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An electrolyte destined for use in a dual-ion battery (DIB) must be stable at the inherently high potential required for anion intercalation in the graphite electrode, while also protecting the Al current collector from anodic dissolution. A higher salt concentration is needed in the electrolyte, in comparison to typical battery electrolytes, to maximize energy density, while ensuring acceptable ionic conductivity and operational safety. In recent years, studies have demonstrated that highly concentrated organic electrolytes, ionic liquids, gel polymer electrolytes (GPEs), ionogels, and water-in-salt electrolytes can potentially be used in DIBs. GPEs can help reduce the use of solvents and thus lead to a substantial change in the Coulombic efficiency, energy density, and long-term cycle life of DIBs. Furthermore, GPEs are suited to manufacture compact DIB designs without separators by virtue of their mechanical strength and electrical performance. In this review, we highlight the latest advances in the application of different electrolytes in DIBs, with particular emphasis on GPEs.

The melting points of ionic liquids (ILs) reported since 2020 were surveyed, collected, and reviewed, which were further combined with the previous data to provide a database with 3129 ILs ranging from 177.15 to 645.9 K in melting points. In addition, the factors that affect the melting point of ILs from macro, micro, and thermodynamic perspectives were summarized and analyzed. Then the development of the quantitative structure-property relationship (QSPR), group contribution method (GCM), and conductor-like screening model for realistic solvents (COSMO-RS) for predicting the melting points of ILs were reviewed and further analyzed. Combined with the evaluation together with the preliminary study conducted in this work, it shows that COSMO-RS is more promising and possible to further improve its performance, and a framework was thus proposed., Funder: Swedish Research Council (101070976); China Scholarship Council (202208320253); STINT (CH2019-8287); National Natural Science Foundation of China (21838004, 22011530112);Full text license: CC BY-NC-ND

Multilayer composite solid electrolytes (CSEs) exhibit many advantages over uniform monolayer CSEs but are hindered by high interlayer resistance and complex preparation methods. Herein, for the first time, a natural sedimentation strategy was developed to construct concentration gradient CSEs (GCSEs) for lithium-metal batteries (LMBs). This method utilizes intrinsic gravity and photopolymerization to achieve multiple functions in the monolayer, avoiding additional interlayer resistance and reducing preparation time. Owning to the concentration gradient structure, the Li+ transport on the PolyIL-rich side relies on the weak solvation of Li+ with EMIMTFSI, while the Li+ transport on the LLZTO-rich side follows the 'vehicular diffusion' mechanism with the aid of TFSI−, improving the Li+ transport and enhances the Li+ transference number, leading to the high stability to 2300 h for the Li//Li cell and stable operation at 4.3 V with 89.6 % capacity retention after 100 cycles for the assembled LMB. Moreover, compared with the monolayer uniform hybrid CSEs, the gradient structure alleviates uncoordinated thermal expansion between LLZTO and PolyIL, avoiding stress increase during cycling and battery capacity fade. This gradient strategy mitigates high interlayer resistance and offers a universal path to address the sluggish Li+ transportation in multilayer CSEs and improves compatibility between the electrolyte and electrodes in fabricating solid-state batteries., Validerad;2024;Nivå 2;2024-03-07 (hanlid);Funder: J. Gust Richert Foundation; National Key Research and Development Program of China (2022YFA1504103); Major Program of National Nature Science Foundation of China (21890762);Full text license: CC BY

Given the potential of ionic liquids (ILs) for batteries, supercapacitors and advanced lubricants, it is crucial to understand how electric fields affect the interfacial behaviour in IL-solvent systems and the intricate relationship between nanostructure and tribotronic properties. This thesis investigates the structural and compositional changes of ILs with different solvents at electrified interfaces. The four papers constituting this thesis can be broadly divided into two studies. The first study outlines the electro-interfacial behaviour of various monocationic (MILs) and dicationic ILs (DILs) dispersed in propylene carbonate. Combining electrochemical quartz crystal microbalance, neutron reflectivity (EC-NR), and atomic force microscopy, a voltage-induced interphase transition from a self-assembled cation bilayer to a conventional electrical double-layer structure has been revealed in bis(oxalato)borate anion MILs. This interphase transition has not been observed in DILs, attributed to the dual charge centres reducing the segregation between polar and apolar domains of dications for self-assembly interaction. The second study explores three MILs sharing the same phosphonium cation with varying orthoborate-based anions dissolved in 2-ethylhexyl laurate (2-EHL). EC-NR measurements reveal a solvent-rich interfacial corona layer and the subtlety of anion architecture in tuning electro-interfacial properties. Meanwhile, EC-NR has been used as a complementary probe to elucidate the nano-scale structural and compositional changes in the boundary films of IL/2-EHL systems with varying potentials, providing a direct link between the molecular controllability and macroscopic tribotronic performance studies. This thesis contributes to the fundamental understanding of electro-interfacial behaviour and controllability of IL-solvent systems and offers valuable molecular insights for deploying these novel ILs as additives in advanced tribological and electrochemical contexts, Med tanke på potentialen hos jonvätskor (IL) för batterier, superkondensatorer och avancerade smörjmedel är det viktigt att förstå hur elektriska fält påverkar gränsytans beteende i IL-lösningsmedelssystem och det intrikata förhållandet mellan nanostrukturer och tribotroniska egenskaper. Denna avhandling undersöks strukturella och kompositionella förändringar av ILs med olika lösningsmedel vid elektrifierade gränssnitt. Avhandlingen baseras på fyra artiklar och kan grovt delas i två bredare studier. Den första studien beskriver det elektro-interfaciala beteendet hos olika monokatjoniska (MILs) och dikatjoniska ILs (DILs) dispergerade i propylenkarbonat. Kombinationen av elektrokemisk kvartskristallmikro-balans, neutronreflektivitet (EC-NR) och atomkraftsmikroskopi har lett till avslöjandet av en spänningsinducerad fasövergång från ett självassocierad katjonbilager till en konventionell elektrisk dubbelskiktsstruktur i MIL med bis(oxalato)boratanjon. Denna interfasövergång har inte observerats i DILs, vilket tillskrivs de dubbla laddningscentra som minskar segregeringen mellan polära och apolära domäner av dikationer för självassoceringsinteraktion. Den andra studien undersöker tre MIL som delar samma fosfoniumkatjon med olika ortoboratbaserade anjoner löst i 2-etylhexyllaurat (2-EHL). EC-NR-mätningar avslöjar ett lösningsmedelsrikt korona-skikt i gränsytan och hur anjonarkitekturen påverkar de elektro-interfaciala egenskaperna. Samtidigt har EC-NR belyst de nanoskaliga strukturella och kompositionella förändringarna i gränsskikten i IL/2-EHL-system med varierande potentialer, vilket ger en direkt koppling av den molekylära styrbarheten och makroskopiska tribotroniska prestandan. Denna avhandling bidrar till den grundläggande förståelsen av elektro-interfacial beteende och styrbarhet hos IL-lösningsmedelssystem och erbjuder värdefulla molekylära insikter för att använda dessa nya IL som tillsatser i avancerade tribologiska och elektrokemiska sammanhang., QC 20240112

In this work, biocompatible composite fibers were prepared from human hair keratin and plant cellulose with different proportions by the wet-spinning method, and their properties and performance, including chemical structures, morphology, mechanical strength, and cell proliferation and attachment, were systematically investigated. It showed that the best proportion of the keratin/cellulose mass ratio was 30:70, and its tensile strength reached 277 MPa (elongation at break can be 27%), which is higher than that of the regenerated cellulose fiber (193 MPa, 12%). Its viability and proliferation of L929 murine fibroblast cells are also better than those of the regenerated cellulose fiber. Atomistic simulations were carried out and demonstrated the formation of hydrogen bonds between keratin and cellulose molecules, clarifying that the ratio of keratin has a significant effect on the aggregation structures in the solution and that the hydrogen bonds formed between keratin and cellulose molecules have a distinct contribution to the biocompatible composites. This work demonstrates the potential of the prepared composite fiber in biomedical applications and provides an innovative way to utilize waste human hair as a high-value raw material., Validerad;2024;Nivå 2;2024-01-17 (joosat);Funder: National Natural Science Foundation of China (grant no.22178342); Zhengzhou High-Level Talent (20180300045); Scientific and Technological Project of Henan Province (212102210035);Full text license: CC BY

The need of new electrolytes with wide electrochemical window, good stability and conductivity has promoted novel ionic liquids (ILs) as new solutions for supercapacitors. In this work, four hydrophobic room temperature ionic liquids based on organic superbase-derived cations and Trifluoromethanesulfonimide (TFSI) anion were synthetized. The structures of the novel ILs were analyzed, characterized and their performance as a supercapacitor electrolyte was evaluated. The ILs have high decomposition temperatures of up to 490 °C and electrochemical window up to 4.8 V. It was found that there was an optimal chemical structure providing the best stability and operational potential window coupled with moderate conductivity. The IL with the shortest alkyl chain structure provided the highest conductivity but suffered from instability. The performance of the ILs with longer alkyl chains was hindered by lower conductivities and, in the case of the largest chemical structures, also by reduced cyclic stabilities in open air. However, the ionic liquid with moderate alkyl chain length was found to be stable even in open air providing decent conductivity, which can be utilized in future research to develop other hydrophobic ionic liquids suitable as supercapacitor electrolytes.

