Ionic Liquids

Consecration texts are among the most important formulas that document religious and social relations from the beginning of the dynastic Period until the end of ancient Egyptian history. The word consecration means setting aside something for a specific purpose. Consecration in tombs carried deep religious Significance, aiming to immortalize the memory of the deceased and ensuring his continuity in the afterlife. There were several formulas used to indicate the word consecration, and these formulas varied them were the formula from period to another, among them were the formula (ir.n.f) meaning "what he did, made, or dedicated," and the formula (di.f) (di.sn) meaning "dedicated - gave - allocated".
This research aims to Study the dedication formulas on false doors during the New Kingdom (from the reign of Queen Hatshepsut to the reign of King Thutmose IV), and to examine the locations where these formulas are recorded on the false doors. The research also aims to identify the scenes accompanying the dedication text

Les électrolytes, au coeur des générateurs électrochimiques, assurent le transport des ions d'une électrode à l'autre et sont un élément essentiel dans la conception de la batterie « idéale ». L'électrolyte doit s'adapter aux matériaux d'électrode utilisés et aux conditions de fonctionnement, il existe ainsi différentes familles d'électrolytes. Après la définition des propriétés requises pour les électrolytes, les avancées récentes obtenues pour ces différents électrolytes seront développées.

Densities, kinematic viscosities, speed of sound and refractive indices of nitromethane and 1-pentanol and their deuterated derivatives CD 3 NO 2 and C 5 H 11 OD were measured. The data obtained allowed to calculate molar volumes, dynamic viscosities, isentropic compressibilities and isobaric thermal expansion. Deuterium isotope effect on the selected physicochemical properties of both nitromethane and 1-pentanol has been determined. Large isotope effects characterizing density, viscosity and speed of sound are observed for nitromethane and much smaller for 1-pentanol. Isotope effects on molar volume are small both for nitromethane and 1-pentanol, but of the opposite sign. These observations are in agreement with the expectations.

Magnesium and its alloys are prone to corrosion upon exposure to atmosphere thus are usually protected by using a pretreatment before being employed. The use of ionic liquids (ILs) has emerged as a novel chemical in corrosion protection of reactive metals such as lithium and magnesium. This paper reviews the use of ILs in the corrosion protection of magnesium and aluminium with respect to a range of IL chemistries. Emphasis has also been placed on characterisation of the passivating films using various techniques, as well as proposed mechanisms for film formation. This review highlights that there is still much research needed to understand how to generate robust passivating films on reactive metal surfaces in the presence of ILs.

Magnesium and its alloys are prone to corrosion upon exposure to atmosphere thus are usually protected by using a pretreatment before being employed. The use of ionic liquids (ILs) has emerged as a novel chemical in corrosion protection of reactive metals such as lithium and magnesium. This paper reviews the use of ILs in the corrosion protection of magnesium and aluminium with respect to a range of IL chemistries. Emphasis has also been placed on characterisation of the passivating films using various techniques, as well as proposed mechanisms for film formation. This review highlights that there is still much research needed to understand how to generate robust passivating films on reactive metal surfaces in the presence of ILs.

This work used a literature search to select the most suitable system for the delignification process of annual plants. This process was evaluated in terms of lignin removal from plant biomass. Based on previous experiments, a low transition temperature mixture (LTTM) was used, which was a mixture of choline chloride and lactic acid in a molar ratio of 1:2. Samples of hemp fibers were examined. The delignification of biomass was monitored by changing the content of the main components. After application of the solvent at a temperature of 100, 120, or 140 °C and a delignification time of 2 or 4 h, the lignin content expressed by Kappa number decreased to the level of 22 to 13.7. Yields of hemp fibers sown after LTTM application ranged from 72.5 to 90.6%. The results confirmed that the use of LTTM (choline chloride/lactic acid) is a suitable system for the extraction of lignin from biomass. The findings showed that LTTM was an effective delignifying agent for hemp, as a relatively low...

The rapid shift toward electric vehicles (EVs) is imperative for achieving the United Nations' net-zero emissions target by 2050. This paper explores deep eutectic solvents (DESs) as sustainable alternatives to traditional solvents in batteries and fuel cells. DESs, sourced from renewables, offer numerous advantages, including low toxicity, affordability, and biodegradability, aligning with sustainable energy goals. The review underscores the importance of addressing challenges such as high viscosity, limited solubility, and compatibility issues for enhanced performance. This study primarily delves into how DESs can boost electrolyte performance through biosubstitution and ion recovery, extending their potential to metal recovery for resource efficiency. Additionally, DESs' flame-retardant, antifreeze properties, and robust thermal and electrochemical stability enhance battery safety, positioning them as a promising avenue for future research. Given the ambitious EV transition targets set globally, this Review provides an overview of DES advancements and their integration with other materials and technologies. Despite potential drawbacks in specific energy and energy density, sodium-based batteries are emerging as a viable alternative to their lithium counterparts. The future of EVs and DESs in battery technology hinges on their economic viability, infrastructure development, and life cycle emissions. In conclusion, this study underscores the pivotal role of DESs in driving sustainable energy solutions during the EV transition. 47 produce electricity through chemical redox reactions, but the 48 sources of energy used for the chemical reaction is different. 49 While batteries produce electricity using stored energy, fuel 50 cells generate power using hydrogen-rich fuel. 5 51 Deep eutectic solvents present a promising avenue for 52 sustainable electrolytes in batteries and fuel cells. 6,7 DES 53 enable biosubstitution opportunities and improved ion 54 recovery, enhancing electrolyte performance. 8,9 However, 55 challenges such as material compatibility, thermal stability, 56 and low energy density must be overcome. 10,11 57 In battery EVs, batteries store and deliver energy to the 58 powertrain, whereas a fuel cell EV generates electricity using 59 hydrogen as a fuel, which subsequently delivers energy to the

