Search results for: zeolite catalysts

Authors: S. F. H. Tasfy, N. A. M. Zabidi, M. S. Shaharun

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Carbon dioxide is highly thermochemical stable molecules where it is very difficult to activate the molecule and achieve higher catalytic conversion into alcohols or other hydrocarbon compounds. In this paper, series of the bimetallic Cu/ZnO-based catalyst supported by SBA-15 were systematically prepared via impregnation technique with different Cu: Zn ratio for hydrogenation of CO₂ to methanol. The synthesized catalysts were characterized by transmission electron microscopy (TEM), temperature programmed desorption, reduction, oxidation and pulse chemisorption (TPDRO), and surface area determination was also performed. All catalysts were tested with respect to the hydrogenation of CO₂ to methanol in microactivity fixed-bed reactor at 250^oC, 2.25 MPa, and H₂/CO₂ ratio of 3. The results demonstrate that the catalytic structure, activity, and methanol selectivity was strongly affected by the ratio between Cu: Zn, Where higher catalytic activity of 14 % and methanol selectivity of 92 % was obtained over Cu/ZnO-SBA-15 catalyst with Cu:Zn ratio of 7:3 wt. %. Comparing with the single catalyst, the synergetic between Cu and Zn provides additional active sites to adsorb more H₂ and CO₂ and accelerate the CO₂ conversion, resulting in higher methanol production under mild reaction conditions.

Keywords: hydrogenation of carbon dioxide, methanol synthesis, Cu/ZnO-based catalyst, mesoporous silica (SBA-15), metal ratio

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Authors: Wei-Jing Li, Ren-Xuan Yang, Kui-Hao Chuang, Ming-Yen Wey

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Nowadays, plastic product and utilization are extensive and have greatly improved our life. Yet, plastic wastes are stable and non-biodegradable challenging issues to the environment. Waste-to-energy strategies emerge a promising way for waste management. This work investigated the co-production of hydrogen and carbon nanotubes from the syngas which was from the gasification of polypropylene. A nickel-silica core-shell catalyst was applied for syngas reaction from plastic waste gasification in a fixed-bed reactor. SiO2 were prepared through various synthesis solvents by Stöber process. Ni plays a role as modified SiO2 support, which were synthesized by deposition-precipitation method. Core-shell catalysts have strong interaction between active phase and support, in order to avoid catalyst sintering. Moreover, Fe or Co metal acts as promoter to enhance catalytic activity. The effects of calcined atmosphere, second metal addition, and reaction temperature on hydrogen production and carbon yield were examined. In this study, the catalytic activity and carbon yield results revealed that the Ni/SiO2 catalyst calcined under H2 atmosphere exhibited the best performance. Furthermore, Co promoted Ni/SiO2 catalyst produced 3 times more than Ni/SiO2 on carbon yield at long-term operation. The structure and morphological nature of the calcined and spent catalysts were examined using different characterization techniques including scanning electron microscopy, transmission electron microscopy, X-ray diffraction. In addition, the quality and thermal stability of the nano-carbon materials were also evaluated by Raman spectroscopy and thermogravimetric analysis.

Keywords: plastic wastes, hydrogen, carbon nanotube, core-shell catalysts

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

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

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

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Authors: Thabelo Nelushi, Michael Scurrell, Tumelo Seadira

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Global warming is one of the most important environmental issues which arise from occurrence of gases such as carbon dioxide (CO2) and methane (CH4) in the atmosphere. Exposure to these greenhouse gases results in health risk. Hydrogen is regarded as an alternative energy source which is a clean energy carrier for the future. There are different methods to produce hydrogen such as steam reforming, coal gasification etc., however the challenge with these processes is that they emit CO and CO2 gases and are costly. Photocatalytic reforming is a substitute process which is fascinating due to the combination of solar energy and renewable sources and the use of semiconductor materials such as catalysts. TiO2 is regarded as the most promising catalysts. TiO2 nanoparticles prepared by hydrothermal method and Ag/TiO2 are being investigated for photocatalytic production of hydrogen from butanol. The samples were characterized by raman spectroscopy, TEM/SEM, XRD, XPS, EDAX, DRS and BET surface area. 2 wt% Ag-doped TiO2 nanoparticle showed enhanced hydrogen production compared to a non-doped TiO2. The results of characterization and photoactivity shows that TiO2 nanoparticles play a very important role in producing high hydrogen by utilizing solar irradiation.

Keywords: butanol, hydrogen production, silver particles, TiO2 nanoparticles

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Authors: Samira Rostom, Robert Symonds, Robin W. Hughes

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Hydrogen is considered as one of the most important clean and renewable energy carriers for a sustainable energy future. However, its efficient and cost-effective purification remains challenging. This paper presents the potential of using metal–organic frameworks (MOFs) in combination with pressure swing adsorption (PSA) technology for syngas based H2 purification. PSA process analysis is done considering high pressure and elevated temperature process conditions, it reduces the demand for off-gas recycle to the fuel reactor and simultaneously permits higher desorption pressure, thereby reducing the parasitic load on the hydrogen compressor. The elevated pressure and temperature adsorption we present here is beneficial to minimizing overall process heating and cooling demand compared to existing processes. Here, we report the comparative performance of zeolite-5A, Cu-BTC, and the mix of zeolite-5A/Cu-BTC for H2 purification from syngas typical of those exiting water-gas-shift reactors. The MOFs were synthesized hydrothermally and then mixed systematically at different weight ratios to find the optimum composition based on the adsorption performance. The formation of different compounds were characterized by XRD, N2 adsorption and desorption, SEM, FT-IR, TG, and water vapor adsorption technologies. Single-component adsorption isotherms of CO2, CO, CH4, N2, and H2 over single materials and composites were measured at elevated pressures and different temperatures to determine their equilibrium adsorption capacity. The examination of the stability and regeneration performance of metal–organic frameworks was carried out using a gravimetric system at temperature ranges of 25-150℃ for a pressure range of 0-30 bar. The studies of adsorption/desorption on the MOFs showed selective adsorption of CO2, CH4, CO, and N2 over H2. Overall, the findings of this study suggest that the Ni-MOF-74/Cu-BTC composites are promising candidates for industrial H2 purification processes.