The concept of confining ionic liquids (ILs) in developing quasi-solid-state electrolytes (QSSEs) has been proposed, where ILs are dispersed in polymer networks/backbones and/or filler/host pores, forming the so-called confinement, and great research progress and promising research results have been achieved. In this review, the progress and achievement in developing QSSEs using IL-confinement for lithium metal batteries (LMBs), together with advanced characterizations and simulations, were surveyed, summarized, and analyzed, where the influence of specific parameters, such as IL (type, content, etc.), substrate (type, structure, surface properties, etc.), confinement methods, and so on, was discussed. The confinement concept was further compared with the conventional one in other research areas. It indicates that the IL-confinement in QSSEs improves the performance of electrolytes, for example, increasing the ionic conductivity, widening the electrochemical window, and enhancing the cycle performance of the assembled cells, and being different from those in other areas, i.e., the IL-confinement concept in the battery area is in a broad extent. Finally, insights into developing QSSEs in LMBs with the confinement strategy were provided to promote the development and application of QSSE LMBs., Validerad;2024;Nivå 2;2024-04-03 (hanlid);Full text license: CC BY-NC

An electrolyte destined for use in a dual-ion battery (DIB) must be stable at the inherently high potential required for anion intercalation in the graphite electrode, while also protecting the Al current collector from anodic dissolution. A higher salt concentration is needed in the electrolyte, in comparison to typical battery electrolytes, to maximize energy density, while ensuring acceptable ionic conductivity and operational safety. In recent years, studies have demonstrated that highly concentrated organic electrolytes, ionic liquids, gel polymer electrolytes (GPEs), ionogels, and water-in-salt electrolytes can potentially be used in DIBs. GPEs can help reduce the use of solvents and thus lead to a substantial change in the Coulombic efficiency, energy density, and long-term cycle life of DIBs. Furthermore, GPEs are suited to manufacture compact DIB designs without separators by virtue of their mechanical strength and electrical performance. In this review, we highlight the latest advances in the application of different electrolytes in DIBs, with particular emphasis on GPEs.

Multilayer composite solid electrolytes (CSEs) exhibit many advantages over uniform monolayer CSEs but are hindered by high interlayer resistance and complex preparation methods. Herein, for the first time, a natural sedimentation strategy was developed to construct concentration gradient CSEs (GCSEs) for lithium-metal batteries (LMBs). This method utilizes intrinsic gravity and photopolymerization to achieve multiple functions in the monolayer, avoiding additional interlayer resistance and reducing preparation time. Owning to the concentration gradient structure, the Li+ transport on the PolyIL-rich side relies on the weak solvation of Li+ with EMIMTFSI, while the Li+ transport on the LLZTO-rich side follows the 'vehicular diffusion' mechanism with the aid of TFSI−, improving the Li+ transport and enhances the Li+ transference number, leading to the high stability to 2300 h for the Li//Li cell and stable operation at 4.3 V with 89.6 % capacity retention after 100 cycles for the assembled LMB. Moreover, compared with the monolayer uniform hybrid CSEs, the gradient structure alleviates uncoordinated thermal expansion between LLZTO and PolyIL, avoiding stress increase during cycling and battery capacity fade. This gradient strategy mitigates high interlayer resistance and offers a universal path to address the sluggish Li+ transportation in multilayer CSEs and improves compatibility between the electrolyte and electrodes in fabricating solid-state batteries., Validerad;2024;Nivå 2;2024-03-07 (hanlid);Funder: J. Gust Richert Foundation; National Key Research and Development Program of China (2022YFA1504103); Major Program of National Nature Science Foundation of China (21890762);Full text license: CC BY

In this work, biocompatible composite fibers were prepared from human hair keratin and plant cellulose with different proportions by the wet-spinning method, and their properties and performance, including chemical structures, morphology, mechanical strength, and cell proliferation and attachment, were systematically investigated. It showed that the best proportion of the keratin/cellulose mass ratio was 30:70, and its tensile strength reached 277 MPa (elongation at break can be 27%), which is higher than that of the regenerated cellulose fiber (193 MPa, 12%). Its viability and proliferation of L929 murine fibroblast cells are also better than those of the regenerated cellulose fiber. Atomistic simulations were carried out and demonstrated the formation of hydrogen bonds between keratin and cellulose molecules, clarifying that the ratio of keratin has a significant effect on the aggregation structures in the solution and that the hydrogen bonds formed between keratin and cellulose molecules have a distinct contribution to the biocompatible composites. This work demonstrates the potential of the prepared composite fiber in biomedical applications and provides an innovative way to utilize waste human hair as a high-value raw material., Validerad;2024;Nivå 2;2024-01-17 (joosat);Funder: National Natural Science Foundation of China (grant no.22178342); Zhengzhou High-Level Talent (20180300045); Scientific and Technological Project of Henan Province (212102210035);Full text license: CC BY

The need of new electrolytes with wide electrochemical window, good stability and conductivity has promoted novel ionic liquids (ILs) as new solutions for supercapacitors. In this work, four hydrophobic room temperature ionic liquids based on organic superbase-derived cations and Trifluoromethanesulfonimide (TFSI) anion were synthetized. The structures of the novel ILs were analyzed, characterized and their performance as a supercapacitor electrolyte was evaluated. The ILs have high decomposition temperatures of up to 490 °C and electrochemical window up to 4.8 V. It was found that there was an optimal chemical structure providing the best stability and operational potential window coupled with moderate conductivity. The IL with the shortest alkyl chain structure provided the highest conductivity but suffered from instability. The performance of the ILs with longer alkyl chains was hindered by lower conductivities and, in the case of the largest chemical structures, also by reduced cyclic stabilities in open air. However, the ionic liquid with moderate alkyl chain length was found to be stable even in open air providing decent conductivity, which can be utilized in future research to develop other hydrophobic ionic liquids suitable as supercapacitor electrolytes.

This work describes the process of toxicity prediction of ionic liquids, specifically toxicity with respect to the IPC-81 rat cell line. We studied 355 molecular structures of ionic liquids, whose three-dimensional geometry is encoded by means of symbol strings such as Simplified Molecular Input Line Entry System (SMILES) language. The feeding of the input data to the different machine learning models requires that the geometrical and near atomic neighbor information of each ionic liquid be mapped or transformed to numerical vector notation (xi) using the following two molecular descriptors: Atom-Centered Symmetry Functions (ACSF), and Extended Connectivity Fingerprints (ECFP). Three machine learning algorithms: Extreme Gradient Boosting (XGBoost), Support Vector Regression (SVR) and Kernel Ridge Regression (KRR) were used to build the predictive mathematical regression model relating the input values xi to the response value represented by the logarithm of the mean effective concentration (yi = logEC50) in the toxicity assessment, using the coefficient of determination (r2) as a metric of the degree of fitness. The results obtained indicated that the ECFP combination with a radial distance of 6 atomic neighbors in conjunction with the KRR algorithm provides the best average fit with r2=0.8602±0.032, and with respect to the ACSF molecular descriptor the best average fit was obtained with the XGBoost algorithm with r2=0.8029±0.055.

