Search results for: copper-manganese catalysts
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 454

Search results for: copper-manganese catalysts

184 Synthesis of Iso-Amyl, Benzyl and Cinnamyl Esters over Active, Selective, Reusable and Eco-Friendly Natural Silica Catalyst

Authors: Abd El-Aziz Said

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In this study, natural silica was used as an active, selective, reusable and eco-friendly catalyst for the liquid phase synthesis of iso-amyl, benzyl and cinnamyl esters. The original and calcined natural silica were characterized by TG-DTA, XRF, XRD, FTIR, SEM, and N2-sorption analysis. The surface acidity of the catalysts was determined using isopropanol dehydration and the strength of available acid sites was measured using chemisorption of pyridine (PY) and dimethyl pyridine (DMPY). The results of acidity specified that the acidic sites are of Brönsted type, while PY-TPD demonstrated that almost of the acidic sites over the surface of natural silica are of weak and intermediate strength. The catalytic activity of natural silica towards esterification of acetic acid with alcohols was extensively studied. The results revealed that natural silica had high catalytic activity with 100% selectivity to all targeted esters. In addition, the yields obtained in batch methods were 83, 81, and 80%, respectively, whereas these yields after simple distillation were improved 97, 99.5, and 90%, respectively.

Keywords: liquid-phase esterification, natural silica, acidity esters, characterization

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183 Investigation on the Kinetic Mechanism of the Reduction of Fe₂O₃/CoO-Decorated Carbon Xerogel

Authors: Mohammad Reza Ghaani, Michele Catti

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The reduction of CoO/Fe₂O₃ oxides supported on carbon xerogels was studied to elucidate the effect of nano-size distribution of the catalyst in carbon matrices. Resorcinol formaldehyde xerogels were synthesized, impregnated with iron and cobalt nitrates, and subsequently heated to obtain the oxides. The mechanism of oxide reduction to metal was investigated by in-situ synchrotron X-ray diffraction in dynamic, non-isothermal conditions. Kinetic profiles of the reactions were obtained by plotting the diffraction intensities of selected Bragg peaks vs. temperature. The extracted Temperature-Programmed-Reduction (TPR) diagrams were analyzed by appropriate kinetic models, leading to best results with the Avrami-Erofeev model for all reduction reactions considered. The activation energies for the two-step reduction of iron oxide were 65 and 37 kJmol⁻¹, respectively. The average value for the reduction of CoO to Co was found to be around 21 kJ mol⁻¹. Such results may contribute to develop efficient and inexpensive non-noble metal-based catalysts in element form, e.g., Fe, Co, via heterogenization of metal complexes on mesoporous supports.

Keywords: non-isothermal kinetics, carbon aerogel, in-situ synchrotron X-ray diffraction, reduction mechanisms

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182 Optimization of Biodiesel Production from Palm Oil over Mg-Al Modified K-10 Clay Catalyst

Authors: Muhammad Ayoub, Abrar Inayat, Bhajan Lal, Sintayehu Mekuria Hailegiorgis

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Biodiesel which comes from pure renewable resources provide an alternative fuel option for future because of limited fossil fuel resources as well as environmental concerns. The transesterification of vegetable oils for biodiesel production is a promising process to overcome this future crises of energy. The use of heterogeneous catalysts greatly simplifies the technological process by facilitating the separation of the post-reaction mixture. The purpose of the present work was to examine a heterogeneous catalyst, in particular, Mg-Al modified K-10 clay, to produce methyl esters of palm oil. The prepared catalyst was well characterized by different latest techniques. In this study, the transesterification of palm oil with methanol was studied in a heterogeneous system in the presence of Mg-Al modified K-10 clay as solid base catalyst and then optimized these results with the help of Design of Experiments software. The results showed that methanol is the best alcohol for this reaction condition. The best results was achieved for optimization of biodiesel process. The maximum conversion of triglyceride (88%) was noted after 8 h of reaction at 60 ̊C, with a 6:1 molar ratio of methanol to palm oil and 3 wt % of prepared catalyst.

Keywords: palm oil, transestrefication, clay, biodiesel, mesoporous clay, K-10

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181 Alcoxysilanes Production from Silica and Dimethylcarbonate Promoted by Alkali Bases: A DFT Investigation of the Reaction Mechanism

Authors: Valeria Butera, Norihisa Fukaya, Jun-Chu Choi, Kazuhiko Sato, Yoong-Kee Choe

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Several silicon dioxide sources can react with dimethyl carbonate (DMC) in presence of alkali bases catalysts to ultimately produce tetramethoxysilane (TMOS). Experimental findings suggested that the reaction proceeds through several steps in which the first molecule of DMC is converted to dimethylsilyloxide (DMOS) and CO₂. Following the same mechanistic steps, a second molecule of DMC reacts with the DMOS to afford the final product TMOS. Using a cluster model approach, a quantum-mechanical investigation of the first part of the reaction leading to DMOS formation is reported with a twofold purpose: (1) verify the viability of the reaction mechanism proposed on the basis of experimental evidences .(2) compare the behaviors of three different alkali hydroxides MOH, where M=Li, K and Cs, to determine whether diverse ionic radius and charge density can be considered responsible for the observed differences in reactivity. Our findings confirm the observed experimental trend and furnish important information about the effective role of the alkali hydroxides giving an explanation of the different catalytic activity of the three metal cations.

