Aqueous Electrolyte Solutions Research Articles

Unraveling the phase diagram-ion transport relationship in aqueous electrolyte solutions and correlating conductivity with concentration and temperature by semi-empirical modeling

The relationship between structure and ion transport in liquid electrolyte solutions is not well understood over the whole concentration and temperature ranges. In this work, we have studied the ionic conductivity (κ) as a function of molar fraction (x) and Temperature (T) for aqueous solutions of salts with nitrate anion and different cations (proton, lithium, calcium, and ammonium) along with their liquid-solid phase diagrams. The connection between the known features in the phase diagrams and the ionic conductivity isotherms is established with an insight on the conductivity mechanism. Also, known isothermal (κ vs.. x) and iso-compositional (κ vs.. T) equations along with a proposed two variables semi-empirical model (κ = f (x, T)) were fitted to the collected data to validate their accuracy. The role of activation energy and free volume in controlling ionic conductivity is discussed. This work brings us closer to the development of a phenomenological model to describe the structure and transport in liquid electrolyte solutions.

Ag-Based Gas Diffusion Electrodes for the Electrochemical CO2 Reduction by Pulsed Hydrogen Bubble Templation

Energy-conversion technologies like the electrocatalytic nitrogen reduction reaction (N2RR), carbon monoxide reduction reaction (CORR) and in particular the electrochemical carbon dioxide reduction reaction (CO2RR) can contribute decisively to overcome the challenge of reducing greenhouse gas emissions. By reducing CO2 electrochemically, the carbon-cycle can be closed and industrially desired chemicals like syngas (CO + H2), formic and acetic acid, or hydrocarbons, such as methanol and ethylene, can be produced fossil-fuel free, depending on the catalyst material applied. Ag-based catalysts are very promising in the field of CO2RR, since they show high selectivities towards the reduction of CO2 to CO and current efficiencies of up to 100 %. In aqueous-fed systems, a significant drawback is the limited CO2 solubility, resulting in long diffusion pathways of CO2 within the bulk electrolyte 1, 2. Consequently, industrial conditions cannot be reached for CO2 electrolysis in aqueous solution in H-cell configurations due to the CO2 depletion within the porous electrodes that limit lab scale testing of CO2RR to current densities of approx. 35 mAcm-². One way to achieve commercially relevant current densities (> 200 mAcm-²) is the utilization of gas diffusion electrodes (GDEs) in flow cell configuration. These enable a decrease in CO2 diffusion lengths to approx. 50 nm, enhancing the mass transport to the catalyst 3.In our contribution, we will demonstrate a facile and fast production process of Ag-based GDEs by combining pulsed electrochemical deposition of the Ag catalyst with ionomer infiltration of the electrode. Using the dynamic hydrogen bubble templation method (DHBT), we utilized the parasitic hydrogen evolution reaction (HER) to aid in a solvent free structuring of the 3D catalyst network. In this work, we focused on the deposition parameters by varying different pulse-to-pause ratios in order to increase the amount of deposited catalyst and thus, successfully reduced the overpotential during CO2RR operation (Fig. 1, left). To inhibit electrode flooding and decrease CO2 mass transport limitations during CO2RR, we infiltrated the electrode with a perfluorinated ionomer. SEM and EDS analyses showed a uniform Ag/F distribution along the cross section of the electrodes (Fig. 1, right), which resulted in the conversion of CO2 to CO at industrially viable current densities.References S. Hernandez-Aldave and E. Andreoli, Catalysts, 10(6), 713 (2020).Z. Sun, T. Ma, H. Tao, Q. Fan and B. Han, Chem, 3(4), 560–587 (2017).T. Burdyny and W. A. Smith, Energy Environ. Sci., 12(5), 1442–1453 (2019). Figure 1