Keywords: MOF, H2 purification, high T, PSA

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Authors: Amit Keshav

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Waste bone, produced in large quantity (8-10 kg./day) from a slaughterhouse, could be a cheap (cost $0.20 per kg) substitute for commercial catalysts. In the present work, catalyst for esterification reaction was prepared from waste bone and characterized by various techniques. Bone was deoiled and then sulfonated. Fourier-transform infrared spectroscopy (FTIR) spectra of prepared catalyst predicted –OH vibration at 3416 and 1630 cm⁻¹, S-O stretching at 1124 cm⁻¹ and intense bands of hydroxypatite in a region between 500 and 700 cm⁻¹. X-ray diffraction (XRD) predicts peaks of hydroxyapatite, CaO, and tricalcium phosphate. Scanning electron microscope (SEM) was employed to reveal the presence of non-uniformity deposited fine particles on the catalyst surface that represents active acidic sites. The prepared catalyst was employed to study its performance on esterification reaction between acrylic acid and ethanol in a molar ratio of 1:1 at a set temperature of 60 °C. Results show an equilibrium conversion of 49% which is matched to the commercial catalysts employed in literature. Thus waste bone could be a good catalyst for acrylic acid removal from waste industrial streams via the process of esterification.Keywords— Heterogeneous catalyst, characterization, esterification, equilibrium conversion

Keywords: heterogeneous catalyst, characterization, esterification, equilibrium conversion

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Authors: Oluwaseun A. Oyetade, Roelof J. Kriek

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The development of effective catalysts for the oxygen evolution reaction (OER) is of great importance to combat energy-related concerns in the environment. Herein, we report a one-step solvothermal method employed for the fabrication of nickel selenide hybrids (NiSe-Ni₃Se₂) and a series of nickel selenide hybrid/multiwalled carbon nanotube composites (NiSe-Ni₃Se₂/MWCNT) as electrocatalysts for OER in alkaline media. The catalytic activities of these catalysts were investigated via several electrochemical characterization techniques, such as linear sweep voltammetry, chronoamperometric studies at constant potential, electrochemical surface area determination, and Tafel slope calculation, under alkaline conditions. Morphological observations demonstrated the agglomeration of non-uniform NiSe-Ni₃Se₂ microspheres around carbon nanotubes (CNTs), demonstrating the successful synthesis of NiSe-Ni₃Se₂/MWCNT nanocomposites. Among the tested electrocatalysts, the 20% NiSe-Ni₃Se₂/MWCNT nanocomposite demonstrated the highest activity, exhibiting an overpotential of 325 mV to achieve a current density of 10 mA.cm⁻² in 0.1 mol.dm⁻³ KOH solution. The NiSe-Ni₃Se₂/MWCNT nanocomposites showed improved activity toward OER compared to bare NiSe-Ni₃Se₂ hybrids and MWCNTs, exhibiting an overpotential of 528, 392 and 434 mV for 10%, 30% and 50% NiSe-Ni₃Se₂/MWCNT nanocomposites, respectively. These results compare favourably to the overpotential of noble catalysts, such as RuO₂ and IrO₂. Our results imply that the addition of MWCNTs increased the activity of NiSe-Ni₃Se₂ hybrids due to an increased number of catalytic sites, dispersion of NiSe-Ni₃Se₂ hybrid nanoparticles, and electronic conductivity of the nanocomposites. These nanocomposites also demonstrated better long-term stability compared to NiSe-Ni₃Se₂ hybrids and MWCNTs. Hence, NiSe-Ni₃Se₂/MWCNT nanocomposites possess the potential as effective electrocatalysts for OER in alkaline media.

Keywords: carbon nanotubes, electrocatalysts, nanocomposites, nickel selenide hybrids, oxygen evolution reaction

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Authors: Jinrui Zhang, Tianlong Yang, Ying Pan

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Methane and carbon dioxide are major greenhouse gases contributor. CO₂ dry reforming of methane (DRM) for syngas production is a promising approach to reducing global CO₂ emission and extensive utilization of natural gas. However, the reported catalysts endured rapid deactivation due to severe carbon deposition at high temperature. Here, CO₂ reduction by CH4 on hexagonal nano-nickel flakes packed by porous SiO₂ (Ni@SiO₂) catalysts driven by thermal and solar light are tested. High resistance to carbon deposition and higher reactive activity are demonstrated under focused solar light at moderate temperature (400-500 ℃). Furthermore, the photocatalytic DRM under different wavelength is investigated, and even IR irradiation can enhance the catalytic activity. The mechanism of light-enhanced reaction reactivity and equilibrium is investigated by Infrared and Raman spectroscopy, and the unique reaction pathway with light is depicted. The photo-enhanced DRM provides a promising method of renewable solar energy conversion and CO₂ emission reduction due to the excellent activity and durability.

Keywords: CO₂ emission reduction, methane, photocatalytic DRM, resistance to carbon deposition, syngas

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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: L. B. Naves, L. Almeida

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The development of Drugs Delivery System (DDS), has been wildly investigated in the last decades. In this paper, first a general overview of traditional and modern wound dressing is presented. This is followed by a review of what scientist have done in the medical environment, focusing the possibility to develop a new alternative for DDS through transdermal pathway, aiming to treat melanoma skin cancer.

