Search results for: single metal atom catalysts

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: Wael A. Aboutaleb, Ahmed M. A. El Naggar, Heba M. Gobara

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This research work reports the photocatalytic production of hydrogen from water-methanol mixture using three different 15% ceria/iron oxide catalysts. The catalysts were prepared by physical mixing, precipitation, and ultrasonication methods and labeled as catalysts A-C. The structural and texture properties of the obtained catalysts were confirmed by X-ray diffraction (XRD), BET-surface area analysis and transmission electron microscopy (TEM). The photocatalytic activity of the three catalysts towards hydrogen generation was then tested. Promising hydrogen productivity was obtained by the three catalysts however different gases compositions were obtained by each type of catalyst. Specifically, catalyst A had produced hydrogen mixed with CO₂ while the composite structure (catalyst B) had generated only pure H₂. In the case of catalyst C, syngas made of H₂ and CO was revealed, as a novel product, for the first time, in such process.

Keywords: hydrogen production, water splitting, photocatalysts, clean energy

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Authors: Abhishek Kumar, Mohamed Awadein, Georg Gramse, Luyang Song, He Sun, Wolfgang Schofberger, Stefan Müllegger

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Electron transfer is a crucial part of chemical reactions which drive everyday processes. With the help of an electro-chemical radio frequency scanning tunneling microscopy (EC-RF-STM) setup, we are observing single electron mediated oxidation-reduction processes in molecules like ferrocene and transition metal corroles. Combining the techniques of scanning microwave microscopy and cyclic voltammetry allows us to monitor such processes with attoampere sensitivity. A systematic study of such phenomena would be critical to understanding the nano-scale behavior of catalysts, molecular sensors, and batteries relevant to the development of novel material and energy applications.

Keywords: radiofrequency, STM, cyclic voltammetry, ferrocene

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Authors: Lin Huang, Bo Wang, Armando Borgna

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Dehydration of glycerol to acrolein was conducted with solid acid catalysts in liquid phase in a batch reactor and in gas phase in a fix-bed reactor, respectively. In the liquid-phase reaction, ZSM-5, H3PO4-modified ZSM-5 and heteropolyacids including H3PW12O40•xH2O (HPW) and Cs2.5H0.5PW12O40 (CsPW) were studied as catalysts. High temperatures and high boiling point solvents such as sulfolane improved the selectivity to acrolein through suppressing the formation of polyglycerols and coke. Catalytic results and temperature-programmed desorption of ammonia showed that the yield of acrolein increased with increasing catalyst acidity within the range of weak acid strength. Weak acid sites favored the selectivity to acrolein whereas strong acid sites promoted the formation of coke. ZSM-5 possessing only acid sites led to a high acrolein yield, while heteropolyacid catalysts with strong acid sites produced a low acrolein yield. In the gas-phase reaction, HPW and CsPW supported on metal oxides such as SiO2, γ-Al2O3, SiO2-Al2O3, ZrO2 and silicate TUD-1 were studied as catalysts. HPW/TUD-1 was most active for the production of acrolein, followed by HPW/SiO2. An acrolein yield of 61 % was obtained over HPW/TUD-1. X-ray diffraction study suggested that HPW and CsPW were stable and more dispersed on SiO2, silicate TUD-1 and SiO2-Al2O3. It was found that the structures of HPW and CsPW were destroyed by interaction with γ-Al2O3 and ZrO2. Compared to CsPW/TUD-1, the higher acrolein yield with HPW/TUD-1 may be attributed to more Brønsted acid sites on HPW/TUD-1, based on preliminary pyridine adsorption IR study.

Keywords: dehydration, glycerol, acrolein, solid acid catalysts, gas-phase, liquid-phase

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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: Krasimir Ivanov, Elitsa Kolentsova, Dimitar Dimitrov, Petya Petrova, Tatyana Tabakova

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This work studies the effect of chemical composition on the activity and selectivity of γ–alumina supported CuO/ MnO2/Cr2O3 catalysts toward deep oxidation of CO, dimethyl ether (DME) and methanol. The catalysts were prepared by impregnation of the support with an aqueous solution of copper nitrate, manganese nitrate and CrO3 under different conditions. Thermal, XRD and TPR analysis were performed. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor. Flow-line equipment with an adiabatic reactor for simultaneous oxidation of all compounds under the conditions that mimic closely the industrial ones was used. The reactant and product gases were analyzed by means of on-line gas chromatographs. On the basis of XRD analysis it can be concluded that the active component of the mixed Cu-Mn-Cr/γ–alumina catalysts consists of at least six compounds – CuO, Cr2O3, MnO2, Cu1.5Mn1.5O4, Cu1.5Cr1.5O4 and CuCr2O4, depending on the Cu/Mn/Cr molar ratio. Chemical composition strongly influences catalytic properties, this influence being quite variable with regards to the different processes. The rate of CO oxidation rapidly decrease with increasing of chromium content in the active component while for the DME was observed the reverse trend. It was concluded that the best compromise are the catalysts with Cu/(Mn + Cr) molar ratio 1:5 and Mn/Cr molar ratio from 1:3 to 1:4.

