Search results for: metal loaded catalysts

Authors: Yuri A. Kalvachev, Totka D. Todorova

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Zeolite mordenite has been investigated as a transition metal support for the preparation of efficient catalysts in the oxidation of volatile organic compounds (VOCs). The highly crystalline mordenite samples were treated with hydrofluoric acid and ammonium fluoride to get hierarchical material with secondary porosity. The obtained supports by this method have a high active surface area, good diffusion properties and prevent the extraction of metal components during catalytic reactions. The active metal phases platinum and copper were loaded by impregnation on both mordenite materials (parent and acid treated counterparts). Monometalic Pt and Cu, and bimetallic Pt/Cu catalysts were obtained. The metal phases were fine dispersed as nanoparticles on the functional porous materials. The catalysts synthesized in this way were investigated in the reaction of complete oxidation of propane and benzene. Platinum, copper and platinum/copper were loaded and there catalytic activity was investigated and compared. All samples are characterized by X-ray diffraction analysis, nitrogen adsorption, scanning electron microscopy (SEM), X-ray photoelectron measurements (XPS) and temperature programed reduction (TPR). The catalytic activity of the samples obtained is investigated in the reaction of complete oxidation of propane and benzene by using of Gas Chromatography (GC). The oxidation of three organic molecules was investigated—methane, propane and benzene. The activity of metal loaded mordenite catalysts for methane oxidation is almost the same for parent and treated mordenite as a support. For bigger molecules as propane and benzene, the activity of catalysts based on treated mordenite is higher than those based on parent zeolite.

Keywords: metal loaded catalysts, mordenite, VOCs oxidation, zeolites

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Authors: Napat Hataivichian

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The effect of transition metal doping on Pt/Al2O3 catalyst used in propane dehydrogenation reaction at 500˚C was studied. The preparation methods investigated were sequential impregnation (Pt followed by the 2nd metal or the 2nd metal followed by Pt) and co-impregnation. The metal contents of these catalysts were fixed as the weight ratio of Pt per the 2nd metal of around 0.075. These catalysts were characterized by N2-physisorption, TPR, CO-chemisorption and NH3-TPD. It was found that the impregnated 2nd metal had an effect upon reducibility of Pt due to its interaction with transition metal-containing structure. This was in agreement with the CO-chemisorption result that the presence of Pt metal, which is a result from Pt species reduction, was decreased. The total acidity of bimetallic catalysts is decreased but the strong acidity is slightly increased. It was found that the stability of bimetallic catalysts prepared by co-impregnation and sequential impregnation where the 2nd metal was impregnated before Pt were better than that of monometallic catalyst (undoped Pt one) due to the forming of Pt sites located on the transition metal-oxide modified surface. Among all preparation methods, the sequential impregnation method- having Pt impregnated before the 2nd metal gave the worst stability because this catalyst lacked the modified Pt sites and some fraction of Pt sites was covered by the 2nd metal.

Keywords: alumina, dehydrogenation, platinum, transition metal

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Authors: Noreen Sajjad Ghulam Hussain

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Catalysts are prepared by simple physical mixing and thermal treatment of support and metal acetate precursors.The effect of metal ratio and metal loading to produce highly active catalyst for the oxidation of benzyl alcohol are studied.

Keywords: catalyst, acetates, benzyl alcohols

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

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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: Liang-Yi Lin, Hsunling Bai

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In this work, transition metal (metal= Co, Fe, Ni, Cu, and Mn) modified cerium oxide catalysts supported on mesoporous aluminosilicate particles (Ce/Al-MSPs) were prepared using waste silicate as the precursors through aerosol-assisted flow process, and their catalytic performances were investigated for acetone incineration. Tests on the bimetallic Ce/Al-MSPs and Mn/Al-MSPs and trimetallic Mn-Ce, Fe-Ce, Co-Ce, Ni-Ce, and Cu-Ce/Al-MSPs in the temperature range of 100-300 oC demonstrated that Ce was the main active metal while Mn acted as a suitable promoter in acetone incineration reactions. Among tested catalysts, Mn-Ce/Al-MSPs with a Mn/Ce molar ratio of 2/1 exhibited the highest acetone catalytic activity. Moreover, the synergetic effect was observed for trimetallic Mn-Ce/Al-MSPs on the acetone removal as compared to the bimetallic Ce/Al-MSPs or Mn/Al-MSPs catalysts.