Keywords: cancer therapy, dressing polymers, melanoma, wound healing

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Authors: Tatiana L. Avalos-Rendon, Elias A. Pasten Chelala, Carlos J. Mendoza EScobedo, Ignacio A. Figueroa, Victor H. Lara, Luis M. Palacios-Romero

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The cement industry is facing cost increments in energy supply, requirements for reduction of CO₂, and insufficient supply of raw materials of good quality. According to all these environmental issues, cement industry must change its consumption patterns and reduce CO₂ emissions to the atmosphere. This can be achieved by generating environmental consciousness, which encourages the use of industrial by-products and/or recycling for the production of cement, as well as alternate, environment-friendly methods of synthesis which reduce CO₂. Calcination is the conventional method for the obtainment of Portland cement clinker. This method consists of grinding and mixing of raw materials (limestone, clay, etc.) in an adequate dosage. Resulting mix has a clinkerization temperature of 1450 °C so that the formation of the main component occur: alite (Ca₃SiO₅, C₃S). Considering that the energy required to produce C₃S is 1810 kJ kg -1, calcination method for the obtainment of clinker represents two major disadvantages: long thermal treatment and elevated temperatures of synthesis, both of which cause high emissions of carbon dioxide (CO₂) to the atmosphere. Belite Portland clinker is characterized by having a low content of calcium oxide (CaO), causing the presence of alite to diminish and favoring the formation of belite (β-Ca₂SiO₄, C₂S), so production of clinker requires a reduced energy consumption (1350 kJ kg-1), releasing less CO₂ to the atmosphere. Conventionally, β-Ca₂SiO₄ is synthetized by the calcination of calcium carbonate (CaCO₃) and silicon dioxide (SiO₂) through the reaction in solid state at temperatures greater than 1300 °C. Resulting belite shows low hydraulic reactivity. Therefore, this study concerns a new simple modified combustion method for the synthesis of two belite cements at low temperatures (1000 °C). Silica fume, as subproduct of metallurgic industry and commercial natural zeolite were utilized as raw materials. These are considered low-cost materials and were utilized with no additional purification process. Belite cements properties were characterized by XRD, SEM, EDS and BET techniques. Hydration capacity of belite cements was calculated while the mechanical strength was determined in ordinary Portland cement specimens (PC) with a 10% partial replacement of the belite cements obtained. Results showed belite cements presented relatively high surface áreas, at early ages mechanical strengths similar to those of alite cement and comparable to strengths of belite cements obtained by different synthesis methods. Cements obtained in this work present good hydraulic reactivity properties.

Keywords: belite, silica fume, zeolite, hydraulic reactivity

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Authors: Thirupathi Thippani, Kothandaraman Ramanujam

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Current research on energy storage has been paid to metal-air batteries, because of attractive alternate energy source for the future. Metal – air batteries have the probability to significantly increase the power density, decrease the cost of energy storage and also used for a long time due to its high energy density, low-level pollution, light weight. The performance of these batteries mostly restricted by the slow kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on cathode during battery discharge and charge. The ORR and OER are conventionally carried out with precious metals (such as Pt) and metal oxides (such as RuO₂ and IrO₂) as catalysts separately. However, these metal-based catalysts are regularly undergoing some difficulties, including high cost, low selectivity, poor stability and unfavorable to environmental effects. So, in order to develop the active, stable, corrosion resistance and inexpensive bi-functional catalyst material is mandatory for the commercialization of zinc-air rechargeable battery technology. We have attempted and synthesized non-precious metal (NPM) catalysts comprising cobalt and N-doped multiwalled carbon nanotubes (N-MWCNTs-Co) were synthesized by the solid-state pyrolysis (SSP) of melamine with Co₃O₄. N-MWCNTs-Co acts as an excellent electrocatalyst for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), and hence can be used in secondary metal-air batteries and in unitized regenerative fuel cells. It is important to study the OER and ORR at high concentrations of KOH as most of the metal-air batteries employ KOH concentrations > 4M. In the first 16 cycles of the zinc-air battery while using N-MWCNTs-Co, 20 wt.% Pt/C or 20 wt.% IrO₂/C as air electrodes. In the ORR regime (the discharge profile of the zinc-air battery), the cell voltage exhibited by N-MWCNTs-Co was 44 and 83 mV higher (based on 5th cycle) in comparison to of 20 wt.% Pt/C and 20 wt.% IrO₂/C respectively. To demonstrate this promise, a zinc-air battery was assembled and tested at a current density of 0.5 Ag⁻¹ for charge-discharge 100 cycles.

Keywords: oxygen reduction reaction (ORR), oxygen evolution reaction(OER), non-platinum, zinc air battery

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Authors: Pradeep Lamichhane, Nima Pourali, E. V. Rebrov, Volker Hessel

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Nitrogen fixation is critical for plants for the biosynthesis of protein and nucleic acid. Most of our atmosphere is nitrogen, yet plants cannot directly absorb it from the air, and natural nitrogen fixation is insufficient to meet the demands. This experiment used a fast-modulated surface-confined atmospheric pressure plasma created by a 6 kV (peak-peak) sinusoidal power source with a repetition frequency of 68 kHz to fix nitrogen. Plasmas have been proposed for excitation of nitrogen gas, which quickly oxidised to NOX. With different N2/O2 input ratios, the rate of NOX generation was investigated. The rate of NOX production was shown to be optimal for mixtures of 60–70% O2 with N2. To boost NOX production in plasma, metal oxide catalysts based on TiO2 were coated over the dielectric layer of a reactor. These results demonstrate that nitrogen activation was more advantageous in surface-confined plasma sources because micro-discharges formed on the sharp edges of the electrodes, which is a primary function attributed to NOX synthesis and is further enhanced by metal oxide catalysts. The energy-efficient and sustainable NOX synthesis described in this study will offer a fresh perspective for ongoing research on green nitrogen fixation techniques.

Keywords: nitrogen fixation, fast-modulated, surface-confined, sustainable

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Authors: A. Feliczak Guzik, I. Nowak

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Zeolites, classified as microporous materials, are a large group of crystalline aluminosilicate materials commonly used in the chemical industry. These materials are characterized by large specific surface area, high adsorption capacity, hydrothermal and thermal stability. However, the micropores present in them impose strong mass transfer limitations, resulting in low catalytic performance. Consequently, mesoporous (hierarchical) zeolites have attracted considerable attention from researchers. These materials possess additional porosity in the mesopore size region (2-50 nm according to IUPAC). Mesoporous zeolites, based on commercial MFI-type zeolites modified with silver, were synthesized as follows: 0.5 g of zeolite was dispersed in a mixture containing CTABr (template), water, ethanol, and ammonia under ultrasound for 30 min at 65°C. The silicon source, which was tetraethyl orthosilicate, was then added and stirred for 4 h. After this time, silver(I) nitrate was added. In a further step, the whole mixture was filtered and washed with water: ethanol mixture. The template was removed by calcination at 550°C for 5h. All the materials obtained were characterized by the following techniques: X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), nitrogen adsorption/desorption isotherms, FTIR spectroscopy. X-ray diffraction and low-temperature nitrogen adsorption/desorption isotherms revealed additional secondary porosity. Moreover, the structure of the commercial zeolite was preserved during most of the material syntheses. The aforementioned materials were used in the epoxidation reaction of cyclohexene using conventional heating and microwave radiation heating. The composition of the reaction mixture was analyzed every 1 h by gas chromatography. As a result, about 60% conversion of cyclohexene and high selectivity to the desired reaction products i.e., 1,2-epoxy cyclohexane and 1,2-cyclohexane diol, were obtained.