Keywords: Cu-Mn-Cr oxide catalysts, volatile organic compounds, deep oxidation, dimethyl ether (DME)

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Authors: Maksudur Rahman Khan, Kar Min Chan, Huei Ruey Ong, Chin Kui Cheng, Wasikur Rahman

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Microbial fuel cells (MFCs) represent a promising technology for simultaneous bioelectricity generation and wastewater treatment. Catalysts are significant portions of the cost of microbial fuel cell cathodes. Many materials have been tested as aqueous cathodes, but air-cathodes are needed to avoid energy demands for water aeration. The sluggish oxygen reduction reaction (ORR) rate at air cathode necessitates efficient electrocatalyst such as carbon supported platinum catalyst (Pt/C) which is very costly. Manganese oxide (MnO2) was a representative metal oxide which has been studied as a promising alternative electrocatalyst for ORR and has been tested in air-cathode MFCs. However, the single MnO2 has poor electric conductivity and low stability. In the present work, the MnO2 catalyst has been modified by doping Pt nanoparticle. The goal of the work was to improve the performance of the MFC with minimum Pt loading. MnO2 and Pt nanoparticles were prepared by hydrothermal and sol-gel methods, respectively. Wet impregnation method was used to synthesize Pt/MnO2 catalyst. The catalysts were further used as cathode catalysts in air-cathode cubic MFCs, in which anaerobic sludge was inoculated as biocatalysts and palm oil mill effluent (POME) was used as the substrate in the anode chamber. The as-prepared Pt/MnO2 was characterized comprehensively through field emission scanning electron microscope (FESEM), X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) where its surface morphology, crystallinity, oxidation state and electrochemical activity were examined, respectively. XPS revealed Mn (IV) oxidation state and Pt (0) nanoparticle metal, indicating the presence of MnO2 and Pt. Morphology of Pt/MnO2 observed from FESEM shows that the doping of Pt did not cause change in needle-like shape of MnO2 which provides large contacting surface area. The electrochemical active area of the Pt/MnO2 catalysts has been increased from 276 to 617 m2/g with the increase in Pt loading from 0.2 to 0.8 wt%. The CV results in O2 saturated neutral Na2SO4 solution showed that MnO2 and Pt/MnO2 catalysts could catalyze ORR with different catalytic activities. MFC with Pt/MnO2 (0.4 wt% Pt) as air cathode catalyst generates a maximum power density of 165 mW/m3, which is higher than that of MFC with MnO2 catalyst (95 mW/m3). The open circuit voltage (OCV) of the MFC operated with MnO2 cathode gradually decreased during 14 days of operation, whereas the MFC with Pt/MnO2 cathode remained almost constant throughout the operation suggesting the higher stability of the Pt/MnO2 catalyst. Therefore, Pt/MnO2 with 0.4 wt% Pt successfully demonstrated as an efficient and low cost electrocatalyst for ORR in air cathode MFC with higher electrochemical activity, stability and hence enhanced performance.

Keywords: microbial fuel cell, oxygen reduction reaction, Pt/MnO2, palm oil mill effluent, polarization curve

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Authors: Hilal Kivrak, Aykut ÇağLar, Nahit Aktaş, Ali Osman Solak

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At present, Cd/TiO₂ and CdTe/TiO₂ catalysts are prepared via sodium borohydride (NaBH4) reduction method. These catalysts are characterized by fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). These Cd/TiO₂ and CdTe/TiO₂ are employed as catalysts for the photocatalytic oxidation of glucose. Cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) measurements are used to investigate their glucose electrooxidation activities of catalysts at long and under UV illumination (ʎ=354 nm). CdTe/TiO₂ catalyst is showed the best photocatalytic glucose electrooxidation activity compared to Cd/TiO₂ catalyst.

Keywords: cadmium, NaBH4 reduction method, photocatalytic glucose electrooxidation, Tellerium, TiO2

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Authors: R. H. Hwang, J. H. Park, K. B. Yi

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Nitrous oxide (N2O) is now distinguished as an environmental pollutant. N2O is one of the representative greenhouse gases and N2O is produced by both natural and anthropogenic sources. So, it is very important to reduce N2O. N2O abatement processes are various processes such as HC-SCR, NH3-SCR and decomposition process. Among them, decomposition process is advantageous because it does not use a reducing agent. N2O decomposition is a reaction in which N2O is decomposed into N2 and O2. There are noble metals, transition metal ion-exchanged zeolites, pure and mixed oxides for N2O decomposition catalyst. Among the various catalysts, cobalt-based catalysts derived from hydrotalcites gathered much attention because spinel catalysts having large surface areas and high thermal stabilities. In this study, the effect of promoter and K addition on the activity was compared and analyzed. Co3O4 catalysts for N2O decomposition were prepared by co- precipitation method. Ce and Zr were added during the preparation of the catalyst as promoter with the molar ratio (Ce or Zr) / Co = 0.05. In addition, 1 wt% K2CO3 was doped to the prepared catalyst with impregnation method to investigate the effect of K on the catalyst performance. Characterizations of catalysts were carried out with SEM, BET, XRD, XPS and H2-TPR. The catalytic activity tests were carried out at a GHSV of 45,000 h-1 and a temperature range of 250 ~ 375 ℃. The Co3O4 catalysts showed a spinel crystal phase, and the addition of the promoter increased the specific surface area and reduced the particle and crystal size. It was exhibited that the doping of K improves the catalytic activity by increasing the concentration of Co2+ in the catalyst which is an active site for catalytic reaction. As a result, the K-doped catalyst showed higher activity than the promoter added. Also, it was found through experiments that Co2+ concentration and reduction temperature greatly affect the reactivity.