important aspect in biofuel conversion is glucose isomerization step using zeolites. Zeolites are crystalline solids that have wide applications in industrial areas for its hydrocarbon conversion, adsorption of molecules. In this study, we report MD simulation studies on glucose solution diffusion into zeolite structure as a function of temperature and pressure. Development of united-atom force field for PBILs, for phosphonium cation with anions of chloride and acetate, is considered in this study. Force field parameterization was considered for these ionic liquids with a variation of alkyl chain length in phosphonium ion with chloride and acetate anions. Performance of force field parameters was analyzed by calculating properties such as density and viscosity at various temperature and compared with available experimental data. Efficient algorithm techniques were developed in molecular simulations that will reduce computational load in calculating non-bonded interactions. We introduce theory of local sample (TLS) in calculating non-bonded interactions acting on atoms. Another algorithmic improvement in MD simulations is calculating force acting on atoms based on previous time steps, that achieves up to 50 % reduction in computational time.

Highly fluorinated fullerenes with a chemical composition of C 60 F 48 have been prepared and characterized. Their solubility of the new nanomaterials in the ionic liquid (IL) has been compared with raw fullerenes C 60 . Fluorination may appear as a convenient method to enhance the solubility of carbonaceous nanomaterials in a fluorinated based anion IL. Indeed, the ability of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BmIm][NTf 2 ]), to solubilize C 60 and C 60 F 48 was investigated using optical microscopy and UV-vis spectroscopy. While C 60 has very poor solubility in this IL (below 0.07 mmol/L), the solubility increases at least eightfold, i.e. more than 1.0 mg/mL (or 0.61 mmol/L) for C 60 F 48 samples . The presence of fluorine atoms on fullerene seems to enhance the stability of the solvated molecules in IL thanks to the limitation of the aggregation of C 60 F 48 in [BmIm][NTf 2 ]. This improvement of the solubility could be explained by the beneficial effect of the fluorination that induces a decrease of the interaction between carbonaceous solutes as the carbon hybridization changes from sp 2 to sp 3 through the formation of C-F covalent bonds and thus enhances the interaction between the solvent and the solute. Fluorination appears as an efficient approach to limit the use of volatile organic compounds usually used as co-solvent to enhance the dispersion mechanism.

One of the main problems of deodorizer distillates is the difficulty in separating free carboxylic fatty acids (FFA) from the remaining added-value components, such as squalene. A two-step novel strategy for the valorization of olive oil deodorizer distillate (OODD) is presented, based on the use of choline hydrogen carbonate and supercritical carbon dioxide (scCO 2 ). In the first step, the FFA present in OODD were neutralized with choline hydrogen carbonate to form choline carboxylates. The choline carboxylates obtained are of interest to the cosmetic industry. Due to their ionic character, they are insoluble in scCO 2 . Therefore in the second step, the reaction mixture was subjected to extraction with scCO 2 at 15 MPa, 313 K and a gas flow rate of 2 ml min À1 , yielding an extract with a maximum FFA content of ca. 3% (w/w). A valorization supply chain of OODD is proposed.

Anhydrous ethanol is a promising alternative to gasoline in fuel engines. However, since ethanol forms an azeotrope with water, high-energy-consumption separation techniques such as azeotropic distillation, extractive distillation, and molecular sieves are needed to produce anhydrous ethanol. This work discusses the potential development of an integrated process for bioethanol production using ionic liquids and Ceratonia siliqua as a carbohydrate source for further fermentation of the aqueous extracts. A four-stage counter-current system was designed to improve the sugar extraction yield to values close to 99%. The alcoholic fermentation of the extracts showed ethanol concentrations of 95 g/L using the microorganism Saccharomyces cerevisae. The production of anhydrous ethanol through extractive distillation with ethylene glycol was simulated using CHEMCAD software, with an energy consumption of 13.23 MJ/Kg of anhydrous ethanol. Finally, several ionic liquids were analyzed and are pr...

Biodiesel synthesis using heterogenous catalyst usually results in compromise rate of reaction due to mass transfer limitation during the reaction. An alternative is reported in this paper to produce biodiesel from free fatty acids in a liquid-liquid system using immobilized lipase. The yield of reversible reactions, which is naturally deteriorated by the presence of water because of thermodynamic limitation, nevertheless remained and the rate increased until 2 manifolds when water was initially added from 0.15 wt% to 15 wt%. The reaction tests were conducted in a batch reactor at 45 o C using the feed ratio,  (0 <  < 2.5) and all runs were performed under free mass transport limitation. The result also shows that the increment of rates were prominent in excess oleic acid mixtures implying the enhancement of clearly discriminated liquid phase during the reaction.

Invasive plant species, while detrimental to native ecosystems, present untapped potential as renewable sources for biomaterial development. This research explores how invasive flora can be reimagined as sustainable raw materials by applying allometry principles to scale their utilization across diverse domains, including architecture, product design, and textiles. Using Celastrus orbiculatus (Oriental Bittersweet) as a case study, the research investigates it’s anatomical and compositional properties to identify potential biomaterial applications.