Keywords: catalytic application, characterization, epoxidation, hierarchical zeolites, synthesis

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Authors: Sharmin Sultana, Nicolas Nuns, Pardis Simon, Jean-Marc Giraudon, Jean-Francois Lamonior, Nathalie D. Geyter, Rino Morent

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Environmental issues, especially air pollution, have become a huge concern of environmental legislation as a consequence of growing awareness in our global world. In this regard, control of volatile organic compounds (VOCs) emission has become an important issue due to their potential toxicity, carcinogenicity, and mutagenicity. The research of innovative technologies for VOC abatement is stimulated to accommodate the new stringent standards in terms of VOC emission. One emerging strategy is the coupling of 2 existing complementary technologies, namely here non-thermal plasma (NTP) and heterogeneous catalysis, to get a more efficient process for VOC removal in air. The objective of this current work is to investigate the abatement of trichloroethylene (TCE-highly toxic chlorinated VOC) from moist air (RH=15%) as a function of time by combined use of multi-pin-to-plate negative DC corona/glow discharge with Fe-doped cryptomelanes catalyst downstream i.e. post plasma-catalysis (PPC) process. For catalyst alone case, experiments reveal that, initially, Fe doped cryptomelane (regardless the mode of Fe incorporation by co-precipitation (Fe-K-OMS-2)/ impregnation (Fe/K-OMS-2)) exhibits excellent activity to decompose TCE compared to cryptomelane (K-OMS-2) itself. A maximum obtained value of TCE abatement after 6 min is as follows: Fe-KOMS-2 (73.3%) > Fe/KOMS-2 (48.5) > KOMS-2 (22.6%). However, with prolonged operation time, whatever the catalyst under concern, the abatement of TCE decreases. After 111 min time of exposure, the catalysts can be ranked as follows: Fe/KOMS-2 (11%) < K-OMS-2 (12.3%) < Fe-KOMS-2 (14.5%). Clearly, this phenomenon indicates catalyst deactivation either by chlorination or by blocking the active sites. Remarkably, in PPC configuration (energy density = 60 J/L, catalyst temperature = 150°C), experiments reveal an enhanced performance towards TCE removal regardless the type of catalyst. After 6 min time on stream, the TCE removal efficiency amount as follows: K-OMS-2 (60%) < Fe/K-OMS-2 (79%) < Fe-K-OMS-2 (99.3%). The enhanced performances over Fe-K-OMS-2 catalyst are attributed to its high surface oxygen mobility and structural defects leading to high O₃ decomposition efficiency to give active species able to oxidize the plasma processed hazardous\by-products and the possibly remaining VOC into CO₂. Moreover, both undoped and doped catalysts remain strongly capable to abate TCE with time on stream. The TCE removal efficiencies of the PPC processes with Fe/KOMS-2 and KOMS-2 catalysts are not affected by time on stream indicating an excellent catalyst stability. When using the Fe-K-OMS-2 as catalyst, TCE abatement slightly reduces with time on stream. However, it is noteworthy to stress that still a constant abatement of 83% is observed during at least 30 minutes. These results prove that the combination of NTP with catalysts not only increases the catalytic activity but also allows to avoid, to some extent, the poisoning of catalytic sites resulting in an enhanced catalyst stability. In order to better understand the different surface processes occurring in the course of the total TCE oxidation in PPC experiments, a detailed X-ray Photoelectron Spectroscopy (XPS) and Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) study on the fresh and used catalysts is in progress.

Keywords: Fe doped cryptomelane, non-thermal plasma, plasma-catalysis, stability, trichloroethylene

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Authors: Beena Sethi

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This work involves the degradation of plastic waste in the presence of three different nanocatalysts. A thin film of LLDPE was formed with all three nanocatalysts separately in the solvent. Thermo Gravimetric Analysis (TGA) and Differential Scanning Calorimetric (DSC) analysis of polymers suggest that the presence of these catalysts lowers the degradation temperature and the change mechanism of degradation. Gas chromatographic analysis was carried out for two films. In gas chromatography (GC) analysis, it was found that degradation of pure polymer produces only 32% C3/C4 hydrocarbons and 67.6% C5/C9 hydrocarbons. In the presence of these catalysts, more than 80% of polymer by weight was converted into either liquid or gaseous hydrocarbons. Change in the mechanism of degradation of polymer was observed therefore more C3/C4 hydrocarbons along with valuable feedstock are produced. Adjustment of dose of nanocatalyst, use of nano-admixtures and recycling of catalyst can make this catalytic feedstock recycling method a good tool to get sustainable environment. The obtained products can be utilized as fuel or can be transformed into other useful products. In accordance with the principles of sustainable development, chemical recycling i.e. tertiary recycling of polymers along with the reuse (zero order recycling) of plastics can be the most appropriate and promising method in this direction. The tertiary recycling is attracting much attention from the viewpoint of the energy resource.