Keywords: Co₃O4, K-doped, N₂O decomposition, promoter

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Authors: Reza Vakili, Xiaolei Fan, Alex Walton

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The first near ambient pressure (NAP)-XPS study of CO oxidation over Pt nanoparticles (NPs) incorporated into Zr-based UiO (UiO for Universitetet i Oslo) MOFs was carried out. For this purpose, the MOF-based Catalysts were prepared by wetness impregnation (WI-PtNPs@UiO-67) and linker design (LD-PtNPs@UiO-67) methods along with PtNPs@ZrO₂ as the control catalyst. Firstly, the as-synthesized catalysts were reduced in situ prior to the operando XPS analysis. The existence of Pt(II) species was proved in UiO-67 by observing Pt 4f core level peaks at a high binding energy of 72.6 ± 0.1 eV. However, by heating the WI-PtNPs@UiO-67 catalyst in situ to 200 °C under vacuum, the higher BE components disappear, leaving only the metallic Pt 4f doublet, confirming the formation of Pt NPs. The complete reduction of LD-PtNPs@UiO-67 is achieved at 250 °C and 1 mbar H₂. To understand the chemical state of Pt NPs in UiO-67 during catalytic turnover, we analyzed the Pt 4f region using operando NAP-XPS in the temperature-programmed measurements (100-260 °C) with reference to PtNPs@ZrO₂ catalyst. CO conversion during NAP-XPS experiments with the stoichiometric mixture shows that LD-PtNPs@UiO-67 has a better CO turnover frequency (TOF, 0.066 s⁻¹ at 260 °C) than the other two (ca. 0.055 s⁻¹). Pt 4f peaks only show one chemical species present at all temperatures, but the core level BE shifts change as a function of reaction temperature, i.e., Pt 4f peak from 71.8 eV at T < 200 °C to 71.2 eV at T > 200 °C. As this higher BE state of 71.8 eV was not observed after in situ reductions of the catalysts and only once the CO/O₂ mixture was introduced, we attribute it to the surface saturation of Pt NPs with adsorbed CO. In general, the quantitative analysis of Pt 4f data from the operando NAP-XPS experiments shows that the surface chemistry of the Pt active phase in the two PtNPs@UiO-67 catalysts is the same, comparable to that of PtNPs@ZrO₂. The observed difference in the catalytic activity can be attributed to the particle sizes of Pt NPs, as well as the dispersion of active phase in the support, which are different in the three catalysts.

Keywords: CO oxidation, heterogeneous catalysis, MOFs, Metal Organic Frameworks, NAP-XPS, Near Ambient Pressure X-ray Photoelectron Spectroscopy

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Authors: Silindile Gumede, Amir Hossein Mohammadi, Mbuyu Germain Ntunka

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Goal 12 of the 17 Sustainable Development Goals (SDGs) encourages sustainable consumption and production patterns. This necessitates achieving the environmentally safe management of chemicals and all wastes throughout their life cycle and the proper disposal of pollutants and toxic waste. Fluid catalytic cracking (FCC) catalysts are widely used in the refinery to convert heavy feedstocks to lighter ones. During the refining processes, the catalysts are deactivated and discarded as hazardous toxic solid waste. Spent catalysts (SC) contain high-cost metal, and the recovery of metals from SCs is a tactical plan for supplying part of the demand for these substances and minimizing the environmental impacts. Leaching followed by solvent extraction, has been found to be the most efficient method to recover valuable metals with high purity from spent catalysts. However, the use of inorganic acids during the leaching process causes a secondary environmental issue. Therefore, it is necessary to explore other alternative efficient leaching agents that are economical and environmentally friendly. In this study, the waste catalyst was collected from a domestic refinery and was characterised using XRD, ICP, XRF, and SEM. Response surface methodology (RSM) and Box Behnken design were used to model and optimize the influence of some parameters affecting the acidic leaching process. The parameters selected in this investigation were the acid concentration, temperature, and leaching time. From the characterisation results, it was found that the spent catalyst consists of high concentrations of Vanadium (V) and Nickel (Ni); hence this study focuses on the leaching of Ni and V using a biodegradable acid to eliminate the formation of the secondary pollution.

