Search results for: perovskite catalyst

Authors: Roghaye Behroozi

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The development of functionalized metal complexes and nanomaterials has gained significant attention due to their potential in catalyzing selective oxidation and coupling reactions. These catalysts play a crucial role in various industrial and pharmaceutical processes, enhancing the efficiency, selectivity, and sustainability of chemical reactions. This research aims to design and synthesize new functionalized metal complexes and nanomaterials to explore their catalytic applications in the selective oxidation of alcohols and coupling reactions, focusing on improving yield, selectivity, and catalyst reusability. The study involves the synthesis of a nickel Schiff base complex stabilized within 41-MCM as a heterogeneous catalyst. A Schiff base ligand derived from glycine was used to create a tin (IV) metal complex characterized through spectroscopic techniques and computational analysis. Additionally, iron-based magnetic nanoparticles functionalized with melamine were synthesized for catalytic evaluation. Lastly, a palladium (IV) complex was prepared, and its oxidative stability was analyzed. The nickel Schiff base catalyst showed high selectivity in converting primary and secondary alcohols to aldehydes and ketones, with yields ranging from 73% to 90%. The tin (IV) complex demonstrated accurate structural and electronic properties, with consistent results between experimental and computational data. The melamine-functionalized iron nanoparticles exhibited efficient catalytic activity in producing triazoles, with enhanced reaction speed and reusability. The palladium (IV) complex displayed remarkable stability and low reactivity towards C–C bond formation due to its symmetrical structure. The synthesized metal complexes and nanomaterials demonstrated significant potential as efficient, selective, and reusable catalysts for oxidation and coupling reactions. These findings pave the way for developing environmentally friendly and cost-effective catalytic systems for industrial applications.

Keywords: catalysts, Schiff base complexes, metal-organic frameworks, oxidation reactions, nanoparticles, reusability

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Authors: Yingjeng James Li, Chiao-Chih Hu

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Membrane electrode assemblies (MEAs) for proton exchange membrane fuel cell (PEMFC) applications were prepared by using 10 and 15 um PEMs. Except for different membrane thicknesses, these MEAs were prepared by the same conditions. They were prepared by using catalyst coated membrane (CCM) process. The catalyst employed is 40% Pt/C, and the Pt loading is 0.5mg/cm² for the sum of anode and cathode. Active area of the MEAs employed in this study is 5cm*5cm=25cm². In polarization measurements, the flow rates were always set at 1.2 stoic for anode and 3.0 stoic for cathode. The outlets were in open-end mode. The flow filed is tri-serpentine design. The cell temperatures and the humidification conditions were varied for the purpose of MEA performance observations. It was found that the performance of these two types of MEAs is about the same at fully or partially humidified operation conditions; however, 10um MEA exhibits higher current density in dry or low humidified conditions. For example, at 70C cell, 100% RH, and 0.6V condition, both MEAs have similar current density which is 1320 and 1342mA/cm² for 15um and 10um product, respectively. However, when in operation without external humidification, 10um MEA can produce 1085mA/cm²; whereas 15um MEA produces only 720mA/cm².

Keywords: fuel cell, membrane electrode assembly, PEFC, PEMFC, proton exchange membrane

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Authors: Adriana-Gabriela Plaiasu, Catalin Marian Ducu

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The interest in the unique properties associated with materials having structures on a nanometer scale has been increasing at an exponential rate in last decade. Among the functional mineral compounds such as perovskite (CaTiO3), rutile (TiO2), CaF2, spinel (MgAl2O4), wurtzite (ZnS), zincite (ZnO) and the cupric oxide (CuO) has been used in numerous applications such as catalysis, semiconductors, batteries, gas sensors, biosensors, field transistors and medicine. The Solar Physical Vapor Deposition (SPVD) presented in the paper as elaboration method is an original process to prepare nanopowders working under concentrated sunlight in 2kW solar furnaces. The influence of the synthesis parameters on the chemical and microstructural characteristics of zinc and manganese oxides synthesized nanophases has been systematically studied using XRD, TEM and SEM.

Keywords: characterization, morphological, nano-oxides, structural

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Authors: Su-Ning Wang, Yao-Qiang Chen

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The CeO2-ZrO2-La2O3-Al2O3 composite oxides are synthesized using co-precipitation method by two different reactors (i.e. continuous stirred-tank reactor and batch reactor), and the corresponding Rh-only three-way catalysts are obtained by wet-impregnation approach. The textural, structural, morphology and redox properties of the support materials, as well as the catalytic performance of the Rh-only catalyst are investigated systematically. The results reveal that the materials (CZLA-C) synthesized by continuous stirred-tank reactor have a better physic-chemical properties than the counterpart material (CZLA-B) prepared by batch reactor. After aging treatment at 1000 ℃ for 5 h, the BET surface area and pore volume of S1 reach up to 76 m2 g-1 and 0.36 mL/g, respectively, which is higher than that of S2. The XRD and Raman results demonstrate that a high structural stability is obtained by S1 because of the negligible lattice variation and the slight grain growth after aging treatment. The SEM and TEM images display that the morphology of S1 is assembled by many homogeneous primary nanoparticles (about 6.12 nm) that are connected to form mesoporous structure The TPR measurement shows that S1 possesses a higher reduction ability than S2. Compared with the catalyst supported on the CZLA-B, the as-prepared CZLA-C demonstrates an improved three-way catalytic activity both before and after aging treatment.