Keywords: Alcoxysilanes production, cluster model approach, DFT, DMC conversion

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180 A Two-Step, Temperature-Staged, Direct Coal Liquefaction Process

Authors: Reyna Singh, David Lokhat, Milan Carsky

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The world crude oil demand is projected to rise to 108.5 million bbl/d by the year 2035. With reserves estimated at 869 billion tonnes worldwide, coal is an abundant resource. This work was aimed at producing a high value hydrocarbon liquid product from the Direct Coal Liquefaction (DCL) process at, comparatively, mild operating conditions. Via hydrogenation, the temperature-staged approach was investigated. In a two reactor lab-scale pilot plant facility, the objectives included maximising thermal dissolution of the coal in the presence of a hydrogen donor solvent in the first stage, subsequently promoting hydrogen saturation and hydrodesulphurization (HDS) performance in the second. The feed slurry consisted of high grade, pulverized bituminous coal on a moisture-free basis with a size fraction of < 100μm; and Tetralin mixed in 2:1 and 3:1 solvent/coal ratios. Magnetite (Fe3O4) at 0.25wt% of the dry coal feed was added for the catalysed runs. For both stages, hydrogen gas was used to maintain a system pressure of 100barg. In the first stage, temperatures of 250℃ and 300℃, reaction times of 30 and 60 minutes were investigated in an agitated batch reactor. The first stage liquid product was pumped into the second stage vertical reactor, which was designed to counter-currently contact the hydrogen rich gas stream and incoming liquid flow in the fixed catalyst bed. Two commercial hydrotreating catalysts; Cobalt-Molybdenum (CoMo) and Nickel-Molybdenum (NiMo); were compared in terms of their conversion, selectivity and HDS performance at temperatures 50℃ higher than the respective first stage tests. The catalysts were activated at 300°C with a hydrogen flowrate of approximately 10 ml/min prior to the testing. A gas-liquid separator at the outlet of the reactor ensured that the gas was exhausted to the online VARIOplus gas analyser. The liquid was collected and sampled for analysis using Gas Chromatography-Mass Spectrometry (GC-MS). Internal standard quantification methods for the sulphur content, the BTX (benzene, toluene, and xylene) and alkene quality; alkanes and polycyclic aromatic hydrocarbon (PAH) compounds in the liquid products were guided by ASTM standards of practice for hydrocarbon analysis. In the first stage, using a 2:1 solvent/coal ratio, an increased coal to liquid conversion was favoured by a lower operating temperature of 250℃, 60 minutes and a system catalysed by magnetite. Tetralin functioned effectively as the hydrogen donor solvent. A 3:1 ratio favoured increased concentrations of the long chain alkanes undecane and dodecane, unsaturated alkenes octene and nonene and PAH compounds such as indene. The second stage product distribution showed an increase in the BTX quality of the liquid product, branched chain alkanes and a reduction in the sulphur concentration. As an HDS performer and selectivity to the production of long and branched chain alkanes, NiMo performed better than CoMo. CoMo is selective to a higher concentration of cyclohexane. For 16 days on stream each, NiMo had a higher activity than CoMo. The potential to cover the demand for low–sulphur, crude diesel and solvents from the production of high value hydrocarbon liquid in the said process, is thus demonstrated.

Keywords: catalyst, coal, liquefaction, temperature-staged

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179 Bio-Furan Based Poly (β-Thioether Ester) Synthesized via Thiol-Michael Addition Polymerization with Tunable Structure and Properties

Authors: Daihui Zhang, Marie J. Dumont

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A derivative of 5-hydroxymethylfurfural (HMF) was synthesized for the thiol-Michael addition reaction. The efficiency of the catalysts (base and nucleophiles) and side reactions during the thiol-Michael addition were investigated. Dimethylphenylphosphine efficiently initiated the thiol-Michael addition polymerization for synthesizing a series of bio-based furan polymers with different structure and properties. The benzene rings or hydroxyl groups present in the polymer chains increased the glass transition temperature (Tg) of poly (β-thioether ester). Additionally, copolymers with various compositions were obtained via adding different ratio of 1,6-hexanedithiols to 1,4-benzenedithiols. 1H NMR analysis revealed that experimental ratios of two dithiols monomers matched well with theoretical ratios. The occurrence of a reversible Diels-Alder reaction between furan rings and maleimide groups allowed poly (β-thioether ester) to be dynamically crosslinked. These polymers offer the potentials to produce materials from biomass that have both practical mechanical properties and reprocessing ability.

Keywords: copolymers, Diels-Alder reaction, hydroxymethylfurfural, Thiol-Michael addition

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178 Synthesis of Gold Nanoparticles Stabilized in Na-Montmorillonite for Nitrophenol Reduction

Authors: Fatima Ammari, Meriem Chenouf

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Synthesis of gold nano particles has attracted much attention since the pioneering discovery of the high catalytic activity of supported gold nano particles in the reaction of CO oxidation at low temperature. In this research field, we used Na-montmorillonite for gold nanoparticles stabilization; different loading percentage 1, 2 and 5%. The gold nano particles were obtained using chemical reduction method using NaBH4 as reductant agent. The obtained gold nano particles Au-mont stabilized in Na-montmorillonite were used as catalysts for reduction of 4-nitrophenol to aminophenol with sodium borohydride at room temperature. The UV-Vis results confirm directly the gold nano particles formation. The XRD and N2 adsorption results showed the formation of gold nano particles in the pores of montmorillonite with an average size of 5 nm obtained on samples with 2%Au-mont. The gold particles size increased with the increase of gold loading percentage. The reduction reaction of 4-nitrophenol into 4-aminophenol with NaBH4 catalyzed by Au-Na-montmorillonite catalyst exhibits remarkably a high activity; the reaction was completed within 9 min for 1Au-mont and within 3 min for 2Au-mont.

Keywords: chemical reduction, gold, montmorillonite, nano particles, 4-nitrophenol

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177 ZnMn₂O₄ / Carbon Composite Recycled from Spent Zinc-Carbon Batteries for Zn-Air Battery Applications

Authors: Nivedha L. K., Dhinesh Kumar Murugaiah, Ganapathi Rao Kandregula, Raja Murugan, Kothandaraman R.