Recently, we reported the discovery of a novel endoglucanase of the glycoside hydrolase family 12 (GH12), designated IfCelS12A, from the haloalkaliphilic anaerobic bacterium Iocasia fonsfrigidae strain SP3-1, which was isolated from a hypersaline pond in the Samut Sakhon province of Thailand (ca. 2017). IfCelS12A exhibits high substrate specificity on carboxymethyl cellulose and amorphous cellulose but low substrate specificity on b-1,3;1,4-glucan. Unlike some endoglucanases of the GH12 family, IfCelS12A does not exhibit hydrolytic activity on crystalline cellulose (i.e., Avicel™). High-Pressure Liquid Chromatography (HPLC) and Thin Layer Chromatography (TLC) analyses of products resulting from IfCelS12-mediated hydrolysis indicate mode of action for this enzyme. Notably, IfCelS12A preferentially hydrolyzes cellotetraoses, cellopentaoses, and cellohexaoses with negligible activity on cellobiose or cellotriose. Kinetic analysis with cellopentaose and barely b-D-glucan as cellulosic substrates were conducted. On cellopentaose, IfCelS12A demonstrates a 16-fold increase in activity (KM = 0.27 mM; kcat = 0.36 s-1; kcat/KM = 1.34 mM-1 s-1) compared to the enzymatic hydrolysis of barley b-D-glucan (KM: 0.04 mM, kcat: 0.51 s-1, kcat/KM = 0.08 mM-1 s-1). Moreover, IfCelS12A enzymatic efficacy is stable in hypersaline sodium chlorids (NaCl) solutions (up to 10% NaCl). Specifically, IfCel12A retains notable activity after 24 h at 2M NaCl (10% saline solution). IfCelS12A used as a cocktail component with other cellulolytic enzymes and in conjunction with mobile sequestration platform technology offers additional options for deconstruction of ionic liquid-pretreated cellulosic feedstock. KEY POINTS: • IfCelS12A from an anaerobic alkaliphile Iocasia fronsfrigidae shows salt tolerance • IfCelS12A in cocktails with other enzymes efficiently degrades cellulosic biomass • IfCelS12A used with mobile enzyme sequestration platforms enhances hydrolysis.

Visualizing the network of a solvent-swollen polymer gel remains problematic. To address this challenge, open transmission electron microscopy (TEM) was applied to thin gel films permeated by a nonvolatile ionic liquid. The targeted physical gels were prepared by cooling concentrated solutions of poly(ethylene glycol) in 1-ethyl-3-methyl imidazolium ethyl sulfate [EMIM][EtSO4]. During the cooling, gelation occurred by a frustrated crystallization of the dissolved polymer, leading to a percolated, solvent-permeated semicrystalline network in which nanoscale polymer crystals acted as crosslinks. Crystalline features ranging from ~5 to ~200 nm were observed, with the visible network strands dominantly consisting of long curvilinear crystallites of ~15–20 nm diameter. Nascent spherulites irregularly decorated the network, creating a complex structural hierarchy that complicated analyses. Lacking diffraction contrast, TEM did not visualize the many disordered, fully solvated PEG chains present in the voids between crystals. Recognizing that a network's three dimensionality is ambiguous when assessed through two-dimensional microscopy projections, a small gel region was studied by TEM tomography, revealing a nearly isotropic three-dimensional arrangement of the curvilinear crystallites, which displayed remarkably uniform cylindrical cross sections.

Lignin valorization is advantageous for biorefineries to produce aromatic compounds, fragrance, biofuel, material, and commodity chemicals, which could be an alternative of crude oil-derived products. However, several barriers are involved in natural lignin extraction and depolymerization, which need to be solved for its full utilization. The electrochemical oxidative upgrading of lignin into the oxygenated molecule is a promising method, which cleaves the C–O and C–C bond by direct oxidative or indirect oxidative method. As promising solvents, electrolytes, as well as catalysts in organic synthesis and electrochemical processes, ionic liquids (ILs) and deep eutectic solvents (DESs) have gained significant attention as dissolution media and catalysts for lignin depolymerization. In this work, aromatic carbon-rich lignin macromolecule depolymerization in ILs/DESs was reviewed to gain a better understanding of barriers, covering the interaction of ILs/DESs with lignin structure, degradation mechanism, thermochemical and electrochemical transformations, as well as COSMO-RS theoretical modeling and screening. In-situ generation of free radicals as catalysts (reactive oxygen species or H2O2) for lignin degradation into value-added products was also discussed. All these studies give importance to ILs/DESs for thermochemical, electrochemical lignin cleavage and upgrading to value-added products for achieving sustainable future goals., Validerad;2024;Nivå 2;2024-08-08 (hanlid);Funder: Bio4-Energy;Full text license: CC BY

The electrolyte perturbed-chain statistical associating fluids theory (ePC-SAFT) coupled with free volume theory (FVT) was combined with Einstein relation, that is, ePC-SAFT-FVT-E, to describe self-diffusion coefficients (SDCs) of ionic liquids (ILs). In modeling, ePC-SAFT was used to calculate density, while FVT parameters, determined from viscosity data, were utilized to calculate the summation of ionic SDCs through the Einstein relation with one parameter. Two strategies were employed to determine this parameter: fitting experimental data for each IL or estimating a universal parameter from van der Waals volume. Comparative analysis reveals good agreement with experimental data, with average absolute relative deviations (ARDs) of 8.14% (strategy 1) and 10.29% (strategy 2). Subsequently, cationic and anionic SDCs were reliably determined from the summation of ionic SDCs, with average ARDs of 10.80% and 10.21%, respectively. This study indicates the ePC-SAFT-FVT-E model, employing viscosity-derived parameters and three universal parameters, reliably predicts SDCs of ILs in wide temperature and pressure ranges., Validerad;2024;Nivå 2;2024-08-01 (signyg);Funder: National Natural Science Foundation of China (22011530112); State Key Laboratory of Material-Oriented Chemical Engineering in China;Full text license: CC BY

Three nonhalogenated ionic liquids (ILs) dissolved in 2-ethylhexyl laurate (2-EHL), a biodegradable oil, are investigated in terms of their bulk and electro-interfacial nanoscale structures using small-angle neutron scattering (SANS) and neutron reflectivity (NR). The ILs share the same trihexyl(tetradecyl)phosphonium ([P6,6,6,14]+) cation paired with different anions, bis(mandelato)borate ([BMB]−), bis(oxalato)borate ([BOB]−), and bis(salicylato)borate ([BScB]−). SANS shows a high aspect ratio tubular self-assembly structure characterized by an IL core of alternating cations and anions with a 2-EHL-rich shell or corona in the bulk, the geometry of which depends upon the anion structure and concentration. NR also reveals a solvent-rich interfacial corona layer. Their electro-responsive behavior, pertaining to the structuring and composition of the interfacial layers, is also influenced by the anion identity. [P6,6,6,14][BOB] exhibits distinct electroresponsiveness to applied potentials, suggesting an ion exchange behavior from cation-dominated to anion-rich. Conversely, [P6,6,6,14][BMB] and [P6,6,6,14][BScB] demonstrate minimal electroresponses across all studied potentials, related to their different dissociative and diffusive behavior. A mixed system is dominated by the least soluble IL but exhibits an increase in disorder. This work reveals the subtlety of anion architecture in tuning bulk and electro-interfacial properties, offering valuable molecular insights for deploying nonhalogenated ILs as additives in biodegradable lubricants and supercapacitors., We acknowledge the support of the Australian Centre for Neutron Scattering, ANSTO, and the Australian Government through the National Collaborative Research Infrastructure Strategy (NCRIS), in using the neutron research infrastructure used in this work via ACNS proposal P13958 on the BILBY SANS and proposal P8264 on the PLATYPUS NR instrument. We gratefully acknowledge Institut Laue-Langevin (ILL), France, for access to SuperADAM (doi:10.5291/ILL-DATA.9-13-1006). We acknowledge the support of the Australian Government in provision of access to ANSTO's National Deuteration Facility which is partly funded through NCRIS. Prof. Oleg N. Antzutkin (Luleå University of Technology) is gratefully acknowledged for providing the ILs. The authors thank Prof. Thomas Norrby (KTH Royal Institute of Technology and Nynas AB) for insightful discussions on 2-EHL properties and applications. The authors would also like to thank Dr. Alexei Vorobiev for his support during the SuperADAM beamtime and Dr. Brando Adranno, Dr. Olivier Renier, Anthony Boudier, and Filip Mehler for their experimental support. Daniel Morris is thanked for valuable assistance performing SANS experiments. SL and GP also thank Dr. Adrian Iovan (KTH Nanolab) for his help with the preparation of the gold electrode via the electron beam evaporator. The Knut and Alice Wallenberg Foundation (Project no. KAW2012.0078), the Swedish Research Council, VR (Project no. 2017-04080), the Swedish Foundation for Strategic Research (Project no. EM16-0013, "REFIT"), Vinnova (Project no. 2020-03801), and Villum Foundation (Villum Investigator awards to AVM) are acknowledged for their financial support. We also thank the Danish Agency for Science, Technology, and Innovation for funding the instrument center DanScatt (Grant no. 2021 7129-00006B).