The integration of allometry—the study of size and shape correlations across biological structures—enables a systemic framework to adapt material properties for scalability and functionality. Prototypes developed would include bio-composites, structural panels, and biodegradable packaging solutions, demonstrating the feasibility of transforming invasive biomass into high-value materials. Furthermore, the paper examines lifecycle analyses, environmental impacts, and economic benefits, emphasizing localized harvesting and processing to align with circular economy principles. The findings present a paradigm shift: viewing invasive plants not as ecological threats but as resources for regenerative design.

Chiral supported ionic liquid phase (CSILP) catalysts were prepared by physical adsorption (within highly porous carbons or mesoporous silica) of Ir, Ru and Rh complexes as IrCl(COD)-(S,S)-BDPP, [IrCl-(S)-BINAP] 2 , RuCl(p-cymene)[(S,S)-Ts-DPEN], RuOTf(p-cymene)[(S,S)-Ts-DPEN], [Rh(COD)(S,S)-DIPAMP][BF 4 ], and [Rh(COD)(R,R)-Me-DuPHOS][BF 4 ]. For the syntheses of CSILP catalysts [EMIM][NTf 2 ], [BMIM][BF 4 ] and [BMIM][PF 6 ] ionic liquids were used. Comparative homogeneous and heterogeneous experiments were carried out using the asymmetric hydrogenation of double C N and C C bonds in trimethylindolenine, 2-methylquinoline and dimethylitaconate, respectively. The conversion and enantioselectivity was found to depend on the nature of the complex (metal and ligand), the immobilization method used, nature of the ionic liquid, nature of the support and the experimental conditions.

In the present paper the authors targeted to present the recent ionic liquids doped polymer electrolyte and tested its electrochemical, thermal, and physicochemical properties, which are decisive for electrochemical devices. Ionic liquids can also be considered designer solvents to substitute the more flammable organic carbonates and enhance the green credentials and performance of renewable energy storage devices, mainly supercapacitors and lithium-ion batteries. This review presents the recent ionic liquids doped electrolyte electrochemical, thermal, and physicochemical properties, which are decisive for supercapacitors and lithium-ion batteries. Ionic liquids can also be considered designer solvents to substitute the more flammable organic carbonates and enhance the green credentials and performance of renewable energy storage devices like supercapacitors and batteries.

The impurities CO 2 and H 2 S in natural gas (NG) are recognized as major contaminants that exacerbate economic, operational, and environmental losses. Generally, these undesirable impurities are removed using wellestablished amine-based absorption methods. However, typical methods in this category are cost-intensive, primarily due to their high operating and maintenance costs. The ionic liquids (ILs) are emerging as alternative solvents owing to their lower regeneration costs and non-flammable nature. However, ILs could not attain a significant attention from practitioners due to the lack of effective communication between industry and academia. In this context, a comprehensive review and analysis of specific ILs that can simultaneously remove H 2 S and CO 2 is proposed. This article highlights the major challenges and issues associated with various acid gases removal approaches, particularly IL-based absorption techniques. Recent developments toward solving the major issues associated with absorption using ILs are assessed to highlight areas for further improvement. The acid gas solubility data for ILs are analyzed to evaluate the feasibility and associated major constraints for largescale process designs using commercial process simulators. Furthermore, the fundamentals for the process systems engineering-based investigations using ILs are also highlighted and evaluated. This study concludes that ILs have the potential to completely replace conventional solvents, have synergistic effects in terms of energy savings, and provide feasible solutions to maintenance-related issues.

Rigid environmental regulations and the energy crisis are pursuing researchers to investigate eco-friendly and more energy-generating alternatives to conventional resources. Biomass has the required potential and is drawing keen attention, especially in the field of energy. This work includes the thermal decomposition of almond shells under pyrolysis (N 2) conditions in a thermogravimetric analyzer (TGA) and estimated pyrolysis product gas composition and thermo-kinetic parameters. Pyrolysis experiments were conducted at heating rates of 10°C/min, 20°C/min, and 30°C/min. Using 11 reaction models, the Coats-Redfern method was applied to determine kinetic and thermodynamic parameters. The pyrolysis product gas composition was estimated using correlations based on elemental composition and pyrolysis temperature. Thermal decomposition mainly occurred in the temperature range 150-550°C with a peak temperature of 292°C, 310°C, and 321°C for the three heating rates, i.e. 10°C/min, 20°C/min, and 30°C/min, respectively, and 99.40% total weight loss. High regression coefficients (R 2) in the range of 0.90-0.99 were obtained for the Coats-Redfern models. High mean relative reactivity (0.04%min-1 °C-1) and low activation energies showed a high tendency to degrade thermally. The overall activation energy Eα range for almond shell was 2-84 kJ/mol at all heating rates. The pyrolysis gas composition showed good agreement with the experimental results of similar biomass.