Keywords: eco-friendly leaching, optimization, metal recovery, leaching

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Authors: Tieling Xing, Jinqiu Yang, Guoqiang Chen

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

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

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Authors: Javaid Butt, Habtom Mebrahtu, Hassan Shirvani

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The paper presents a new additive manufacturing process for the production of metal and composite parts. It is termed as composite metal foil manufacturing and is a combination of laminated object manufacturing and brazing techniques. The process has been described in detail and is being used to produce dissimilar aluminum to copper foil single lap joints. A three dimensional finite element model has been developed to study the thermo-mechanical characteristics of the dissimilar Al/Cu single lap joint. The effects of thermal stress and strain have been analyzed by carrying out transient thermal analysis on the heated plates used to join the two 0.1mm thin metal foils. Tensile test has been carried out on the foils before joining and after the single Al/Cu lap joints are made, they are subjected to tensile lap-shear test to analyze the effect of heat on the foils. The analyses are designed to assess the mechanical integrity of the foils after the brazing process and understand whether or not the heat treatment has an effect on the fracture modes of the produced specimens.

Keywords: brazing, laminated object manufacturing, tensile lap-shear test, thermo-mechanical analysis

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Authors: Jaemin Kim, Ilsun Pang, Yongrae Cho, Kwanghun Kim, Sungsun Baik

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Manufacturing cost reduction is becoming more important due to excessive oversupply of Single crystalline ingot in recent solar market. Many companies are carrying out extensive research to grow more than one Single crystalline ingot in one batch to reduce manufacturing cost. However what most companies are finding difficult in this process is the effect on ingot due to increasing levels of impurities. Every ingot leaves a certain amount of melt after it is fully grown. This is the impurity that lowers the ingot quality. This impurity increase in the batch after second, third and more are grown subsequently in one batch. In order to solve this problem, the experiment to remove the residual melt in high temperature of hot zone was performed and succeeded. Theoretical average metal concentration of second ingot by new method was calculated and compared to it by conventional method.

Keywords: single crystal, solar cell, metal impurity, Ingot

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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: Patrizia Frontera, Anastasia Macario, Sebastiano Candamano, Fortunato Crea, Pierluigi Antonucci

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The increasing of the world energy demand makes today biomass an attractive energy source, based on the minimizing of CO2 emission and on the global warming reduction purposes. Recently, COP-21, the international meeting on global climate change, defined the roadmap for sustainable worldwide development, based on low-carbon containing fuel. Hydrogen is an energy vector able to substitute the conventional fuels from petroleum. Ethanol for hydrogen production represents a valid alternative to the fossil sources due to its low toxicity, low production costs, high biodegradability, high H2 content and renewability. Ethanol conversion to generate hydrogen by a combination of partial oxidation and steam reforming reactions is generally called auto-thermal reforming (ATR). The ATR process is advantageous due to the low energy requirements and to the reduced carbonaceous deposits formation. Catalyst plays a pivotal role in the ATR process, especially towards the process selectivity and the carbonaceous deposits formation. Bimetallic or trimetallic catalysts, as well as catalysts with doped-promoters supports, may exhibit high activity, selectivity and deactivation resistance with respect to the corresponding monometallic ones. In this work, NiMoCo/GDC, NiMoCu/GDC and NiMoRe/GDC (where GDC is Gadolinia Doped Ceria support and the metal composition is 60:30:10 for all catalyst) have been prepared by impregnation method. The support, Gadolinia 0.2 Doped Ceria 0.8, was impregnated by metal precursors solubilized in aqueous ethanol solution (50%) at room temperature for 6 hours. After this, the catalysts were dried at 100°C for 8 hours and, subsequently, calcined at 600°C in order to have the metal oxides. Finally, active catalysts were obtained by reduction procedure (H2 atmosphere at 500°C for 6 hours). All sample were characterized by different analytical techniques (XRD, SEM-EDX, XPS, CHNS, H2-TPR and Raman Spectorscopy). Catalytic experiments (auto-thermal reforming of ethanol) were carried out in the temperature range 500-800°C under atmospheric pressure, using a continuous fixed-bed microreactor. Effluent gases from the reactor were analyzed by two Varian CP4900 chromarographs with a TCD detector. The analytical investigation focused on the preventing of the coke deposition, the metals sintering effect and the sulfur poisoning. Hydrogen productivity, ethanol conversion and products distribution were measured and analyzed. At 600°C, all tri-metallic catalysts show the best performance: H2 + CO reaching almost the 77 vol.% in the final gases. While NiMoCo/GDC catalyst shows the best selectivity to hydrogen whit respect to the other tri-metallic catalysts (41 vol.% at 600°C). On the other hand, NiMoCu/GDC and NiMoRe/GDC demonstrated high sulfur poisoning resistance (up to 200 cc/min) with respect to the NiMoCo/GDC catalyst. The correlation among catalytic results and surface properties of the catalysts will be discussed.