Keywords: acetone, catalytic oxidation, cerium oxide, mesoporous silica

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Authors: Yuxi Zhu, Zhenqian Chen

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It is of great interest to investigate the thermal properties of non-precious metal catalysts for Proton exchange membrane fuel cell (PEMFC) based on the thermal management requirements. Due to the low symmetry of materials, to accurately obtain the thermal conductivity of materials, it is necessary to obtain the second and third order force constants by combining density functional theory and machine learning interatomic potential. To be specific, the interatomic force constants are obtained by moment tensor potential (MTP), which is trained by the computational trajectory of Ab initio molecular dynamics (AIMD) at 50, 300, 600, and 900 K for 1 ps each, with a time step of 1 fs in the AIMD computation. And then the thermal conductivity can be obtained by solving the Boltzmann transport equation. In this paper, the thermal transport properties of single metal atom catalysts are studied for the first time to our best knowledge by machine-learning interatomic potential (MLIP). Results show that the single metal atom catalysts exhibit anisotropic thermal conductivities and partially exhibit good thermal conductivity. The average lattice thermal conductivities of G-FeN₄, G-CoN₄ and G-NiN₄ at 300 K are 88.61 W/mK, 205.32 W/mK and 210.57 W/mK, respectively. While other single metal atom catalysts show low thermal conductivity due to their low phonon lifetime. The results also show that low-frequency phonons (0-10 THz) dominate thermal transport properties. The results provide theoretical insights into the application of single metal atom catalysts in thermal management.

Keywords: proton exchange membrane fuel cell, single metal atom catalysts, density functional theory, thermal conductivity, machine-learning interatomic potential

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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: Muhammad Ajmal, Muhammad Siddiq, Nurettin Sahiner

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We prepared poly(methacrylic acid-co-acrylonitrile) (p(MAc-co-AN)) microgels by inverse suspension polymerization, and converted the nitrile groups into amidoxime groups to obtain more hydrophilic amidoximated poly(methacrylic acid-co-acrylonitile) (amid-p(MAc-co-AN)) microgels. Amid-microgels were used as microreactors for in situ synthesis of copper and cobalt nanoparticles. Cu (II) and Co (II) ions were loaded into microgels from their aqueous metal salt solutions and then converted to corresponding metal nanoparticle (MNP) by treating the loaded metal ions with sodium borohydride (NaBH4). The characterization of the prepared microgels and microgel metal nanoparticle composites was carried out by SEM, TEM and TG analysis. The amounts of metal nanoparticles within microgels were estimated by AAS measurements by dissolving the MNP entrapped within microgels by concentrated HCl acid treatment. Catalytic performances of the prepared amid-p(MAc-co-AN)-M (M: Cu, Co) microgel composites were investigated by using them as catalyst for the degradation of cationic and anionic organic dyes such as eosin Y (EY), methylene blue (MB) and methyl Orange (MO), and for the reduction of nitro aromatic pollutants like 2-nitrophenol (2-NP) and 4-nitrophenol (4-NP) to their corresponding amino phenols. Here, we also report for the first time, the simultaneous degradation/reduction of MB, EY, and 4-NP by amid-p(MAc-co-AN)-Cu microgel composites. Different parameters affecting the reduction rates such as metal types, amount of catalysts, temperature and the amount of reducing agent were investigated.

Keywords: microgels, nanoparticles, catalyst, pollutants

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Authors: Davyd Urbanas, Pranas Baltrenas

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It is well-known that, despite the constant increase of alternative energy sources usage, today combustible fuels are still widely used in power engineering. As a result of fuel combustion, significant amounts of nitrogen oxides (NOx) and carbon monoxide (CO is a product of incomplete combustion) are supplied to the atmosphere. Also, these pollutants are formed in industry (chemical production, refining, and metal production). In this work, the investigation of nitrogen oxides CO-selective catalytic reduction using new grain load-type catalysts was carried out. The catalysts containing the substrate and a thin active coating made of transition metal (Mn, Cu, and Nb) oxides were prepared with the use of electroless chemical deposition method. Chemical composition, chemical state, and morphology of the formed active coating were investigated using ICP-OES, EDX, SEM, and XPS techniques. The obtained results revealed that the prepared catalysts (Cu-Mn-oxide and Cu-Mn-Nb-oxide) have rough and developed surface and can be successfully used for the flue gas catalytic purification. The significant advantage of prepared catalysts is their suitability from technological application point of view, which differs this work from others dedicated to gas purification by SCR.

