Anion Size Research Articles

The influence of anion size on the thermoelectric properties and Seebeck coefficient inversion in PDPP-4T

The influence of anion size on the thermoelectric properties and Seebeck coefficient inversion in PDPP-4T

Anion Selectivities in Zwitterion Grafted Nanopores: Effect of Zwitterion Architecture.

The separation of ions of similar charge is a crucial challenge in many applications, from water treatment to precious metal recovery. Membranes with cross-linked zwitterionic amphiphilic copolymer (ZAC-X) selective layers, which feature self-assembled, zwitterion-lined nanodomains for permeation, offer unique permselectivity between monovalent anions (e.g., Cl-/F-). This has motivated studies on the mechanisms of transport and selectivity in this family of materials. In this study, we conducted molecular dynamics simulations of aqueous salt solutions within zwitterion-functionalized nanopores to elucidate the influence of dipole orientation of the ZI ligands on anion diffusivities, partitioning, and permeabilities. Our model compares systems with contrasting ZI organization: surface-cation-anion (S-ZI+-ZI-, Motif A) and surface-anion-cation (S-ZI--ZI+, Motif B). Our results reveal that Motif A exhibits less pronounced ion pairing due to a spatial separation in the radial profiles of cations and anions. Motif B demonstrates prominent ion pairing for smaller anions owing to their overlap with cation distributions. Further, our potential of mean force profiles reveals that anion partitioning increases with anion size in both ligand motifs, whereas Motif B exhibits significantly higher partitioning selectivity toward larger anions compared to Motif A. Our results for ion diffusivities show that the self-diffusivities of both anions and cations are lower for Motif B compared to Motif A. Such trends in anion partitioning and diffusivities can be explained by differences in the interactions and steric hindrance experienced by the anionic species in Motifs A and B. Finally, our results for anion permselectivity, obtained by combining partitioning and diffusivity, indicate that partitioning trends dominate over diffusivity trends. Consequently, anion permeability increases with anion size, and ligand Motif B yields much higher permselectivity toward larger anions compared to ligand Motif A.

Relationship between Structure and Properties of Bio-Based Aromatic Ionic Liquids for Tribological Applications

This study examined six phosphonium-based room-temperature ionic liquids (PRTILs) having trihexyltetradecyl- or tributyltetradecyl-phosphonium cations with saccharinate, salicylate, or benzoate anions, and obtained a feature parameter to correlate their cationic chain length, anionic ring size, and contact angle with tribological properties. PRTILs with trihexyltetradecyl-phosphonium cations had lower coefficient of friction (COF) and wear than PRTILs with tributyltetradecyl- phosphonium cations, a trend attributed to the additional methylene groups providing lower contact angle. For either cation, PRTILs with the saccharinate anion exhibited much lower COF and wear than single-ring anions, due to the formation of a low-shear-strength-tribofilm facilitated by the double-ring structure and sulfur of saccharinate. Overall, this study revealed PRTIL interfacial mechanisms that can be used to identify anion-cation combinations with optimal tribological performance.

The Wood-rot Basidiomycete Candolleomyces eurysporus VAST02.52 Produces a Versatile Peroxidase that Catalyses the Biotransformation of α-Pinene to Release Verbenone

