Keywords: metal alkoxides, metal carbonates, metal hydroxycarbonates, CO₂ insertion, solubilization

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Authors: Zohreh Derikvand

Abstract:

One new 2D metal-organic coordination polymer of Ni(II) namely [Ni2(ndc)2(DMSO)4(H2O)]n, where ndc = naphthalene-1,4-dicarboxylic acid and DMSO= dimethyl sulfoxide has been synthesized and characterized by elemental analysis, spectral (IR, UV-Vis), thermal (TG/DTG) analysis and single crystal X-ray diffraction. Compound 1 possesses a 2D layer structure constructed from dinuclear nickel(II) building blocks in which two crystallographically independent Ni2+ ions are bridged by ndc2– ligands and water molecule. The ndc2– ligands adopt μ3 bridging modes, linking the metal centers into a two-dimensional coordination framework. The two independent NiII cations are surrounded by dimethyl sulfoxide and naphthalene-1,4-dicarboxylate molecules in distorted octahedron geometry. In the crystal structures of 1 there are non-classical hydrogen bonding arrangements and C-H–π stacking interactions. Electrochemical behavior of [Ni2(ndc)2(DMSO)4(H2O)]n, (Ni-NDA) on the surface of carbon nanotube (CNTs) glassy carbon electrode (GCE) was described. The surface structure and composition of the sensor were characterized by scanning electron microscopy (SEM). Oxidation of fructose on the surface of modified electrode was investigated with cyclic voltammetry and electrochemical impedance spectroscopy (EIS) and the results showed that the Ni-NDA/CNTs film displays excellent electrochemical catalytic activities towards fructose oxidation.

Keywords: naphthalene-1, 4-dicarboxylic acid, crystal structure, coordination polymer, electrocatalysis, impedance spectroscopy

Procedia PDF Downloads 317

Authors: Chaima Zoulikha Tabet Zatla, Nihel Dib, Sumeya Bedrane, Juan Carlos Hernandez Garrido, Redouane Bachir, Miguel Angel Cauqui, Jose Juan Calvino Gamez

Abstract:

These last year's our planet has witnessed global warming, which is a serious threat to our lives; it has many causes, such as the CO₂ excess in the atmosphere that results from our activity, for the purpose of living in a neater and better environment, working and improving an eco-responsible energy system is a must. Valorization of biomass to produce biofuels is among the most compelling routes to decrease air pollution without considerable modification in current vehicle technology. Effective transformation of lignocellulosic biomass-derived compounds into liquid fuels and value-added chemicals is an economically viable solution. Presently, very competitive technics for the conversion of lignocellulosic biomass into platform chemicals, such as furfural and Hydroxymethylfurfural (HMF), are used. Furfural (C₅H₄O₂) is a major hemi cellulosic biomass-derived platform molecule. In our work, we focus on the valorization of lignocellulosic biomass derivative furfural that is transformed into biofuel through a hydrodeoxygenation reaction in general and involving a catalytic process. In order to get to this point, we are synthesizing and characterizing a series of catalysts with different amounts of Ru (0.5%, 1% and 2%) supported on alumina-silica mixed oxides with various molar ratios (Si/Al = 2.5; 5; 7; 10; 15). These catalysts will be characterized by numerous technics such as N₂ adsorption/desorption, Pyridine adsorption (acidity measure), FTIR, X-rays diffraction, AAS, TEM and SEM.

Keywords: furfural, ruthenium, silica-alumina, biomass, biofuel

Procedia PDF Downloads 66

Authors: Sanjeeb Sutradhar, Archita Patnaik

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Histidine is one of the twenty-two naturally occurring essential amino acids exhibiting two conformations, L-histidine and D-histidine. D-Histidine is biologically inert, while L-histidine is bioactive because of its conversion to neurotransmitter or neuromodulator histamine in both brain as well as central nervous system. The deficiency of L-histidine causes serious diseases like Parkinson’s disease, epilepsy and the failure of normal erythropoiesis development. Gold nanocomposites are attractive materials due to their excellent biocompatibility and are easy to adsorb on the electrode surface. In the present investigation, hydrophobic fullerene-C60 was functionalized with homocysteine via nucleophilic addition reaction to make it hydrophilic and to successively make the nanocomposite with in-situ prepared gold nanoparticles with ascorbic acid as reducing agent. The electronic structure calculations of the AuNPs@Hcys-C60 nanocomposite showed a drastic reduction of HOMO-LUMO gap compared to the corresponding molecules of interest, indicating enhanced electron transportability to the electrode surface. In addition, the electrostatic potential map of the nanocomposite showed the charge was distributed over either end of the nanocomposite, evidencing faster direct electron transfer from nanocomposite to the electrode surface. This nanocomposite showed catalytic activity; the nanocomposite modified glassy carbon electrode showed a tenfold higher kₑt, the electron transfer rate constant than the bare glassy carbon electrode. Significant improvement in its sensing behavior by square wave voltammetry was noted.