Keywords: flue gas, nitrogen oxides, selective catalytic reduction, transition metal oxides

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Authors: Khaled Alshammari

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A facile approach to synthesizing highly active and stable Au/NiO catalysts for the hydrogenation of nitro-aromatics is reported. Preformed gold nanoparticles have been immobilized onto NiO using a colloidal method. In this article, the reduction of 4-nitrophenol with NaBH4 has been used as a model reaction to investigate the catalytic activity of synthesized Au/NiO catalysts. In addition, we report a systematic study of the reduction kinetics and the influence of specific reaction parameters such as (i) temperature, (ii) stirring rate, (iii) sodium borohydride concentration and (iv) substrate/metal molar ratio. The reaction has been performed at a substrate/metal molar ratio of 7.4, a ratio significantly higher than previously reported. The reusability of the catalyst has been examined, with little to no decrease in activity observed over 5 catalytic cycles. Systematic variation of Au loading reveals the successful synthesis of low-cost and efficient Au/NiO catalysts at very low Au content and using high substrate/metal molar ratios.

Keywords: nonochemistry, catalyst, nanoparticles supported, characterization of materials, colloidal nanoparticles

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Authors: Przemyslaw J. Jodlowski, Roman J. Jedrzejczyk, Damian K. Chlebda, Anna Dziedzicka, Lukasz Kuterasinski, Anna Gancarczyk, Maciej Sitarz

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The aim of this study was to obtain highly active catalysts based on non-noble metal oxides supported on zirconia prepared via a sonochemical method. In this study, the influence of the stabilizers addition during the preparation step was checked. The final catalysts were characterized by using such characterization methods as X-ray Diffraction (XRD), nitrogen adsorption, X-ray fluorescence (XRF), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and µRaman. The proposed preparation method allowed to obtain uniformly dispersed metal-oxide nanoparticles at the support’s surface. The catalytic activity of prepared catalyst samples was measured in a methane combustion reaction. The activity of the catalysts prepared by the sonochemical method was considerably higher than their counterparts prepared by the incipient wetness method.

Keywords: methane catalytic combustion, nanoparticles, non-noble metals, sonochemistry

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Authors: Kalyani Mer

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

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

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Authors: Hanjie Xie, Raphael Semiat, Ziyi Zhong

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It is well known that many oxidation reactions in nature are closely related to the origin and life activities. One of the features of these natural reactions is that they can proceed under mild conditions employing the oxidant of molecular oxygen (O₂) in the air and enzymes as catalysts. Catalysis is also a necessary part of life for human beings, as many chemical and pharmaceutical industrial processes need to use catalysts. However, most heterogeneous catalytic reactions must be run at high operational reaction temperatures and pressures. It is not strange that, in recent years, research interest has been redirected to green catalysis, e.g., trying to run catalytic reactions under relatively mild conditions as much as possible, which needs to employ green solvents, green oxidants such O₂, particularly air, and novel catalysts. This work reports the efficient binary Fe-Mn metal oxide catalysts for low-temperature formaldehyde (HCHO) oxidation, a toxic pollutant in the air, particularly in indoor environments. We prepared a series of nanosized FeMn oxide catalysts and found that when the molar ratio of Fe/Mn = 1:1, the catalyst exhibited the highest catalytic activity. At room temperature, we realized the complete oxidation of HCHO on this catalyst for 20 h with a high GHSV of 150 L g⁻¹ h⁻¹. After a systematic investigation of the catalyst structure and the reaction, we identified the reaction intermediates, including dioxymethylene, formate, carbonate, etc. It is found that the oxygen vacancies and the derived active oxygen species contributed to this high-low-temperature catalytic activity. These findings deepen the understanding of the catalysis of these binary Fe-Mn metal oxide catalysts.

Keywords: oxygen vacancy, catalytic oxidation, binary transition oxide, formaldehyde

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Authors: Silviya Todorova, Anton Naydenov, Ralitsa Velinova, Alexander Larin

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Catalytic combustion of methane has been extensively investigated for emission control and power generation during the last decades. The alumina-supported palladium catalyst is widely accepted as the most active catalysts for catalytic combustion of methane. The activity of Pd/Al₂O₃ decreases during the time on stream, especially underwater vapor. The following order of activity in the reaction of complete oxidation of methane was established: Co₃O₄> CuO>NiO> Mn₂O₃> Cr₂O₃. It may be expected that the combination between Pd and these oxides could lead to the promising catalysts in the reaction of complete methane. In the present work, we investigate the activity of Pd/Al₂O₃ catalysts promoted with other metal oxides (MOx; M= Ni, Co, Ce). The Pd-based catalysts modified by metal oxide were prepared by sequential impregnation of Al₂O₃ with aqueous solutions of Me(NO₃)₂.6H₂O and Pd(NO₃)₂H₂O. All samples were characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS). An improvement of activity was observed after modification with different oxides. The results demonstrate that the Pd/Al₂O₃ catalysts modified with Co and Ce by impregnation with a common solution of respective salts, exhibit the most promising catalytic activity for methane oxidation. Most probably, the presence of Co₃O₄ and CeO₂ on catalytic surface increases surface oxygen and therefore leads to the better reactivity in methane combustion.