In this work, the impact of ionic liquid (IL) pretreatment of spent co ee ground (SCG) is assessed using three analytical techniques. Four di erent classes of ILs were employed to compare the e ect of cations and anions. Thermogravimetric analysis under N2 environment was done to collect analytical data at 20 °C/min. Reactivity analysis evaluated mean relative reactivity (Rm) and pyrolysis factor (PF), kinetic analysis determined activation energy (Ea) and pre-exponential factor (A), while thermodynamic analysis helped to nd enthalpy change (ΔH), Gibbs free energy change (ΔG), and entropy change (ΔS). IL treatment aided thermal breakdown by increasing the mass loss % from 93% for untreated SCG to 97% after IL treatment. Decomposition rate for the IL treated samples was calculated to be in the range of 6.7-7%min-1. All the ILs increased Rm, with the largest increase from 2.42*102 to 2.57*102 % min-1°C-1; they also decreased the Ea of SCG from 42.25 to as low as 29.91 kJ/mole. This might be induced by the breakdown of the lignin structure of SCG by IL treatment leaving it sensitive to heat treatment. IL-treated SCG ΔS values indicate increased disorder and thermal instability. Among the studied ILs, relatively inexpensive and infrequently used [P66614] [Cl] and [N1444] [Cl] fared better than imidazolium based ILs. This study could provide useful knowledge in nding e ective cations for designing taskspeci c ILs for the thermochemical conversion process.

Three novel acetate and formate ammonium salts of N-(2-hydroxyethyl)-ethylenediamine (Hydeten) were synthesized as room temperature ionic liquids (RTILs) {2-(2-hydroxy ethylamino)-ethanaminium formate (IL1a), 2-amino-N-(2-hydroxyethyl)-ethanaminium formate (IL1b), and 2-(2-hydroxyethylamino)-ethanaminium acetate (IL2)}. Their structures were characterized by using elemental analysis, FT-IR, 1 H and 13 C NMR techniques. Some thermal properties of these ILs were determined by using TG and DSC techniques. Real dielectric (ε′)-frequency (ω), imaginary dielectric (ε″)-frequency (ω), and conductivity (σ AC )-frequency (ω) relationships of IL1a-b, IL2, and doped IL1-2 were investigated. These ILs were also tested as solvent or catalyst in the synthesis of some organic compounds.

Inspired by biological neural systems, neuromorphic devices may open up new computing paradigms to explore cognition, learning and limits of parallel computation. Here we report the demonstration of a synaptic transistor with SmNiO 3 , a correlated electron system with insulator-metal transition temperature at 130°C in bulk form. Non-volatile resistance and synaptic multilevel analogue states are demonstrated by control over composition in ionic liquid-gated devices on silicon platforms. The extent of the resistance modulation can be dramatically controlled by the film microstructure. By simulating the time difference between postneuron and preneuron spikes as the input parameter of a gate bias voltage pulse, synaptic spike-timing-dependent plasticity learning behaviour is realized. The extreme sensitivity of electrical properties to defects in correlated oxides may make them a particularly suitable class of materials to realize artificial biological circuits that can be operated at and above room temperature and seamlessly integrated into conventional electronic circuits.

The extraction mechanism of Pt(IV) from aqueous HCl solutions towards the ionic liquid 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) ) is deciphered. To that end, aqueous speciation of Pt(IV) as a function of HCl was studied by 195 Pt NMR. Influence of the concentration of HCl (ranging from 1 to 12 M) and of the initial concentration of Pt (IV) (ranging from 10 À5 to 10 À2 M) in the aqueous phase on the distribution coefficients of Pt(IV) was systematically investigated. The decrease in D with the concentrations of HCl and Pt(IV) observed is quantitatively very well described with a model using three chemical equilibria, namely the solubility of the ionic liquid in water, the extraction of PtCl 6 2À through an ion-pair formation and that of Cl À towards the ionic liquid phase. D values were then predicted over a wider range of concentrations for HCl and PtCl 6 . Alternatively, the extraction of PtCl 6 2À was described using an anion exchange hypothesis and it is demonstrated that these two apparently different mechanisms are actually equivalent within hydrophobic ionic liquids. Because the two versions of the extraction model presented here are not specific to PtCl 6 2À or the ionic liquid, they can be generalized to the extraction of any charged (metal) complex and any hydrophobic ionic liquid, allowing us to outline a general uncertainty principle in the determination of extraction mechanisms in systems involving ionic liquids [a] Prof. N. Papaiconomou

The effects of the incorporation of ethylene carbonate (EC) or dimethyl carbonate on the physicochemical and electrochemical properties of ionic liquids (ILs) based on aliphatic quaternary ammonium and imide anion were studied. The evolution of the melting point, glass transition, ionic conductivity, diffusion coefficient, and electrochemical stability were evaluated. The addition of a low amount of solvent, that is, 20 wt %, allows us to improve significantly the conductivity values, reaching 12 mS/cm at 40 °C. The incorporation of a polar solvent, EC, has no positive effect on the IL dissociation. Moreover, the incorporation of EC in ILs improves the electrochemical stability toward reduction, whereas the high anodic stability is maintained. The addition of LiTFSI in IL + solvent electrolytes has been investigated. Although this addition reduces the ionic conductivity, this decrease is less pronounced than in pure ILs, showing the beneficial effect of the additive solvent.

This paper deals with the performance of anhydrous proton-conducting polymers obtained by blending modified Nafion 1 membranes with proton conducting ionic liquids (PILs). It has been shown that the conductivities depend more on the PIL uptake than on its intrinsic conductivity. Conductivities at 130-C approaching those of current Nafion membranes at 80-C and 98% relative humidity were obtained with the best blends. These data allow considering MEA operating at 120-130-C based on membrane and electrodes incorporating these blends. This is clearly a positive feature for an implementation in hybrid vehicles powered by proton exchange membrane fuel cells (PEMFCs) operating above 100-C. Lastly, preliminary results for a PIL based on a half-neutralized diamine show an improvement in oxidation and, provided that the neutralization is optimized, a neat reinforcement of the Nafion membrane can be expected.