Reversible Redox Probes to Determine the Band Edge Locations for Nano-TiO2

Semiconductor (photo-)electrocatalysts show immense promise in answering the difficulties faced in CO2 electrolysis in relation to the reduction product selectivity. We thus see materials like ZnO[1], Cu2-xSe[2], MoS2 [3], TiO2 [4] and their numerous composites being frequently investigated for their catalytic properties in CO2 (photo-)electroreduction. These catalysts are fabricated via varying techniques and can assume very different thicknesses and morphologies. Although the nano-semiconductors may behave differently, often only the bulk properties are considered when proposing possible reaction pathways. Determining band edge locations of semiconductors in solutions is one such case, where Mott-Schottky (MS) measurements are a widely accepted strategy. The measurement of the potential dependence of the capacitance of the semiconductor space-charge layer under depletion indeed forms an elegant method to determine the flat-band potential and hence the band edge positions for bulk semiconductors in solution. However, the MS method cannot be used for nano-structured semiconductor electrodes in the form of thin films, nanorods or nanoparticles coated on conducting substrates, as their nano-dimensions are typically much smaller than that of a semiconductor depletion layer.In this work, we explored an alternate strategy to determine band edge positions of nano-semiconductors using reversible redox probes. A model thin film system comprised of 30nm anatase TiO2 is used to demonstrate the feasibility of the strategy in aqueous electrolyte solutions. Fe, Ru and Cr based reversible redox species were used as electrochemical probes in cyclic voltammetry experiments with varying solution pH. Based on the presence/absence of the reversible behavior of these probes, we can deduce the TiO2 band edge locations. The procedure also allows us to draw parallels between semiconductor-metal and semiconductor-solution interfaces to gain new insights into the CO2 reduction mechanism on such semiconductor electrodes. Figure 1

In-Situ Low-Frequency SERS Observation at Various Electrochemical Interfaces

Surface-selective vibrational spectroscopy, which is a powerful tool to study electrochemical interfaces, is typically operated in the mid-infrared region; chemical information obtained can give deep insights into electrochemical reactions at the molecular level. However, when the vibrational frequency range is extended into far-infrared or terahertz (THz) region, one can expect to obtain additional information about the interfaces because external vibrations such as surface-adsorbate vibrations and intermolecular vibrations appear in this range. Unfortunately, most of vibrational methods using THz radiation are not suitable for surface-selective observation of buried electrochemical interfaces. On the other hand, surface-enhanced Raman scattering (SERS) is potentially capable of detecting low-frequency vibrations at interfaces. Recently, the detectable frequency range of SERS has been extended into the low-frequency region down to 10 cm-1 [1], and then a vibrational analysis procedure for such low-frequency region has also been developed using a density of states format of SERS spectrum [2-4]. Using this method, for example, we have simultaneously observed both chemical information and molecular mass of surface adsorbates at interfaces [5]. In this talk, we focus on intermolecular interactions such as hydrogen bonding and anion-cation interactions at electrochemical interfaces. We present in-situ low-frequency SERS observation at various electrochemical interfaces under potential control [6].To obtain low-frequency SERS spectra, volume Bragg grating filters were used for both monochromatization of He-Ne laser radiation of 632.8 nm and removal of Rayleigh scattered light. SERS-active Au electrodes were prepared by electrochemical surface roughening in 0.1M KCl solution. For SERS-active Pt electrodes, monoatomic Pt overlayers were formed on the roughened Au surfaces. SERS spectra for both aqueous electrolyte solutions and ionic liquid electrolyte solutions were measured on these electrode surfaces under application of electrochemical potentials. The measured spectra were converted to density states of formats by reducing the Purcell factor, Bose-Einstein thermal factor, and frequency factor.Fig. 1 shows measured and reduced SERS spectra for 0.1M H2SO4/Au interface in the low-frequency region covering both Stokes and anti-Stokes branches. In the measured spectrum, vibrational features are not recognized because the huge background continuum dominates in the spectrum. This background continuum, caused by plasmon-enhanced electronic Raman scattering in the conduction band of Au, can be reduced in the density states of format, leading to considerable improvement in analyzability of vibrational features. Indeed, THz vibrational features are clearly unveiled in the reduced spectrum. Incidentally, the symmetry of the response between the Stokes and anti-Stokes branches in the reduced spectrum indicates that the SERS spectrum is properly converted to the reduced form because the Stokes and anti-Stokes Raman processes are connected due to the time reversal symmetry. Potential-dependence of these THz vibrational features will be discussed in the talk.[1] M. Inagaki, K. Motobayashi, K. Ikeda, J. Phys. Chem. Lett., 8, 4236-4240 (2017).[2] M. Inagaki, T. Isogai, K. Motobayashi, K. -Q. Lin, B. Ren, K. Ikeda, Chem. Sci., 11, 9807-9717 (2020).[3] M. Inagaki, K. Motobayashi, K. Ikeda, Nanoscale, 12, 22988-22994 (2020).[4] R. Kamimura, T. Kondo, K. Motobayashi, K. Ikeda, Phys. Status Solidi B, 259, 2100589 (2022).[5] T. Kondo, M. Inagaki, K. Motobayashi, K. Ikeda, Catal. Sci. Technol., 12, 2670-2676 (2022).[6] T. Isogai, M. Inagaki, M. Uranagase, K. Motobayashi, S. Ogata, K. Ikeda, submitted. Figure 1