Keywords: methane combustion, palladium, Co-Ce, Ni-Ce

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Authors: Kritsada Pipitthapan

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WO3/SiO2 catalysts were modified by an ion exchange method with sodium hydroxide or potassium hydroxide solution. The performance of the modified catalysts was tested in the metathesis of ethylene and trans-2-butene to propylene. During ion exchange, sodium and potassium ions played different roles. Sodium modified catalysts revealed constant trans-2-butene conversion and propylene selectivity when the concentrations of sodium in the solution were varied. In contrast, potassium modified catalysts showed reduction of the conversion and increase of the selectivity. From these results, potassium hydroxide may affect the transformation of tungsten oxide active species, resulting in the decrease in conversion whereas sodium hydroxide did not. Moreover, the modification of catalysts by this method improved the catalyst stability by lowering the amount of coke deposited on the catalyst surface.

Keywords: acid sites, alkali metal, isomerization, metathesis

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Authors: Azeem Ur Rehman, Asma Tayyaba

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This article deals with the promotional effects of CeO2 on PtPd/CeO2-OMC electro catalysts. The synthesized catalysts are characterized using different physico chemical techniques and evaluated in a formic acid oxidation fuel cell. N2 adsorption/desorption analysis shows that CeO2 modification increases the surface area of OMC from 1005 m2/g to 1119 m2/g. SEM, XRD and TEM analysis reveal that the presence of CeO2 enhances the active metal(s) dispersion on the CeO2-OMC surface. The average particle size of the dispersed metal decreases with the increase of Pt/Pd ratio on CeO2-OMC support. Cyclic voltametry measurement of Pd/CeO2-OMC gives 12 % higher anodic current activity with 83 mV negative shift of the peak potential as compared to unmodified Pd/OMC. In bimetallic catalysts, the addition of Pt improves the activity and stability of the catalysts significantly. Among the bimetallic samples, Pd3Pt1/CeO2-OMC displays superior current density (74.6 mA/cm2), which is 28.3 times higher than that of Pt/CeO2-OMC. It also shows higher stability in extended period of runs with least indication of CO poisoning effects.

Keywords: CeO2, ordered mesoporous carbon (OMC), electro catalyst, formic acid fuel cell

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Authors: Boldin Roman, Liliana Analía Diaz

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As the hydrogen economy continues to expand, reducing energy consumption and emissions while stimulating economic growth, the development of efficient and cost-effective hydrogen production technologies is critical. Among various methods, anion exchange membrane (AEM) water electrolysis stands out due to its potential for using non-noble metal catalysts. The exploration and enhancement of non-noble metal catalysts, such as NiFe-type catalysts, are pivotal for the advancement of AEM technology, ensuring its commercial viability and environmental sustainability. NiFe-type catalysts were synthesized through electrodeposition and characterized both electrochemically and physico-chemically. Various supports, including Ni foam and Ni mesh, were used as porous transport layers (PTLs) to evaluate the effective catalyst thickness and the influence of the PTL in a 5 cm² AEM electrolyzer. This methodological approach allows for a detailed assessment of catalyst performance under operational conditions typical of industrial hydrogen production. The study revealed that electrodeposited non-noble multi-metallic catalysts maintain stable performance as anodes in AEM water electrolysis. NiFe-type catalysts demonstrated superior activity, with the NiFeCoP alloy outperforming others by delivering the lowest overpotential and the highest current density. Furthermore, the use of different PTLs showed significant effects on the electrochemical behavior of the catalysts, indicating that PTL selection is crucial for optimizing performance and efficiency in AEM electrolyzers. Conclusion: The research underscores the potential of non-noble metal catalysts in enhancing efficiency and reducing the costs of AEM electrolysers. The findings highlight the importance of catalyst and PTL optimization in developing scalable and economically viable hydrogen production technologies. Continued innovation in this area is essential for supporting the growth of the hydrogen economy and achieving sustainable energy solutions.

Keywords: AEMWE, electrocatalyst, hydrogen production, water electrolysis.