Current sensor devices for the detection of methane or natural gas emission are either expensive and have high power requirements or fail to provide a rapid response. This report describes an electrochemical methane sensor utilizing a non-volatile and conductive pyrrolidinium-based ionic liquid (IL) electrolyte and an innovative internal standard method for methane and oxygen dual-gas detection with high sensitivity, selectivity, and stability. At a platinum electrode in bis(trifluoromethylsulfonyl)imide (NTf2)-based ILs, methane is electro-oxidized to produce CO2 and water when an oxygen reduction process is included. The in situ generated CO2 arising from methane oxidation was shown to provide an excellent internal standard for quantification of the electrochemical oxygen sensor signal. The simultaneous quantification of both methane and oxygen in real time strengthens the reliability of the measurements by cross-validation of two ambient gases occurring within a single sample mat...

The effect of three compounds of non ionic surfactants, namely, ethoxylated fatty amines with different number of ethylene oxide unit on the corrosion of carbon steel (Type L52) in 1 M HCl has been studied using weight loss and galvanostatic polarization measurements. The percentage inhibition efficiency was found to increase with increasing concentration of inhibitor, number of ethylene oxide units and with decreasing temperature. The inhibitive effect of these compounds was interpreted in view of their adsorption on the steel surface, through their ethoxy groups. The adsorption of these compounds was found to obey the Langmuir isotherm. The effect of temperature on the rate of corrosion in the absence and presence of these compounds was also studied. Some activated thermodynamic parameters were calculated.

The focus of this review is primarily on the sequence of structural changes at micro and molecular level during carbonization of cellulosic fibres. The influence of various operational parameters such as the pyrolytic temperature and the stabilization agents also discussed as is the effect of the initial properties of the cellulose fibre on the final properties of the carbon fibre.

Chemical reduction of dioxygen in organic solvents for the production of reactive oxygen species or the concomitant oxidation of organic substrates can be enhanced by the separation of products and educts in biphasic liquid systems. Here, the coupled electron and ion transfer processes is studied as well as reagent fluxes across the liquid j liquid interface for the chemical reduction of dioxygen by decamethylferrocene (DMFc) in a dichloroethane-based organic electrolyte forming an interface with an aqueous electrolyte containing alkali metal ions. This interface is stabilized at the orifice of a pipette, across which a Galvani potential difference is externally applied and precisely adjusted to enforce the transfer of different alkali metal ions from the aqueous to the organic electrolyte. The oxygen reduction is followed by H 2 O 2 detection in the aqueous phase close to the interface by a microelectrode of a scanning electrochemical microscope (SECM). The results prove a strong catalytic effect of hydrated alkali metal ions on the formation rate of H 2 O 2 , which varies systematically with the acidity of the transferred alkali metal ions in the organic phase.

The utilization of vast coal deposits around the globe as an energy source is significantly limited in scope owing to environmental risks. In this context, ionic liquids (ILs) provide a novel solution as eco-friendly pretreatment agents. This work examined the effects of IL pretreatment on the gasification of low-grade coal using a simulation model in Aspen Plus ®. Four ILs, 1-butyl-3-methylimidazolium chloride [Bmim][Cl], 1-ethyl-3-methylimidazolium chloride [Emim][Cl], trihexyltetradecylphosphonium chloride [P66614] [Cl], and tributylmethylammonium chloride [N1444] [Cl], were employed in this study. A comparative and sensitivity analysis was conducted on untreated and IL-pretreated coal samples using an equilibrium-based steam-O2 gasification model designed in Aspen Plus ®. The model was validated and utilized to vary the oxygen/fuel (O2/F) ratio, steam/fuel (S/F) ratio, and temperature within the specified ranges (700-950°C, 0.1-0.6, and 2-4, respectively). The results showed that all the ILs increased CO and H2, and decreased CO2 and CH4, in the syngas produced by coal gasification. The biggest change was affected by [P66614] [Cl], which increased CO and H2 from 12 mol% and 42 mol % to 16 mol% and 50 mol %, respectively, and reduced CO2 and CH4 from 35 mol% and 3.5 mol% to 29 mol% and 2 mol%, respectively. The lower heating value (LHV) of syngas was increased from 7.37 MJ/Nm 3 for untreated coal to 7.61, 7.56, 8.1, and 7.56 MJ/Nm 3 for coal treated by [Bmim][Cl], [Emim][Cl], [P66614] [Cl], and [N1444] [Cl], respectively. As opposed to raw coal, [Bmim][Cl] and [P66614] [Cl] generated more CGE, ENE, and EXE. The highest CGE, ENE, and EXE of 19, 13.3, and 38.3% were achieved by [P66614] [Cl] treated coal. Syngas having higher H2/CO ratio and LHV were produced at low temperatures, low O2/F ratio, and high S/F ratio. The results of this investigation demonstrated that ILs composed of ammonium and phosphonium might be useful coal pretreatment agents in thermochemical conversion processes.