Keywords: composite oxides, reactor, catalysis, catalytic performance

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Authors: Abhishek Chandra, Man Singh

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Highly stable and homogeneously dispersed amino acid coated silver nanoparticles (ANP) of ≈ 10 nm diameter, ranging from 420 to 430 nm are prepared on AgNO3 solution addition to gum of Azadirachta indica solution at 373.15 K. The amino acids were selected based on their polarity. The synthesized nanoparticles were characterized by UV-Vis, FTIR spectroscopy, HR-TEM, XRD, SEM and 1H-NMR. The coated nanoparticles were used as catalyst for the reduction of methylene blue dye in presence of Sn(II) in aqueous, anionic and cationic micellar media. The rate of reduction of dye was determined by measuring the absorbance at 660 nm, spectrophotometrically and followed the order: Kcationic > Kanionic > Kwater. After 12 min and in absence of the ANP, only 2%, 3% and 6% of the dye reduction was completed in aqueous, anionic and cationic micellar media respectively while, in presence of ANP coated by polar neutral amino acid with non-polar -R group, the reduction completed to 84%, 95% and 98% respectively. The ANP coated with polar neutral amino acid having non-polar -R group, increased the rate of reduction of the dye by 94, 3205 and 6370 folds in aqueous, anionic and cationic micellar media respectively. Also, the rate of reduction of the dye increased by three folds when the micellar media was changed from anionic to cationic when the ANP is coated by a polar neutral amino acid having a non-polar -R group.

Keywords: silver nanoparticle, surfactant, methylene blue, amino acid

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Authors: Ines Nitoi, Petruta Oancea, Lucian Constantin, Laurentiu Dinu, Maria Crisan, Malina Raileanu, Ionut Cristea

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2,4,6-Trinitrotoluene (TNT) is the most common pollutant identified in wastewater generated from munitions plants where this explosive is synthesized or handled (munitions load, assembly and pack operations). Due to their toxic and suspected carcinogenic characteristics, nitroaromatic compounds like TNT are included on the list of prioritary pollutants and strictly regulated in EU countries. Since their presence in water bodies is risky for human health and aquatic life, development of powerful, modern treatment methods like photocatalysis are needed in order to assures environmental pollution mitigation. The photocatalytic degradation of TNT was carried out at pH=7.8, in aqueous TiO2 based catalyst suspension, under sunlight irradiation. The enhanced photo activity of catalyst in visible domain was assured by 0.5% Fe doping. TNT degradation experiments were performed using a tubular collector type solar photoreactor (26 UV permeable silica glass tubes series connected), plug in a total recycle loops. The influence of substrate concentration and catalyst dose on the pollutant degradation and mineralization by-products (NO2-, NO3-, NH4+) formation efficiencies was studied. In order to compare the experimental results obtained in various working conditions, the pollutant and mineralization by-products measured concentrations have been considered as functions of irradiation time and cumulative photonic energy Qhν incident on the reactor surface (kJ/L). In the tested experimental conditions, at tens mg/L pollutant concentration, increase of 0,5%-TiO2 dose up to 200mg/L leads to the enhancement of CB degradation efficiency. Since, doubling of TNT content has a negative effect on pollutant degradation efficiency, in similar experimental condition, prolonged irradiation time from 360 to 480 min was necessary in order to assures the compliance of treated effluent with limits imposed by EU legislation (TNT ≤ 10µg/L).

Keywords: wastewater treatment, TNT, photocatalysis, environmental engineering

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Authors: Shuwen Wu, Zhi LI

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

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

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Authors: Tae Hyun Ahn, Gyo Woo Lee, Man Young Kim

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Because of high thermal efficiency and low CO2 emission, diesel engines are being used widely in many industrial fields although it makes many PM and NOx which give both human health and environment a negative effect. NOx regulations for diesel engines, however, are being strengthened and it is impossible to meet the emission standard without NOx reduction devices such as SCR (Selective Catalytic Reduction), LNC (Lean NOx Catalyst), and LNT (Lean NOx Trap). Among the NOx reduction devices, urea-SCR system is known as the most stable and efficient method to solve the problem of NOx emission. But this device has some issues associated with the ammonia slip phenomenon which is occurred by shortage of evaporation and thermolysis time, and that makes it difficult to achieve uniform distribution of the injected urea in front of monolith. Therefore, this study has focused on the mixing enhancement between urea and exhaust gases to enhance the efficiency of the SCR catalyst equipped in catalytic muffler by changing inlet gas temperature and spray conditions to improve the spray uniformity of the urea water solution. Finally, it can be found that various parameters such as inlet gas temperature and injector and injection angles significantly affect the evaporation and mixing of the urea water solution with exhaust gases, and therefore, optimization of these parameters are required.