Keywords: catalysts, ceria, ethanol, gadolinia, hydrogen, Nickel

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Authors: Ahmed I. Osman, Jehad K. Abu-Dahrieh, Jillian M. Thompson, David W. Rooney

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Natural gas (the main constituent is Methane 95%) is considered as an alternative to petroleum for the production of synthetics fuels. Nowadays, methane combustion at low temperature has received much attention however; it is the most difficult hydrocarbon to be combusted. Co/Mo and (4:1 wt/wt) catalysts were prepared from a range of different precursors and used for the low temperature total methane oxidation (TMO). The catalysts were characterized by, XRD, BET and H2-TPR and tested under reaction temperatures of 250-400 °C with a GHSV= 36,000 mL g-1 h-1. It was found that the combustion temperature was dependent on the type of the precursor, and that those containing chloride led to catalysts with lower activity. The optimum catalyst was Co/Mo (4:1wt/wt) where greater than 20% methane conversion was observed at 250 °C. This catalyst showed a high degree of stability for TMO, showing no deactivation during 50 hours of time on stream.

Keywords: methane low temperature total oxidation, oxygen carrier, Co/Mo, Co/Mn

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Authors: S. Said, Samira M. Abdel-Azim, Aya M. Matloob

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Nowadays, one of the most important industries is how to prepare a starting material like (styrene) which is used for the preparation of many petrochemical products in simple and inexpensive ways. Oxidative dehydrogenation of ethylbenzene (using CO2 as a soft oxidant) can solve this issue when using highly effective catalysts like SnO₂ and its nanocomposites (V₂Ox/SnO₂.) This study shows the effect of different synthesis methods of SnO₂ either by ethylene glycol or MOF then, uses the impregnation method for the preparation of its nanocomposite catalysts (V₂Ox/SnO₂.). The prepared catalysts were characterized by using different analytical techniques like XRD, BET, FTIR, TGA, XPS, and H₂-TPR. Oxidative dehydrogenation experimental results demonstrated that the composite V loading of 1 and 5 wt.% V₂Ox/SnO₂ (MOF &EG) catalyst exhibited extraordinarily high catalytic performance with selectivity toward styrene formation > 90% at 500oC, which can be attributed to the superior surface, textural, and structural properties of nanocomposites catalysts.

Keywords: SnO₂, vanadium oxide, ethylbenzene dehydrogenation, styrene, CO₂

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Authors: Shi Yu Wang, Qian Wei Zhang, He Li, Hao Han He, Yun Bo Li

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The spatial controls of electromagnetic (EM) waves have always been a research hot spot in recent years. And the rapid development of metasurface-based technologies has provided more freedoms for manipulating the EM waves. Here we propose the design of reconfigurable and non-reciprocal metasurface with independent controls of transmission gain, attenuation and phase. The proposed meta-atom mainly consists of the cascaded textures including the receiving antenna, the middle layer in which the power amplifiers (PAs), programmable attenuator and phase shifter locate, and the transmitting antenna. The programmable attenuator and phase shifter can realize the dynamic controls of transmission amplitude and phase independently, and the PA devices in the meta-atom can actualize the performance of non-reciprocal transmission. The proposed meta-atom is analyzed applying field-circuit co-simulation and a sample of the meta-atom is fabricated and measured under using two standard waveguides. The measured results verify the ability of the independent manipulation for transmission amplitude and phase of the proposed the meta-atom and the design method has been verified very well correspondingly.

Keywords: active circuits, independent controls of multiple electromagnetic features, non-reciprocal electromagnetic transmission, reconfigurable and programmable

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Authors: Akila Tayeb-Benmachiche, Saber-Mustapha Zendaoui, Salah-Eddine Bouaoud, Bachir Zouchoune

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The variation of the metal coordination site in π-coordinated polycyclic aromatic hydrocarbons (PAH) corresponds to the haptotropic rearrangement or haptotropic migration in which the metal fragment MLn is considered as the moveable moiety that is shifted between two rings of polycyclic or heteropolycyclic ligands. These structural characteristics and dynamical properties give to this category of transition metal complexes a considerable interest. We have investigated the coordination and the haptotropic shifts of (CO)3Ti and CpV moieties over the phenanthridine aromatic system and according to the metal atom nature. The optimization of (CO)3Ti(PHND) and CpV(PHND), using the Amsterdam Density Functional (ADF) program, without a symmetrical restriction of geometry gives an η6 coordination mode of the C6 and C5N rings, which in turn give rise to a six low-lying deficient 16-MVE of each (CO)3Ti(PHND) and CpV(PHND) structure (three singlet and three triplet state structures for Ti complexes and three triplet and three quintet state structures for V complexes). Thus, the η6–η6 haptotropic migration of the metal fragment MLn from the terminal C6 ring to the central C5N ring has been achieved by a loss of energy. However, its η6–η6 haptotropic migration from central C5N ring to the terminal C6 rings has been accomplished by a gain of energy. These results show the capability of the phenanthridine ligand to adapt itself to the electronic demand of the metal in agreement with the nature of the metal–ligand bonding and demonstrate that this theoretical study can also be applied to large fused π-systems.