Keywords: fullerene-C60, gold nanocomposites, L-Histidine, square wave voltammetry

Procedia PDF Downloads 236

Authors: Masoumeh Tabatabaee, Zahra Shahryarzadeh, Masoud R. Shishebor

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Advanced oxidation process (AOPs) is alternative method for the complete degradation many organic pollutants. When a photocatalyst absorbs radiation whose energy hν > Eg an ē from its filled valance band (VB) is promoted to its conduction band (CB) and valance band holes h+ are formed. Electron would reduce any available species, including O2, water and hydroxide ion to form hydroxyl radicals. ZnO and TiO2 are important photocatalysts with high catalytic activity that have attracted much research attention. TiO2 can only absorb a small portion of solar spectrum in the UV region and many methods such as dye sensitization, doping of other metals and using TiO2 with another semiconductor have been used to improve the photocatalytic activity of TiO2 under solar irradiation. Studies have shown that the use of metal oxides or sulfide such as WO3, MoO3, SiO2, MgO, ZnO, and CdS with TiO2 can significantly enhance the photocatalytic activity of TiO2. Due to similarity of photodegradation mechanism of ZnO with TiO2, it is a suitable semiconductor using with TiO2 and recently nanosized bicomponent TiO2-ZnO photocatalysts were prepared and used for degradation of some pollutants. In this study, Nano-sized ZnO/TiO2 composite was synthesized. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM) were used to characterize the structure and morphology of it. The effect of photocatalytic activity of prepared ZnO/TiO2 on the degradation of cyanide ion under UV was investigated. The effect of various parameters such as ZnO/TiO2 concentration, amount of photocatalyst, amount of H2O2, initial dye or cyanide ion concentration, pH and irradiation time on were investigated. Results show that more than 95% of 4 mgL-1 cyanide ion degraded after 60-min reaction time and under UV irradiation.

Keywords: photodegradation, ZnO/TiO2, nanoparticle, cyanide ion

Procedia PDF Downloads 377

Authors: Wai Keng Teng, Gek Cheng Ngoh, Rozita Yusoff, Mohamed Kheireddine Aroua

Abstract:

As a by-product of the biodiesel industries, glycerol has been vastly generated which surpasses the market demand. It is imperative to develop an efficient glycerol valorization processes in minimizing the net energy requirement and intensifying the biodiesel production. In this study, base-catalyzed transesterification of glycerol with dimethyl carbonate using microwave irradiation as heating method to produce glycerol carbonate was conducted by varing grades of glycerol i.e. 70%, 86% and 99% purity that obtained from biodiesel plant. Metal oxide catalysts were used with varying operating parameters including reaction time, DMC/glycerol molar ratio, catalyst weight %, temperature and stirring speed. From the study on the effect of different operating parameters; it was found that the type of catalyst used has the most significant effect on the transesterification reaction. Admist the metal oxide catalysts examined, CaO gave the best performance. This study indicates the feasibility of producing glycerol carbonate using different grade of glycerol in both conventional thermal activation and microwave irradiation with CaO as catalyst. Microwave assisted transesterification (MAT) of glycerol into glycerol carbonate has demostrated itself as an energy efficient route by achieving 94.3% yield of GC at 65°C, 5 minutes reaction time, 1 wt% CaO and DMC/glycerol molar ratio of 2. The advantages of MAT transesterification route has made the direct utilization of bioglycerol from biodiesel production without the need of purification. This has marked a more economical and less-energy intensive glycerol carbonate synthesis route.

Keywords: base-catalyzed transesterification, glycerol, glycerol carbonate, microwave irradiation

Procedia PDF Downloads 273

Authors: Panumard Kaewmora, Thirasak Rirksomboon, Vissanu Meeyoo

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Due to the globally growing demands of petroleum fuel and fossil fuels, the scarcity or even depletion of fossil fuel sources could be inevitable. Alternatively, the utilization of renewable sources, such as biomass, has become attractive to the community. Biomass can be converted into bio-oil by fast pyrolysis. In water phase of bio-oil, acetic acid which is one of its main components can be converted to hydrogen with high selectivity over effective catalysts in steam reforming process. Steam reforming of acetic acid as model compound has been intensively investigated for hydrogen production using various metal oxide supported nickel catalysts and yet they seem to be rapidly deactivated depending on the support utilized. A catalyst support such as Ce1-xZrxO2 mixed oxide was proposed for alleviating this problem with the anticipation of enhancing hydrogen yield. However, catalyst preparation methods play a significant role in catalytic activity and performance of the catalysts. In this work, Ce0.75Zr0.25O2 mixed oxide solid solution support was prepared by urea hydrolysis using microwave as heat source. After that nickel metal was incorporated at 15 wt% by incipient wetness impregnation method. The catalysts were characterized by several techniques including BET, XRD, H2-TPR, XRF, SEM, and TEM as well as tested for the steam reforming of acetic acid at various operating conditions. Preliminary results showed that a hydrogen yield of ca. 32% with a relatively high acetic conversion was attained at 650°C.

Keywords: acetic acid, steam reforming, microwave, nickel, ceria, zirconia

Procedia PDF Downloads 162