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ZnMn₂O₄, a non-precious metal catalyst for oxygen reduction reaction (ORR), was recycled from the spent primary Zn-C battery and utilized in the zinc-air battery. Catalysts exhibiting facile ORR kinetics are a requirement for building efficient Zinc-air batteries. ZnMn₂O₄ demonstrated excellent catalytic activity towards ORR in an aqueous alkaline medium, with an onset potential of 0. 90 V vs. RHE. The recycled ZnMn₂O₄ manifested a similar performance (at ~ 1.0 V) as the chemically synthesized one with a specific capacity of 210 mAh gzn-¹ at a constant current discharge of 15 mA cm-². A single electrode potential study was done to comprehend the losses at the electrodes and to identify the limiting electrode. Interestingly, the cathode was improving during discharge, which is in contrast to the expectation due to the accumulation of peroxide around the catalytic layer. Although the anode has exhibited minimal polarization, beyond a capacity of 210 mAh g-¹, the supersaturation of electrolyte occurs with zincate ion causing precipitation of ZnO on the cell components, thereby leading to sudden polarization of the cell and hence zinc electrode act as a limiting electrode in this system.

Keywords: battery recycling, oxygen reduction reaction, single electrode measurement, Zn-air battery, ZnMn₂O₄ recovery

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176 Empowering Middle School Math Coordinators as Agents of Transformation: The Impact of the Mitar Program on Mathematical Literacy and Social-Emotional Learning Integration

Authors: Saleit Ron

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The Mitar program was established to drive a shift in middle school mathematics education, emphasizing the connection of math to real-life situations, exploring mathematical modeling and literacy, and integrating social and emotional learning (SEL) components for enhanced excellence. The program envisions math coordinators as catalysts for change, equipping them to create educational materials, strengthen leadership skills, and develop SEL competencies within coordinator communities. These skills are then employed to lead transformative efforts within their respective schools. The program engaged 90 participants across six math coordinator communities during 2022-2023, involving 30-60 hours of annual learning. The process includes formative and summative evaluations through questionnaires and interviews, revealing participants' high contentment and successful integration of acquired skills into their schools. Reflections from participants highlighted the need for enhanced change leadership processes, often seeking more personalized mentoring to navigate challenges effectively.

Keywords: math coordinators, mathematical literacy, mathematical modeling, SEL competencies

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175 A Conceptual Framework for the Adoption of Information and Communication Technology for Anti-Corruption in the DR Congo

Authors: Itulelo Matiyabu Imaja, Patrick Ndayizigamiye, Manoj Maharaj

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There are many catalysts of corruption. These include amongst others, lack of effective control measures to deter or detect corrupt behaviour. Literature suggests that ICT could assist in curbing corruption through the implementation of automated systems, citizens engagement through e-government and online media to name a few. In the Democratic Republic of Congo, lack of transparency and accountability in public funds collection and allocation contribute to corruption in funds mismanagement. Using the accountability theory and available literature, this paper analyses how Democratic Republic of Congo (DRC) institutions could be strengthened through ICT in order to deter instances of corruption. Findings reveal that DRC lacks reliable control, monitoring and evaluation mechanisms that could identify potentially corrupt behavior. In addition, citizens and civil society organizations who are meant to hold the institutions accountable are not given secure platform to express their views and potentially flag any corrupt behavior. Hence, the paper presents a preliminary conceptual framework that depicts how ICT could be used to strengthen current institutions to potentially deter corrupt behavior in public funds management in Congo.

Keywords: corruption, ICT adoption, transparency, DR Congo

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174 Effect of Aging Time on CeO2 Nanoparticle Size Distribution Synthesized via Sol-Gel Method

Authors: Navid Zanganeh, Hafez Balavi, Farbod Sharif, Mahla Zabet, Marzieh Bakhtiary Noodeh

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Cerium oxide (CeO2) also known as cerium dioxide or ceria is a pale yellow-white powder with various applications in the industry from wood coating to cosmetics, filtration, fuel cell electrolytes, gas sensors, hybrid solar cells and catalysts. In this research, attempts were made to synthesize and characterization of CeO2 nano-particles via sol-gel method. In addition, the effect of aging time on the size of particles was investigated. For this purpose, the aging times adjusted 48, 56, 64, and 72 min. The obtained particles were characterized by x-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), transmitted electron microscopy (TEM), and Brunauer–Emmett–Teller (BET). As a result, XRD patterns confirmed the formation of CeO2 nanoparticles. SEM and TEM images illustrated the nano-particles with cluster shape, spherical and a nano-size range which was in agreement with XRD results. The finest particles (7.3 nm) was obtained at the optimum condition which was aging time of 48 min, calcination temperature at 400 ⁰C, and cerium concentration of 0.004 mol. Average specific surface area of the particles at optimum condition was measured by BET analysis and recorded as 47.57 m2/g.

Keywords: aging time, CeO2 nanoparticles, size distribution, sol-gel

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173 Stationary Methanol Steam Reforming to Hydrogen Fuel for Fuel-Cell Filling Stations

Authors: Athanasios A. Tountas, Geoffrey A. Ozin, Mohini M. Sain

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Renewable hydrogen (H₂) carriers such as methanol (MeOH), dimethyl ether (DME), oxymethylene dimethyl ethers (OMEs), and conceivably ammonia (NH₃) can be reformed back into H₂ and are fundamental chemical conversions for the long-term viability of the H₂ economy due to their higher densities and ease of transportability compared to H₂. MeOH is an especially important carrier as it is a simple C1 chemical that can be produced from green solar-PV-generated H₂ and direct-air-captured CO₂ with a current commercially practical solar-to-fuel efficiency of 10% from renewable solar energy. MeOH steam reforming (MSR) in stationary systems next to H₂ fuel-cell filling stations can eliminate the need for onboard mobile reformers, and the former systems can be more robust in terms of attaining strict H₂ product specifications, and MeOH is a safe, lossless, and compact medium for long-term H₂ storage. Both thermal- and photo-catalysts are viable options for achieving the stable, long-term performance of stationary MSR systems.