Background Versatile peroxidase (VP; EC 1.11.1.16) has recently emerged as a novel peroxidase highly valued in biotechnology due to its exceptional ability to oxidize a diverse range of substrates into value-added products. Objectives To gain insight into the versatile peroxidase system from fungi, this study was designed to purify and characterize a CeuVP from the newly isolated fungus Candolleomyces eurysporus and to investigate its involvement in the biotransformation of plant α-pinene. Materials and methods The fungal isolate was identified by analysis of the internal transcribed spacer region. VP-active protein was purified from liquid culture of C. eurysporus VAST02.52 by using fast protein liquid chromatography. The catalytic properties and stability of enzyme were studied for various substrates, different pH- and temperatures. Moreover, its involvement in the biotransformation of plant α-pinene was assessed by HPLC chromatography. Results CeuVP was successfully purified with 27.3-fold purity and a 20.9% yield by using three steps of anion exchange and size exclusion chromatography. The molecular weight of CeuVP was determined to be 40 kDa by SDS-PAGE electrophoresis. This pure enzyme exhibited optimal activity at pH 4.0 and 35 °C. CeuVP showed the highest specific activity of 231.6 U/mg against ABTS, followed by Mn2+ (205.8 U/mg), veratryl alcohol (112.7 U/mg), cathecol (77.8 U/mg), p-aminophenol (68.9 U/mg), RBBR (56.2 U/mg), 4-methoxyphenol (31.1 U/mg), guaiacol (18.3 U/mg), and Reactive Black 5 (12.9 U/mg). Moreover, CeuVP catalyzed the oxidation of α-pinene derived from the essential oil of Eucalyptus robusta to release verbenone as the sole metabolite after a 7 h incubation. Conclusions Versatile peroxidase ( CeuVP) from C. eurysporus VAST02.52 exhibits the highest specific activity against ABTS while also catalyzing oxidation of various substrates tested. Moreover, this study indicated that CeuVP could be effective in the bioconversion of α-pinene into verbenone, a promising compound with numerous applications in the flavors and fragrances industry.

Dependence of Carboxylate Anions on Physicochemical Properties of Tributyloctylphosphonium-Based Ionic Liquids

A new group of tributyloctylphosphonium-based ionic liquids containing several carboxylate anions was designed, prepared and physicochemically characterized. All phosphonium carboxylates obtained in this study became viscous liquids at room temperature. The formate-based ionic liquid exhibited the highest density and number density due to the smallest anion size. All ionic liquids exhibited typical ionic conduction behavior, since the viscosity decreased and the conductivity increased with increasing temperature. It was also found that the viscosity tended to decrease with increasing the carbon numbers of the alkyl chains of lower carboxylate anions. Compared to the propionate-based ionic liquids, lactate-based ionic liquids exhibited higher viscosity. The phosphonium ionic liquids based on carboxylate anions showed higher thermal stability than nitrogen-based counterpart ionic liquids.

Ion specificity on cysteine tripeptides in aqueous environments revealed by molecular simulation

Molecular dynamics simulations were conducted to investigate the interactions of cysteine tripeptides with ions and water molecules in solutions of salts (MA, M = Li+ and Cs+, A = halide ions). The results revealed that as the anion size increases, cations aggregate more easily around the tripeptide, irrespective of capping. Radial distribution function (RDF) analysis showed direct interactions between F− and tricysteine, whereas Cl−, Br−, and I− exhibited indirect binding. Comparison between Li+ and Cs+ systems indicated that the smaller Li+ ions tend to distribute more around the tripeptide, engaging in direct interactions, whereas Cs+ ions interact indirectly, mediated by water molecules. Interaction energy analysis demonstrated that in lithium salt solutions, the total energy of anions with tricysteine decreased with anion size for both capped and uncapped systems. In cesium salt solutions, the anionic I− had the strongest interaction with cysteine tripeptides, and the cationic Cs+ interaction with tripeptides peaked in the CsI solution. The results highlight differences in ionic interactions depending on the anion-cation correlations of different salts.

Effects of Anion Size, Shape, and Solvation in Binding of Nitrate to Octamethyl Calix[4]pyrrole.

We present cryogenic ion vibrational spectroscopy of complexes of the anion receptor octamethyl calix[4]pyrrole (omC4P) with nitrate in vacuo. We compare the resulting vibrational spectrum with that in deuterated acetonitrile solution, and we interpret the results using density functional theory. Nitrate binds to omC4P through hydrogen bonds between the four NH groups of the receptor and a single NO group of the nitrate ion. The shape of the ion breaks the C4v symmetry of the receptor, and this symmetry lowering is encoded in the pattern of the NH stretching modes of omC4P. We compare the spectrum of nitrate-omC4P with that of chloride-omC4P to discuss effects of ion size, shape, and solvent interaction on the ion binding behavior.