Mechanism of Electrochemical Oxidation of Titanium Via Isotopic Labeling, Medium Energy Ion Scattering, Nuclear Reaction Profiling, in-Situ Rutherford Backscattering Spectrometry, and Electrochemical Impedance Spectroscopy

The few nanometres of titanium oxide present on titanium and Ti alloy surfaces are responsible for protecting the underlying metal from oxidation and enabling its use in many high-performance applications. The oxide provides a hard, uniform, and thermodynamically stable protective coating on an otherwise soft and very reactive metal. Because of its passivating oxide film, titanium has found uses in biomedical implants, aerospace engineering, corrosive industrial piping, and other areas where high strength and low weight are required.Our project is aimed at understanding the atomistic mechanisms of TiO2 formation and growth. We have taken several different approaches to investigate the details of this process. In one approach, the electrochemical oxidation mechanism of titanium at applied potentials between 0 and 10 V vs the saturated calomel reference electrode (SCE) was examined for ultra-thin Ti films sputtered onto Si(001) substrates and exposed in-situ to H2 18O, and then anodized in D2 16O. The effects of this isotopic labeling procedure were studied using medium energy ion scattering (MEIS) and nuclear reaction profiling (NRP). Both MEIS and NRP results are consistent in showing that the titanium oxide layer is composed of two distinct regions (Ti16O2/Ti18O2/Ti/Si) for the entire range of the formation voltages (0–10 V vs SCE). The oxygen component of the outermost region consists entirely of 16O, and the 18O region is always adjacent to the Ti metal. No Ti or 18O loss into the electrolyte solution during anodization was detected. The oxide thickened linearly as a function of potential in the 0–10 V range vs SCE, with experimental anodization ratio of 24.5±0.6 Å V−1. Mott–Schottky (MS) analyses showed positive slopes, indicating formation of an n-type TiO2 semiconductor, with O vacancies (or Ti interstitials) as major charge carriers in the 0–10 V range. Charge carrier densities, ND = (0.8-5.0)×1021 cm−3 were calculated from Mott–Schottky analysis and were well within the range of results reported in the literature. We observed a decrease in the charge carrier densities above ∼4 V vs SCE, that can be connected to defect annihilation or minor modification in the structure (electrostatic annealing) of the growing TiO2 film.In a second approach, we are using Rutherford backscattering spectrometry (RBS) for elemental depth profiling during oxide growth to determine oxidation rates and the role of the anodization potential on the Ti oxide layer structure and morphology. RBS is a powerful ion beam-based analytical tool used to determine thickness at the nanometer scale and elemental depth distribution, making it an excellent choice for studying the thin oxide on titanium. A difficulty with using RBS for such studies has been that RBS must function under ultra-high vacuum, and this has made it incompatible with performing aqueous electrochemistry; therefore, RBS had to be performed as an ex situ analysis, like MEIS and NRP. We are overcoming this limitation by using a specially designed in-situ cell with an ion-permeable silicon nitride window to provide a barrier between the ultra-high vacuum (UHV) required to perform RBS and the aqueous electrolyte solution required for anodization. In this cell, the thin silicon nitride window is coated with titanium and functions as the working electrode when exposed to the aqueous electrolyte solution. RBS measurements are taken as the titanium metal is anodized to titanium oxide. RBS is then performed during in-situ anodization, to obtain information about the growth mechanism of titanium oxide. Our initial in-situ RBS results show a significant increase in the oxidation rate of titanium compared to equivalent ex-situ measurements, and we also observe spontaneous TiO2 film growth without applying an anodic polarization. These effects are likely generated by strongly oxidizing water radiolysis products (e.g., H2O2 or ·OH) formed by the action of high-energy He+ ions interacting with the electrolyte solution.This paper discusses our experimental methods and presents an overview of the results and conclusions of this work.