The sustainable development encompasses the search for new materials for energy storage, gas capture, separation, and solvents in industrial processes that can substitute conventional ones in an efficient and clean manner. Ionic liquids (ILs) emerged and have been advanced as alternative materials for such applications, but an obstacle is their hygroscopicity and the effects on their physical properties in the presence of humidity. Several industrial processes depend on the aqueous interfacial properties, and the main focus of this work is the water/IL interface. The behavior of the aqueous ionic liquids at the water-vacuum interface is representative for their water interfacial properties. Using X-ray photoelectron spectroscopy in combination with molecular dynamics simulations we investigate four aqueous IL systems, and provide molecular level insight on the interfacial behaviour of the ionic liquids, such as ion-pair formation, orientation and surface concentration. We find that ionic liquids containing a chloride anion have a lowered surface enrichment due to the low surface propensity of chloride. In contrast, the ionic liquids containing a bistriflimide anion are extremely surface-enriched due to cooperative surface propensity between the cations and anions, forming a two-dimensional ionic liquid on the water surface at low concentrations. Ionic liquids are interesting materials for many applications related to sustainable development, but the effects of water on their properties are insufficiently known. Using X-ray photoelectron spectroscopy and molecular dynamics simulations, we show how the surface propensity of four ionic liquids in aqueous solution vary with the molecular structure of the ions, and discuss the underlying driving forces.+image

The sustainable development encompasses the search for new materials for energy storage, gas capture, separation, and solvents in industrial processes that can substitute conventional ones in an efficient and clean manner. Ionic liquids (ILs) emerged and have been advanced as alternative materials for such applications, but an obstacle is their hygroscopicity and the effects on their physical properties in the presence of humidity. Several industrial processes depend on the aqueous interfacial properties, and the main focus of this work is the water/IL interface. The behavior of the aqueous ionic liquids at the water-vacuum interface is representative for their water interfacial properties. Using X-ray photoelectron spectroscopy in combination with molecular dynamics simulations we investigate four aqueous IL systems, and provide molecular level insight on the interfacial behaviour of the ionic liquids, such as ion-pair formation, orientation and surface concentration. We find that ionic liquids containing a chloride anion have a lowered surface enrichment due to the low surface propensity of chloride. In contrast, the ionic liquids containing a bistriflimide anion are extremely surface-enriched due to cooperative surface propensity between the cations and anions, forming a two-dimensional ionic liquid on the water surface at low concentrations. Ionic liquids are interesting materials for many applications related to sustainable development, but the effects of water on their properties are insufficiently known. Using X-ray photoelectron spectroscopy and molecular dynamics simulations, we show how the surface propensity of four ionic liquids in aqueous solution vary with the molecular structure of the ions, and discuss the underlying driving forces.+image

Lignin valorization is advantageous for biorefineries to produce aromatic compounds, fragrance, biofuel, material, and commodity chemicals, which could be an alternative of crude oil-derived products. However, several barriers are involved in natural lignin extraction and depolymerization, which need to be solved for its full utilization. The electrochemical oxidative upgrading of lignin into the oxygenated molecule is a promising method, which cleaves the C–O and C–C bond by direct oxidative or indirect oxidative method. As promising solvents, electrolytes, as well as catalysts in organic synthesis and electrochemical processes, ionic liquids (ILs) and deep eutectic solvents (DESs) have gained significant attention as dissolution media and catalysts for lignin depolymerization. In this work, aromatic carbon-rich lignin macromolecule depolymerization in ILs/DESs was reviewed to gain a better understanding of barriers, covering the interaction of ILs/DESs with lignin structure, degradation mechanism, thermochemical and electrochemical transformations, as well as COSMO-RS theoretical modeling and screening. In-situ generation of free radicals as catalysts (reactive oxygen species or H2O2) for lignin degradation into value-added products was also discussed. All these studies give importance to ILs/DESs for thermochemical, electrochemical lignin cleavage and upgrading to value-added products for achieving sustainable future goals., Validerad;2024;Nivå 2;2024-08-08 (hanlid);Funder: Bio4-Energy;Full text license: CC BY

The electrolyte perturbed-chain statistical associating fluids theory (ePC-SAFT) coupled with free volume theory (FVT) was combined with Einstein relation, that is, ePC-SAFT-FVT-E, to describe self-diffusion coefficients (SDCs) of ionic liquids (ILs). In modeling, ePC-SAFT was used to calculate density, while FVT parameters, determined from viscosity data, were utilized to calculate the summation of ionic SDCs through the Einstein relation with one parameter. Two strategies were employed to determine this parameter: fitting experimental data for each IL or estimating a universal parameter from van der Waals volume. Comparative analysis reveals good agreement with experimental data, with average absolute relative deviations (ARDs) of 8.14% (strategy 1) and 10.29% (strategy 2). Subsequently, cationic and anionic SDCs were reliably determined from the summation of ionic SDCs, with average ARDs of 10.80% and 10.21%, respectively. This study indicates the ePC-SAFT-FVT-E model, employing viscosity-derived parameters and three universal parameters, reliably predicts SDCs of ILs in wide temperature and pressure ranges., Validerad;2024;Nivå 2;2024-08-01 (signyg);Funder: National Natural Science Foundation of China (22011530112); State Key Laboratory of Material-Oriented Chemical Engineering in China;Full text license: CC BY

Three nonhalogenated ionic liquids (ILs) dissolved in 2-ethylhexyl laurate (2-EHL), a biodegradable oil, are investigated in terms of their bulk and electro-interfacial nanoscale structures using small-angle neutron scattering (SANS) and neutron reflectivity (NR). The ILs share the same trihexyl(tetradecyl)phosphonium ([P6,6,6,14]+) cation paired with different anions, bis(mandelato)borate ([BMB]−), bis(oxalato)borate ([BOB]−), and bis(salicylato)borate ([BScB]−). SANS shows a high aspect ratio tubular self-assembly structure characterized by an IL core of alternating cations and anions with a 2-EHL-rich shell or corona in the bulk, the geometry of which depends upon the anion structure and concentration. NR also reveals a solvent-rich interfacial corona layer. Their electro-responsive behavior, pertaining to the structuring and composition of the interfacial layers, is also influenced by the anion identity. [P6,6,6,14][BOB] exhibits distinct electroresponsiveness to applied potentials, suggesting an ion exchange behavior from cation-dominated to anion-rich. Conversely, [P6,6,6,14][BMB] and [P6,6,6,14][BScB] demonstrate minimal electroresponses across all studied potentials, related to their different dissociative and diffusive behavior. A mixed system is dominated by the least soluble IL but exhibits an increase in disorder. This work reveals the subtlety of anion architecture in tuning bulk and electro-interfacial properties, offering valuable molecular insights for deploying nonhalogenated ILs as additives in biodegradable lubricants and supercapacitors., We acknowledge the support of the Australian Centre for Neutron Scattering, ANSTO, and the Australian Government through the National Collaborative Research Infrastructure Strategy (NCRIS), in using the neutron research infrastructure used in this work via ACNS proposal P13958 on the BILBY SANS and proposal P8264 on the PLATYPUS NR instrument. We gratefully acknowledge Institut Laue-Langevin (ILL), France, for access to SuperADAM (doi:10.5291/ILL-DATA.9-13-1006). We acknowledge the support of the Australian Government in provision of access to ANSTO's National Deuteration Facility which is partly funded through NCRIS. Prof. Oleg N. Antzutkin (Luleå University of Technology) is gratefully acknowledged for providing the ILs. The authors thank Prof. Thomas Norrby (KTH Royal Institute of Technology and Nynas AB) for insightful discussions on 2-EHL properties and applications. The authors would also like to thank Dr. Alexei Vorobiev for his support during the SuperADAM beamtime and Dr. Brando Adranno, Dr. Olivier Renier, Anthony Boudier, and Filip Mehler for their experimental support. Daniel Morris is thanked for valuable assistance performing SANS experiments. SL and GP also thank Dr. Adrian Iovan (KTH Nanolab) for his help with the preparation of the gold electrode via the electron beam evaporator. The Knut and Alice Wallenberg Foundation (Project no. KAW2012.0078), the Swedish Research Council, VR (Project no. 2017-04080), the Swedish Foundation for Strategic Research (Project no. EM16-0013, "REFIT"), Vinnova (Project no. 2020-03801), and Villum Foundation (Villum Investigator awards to AVM) are acknowledged for their financial support. We also thank the Danish Agency for Science, Technology, and Innovation for funding the instrument center DanScatt (Grant no. 2021 7129-00006B).