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Authors: Xin Zhao. Xuerong Zheng. Andrey L. Rogach

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Using single metal atoms has been considered an efficient way to develop new HER and OER catalysts. MXenes, a class of two-dimensional materials, have attracted tremendous interest as promising substrates for single-atom metal catalysts. However, there is still a lack of systematic investigations on the interaction mechanisms between various MXenes substrates and single atoms. Besides, due to the poor interaction between metal atoms and substrates resulting in low loading and stability, dual-atom MXenes-based catalysts have not been successfully synthesized. We summarized the electrocatalytic enhancement mechanism of three MXenes-based single-atom catalysts through experimental and theoretical results demonstrating the stronger hybridization between Co 3d and surface-terminated O 2p orbitals, optimizing the electronic structure of Co single atoms in the composite. This, in turn, lowers the OER and HER energy barriers and accelerates the catalytic kinetics in the case of the Co@V2CTx composite. The poor interaction between single atoms and substrates can be improved by a surface modification to synthesize dual-atom catalysts. The synergistic electronic structure enhances the stability and electrocatalytic activity of the catalyst. Our study provides guidelines for designing single-atom and dual-atom MXene-based electrocatalysts and sheds light on the origins of the catalytic activity of single-atoms on MXene substrates.

Keywords: dual-atom catalyst, single-atom catalyst, MXene substrates, water splitting

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Authors: Francisco Espinosa, Juan Chavarría

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Glycerol is a byproduct of biodiesel production that can be used for aqueous-phase reforming to obtain hydrogen. Iridium is a material that has high activity and hydrogen selectivity for steam phase reforming. Nevertheless, a drawback for the use of iridium in aqueous-phase reforming is the low activity in water-gas shift reaction. Therefore, in this work, it is proposed the use of nickel and copper as a second metal in the catalyst to reach a synergetic effect. Iridium, iridium-nickel and iridium-copper catalysts were prepared by incipient wetness impregnation and evaluated in the aqueous-phase reforming of glycerol using CeO₂ or La₂O₃ as support. The catalysts were characterized by XRD, XPS, and EDX. The reactions were carried out in a fixed bed reactor feeding a solution of glycerol 10 wt% in water at 270°C, and reaction products were analyzed by gas chromatography. It was found that IrNi/CeO₂ reached highest glycerol conversion and hydrogen production, slightly above 70% and 43 vol% respectively. In terms of conversion, iridium is a promising metal, and its activity for hydrogen production can be enhanced when adding a second metal.

Keywords: aqueous-phase reforming, glycerol, hydrogen production, iridium

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Authors: Shannen Lorraine, Paul Maragh, Tara Dasgupta, Kamaluddin Abdur-Rashid

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(R)-(4,4',6,6'-tetramethoxybiphenyl-2,2'-diyl)bis(diphenylphosphine) (R-Ph-Garphos), and (S)-(4,4',6,6'-tetramethoxybiphenyl-2,2'-diyl)bis(diphenylphosphine) (S-Ph-Garphos) are novel, nucleophilic, chiral atropisomeric ligands. The research explored the synthesis of chiral transition metal complexes containing these ligands and their applications in various asymmetric catalytic transformations. Herein, the transition metal complexes having ruthenium(II), rhodium(I) and iridium(I) metal centres will be discussed. These are air stable complexes and were characterized by CHN analysis, 1H, 13C, and 31P NMR spectroscopy, and polarimetry. Currently, there is an emphasis on 'greener' catalysts and the need for 'green' solvents in asymmetric catalysis. As such, the Ph-Garphos ligands were demethylated thereby introducing hydroxyl moieties unto the ligand scaffold. The facile tunability of the biaryl diphosphines led to the preparation of the (R)-(4,4',6,6'-tetrahydroxybiphenyl-2,2'-diyl)bis(diphenylphosphine) (R-Ph-Garphos-OH), and (S)-(4,4',6,6'-tetrahydroxybiphenyl-2,2'-diyl)bis(diphenylphosphine) (S-Ph-Garphos-OH) ligands. These were successfully characterized by CHN analysis, 1H, 13C, and 31P NMR spectroscopy, and polarimetry. The use of the Ph-Garphos and Ph-Garphos-OH ligands and their transition metal complexes in asymmetric hydrogenations will be reported. Additionally, the scope of the research will highlight the applicability of the Ph-Garphos-OH ligand and its transitional metal complexes as 'green' catalysts.

Keywords: catalysis, asymmetric hydrogenation, diphosphine transition metal complexes, Ph-Garphos ligands

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Authors: Shashank Bahri, Divyanshu Arya, Rajni Jain, Sreedevi Upadhyayula