Keywords: UWS (Urea-Water-Solution), selective catalytic reduction (SCR), evaporation, thermolysis, injection

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Authors: Tieling Xing, Jinqiu Yang, Guoqiang Chen

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It is environmentally friendly to use horseradish peroxidase (HRP) instead of the traditional transition metal catalyst for the catalyst of atom transfer radical polymerization (ATRP). Silk fabrics were successfully grafted with hydroxyl-containing acrylate monomer to improve its crease resistance by HRP-catalyzed ATRP method. Taking grafting yield as the evaluation index, single factor tests revealed that the optimum grafting reaction condition was as follow: monomer mass fraction 120-210%(o.w.f), HRP concentration 360-480U/mL, molar ratio of HRP to NaAsc 1:150, reaction temperature 50-60℃, reaction time 24h. Raman spectra showed hydroxyl-containing acrylate monomer were successfully grafted on silk fabrics. SEM figures indicated the surface of grafted silk became rougher, and graft copolymer was distributed evenly on the surface of silk fiber. The crease-resistant recovery property of grafted silk fabric was greatly improved, especially in wet crease recovery angle. The result showed hydroxyl-containing acrylate monomer can be successfully grafted onto silk fabric based on HRP-catalyzed ATRP method.

Keywords: atom transfer radical polymerization, catalysis, horseradish peroxidase, hydroxyl-containing acrylate monomer

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Authors: H. Boucheloukh, S. Rouissa, N. Aoun, M. Beloucifa, T. Sehili, F. Parrino, V. Loddo

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To optimize water purification and wastewater treatment by heterogeneous photocatalysis, we used NiFe₂O₄ as a catalyst and solar irradiation as a source of energy. In this concept, an organic substance present in many industrial effluents was chosen: naproxen ((S)-6-methoxy-α-methyl-2-naphthaleneacetic acid or 2-(6-methoxynaphthalenyl) propanoic), a non-steroidal anti-inflammatory drug. The main objective of this study is to degrade naproxen by an iron and nickel catalyst, the degradation of this organic pollutant by nickel ferrite has been studied in a heterogeneous aqueous medium, with the study of the various factors influencing photocatalysis such as the concentration of matter and the acidity of the medium. The photocatalytic activity was followed by HPLC-UV andUV-Vis spectroscopy. A first-order kinetic model appropriately fitted the experimental data. The degradation of naproxen was also studied in the presence of H₂O₂ as well as in an aqueous solution. The new hetero-system NiFe₂O₄/oxalic acid is also discussed. The fastest naproxen degradation was obtained with NiFe₂O₄/H₂O₂. In a first-place, we detailed the characteristics of the material NiFe₂O₄, which was synthesized by the sol-gel methods, using various analytical techniques: visible UV spectrophotometry, X-ray diffraction, FTIR, cyclic voltammetry, luminescent discharge optical emission spectroscopy.

Keywords: naproxen, nickelate, photocatalysis, oxalic acid

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Authors: Diana Mariz Catangay, Irish-Ann Montano, Frances Janine Suyat

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As an active pedestal for student’s interaction with both issues happening inside the school and out; may it be political, societal, international, or other current events, a school paper should at least meet the standard of providing a representation of the school’s morals and values and help the institution uplift its image. The researchers seek to ascertain how the two student publications from the Philippines’ two prime state universities, the University of the Philippines’ Philippine Collegian, and the Polytechnic University of the Philippines’ the Catalyst, presents iii their school through balanced journalism and objective documentation. The objectives include determining the number of school-related articles published versus those articles that are concerned outside the school’s jurisdiction, analyzing the insight it provides on the image of the university, assessing the similarities and/or differences between the two publications, and, finally, coming up with the conclusion of how the two newspapers uses their medium to present their respective schools. The research used the quantitative method of research in order to further analyze the articles that will serve as bases in coming up with the right conclusion based on the objectives of the study. Coding sheets and coding guides are utilized for the chosen research method. The gathered findings will then be interpreted as fitting to the goal of the research.

Keywords: content analysis, journalistic presentation, student publications, state universities

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Authors: B. M. Patil

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Calcium Zirconate (CaZrO3) has high protonic conductivities at elevated temperature in water or hydrogen atmosphere. Undoped calcium zirconate acts as a p-type semiconductor in air. In this paper, we reported synthesis of CaZrO3 nanoparticles via modified molecular precursor method. The precursor calcium zirconium oxalate (CZO) was synthesized by exchange reaction between freshly generated aqueous solution of sodium zirconyl oxalate and calcium acetate at room temperature. The controlled pyrolysis of CZO in air at 700°C for one hour resulted in the formation nanocrystalline CaZrO3 powder. CaZrO3 obtained by the present method was characterized by Simultaneous thermogravimetry and differential thermogravimetry (TG-DTA), X-ray diffraction (XRD), infra-red spectroscopy and transmission electron microscopy (TEM). The pellets of synthesized CaZrO3 fabricated, sintered at 1000°C for 5 hr and tested as sensors for NO2 and NH3 gases.