The sustainable development encompasses the search for new materials for energy storage, gas capture, separation, and solvents in industrial processes that can substitute conventional ones in an efficient and clean manner. Ionic liquids (ILs) emerged and have been advanced as alternative materials for such applications, but an obstacle is their hygroscopicity and the effects on their physical properties in the presence of humidity. Several industrial processes depend on the aqueous interfacial properties, and the main focus of this work is the water/IL interface. The behavior of the aqueous ionic liquids at the water-vacuum interface is representative for their water interfacial properties. Using X-ray photoelectron spectroscopy in combination with molecular dynamics simulations we investigate four aqueous IL systems, and provide molecular level insight on the interfacial behaviour of the ionic liquids, such as ion-pair formation, orientation and surface concentration. We find that ionic liquids containing a chloride anion have a lowered surface enrichment due to the low surface propensity of chloride. In contrast, the ionic liquids containing a bistriflimide anion are extremely surface-enriched due to cooperative surface propensity between the cations and anions, forming a two-dimensional ionic liquid on the water surface at low concentrations. Ionic liquids are interesting materials for many applications related to sustainable development, but the effects of water on their properties are insufficiently known. Using X-ray photoelectron spectroscopy and molecular dynamics simulations, we show how the surface propensity of four ionic liquids in aqueous solution vary with the molecular structure of the ions, and discuss the underlying driving forces.+image

The solubility and bioavailability of Biopharmaceutics Classification System (BCS) class IV drugs, characterized by their low solubility and low permeability pose significant challenges for oral drug delivery. Drugs such as venetoclax, olaparib, and vemurafenib exhibit limited therapeutic efficacy due to their poor bioavailability. This thesis explores the potential of amphiphilic carnitine-fatty acid ionic liquids for enhancing drug solubility via self-nanoemulsifying systems (SNES). Thermally stable ionic liquids were synthesized with a relatively unexplored biocompatible quaternary ammonium cation called carnitine and several fatty acids as counter ions. The ionic liquids demonstrated improved solubility of several highly insoluble drugs. The development of SNES was conducted with a series of rigorous screening and optimization experiments, leading to formation of stable nano emulsions. The drug loaded SNES formulations showed reduced globule sizes (<150 nm) and uniform dispersion in various pH buffers, equivalent to the environment of the gastrointestinal tract. A comprehensive pharmacokinetics study compared traditional drug (venetoclax) suspension with drug (venetoclax) loaded SNES with one of the selected emulsion formulations, revealing a notable increase in drug absorption and prolonged drug action. This work underscores the potential of ionic liquids and SNES in revolutionizing drug delivery systems, enhancing drug solubility, stability, and bioavailability, leading to more efficient and effective treatments.

This thesis investigates the optimization of washing techniques before bleaching a pulp produced using ionic liquids. One pulp is from softwood and the other from wheat straw. Through experiments with varied temperatures and concentrations, the effectiveness of different washing conditions was evaluated, focusing on their impact on kappa number, viscosity, yield and reject amount for the softwood pulp. The wheat straw pulp was studied using the same optimal washing conditions that gave the best results for the softwood pulp. The results showed that washing at 75°C with 1.5% NaOH was the most effective. After washing, the softwood pulp had a kappa number of 20.0 and a viscosity of 162 mL/g. For the wheat straw pulp, the best result was a wash with 1.5% NaOH at 75°C, resulting in a kappa number of 16.2 and a viscosity of 446 mL/g. The washing process proved effective on a laboratory scale and the next step will be to conduct pilot-scale trials. The trials so far show that there is potential to scale up the washing of pulp produced by ionic liquid-based cooking. After washing, bleaching was performed using sodium chlorite. This method was suitable for laboratory-scale experiments, leading to a kappa number reduction from 20.0 down to 0.39 for the softwood pulp, with a viscosity loss from 162 mg/L down to 152 mL/g and a brightness of ISO 85%. For the wheat straw pulp, the kappa number decreased from 16.2 down to 0.62, the viscosity fall to 272 mL/g from 446 mg/L and the brightness reached ISO 76%. The study demonstrates that washing parameters can be optimized to achieve high brightness of the final bleached pulp without significantly altering its physical properties. The kappa number decreases while the viscosity remains relatively stable for the soft wood pulp, indicating that the process can consistently produce the same results. The wheat straw pulp lost viscosity from a high level. Loss of viscosity must be expected in some extent. The insights from this study reve

Persistent and mobile (PM) chemicals are considered detrimental for drinking water resources as they may pass through all barriers protecting these resources against pollution. However, knowledge on the occurrence of PM chemicals in the water cycle, that make their way into drinking water resources, is still limited. The effluents of six municipal wastewater treatment plants (WWTPs, n = 38), surface water of two rivers (n = 32) and bank filtrate of one site (n = 15) were analyzed for 127 suspected PM chemicals. In the rivers, median concentrations of 92 detected analytes ranged from 0.3 ng/L to 2.6 µg/L (tetrafluoroborate, BF4). Lower than average dilution from WWTP effluent to surface water of 43 PM chemicals suggests significant discharge from other sources. Many of these compounds were industrial chemicals, including cyanoguanidine, trifluoromethanesulfonic acid and BF4. River bank filtration (RBF) reduced the total concentration of 40 quantified compounds by 80 % from 329 µg/L in surface water to 66 µg/L in bank filtrate, on average. Of these, 20 compounds showed good removal (> 80 %), 14 intermediate (80 – 20 %) and 6 no removal (≤ 20 %), among them carbamazepine, hexafluorophosphate, and 2-pyrrolidone. 13 substances occurred at concentrations ≥ 0.1 µg/L in bank filtrate; for six of them toxicological data were insufficient for a health-based risk assessment. The regulatory definition of P and M chemicals, if used together with existing data on environmental half-lives (P) and Koc (M), showed little power to discriminate between chemicals well removed in RBF and those that were hardly removed. This comprehensive field study shows that RBF is a useful but incomplete barrier to retain PM chemicals from surface water. Thus, PM chemicals are, indeed, a challenge for a sustainable water supply.

The sustainable development encompasses the search for new materials for energy storage, gas capture, separation, and solvents in industrial processes that can substitute conventional ones in an efficient and clean manner. Ionic liquids (ILs) emerged and have been advanced as alternative materials for such applications, but an obstacle is their hygroscopicity and the effects on their physical properties in the presence of humidity. Several industrial processes depend on the aqueous interfacial properties, and the main focus of this work is the water/IL interface. The behavior of the aqueous ionic liquids at the water-vacuum interface is representative for their water interfacial properties. Using X-ray photoelectron spectroscopy in combination with molecular dynamics simulations we investigate four aqueous IL systems, and provide molecular level insight on the interfacial behaviour of the ionic liquids, such as ion-pair formation, orientation and surface concentration. We find that ionic liquids containing a chloride anion have a lowered surface enrichment due to the low surface propensity of chloride. In contrast, the ionic liquids containing a bistriflimide anion are extremely surface-enriched due to cooperative surface propensity between the cations and anions, forming a two-dimensional ionic liquid on the water surface at low concentrations. Ionic liquids are interesting materials for many applications related to sustainable development, but the effects of water on their properties are insufficiently known. Using X-ray photoelectron spectroscopy and molecular dynamics simulations, we show how the surface propensity of four ionic liquids in aqueous solution vary with the molecular structure of the ions, and discuss the underlying driving forces.+image

An electrolyte destined for use in a dual-ion battery (DIB) must be stable at the inherently high potential required for anion intercalation in the graphite electrode, while also protecting the Al current collector from anodic dissolution. A higher salt concentration is needed in the electrolyte, in comparison to typical battery electrolytes, to maximize energy density, while ensuring acceptable ionic conductivity and operational safety. In recent years, studies have demonstrated that highly concentrated organic electrolytes, ionic liquids, gel polymer electrolytes (GPEs), ionogels, and water-in-salt electrolytes can potentially be used in DIBs. GPEs can help reduce the use of solvents and thus lead to a substantial change in the Coulombic efficiency, energy density, and long-term cycle life of DIBs. Furthermore, GPEs are suited to manufacture compact DIB designs without separators by virtue of their mechanical strength and electrical performance. In this review, we highlight the latest advances in the application of different electrolytes in DIBs, with particular emphasis on GPEs.

The need of new electrolytes with wide electrochemical window, good stability and conductivity has promoted novel ionic liquids (ILs) as new solutions for supercapacitors. In this work, four hydrophobic room temperature ionic liquids based on organic superbase-derived cations and Trifluoromethanesulfonimide (TFSI) anion were synthetized. The structures of the novel ILs were analyzed, characterized and their performance as a supercapacitor electrolyte was evaluated. The ILs have high decomposition temperatures of up to 490 °C and electrochemical window up to 4.8 V. It was found that there was an optimal chemical structure providing the best stability and operational potential window coupled with moderate conductivity. The IL with the shortest alkyl chain structure provided the highest conductivity but suffered from instability. The performance of the ILs with longer alkyl chains was hindered by lower conductivities and, in the case of the largest chemical structures, also by reduced cyclic stabilities in open air. However, the ionic liquid with moderate alkyl chain length was found to be stable even in open air providing decent conductivity, which can be utilized in future research to develop other hydrophobic ionic liquids suitable as supercapacitor electrolytes.