Modeling Charge Transport in Flowable Suspension Electrolytes

Flowable suspension electrolytes (FSEs) consist of electrically conductive, redox-active, and/or energy-storing particles suspended in aqueous or non-aqueous electrolyte solutions (supporting salt + solvent). These particles, which can range in size from nanometers to micrometers, are subjected to Brownian forces, hydrodynamic forces, hydrophobic interactions, and van der Walls interactions among others. FSEs may enable electrochemical processes where solid reactants can be integrate with flow cells potentially unlocking new approaches to materials processing (e.g., synthesis, extraction/recovery). For example, FSEs has been demonstrated in redox flow batteries, facilitating higher energy densities without sacrificing independent power and energy scaling However, understanding and controlling charge transport through the deformable particle microstructures, especially under shear, is key to enable desirable current distributions and thus effective electrode utilization.In this presentation, we investigate the impact of interparticle interactions, particle volume fractions, and applied shear rate on charge transport through FSEs. At sufficiently large volume fractions above the percolation threshold and stationary conditions, particle interactions in an FSE can drive the formation of networks that span the cell dimensions and provide electronic transport similar to stationary freestanding porous electrodes. However, under flowing conditions, shear forces can break these networks, hampering charge transport. Conversely, increasing attractive particle interactions or particle concentration can strengthen the particle networks and fortifying charge transport, albeit at the expense of fluid viscosity. To better understand these processes, we model the charge transport through these dynamic particle networks, using a combination of local charge transport models and discrete particle simulations, considering the Peclet number (ratio of shearing to Brownian forces) and Mason number (ratio of shearing to attractive forces). Our results contribute to the development of continuum models for charge transport in FSEs, which, in turn, can facilitate efficient and accurate system-level analysis. Acknowledgments This work was funded by the Skoltech – MIT Next Generation Program.

PH Gradients in Spatially Non-Uniform AC Electric Fields around the Charging Frequency; A Study of Two Different Geometries and Electrode Passivation.

Dielectrophoresis (DEP), a precision nonlinear electrokinetic tool utilized within microfluidic devices, can induce bioparticle polarization that manifests as motion in the electric field; this phenomenon has been leveraged for phenotypic cellular and biomolecular detection, making DEP invaluable for diagnostic applications. As device operation times lengthen, reproducibility and precision decrease, which has been postulated to be caused by ion gradients within the supporting electrolyte medium. This research focuses on characterizing pH gradients above, at, and below the electrode charging frequency (0.2-1.4 times charging frequency) in an aqueous electrolyte solution in order to extend the parameter space for which microdevice-imposed artifacts on cells in clinical diagnostic devices have been characterized. The nonlinear alternating current (AC) electric fields (0.07 Vpp/μm) required for DEP were generated via planar T-shaped and star-shaped microelectrodes overlaid by a 70 μm high microfluidic chamber. The experiments were designed to quantify pH changes temporally and spatially in the two microelectrode geometries. In parallel, a 50 nm hafnium oxide (HfO2) thin film on the microelectrodes was tested to provide insights into the role of Faradaic surface reactions on the pH. Electric field simulations were conducted to provide insights into the gradient shape within the microelectrode geometries. Frequency dependence was also examined to ascertain ion electromigration effects above, at, and below the electrode charging frequency. The results revealed Faradaic reactions above, at, and below the electrode charging frequency. Comparison experiments further demonstrated that pH changes caused by Faradaic reactions increased inversely with frequency and were more pronounced in the star-shaped geometry. Finally, HfO2 films demonstrated frequency-dependent properties, impeding Faradaic reactions.