Keywords: fuel-cell vehicle filling stations, methanol steam reforming, hydrogen transport and storage, stationary reformer, liquid hydrogen carriers

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172 Hybrid Treatment Method for Decolorization of Mixed Dyes: Rhodamine-B, Brilliant Green and Congo Red

Authors: D. Naresh Yadav, K. Anand Kishore, Bhaskar Bethi, Shirish H. Sonawane, D. Bhagawan

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The untreated industrial wastewater discharged into the environment causes the contamination of soil, water and air. Advanced treatment methods for enhanced wastewater treatment are attracting substantial interest among the currently employed unit processes in wastewater treatment. The textile industry is one of the predominant in wastewater production at current industrialized situation. The refused dyes at textile industry need to be treated in proper manner before its discharge into water bodies. In the present investigation, hybrid treatment process has been developed for the treatment of synthetic mixed dye wastewater. Photocatalysis and ceramic nanoporous membrane are mainly used for process integration to minimize the fouling and increase the flux. Commercial semiconducting powders (TiO2 and ZnO) has used as a nano photocatalyst for the degradation of mixed dye in the hybrid system. Commercial ceramic nanoporous tubular membranes have been used for the rejection of dye and suspended catalysts. Photocatalysis with catalyst has shown the average of 34% of decolorization (RB-32%, BG-34% and CR-36%), whereas ceramic nanofiltration has shown the 56% (RB-54%, BG-56% and CR-58%) of decolorization. Integration of photocatalysis and ceramic nanofiltration has shown 96% (RB-94%, BG-96% and CR-98%) of dye decolorization over 90 min of operation.

Keywords: photocatalysis, ceramic nanoporous membrane, wastewater treatment, advanced oxidation process, process integration

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171 Treatment of Cyanide Effluents with Platinum Impregned on Mg-Al Layered Hydroxides

Authors: María R. Contreras, Diana Endara

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Cyanide leaching is the most used technology for gold mining industry, which produces large amounts of effluents requiring treatment. In Ecuador the development of gold mining industry has increased, causing significant environmental impacts due to the highly use of cyanide, it is estimated that 10 gr of extracted gold generates 7000 liters of water contaminated with 300mg/L of free cyanide. The most common methods used nowadays are the treatment with peroxodisulfuric acid, ozonation, H₂O₂ and other reactants which are expensive and present disadvantages. Several methods have been developed to treat this contaminant such as heterogeneous catalysts. Layered double hydroxides (LDHs) have received much attention due to their wide applications like a catalysis support. Therefore, in this study, Mg-Al/ LDH was synthetized by coprecipitation method and then platinum was impregned on it, in order to enhance its catalytic activity. Two methods of impregnation were used, the first one, called incipient wet impregnation and the second one was developed by continuous agitation of LDH in contact with chloroplatinic acid solution for 24 h. The support impregnated was analyzed by X-ray diffraction, FTIR and SEM. Finally, the oxidation of cyanide ion was performed by preparing synthetic solutions of sodium cyanide (NaCN) with an initial concentration of 500 mg/L at pH 10,5 and air flow of 180 NL/h. After 8 hours of treatment, an 80% of oxidation of ion cyanide was achieved.

Keywords: catalysis, cyanide, LDHs, mining

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170 A Facile Synthesis Strategy of Saccharine/TiO₂ Composite Heterojunction Catalyst for Co₂RR

Authors: Jenaidullah Batur, Sebghatullah Mudaber

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Currently, there is a list of catalysts that can reduce CO₂ to valuable chemicals and fuels, among them metal oxides such as TiO₂, known as promising photocatalysts to produce hydrogen and CO unless they are at an earlier age and still need to promote activity to able for produce fabricated values. Herein, in this work, we provided a novel, facile and eco-friendly synthesis strategy to synthesize more effective TiO₂-organic composite materials to selectively reduce CO₂ to CO. In this experiment, commercial nanocrystalline TiO₂ and saccharin with Li (LiBr, LiCl) were synthesized using the facile physical grinding in the motel pestle for 10 minutes, then added 10 mL of deionized water (18.2 megaohms) on the 300mg composite catalyst before samples moving for hydrothermal heating for 24 hours at 80 C in the oven. Compared with nanosized TiO₂, the new TiO₂-Sac-Li indeed displays a high CO generation rate of 70.83 μmol/g/h, which is 7 times higher than TiO₂, which shows enhancement in CO₂ reduction and an apparent improvement in charge carrier dynamic. The CO₂ reduction process at the gas-solid interface on TiO₂-Sac-Li composite semiconductors is investigated by functional calculations and several characterization methods. The results indicate that CO₂ can be easily activated by the TiO₂-Sac-Li atoms on the surface. This work innovatively investigates CO₂ reduction in novel composite materials and helps to broaden the applications of composite materials semiconductors.

