Ion Hydration Research Articles

Understanding the Electric Double Layer at the Electrode-Electrolyte Interface: Part I - No Ion Specific Adsorption.

We present a comprehensive mean-field model that takes into account the key components of modern electrical double layer theory at the interface between an electrode and an electrolyte solution. The model considers short-range specific interactions between different species, including electrode-ion repulsion, the hydration of ions, dielectric saturation of solvent (water), and excluded volume (steric) interactions between species. By solving a modified Poisson-Boltzmann equation and using the appropriate results of quantum chemistry calculations on the hydration of ions, we can accurately approximate the differential capacitance profiles of aqueous electrolyte solutions at the boundary with a silver electrode. The specific interactions between the ions and the electrodes in the systems under considerationare assumed to be significantly weaker than their Coulomb interactions. A novel aspect of our research is the investigation of the impact of short-range ion-water interactions on the differential capacitance, which provides new insights into the behavior of the electrical double layer. This model holds the potential to be useful for electrochemical engineers working on the development of supercapacitors and related electrochemical energy storage devices. It serves as a basis for future modeling of electrolyte systems on real electrodes, especially in scenarios where chemical ion-electrode interactions are significant.

Ion-Ion Selectivity of Synthetic Membranes with Confined Nanostructures.

Synthetic membranes featuring confined nanostructures have emerged as a prominent category of leading materials that can selectively separate target ions from complex water matrices. Further advancements in these membranes will pressingly rely on the ability to elucidate the inherent connection between transmembrane ion permeation behaviors and the ion-selective nanostructures. In this review, we first abstract state-of-the-art nanostructures with a diversity of spatial confinements in current synthetic membranes. Next, the underlying mechanisms that govern ion permeation under the spatial nanoconfinement are analyzed. We then proceed to assess ion-selective membrane materials with a focus on their structural merits that allow ultrahigh selectivity for a wide range of monovalent and divalent ions. We also highlight recent advancements in experimental methodologies for measuring ionic permeability, hydration numbers, and energy barriers to transport. We conclude by putting forth the future research prospects and challenges in the realm of high-performance ion-selective membranes.

Cluster Formation Induced by Local Dielectric Saturation in Restricted Primitive Model Electrolytes.

Experiments using the Surface Force Apparatus (SFA) have found anomalously long-ranged charge-charge underscreening in concentrated salt solutions. Meanwhile, theory and simulations have suggested ion clustering to be a possible origin of this behavior. The popular Restricted Primitive Model of electrolyte solutions, in which the solvent is represented by a uniform relative dielectric constant, εr, is unable to resolve the anomalous underscreening seen in experiments. In this work, we modify the Restricted Primitive Model to account for local dielectric saturation within the ion hydration shell. The dielectric "constant" in our model locally decreases from the bulk value to a lower saturated value at the ionic surface. The parameters for the model are deduced so that typical salt solubilities are obtained. Our simulations for both bulk and slit geometries show that our model displays strong cluster formation and these give rise to long-ranged density correlations between charged surfaces, at distances similar to what has been observed in SFA measurements. An electrolyte model wherein the dielectric constant remains uniform does not display similar clusters, even with εr equal to the low saturated value at ion contact. Hence, the observed behaviors are not simply due to an enhanced Coulomb interaction. In the latter case, cluster growth is counteracted by long-ranged repulsions between like-charged ions within clusters; this is an effect that is considerably reduced when the dielectric response drop is local. Our results imply that long-ranged interactions in these systems are mainly due to cluster-cluster correlations, rather than large electrostatic screening lengths.

The Comparison of Catalytic Activity of Carbimazole and Methimazole on Electroreduction of Zinc (II) in Chlorates (VII): Experimental and Molecular Modelling Study.

With the help of electrochemical methods, including CV and EIS, the influence of methimazole, carbimazole, and the concentration of the supporting electrolyte on the kinetics and mechanism of zinc electroreduction on a mercury electrode was compared and analyzed. Moreover, molecular dynamics simulations of zinc/carbimazole and zinc/methimazole solutions were carried out to determine the effect of drugs on the hydration sphere of Zn2+ ions. It was shown that the electroreduction of Zn2+ in the presence of methimazole and carbimazole occurs in two steps and the first one determines the kinetics of the entire process. The presence of both drugs in the solution and the increase in the concentration of the supporting electrolyte reduce the degree of hydration of the depolarizer ions and the hydration of the electrode surface, what is a factor favoring the rate of electroreduction. Based on theoretical studies, the formation of stable complexes between Zn2+ and the molecules of both drugs in a solution was considered unlikely. However, active complexes can be formed between depolarizer ions and molecules adsorbed at the electrode surface. They constitute a bridge facilitating charge exchange during the electrode reaction, revealing the catalytic abilities of methimazole and carbimazole. In the range of cdrug ≤ 1 × 10-3 mol dm-3, carbimazole is a better catalyst, whereas in the range of cdrug ≥ 5 × 10-3 mol dm-3, it is methimazole. The effectiveness of both compounds in catalyzing the first stage of the electrode reaction increases with the increase in the NaClO4 concentration.