The melting points of ionic liquids (ILs) reported since 2020 were surveyed, collected, and reviewed, which were further combined with the previous data to provide a database with 3129 ILs ranging from 177.15 to 645.9 K in melting points. In addition, the factors that affect the melting point of ILs from macro, micro, and thermodynamic perspectives were summarized and analyzed. Then the development of the quantitative structure-property relationship (QSPR), group contribution method (GCM), and conductor-like screening model for realistic solvents (COSMO-RS) for predicting the melting points of ILs were reviewed and further analyzed. Combined with the evaluation together with the preliminary study conducted in this work, it shows that COSMO-RS is more promising and possible to further improve its performance, and a framework was thus proposed., Funder: Swedish Research Council (101070976); China Scholarship Council (202208320253); STINT (CH2019-8287); National Natural Science Foundation of China (21838004, 22011530112);Full text license: CC BY-NC-ND

This work introduces the synthesis of hybrid polymer electrolytes based on polyethylene oxide (PEO) and electrolyte solution bis(trifluoromethane)sulfonimide lithium salt/ionic liquid 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (LiTFSI/EMIMTFSI) with in situ produced and dispersed silica particles by the sol–gel method. Conventional preparation of solid polymer electrolytes was followed by desolvation of lithium salt in a polymer matrix of PEO, which, in some cases, additionally contains plasticizers. This one-pot synthesis is an alternative route for fabricating a solid polymer electrolyte for solid-state batteries. The presence of TFSI- reduces the crystallinity of the PEO matrix (plasticizing effect), increases the dissociation and solubility of LiTFSI in the PEO matrix because of a highly delocalized charge distribution, and reveals excellent thermal, chemical, and electrochemical stability. Tetraethylorthosilicate (TEOS) was chosen due to the slow reaction rate, with the addition of (3-glycidyoxypropyl)trimethoxysilane (GLYMO), which contributes to the formation of a silica network. FTIR studies confirmed the interactions between the silica, the polymer salt, and EMIMTFSI. Impedance spectroscopy measurements were performed in a wide range of temperatures from 25 to 70 °C. The electrochemical performance was explored by assembling electrolytes in LiCoO2 (LCO), NMC(811), and LiFePO4 (LFP) coin half-cells. The HPEf15 shows a discharge capacity of 143 mA/g for NMC(811) at 0.1 C, 134 mA/g for LCO, and 139 mA/g for LFP half-cells at 0.1 C and 55 °C. The LFP half-cell with a discharge capacity of 135 mA/g at 0.1 C (safety potential range of 2.8 to 3.8) obtained a cyclability of 97.5% at 55 °C after 100 cycles. Such a type of electrolyte with high safety and good electrochemical performance provides a potential approach for developing a safer lithium-ion battery.

The need of new electrolytes with wide electrochemical window, good stability and conductivity has promoted novel ionic liquids (ILs) as new solutions for supercapacitors. In this work, four hydrophobic room temperature ionic liquids based on organic superbase-derived cations and Trifluoromethanesulfonimide (TFSI) anion were synthetized. The structures of the novel ILs were analyzed, characterized and their performance as a supercapacitor electrolyte was evaluated. The ILs have high decomposition temperatures of up to 490 °C and electrochemical window up to 4.8 V. It was found that there was an optimal chemical structure providing the best stability and operational potential window coupled with moderate conductivity. The IL with the shortest alkyl chain structure provided the highest conductivity but suffered from instability. The performance of the ILs with longer alkyl chains was hindered by lower conductivities and, in the case of the largest chemical structures, also by reduced cyclic stabilities in open air. However, the ionic liquid with moderate alkyl chain length was found to be stable even in open air providing decent conductivity, which can be utilized in future research to develop other hydrophobic ionic liquids suitable as supercapacitor electrolytes.

An electrolyte destined for use in a dual-ion battery (DIB) must be stable at the inherently high potential required for anion intercalation in the graphite electrode, while also protecting the Al current collector from anodic dissolution. A higher salt concentration is needed in the electrolyte, in comparison to typical battery electrolytes, to maximize energy density, while ensuring acceptable ionic conductivity and operational safety. In recent years, studies have demonstrated that highly concentrated organic electrolytes, ionic liquids, gel polymer electrolytes (GPEs), ionogels, and water-in-salt electrolytes can potentially be used in DIBs. GPEs can help reduce the use of solvents and thus lead to a substantial change in the Coulombic efficiency, energy density, and long-term cycle life of DIBs. Furthermore, GPEs are suited to manufacture compact DIB designs without separators by virtue of their mechanical strength and electrical performance. In this review, we highlight the latest advances in the application of different electrolytes in DIBs, with particular emphasis on GPEs.

The concept of confining ionic liquids (ILs) in developing quasi-solid-state electrolytes (QSSEs) has been proposed, where ILs are dispersed in polymer networks/backbones and/or filler/host pores, forming the so-called confinement, and great research progress and promising research results have been achieved. In this review, the progress and achievement in developing QSSEs using IL-confinement for lithium metal batteries (LMBs), together with advanced characterizations and simulations, were surveyed, summarized, and analyzed, where the influence of specific parameters, such as IL (type, content, etc.), substrate (type, structure, surface properties, etc.), confinement methods, and so on, was discussed. The confinement concept was further compared with the conventional one in other research areas. It indicates that the IL-confinement in QSSEs improves the performance of electrolytes, for example, increasing the ionic conductivity, widening the electrochemical window, and enhancing the cycle performance of the assembled cells, and being different from those in other areas, i.e., the IL-confinement concept in the battery area is in a broad extent. Finally, insights into developing QSSEs in LMBs with the confinement strategy were provided to promote the development and application of QSSE LMBs., Validerad;2024;Nivå 2;2024-04-03 (hanlid);Full text license: CC BY-NC

This thesis is about the experimental characterization of new electrolytes for electrochemical devices for energy storage, particularly, for lithium ion batteries and beyon lithium era. New smart electrolytes based on ionic liquids (ILs) and dopped with electrochemical interest salt and then nanoconfined inside silica matrix to obtain a semisolid, self-standing and handable electrolytic matherial, known as ionogel, keeping the liquid properties desirable for battery electrolytes. The ILs and the ionogels are characterized by means of DSC, TGA, NMR, density, viscosity and electrochemically by different techniques such as BBDS, ionic conductivity, EIS, CV and GCPL.

The number of studies on the solubilities of amino acids in pure ionic liquids is currently very scarce. Focusing on fundamental studies for the recovery of added-value compounds from fisheries and aquaculture discards, in this work the solubility of several amino acids in acetate ionic liquids and their mixtures with water were determined at temperatures ranging from 298.15 K to 328.15 K and atmospheric pressure. Sharing the acetate anion, solubilities were higher in the ionic liquid with 1-ethyl-3-methylimidazolium than with 1-hexyl-3-methylimidazolium cation. Increasing temperatures resulted in enhanced solubilisation. Solubilities in the ionic liquids ranked thus: Pro > OH-Pro > Lys·HCl > Ala > Gly > Cys, with an intermediate position of Arg (the amino acid most influenced by the hydrophobic environment and temperature). In the case of the mixtures with water, the ranking was Pro > Lys·HCl > Ala > Arg > OH-Pro > Gly > Cys. The van't Hoff equation adequately correlated experimental solubilities in the range of temperatures studied, and the process of dissolution was found endothermic and entropy-driven in all the cases. The ionic liquid 1-ethyl-3-methylimidazolium should be considered for the target application and the water content a design variable to analyse

Carotenoids are ubiquitous and versatile isoprenoid compounds. The intake of foods rich in these pigments is often associated with health benefits, attributable to the provitamin A activity of some of them and different mechanisms. The importance of carotenoids and their derivatives for the production of foods and health-promotion through the diet is beyond doubt. In the new circular economy paradigm, the recovery of carotenoids in the biorefinery process is highly desirable, for which greener processes and solvents are being advocated for, considering the many studies being conducted at the laboratory scale. This review summarizes information on different extraction technologies (ultrasound, microwaves, pulsed electric fields, pressurized liquid extraction, sub- and supercritical fluid extraction, and enzyme-assisted extraction) and green solvents (ethyl lactate, 2-methyltetrahydrofuran, natural deep eutectic solvents, and ionic liquids), which are potential substitutes for more toxic and less environmentally friendly solvents. Additionally, it discusses the results of the latest studies on the sustainable green extraction of carotenoids. The conclusions drawn from the review indicate that while laboratory results are often promising, the scalability to real industrial scenarios poses a significant challenge. Furthermore, incorporating life cycle assessment analyses is crucial for a comprehensive evaluation of the sustainability of innovative extraction processes compared to industry-standard methods.