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Petroleum products can be obtained from syngas catalytic conversion using Fischer Tropsch Reaction. The liquid fuels obtained from FTS are sulphur and nitrogen free and thus may easily meet the increasing stringent environment regulations. In the present work we have synthesized Meso porous ZSM-5 supported catalyst. Meso structure were created in H-ZSM-5 crystallites by demetalation via subsequent base and acid treatment. Desilication through base treatment provides H-ZSM-5 with pore size and volumes similar to amorphous SiO2 (Conventional Carrier). Modifying the zeolite texture and surface chemistry by Desilication and acid washing alters its accessibility and interactions with metal phase and consequently the CO adsorption behavior and hydrocarbon product distribution. Increasing the mesoporosity via desilication provides the micro porous zeolite with essential surface area to support optimally sized metal crystallites. This improves the metal dispersion and hence improve the activity of the catalyst. Transition metal (Co) was loaded using wet impregnation method. Synthesized catalysts were characterized by Infrared Spectroscopy, Powdered X-Ray Diffraction, Scanning Electron Microscopy (SEM), BET Method analytical techniques. Acidity of the catalyst which plays an important role in FTS reaction was measured by DRIFT setup pyridine adsorption instead of NH3 Temperature Programmed Desorption. The major difference is that, Pyridine Adsorption can distinguish between Lewis acidity and Bronsted Acidity, thus giving their relative strengths in the catalyst sample, whereas TPD gives total acidity including Lewis and Bronsted ones.

Keywords: mesopourus, fischer tropsch reaction, pyridine adsorrption, drift study

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Authors: Joy Marie Mora, Mark Daniel De Luna, Tsair-Wang Chung

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Transesterification reaction of soybean oil with methanol was carried out to produce fatty acid methyl esters (FAME) using calcined alkali metal (Na and Li) supported by pumice silica as the solid base catalyst. Pumice silica catalyst was activated by loading alkali metal ions to its surface via an ion-exchange method. Response surface methodology (RSM) in combination with Box-Behnken design (BBD) was used to optimize the operating parameters in biodiesel production, namely: reaction temperature, methanol to oil molar ratio, reaction time, and catalyst concentration. Using the optimized sets of parameters, FAME yields using sodium and lithium silicate catalysts were 98.80% and 98.77%, respectively. A pseudo-first order kinetic equation was applied to evaluate the kinetic parameters of the reaction. The prepared catalysts were characterized by several techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET) sorptometer, and scanning electron microscopy (SEM). In addition, the reusability of the catalysts was successfully tested in two subsequent cycles.

Keywords: alkali metal, biodiesel, Box-Behnken design, heterogeneous catalyst, kinetics, optimization, pumice, transesterification

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Authors: Sushil Kumar Saraswat, K. K. Pant

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Co metal supported on SiO2 and Al2O3 catalysts with a metal loading varied from 30 of 70 wt.% were evaluated for decomposition of methane to CO/CO2 free hydrogen and carbon nano materials. The catalytic runs were carried out from 550-800 oC under atmospheric pressure using fixed bed vertical flow reactor. The fresh and spent catalysts were characterized by BET surface area analyzer, TPR, XRD, SEM, TEM, and TG analysis. The data showed that 50% Co/Al2O3 catalyst exhibited remarkable higher activity and stability up to 10 h time-on-stream at 750 oC with respect to H2 production compared to rest of the catalysts. However, the catalytic activity and durability was greatly declined at a higher temperature. The main reason for the catalytic inhibition of Co containing SiO2 catalysts is the higher reduction temperature of Co2SiO4. TEM images illustrate that the carbon materials with various morphologies, carbon nanofibers (CNFs), helical-shaped CNFs, and branched CNFs depending on the catalyst composition and reaction temperature, were obtained. The TG data showed that a higher yield of MWCNTs was achieved over 50% Co/Al2O3 catalyst compared to other catalysts.

Keywords: carbon nanotubes, cobalt, hydrogen production, methane decomposition

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Authors: Ateeq Ur Rehman

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This article deals with the promotional effects of CeO2 on PtPd/CeO2-OMC electrocatalysts. The synthesized catalysts are characterized using different physicochemical techniques and evaluated in a formic acid oxidation fuel cell. N2 adsorption/desorption analysis shows that CeO2 modification increases the surface area of OMC from 1005 m2/g to 1119 m2/g. SEM, XRD and TEM analysis reveal that the presence of CeO2 enhances the active metal(s) dispersion on the CeO2-OMC surface. The average particle size of the dispersed metal decreases with the increase of Pt/Pd ratio on CeO2-OMC support. Cyclic voltametry measurement of Pd/CeO2-OMC gives 12 % higher anodic current activity with 83 mV negative shift of the peak potential as compared to unmodified Pd/OMC. In bimetallic catalysts, the addition of Pt improves the activity and stability of the catalysts significantly. Among the bimetallic samples, Pd3Pt1/CeO2-OMC displays superior current density (74.6 mA/cm2), which is 28.3 times higher than that of Pt/CeO2-OMC. It also shows higher stability in extended period of runs with least indication of CO poisoning effects.