Size sieving and electrostatic exclusion synergetic strategy for high efficiency recovery of superbase-derived ionic liquids via nanofiltration from the spinning process

Superbase-derived ionic liquids (SILs) as the promising green solvents for cellulose spinning process should be urgently and deeply evaluated with respect to their recyclability. Herein, size sieving and electrostatic exclusion synergetic strategy was adopted for recycling four SILs ([DBUH][CH3CH2OCH2COO], [DBUH][CH3OCH2COO], [DBNH][CH3CH2OCH2COO], and [DBNH][CH3OCH2COO]) from aqueous solutions by the nanofiltration membranes (NF270 and NF90) at the first time. NF270 with larger pore and more negative charge was conducive to recycle SIL on account of a higher volume flux and the remarkably high IL rejection (＞95 %) compared to NF90. Rising the pressure and temperature played the positive role in the permeate flux of the membranes, whereas the elevated SIL concentration markedly decreased the electrostatic exclusion, leading to a decline in the recovery efficiency. Benefiting from the size sieving effect, the [DBNH][CH3OCH2COO] with small cation and anion structure could be recovered efficiently due to the high energy gap and big IL aggregates. Conversely, the strong electrostatic attraction was appeared between [DBUH][CH3CH2OCH2COO] (low energy gap and high positive charge density) and the membranes, leading to a decline in recovery efficiency. Furthermore, the combination of nanofiltration and evaporation to recover SIL from spinning wastewater effectively reduced the total recovery cost (1.51 $/Kg) in comparison with the evaporation only. Insight gained from this work suggested a high-efficiency and economical approach could be used in the recovery of SILs with small cations and anions size via large pore nanofiltration membranes during the industrialized cellulose spinning process.

(Invited) Solid/Electrolyte Interface Under Confinement in Divalent Water-in-Salt Electrolytes

Concentrated aqueous electrolytes (water-in-salt electrolytes, WiSEs) have gained increasing attention in the last few years because they display much wider electrochemical stability windows (upwards of 3V) than the thermodynamic limit of water (1.23V), making them exciting candidates for a variety of electrochemical systems including aqueous batteries. Importantly, it is the ions directly at the electrode/electrolyte interface that are key to explaining this unexpected reactivity. The electrode/electrolyte interface is classically thought of as the electrical double layer (EDL), or the ion arrangement at an interface that builds up to neutralize the surface potential. WiSEs present very different EDL structures than do classical dilute electrolytes. However, most work has focused on monovalent WiSEs, primarily motivated by Li-battery applications using lithium bis(trifluoromethylsulphonyl)imide (LiTFSI).In this work, we aim to understand how divalent ions within the WiSE regime alter both the short-range and long-range signatures of the EDL under confinement. For most of the above applications, reactions occur within the pore-space of a porous electrode, which exhibit confined, overlapping EDLs. Therefore, we use confinement as a tool to probe both the short-range layering structure (<10 nm) and electrostatic decay length (~10-100 nm) away from a charged interface with Surface Forces Apparatus (SFA) measurements.Using WiSEs comprising LiTFSI, Zn(TFSI)2, and mixtures of the two salts, we first establish the bulk structure of these electrolytes using Wide Angle X-Ray Scattering and Raman Spectroscopy, which reveal that the anion and cation are closely associated in all electrolytes, regardless of cation valency. Additionally, clusters of ions are formed in all electrolytes, however, the clusters are suppressed with increasing divalent ion fraction. Under confinement, SFA results demonstrate that the thickness of the adsorbed layer of ions at a solid/electrolyte interface grows with increasing divalent ion fraction. Multiple interfacial layers are formed following this adlayer, and these layers seem dependent on anion size, rather than cation. Importantly, all electrolytes exhibit very long electrostatic decay lengths that are insensitive to valency. This work contributes significant fundamental understanding regarding the structure and charge-neutralization mechanism in this class of electrolytes both in the bulk and under confinement at an interface.

Tunable Wettability of a Dual-Faced Covalent Organic Framework Membrane for Enhanced Water Filtration.