Keywords: degradation, differential scanning calorimetry, feedstock recycling, gas chromatography, thermogravimetric analysis

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Authors: Katerina Zaharieva, Vicente Rives, Martin Tsvetkov, Raquel Trujillano, Boris Kunev, Ivan Mitov, Maria Milanova, Zara Cherkezova-Zheleva

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The nanostructured cobalt ferrite-type materials Sample A - Co0.25Fe2.75O4, Sample B - Co0.5Fe2.5O4, and Sample C - CoFe2O4 were prepared by co-precipitation in our previous investigations. The co-precipitated Sample B and Sample C were mechanochemically activated in order to produce Sample D - Co0.5Fe2.5O4 and Sample E- CoFe2O4. The PXRD, Moessbauer and FTIR spectroscopies, specific surface area determination by the BET method, thermal analysis, element chemical analysis and temperature-programmed reduction were used to investigate the prepared nano-sized samples. The changes of the Malachite green dye concentration during reaction of the photocatalytic decolorization using nanostructured cobalt ferrite-type catalysts with different chemical composition are included. The photocatalytic results show that the increase in the degree of incorporation of cobalt ions in the magnetite host structure for co-precipitated cobalt ferrite-type samples results in an increase of the photocatalytic activity: Sample A (4 х10-3 min-1) < Sample B (5 х10-3 min-1) < Sample C (7 х10-3 min-1). Mechanochemically activated photocatalysts showed a higher activity than the co-precipitated ferrite materials: Sample D (16 х10-3 min-1) > Sample E (14 х10-3 min-1) > Sample C (7 х10-3 min-1) > Sample B (5 х10-3 min-1) > Sample A (4 х10-3 min-1). On decreasing the degree of substitution of iron ions by cobalt ones a higher sorption ability of the dye after the dark period for the co-precipitated cobalt ferrite materials was observed: Sample C (72 %) < Sample B (78 %) < Sample A (80 %). Mechanochemically treated ferrite catalysts and co-precipitated Sample B possess similar sorption capacities, Sample D (78 %) ~ Sample E (78 %) ~ Sample B (78 %). The prepared nano-sized cobalt ferrite-type materials demonstrate good photocatalytic and sorption properties. Mechanochemically activated Sample D - Co0.5Fe2.5O4 (16х10-3 min-1) and Sample E-CoFe2O4 (14х10-3 min-1) possess higher photocatalytic activity than that of the most common used UV-light catalyst Degussa P25 (12х10-3 min-1). The dependence of the photo-catalytic activity and sorption properties on the preparation method and different degree of substitution of iron ions by cobalt ions in synthesized cobalt ferrite samples is established. The mechanochemical activation leads to formation of nano-structured cobalt ferrite-type catalysts (Sample D and Sample E) with higher rate constants than those of the ferrite materials (Sample A, Sample B, and Sample C) prepared by the co-precipitation procedure. The increase in the degree of substitution of iron ions by cobalt ones leads to improved photocatalytic properties and lower sorption capacities of the co-precipitated ferrite samples. The good sorption properties between 72 and 80% of the prepared ferrite-type materials show that they could be used as potential cheap absorbents for purification of polluted waters.

Keywords: nanodimensional cobalt ferrites, photocatalyst, synthesis, mechanochemical activation

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Authors: Roghaye Behroozi

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

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

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Authors: Krishnamoorthy Sathiyan, Shanti Gopal Patra, Ronen Bar-Ziv, Tomer Zidki

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Developing efficient non-noble metal catalysts that are cheap and durable for oxygen evolution reaction (OER) is a great challenge. Moreover, altering the electronic structure of the catalyst and structural engineering of the materials provide a new direction for enhancing the OER. Herein, we have successfully synthesized Fe and Co incorporated MoS₂ catalysts, which show improved catalytic activity for OER when compared with MoS₂, Fe-MoS₂, and Co-MoS₂. It was found that at an optimal ratio of Fe and Co, the electronic and structural modification of MoS₂ occurs, which leads to change in orientation and thereby enhances the active catalytic sites on the edges, which are more exposed for OER. The nanocomposites have been well characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and energy dispersive X-ray analysis (EDX), Elemental Mapping, transmission electron microscope (TEM), and high-resolution transmission electron microscope (HR-TEM) analysis. Among all, a particular ratio of FeCo-MoS₂ exhibits a much smaller onset with better catalytic current density. The remarkable catalytic activity is mainly attributed to the synergistic effect from the Fe and Co. Most importantly, our work provides an essential insight in altering the electronic structure of MoS₂ based materials by incorporating promoters such as Co and Fe in an optimal amount, which enhances OER activity.

Keywords: electrocatalysts, molybdenum disulfide, oxygen evolution reaction, transition metals

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Authors: Nadeem Bashir, Ghulam Mustafa Peerzada

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The present study pertains to the nonlinear behavior of acetaminophen based uncatalyzed Belousov-Zhabotinsky (BZ) oscillator and its dynamics in the presence of Ferroin as the catalyst. The role of free metal ions as catalysts was examined and the results compared with corresponding complexed catalysts. Free metal ions were found to be sluggish with respect to the evolution of the oscillatory regime as compared to complexed ones. Effect of change of the ligand moiety of the catalyst complex on the oscillatory parameters was monitored. Since ethanol potentiates the hepatotoxicity caused by acetaminophen in-vivo, it is thought to understand this interaction by virtue of causing perturbation of the acetaminophen based oscillator with different concentrations of the ethanol with and without ferroin as the catalyst. Another dimension to the ethanol effect was added by perturbation of the system with ethanol at different stages of the reaction so as to get an idea whether it is acetaminophen or some reactive intermediate generated in the reaction system which reacts with ethanol. Further, the ferroin-catalyzed oscillator is taken as a prototype inorganic model of the acetaminophen-ethanol syndrome, as ferroin and HOBr were inorganic replacements to Cyt P450 and NADPH in the alcohol metabolism.