Keywords: green chemistry, green synthesis, TiO₂, photocatalyst

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169 Impact of Zn/Cr Ratio on ZnCrOx-SAPO-34 Bifunctional Catalyst for Direct Conversion of Syngas to Light Olefins

Authors: Yuxuan Huang, Weixin Qian, Hongfang Ma, Haitao Zhang, Weiyong Ying

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Light olefins are important building blocks for chemical industry. Direct conversion of syngas to light olefins has been investigated for decades. Meanwhile, the limit for light olefins selectivity described by Anderson-Schulz-Flory (ASF) distribution model is still a great challenge to conventional Fischer-Tropsch synthesis. The emerging strategy called oxide-zeolite concept (OX-ZEO) is a promising way to get rid of this limit. ZnCrOx was prepared by co-precipitation method and (NH4)2CO3 was used as precipitant. SAPO-34 was prepared by hydrothermal synthesis, and Tetraethylammonium hydroxide (TEAOH) was used as template, while silica sol, pseudo-boehmite, and phosphoric acid were Al, Si and P source, respectively. The bifunctional catalyst was prepared by mechanical mixing of ZnCrOx and SAPO-34. Catalytic reactions were carried out under H2/CO=2, 380 ℃, 1 MPa and 6000 mL·gcat-1·h-1 in a fixed-bed reactor with a quartz lining. Catalysts were characterized by XRD, N2 adsorption-desorption, NH3-TPD, H2-TPR, and CO-TPD. The addition of Al as structure promoter enhances CO conversion and selectivity to light olefins. Zn/Cr ratio, which decides the active component content and chemisorption property of the catalyst, influences CO conversion and selectivity to light olefins at the same time. C2-4= distribution of 86% among hydrocarbons at CO conversion of 14% was reached when Zn/Cr=1.5.

Keywords: light olefins, OX-ZEO, Syngas, ZnCrOₓ

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168 Control of Pipeline Gas Quality to Extend Gas Turbine Life

Authors: Peter J. H. Carnell, Panayiotis Theophanous

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Natural gas due to its cleaner combustion characteristics is expected to be the most widely used fuel in the move towards less polluting and renewable energy sources. Thus, the developed world is supplied by a complex network of gas pipelines and natural gas is becoming a major source of fuel. Natural gas delivered directly from the well will differ in composition from gas derived from LNG or produced by anaerobic digestion processes. Each will also have specific contaminants and properties although gas from all sources is likely to enter the distribution system and be blended to provide the desired characteristics such as Higher Heating Value and Wobbe No. The absence of a standard gas composition poses problems when the gas is used as a chemical feedstock, in specialised furnaces or on gas turbines. The chemical industry has suffered in the past as a result of variable gas composition. Transition metal catalysts used in ammonia, methanol and hydrogen plants were easily poisoned by sulphur, chlorides and mercury reducing both activity and catalyst expected lives from years to months. These plants now concentrate on purification and conditioning of the natural gas feed using fixed bed technologies, allowing them to run for several years and having transformed their operations. Similar technologies can be applied to the power industry reducing maintenance requirements and extending the operating life of gas turbines.

Keywords: gas composition, gas conditioning, gas turbines, power generation, purification

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167 Synthesis of Biofuels of New Generation

Authors: Selena Gutiérrez, Araceli Martínez

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One of the most important challenges worldwide, scientific and technological, is to have a sustainable energy source; friendly to the environment and widely available. Currently, the 85% of the energy used comes from the fossil sources. Another important environmental problem is that several rubber products (tires, gloves, hoses, among others) are discarded practically without any treatment. In nature, the degradation of such products will take at least 500 years. In 2009, the worldwide rubber production was about 23.6 million tons. In order to solve this problems, our research focus in an alternative synthesis of biofuels in a two-step approach: The metathesis degradation of industrial rubber (models of rubber waste), and the oligomers transesterification. Thus, cis-1,4-polybutadiene (Mn= 9.1x105, Mw/Mn= 2.2) and styrene-butadiene block copolymers with 30% (Mn= 1.61x105; Mw/Mn= 1.3) and 21% wt styrene (Mn= 1.92x105; Mw/Mn= 1.4) were degraded via metathesis with soybean oil as chain transfer agent (CTA) and green solvent; using [(PCy3)2Cl2Ru=CHPh] and [(1,3-diphenyl-4,5-dihydroimidazol-2-ylidene)(PCy3)Ru=CHPh] catalysts. Afterwards, the products were transesterified by basic homogeneous catalysis. Before transesterification, the polystyrene microblocks (Mn= 16,761; Mw/Mn= 1.2) were isolated. Finally, the biofuels obtained (BO) were purified, characterized and showed similar properties to standards biodiesel (SB) (Norms: EN 14214-03 and ASTM D6751-02), i.e. (SB / BO): molecular weight [Daltons] (570 / 543-596), density [g/cm3] (0.86-0.90 / 0.88), kinematic viscosity [mm2/s] (1.90-6.0 / 3.5-4.5), iodine (97 / 97-98) and cetane number (Min.47 / 56-58).

Keywords: biofuels, industrial rubber, metathesis, vegetable oils

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166 Family Photos as Catalysts for Writing: A Pedagogical Exercise in Visual Analysis with MA Students