Polyphenols are natural compounds with enhanced antioxidant properties. They are present in relatively high concentrations in fruit/vegetable by-products. Therefore, there is a need for the development of efficient and cost-effective methods for the separation and purification of these valuable compounds. Traditional extraction with organic solvents needs to be switched to novel methods that are more efficient, with reduced extraction times and low consumption of organic solvents. Aiming at developing sustainable processes for the separation and purification of phenolic compounds, we used three model compounds, namely resveratrol, quercetin, and gallic acid, to investigate ionic liquid-based aqueous biphasic systems (IL-ABSs) formed by choliniumbased IL in combination with polypropylene glycol with a molecular mass of 400 g/mol (PPG400). The ABS composition in the two-phase region was selected according to a previously determined phase diagram. Extraction studies indicated the preferential partition of resveratrol and quercetin toward the hydrophobic PPG-rich phase that is mainly dominated by its hydrophobic nature and the strong salting-out effect of ILs. On the other hand, due to its considerably hydrophilic nature, gallic acid preferentially migrates toward the IL phase. The achieved results from grape stem extract demonstrated high extraction efficiencies of cholinium dihydrogen phosphate (~99% for resveratrol for the PPG phase and 78% for gallic acid for the IL phase), with considerable selectivity, demonstrating promising outcomes for potential applications.

Due to extensive food production, organophosphate pesticides (OPs) are widely utilized for crop protection, leading to their presence in the environment. The focus of this study was the design of an efficient aqueous biphasic system (ABS) strategy for OP removal, namely, malathion (MAL), azinphos-methyl (AZM), and chlorpyrifos (CHP) from water. Different ionic liquids (ILs) with symmetrical cations were selected as ABS phase- formers (tetrabutylphosphonium salicylate, tetrabutylammonium salicylate, 1,3-dibutylimidazolium dicyanamide, 1,3-dibutylimidazolium salicylate and 1,3-dibutylimidazolium bromide) with citrate salt as a salting-out agent. Initially, phase diagrams were determined, followed by partition studies revealing that the partition of MAL and CHP aligns with the IL- ABS formation trend, while the AZM partition is governed by specific interactions with ILs. For optimization studies, tetrabutylphosphonium-salicylate i.e. [TBP][Sal]-based ABS was chosen, due to obtained high extraction efficiencies of over 99.3 %. After establishing the effects of pH, temperature, tie-line length, and phase ratio on extraction performance, extraction of OPs from a real wastewater sample further confirmed the effectiveness of the designed method achieving complete removal of each pesticide. Furthermore, recovery of IL was achieved using an antisolvent method to precipitate CHP followed by IL-reuse in three consecutive cycles without efficiency decreased. Finally, it was demonstrated that [TBP][Sal] exhibits low cytotoxic potential, indicating that the presence of low amounts of this IL in aqueous media could be acceptable from ecotoxicological standpoint. This study showcased the exceptional potential of the proposed technology for the efficient and sustainable treatment of wastewater contaminated with OPs, affirming its capability to treat significant wastewater volumes.

The sustainable development encompasses the search for new materials for energy storage, gas capture, separation, and solvents in industrial processes that can substitute conventional ones in an efficient and clean manner. Ionic liquids (ILs) emerged and have been advanced as alternative materials for such applications, but an obstacle is their hygroscopicity and the effects on their physical properties in the presence of humidity. Several industrial processes depend on the aqueous interfacial properties, and the main focus of this work is the water/IL interface. The behavior of the aqueous ionic liquids at the water-vacuum interface is representative for their water interfacial properties. Using X-ray photoelectron spectroscopy in combination with molecular dynamics simulations we investigate four aqueous IL systems, and provide molecular level insight on the interfacial behaviour of the ionic liquids, such as ion-pair formation, orientation and surface concentration. We find that ionic liquids containing a chloride anion have a lowered surface enrichment due to the low surface propensity of chloride. In contrast, the ionic liquids containing a bistriflimide anion are extremely surface-enriched due to cooperative surface propensity between the cations and anions, forming a two-dimensional ionic liquid on the water surface at low concentrations. Ionic liquids are interesting materials for many applications related to sustainable development, but the effects of water on their properties are insufficiently known. Using X-ray photoelectron spectroscopy and molecular dynamics simulations, we show how the surface propensity of four ionic liquids in aqueous solution vary with the molecular structure of the ions, and discuss the underlying driving forces.+image

The ionic liquids (ILs) has been widely studied as potential replacements of conventional solvents in the extraction of aromatic hydrocarbons from alkanes. However, the majority of the papers have been focused in obtaining experimental data of liquid-liquid equilibria without studying whole process of extraction and separation of the extracted hydrocarbons from the solvent. In this paper, a computer-aided methodology combining molecular simulation by COSMO-based methodology and process simulation by Aspen Plus has been employed to study the extraction process of aromatic hydrocarbons from pyrolysis gasoline employing a binary mixture of 1-ethyl-4-methylpyridinium bis(trifluoromethylsulfonyl)imide ([4empy][NTf2]) and the 1-ethyl-3-methylimidazolium dicyanamide ([emim][DCA]) ILs as solvent. A comparison between experimental data and the predictions obtained by the COSMO-based thermodynamic model of liquid-liquid and vapor-liquid equilibria and physical properties of the ILs was made for validation purpose. Process simulations were performed employing three configurations with one, two, or three flash distillations in the recovery section and the IL mixture over the whole range of composition as solvent. The configuration with three flash distillations and the binary IL mixture with a 75 % of [4empy][NTf2] were selected as the optimal conditions to increase aromatic recovery and purity., MINECO, Comunidad de Madrid, MINECO, Depto. de Ingeniería Química y de Materiales, Fac. de Ciencias Químicas, TRUE, pub

Está depositada la versión postprint del artículo, Several series of dihalide Pd(ii) compounds bearing pyridyl or isoquinolinylpyrazole ligands have been strategically designed and synthesised to exhibit columnar mesomorphism in wide stability ranges. The coordination of the pyrazoles to the fragments PdX2 (X = Cl, Br, I) generates half-disc molecules that are capable of self-assembling into discotic dimers via intermolecular interactions. This disc-like shape is required for the supramolecular organisation of the lamellar columnar mesophases, which are formed at temperatures below 100 degrees C in most cases. It was found that these metallomesogens behave as 2D proton conducting materials under anhydrous conditions. The high fluidity properties of the mesophase facilitate proton conduction as a result of the spontaneous dissociation of the acidic pyrazole proton at the melting temperature. For the first time, lamellar columnar mesophases are demonstrated to serve as a 2D platform to induce water-free proton conductivity in dihalide Pd(ii) metallomesogens., Ministerio de Economía y Competitividad (España), Universidad Complutense de Madrid, Depto. de Física de Materiales, Fac. de Ciencias Físicas, TRUE, pub

Ionic liquids (ILs) have been extensively studied as replacements to sulfolane in the separation of aromatics from alkanes. The employment of ILs could reduce energy requirements and operating costs of the aromatic extraction unit as a result of their nonvolatile character. However, the ILs studied so far have shown mass-based aromatic distribution ratios lower than the sulfolane values, which would increase the solvent-to-feed ratio in the extractor. To overcome this drawback, we tested the performance of the 1-butyl-3-methylimidazolium tricyanomethanide ([bmim][TCM]) and the 1-butyl-4-methylpyridinium tricyanomethanide ([4bmpy][TCM]) in the separation of toluene from n-heptane, exhibiting the [4bmpy][TCM] mass-based toluene distribution ratios and toluene/n-heptane selectivities higher than those of sulfolane. We also studied the vapor-liquid recovery of the extracted hydrocarbons from the ILs, obtaining relative volatilities of n-heptane from toluene substantially higher in the presence ILs than those without ILs. A thermophysical characterization of the ILs was also made by measuring their densities, viscosities, thermal stabilities, and estimating their maximum operation temperatures. Finally, the regeneration and reuse of the ILs was studied on successive recovery cycles. After five recovery cycles, ILs have shown the same extractive capacity., MINECO, Comunidad de Madrid, Depto. de Ingeniería Química y de Materiales, Fac. de Ciencias Químicas, TRUE, pub

