Cost-Effective Processing of Carbon-Rich Materials in Ionic Liquids: An Expeditious Approach to Biofuels
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ABSTRACT:
SUBMITTER: Naz S
PROVIDER: S-EPMC8567403 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Carbohydrate moieties were combined with various cross-linkable anions (thiocyanate [SCN], tetracyanoborate [TCB], tricyanomethanide [TCM], and dicyanamide [DCA]) and investigated as precursors for the synthesis of nitrogen-doped and nitrogen-/sulfur-co-doped carbons. The influence of the molecular structures of the precursors on their thermophysical properties and the properties of the derived carbon materials was elucidated and compared to petroleum-derived analogs. A carbohydrate-based ionic liquid featuring an [SCN] anion yielded more carbon residues upon carbonization than its 1-ethyl-3-methylimidazolium analog, and the resulting dual-doping of the derived carbon material translated to enhanced catalytic activity in the oxygen reduction reaction.
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Project description:Coconut husks and shells are underutilised agricultural feedstocks in the bio-based industry. These biomass wastes have a higher lignin content than other woody biomass and have excellent potential as raw materials for the production of lignin-based materials. This work demonstrates the performance of a low-cost protic ionic liquid, N,N,N-dimethylbutylammonium hydrogen sulfate ([DMBA][HSO4]), for ionoSolv pretreatment of coconut husk and shell at 150 °C for 45-90 min and 170 °C for 15-60 min. Optimum pretreatment conditions were observed at 170 °C and 45 min for both feedstocks. At these conditions, [DMBA][HSO4] was able to remove almost 77 wt% of the lignin from the husk; leaving a cellulosic rich pulp behind, which released 82 % of the theoretical maximum glucose after enzymatic saccharification. The pretreated shell, by comparison, achieved 82 wt% lignin removal and 89 % glucose yield and these higher values could be attributed to the highly porous structure of coconut shell cell walls. The cleavage of the β-O-4 aryl ether linkages of lignin followed by extensive C-C condensation in the lignin at longer pretreatment times was shown by HSQC NMR analysis. This extensive condensation was evidenced by molecular weights > 10,000 g/mol exhibited by lignin precipitated after pretreatment at high temperature and long times. The high degree of lignin removal and high glucose release from both feedstocks demonstrate that [DMBA][HSO4] is an excellent ionic liquid for fractionation of very lignin-rich biomass.
| S-EPMC9005540 | biostudies-literature
Project description:The potential applications of cationic poly(ionic liquids) range from medicine to energy storage, and the development of efficient synthetic strategies to target innovative cationic building blocks is an important goal. A post-polymerization click reaction is reported that provides facile access to trisaminocyclopropenium (TAC) ion-functionalized macromolecules of various architectures, which are the first class of polyelectrolytes that bear a formal charge on carbon. Quantitative conversions of polymers comprising pendant or main-chain secondary amines were observed for an array of TAC derivatives in three hours using near equimolar quantities of cyclopropenium chlorides. The resulting TAC polymers are biocompatible and efficient transfection agents. This robust, efficient, and orthogonal click reaction of an ionic liquid, which we term ClickabIL, allows straightforward screening of polymeric TAC derivatives. This platform provides a modular route to synthesize and study various properties of novel TAC-based polymers.
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Project description:Sludge produced from wastewater treatment has little to no value and is typically treated through volume reduction techniques, such as dewatering, thickening, or digestion. However, these methods inherently increase heavy metal concentrations, which makes the sludge unsuitable for land spreading and difficult to dispose of, owing to strict legal requirements/regulations concerning these metals. We addressed this problem, for the first time, by using recyclable low-cost protic ionic liquids to complex these toxic metals through a chemical fractionation process. Sewage sludge samples collected from wastewater plants in the UK were heated with methylimidazolium chloride ([Hmim]Cl, triethylammonium hydrogen sulfate ([TEA][HSO4]) and dimethylbutylammonium hydrogen sulfate ([DMBA][HSO4]) under various operating temperatures, times and solids loadings to separate the sludge from its metal contaminants. Analysis of the residual solid product and metal-rich ionic liquid liquor using inductively coupled plasma-emission spectrometry showed that [Hmim]Cl extracted >90% of CdII, NiII, ZnII, and PbII without altering the phosphorus content, while other toxic metals such as CrIII, CrVI and AsIII were more readily removed (>80%) with [TEA][HSO4]. We test the recyclability of [Hmim]Cl, showing insignificant efficiency losses over 6 cycles and discuss the possibilities of using electrochemical deposition to prevent the buildup of metal in the IL. This approach opens up new avenues for sewage sludge valorization, including potential applications in emulsion fuels or fertilizer development, accessed by techno-economic analysis.