Membrane technology plays a central role in advancing separation processes, particularly in water treatment. Covalent organic frameworks (COFs) have transformative potential in this field due to their adjustable structures and robustness. However, conventional COF membrane synthesis methods are often associated with challenges, such as time-consuming processes and limited control over surface properties. Our study demonstrates a rapid, microwave-assisted method to synthesize self-standing COF membranes within minutes. This approach allows control over the wettability of the surface and achieves superhydrophilic and near-hydrophobic properties. A thorough characterization of the membrane allows a detailed analysis of the membrane properties and the difference in wettability between its two faces. Microwave activation accelerates the self-assembly of the COF nanosheets, whereby the thickness of the membrane can be controlled by adjusting the time of the reaction. The superhydrophilic vapor side of the membrane results from -NH2 reactions with acetic acid, while the nearly hydrophobic dioxane side has terminal aldehyde groups. Leveraging the superhydrophilic face, water filtration at high water flux, complete oil removal, increased rejection with anionic dye size, and resistance to organic fouling were achieved. The TTA-DFP-COF membrane opens new avenues for research to address the urgent need for water purification, distinguished by its synthesis speed, simplicity, and superior separation capabilities.

Cation valency in water-in-salt electrolytes alters the short- and long-range structure of the electrical double layer

Highly concentrated aqueous electrolytes (termed water-in-salt electrolytes, WiSEs) at solid-liquid interfaces are ubiquitous in myriad applications including biological signaling, electrosynthesis, and energy storage. This interface, known as the electrical double layer (EDL), has a different structure in WiSEs than in dilute electrolytes. Here, we investigate how divalent salts [zinc bis(trifluoromethylsulfonyl)imide, Zn(TFSI)2], as well as mixtures of mono- and divalent salts [lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) mixed with Zn(TFSI)2], affect the short- and long-range structure of the EDL under confinement using a multimodal combination of scattering, spectroscopy, and surface forces measurements. Raman spectroscopy of bulk electrolytes suggests that the cation is closely associated with the anion regardless of valency. Wide-angle X-ray scattering reveals that all bulk electrolytes form ion clusters; however, the clusters are suppressed with increasing concentration of the divalent ion. To probe the EDL under confinement, we use a Surface Forces Apparatus and demonstrate that the thickness of the adsorbed layer of ions at the interface grows with increasing divalent ion concentration. Multiple interfacial layers form following this adlayer; their thicknesses appear dependent on anion size, rather than cation. Importantly, all electrolytes exhibit very long electrostatic decay lengths that are insensitive to valency. It is likely that in the WiSE regime, electrostatic screening is mediated by the formation of ion clusters rather than individual well-solvated ions. This work contributes to understanding the structure and charge-neutralization mechanism in this class of electrolytes and the interfacial behavior of mixed-electrolyte systems encountered in electrochemistry and biology.

Small sized of anion doping effect on semiconducting single-walled carbon nanotube network for field-effect transistors

Carbon nanotubes have shown great promise for high-performance, large-area, solution processable field-effect transistors due to their exceptional charge transport properties. In this study, we utilize the spin-coating method to form networks from selectively sorted semiconducting single-walled carbon nanotubes (s-SWNTs), aiming for scalable electronic device fabrication. The one-dimensional nature of s-SWNTs, however, introduces significant roughness and charge trap sites, hindering charge transport due to the van der Waals gap (∼0.32 nm) between nanotubes. Addressing this, we explored the effects of anion doping on the spin-coated s-SWNT random network, with a focus on the influence of the small size of halogen anions (0.13–0.22 nm) on these electronic properties. Raman and ultraviolet–visible–near-infrared optical spectroscopy results indicate that smaller anions significantly enhance doping effects through strong non-covalent anion–π interactions, improving charge transport and carrier injection efficiency in s-SWNTs, especially for n-type operation. This improvement is inversely proportional to the size of the halogen anions, with the smallest anion (fluorine) effectively transitioning the electrical characteristics of the s-SWNT network from ambipolar to n-type by reducing both junction and contact resistances through anion doping, based on anion–π interaction.

New ion radii for oxides and oxysalts, fluorides, chlorides and nitrides.