Physicochemical and sweetness behavior of kosmotropic and chaotropic ions in aqueous solutions of polyhydroxy compound

Hydrated ions have essential applications in biochemical processes. The objective of the present work is to study the behaviour of kosmotropic and chaotropic ions in aqueous solutions of polyhydroxy compounds in terms of sweetness response, volumetric and acoustic parameters such as apparent molar volume (∅v), apparent specific volume (ASV), compressibility (∅k0) etc. at different temperatures 20 °C – 45 °C and 101 kPa. The positive ∅v values of arabitol showed more kosmotropic nature for Na+ ion developing more stabilize structure of arabitol with water through strong hydrogen bonding, while the presence of K+ and Cl- form weak hydrogen bonding with water termed as chaotropic ions. The ASV values showed that arabitol remained sweet in the presence of electrolytes. The negative results of ∅k0 for arabitol in aqueous electrolytic solutions give valuable information about interactions occurring among solute, electrolytic ions, and water molecules. The structure-making/breaking behaviour has been observed by Hepler’s constant (∂2∅vo/∂T2)p.

Solubility modeling of hydrogen sulfide in aqueous sodium salt solutions

Accurate solubility prediction of hydrogen sulfide in aqueous electrolyte solutions is critical for gas exploitation and geological storage. However, there is a lack of electrolyte Equation of State model that can accurately calculate the solubilities of hydrogen sulfide in aqueous electrolyte solutions over wide ranges of temperature, pressure, and salt molality. This work presents a modeling study on the solubilities of hydrogen sulfide in pure water and several aqueous sodium salt solutions. The thermodynamic framework used in this work is an electrolyte version of Cubic-Plus-Association Equation of State. The model’s temperature-dependent ion-gas binary interaction parameters are obtained by regressing the experimental solubilities in the aqueous electrolyte solutions. The modeling results show that the electrolyte Cubic-Plus-Association Equation of State can satisfactorily correlate the solubilities of hydrogen sulfide in aqueous electrolyte solutions over wide ranges of temperature, pressure, and salt molality. For the typical water–sodium chloride–hydrogen sulfide system, the model can satisfactorily correlate the gas solubilities with the mean relative deviation being 6.2%, with the temperature up to 593.95 K, pressure up to 32.30 MPa, and salt molality up to 6.0 mol⋅kg−1 water. Moreover, the salting-out effects and model adaptability are analyzed and discussed.

Mixed Solvent Electrolyte Solutions: A Review and Calculations with the eSAFT-VR Mie Equation of State.

In this work, mixed-solvent mean ionic activity coefficients (MIAC), vapor-liquid equilibrium (VLE), and liquid-liquid equilibrium (LLE) of electrolyte solutions have been addressed. An extended literature review of existing electrolyte activity coefficient models (eGE) and electrolyte equations of state (eEoS) for modeling mixed solvent electrolyte systems is first presented, focusing on the details of the models in terms of physical and electrolyte terms, relative static permittivity, and parameterization. The analysis of this literature reveals that the property predictions can be ranked, from the easiest to the most difficult, in the following order: VLE, MIAC, and LLE. We have then used our previously developed eSAFT-VR Mie model to predict MIAC, VLE, and LLE in mixed solvents without fitting any new adjustable parameters. The model was parameterized on MIAC of aqueous electrolyte solutions and successfully extended to nonaqueous, single solvent electrolyte solutions without any new adjustable parameters by using a salt-dependent expression for the relative static permittivity. Our approach yields excellent results for MIAC and VLE of mixed solvent electrolyte solutions, while being fully predictive. LLE is significantly more challenging, and an accurate model for the salt-free solution is crucial for accurate calculations. When the compositions of the two phases in the binary salt-free system are accurately captured, then the electrolyte extension of our model shows a lot of potential and is currently among the best eEoS for LLE prediction in the literature.