Keywords: electronic structure, bonding analysis, density functional theory, coordination chemistry haptotropic migration

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Authors: K. Mondal, S. Talapatra, M. Terrones, S. Pokhrel, C. Frizzel, B. Sumpter, V. Meunier, A. L. Elias

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Worldwide energy independence is reliant on the ability to leverage locally available resources for fuel production. Recently, syngas produced through gasification of carbonaceous materials provided a gateway to a host of processes for the production of various chemicals including transportation fuels. The basis of the production of gasoline and diesel-like fuels is the Fischer Tropsch Synthesis (FTS) process: A catalyzed chemical reaction that converts a mixture of carbon monoxide (CO) and hydrogen (H₂) into long chain hydrocarbons. Until now, it has been argued that only transition metal catalysts (usually Co or Fe) are active toward the CO hydrogenation and subsequent chain growth in the presence of hydrogen. In this paper, we demonstrate that carbon nanotube (CNT) surfaces are also capable of hydro-deoxygenating CO and producing long chain hydrocarbons similar to that obtained through the FTS but with orders of magnitude higher conversion efficiencies than the present state-of-the-art FTS catalysts. We have used advanced experimental tools such as XPS and microscopy techniques to characterize CNTs and identify C-O functional groups as the active sites for the enhanced catalytic activity. Furthermore, we have conducted quantum Density Functional Theory (DFT) calculations to confirm that C-O groups (inherent on CNT surfaces) could indeed be catalytically active towards reduction of CO with H₂, and capable of sustaining chain growth. The DFT calculations have shown that the kinetically and thermodynamically feasible route for CO insertion and hydro-deoxygenation are different from that on transition metal catalysts. Experiments on a continuous flow tubular reactor with various nearly metal-free CNTs have been carried out and the products have been analyzed. CNTs functionalized by various methods were evaluated under different conditions. Reactor tests revealed that the hydrogen pre-treatment reduced the activity of the catalysts to negligible levels. Without the pretreatment, the activity for CO conversion as found to be 7 µmol CO/g CNT/s. The O-functionalized samples showed very activities greater than 85 µmol CO/g CNT/s with nearly 100% conversion. Analyses show that CO hydro-deoxygenation occurred at the C-O/O-H functional groups. It was found that while the products were similar to FT products, differences in selectivities were observed which, in turn, was a result of a different catalytic mechanism. These findings now open a new paradigm for CNT-based hydrogenation catalysts and constitute a defining point for obtaining clean, earth abundant, alternative fuels through the use of efficient and renewable catalyst.

Keywords: CNT, CO Hydrodeoxygenation, DFT, liquid fuels, XPS, XTL

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Authors: Bayan Alqassem, Israa A. Othman, Mohammed Abu Haija, Fawzi Banat

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The treatment of wastewater from highly toxic pollutants is one of the most challenging issues for humanity. In this study, the advanced oxidation process (AOP) was employed to study the catalytic degradation of phenol using different ferrite catalysts which are CoFe₂O₄, CrFe₂O₄, CuFe₂O₄, MgFe₂O₄, MnFe₂O₄, NiFe₂O₄ and ZnFe₂O₄. The ferrite catalysts were prepared via sol-gel and co-precipitation methods. Different ferrite composites were also prepared either by varying the metal ratios or incorporating chemically reduced graphene oxide in the ferrite cluster. The effect of phosphoric acid treatment on the copper ferrite activity. All of the prepared catalysts were characterized using infrared spectroscopy (IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The ferrites catalytic activities were tested towards phenol degradation using high performance liquid chromatography (HPLC). The experimental results showed that ferrites prepared through sol-gel route were more active than those of the co-precipitation method towards phenol degradation. In both cases, CuFe₂O₄ exhibited the highest degradation of phenol compared to the other ferrites. The photocatalytic properties of the ferrites were also investigated.

Keywords: ferrite catalyst, ferrite composites, phenol degradation, photocatalysis

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Authors: Ana M. Antolín, Sandra Contreras, Francesc Medina, Didier Tichit