In this work, we synthesized a new ionic liquid ([C8-Tropine].Cl) by combining tropine with 1-chlorooctane without the use of any solvent. Prepared ionic liquid was characterized utilizing Mass, TGA, CHN, FESEM, NMR, and FT-IR analysis techniques. Potential energy surfaces of different pathways and calculated energy barriers beside a few NMR chemical shifts were explored to determine the structure of the catalyst. According to the Curtin-Hammett principle, two different products can be obtained, named Min2a and Min2b, in a ratio of 0.26:1 which the structures of these products were determined by comparing the experimental and calculated NMR chemical shifts. The calculations were performed using the DFT (B3LYP) computational method with 6-31+G(d,p) and 6-311G(d,p) basis sets. The antibacterial activity of the catalyst was evaluated against Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) using the agar well diffusion method. After the identification of the synthesized ionic liquid, it was utilized as an efficient catalyst for the synthesis of pyrido[2,3d]pyrimidines, 1,2,4-triazolo[4,3-a]pyrimidines, bis-2-amino-4H-pyrane and spiro-2-amino-4H-pyran-oxyindole derivatives. These methods stand out for their convenient and uncomplicated catalyst preparation, minimal catalyst usage, straightforward work-up procedures, quick reaction times, and the ability to achieve good to high product yields under environmentally friendly conditions. Furthermore, the catalyst can be easily recovered and reused several times.

Os métodos computacionais da química quântica foram empregados para estudar as estruturas moleculares e as energias de interação de cátions e ânions que são componentes de alguns líquidos iônicos funcionalizados, derivados do imidazólio. O estudo teve como objetivo comparar e relacionar os efeitos da presença de funcionalização nos substituintes das posições 1 e 3 do cátion imidazólio, nas propriedades desses líquidos iônicos. Essa funcionalização pode ocorrer pela presença de insaturações, grupos aromáticos, éteres, álcoois, tióis, aminas, nitrilas entre outros grupos nas cadeias dos substituintes. Nesta tese são reportados os estudos dos complexos formados por ânions tetrafluorborato e cátions imidazólio substituídos por grupos metila, etila, propila, butila, isobutila, vinila, propargila, alila, crotila e metalila, observando assim o efeito da presença de substituintes contendo cadeias insaturadas em comparação com os de cadeias saturadas nas estruturas, distribuições de carga, energias de interação e propriedades físico-químicas desses sistemas. Nesses sistemas foram observados intensos efeitos de polarização e transferência de carga ânion-cátion. Foram encontradas diversas relações entre volumes iônicos, energias de interação dos íons e as propriedades de transporte dos respectivos líquidos iônicos. Palavras-chave: Líquidos iônicos, tetrafluorboratos de imidazólio, substituintes insaturados, pares iônicos, estrutura, distribuição de carga, interações intermoleculares, propriedades físico-químicas.

Os métodos computacionais da química quântica foram empregados para estudar as estruturas moleculares e as energias de interação de cátions e ânions que são componentes de alguns líquidos iônicos funcionalizados, derivados do imidazólio. O estudo teve como objetivo comparar e relacionar os efeitos da presença de funcionalização nos substituintes das posições 1 e 3 do cátion imidazólio, nas propriedades desses líquidos iônicos. Essa funcionalização pode ocorrer pela presença de insaturações, grupos aromáticos, éteres, álcoois, tióis, aminas, nitrilas entre outros grupos nas cadeias dos substituintes. Nesta tese são reportados os estudos dos complexos formados por ânions tetrafluorborato e cátions imidazólio substituídos por grupos metila, etila, propila, butila, isobutila, vinila, propargila, alila, crotila e metalila, observando assim o efeito da presença de substituintes contendo cadeias insaturadas em comparação com os de cadeias saturadas nas estruturas, distribuições de carga, energias de interação e propriedades físico-químicas desses sistemas. Nesses sistemas foram observados intensos efeitos de polarização e transferência de carga ânion-cátion. Foram encontradas diversas relações entre volumes iônicos, energias de interação dos íons e as propriedades de transporte dos respectivos líquidos iônicos. Palavras-chave: Líquidos iônicos, tetrafluorboratos de imidazólio, substituintes insaturados, pares iônicos, estrutura, distribuição de carga, interações intermoleculares, propriedades físico-químicas.

The solubility of palladium hexafluoroacetylacetonate [Pd(hfac) 2 ] and nickel hexafluoroacetylacetonate dihydrate [Ni(hfac) 2 •2H 2 O] in supercritical CO 2 (scCO 2 ) has been measured using a high-pressure variable volume view cell. At 313.2 K and 8.9 MPa, the solubility of Pd(hfac) 2 is above 3.6 wt% (3.15 × 10 -3 mole fraction). Solubility measurements of Ni(hfac) 2 •2H 2 O were also carried out at 313.2, 323.2 and 333.2 K in the 9.4-25.1 MPa pressure range. Ni(hfac) 2 •2H 2 O mole fraction solubility values vary from 2.95 × 10 -5 to 2.02 × 10 -4 . For a given temperature, the solubility increases with pressure due to the higher density of the solvent. At constant pressure, however, a crossover has been observed. At mole fractions below ca. 1.2 × 10 -4 , solubility decreases with temperature due to the decrease in density of the fluid. On the contrary, at higher concentrations, solubility increases with temperature due to the increase in the solute vapour pressure. Ni(hfac) 2 •2H 2 O solubility data were satisfactorily correlated to semi-empirical equations. The solubility of Ni(hfac) 2 •2H 2 O in scCO 2 was more than 2 orders of magnitude lower than the solubility of Pd(hfac) 2 at similar conditions. This is related to the presence of water molecules bound to Ni in the precursor which allow the formation of intermolecular hydrogen bonds and may cause the formation of a molecules network. Adding a small amount of a polar modifier such as ethanol (2-6.5 mol%) to scCO 2 increased substantially the solubility of the precursor. At EtOH concentrations close to 5 mol%, the solubilisation pressures were rather independent of the Ni(hfac) 2 •2H 2 O concentration in the 1-6 × 10 -3 mole fraction range. The large solubility increase observed in scCO 2 modified with EtOH may be related to the rupture of the hydrogen bonded Ni(hfac) 2 •2H 2 O network due to the better solvation of the complex in the CO 2 /EtOH mixture possibly by hydrogen bonding between Ni(hfac) 2 •2H 2 O and EtOH.