Development of binder-free MoTe2/rGO electrode via hydrothermal route for supercapacitor application

The rising prevalence of electronic devices necessitates the application of supercapacitors, which rely on electrochemically active materials with high capacitive performance. Two-dimensional (2D) molybdenum ditelluride (MoTe2) nanoarrays have piqued great interest due to their wide-range applications including supercapacitor material, because of the inherent layered structure, low band gap and comparable conductivity. On the other hand, its self-aggregations decrease its chemical stability and activity, which remains a major barrier to its actual application. By combining with carbon-based reduced graphene oxide (rGO), self-aggregation and electrochemical activity can be improved significantly. In this research, MoTe2-supported rGO (MoTe2/rGO) was fabricated via a low-cost facile hydrothermal approach and characterised by fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), and energy dispersive X-ray spectroscopy (EDX) that is inclined with scanning electron microscope (SEM). Electrochemical assessments were also accomplished in an aqueous electrolytic solution of 2.0 M potassium hydroxide (KOH) for supercapacitor performance. The MoTe2/rGO shows exceptional specific capacitance (Cs) of 1196 F g−1, specific energy of 83.06 Wh kg−1- as well as 353.5 W kg−1 specific power at a current density of 1 A g−1 measured from galvanostatic charge/discharge (GCD) profile. On the other hand, the composite shows specific capacitance of 757.40 F g−1 measure via cyclic voltammetry (CV) at a scan rate of 5 mV s−1. Additionally, the nanohybrid shows a robust retention capacitance of 94.23% after 5000th successive cycles at 1 A g−1. The mechanical flexibility, intense cooperation and combined effects of MoTe2 and rGO nanosheets are responsible for the exceptional performance of supercapacitor applications. Because of its enormous potential for green energy generation and its simplicity of manufacture in a single step, MoTe2/rGO nanocomposite can serve as an electrode for extraordinary supercapacitors.

A manganese dioxide nanoparticle-bimetallic metal organic framework composite for selective and sensitive detection of vitamin D3 in human plasma.

For the first time a metal organic framework nanomaterial has been developedcomprising manganese dioxide nanoparticle and iron and zinc metal ions interlinked with each other via terephthalic acid. The framework shape was identified as an elongated hexagonal nanorod (TEM) with varying functional groups (FT-IR) and diffraction patterns (XRD). The framework nanocomposite as such in aqueous acidic electrolyte solution has displayed an excellent conductivity (redox behavior) and surface excess (3.08 × 10-8 cm-2). Under the optimized conditions (0.1 M H2SO4 as electrolyte, 50 mV/s scan rate, +1.26 V (vs Ag/AgCl)), the metal organic framework coated electrode has selectively identified vitamin D3 (VD3) in the presence of various other interfering molecules and displayed excellent limit of detection (1.9 ng mL-1). The developed sensor has been applied to the determination of VD3 in extracted human plasma samples (RSD of 0.3-2.6 % and recovery of 96-102 %), and the obtained VD3 values are similar to HPLC-UV method.

Novel Phosphate Conversion Coating with Superior Corrosion Resistance on the Mg-Al-RE Alloy Based on the Introduction of Silane.

A novel chemical conversion method based on an aqueous electrolyte solution containing hydrolyzed silane as a crucial film-forming agent has been developed successfully. An organic/inorganic composite coating with superior corrosion protection was fabricated on the Mg-Al-RE alloy. The micro-morphology and chemical composition of the coating were examined using scanning electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. The prepared conversion coating possesses a double-layer structure, with a dense bottom layer and a loose outer layer containing microcracks. In addition, the anti-corrosion capacity of various samples was evaluated using salt spray, hydrogen evolution, and electrochemical tests. The analysis revealed that the samples converted by 3-aminopropyl triethoxysilane (APTES)-phosphate solution possessed a higher corrosion resistance. Compared to the blank sample, a 2 orders of magnitude reduction in icorr (6.678 × 10-7 A/cm2) and a 1.360 V improvement in Ecorr were observed. The MPCC-Si sample exhibited the lowest hydrogen evolution rate, indicating the best corrosion protection. Also, the rust grade could still reach 7 after 72 h of the neutral salt spray test.