This article belongs to the Special Issue Applied Biocatalysis in Europe: A Sustainable Tool for Improving Life Quality, The use of biocatalysts in organic chemistry for catalyzing chemo-, regio- and stereoselective transformations has become an usual tool in the last years, both at lab and industrial scale. This is not only because of their exquisite precision, but also due to the inherent increase in the process sustainability. Nevertheless, most of the interesting industrial reactions involve water-insoluble substrates, so the use of (generally not green) organic solvents is generally required. Although lipases are capable of maintaining their catalytic precision working in those solvents, reactions are usually very slow and consequently not very appropriate for industrial purposes. Increasing reaction temperature would accelerate the reaction rate, but this should require the use of lipases from thermophiles, which tend to be more enantioselective at lower temperatures, as they are more rigid than those from mesophiles. Therefore, the ideal scenario would require a thermophilic lipase capable of retaining high enantioselectivity at high temperatures. In this paper, we describe the use of lipase from Geobacillus thermocatenolatus as catalyst in the ethanolysis of racemic 2-(butyryloxy)-2-phenylacetic to furnish both enantiomers of mandelic acid, an useful intermediate in the synthesis of many drugs and active products. The catalytic performance at high temperature in a conventional organic solvent (isooctane) and four imidazolium-based ionic liquids was assessed. The best results were obtained using 1-ethyl-3-methyl imidazolium tetrafluoroborate (EMIMBF4) and 1-ethyl-3-methyl imidazolium hexafluorophosphate (EMIMPF6) at temperatures as high as 120 °C, observing in both cases very fast and enantioselective kinetic resolutions, respectively leading exclusively to the (S) or to the (R)-enantiomer of mandelic acid, depending on the anion component of the ionic liquid., Banco Santander, Universidad Complutense de Madrid, Ministerio de Economía, Comercio y Empresa, Depto. de Química en Ciencias Farmacéuticas, Fac. de Farmacia, TRUE, pub

The pyrolysis gasoline is one of the main sources of aromatic hydrocarbons as a result of their high content in these compounds. Organic solvents such as sulfolane are currently employed in the extraction of aromatic but the ionic liquids (ILs) have been recently proposed as potential replacement. In this work, we have studied the use of the bis(1-ethyl-3-methylimidazolium) tetrathiocyanatocobaltate ([emim]2[Co(SCN)4]) and bis(1-butyl-3-methylimidazolium) tetrathiocyanatocobaltate ([bmim]2[Co(SCN)4]) ILs in the extraction of aromatic hydrocarbons from pyrolysis gasoline. The extractive properties of both tetrathiocyanatocobaltate-based ILs were compared to those of other promising ILs and sulfolane, showing the highest values. To perform the simulation of the whole process, we have experimentally studied the liquid-liquid extraction of aromatics from pyrolysis gasoline and the recovery of the extracted hydrocarbons from the ILs. In addition, a thermophysical characterization of the ionic solvents was performed measuring their densities, viscosities, thermal stabilities, maximum operation temperatures, and specific heats. Employing the experimental data, the extractor was simulated using the Kremser equation whereas the recovery section formed by flash distillation units was simulated using a new algorithm specifically design to the case of a high concentration of non-volatile compounds., MINECO, Comunidad de Madrid, Depto. de Ingeniería Química y de Materiales, Fac. de Ciencias Químicas, TRUE, pub

A complementary double‐covalent functionalization of single‐wall carbon nanotubes (SWCNTs) that involves both solubilizing ionic liquids and electroactive moieties is reported. Our strategy is a simple and efficient methodology based on the stepwise functionalization of the nanotube surface with two different organic moieties. In a first instance, oxidized SWCNTs are amidated with ionic liquid precursors, and further treated with butyl bromide to afford SWCNTs functionalized with 1‐butylimidazolium bromide. This approach allows tuneable polarity induced by anion exchange, which has an effect on the relative solubility of the modified SWCNTs in water. Subsequently, a 1,3‐dipolar cycloaddition reaction was performed to introduce the electron‐acceptor 11,11,12,12‐tetracyano‐9,10‐anthra‐quinodimethane (TCAQ) unit on the SWCNTs. Furthermore, to evaluate the influence of the functional group position, the TCAQ electroactive molecule was anchored through an esterification reaction onto previously oxidized SWCNTs, followed by the Tour reaction to introduce the ionic liquid functions. IR and Raman spectroscopies, thermogravimetric analysis (TGA), UV/Vis/NIR spectroscopy, transmission electron microscopy (TEM), and X‐ray photoelectron spectroscopy (XPS) were employed and clearly confirmed the double‐covalent functionalization of the SWCNTs., Depto. de Química Orgánica, Fac. de Ciencias Químicas, TRUE, pub

This work was performed thanks to the financial support of the “Ministerio de Economı́a y Competitividad” under the funded project CTQ2013-42006-R, Se espera que los líquidos iónicos sean disolventes potenciales para la biorrefinería. biorrefinería. Sin embargo, su elevado coste ha limitado su reciclado es esencial para el proceso. En este trabajo se estudia la capacidad de recuperar y reutilizar el líquido iónico cloruro de 1-alil-3- metilimidazolio ([Amim][Cl]) en el fraccionamiento de madera de Pinus radiata mediante microondas. madera de Pinus radiata mediante calentamiento por microondas. En el proceso propuesto, se obtuvieron materiales ricos en celulosa y lignina. El líquido iónico utilizado se recuperó y reutilizó en los próximos ciclos hasta cinco veces. La caracterización del [Amim][Cl] recuperado demostró que, aunque la estructura del líquido iónico permanecía inalterada, se acumulaban algunas fracciones leñosas. Como consecuencia, se obtuvo una reducción de los rendimientos de fraccionamiento y se produjeron variaciones de la composición y amorfidad de las fracciones recuperadas. Mediante un balance de masas global, este estudio da una aproximación global de la concentración de los principales componentes y de las corrientes características que intervienen en los sucesivos ciclos., Ministerio de Economía y Competitividad, Depto. de Ingeniería Química y de Materiales, Fac. de Ciencias Químicas, TRUE, inpress

As an example of a carbon capture approach, we have developed 2D CFD model in Comsol Multiphysics in which we investigated CO2 absorption in an ionic liquid ([Bmim][TCM]). Factors such as pressure (1–20 bar), temperature (278–330 K), inlet gas velocity (0.0001–1ms-1), sparger diameter to column diameter ratio (0.1–0.5), and column height to diameter ratio (1–3) were investigated. A quadratic model for absorption behavior (p-value < 0.0001 and R2 0.98) was developed. Four sparger geometries were considered, and the optimal values for column height to diameter and sparger diameter to column diameter were computed. The maximum CO2 concentration was obtained at a pressure of 18.26 bar, temperature of 309.5 K, velocity of 0.825 ms-1, sparger diameter to column diameter of 0.414, and column height to diameter of 2.5.

Particleboards with different combinations of the adhesive material imidazole, citric acid, and sorbitol were produced. Softwood sawdust from a Swedish sawmill was mixed with an aqueous solution of the chemicals and then dried to 0% moisture content prior to pressing. The boards were pressed to a target density of 700 kg m−3 at either 200 °C or 220 °C for 10 min. The hygroscopic and mechanical properties of the boards were clearly better at 220 °C than 200 °C for all used chemical combinations. A combination of imidazole (14.4 wt%) and citric acid (11.3 wt%) led to the best results, where the thickness swelling after 24 h of water immersion was 6.3% and the internal bonding strength was 0.57 MPa. The modulus of rupture and modulus of elasticity were 3.3 MPa and 1.1 GPa, respectively. Cyclic accelerated weathering showed exceptional stability with a thickness change after boiling and drying of only 2.1% compared to the initial dry thickness. This study indicates that the presence of imidazole leads to greatly improved hygroscopic properties and good internal bonding strength when used in particleboards., Validerad;2023;Nivå 2;2023-11-20 (hanlid);Full text license: CC BY, CT WOOD, Multifunktionella byggskivor av sågspån

Particleboards with different combinations of the adhesive material imidazole, citric acid, and sorbitol were produced. Softwood sawdust from a Swedish sawmill was mixed with an aqueous solution of the chemicals and then dried to 0% moisture content prior to pressing. The boards were pressed to a target density of 700 kg m−3 at either 200 °C or 220 °C for 10 min. The hygroscopic and mechanical properties of the boards were clearly better at 220 °C than 200 °C for all used chemical combinations. A combination of imidazole (14.4 wt%) and citric acid (11.3 wt%) led to the best results, where the thickness swelling after 24 h of water immersion was 6.3% and the internal bonding strength was 0.57 MPa. The modulus of rupture and modulus of elasticity were 3.3 MPa and 1.1 GPa, respectively. Cyclic accelerated weathering showed exceptional stability with a thickness change after boiling and drying of only 2.1% compared to the initial dry thickness. This study indicates that the presence of imidazole leads to greatly improved hygroscopic properties and good internal bonding strength when used in particleboards., Validerad;2023;Nivå 2;2023-11-20 (hanlid);Full text license: CC BY, CT WOOD, Multifunktionella byggskivor av sågspån