Authors: Susana Barreto

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This paper explores a pedagogical exercise that employs family photos as catalysts for teaching visual analysis and inspiring academic writing among MA students. The study aimed to achieve two primary objectives: to impart students with the skills of analyzing images or artifacts and to ignite their writing for research purposes. Conducted at Viana Polytechnic in Portugal, the exercise involved two classes on Arts Management and Art Education Master course comprising approximately twenty students from diverse academic backgrounds, including Economics, Design, Fine Arts, and Sociology, among others. The exploratory exercise involved selecting an old family photo, analyzing its content and context, and deconstructing the chosen images in an intuitive and systematic manner. Students were encouraged to engage in photo elicitation, seeking insights from family/friends to gain multigenerational perspectives on the images. The feedback received from this exercise was consistently positive, largely due to the personal connection students felt with the objects of analysis. Family photos, with their emotional significance, fostered deeper engagement and motivation in the learning process. Furthermore, visual analysing family photos stimulated critical thinking as students interpreted the composition, subject matter, and potential meanings embedded in the images. This practice enhanced their ability to comprehend complex visual representations and construct compelling visual narratives, thereby facilitating the writing process. The exercise also facilitated the identification of patterns, similarities, and differences by comparing different family photos, leading to a more comprehensive analysis of visual elements and themes. Throughout the exercise, students found analyzing their own photographs both enjoyable and insightful. They progressed through preliminary analysis, explored content and context, and artfully interwove these components. Additionally, students experimented with various techniques such as converting photos to black and white, altering framing angles, and adjusting sizes to unveil hidden meanings.The methodology employed included observation, documental analysis of written reports, and student interviews. By including students from diverse academic backgrounds, the study enhanced its external validity, enabling a broader range of perspectives and insights during the exercise. Furthermore, encouraging students to seek multigenerational perspectives from family and friends added depth to the analysis, enriching the learning experience and broadening the understanding of the cultural and historical context associated with the family photos Highlighting the emotional significance of these family photos and the personal connection students felt with the objects of analysis fosters a deeper connection to the subject matter. Moreover, the emphasis on stimulating critical thinking through the analysis of composition, subject matter, and potential meanings in family photos suggests a targeted approach to developing analytical skills. This improvement focuses specifically on critical thinking and visual analysis, enhancing the overall quality of the exercise. Additionally, the inclusion of a step where students compare different family photos to identify patterns, similarities, and differences further enhances the depth of the analysis. This comparative approach adds a layer of complexity to the exercise, ultimately leading to a more comprehensive understanding of visual elements and themes. The expected results of this study will culminate in a set of practical recommendations for implementing this exercise in academic settings.

Keywords: visual analysis, academic writing, pedagogical exercise, family photos

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165 Chiral Ruthenium Aminophosphine and Phosphine Iminopyridine Complexes: Synthesis and Application to Asymmetric Hydrogenation and Transfer Hydrogenation

Authors: Littlelet N. Scarlet, Kamaluddin Abdur-Rashid, Paul T. Maragh, Tara Dasgupta

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Aminophosphines are a privileged class of ancillary ligands with emerging importance in homogeneous catalysis. The unique combination of soft phosphorus (P) and hard nitrogen (N) centres affords a variety of transition metal complexes as potential pre-catalysts for synthetically useful reactions. Herein three ligand systems will be reported; two bidentate ligands - (S)-8-(diphenyl-phosphino)-1,2,3,4-tetrahydronaphthalen-1-amine, (S)THNANH2, and (Rc)-1-((Sp)-2-diphenylphosphino) ferrocenylethylamine, (RcSp)PPFNH2 - and a tridentate (Rc)-1-((Sp)-2-diphenylphosphino) ferrocenylimino-pyridine, (RcSp)PPFNNH2 ligand; the latter prepared from the condensation of selected ferrocene aminophosphines with pyridine-2-carboxaldehyde. Suitable combinations of these aminophosphine ligands with ruthenium precursors have afforded highly efficient systems for the asymmetric hydrogenation and transfer hydrogenation of selected ketones in 2-propanol. The Ru-(S)THNANH2 precatalyst was the most efficient in the asymmetric hydrogenation of selected ketones with 100% conversions within 4 hours at a catalyst loading of 0.1 mol%. The Ru-(RcSp)PPFNNH2 precatalyst was the most efficient in the asymmetric transfer hydrogenation of the ketones with conversions as high as 98% with 0.1 mol% catalyst. However, the enantioselectivities were generally low.

Keywords: aminophosphine, asymmetric hydrogenation, homogeneous catalysis, ruthenium (II), transfer hydrogenation

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164 Investigation of the Flow Characteristics in a Catalytic Muffler with Perforated Inlet Cone

Authors: Gyo Woo Lee, Man Young Kim

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Emission regulations for diesel engines are being strengthened and it is impossible to meet the standards without exhaust after-treatment systems. Lack of the space in many diesel vehicles, however, make it difficult to design and install stand-alone catalytic converters such as DOC, DPF, and SCR in the vehicle exhaust systems. Accordingly, those have been installed inside the muffler to save the space, and referred to the catalytic muffler. However, that has complex internal structure with perforated plate and pipe for noise and monolithic catalyst for emission reduction. For this reason, flow uniformity and pressure drop, which affect efficiency of catalyst and engine performance, respectively, should be examined when the catalytic muffler is designed. In this work, therefore, the flow uniformity and pressure drop to improve the performance of the catalytic converter and the engine have been numerically investigated by changing various design parameters such as inlet shape, porosity, and outlet shape of the muffler using the three-dimensional turbulent flow of the incompressible, non-reacting, and steady state inside the catalytic muffler. Finally, it can be found that the shape, in which the muffler has perforated pipe inside the inlet part, has higher uniformity index and lower pressure drop than others considered in this work.

Keywords: catalytic muffler, perforated inlet cone, catalysts, perforated pipe, flow uniformity, pressure drop

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163 Development of Rh/Ce-Zr-La/Al2O3 TWCs’ Wash Coat: Effect of Reactor on Catalytic and Thermal Stability

Authors: Su-Ning Wang, Yao-Qiang Chen

Abstract:

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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162 Vapor Phase Transesterification of Dimethyl Malonate with Phenol over Cordierite Honeycomb Coated with Zirconia and Its Modified Forms

Authors: Prathap S. Raghavendra, Mohamed S. Z. Shamshuddin, Thimmaraju N. Venkatesh

Abstract:

The transesterification of dimethyl malonate (DMM) with phenol has been studied in vapour phase over cordierite honeycomb coated with solid acid catalysts such as ZrO2,Mo(VI)/ZrO2 and SO42-/ZrO2. The catalytic materials were prepared honeycomb coated and powder forms and characterized for their total surface acidity by NH3-TPD and crystalinity by powder XRD methods. Phenyl methyl malonate (PMM) and diphenyl malonate (DPM) were obtained as the reaction products. A good conversion of DMM (up to 82%) of MPM with 95% selectivity was observed when the reactions were carried out at a catalyst bed temperature of 200 °C and flow-rate of 10 mL/h in presence of Mo(VI)/ZrO2 as catalyst. But over SO42-/ZrO2 catalyst, the yield of DPM was found to be higher. The results have been interpreted based on the variation of acidic properties and powder XRD phases of zirconia on incorporation of Mo(VI) or SO42– ions. Transesterification reactions were also carried out over powder forms of the catalytic materials and the yield of the desired phenyl ester products were compared with that of the HC coated catalytic materials. The solid acids were found to be reusable when used for at least 5 reaction cycles.