Atomic insights into the heterogeneity and the interface interactions of nanoconfined aqueous electrolyte solution

The structure and properties of nanoconfined electrolyte (nano electrolyte) solutions are important subjects in biochemistry, electrochemistry, separation science, etc. In the present work, neutron scattering and data driven reverse Monte Carlo were employed to quantitatively reveal the microstructure of aqueous CaCl2 solution in mesoporous silica MCM-41 at the atomic level. The electrolyte solution distributes in-homogeneously in the pores of mesoporous silica along the radial direction, which can be divided into the core, the transition, and the interface regions. The hydrogen bond structure of water in nano electrolytes is strengthened in the core region, analogous to that of nano water confined in nanochannels, and the ion association was enhanced in the transition region. The structure of the solution in the interface region was analogous to the bulk electrolyte solution under high pressure because of the confinement and interface effects. When the package ratio of nano electrolyte solution is insufficient, small amount of solution quasi-monolayer adsorb on the internal surface of mesoporous silica, the majority solution preferentially forms clusters with different sizes to adhere to the wetted interface. The anomalous hydrogen-bonding structure and ion association found in the present work improve our understanding of nanoconfined electrolyte solutions.

Extraction of Copper Ions with Composite Sorbents Based on Chitosan from Aqueous Solutions of Electrolytes in the Presence of a Surfactant

Extraction of Copper Ions with Composite Sorbents Based on Chitosan from Aqueous Solutions of Electrolytes in the Presence of a Surfactant

Facile hydrothermal synthesis of monoclinic VO2/graphene nanowhisker composite for enhanced performance electrode material for energy storage applications

Vanadium dioxide/reduced graphene oxide (VO2/G) nanowhisker composites are synthesized under hydrothermal conditions by a simple method. VO2 nanowhisker and 2D flexible graphene sheets are formed during the formation of VO2/G architecture to build interconnected porous microstructure via hydrogen bonding which allows charging and ion transport in the electrode. The composite electrode shows outstanding electrochemical performances due to the hierarchical network structure and pseudo-capacity contribution from VO2 nanowhiskers. The composite electrode used for electrochemical investigations in the aqueous electrolyte solution of 1 M Na2SO4. Noteworthy is the galvanostatic charge-discharge test which shows that, with a current density of 1 Ag−1, the specific capacitance value of the composite attained a high value of 294.5 Fg−1, which is significantly better than pure vanadium dioxide (VO2), and retains its capacitance at 203 Fg−1 at 10 Ag−1. The specific capacitance remained 96.3 % after 5000 continuous discharge cycles at 0.6 Ag−1 and shows an excellent cycle life for the material. It has also a high power density with a reasonably high-energy density. (i.e) energy density reached 48.07 Wh kg−1 at a power density of 213.6 Wkg−1. The results of the composite electrode were due to synergistic effects of VO2 and graphene, and excellent VO2 redox activity coupled with high electronic graphene sheet conductivity.

Computation of Electrical Conductivities of Aqueous Electrolyte Solutions: Two Surfaces, One Property.