The evaluation of the adsorption capacity of amine-functionalized silica coated iron oxide magnetic particles (Fe 3 O 4 /SiO 2-NH 2) as a highly recyclable adsorbent for Congo Red (CR) and Eriochrome Black T (EBT) azo-dyes from water is reported. The Fe 3 O 4 /SiO 2-NH 2 were prepared by a simple co-precipitation method of iron oxide (Fe 3 O 4) nanoparticles followed by silica coating on oleic acid coated Fe 3 O 4. A series of investigation was performed to assess the various experimental parameters like contact time (0-360 min), pH (3-10), stirring speed (0-500 rpm), adsorbent dosages (0.02-0.12 g) and initial concentrations (0.02-0.15 mg mL À 1) of dyes. According to the Langmuir iso-therm, the maximum adsorption capacities of CR and EBT on Fe 3 O 4 /SiO 2-NH 2 particles were found to be 211.86 mg g À 1 and 81.98 mg g À 1 , respectively. In comparison, the pseudo-second order model provided adsorption capacities of 200.40 mg g À 1 for CR and 80.91 mg g À 1 for EBT. Additionally, the maximum adsorption amounts of CR and EBT on Fe 3 O 4 /SiO 2-NH 2 particles were 179.37 mg g À 1 and 75.43 mg g À 1 , achieved within 300 min and 180 min at pH 3, respectively. The dye-loaded particles were recoverable for CR and EBT removal by simple regeneration with 0.1 molL À 1 NaOH solution to use the particles until more than five cycles.

fractionated cellulose and hemicellulose components. The electro-assisted DES process offers a potential platform for lignocellulosic biomass fractionation at ambient conditions. According to the life cycle cost analysis (LCCA), the estimated cost of producing hydrogen from 100 g of wheat straw is only $37.24, demonstrating its potential for commercial viability.

Thermoelectric materials are attracting attention for their ability to convert heat into electricity, traditionally assessed through a figure of merit (ZT) depending on the electrical conductivity, Seebeck coefficient, and thermal conductivity. Developing efficient ionic thermoelectric materials presents challenges as they cannot integrate directly into standard generators. However, they can utilize the ionic thermoelectric effect to charge supercapacitors. This study investigates lignin, an abundant plant-based waste, as a basis for ionic thermoelectric systems, combining sustainability and thermoelectric efficiently. Lignin-based hydrogels with varying compositions were examined for their thermoelectric properties, revealing gigantic ionic Seebeck coefficients of up to 30.4 mV K-1 and good conductivity, reaching 5.87 S m-1. The optimal hydrogel composition displayed a high-power factor of 4187 μW m-1 K-2 , and an impressive ionic iZT value of 3.5, showcasing the potential of lignin-based hydrogels for ionic thermoelectric systems. This research suggests a promising avenue for addressing environmental and economic challenges in energy production.

Ionic liquids (ILs) have received much attention as ''green'' alternatives to traditional solvents because they do not evaporate, eliminating concerns over fugitive emissions. However, if ionic liquids are used in industrial applications, they may enter aquatic systems via effluent, and their fate and transport may be influenced by sorption to sediments. In this study, we conducted batch mixing experiments with four alkylmethylimidizolium-based ILs and four types of aquatic sediments to asses the capacity for natural aquatic sediments to remove these chemicals from the water column. The concentration isotherms were non linear with point estimates of the distribution coefficient (K d ) decreasing with increasing concentration. Apparent distribution coefficients ranged from 7.9 to 95.7 l kg À1 at an initial concentration of 0.5 mM and were positively related to sediment organic matter (SOM) content. These K d values indicate that the ILs did not sorb strongly to the tested sediments. Increased alkyl chain length did not lead to increased sorption suggesting that hydrophobic interactions were not the most important sorption mechanism. We conclude that aquatic sediments have a limited capacity to sorb alkylmethylimidazolium ILs and that the transport of these contaminants in aquatic systems will not be strongly attenuated by sediments.

Over the last few years, researchers have started to explore a particular class of compounds defined as ionic liquids (ILs) in attempts to use their unique characteristics. Since ILs have a very low vapor pressure, these fascinating compounds hold great potential as high performance chemicals for several applications in the (bio)pharmaceutical industry. In general, and unlike common organic solvents with comparable polarities, ILs are quite compatible with enzymes (enhancing their structural and chemical stability) and other proteins, since they can promote higher selectivities, faster reaction rates and greater enzyme stabilities in biocatalytic reactions providing, at the same time, a path for the structural and functional stabilization of protein entities. ILs appear to enhance the delivery of macromolecules, particularly protein entities, and their interactions with ILs will be tackled in detail in this review paper.

A novel approach for attaching well-dispersed cobalt nanoparticles homogeneously onto carbon nanotubes via metal organic chemical vapor deposition technique is reported. The obtained Co/CNTs catalysts feature a narrow size distribution of Co particles centering around 7.5 nm, and show high activity and regioselectivity for hydroformylation of 1-octene.