Keywords: CaZrO3, CZO, NO2, NH3

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Authors: A. A. Azab

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In this work, Sm0.6Sr0.4CoxMn1-xO3 (x=0, 0.1, 0.2 and 0.3) was synthesized by sol-gel method for magnetocaloric effect (MCE) applications. XRD analysis confirmed formation of the required orthorhombic phase of perovskite, and there is crystallographic phase transition as a result of substitution. Maxwell-Wagner interfacial polarisation and Koops phenomenological theory were used to investigate and analyze the temperature and frequency dependency of the dielectric permittivity. The phase transition from the ferromagnetic to the paramagnetic state was demonstrated to be second order. Based on the isothermal magnetization curves obtained at various temperatures, the magnetic entropy change was calculated. A magnetocaloric effect (MCE) over a wide temperature range was studied by determining DSM and the relative cooling power (RCP).

Keywords: magnetocaloric effect, pperovskite, magnetic phase transition, dielectric permittivity

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Authors: Asmaa Zaraq

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In the present work we report X-ray powder diffraction measurements of SrCaCoTeO6 and SrCaNiTeO6, at different temperatures. The crystal structures at room temperature of both compounds are determined; and results showing the existence of high-temperature phase transitions in them are presented. Both compounds have double perovskite structure with 1:1 ordered arrangement of the B site cations. At room temperature their symmetries are described with the P21/n space group, that correspond to the (a+b-b-) tilt system. The evolution with temperature of the structure of both compounds shows the presence of three phase transitions: a continuous one, at 450 and 500 K, a discontinuous one, at 700 and 775 K, and a continuous one at 900 and 950 K for SrCaCoTeO6 and SrCaNiTeO6, respectively with the following phase-transition sequence: P21/n → I2/m → I4/m → Fm-3m.

Keywords: double perovskites, caracterisation DRX, transition de phase

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

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

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

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Authors: Weerinda Appamana, Jirapong Keawkoon, Yamonporn Pacthong, Jirathiti Chitsanguansuk, Yanyong Sookklay

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In the present work, spinning disc reactor has been used for the intensification of synthesis of biodiesel from refined palm oil (RPO) based on the transesterification reaction. Experiments have been performed using different spinning disc surface and under varying operating parameters viz. molar ratio of oil to methanol (over the range of 1:4.5–1:9), rotational speed (over the range of 500–2,000 rpm), total flow rate (over the range of 260-520 ml/min), and KOH catalyst loading of 1.50% by weight of oil. Maximum FAME (fatty acid methyl esters) yield (97.5 %) of biodiesel from RPO was obtained at oil to methanol ratio of 1:6, temperature of 60 °C, and rotational speed of 1500 rpm and flow rate of 520 mL/min using groove disc at KOH catalyst loading of 1.5 wt%. Also, higher yield efficiency (biodiesel produced per unit energy consumed) was obtained for using the spinning disc reactor based approach as compared to the ultrasound hydrodynamic cavitation and conventional mechanical stirrer reactors. It obviously offers a significant reduction in the reaction time for the transesterification, especially when compared with the reaction time of 90 minutes required for the conventional mechanical stirrer. It can be concluded that the spinning disk reactor is a promising alternative method for continuous biodiesel production.

Keywords: spinning disc reactor, biodiesel, process intensification, yield efficiency

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Authors: André Luis Lima de Oliveira, Vera Lúcia Viana do Nascimento, Victória Maura Silva Bermudez, Mauricio Nunes Kleinberg, João Carlos da Costa Assunção, José Osvaldo Beserra Carioca

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The objective of this study was to synthesize a triglyceride with high content of unsaturated fatty acids from salmon oil (Salmo salar L.) by esterification with glycerol catalyzed dealuminized zeolite. A kinetic study was conducted to determine the reaction order and the activation energy. A statistical study was conducted to determine optimal reaction conditions. Initially, the crude oil was refined salmon physically and chemically. The crude oil was hydrolyzed and unsaturated free fatty acids were separated by urea complexation method. An experimental project to verify the parameters (temperature, glycerin and catalyst) with the greatest impact on the reaction was developed. In experiments aliquots were taken at predetermined times to measure the amount of free fatty acids. Pareto, surface, contour and hub graphs were used to determine the factors that maximized the reaction. According to the graphs the best reaction conditions were: temperature 80 ° C, the proportion glycerine/oil 5: 1 and 1% of catalyst. The kinetic data showed that the system was compatible with a second-order reaction. After analyzing the rate constant versus temperature charts a value of 85.31 kJ/mol was obtained for the reaction activation energy.