In this work, we computed electrical conductivities under ambient conditions of aqueous NaCl and KCl solutions by using the Einstein-Helfand equation. Common force fields (charge q = ±1 e) do not reproduce the experimental values of electrical conductivities, viscosities, and diffusion coefficients. Recently, we proposed the idea of using different charges to describe the potential energy surface (PES) and the dipole moment surface (DMS). In this work, we implement this concept. The equilibrium trajectories required to evaluate electrical conductivities (within linear response theory) were obtained by using scaled charges (with the value q = ±0.75 e) to describe the PES. The potential parameters were those of the Madrid-Transport force field, which accurately describe viscosities and diffusion coefficients of these ionic solutions. However, integer charges were used to compute the conductivities (thus describing the DMS). The basic idea is that although the scaled charge describes the ion-water interaction better, the integer charge reflects the value of the charge that is transported due to the electric field. The agreement obtained with experiments is excellent, as for the first time electrical conductivities (and the other transport properties) of NaCl and KCl electrolyte solutions are described with high accuracy for the whole concentration range up to their solubility limit. Finally, we propose an easy way to obtain a rough estimate of the actual electrical conductivity of the potential model under consideration using the approximate Nernst-Einstein equation, which neglects correlations between different ions.

Effective Interactions between Double-Stranded DNA Molecules in Aqueous Electrolyte Solutions: Effects of Molecular Architecture and Counterion Valency.

A computational investigation of the effects of molecular topology, namely, linear and circular, as well as counterion valency, on the ensuing pairwise effective interactions between DNA molecules in an unlinked state is presented. Umbrella sampling simulations have been performed through the introduction of bias potential along a reaction coordinate defined as the distance between the centers-of-mass of pairs of DNA molecules, and effective pair interaction potentials have been computed by employing the weighted histogram analysis method. An interesting comparison can be drawn between the different DNA topologies studied here, especially with regard to the contrasting effects of divalent counterions on the effective pair potentials: while DNA-DNA repulsion in short center-of-mass distances decreases significantly in the presence of divalent counterion-ions (as compared to monovalent ions) for linear DNA, the opposite effect occurs for the DNA minicircles. This can be attributed to the fact that linear DNA fragments can easily adopt relative orientations that minimize electrostatic and steric repulsions by rotating relative to one another and by exhibiting more pronounced bending due to the presence of free ends.

Self-Consistent Implementation of a Solvation Free Energy Framework to Predict the Salt Solubilities of Six Alkali Halides.

To assess the salt solubilities of six alkali halides in aqueous systems, we proposed a thermodynamic cycle and an efficient molecular modeling methodology. The Gibbs free energy changes for vaporization, dissociation, and dissolution were calculated using the experimental data of ionic thermodynamic properties obtained from the NBS tables. Additionally, the Marcus' and Tissandier's solvation free energy data for Li+, Na+, K+, Cl-, and Br- ions were compared with the conventional solvation free energies by substituting into our self-consistent thermodynamic cycle. Furthermore, Tissandier's absolute solvation free energy data were used as the training set to refit the Lennard-Jones parameters of OPLS-AA force field for ions. To predict salt solubilities, an assumption of a pseudo-solvent was proposed to characterize the coupling work of a solute with its environment from infinitely diluted to saturated solutions, indicating that the Gibbs energy change of solvation process is a function of ionic strength. Following the self-consistency of the cycle, the newly derived formulas were used to determine the salt solubilities by interpolating the intersection of Gibbs free energy of dissolution and the zero free energy line. The refined ion parameters can also predict the structure and thermodynamic properties of aqueous electrolyte solutions, such as densities, pair correlation functions, hydration numbers, mean activity coefficients, vapor pressures, and the radial dependences of the net charge at 298.15 K and 1 bar. Our method can be used to characterize the solid-liquid equilibria of ions or charged particles in aqueous systems. Furthermore, for highly concentrated strong electrolyte systems, it is essential to introduce accurate water models and polarizable force fields.

Exploring nucleation modeling of the voltammetry of solid-to-solid-state redox processes with phase changes

An operational description of the linear potential scan voltammetry of solids experiencing a solid-state redox transformation with phase changes is described. The modeling is based on the application of nucleation equations of solid-state reaction kinetics to express the transferred charge/applied potential relationships. The flexible use of Prout-Tompkins and Avrami-Erofe’ev kinetics permits a satisfactory description of the voltammetry of solid-to-solid redox transformations with phase segregation. The model satisfactorily applies to reproduce linear potential scan curves recorded for graphite electrodes modified with several lead compounds in contact with aqueous electrolyte solutions.