Keywords: Belousov-Zhabotinsky reaction, ferroin, Paracetamol-Ethanol syndrome, kinetics

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Authors: Smita Mondal, Dinesh Kumar Pandey, Prakash Biswas

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During past two decades, considerable attention has been given to the value addition of biodiesel derived glycerol (~10wt.%) to make the biodiesel industry economically viable. Among the various glycerol value-addition methods, hydrogenolysis of glycerol to 1,2-propanediol is one of the attractive and promising routes. In this study, highly active and selective γ-Al₂O₃ supported bimetallic Cu-Ni catalyst was developed for selective hydrogenolysis of glycerol to 1,2-propanediol in the liquid phase. The catalytic performance was evaluated in a high-pressure autoclave reactor. The formation of mixed oxide indicated the strong interaction of Cu, Ni with the alumina support. Experimental results demonstrated that bimetallic copper-nickel catalyst was more active and selective to 1,2-PDO as compared to monometallic catalysts due to bifunctional behavior. To verify the effect of calcination temperature on the formation of Cu-Ni mixed oxide phase, the calcination temperature of 20wt.% Cu:Ni(1:1)/Al₂O₃ catalyst was varied from 300°C-550°C. The physicochemical properties of the catalysts were characterized by various techniques such as specific surface area (BET), X-ray diffraction study (XRD), temperature programmed reduction (TPR), and temperature programmed desorption (TPD). The BET surface area and pore volume of the catalysts were in the range of 71-78 m²g⁻¹, and 0.12-0.15 cm³g⁻¹, respectively. The peaks at the 2θ range of 43.3°-45.5° and 50.4°-52°, was corresponded to the copper-nickel mixed oxidephase [JCPDS: 78-1602]. The formation of mixed oxide indicated the strong interaction of Cu, Ni with the alumina support. The crystallite size decreased with increasing the calcination temperature up to 450°C. Further, the crystallite size was increased due to agglomeration. Smaller crystallite size of 16.5 nm was obtained for the catalyst calcined at 400°C. Total acidic sites of the catalysts were determined by NH₃-TPD, and the maximum total acidic of 0.609 mmol NH₃ gcat⁻¹ was obtained over the catalyst calcined at 400°C. TPR data suggested the maximum of 75% degree of reduction of catalyst calcined at 400°C among all others. Further, 20wt.%Cu:Ni(1:1)/γ-Al₂O₃ catalyst calcined at 400°C exhibited highest catalytic activity ( > 70%) and 1,2-PDO selectivity ( > 85%) at mild reaction condition due to highest acidity, highest degree of reduction, smallest crystallite size. Further, the modified Power law kinetic model was developed to understand the true kinetic behaviour of hydrogenolysis of glycerol over 20wt.%Cu:Ni(1:1)/γ-Al₂O₃ catalyst. Rate equations obtained from the model was solved by ode23 using MATLAB coupled with Genetic Algorithm. Results demonstrated that the model predicted data were very well fitted with the experimental data. The activation energy of the formation of 1,2-PDO was found to be 45 kJ mol⁻¹.

Keywords: glycerol, 1, 2-PDO, calcination, kinetic

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Authors: I. Ben Kaddour, S. Larbaoui

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Since their first synthesis, the Silicoaluminophosphates materials have proved their efficiency as a good adsorbent and catalyst in several environmental and energetic applications. In this work, the photocatalytic hydrogen production from water splitting reactions has been conducted under visible radiations in the presence of a series of iron and/or titanium-containing microporous silico-alumino-phosphates materials synthesized by hydrothermal method, using triethylamine as an organic structuring agent to obtain the AFI structure type. These photo-catalysts were then characterized by various physicochemical methods to determine their structural, textural and morphological properties such as X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM) coupled with X rays microanalysis, nitrogen adsorption measurements, UV-visible diffuse reflectance spectroscopy (UV-Vis-DRS), and X-rays photoelectron spectroscopy (XPS) and the analysis revealed that these materials have significant photocatalytic properties. The hydrogen production process has been followed by photoelectrochemical characterization (PEC). The results showed that hydrogen is the only gas produced, and the reaction takes place in the conduction band where water is reduced to hydrogen. The electron recombination has also been avoided, as holes are entrapped using hole scavengers. In addition, these catalysts have been shown to remain stable during reuse for up to five cycles.

Keywords: photocatalysis, SAPO-5, hydrothermal synthesis, hydrogen production

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Authors: Dileep Maarisetty, Janaki Komandur, Saroj S. Baral

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In the current work, photocatalytic degradation of phenol was carried both in UV and visible light to find the slowest step that is limiting the rate of photo-degradation process. Characterization such as XRD, SEM, FT-IR, TEM, XPS, UV-DRS, PL, BET, UPS, ESR and zeta potential experiments were conducted to assess the credibility of catalysts in boosting the photocatalytic activity. To explore the synergy, TiO₂ was doped with graphene and alumina. The orbital hybridization with alumina doping (mediated by graphene) resulted in higher electron transfer from the conduction band of TiO₂ to alumina surface where oxygen reduction reactions (ORR) occur. Besides, the doping of alumina and graphene introduced defects into Ti lattice and helped in improving the adsorptive properties of modified photo-catalyst. Results showed that these defects promoted the oxygen reduction reactions (ORR) on the catalyst’s surface. ORR activity aims at producing reactive oxygen species (ROS). These ROS species oxidizes the phenol molecules which is adsorbed on the surface of photo-catalysts, thereby driving the photocatalytic reactions. Since mass transfer is considered as rate limiting step, various mathematical models were applied to the experimental data to probe the best fit. By varying the parameters, it was found that intra-particle diffusion was the slowest step in the degradation process. Lagergren model gave the best R² values indicating the nature of rate kinetics. Similarly, different adsorption isotherms were employed and realized that Langmuir isotherm suits the best with tremendous increase in uptake capacity (mg/g) of TiO₂-rGO-Al₂O₃ as compared undoped TiO₂. This further assisted in higher adsorption of phenol molecules. The results obtained from experimental, kinetic modelling and adsorption isotherms; it is concluded that apart from changes in surface, optoelectronic and morphological properties that enhanced the photocatalytic activity, the intra-particle diffusion within the catalyst’s pores serve as rate-limiting step in deciding the fate of photo-catalytic degradation of phenol.