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Project description:Carbon dioxide, as a promising C1 synthon, has attracted great interest in organic synthesis. Due to the thermodynamic stability and kinetic inertness of CO2, developing efficient strategies for CO2 activation and subsequent conversion is very crucial. In this context, Ionic liquids (ILs) show great potential for capturing and activating CO2 owing to their unique structures and properties, making them become ideal alternatives to volatile organic solvents and/or catalysts for CO2 transformation. This minireview aims at summarizing ILs-promoted reactions of CO2 with N-nucleophiles (primary amines)/O-nucleophiles (primary alcohols, water). Two catalytic systems i.e., metal/ILs binary systems such as Cu/ILs systems and Ag/ILs systems as well as single ILs systems including anion-functionalized ILs and bifunctionalized ILs have been developed for CO2 catalytic conversion, for instance, carboxylative cyclization of nucleophiles e.g., propargylic alcohols, amines, 2-aminobenzonitriles and o-aminobenzenethiol, and formylation of amines or 2-aminothiophenols with hydrosilanes to afford various value-added chemicals e.g., cyclic carbamates, unsymmetrical organic carbonates, ?-hydroxyl ketones, and benzimidazolones. In a word, IL could provide a powerful tool for efficient CO2 utilization.
| S-EPMC6186839 | biostudies-literature
Project description:Over the past decade many works have focused on various aspects of the dynamics of liquids confined at the nanoscale such as e.g. water flow enhancement through carbon nanotubes (CNTs). Transport of room temperature ionic liquids (RTILs) through various nanochannels has also been explored and some conflicting findings about their translational dynamics have been reported. In this work, we focus on translational dynamics of RTILs confined in various CNTs. By means of molecular dynamics simulations we highlight a substantially enhanced diffusion of confined RTILs with an increase up to two orders of magnitude with respect to bulk-phase properties. This ultrafast diffusion of RTILs inside CNTs is shown to result from the combination of various factors such as low friction, molecular stacking, size, helicity, curvature and cooperative dynamics effects.
| S-EPMC4917821 | biostudies-literature
Project description:Ionic Liquids are a broad group of salts with low melting points that can be specifically tuned for a broad range of applications. Despite being initially considered “green” solvents, their better environmental friendliness compared to traditional solvents has been increasingly challenged. In this study, we aimed to investigate the molecular effects of ILs exposure by using RNA-sequencing to study differential gene expression patterns. Thus, we exposed Daphnia magna to 1-ethyl-3-methylimidazolium chloride ([C2mim]Cl), 1-dodecyl chloride-3-methylimidazolium ([C12mim]Cl) and cholinium chloride ([Chol]Cl). Results suggest that the three ILs share several mechanisms of toxicity, including cellular membrane and cytoskeleton damage, oxidative stress, inhibition of antioxidant enzymes, mitochondrial affectation, changes in protein biosynthesis and energy production, DNA damage, and ultimately, programmed cell death and disease initiation. Overall, the dataset revealed that [C2mim]Cl and [C12mim]Cl were, respectively, the least and the most toxic ILs at the transcriptional level. Also, it is reinforced that [Chol]Cl is not devoid of environmental hazardous potential. Unique gene expression signatures could also be identified for each IL.
2021-08-13 | GSE156769 | GEO
Project description:Ionic liquids are well known for their high gas absorption capacity. It is shown that this is not a solvent constant, but can be enhanced by another factor of 10 by pore confinement, here of the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate (EmimOAc) in the pores of carbon materials. A matrix of four different carbon compounds with micro- and mesopores as well as with and without nitrogen doping is utilized to investigate the influence of the carbons structure on the nitrogen uptake in the pore-confined EmimOAc. In general, the absorption is most improved for IL in micropores and in nitrogen-doped carbon. This effect is so large that it is already seen in TGA and DSC experiments. Due to the low vapor pressure of the IL, standard volumetric sorption experiments can be used to quantify details of this effect. It is reasoned that it is the change of the molecular arrangement of the ions in the restricted space of the pores that creates additional free volume to host molecular nitrogen.
| S-EPMC8251693 | biostudies-literature
Project description:A multifunctional designing approach is of great importance for advanced composite applications. This study assessed the use of ionic liquids (ILs) to modify the surface of carbon fiber (CF) and impart multifunctional characteristics to it. For that, ethanolic solutions of different ILs, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium chloride and 1-(2-hydroxyethyl)-3-methylimidazolium chloride, at different concentrations, were used to treat the CF. Fourier-transform infrared spectroscopy confirmed the presence of IL on the CF surface. The contact angle for 1% w/v IL-treated CF and DGEBA epoxy decreased by up to 35%, corresponding to an increase in surface energy of fiber, accompanied by an increase of 91% in interfacial shear strength. These enhancements were achieved with the hydroxy-functionalized IL, showing the tunability of CF properties through the N-imidazolium substituent. An increase in crystallite size along the basal plane was also found due to the ordering of the graphitic structure on the surface. Moreover, there was a decrease in electrical resistivity of 77%. In all, the imidazolium ILs were considered a promising approach to induce multifunctional characteristics, namely enhanced interfacial strength and electrical conductivity, to unsized CF, which can also be beneficial for recycled fibers without deteriorating their inherent surface properties.
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Project description:Silk fibroin is a biobased material with excellent biocompatibility and mechanical properties, but its use in bioelectronics is hampered by the difficult dissolution and low intrinsic conductivity. Some ionic liquids are known to dissolve fibroin but removed after fibroin processing. However, ionic liquids and fibroin can cooperatively give rise to functional materials, and there are untapped opportunities in this combination. The dissolution of fibroin, followed by gelation, in designer ionic liquids from the imidazolium chloride family with varied alkyl chain lengths (2-10 carbons) is shown here. The alkyl chain length of the anion has a large impact on fibroin secondary structure which adopts unconventional arrangements, yielding robust gels with distinct hierarchical organization. Furthermore, and due to their remarkable air-stability and ionic conductivity, fibroin ionogels are exploited as active electrical gas sensors in an electronic nose revealing the unravelled possibilities of fibroin in soft and flexible electronics.
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