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Introduction: High levels of nitrates (> 50 ppm NO3-) in drinking water are potentially risky to human health. In the recent years, the trend of nitrate concentration in groundwater is rising in the EU and other countries. Conventional catalytic nitrate reduction processes into N2 and H2O lead to some toxic intermediates and by-products, such as NO2-, NH4+, and NOx gases. Alternatively, photocatalytic nitrate removal using solar irradiation and heterogeneous catalysts is a very promising and ecofriendly technique. It has been scarcely performed and more research on highly efficient catalysts is still needed. In this work, different nanocatalysts supported on Aeroxide Titania P25 (P25) have been prepared varying: 0.5-4 % wt. Ag); Pt (2, 4 % wt.); Pt precursor (H2PtCl6/K2PtCl6); and impregnation order of both metals. Pt was chosen in order to increase the selectivity to N2 and decrease that to NO2-. Catalysts were characterized by nitrogen physisorption, X-Ray diffraction, UV-visible spectroscopy, TEM and X Ray-Photoelectron Spectroscopy. The aim was to determine the influence of the composition and the preparation method of the catalysts on the conversion and selectivity in the nitrate reduction, as well as going through an overall and better understanding of the process. Nanocatalysts synthesis: For the mono and bimetallic catalysts preparation, wise-drop wetness impregnation of the precursors (AgNO3, H2PtCl6, K2PtCl6) followed by a reduction step (NaBH4) was used to obtain the metal colloids. Results and conclusions: Denitration experiments were performed in a 350 mL PTFE batch reactor under inert standard operational conditions, ultraviolet irradiations (λ=254 nm (UV-C); λ=365 nm (UV-A)), and presence/absence of hydrogen gas as a reducing agent, contrary to most studies using oxalic or formic acid. Samples were analyzed by Ionic Chromatography. Blank experiments using respectively P25 (dark conditions), hydrogen only and UV irradiations without hydrogen demonstrated a clear influence of the presence of hydrogen on nitrate reduction. Also, they demonstrated that UV irradiation increased the selectivity to N2. Interestingly, the best activity was obtained under ultraviolet lamps, especially at a closer wavelength to visible light irradiation (λ = 365 nm) and H2. 2% Ag/P25 leaded to the highest NO3- conversion among the monometallic catalysts. However, nitrite quantities have to be diminished. On the other hand, practically no nitrate conversion was observed with the monometallics based on Pt/P25. Therefore, the amount of 2% Ag was chosen for the bimetallic catalysts. Regarding the bimetallic catalysts, it is observed that the metal impregnation order, amount and Pt precursor highly affects the results. Higher selectivity to the desirable N2 gas is obtained when Pt was firstly added, especially with K2PtCl6 as Pt precursor. This suggests that when Pt is secondly added, it covers the Ag particles, which are the most active in this reaction. It could be concluded that Ag allows the nitrate reduction step to nitrite, and Pt the nitrite reduction step toward the desirable N2 gas.

Keywords: heterogeneous catalysis, hydrogenation, nanocatalyst, nitrate removal, photocatalysis

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Authors: Nassira Ouslimani

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The electronic structure of transition metals gives them many catalytic possibilities in many types of reactions, particularly cobalt and molybdenum. It is in this context that this study is part of the synthesis and characterization of mass catalysts based on cobalt and molybdenum Co1₋xMoO4 (X=0 and X=0.5 and X=1). The two catalysts were prepared by Co-precipitation using ammonia as a precipitating agent and one by precipitation. The samples obtained were analyzed by numerous physic-chemical analysis techniques: ATG-ATD-DSC, DRX-HT, SEM-EDX, and the elemental composition of the catalysts was verified by SAA as well as the FTIR. The ATG-DSC shows a mass loss for all the catalysts of approximately 8%, corresponding to the loss of water and the decomposition of nitrates. The DRX-HT analysis allows the detection of the two CoMoO4 phases with diffraction peaks which increase with the increase in temperature. The results of the FTIR analysis made it possible to highlight the vibration modes of the bonds of the structure of the prepared catalysts. The SEM images of the solids show very different textures with almost homogeneous surfaces with a more regular particle size distribution and a more defined grain shape. The EDX analysis showed the presence of the elements Co, Mo, and O in proportions very close to the nominal proportions. Finally, the actual composition, evaluated by SAA, is close to the theoretical composition fixed during the preparation. This testifies to the good conditions for the preparation of the catalysts by the co-precipitation method.

Keywords: catalytic, molybdenum, coprecipitation, cobalt, ammonia

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Authors: Kriangkrai Aranyarat

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The effect of N2 pretreatment on the catalytic activity of tungsten-based catalysts was investigated in the metathesis of ethylene and trans-2-butene at 450oC and atmospheric pressure. The presence of tungsten active species was confirmed by UV-Vis and Raman spectroscopy. Compared to the WO3-based catalysts treated in air, higher amount of WO42- tetrahedral species and lower amount of WO3 crystalline species were observed on the N2-treated ones. These contribute to the higher conversion of 2-butene and propylene selectivity during 10 h time-on-stream. Moreover, N2 treatment led to lower amount of coke formation as revealed by TPO of the spent catalysts.

Keywords: metathesis, pretreatment, propylene, tungsten

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Authors: Katya Milenova, Penko Nikolov, Irina Stambolova, Plamen Nikolov, Vladimir Blaskov

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In the recent article, a comparison was made between Cu and TiO2 supported catalysts on activated carbon for ozone decomposition reaction. The activated carbon support in the case of TiO2/AC sample was prepared by physicochemical pyrolysis and for Cu/AC samples the supports are chemically modified carbons. The prepared catalysts were synthesized by impregnation method. The samples were annealed in two different regimes-in air and under vacuum. To examine adsorption efficiency of the samples BET method was used. All investigated catalysts supported on chemically modified carbons have higher specific surface area compared to the specific surface area of TiO2 supported catalysts, varying in the range 590÷620 m2/g. The method of synthesis of the precursors had influenced catalytic activity.