Keywords: esterification, kinect, oil, salmon

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Authors: M. A. Ghebouli, A. Bouhemadou, H. Choutri, L. Louaila

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Some physical properties of the cubic perovskites CsXF3 (X = Sr, Ca, and Hg) have been investigated using pseudopotential plane–wave (PP-PW) method based on the density functional theory (DFT). The calculated lattice constants within GGA (PBE) and LDA (CA-PZ) agree reasonably with the available experiment data. The elastic constants and their pressure derivatives are predicted using the static finite strain technique. We derived the bulk and shear moduli, Young’s modulus, Poisson’s ratio and Lamé’s constants for ideal polycrystalline aggregates. The analysis of B/G ratio indicates that CsXF3 (X = Ca, Sr, and Hg) are ductile materials. The thermal effect on the volume, bulk modulus, heat capacities CV, CP, and Debye temperature was predicted.

Keywords: perovskite, PP-PW method, elastic constants, electronic band structure

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

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

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

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Authors: Mohammadreza Akbari, Pooya Soleimani Besheli, Reza khalili, Sara Akbari, Davood Domiri Ganji

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In this symposium, our aims are accuracy, capabilities and power at solving of the complicate non-linear differential at the reaction chemical in the catalyst reactor (heterogeneous reaction). Our purpose is to enhance the ability of solving the mentioned nonlinear differential equations at chemical engineering and similar issues with a simple and innovative approach which entitled ‘’Akbari-Ganji's Method’’ or ‘’AGM’’. In this paper we solve many examples of nonlinear differential equations of chemical reactions and its investigate. The chemical reactor with the energy changing (non-isotherm) in two reactors of mixed and plug are separately studied and the nonlinear differential equations obtained from the reaction behavior in these systems are solved by a new method. Practically, the reactions with the energy changing (heat or cold) have an important effect on designing and function of the reactors. This means that possibility of reaching the optimal conditions of operation for the maximum conversion depending on nonlinear nature of the reaction velocity toward temperature, results in the complexity of the operation in the reactor. In this case, the differential equation set which governs the reactors can be obtained simultaneous solution of mass equilibrium and energy and temperature changing at concentration.

Keywords: new method (AGM), nonlinear differential equation, tubular and mixed reactors, catalyst bed

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Authors: Rauf Razzaq, Kaiwu Dong, Muhammad Sharif, Ralf Jackstell, Matthias Beller

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Carbon dioxide (CO2), a key greenhouse gas produced from both anthropogenic and natural sources, has been recently considered to be an important C1 building-block for the synthesis of many industrial fuels and chemicals. Catalytic hydrogenation of CO2 using a heterogeneous system is regarded as an efficient process for CO2 valorization. In this regard CO2 reduction to CO via the reverse water gas shift reaction (RWGSR) has attracted much attention as a viable process for large scale commercial CO2 utilization. This process can generate syn-gas (CO+H2) which can provide an alternative route to direct CO2 conversion to methanol and/or liquid HCs from FT reaction. Herein, we report a highly active and selective silica supported copper catalyst with efficient CO2 reduction to CO in a slurry-bed batch autoclave reactor. The reactions were carried out at 200°C and 60 bar initial pressure with CO2/H2 ratio of 1:3 with varying temperature, pressure and fed-gas ratio. The gaseous phase products were analyzed using FID while the liquid products were analyzed by using FID detectors. It was found that Cu/SiO2 catalyst prepared using novel ammonia precipitation-urea gelation method achieved 26% CO2 conversion with a CO and methanol selectivity of 98 and 2% respectively. The high catalytic activity could be attributed to its strong metal-support interaction with highly dispersed and stabilized Cu+ species active for RWGSR. So, it can be concluded that reduction of CO2 to CO via RWGSR could address the problem of using CO2 gas in C1 chemistry.

Keywords: CO2 reduction, methanol, slurry reactor, synthesis gas

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Authors: Anurag Kumar Pandey, Tapan Kumar Nath, Santanu Dhara

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Polluted water by industrial effluents or dyes has become a major global concern, particularly in developing countries. Such environmental contaminants constitute a serious threat to biodiversity, ecosystems, and human health worldwide; thus, their treatment is critical. The usage of nanoparticles has been discovered to be a potential water treatment method with high efficiency, cheap manufacturing costs, and green synthesis. Carbon dots have attracted the interest of researchers due to their unique properties, such as high water solubility, ease of production, great electron-donating ability, and low toxicity. In this context, we synthesized iodine-doped clove buds-derived carbon dots (I-CCDs) for the Fenton-like degradation of environmental contaminants in water (such as methylene blue (MB) and rhodamine-B (Rh-B) dye). The formation of I-CCDs has been confirmed using various spectroscopy techniques. I-CCDs have demonstrated remarkable optical, cytocompatibility, and antibacterial capabilities. The C-dots that were synthesized were found to be an effective catalyst for the reduction of MB and Rh-B utilizing NaBH4 as a reducing agent. UV-visible spectroscopy was used to construct a detailed pathway for dye reduction step by step. As-prepared I-CCDs have the potential to be a promising solution for wastewater purification and treatment systems.