This study aims to identify the offering table No. IS 3285 in the Ismailia Museum of Antiquities, which belongs to an employee called Ahmose "IaH-ms" who was a contemporary of the reign of King "Thutmose III" of the Eighteenth Dynasty. The painting has not been studied or published before. It represents an offering table made of black granite and in good condition. It is considered one of the funerary paintings placed inside the tomb to immortalize the memory of its owner, as it provides him with offerings in his afterlife. That is, it is the first guarantor of immortalizing the memory of the deceased, and the most widespread among individuals in ancient Egypt. The offering table follows the common and well-known type of offering tables from that period, whether in shape or in the text mentioned on it. Besides, the material it is made of, the method of its manufacture, and the precision of its engraving indicate the wealth of its owner. It is distinguished from many tables made of limestone, which was poorly carved, indicating the status and wealth of IaH-ms according to his position.

Following the trend of transport decarbonization, biodiesel has become a promising alternative fuel option. Its production includes multiple steps, all of which can be time-consuming and energy intensive. Improving any of these steps could bring considerable environmental and economic benefits. The utilization of deep eutectic solvents (DESs) for glycerol extraction from crude biodiesel has predominantly been explored as a batch process. This work provides insight into continuous column extraction. Different waste cooking oils were used to produce biodiesel via transesterification with methanol, and the selective solvent for purification was DES choline chloride-ethylene glycol (1:2.5, mol.). A laboratory Karr column at different pulsation frequencies and DES to biodiesel mass ratio was used for extraction. Plate material (steel and 3D printed PETG) and geometry influence on the efficiency of extraction were investigated. Contact angle measurement was used to measure the surface free energy of steel and PETG and the spreading ability of biodiesel and DESs on both materials. Extraction efficiency was analyzed by several analytical techniques. Higher efficiency was observed with steel plates of a triangular pitch hole arrangement. Increasing the mixing intensity and DES to biodiesel mass ratio further increased the efficiency of extraction.

Ionic liquids (ILs) are low-melting organic salts that are being researched intensively as possible environmentally friendly replacements for volatile organic solvents. Despite their nonmeasurable vapor pressure, some quantities of ILs soon will be present in effluent discharges because solubility of ILs in water is small, but far from negligible. Therefore, it is important to understand how ILs will influence aquatic ecosystems. In the present study, the toxic effects of imidazolium-based ILs (1-butyl-3-methylimidazolium cation associated with bromide [BMIM][Br] and tetrafluoroborate [BMIM][BF 4 ]) to the freshwater green alga Selenastrum capricornutum were investigated. Two approaches were followed to quantify toxicity of these compounds: Analyses of photosynthetic activity and cell proliferation. The obtained data showed that the relative declines of growth rates generally were more pronounced than those of photosynthetic activity. The ecotoxicity of a range of common organic solvents also was examined. It was revealed that both imidazolium-based ILs studied were some orders of magnitude more toxic than methanol, isopropanol, and dimethylformamide. In addition, with respect to IL incorporating perfluorinated anion, EC50 values (concentrations which lead to a 50% reduction of the exposed organisms relative to control) of the previously prepared stock solution were significantly lower compared to those of the freshly made one. This might be due to hydrolytic effects of [BMIM][BF 4 ] leading to fluoride formation, which was confirmed by ion chromatography analysis. This indicates that, after ILs are discharged into the aqueous system, they can become more toxic than expected by laboratory data with fresh ILs.

The possible application of imidazolium ionic liquids as energy-efficient green material for extractive deep desulfurization of liquid fuel has been investigated. 1-Butyl-3-methylimidazolium chloride [BMIM]Cl was synthesized by nucleophilic substitution reaction of n-methylimidazolium and 1-chlorobutane. Molecular structures of the ILs were confirmed by FTIR, 1 H-NMR, and 13 C-NMR. The thermal properties, conductivity, solubility, water content and viscosity analysis of [BMIM]Cl were carried out. The effects of reaction time, reaction temperature, sulfur compounds, and recycling of IL without regeneration on dibenzothiophene removal of liquid fuel were presented. In the extractive desulfurization process, the removal of dibenzothiophene in n-dodecane using [BMIM]Cl was 81% with mass ratio of 1 : 1, in 30 min at 30 ∘ C under the mild reaction conditions. Also, desulfurization of real fuels with IL and multistage extraction were studied. The results of this work might offer significant insights in the perceptive use of imidazoled ILs as energy-efficient green material for extractive deep desulfurization of liquid fuels as it can be reused without regeneration with considerable extraction efficiency.

Reducing the particle size of ceria nanostrutures could provide an efficient approach to improve gas sensing properties thereof. Here, we synthesized small CeO 2 nanoparticles (3-5 nm) in the support of [EMIM][Tf 2 N] ionic liquid. The obtained CeO 2 nanoparticles showed relatively large surface areas (68.29 m 3 /g) and especially high content of Ce 3+ ions (13.5 %), which increase the chemisorption of reagents and oxygen leading on enhancing gas sensing performance. Namely, at the optimal operating temperature of 400 o C, the gas response of synthesized CeO 2 sensor to 100 ppm of ethanol was 2.3, which was 1.83 times higher than that of commercial one (1.26). The superior gas sensing mechanism of synthesized CeO 2 was also discussed on the basis of the electrical resistance change. The present work could provide novel pathway to synthesize ceria and related materials, which would be possibly expected to be potential candidates for gas sensing, by the use of ionic liquid hereafter.