Ion radii are derived here from the characteristic (grand mean) bond lengths for (i) 135 ions bonded to oxygen in 459 configurations (on the basis of coordination number) using 177 143 bond lengths extracted from 30 805 ordered coordination polyhedra from 9210 crystal structures; and (ii) 76 ions bonded to nitrogen in 137 configurations using 4048 bond lengths extracted from 875 ordered coordination polyhedra from 434 crystal structures. There are two broad categories of use for ion radii: (1) those methods which use the relative sizes of cation and anion radii to predict local atomic arrangements; (2) those methods which compare the radii of different cations (or the radii of different anions) to predict local atomic arrangements. There is much uncertainty with regard to the relative sizes of cations and anions, giving rise to the common failure of type (1) methods, e.g. Pauling's first rule which purports to relate the coordination adopted by cations to the radius ratio of the constituent cation and anion. Conversely, type (2) methods, which involve comparing the sizes of different cations with each other (or different anions with each other), can give very accurate predictions of site occupancies, physical properties etc. Methods belonging to type (2) can equally well use the characteristic bond lengths themselves (from which the radii are derived) in place of radii to develop correlations and predict crystal properties. Extensive quantum-mechanical calculations of electron density in crystals in the literature indicate that the radii of both cations and anions are quite variable with local arrangement, suggesting significant problems with any use of ion radii. However, the dichotomy between the experimentally derived ion radii and the quantum-mechanical calculations of electron density in crystals is removed by the recognition that ion radii are proxy variables for characteristic bond lengths in type (2) relations.

Expected and unexpected structural phase transitions in K2ReBr6 and K2ReI6

The structure and magnetic properties of the two vacancy ordered double perovskites, K2ReBr6 and K2ReI6, are described. At room temperature, K2ReBr6 has a cubic structure in space group Fm3‾m that transforms to a tetragonal structure described in P4/mnc just below 290 K. Further cooling results in a second phase transition to a monoclinic structure in P21/n. The larger size of the iodide anion, compared to bromide, reduces the Goldschmidt tolerance factor and results in the monoclinic structure appearing at room temperature. The sequence of structures observed for K2ReBr6, Fm3‾m→P4/mnc→P21/n, mirrors that of other 5d potassium hexabromides including K2OsBr6 and K2PtBr6 but is different than that seen for K2ReCl6. Unexpectedly, K2ReI6 undergoes a first-order transition from P21/n→Fm3‾m upon heating with both phases co-existing over a limited temperature range. K2ReI6 decomposes upon standing or heating, while K2ReBr6 remains stable in the laboratory for several months. Magnetic susceptibility measurements show both compounds undergo antiferromagnetic ordering at low temperatures and the Néel temperature, estimated from the magnetic susceptibility measurements, increases as the size of the halide increases; 8.2 K for K2ReCl6, 16.1 K for K2ReBr6, 26.9 K for K2ReI6.

Identification and Characterization of Pectate Lyase as a Novel Allergen in Artemisia sieversiana Pollen

Introduction: Artemisia species are widely spread in north hemisphere. Artemisia sieversiana pollen is one of the common pollen allergens in the north of China. At present, seven allergens were identified and had been listed officially from A. sieversiana pollen, but the remaining allergens are still insufficiently studied, which need to be found. Methods: Pectate lyase was purified from the extracts of A. sieversiana pollen by anion exchange, size exclusion, and HPLC-hydrophobic interaction chromatography. The gene of A. sieversiana pectate lyase (Art si pectate lyase) was cloned and expressed in Escherichia coli. The enzyme activity and circular dichroism (CD) spectrum of natural and recombinant proteins were analyzed. The allergenicity of Art si pectate lyase was characterized by enzyme-linked immunosorbent assay (ELISA), Western blot, inhibition ELISA, and basophil activation test. The allergen’s physicochemical properties, three-dimensional structure, sequence profiles with homologous allergens and phylogenetic tree were analyzed by in silico methods. Results: Natural Art si pectate lyase (nArt si pectate lyase) was purified from A. sieversiana pollen extracts by three chromatographic strategies. The cDNA sequence of Art si pectate lyase had a 1191-bp open reading frame encoding 396 amino acids. Both natural and recombinant pectate lyase (rArt si pectate lyase) exhibited similar CD spectrum, and nArt si pectate lyase had higher enzymatic activity. Moreover, the specific immunoglobulin E (IgE) binding rate against nArt si pectate lyase and rArt si pectate lyase was determined as 40% (6/15) in patients’ serum with Artemisia species pollen allergy by ELISA. The nArt si pectate lyase and rArt si pectate lyase could inhibit 76.11% and 47.26% of IgE binding activities to the pollen extracts, respectively. Art si pectate lyase was also confirmed to activate patients’ basophils. Its structure contains a predominant motif of classic parallel helical core, consisting of three parallel β-sheets, and two highly conserved features (vWiDH, RxPxxR) which may contribute to pectate lyase activity. Moreover, Art si pectate lyase shared the highest sequence identity of 73.0% with Art v 6 among currently recognized pectate lyase allergen, both were clustered into the same branch in the phylogenetic tree. Conclusion: In this study, pectate lyase was identified and comprehensively characterized as a novel allergen in A. sieversiana pollen. The findings enriched the allergen information for this pollen and promoted the development of component-resolved diagnosis and molecular therapy of A. sieversiana pollen allergy.