Keywords: ORR, phenol degradation, photo-catalyst, rate kinetics

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Authors: Sunil P. Lonkar, Vishnu V. Pillai, Saeed Alhassan

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Design and development of highly efficient, inexpensive, and long-term stable earth-abundant electrocatalysts hold tremendous promise for hydrogen evolution reaction (HER) in water electrolysis. The 2D transition metal dichalcogenides, especially molybdenum disulfide attracted a great deal of interests due to its high electrocatalytic activity. However, due to its poor electrical conductivity and limited exposed active sites, the performance of these catalysts is limited. In this context, a facile and scalable synthesis method for fabrication nanostructured electrocatalysts composed 3D graphene porous aerogels supported with MoS₂ and WS₂ is highly desired. Here we developed a highly active and stable electrocatalyst catalyst for the HER by growing it into a 3D porous architecture on conducting graphene. The resulting nanohybrids were thoroughly investigated by means of several characterization techniques to understand structure and properties. Moreover, the HER performance of these 3D catalysts is expected to greatly improve in compared to other, well-known catalysts which mainly benefits from the improved electrical conductivity of the by graphene and porous structures of the support. This technologically scalable process can afford efficient electrocatalysts for hydrogen evolution reactions (HER) and hydrodesulfurization catalysts for sulfur-rich petroleum fuels. Owing to the lower cost and higher performance, the resulting materials holds high potential for various energy and catalysis applications. In typical hydrothermal method, sonicated GO aqueous dispersion (5 mg mL⁻¹) was mixed with ammonium tetrathiomolybdate (ATTM) and tungsten molybdate was treated in a sealed Teflon autoclave at 200 ◦C for 4h. After cooling, a black solid macroporous hydrogel was recovered washed under running de-ionized water to remove any by products and metal ions. The obtained hydrogels were then freeze-dried for 24 h and was further subjected to thermal annealing driven crystallization at 600 ◦C for 2h to ensure complete thermal reduction of RGO into graphene and formation of highly crystalline MoS₂ and WoS₂ phases. The resulting 3D nanohybrids were characterized to understand the structure and properties. The SEM-EDS clearly reveals the formation of highly porous material with a uniform distribution of MoS₂ and WS₂ phases. In conclusion, a novice strategy for fabrication of 3D nanostructured MoS₂-WS₂/graphene is presented. The characterizations revealed that the in-situ formed promoters uniformly dispersed on to few layered MoS₂¬-WS₂ nanosheets that are well-supported on graphene surface. The resulting 3D hybrids hold high promise as potential electrocatalyst and hydrodesulfurization catalyst.

Keywords: electrocatalysts, graphene, transition metal chalcogenide, 3D assembly

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Authors: Mulugeta Gurum Gerechal

Abstract:

Nowadays, the photocatalytic mechanism of water purification using nanoparticles has gained wider acceptance. For this purpose, the crystal form of N- TiO₂ and Ag-TiO₂ was prepared from TiCl₄, urea, NH₄OH, and AgNO₃ by sol-gel method and simple solid phase reaction followed by calcination at a temperature of 400°C for 4h at each. The synthesized photocatalysts were characterized using XRD, SEM, and UV-visible diffuse reflectance spectra. In the experiment, it was found that the absorption edge of N-TiO₂ was an efficient shift to visible light as compared to Ag-TiO₂. The XRD diffraction makes the particle size of N-TiO₂ smaller than Ag-TiO₂. The effect of catalyst loading and the effect of temperature on the photocatalytic efficiency of the prepared samples was tested using methylene blue as a target pollutant. The photocatalytic degradation efficiency of the catalysts for methylene blue was increased from 57.05 to 96.02% under solar radiation as the amount of the catalyst increased from 0.15 to 0.45 gram for N-TiO₂. Similarly, photocatalytic degradation of methylene blue was increased from 40.32 to 81.21% as the amount of Ag-TiO₂ increased from 0.05g to 0.1g. In addition, the photocatalytic degradation efficiency of the catalysts for the removal of methylene blue was increased from 58.00 to 98.00 and 47.00 to 81.21% under solar radiation as the calcination temperature of the catalyst increased from 300 to 500 for N-TiO₂ for Ag-TiO₂ 300 to 400⁰C. However, a further increase in catalyst loading and calcination temperature was found to decrease the degradation efficiency.

Keywords: photocatalysis, degradation, nanoparticles, catalyst loading, calcination, methylene blue

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Authors: S. Assylbekova, D. Zolotareva, A. Dauletbakov, Ye. Belyankova, S. Bayazit, A. Basharimova, A. Zazybin, A. Isimberlenova, A. Kakimova, M. Aydemir, A. Kairullinova

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Transfer hydrogenation (TH) is a key process in organic chemistry, especially in pharmaceutical and agrochemical synthesis, offering a safer and more sustainable approach compared to traditional methods. This work is devoted to the synthesis and use of ruthenium catalysts containing phosphinite ligands in TH reactions. Ruthenium complexes are particularly noteworthy for their effectiveness in asymmetric TH. Their stability and adaptability to different reaction environments make them ideal for both laboratory-scale and industrial applications. Phosphinite ligands (P(OR)R'2) are used in the synthesis of complexes to improve their properties. These ligands are known for their ability to finely tune the electronic and steric properties of metal centers. The electron-donating nature of the phosphorus atom, combined with the variability in the R and R' groups, allows for significant customization of the catalyst's properties. The purpose and difference of the work is to study the incorporation of a hydrophilic ionic liquid into the composition of a phosphinite ligand, which will then be converted into a catalyst. The technique involves the synthesis of a phosphinite ligand with an ionic liquid at room temperature under an inert atmosphere and then a ruthenium complex. Next, the TH reactions of acetophenone and its derivatives are carried out using the resulting catalyst. The conversion of ketone to alcohol is analyzed using a gas chromatograph. This study contributes to the understanding of the influence of catalyst physico-chemical properties on transfer hydrogenation results.