Keywords: CeO2, ordered mesoporous carbon (OMC), nano particles, formic acid fuel cell

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Authors: Shalini Arora, Sri Sivakumar

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

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

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Authors: Andrea M. Rivas-Castillo, Marlenne Gómez-Ramirez, Isela Rodríguez-Pozos, Norma G. Rojas-Avelizapa

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Spent catalysts are considered as hazardous residues of major concern, mainly due to the simultaneous presence of several metals in elevated concentrations. Although hydrometallurgical, pyrometallurgical and chelating agent methods are available to remove and recover some metals contained in spent catalysts; these procedures generate potentially hazardous wastes and the emission of harmful gases. Thus, biotechnological treatments are currently gaining importance to avoid the negative impacts of chemical technologies. To this end, diverse microorganisms have been used to assess the removal of metals from spent catalysts, comprising bacteria, archaea and fungi, whose resistance and metal uptake capabilities differ depending on the microorganism tested. Acidophilic sulfur oxidizing bacteria have been used to investigate the biotreatment and extraction of valuable metals from spent catalysts, namely Acidithiobacillus thiooxidans and Acidithiobacillus ferroxidans, as they present the ability to produce leaching agents such as sulfuric acid and sulfur oxidation intermediates. In the present work, the ability of A. thiooxidans DSM 26636 for the bioleaching of metals contained in five different spent catalysts was assessed by growing the culture in modified Starkey mineral medium (with elemental sulfur at 1%, w/v), and 1% (w/v) pulp density of each residue for up to 21 days at 30 °C and 150 rpm. Sulfur-oxidizing activity was periodically evaluated by determining sulfate concentration in the supernatants according to the NMX-k-436-1977 method. The production of sulfuric acid was assessed in the supernatants as well, by a titration procedure using NaOH 0.5 M with bromothymol blue as acid-base indicator, and by measuring pH using a digital potentiometer. On the other hand, Inductively Coupled Plasma - Optical Emission Spectrometry was used to analyze metal removal from the five different spent catalysts by A. thiooxidans DSM 26636. Results obtained show that, as could be expected, sulfuric acid production is directly related to the diminish of pH, and also to highest metal removal efficiencies. It was observed that Al and Fe are recurrently removed from refinery spent catalysts regardless of their origin and previous usage, although these removals may vary from 9.5 ± 2.2 to 439 ± 3.9 mg/kg for Al, and from 7.13 ± 0.31 to 368.4 ± 47.8 mg/kg for Fe, depending on the spent catalyst proven. Besides, bioleaching of metals like Mg, Ni, and Si was also obtained from automotive spent catalysts, which removals were of up to 66 ± 2.2, 6.2±0.07, and 100±2.4, respectively. Hence, the data presented here exhibit the potential of A. thiooxidans DSM 26636 for the simultaneous bioleaching of metals contained in spent catalysts from diverse provenance.

Keywords: bioleaching, metal removal, spent catalysts, Acidithiobacillus thiooxidans

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Authors: Ts. Lazarova, V. Tumbalev, S. Atanacova-Vladimirova, G. Ivanov, A. Naydenov, D. Kovacheva

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Methane is a major Greenhouse Gas (GHG) that accounts for 14% of the world’s total amount of GHG emissions, originating mainly from agriculture, Coal mines, land fields, wastewater and oil and gas facilities. Nowadays the problem caused by the methane emissions has been a subject of an increased concern. One of the methods for neutralization of the methane emissions is it's complete catalytic oxidation. The efforts of the researchers are focused on the development of new types of catalysts and optimizing the existing catalytic systems in order to prevent the sintering of the palladium, providing at the same time a sufficient activity at temperatures below 500oC. The aim of the present work is to prepare mixed Cu-Ag-Pd oxide catalysts supported on alumina and to test them for methane complete catalytic oxidation. Cu-Ag-Pd/Al2O3 were prepared on a γ-Al2O3 (BET surface area = 220 m2/g) by the incipient wetness method using the corresponding metal nitrates (Cu:Ag = 90:10, Cu:Pd =97:3, Cu:Ag:Pd= 87:10:3) as precursors. A second set of samples were prepared with addition of urea to the metal nitrate solutions with the above mentioned ratios assuming increased dispersivity of the catalysts. The catalyst samples were dried at 100°C for 3 hours and calcined at 550°C for 30 minutes. Catalysts samples were characterized using X-ray diffraction (XRD), low temperature adsorption of nitrogen (BET) and scanning electron microscopy (SEM). The catalytic activity tests were carried out in a continuous flow type of reactor at atmospheric pressure. The effect of catalyst aging at 500 oC for 120 h on the methane combustion activity was also investigated. The results clearly indicate the synergetic effect of Ag and Pd on the catalytic activity.