Rational design of bilayer heterogeneous poly(ionic liquid)s electrolytes for high-performance flexible supercapacitors with ultraslow self-discharge rate

Supercapacitors have high power density and long cyclic life, but always face a great challenge of rapid self-discharge. Herein, we design a series of bilayer heterogeneous poly(ionic liquid)s electrolytes (BHPE) with anionic and cationic poly(ionic liquid)s (PolyILs), to construct high-performance supercapacitors with ultraslow self-discharge rate. Zeta potential and ionic conductivity of cationic PolyILs are adjusted by changing the volume of counter anions (BF4-, PF6-, TFSI-) and the length of alkyl side chain (ethyl, butyl and hexyl). Both experimental and simulated results reveal that the interaction energy between the cationic PolyILs and counter anion greatly depends on the sizes of anions and the lengths of alkyl side chains of cationic PolyILs, which has intrinsic effect on the zeta potential difference between anionic and cationic PolyILs of the BHPEs, and further can efficiently regulate the self-discharge rate of supercapacitors. The developed supercapacitor based on BHPE with using cationic PolyILs with small anion of BF4- and long alkyl side chain of hexyl exhibits an ultraslow self-discharge rate of −0.04 V h−1 and a high energy density of 34.8 Wh kg−1, which shows great promise for further practical applications in the future.

Mesomorphism, high-contrast negative fluorosolvatochromism and photoinduced fluorescence conversion of thienylcyanostyrene-pyridinium salts

Novel thienylcyanostyrene and pyridinium-based luminescent ionic liquid crystals (ILCs) characterized with different length of N-alkyl chains (N–C3H7 and N–C8H17) and different size of counter anions (Br−, BF4−, PF6− and Tf2N−) on pyridinium moiety have been synthesized. The chemical modifications of N-alkyl chains and counter anions are easily achieved via pyridine alkylation followed with further ion exchanges, which played a key role in tuning supramolecular self-assembly of these ILCs. The compounds with shorter N–C3 alkyl chain (E-CTPC3X, X = Br−, BF4−, PF6− and Tf2N−) can self-assemble into 3D cubic phase or 2D hexagonal columnar phase depending on the size of counter anion, while the analogues with longer N–C8 alkyl chain (E-CTPC8X, X = BF4− and Tf2N−) only result smectic A phases. Moreover, the prolongation of the N-alkyl chain or enlargement of counter anion could significantly decrease the clear points of LC phases avoiding the thermal decomposition at high temperature, whereas introducing counter anions such as BF4−, PF6− that can form hydrogen bonds have stabilized the LC phases. The notable negative fluorosolvatochromism and the photoinduced fluorescence conversion with high-contrast of these ILCs were observed using UV–vis absorption and photoluminescence (PL) spectra, and was further analyzed by dynamic 1H NMR. These ILCs had been used as dopant to modify the n-Si/PEDOT:PSS heterojunction solar cells (HSCs) with 2 fold hole mobility (μhole) enhancement of the PEDOT:PSS layer.