Keywords: transfer hydrogenation, ruthenium, catalysts, phosphinite ligands

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Authors: Mulugeta Gurum Gerechal

Abstract:

Nowadays, the photocatalytic mechanism of water purification using nanoparticles has gained wider acceptance. For this purpose, the Crystal form of N- TiO₂ and Ag-TiO₂ was prepared from TiCl₄, Urea, NH₄OH and AgNO₃ by sol-gel method and simple solid phase reaction followed by calcination at a temperature of 400 °C for 4h at each. The synthesized photocatalysts were characterized using XRD, SEM and UV-visible diffuse reflectance spectra. In the experiment, it was found that the absorption edge of N-TiO₂ was a well efficient shift to visible light as compared to Ag-TiO₂. The XRD diffraction makes the particle size of N-TiO₂ smaller than Ag-TiO₂. The effect of catalyst loading and the effect of temperature on the photocatalytic efficiency of the prepared samples was tested using methylene blue as a target pollutant. The photocatalytic degradation efficiency of the catalysts for methylene blue was increased from 57.05 to 96.02% under solar radiation as the amount of the catalyst increased from 0.15 to 0.45 gram for N-TiO₂. Similarly, photocatalytic degradation of methylene blue was increased from 40.32 to 81.21% as the amount of Ag-TiO₂ increased from 0.05g to 0.1g. In addition, the photocatalytic degradation efficiency of the catalysts for the removal of methylene blue was increased from 58.00 to 98.00 and 47.00 to 81.21 % under solar radiation as the calcination temperature of the catalyst increased from 300 to 500 for N-TiO₂ for Ag-TiO₂ 300 to 4000C. However, a further increase in catalyst loading and calcination temperature was found to decrease the degradation efficiency.

Keywords: photocatalysis, degradation, nanoparticles, catalyst loading, calcination and methylene blue

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Authors: Hristina Šalipur, Jasmina Dostanić, Davor Lončarević, Matej Huš

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Photocatalytic water splitting/alcohol photoreforming has been used for the conversion of sunlight energy in the process of hydrogen production due to its sustainability, environmental safety, effectiveness and simplicity. Titanate nanotubes are frequently studied materials since they combine the properties of photo-active semiconductors with the properties of layered titanates, such as the ion-exchange ability. Platinum (Pt) doping into titanate structure has been considered an effective strategy in better separation efficiency of electron-hole pairs and lowering the overpotential for hydrogen production, which results in higher photocatalytic activity. In our work, Pt doped titanate catalysts were synthesized via simple alkaline hydrothermal treatment, incipient wetness impregnation method and temperature-programmed reduction. The structural, morphological and optical properties of the prepared catalysts were investigated using various characterization techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 physisorption, and diffuse reflectance spectroscopy (DRS). The activities of the prepared Pt-doped titanate photocatalysts were tested for hydrogen production via photocatalytic water splitting/alcohol photoreforming process under simulated solar light irradiation. Characterization of synthesized Pt doped titanate catalysts showed crystalline anatase phase, preserved nanotubular structure and high specific surface area. The result showed enhancement of activity in photocatalytic water splitting/alcohol photoreforming in the following order 2-butanol>1-butanol>tert-butanol, with obtained maximal hydrogen production rate of 7.5, 5.3 and 2 mmol g-1 h-1, respectively. Different possible factors influencing the hole scavenging ability, such as hole scavenger redox potential and diffusivity, adsorption and desorption rate of the hole scavenger on the surface and stability of the alcohol radical species generated via hole scavenging, were investigated. The theoretical evaluation using density functional theory (DFT) further elucidated the reaction kinetics and detailed mechanism of photocatalytic water splitting/alcohol photoreforming.

Keywords: hydrogen production, platinum, semiconductor, water splitting, density functional theory

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Authors: Victor R. Thulari, John Akach, Haleden Chiririwa, Aoyi Ochieng

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Solar-light activated titanium dioxide photocatalysts were prepared by hydrolysis of titanium (IV) isopropoxide with thiourea, followed by calcinations at 450 °C. The experiments demonstrated that methyl orange in aqueous solutions were successfully degraded under solar light using doped TiO₂. The photocatalytic oxidation of a mono azo methyl-orange dye has been investigated in multi ion doped TiO₂ and solar light. Solutions were irradiated by solar-light until high removal was achieved. It was found that there was no degradation of methyl orange in the dark and in the absence of TiO₂. Varieties of laboratory prepared TiO₂ catalysts both un-doped and doped using titanium (IV) isopropoxide and thiourea as a dopant were tested in order to compare their photoreactivity. As a result, it was found that the efficiency of the process strongly depends on the working conditions. The highest degradation rate of methyl orange was obtained at optimum dosage using commercially produced TiO₂. Our work focused on laboratory synthesized catalyst and the maximum methyl orange removal was achieved at 81% with catalyst loading of 0.04 g/L, initial pH of 3 and methyl orange concentration of 0.005 g/L using multi-ion doped catalyst. The kinetics of photocatalytic methyl orange dye stuff degradation was found to follow a pseudo-first-order rate law. The presence of the multi-ion dopant (thiourea) enhanced the photoefficiency of the titanium dioxide catalyst.

Keywords: degradation, kinetics, methyl orange, photocatalysis

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Authors: Merouani Djilali Redha, F. Abdelmalek, A. A. Addou

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Advanced oxidation processes (AOPs) utilizing Homogenous photocatalysis (Fenton and photo-Fenton reactions), and Heterogeneous photocatalyse (TiO2 and ZnO) were investigated for the degradation of commercial azo dye ‘Orange G’ wastewater. Fenton and photo-Fenton experimental conditions were: Hydrogen peroxide concentration (10-2 M), Ferrous ions concentration (5.10-4 M), pH (2.8 – 3), UV lamp power (6 watt). Adding more ferrous ions enhanced the oxidation rate for the H2O2/Fe2+ and UV/H2O2/Fe2+ processes. The optimum catalyst loading was found 2.0 g.L-1 in our case for both catalysts TiO2 and ZnO. A comparative study of the photocatalytic degradation showed that these two catalysts have a comparable reactivity; it follows a pseudo-first-order kinetics. The degradation trends followed the order: UV365/Fenton > UV365/TiO2 > Solar Fenton > Solar TiO2 > Fenton ~UV365/ZnO. Among AOPs, processes using Fenton type reagent are relatively cheap and easy to operate and maintain. Moreover, UV365/Fenton process has been shown as effective in the treatment of OG dye. Dye was degraded following second-order kinetics. The rate constants was 0,041 .10+6 L.M-1.min-1. The degradation was followed by spectrophotometric method, chemical oxygen demand (COD) measures and high performance liquid chromatography analyses (HPLC). Some aromatic and aliphatic degradation compounds were identified. Degradation of Orange G by UV Fenton mechanism was also proposed.

Keywords: AOPs, homogeneous catalysis, heterogeneous catalysis, acid orange 10, hydroxyl radical

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