Keywords: iodine-doped carbon dots, wastewater treatment and purification, environmental friendly, antibacterial

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Authors: Sarmistha Baruah, Akshai Kumar, Nageswara Rao Peela

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The global energy crisis due to the dependence on fossil fuels and its limited reserves as well as environmental pollution are key concerns to the research communities. However, the implementation of alcohol-based fuel cells such as methanol is anticipated as a reliable source of future energy technology due to their high energy density, environment friendliness, ease of storage, transportation, etc. To drive the anodic methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs), an active and long-lasting catalyst is necessary for efficient energy conversion from methanol. Recently, transition metal-zeolite-based materials have been considered versatile catalysts for a variety of industrial and lab-scale processes. Large specific surface area, well-organized micropores, and adjustable acidity/basicity are characteristics of zeolites that make them excellent supports for immobilizing small-sized and highly dispersed metal species. Significant advancement in the production and characterization of well-defined metal clusters encapsulated within zeolite matrix has substantially expanded the library of materials available, and consequently, their catalytic efficacy. In this context, we developed bimetallic Ni-Co catalysts encapsulated within LTA (also known as 4A) zeolite via a method combined with the in-situ encapsulation of metal species using hydrothermal treatment followed by a chemical reduction process. The prepared catalyst was characterized using advanced characterization techniques, such as X-ray diffraction (XRD), field emission transmission electron microscope (FETEM), field emission scanning electron microscope (FESEM), energy dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of the catalyst for MOR was carried out in an alkaline medium at room temperature using techniques such as cyclic voltammetry (CV), and chronoamperometry (CA). The resulting catalyst exhibited better catalytic activity of 12.1 mA cm-2 at 1.12 V vs Ag/AgCl and retained remarkable stability (~77%) even after 1000 cycles CV test for the electro-oxidation of methanol in alkaline media without any significant microstructural changes. The high surface area, better Ni-Co species integration in the zeolite, and the ample amount of surface hydroxyl groups contribute to highly dispersed active sites and quick analyte diffusion, which provide notable MOR kinetics. Thus, this study will open up new possibilities to develop a noble metal-free zeolite-based electrocatalyst due to its simple synthesis steps, large-scale fabrication, improved stability, and efficient activity for DMFC application.

Keywords: alkaline media, bimetallic, encapsulation, methanol oxidation reaction, LTA zeolite.

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Authors: Elvis Medina, Alejandro Karelovic, Romel Jiménez

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Catalytic ammonia decomposition represents an attractive alternative due to its high H₂ content (17.8% w/w), a product stream free of COₓ, among others; however, challenges need to be addressed for its consolidation as an H₂ chemical storage technology, especially, those focused on the synthesis of efficient bimetallic catalytic systems, as an alternative to the price and scarcity of ruthenium, the most active catalyst reported. In this sense, from the perspective of rational catalyst design, adjusting the main catalytic activity descriptor, a screening of supported catalysts with different compositional settings of cobalt-molybdenum metals is presented to evaluate their effect on the catalytic decomposition rate of ammonia. Subsequently, a kinetic study on the supported monometallic Co and Mo catalysts, as well as on the bimetallic CoMo catalyst with the highest activity is shown. The synthesis of catalysts supported on γ-alumina was carried out using the Charge Enhanced Dry Impregnation (CEDI) method, all with a 5% w/w loading metal. Seeking to maintain uniform dispersion, the catalysts were oxidized and activated (In-situ activation) using a flow of anhydrous air and hydrogen, respectively, under the same conditions: 40 ml min⁻¹ and 5 °C min⁻¹ from room temperature to 600 °C. Catalytic tests were carried out in a fixed-bed reactor, confirming the absence of transport limitations, as well as an Approach to equilibrium (< 1 x 10⁻⁴). The reaction rate on all catalysts was measured between 400 and 500 ºC at 53.09 kPa NH3. The synergy theoretically (DFT) reported for bimetallic catalysts was confirmed experimentally. Specifically, it was observed that the catalyst composed mainly of 75 mol% cobalt proved to be the most active in the experiments, followed by the monometallic cobalt and molybdenum catalysts, in this order of activity as referred to in the literature. A kinetic study was performed at 10.13 – 101.32 kPa NH3 and at four equidistant temperatures between 437 and 475 °C the data were adjusted to an LHHW-type model, which considered the desorption of nitrogen atoms from the active phase surface as the rate determining step (RDS). The regression analysis were carried out under an integral regime, using a minimization algorithm based on SLSQP. The physical meaning of the parameters adjusted in the kinetic model, such as the RDS rate constant (k₅) and the lumped adsorption constant of the quasi-equilibrated steps (α) was confirmed through their Arrhenius and Van't Hoff-type behavior (R² > 0.98), respectively. From an energetic perspective, the activation energy for cobalt, cobalt-molybdenum, and molybdenum was 115.2, 106.8, and 177.5 kJ mol⁻¹, respectively. With this evidence and considering the volcano shape described by the ammonia decomposition rate in relation to the metal composition ratio, the synergistic behavior of the system is clearly observed. However, since characterizations by XRD and TEM were inconclusive, the formation of intermetallic compounds should be still verified using HRTEM-EDS. From this point onwards, our objective is to incorporate parameters into the kinetic expressions that consider both compositional and structural elements and explore how these can maximize or influence H₂ production.