Keywords: cordierite honeycomb, methyl phenyl malonate, vapour phase transesterification, zirconia

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161 Ill-Defined and Ill-Equipped: Understanding the Limits of the Concept of Truth in South Africa’S Truth and Reconciliation Commission

Authors: Keo Mbebe

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The South African Truth and Reconciliation Commission (TRC) is widely regarded as a blueprint for countries seeking to transcend the atrocities of their past and create a new human rights-based administration. The aim of these societies is to establish historical truth. Within the TRC, the aspects of truth-finding and truth-telling were considered to be catalysts for national unity and reconciliation. Truth-seeking, in addition, was mandated in the Promotion of National Unity and Reconciliation Act (TRC Act), which is the legislation behind the TRC. However, there is an incongruency between the conception of truth outlined in the Act, and the conception of truth explained in the Report of the TRC proceedings. The aim of this paper is to delineate these two kinds of “truth” and to critically analyze them. Doing so, it will then be evident in the discussion that there is a need for substantial clarity in the conception of truth used in transitional justice settings based on truth-finding and truth-seeking, and the paper will present ways in which such clarity may be achieved. The paper will begin with a philosophical engagement on the notion of historical truth used by the TRC legislation. Thereafter, the historical background to the political context in which the TRC Act was mandated will be provided. The next section would then be a sketch of the conceptions of historical truth and historical injustice in the Act, as well as its supporting documents. Lastly, it will be argued that the subversion of the TRC’s mandate to promote reconciliation and national unity by bringing to light past human rights violations during apartheid is betrayed by its amorphous conception of historical truth.

Keywords: historical truth, human rights, transitional justice, truth commission

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160 Discovery of Two-dimensional Hexagonal MBene HfBO

Authors: Nanxi Miao, Junjie Wang

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The discovery of 2D materials with distinct compositions and properties has been a research aim since the report of graphene. One of the latest members of the 2D material family is MXene, which is produced from the topochemical deintercalation of the A layer from a laminate MAX phase. Recently, analogous 2D MBenes (transitional metal borides) have been predicted by theoretical calculations as excellent alternatives in applications such as metal-ion batteries, magnetic devices, and catalysts. However, the practical applications of two-dimensional (2D) transition-metal borides (MBenes) have been severely hindered by the lack of accessible MBenes because of the difficulties in the selective etching of traditional ternary MAB phases with orthorhombic symmetry (ort-MAB). Here, we discover a family of ternary hexagonal MAB (h-MAB) phases and 2D hexagonal MBenes (h-MBenes) by ab initio predictions and experiments. Calculations suggest that the ternary h-MAB phases are more suitable precursors for MBenes than the ort-MAB phases. Based on the prediction, we report the experimental synthesis of h-MBene HfBO by selective removal of in from h-MAB Hf2InB2. The synthesized 2D HfBO delivered a specific capacity of 420 mAh g-1 as an anode material in lithium-ion batteries, demonstrating the potential for energy-storage applications. The discovery of this h-MBene HfBO added a new member to the growing family of 2D materials and provided opportunities for a wide range of novel applications.

Keywords: 2D materials, DFT calculations, high-throughput screening, lithium-ion batteries

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159 Point-Mutation in a Rationally Engineered Esterase Inverts its Enantioselectivity

Authors: Yasser Gaber, Mohamed Ismail, Serena Bisagni, Mohamad Takwa, Rajni Hatti-Kaul

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Enzymes are safe and selective catalysts. They skillfully catalyze chemical reactions; however, the native form is not usually suitable for industrial applications. Enzymes are therefore engineered by several techniques to meet the required catalytic task. Clopidogrel is recorded among the five best selling pharmaceutical in 2010 under the brand name Plavix. The commonly used route for production of the drug on an industrial scale is the synthesis of the racemic mixture followed by diastereomeric resolution to obtain the pure S isomer. The process consumes a lot of solvents and chemicals. We have evaluated a biocatalytic cleaner approach for asymmetric hydrolysis of racemic clopidogrel. Initial screening of a selected number of hydrolases showed only one enzyme EST to exhibit activity and selectivity towards the desired stereoisomer. As the crude EST is a mixture of several isoenzymes, a homology model of EST-1 was used in molecular dynamic simulations to study the interaction of the enzyme with R and S isomers of clopidogrel. Analysis of the geometric hindrances of the tetrahedral intermediates revealed a potential site for mutagenesis in order to improve the activity and the selectivity. Single point mutation showed dramatic increase in activity and inversion of the enantioselectivity (400 fold change in E value).