Keywords: catalysts, XRD, BET, SEM, catalytic oxidation

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Authors: Jyh-Cherng Chen, Chih-Shiang You, Jie-Shian Cheng

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This study aims to recycle and reuse of spent lithium-cobalt battery and lithium-iron battery in the production of environmental catalysts. The characteristics and catalytic activities of synthesized catalysts for different air pollutants are analyzed and tested. The results show that the major metals in spent lithium-cobalt batteries are lithium 5%, cobalt 50%, nickel 3%, manganese 3% and the major metals in spent lithium-iron batteries are lithium 4%, iron 27%, and copper 4%. The catalytic activities of metal powders in the anode of spent lithium batteries are bad. With using the precipitation-oxidation method to prepare the lithium-cobalt catalysts from spent lithium-cobalt batteries, their catalytic activities for propane decomposition, CO oxidation, and NO reduction are well improved and excellent. The conversion efficiencies of the regenerated lithium-cobalt catalysts for those three gas pollutants are all above 99% even at low temperatures 200-300 °C. However, the catalytic activities of regenerated lithium-iron catalysts from spent lithium-iron batteries are unsatisfied.

Keywords: catalyst, lithium-cobalt battery, lithium-iron battery, recycle and reuse

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Authors: Seyed Mohamad Rasool Mirkarimi, David Chiaramonti, Samir Bensaid

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Catalytic methane decomposition (CMD, reaction 4) is a one-step process for hydrogen production where carbon in the methane molecule is sequestered in the form of stable and higher-value carbon materials. Metallic catalysts and carbon-based catalysts are two major types of catalysts utilized for the CDM process. Although carbon-based catalysts have lower activity compared to metallic ones, they are less expensive and offer high thermal stability and strong resistance to chemical impurities such as sulfur. Also, it would require less costly separation methods as some of the carbon-based catalysts may not have an active metal component in them. Since the regeneration of metallic catalysts requires burning of the C on their surfaces, which emits CO/CO2, in some cases, using carbon-based catalysts would be recommended because regeneration can be completely avoided, and the catalyst can be directly used in other processes. This work focuses on the effect of biochar as a carbon-based catalyst for the conversion of methane into hydrogen and carbon. Biochar produced from the pyrolysis of poplar wood and activated biochar are used as catalysts for this process. In order to observe the impact of carbon-based catalysts on methane conversion, methane cracking in the absence and presence of catalysts for a gas stream with different levels of methane concentration should be performed. The results of these experiments prove conversion of methane in the absence of catalysts at 900 °C is negligible, whereas in the presence of biochar and activated biochar, significant growth has been observed. Comparing the results of the tests related to using char and activated char shows the enhancement obtained in BET surface area of the catalyst through activation leads to more than 10 vol.% methane conversion.

Keywords: hydrogen production, catalytic methane decomposition, biochar, activated biochar, carbon-based catalyts

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Authors: Rana Th. A. Al-Rubaye, Arthur A. Garforth

Abstract:

This work details the generation of thin films of structured zeolite catalysts (ZSM–5 and Y) onto the surface of a metal substrate (FeCrAlloy) using in-situ hydrothermal synthesis. In addition, the zeolite Y is post-synthetically modified by acidified ammonium ion exchange to generate US-Y. Finally the catalytic activity of the structured ZSM-5 catalyst films (Si/Al = 11, thickness 146 µm) and structured US–Y catalyst film (Si/Al = 8, thickness 23µm) were compared with the pelleted powder form of ZSM–5 and USY catalysts of similar Si/Al ratios. The structured catalyst films have been characterised using a range of techniques, including X-ray diffraction (XRD), Electron microscopy (SEM), Energy Dispersive X–ray analysis (EDX) and Thermogravimetric Analysis (TGA). The transition from oxide-on-alloy wires to hydrothermally synthesised uniformly zeolite coated surfaces was followed using SEM and XRD. In addition, the robustness of the prepared coating was confirmed by subjecting these to thermal cycling (ambient to 550°C). The cracking of n–heptane over the pellets and structured catalysts for both ZSM–5 and Y zeolite showed very similar product selectivities for similar amounts of catalyst with an apparent activation energy of around 60 kJ mol-1. This paper demonstrates that structured catalysts can be manufactured with excellent zeolite adherence and when suitably activated/modified give comparable cracking results to the pelleted powder forms. These structured catalysts will improve temperature distribution in highly exothermic and endothermic catalysed processes.

Keywords: FeCrAlloy, structured catalyst, zeolite Y, zeolite ZSM-5

Procedia PDF Downloads 381