Keywords: CEDI, hydrogen carrier, LHHW, RDS

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Authors: Dorottya Guban, Irina Borbath, Istvan Bakos, Peter Nemeth, Andras Tompos

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One of the greatest challenges of the implementation of polymer electrolyte membrane fuel cells (PEMFCs) is to find active and durable electrocatalysts. The cell performance is always limited by the oxygen reduction reaction (ORR) on the cathode since it is at least 6 orders of magnitude slower than the hydrogen oxidation on the anode. Therefore high loading of Pt is required. Catalyst corrosion is also more significant on the cathode, especially in case of mobile applications, where rapid changes of loading have to be tolerated. Pt-Sn bulk alloys and SnO2-decorated Pt3Sn nanostructures are among the most studied bimetallic systems for fuel cell applications. Exclusive formation of supported Sn-Pt alloy phases with different Pt/Sn ratios can be achieved by using controlled surface reactions (CSRs) between hydrogen adsorbed on Pt sites and tetraethyl tin. In this contribution our results for commercial and a home-made 20 wt.% Pt/C catalysts modified by tin anchoring via CSRs are presented. The parent Pt/C catalysts were synthesized by modified NaBH4-assisted ethylene-glycol reduction method using ethanol as a solvent, which resulted either in dispersed and highly stable Pt nanoparticles or evenly distributed raspberry-like agglomerates according to the chosen synthesis parameters. The 20 wt.% Pt/C catalysts prepared that way showed improved electrocatalytic performance in the ORR and stability in comparison to the commercial 20 wt.% Pt/C catalysts. Then, in order to obtain Sn-Pt/C catalysts with Pt/Sn= 3 ratio, the Pt/C catalysts were modified with tetraethyl tin (SnEt4) using three and five consecutive tin anchoring periods. According to in situ XPS studies in case of catalysts with highly dispersed Pt nanoparticles, pre-treatment in hydrogen even at 170°C resulted in complete reduction of the ionic tin to Sn0. No evidence of the presence of SnO2 phase was found by means of the XRD and EDS analysis. These results demonstrate that the method of CSRs is a powerful tool to create Pt-Sn bimetallic nanoparticles exclusively, without tin deposition onto the carbon support. On the contrary, the XPS results revealed that the tin-modified catalysts with raspberry-like Pt agglomerates always contained a fraction of non-reducible tin oxide. At the same time, they showed increased activity and long-term stability in the ORR than Pt/C, which was assigned to the presence of SnO2 in close proximity/contact with Pt-Sn alloy phase. It has been demonstrated that the content and dispersion of the fcc Pt3Sn phase within the electrocatalysts can be controlled by tuning the reaction conditions of CSRs. The bimetallic catalysts displayed an outstanding performance in the ORR. The preparation of a highly dispersed 20Pt/C catalyst permits to decrease the Pt content without relevant decline in the electrocatalytic performance of the catalysts.

Keywords: anode catalyst, cathode catalyst, controlled surface reactions, oxygen reduction reaction, PtSn/C electrocatalyst

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Authors: Loganathan Kumaresan, Velusamy Chidambaram, Arumugam Velayutham Karthikeyani, Alex Cheru Pulikottil, Madhusudan Sau, Gurpreet Singh Kapur, Sankara Sri Venkata Ramakumar

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Environmentally driven regulations throughout the world stipulate dramatic improvements in the quality of transportation fuels and refining operations. The exhaust gases like CO, NOx, and SOx from stationary sources (e.g., refinery) and motor vehicles contribute to a large extent for air pollution. The refining industry is under constant environmental pressure to achieve more rigorous standards on sulphur content in the fuel used in the transportation sector and other off-gas emissions. Fluid catalytic cracking unit (FCCU) is a major secondary process in refinery for gasoline and diesel production. CO-combustion promoter additive and gasoline sulphur reduction (GSR) additive are catalytic systems used in FCCU to assist the combustion of CO to CO₂ in the regenerator and regulate sulphur in gasoline faction respectively along with main FCC catalyst. Effectiveness of these catalysts is governed by the active metal used, its dispersion, the type of base material employed, and retention characteristics of additive in FCCU such as attrition resistance and density. The challenge is to have a high-density microsphere catalyst support for its retention and high activity of the active metals as these catalyst additives are used in low concentration compare to the main FCC catalyst. The present paper discusses in the first part development of high dense microsphere of nanocrystalline alumina by hydro-thermal method for CO combustion promoter application. Performance evaluation of additive was conducted under simulated regenerator conditions and shows CO combustion efficiency above 90%. The second part discusses the efficacy of a co-precipitation method for the generation of the active crystalline spinels of Zn, Mg, and Cu with aluminium oxides as an additive. The characterization and micro activity test using heavy combined hydrocarbon feedstock at FCC unit conditions for evaluating gasoline sulphur reduction activity are studied. These additives were characterized by X-Ray Diffraction, NH₃-TPD & N₂ sorption analysis, TPR analysis to establish structure-activity relationship. The reaction of sulphur removal mechanisms involving hydrogen transfer reaction, aromatization and alkylation functionalities are established to rank GSR additives for their activity, selectivity, and gasoline sulphur removal efficiency. The sulphur shifting in other liquid products such as heavy naphtha, light cycle oil, and clarified oil were also studied. PIONA analysis of liquid product reveals 20-40% reduction of sulphur in gasoline without compromising research octane number (RON) of gasoline and olefins content.