Keywords: biocatalysis, biotechnology, enzyme, protein engineering, molecular modeling

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158 Flame Retardancy of Organophosphorus Compound on Cellulose - an Eco Friendly Concern

Authors: M. A. Hannan, N. Matthias Neisius

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Organophosphorus compound diethyloxymethyl-9-oxa-10-phosphaphenanthrene-10-oxide (DOPAC) was applied on cotton cellulose to impart eco-friendly flame retardant property to it. Here acetal linkage was introduced rather than conventionally used ester linkage to rescue from the undurability problem of flame retardant compound. Some acidic catalysts, sodium dihydrogen phosphate (NaH2PO4), ammonium dihydrogen phosphate (NH4H2PO4) and phosphoric acid (H3PO4) were successfully used to form acetal linkage between the base material and flame retardant compound. Inspiring limiting oxygen index (LOI) value of 22.4 was found after exclusive washing treatment. A good outcome of total heat of combustion (THC) 6.05 KJ/g was found possible during pyrolysis combustion flow calorimetry (PCFC) test of the treated sample. Low temperature dehydration with sufficient amount of char residue (14.89%) was experienced in case of treated sample. In addition, the temperature of peak heat release rate (TPHRR) 343.061°C supported the expected low temperature pyrolysis in condensed phase mechanism. With the consequence of pyrolysis effects, thermogravimetric analysis (TGA) also reported inspiring weight retention% of the treated samples.

Keywords: acetal linkage, char residue, cotton cellulose, flame retardant, loi, low temperature pyrolysis, organophosphorus, THC, THRR

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157 Synthesis of Biologically Active Heterocyclic Compounds via C-H Bond Activation

Authors: Neeraj Kumar Mishra, In Su Kim

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The isoindoline, indazole and indole heterocycles are ubiquitous structural motif found in heterocyclic compounds as they exhibit biological and medicinal applications. For example, isoindoline motif is present in molecules that act as endothelin-A receptor antagonists and dipeptidyl peptidase inhibitors. Moreover, isoindoline derivatives are very crucial constituents in the field of materials science as attractive candidates for organic light-emitting devices. However, compounds containing the indazole motif are known to exhibit to a variety of biological activities, such as estrogen receptor, HIV protease inhibition and anti-tumor activity. The prevalence of indazoles and indoles has led to the development of many useful methods for their preparation. Thus, isoindoline, indazole and indole heterocycles can be new candidates for the next generation of pharmaceuticals. Therefore, the development of highly efficient strategies for the formation of these heterocyclic architectures is an area of great interest in organic synthesis. The past years, transition-metal-catalyzed C−H activation followed by annulation reaction has been frequently used as a powerful tool to construct various heterocycles. Herein, we describe our recent achievements about the transition-metal-catalyzed tandem cyclization reactions of N-benzyltriflamides, 1,2-disubstituted arylhydrazines, acetanilides, etc. via C−H bond activation to access the corresponding bioactive heterocylic scaffolds.

Keywords: biologically active, C-H activation, heterocyclic compounds, transition-metal catalysts

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156 Atomic Layer Deposition of MoO₃ on Mesoporous γ-Al₂O₃ Prepared by Sol-Gel Method as Efficient Catalyst for Oxidative Desulfurization of Refractory Dibenzothiophene Compound

Authors: S. Said, Asmaa A. Abdulrahman

Abstract:

MoOₓ/Al₂O₃ based catalyst has long been widely used as an active catalyst in oxidative desulfurization reaction due to its high stability under severe reaction conditions and high resistance to sulfur poisoning. In this context, 4 & 9wt.% MoO₃ grafted on mesoporous γ-Al₂O₃ has been synthesized using the modified atomic layer deposition (ALD) method. Another MoO₃/Al₂O₃ sample was prepared by the conventional wetness impregnation (IM) method, for comparison. The effect of the preparation methods on the metal-support interaction was evaluated using different characterization techniques, including X-ray diffraction, X-ray photoelectron spectroscopy (XPS), N₂-physisorption, transmission electron microscopy (TEM), H₂- temperature-programmed reduction and FT-IR. Oxidative desulfurization (ODS) reaction of the model fuel oil was used as a probe reaction to examine the catalytic efficiency of the prepared catalysts. ALD method led to samples with much better physicochemical properties than those of the prepared one via the impregnation method. However, the 9 wt.%MoO₃/Al₂O₃ (ALD) catalyst in the ODS reaction of model fuel oil shows enhanced catalytic performance with ~90%, which has been attributed to the more Mo⁶⁺ surface concentrations relative to Al³⁺ with large pore diameter and surface area. The kinetic study shows that the ODS of DBT follows a pseudo first-order rate reaction.

Keywords: mesoporous Al₂O₃, xMoO₃/Al₂O₃, atomic layer deposition, wetness impregnation, ODS, DBT

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155 Enhanced Energy Powers via Composites of Piezoelectric CH₃NH₃PbI₃ and Flexoelectric Zn-Al:Layered Double Hydroxides (LDH) Nanosheets

Authors: Soon-Gil Yoon, Min-Ju Choi, Sung-Ho Shin, Junghyo Nah, Jin-Seok Choi, Hyun-A Song, Goeun Choi, Jin-Ho Choy

Abstract:

Layered double hydroxides (LDHs) with positively charged brucite-like layers and negatively charged interlayer anions are considered a critical nanoscale building block with potential for application in catalysts, biological sensors, and optical, electrical, and magnetic devices. LDHs also have a great potential as an energy conversion device, a key component in common modern electronics. Although LDHs are theoretically predicted to be centrosymmetric, we report here the first observations of the flexoelectric nature of LDHs and demonstrate their potential as an effective energy conversion material. We clearly show a linear energy conversion relationship between the output powers and curvature radius via bending with both the LDH nanosheets and thin films, revealing a direct evidence for flexoelectric effects. These findings potentially open up avenues to incorporate a flexoelectric coupling phenomenon into centrosymmetric materials such as LDHs and to harvest high-power energy using LDH nanosheets. In the present study, for enhancement of the output power, Zn-Al:LDH nanosheets were composited with piezoelectric CH3NH3PbI3 (MAPbI3) dye films and their enhanced energy harvesting was demonstrated in detail.

Keywords: layered double hydroxides, flexoelectric, piezoelectric, energy harvesting

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