Keywords: activated carbon, adsorption, copper, ozone decomposition, TiO2

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Authors: Nurul Huda Baharuddin, Nik Meriam Nik Sulaiman, Mohammed Kheireddine Aroua

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The effects of pH, polymer concentration, and metal ions feed concentration for four selected heavy metals Zn (II), Pb (II), Cr (III) and Cr (VI) were tested by using Polymer Enhanced Ultrafiltration (PEUF). An alternative biopolymer namely unmodified starch is proposed as a binding reagent in consequences, as compared to commonly used water-soluble polymers namely polyethylene glycol (PEG) and polyethyleneimine (PEI) in the removal of selected four heavy metal ions. The speciation species profiles of four selected complexes ions namely Zn (II), Pb (II), Cr (III) and Cr (VI) and the present of hydroxides ions (OH-) in variously charged ions were investigated by available software at certain pH range. In corresponds to identify the potential of complexation behavior between metal ion-polymers, potentiometric titration studies were obtained at first before carried out experimental works. Experimental works were done using ultrafiltration systems obtained by laboratory ultrafiltration bench scale equipped with 10 kDa polysulfone hollow fiber membrane. Throughout the laboratory works, the rejection coefficient and permeate flux were found to be significantly affected by the main operating parameter, namely the effects of pH, polymer composition and metal ions concentrations. The interaction of complexation between two binding polymers namely unmodified starch and PEG were occurred due to physical attraction of metal ions to the polymer on the molecular surface with high possibility of chemical occurrence. However, these selected metal ions are mainly complexes by polymer functional groups whenever there is interaction with PEI polymer. For study of single metal ions solutions, Zn (II) ions' rejections approaching over 90% were obtained at pH 7 for each tested polymer. This behavior was similar to Pb (II), Cr (III) and Cr (VI); where the rejections were obtained at lower acidic pH and increased at neutral pH of 7. Different behavior was found by Cr (VI) ions where a high rejection was only achieved at acidic pH region with PEI. Polymer concentration and metal ions concentration are found to have a significant effect on rejections. For mixed metal ion solutions, the behavior of metal ion rejections was similar to single metal ion solutions for investigation on the effects of pH. Rejection values were high at pH 7 for Zn (II) pH 7 for Zn (II) and Cr (III) ions, corresponding to higher rejections with unmodified starch. Pb (II) ions obtained high rejections when tested with PEG whenever carried out in mixed metal ion solutions. High Cr (VI) ions' rejection was found with PEI in single and mixed metal ions solutions at neutral pH range. The influence of starch’s granule structure towards the rejections of these four selected metal ions is found to be attracted in a non-ionic manner. No significant effects on permeate flux were obtained when tested at different pH ranges, polymer concentrations and metal ions feed either by single or mixtures metal ions solutions. Canizares Model was employed as the theoretical model to predict permeate flux and metal ions retention on the study of heavy metal ions removal.

Keywords: polyethyleneimine, polyethylene glycol, polymer-enhanced ultrafiltration, unmodified starch

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Authors: Neha Thakur, Pravin S. More

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The interaction of CO, H2 and LPG with Cu-dosed SnO2 catalysts was studied by means of Fourier transform infrared spectroscopy (FTIR). With increasing Cu loading, pronounced and progressive red shifts of the C–O stretching frequency associated with molecular CO adsorbed on the Cu/SnO2 component were observed. This decrease in n(CO) correlates with enhancement of CO dissociation at higher temperatures on Cu promoted SnO2 catalysts under conditions, where clean Cu is almost ineffective. In the conclusion, the capability of our technique is discussed, and a technique for enhancing the sensitivity in our technique is proposed.

Keywords: FTIR, spectroscopic, dissociation, n(CO)

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Authors: D. Amaranatha Reddy

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Highly efficient and stable co-catalysts materials is of great important for boosting photo charge carrier’s separation, transportation efficiency, and accelerating the catalytic reactive sites of semiconductor photocatalysts. As a result, it is of decisive importance to fabricate low price noble metal free co-catalysts with high catalytic reactivity, but it remains very challenging. Considering this challenge here, dual metal organic frame work derived N-Doped Fe3C nanocages have been rationally designed and decorated with ultrathin ZnIn2S4 nanosheets for efficient photocatalytic hydrogen generation. The fabrication strategy precisely integrates co-catalyst nanocages with ultrathin two-dimensional (2D) semiconductor nanosheets by providing tightly interconnected nano-junctions and helps to suppress the charge carrier’s recombination rate. Furthermore, constructed highly porous hybrid structures expose ample active sites for catalytic reduction reactions and harvest visible light more effectively by light scattering. As a result, fabricated nanostructures exhibit superior solar driven hydrogen evolution rate (9600 µmol/g/h) with an apparent quantum efficiency of 3.6 %, which is relatively higher than the Pt noble metal co-catalyst systems and earlier reported ZnIn2S4 based nanohybrids. We believe that the present work promotes the application of sulfide based nanostructures in solar driven hydrogen production.

Keywords: photocatalysis, water splitting, hydrogen fuel production, solar-driven hydrogen

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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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