Keywords: hydrothermal, nanocrystalline, spinel, sulphur reduction

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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: Joudia Akil, Stephane Siffert, Laurence Pirault-Roy, Renaud Cousin, Christophe Poupin

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Oxyfuel combustion is a promising method that enables to obtain a CO2 rich stream, with water vapor ( ̴10%), unburned components such as CO and NO, which must be cleaned before the use of CO2. Our objective is then the final treatment of CO and NO by catalysis. Three-way catalysts are well-developed material for simultaneous conversion of NO, CO and hydrocarbons. Pt and/or Rh ensure a quasi-complete removal of NOx, CO and HC and there is also a growing interest in partly replacing Pt with less-expensive Pd. The use of alumina and ceria as support ensures, respectively, the stabilization of such species in active state and discharging or storing oxygen to control the oxidation of CO and HC and the reduction of NOx. In this work, we will compare different metals (Pd, Rh and Pt) supported on Al2O3 and CeO2, for CO2 purification from oxyfuel combustion. The catalyst must reduce NO by CO in an oxidizing environment, in the presence of CO2 rich stream and resistant to water. In this study, Al2O3 and CeO2 were used as support materials of the catalysts. 1wt% M/Support where M = Pd, Rh or Pt catalysts were obtained by wet impregnation on supports with a precursor of palladium [Pd(acac)2], rhodium [Rh(NO3)3] and platinum [Pt(NO2)2(NO3)2]. Materials were characterized by BET surface area, H2 chemisorption, and TEM. Catalytic activity was evaluated in CO2 purification which is carried out in a fixed-bed flow reactor containing 150 mg of catalyst at atmospheric pressure. The flow of the reactant gases is composed of: 20% CO2, 10% O2, 0.5% CO, 0.02% NO and 8.2% H2O (He as eluent gas) with a total flow of 200 mL.min−1, with same GHSV (2.24x104 h-1). The catalytic performances of the samples were investigated with and without water. It shows that the total oxidation of CO occurred over the different materials. This study evidenced an important effect of the nature of the metals, supports and the presence or absence of H2O during the reduction of NO by CO in oxyfuel combustions conditions. Rh based catalysts show that the addition of water has a very positive influence especially on the Rh catalyst on CeO2. Pt based catalysts keep a good activity despite the addition of water on the both supports studied. For the NO reduction, addition of water act as a poison with Pd catalysts. The interesting results of Rh based catalysts with water can be explained by a production of hydrogen through the water gas shift reaction. The produced hydrogen acts as a more effective reductant than CO for NO removal. Furthermore, in TWCs, Rh is the main component responsible for NOx reduction due to its especially high activity for NO dissociation. Moreover, cerium oxide is a promotor for WGSR.

Keywords: carbon dioxide, environmental chemistry, heterogeneous catalysis

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Authors: Sam Bahreini, Payam Hayati

Abstract:

Metal-organic coordination [Cu(L)₄(SCN)₂] was synthesized applying ultrasonic irradiation, and its photocatalytic performance for the degradation of Remdesivir (RS) under sunlight irradiation was systematically explored for the first time in this study. The physicochemical properties of the synthesized photocatalyst were investigated using Fourier-transform infrared (FT-IR), field emission scanning electron microscopy (FE-SEM), powder x-ray diffraction (PXRD), energy-dispersive x-ray (EDX), thermal gravimetric analysis (TGA), diffuse reflectance spectroscopy (DRS) techniques. Systematic examinations were carried out by changing irradiation time, temperature, solution pH value, contact time, RS concentration, and catalyst dosage. The photodegradation kinetic profiles were modeled in pseudo-first order, pseudo-second-order, and intraparticle diffusion models reflected that photodegradation onto [Cu(L)₄(SCN)₂] catalyst follows pseudo-first order kinetic model. The fabricated [Cu(L)₄(SCN)₂] nanostructure bandgap was determined as 2.60 eV utilizing the Kubelka-Munk formula from the diffuse reflectance spectroscopy method. Decreasing chemical oxygen demand (COD) (from 70.5 mgL-1 to 36.4 mgL-1) under optimal conditions well confirmed mineralizing of the RS drug. The values of ΔH° and ΔS° was negative, implying the process of adsorption is spontaneous and more favorable in lower temperatures.

Keywords: Photocatalytic degradation, COVID-19, density functional theory (DFT), molecular electrostatic potential (MEP)

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