Electrolyte effects on the alkaline hydrogen evolution reaction: A mean-field approach

This paper introduces the combination of an advanced double-layer model with electrochemical kinetics to explain electrolyte effects on the alkaline hydrogen evolution reaction. It is known from experimental studies that the alkaline hydrogen evolution current shows a strong dependence on the concentration and identity of cations in the electrolyte, but is independent of pH. To explain these effects, we formulate the faradaic current in terms of the electric potential in the double layer, which is calculated using a mean-field model that takes into account the cation and anion sizes as well as the electric dipole moment of water molecules. We propose that the Volmer step consists of two activated processes: a water reduction sub-step, and a sub-step in which OH− is transferred away from the reaction plane through the double layer. Either of these sub-steps may limit the rate. The proposed models for these sub-steps qualitatively explain experimental observations, including cation effects, pH-independence, and the trend reversal between gold and platinum electrodes. We also assess the quantitative accuracy of the water-reduction-limited current model; we suggest that the predicted functional relationship is valid as long as the hydrogen bonding structure of water near the electrode is sufficiently maintained.

Evolution of Surface Tension and Hansen Parameters of a Homologous Series of Imidazolium-Based Ionic Liquids.

In this study, we systematically analyze the surface tension and Hansen solubility parameters (HSPs) of imidazolium-based ionic liquids (ILs) with different anions ([NTf2]-, [PF6]-, [I]-, and [Br]-). These anions are combined with the classical 1-alkyl-3-methyl-substituted imidazolium cations ([CnC1Im]+) and a group of oligoether-functionalized imidazolium cations ([(mPEGn)2Im]+) based on methylated polyethylene glycol (mPEGn). In detail, the influences of the length of the alkyl- and the mPEGn-chain, the anion size, and the water content are investigated experimentally. For [CnC1Im]+-based ILs, the surface tension decreases with increasing alkyl chain length in all cases, but the magnitude of this decrease depends on the size of the anion ([NTf2]- < [PF6]- < [Br]- ≤ [I]-). Molecular dynamics (MD) simulations on [CnC1Im]+-based ILs indicate that these differences are caused by the interplay of charged and uncharged domains, in particular in the different anions, which affects the ability of the alkyl chains of the cation to orient toward the liquid-gas interface. An increase in the mPEGn-chain length of the [(mPEGn)2Im][A] ILs does not significantly influence the surface tension. These changes upon variation of the cation/anion combination do not correlate with the evolution of the HSPs for the two sets of ILs. Finally, our data suggest that significant water contents up to water mole fractions of x(H2O) = 0.25 do not significantly affect the surface tension of the studied binary IL-water mixtures.

Ionic liquids and Graphene: The ultimate combination for High-Performance supercapacitors

Ionic liquids (ILs), due to their tunable propensities and properties, are discussed as a new class of solvents for scientific and industrial applications. Developing novel processes and applying ionic liquids further accelerate the growth of our fundamental and engineering understanding.In this work, the structure of four ILs, 1-ethyl-3-methylimidazolium tetrafluoroborate formate (Emim+BF4−)/chloride (Emim+Cl−)/Nitrate (Emim+NO3−), and thiocyanate (Emim+SCN−) is reported. Then via employing classical molecular dynamics and well-tempered metadynamics simulations their dynamics are investigated. The dynamics of ILs are represented by studying mean squared displacements. Additionally, the increased size and weight of anions interacting with the Emim+ cation cause the dynamics to become slow. Therefore, due to the higher molecular weight, the BF4− anion has lower diffusion than any other. Indeed, radial distribution functions between cations and anions reveal the structural arrangement in ILs. On the other hand, it is unexpectedly found that a certain amount of ILs are distributed near the electrode surface. Such phenomena occur because of the relatively strong ionic interactions between cations and anions; also, the π–π stacking between cations and graphene caused their interactions to become stronger. Furthermore, the atoms in molecules (AIM) analyses identified several interatomic interactions between the ILs and graphene. The free energy values for the ILs at their global minima are about ∼ -271.79, −267.93, −251.37 kJ mol−1 and ∼ -241.98 kJ mol−1 in systems Emim+/Cl−, Emim//NO3−, Emim+/SCN−, and Emim+/BF4−, respectively. Our findings represent a crucial step towards interpreting the complex interactions and nanostructures at the electrolyte–electrode interface, which could be beneficial for designing high-performance supercapacitors in energy storage using carbon electrodes and IL electrolytes in experiments.