Scattering approaches to unravel protein solution behaviors in ionic liquids and deep eutectic solvents: From basic principles to recent developments

Proteins in ionic liquids (ILs) and deep eutectic solvents (DESs) have gained significant attention due to their potential applications in various fields, including biocatalysis, bioseparation, biomolecular delivery, and structural biology. Scattering approaches including dynamic light scattering (DLS) and small-angle X-ray and neutron scattering (SAXS and SANS) have been used to understand the solution behavior of proteins at the nanoscale and microscale. This review provides a thorough exploration of the application of these scattering techniques to elucidate protein properties in ILs and DESs. Specifically, the review begins with the theoretical foundations of the relevant scattering approaches and describes the essential solvent properties of ILs and DESs linked to scattering such as refractive index, scattering length density, ion-pairs, liquid nanostructure, solvent aggregation, and specific ion effects. Next, a detailed introduction is provided on protein properties such as type, concentration, size, flexibility and structure as observed through scattering methodologies. This is followed by a review of the literature on the use of scattering for proteins in ILs and DESs. It is highlighted that enhanced data analysis and modeling tools are necessary for assessing protein flexibility and structure, and for understanding protein hydration, aggregation and specific ion effects. It is also noted that complementary approaches are recommended for comprehensively understanding the behavior of proteins in solution due to the complex interplay of factors, including ion-binding, dynamic hydration, intermolecular interactions, and specific ion effects. Finally, the challenges and potential research directions for this field are proposed, including experimental design, data analysis approaches, and supporting methods to obtain fundamental understandings of complex protein behavior and protein systems in solution. We envisage that this review will support further studies of protein interface science, and in particular studies on solvent and ion effects on proteins.

Characterization of pore water microdynamics and microstructure of clays: The effect of pore fluid chemistry and temperature

It is crucial to figure out the microdynamics of pore water and the microstructure of clays under various thermal and chemical environments when characterizing the physical properties of clays. In this study water microdynamics in clay was investigated via the nuclear magnetic resonance (NMR) technique. The NMR measurements were performed on three clays saturated with distilled water and three salt solutions from 25 to 75°C. The saline and thermal effect on soil-water interaction, water microdynamics and microstructure of clays has been investigated through relaxation times by invoking the DDL theory and the ionic hydration mechanism. Number of jumps (τS/τm) for water molecule is 82 for soils A or C and 520 for soil B when saturated with distilled water, implying the larger surface molecular affinity of soil B. Salt solutions increase the values of τS/τm in the sequence of K+>Ca2+>Na+. Effective activation energy of pore waterΔE= 2.33 kcal/mol, 1.49 kcal/mol and 1.19 kcal/mol for soils A, B and C when saturated with distilled water are obtained. The effect of salt solution on ΔE depends on cation exchange capacity (CEC) and specific surface area (SSA), the larger the CEC and SSA, the smaller the saline effect. In addition, it is found that the pore size distribution of the compacted clay is bimodal, and inter-aggregate pores are greatly influenced by pore fluid chemistry, due to clay aggregation.

Response of Ionic Hydration Structure and Selective Transport Behavior to Aqueous Solution Chemistry during Nanofiltration.

The effect of aqueous solution chemistry on the ionic hydration structure and its corresponding nanofiltration (NF) selectivity is a research gap concerning ion-selective transport. In this study, the hydration distribution of two typical monovalent anions (Cl- and NO3-) under different aqueous solution chemical conditions and the corresponding transmembrane selectivity during NF were investigated by using in situ liquid time-of-flight secondary ion mass spectrometry in combination with molecular dynamics simulations. We demonstrate the inextricable link between the ion hydration structure and the pore steric effect and further find that ionic transmembrane transport can be regulated by breaking the balance between the hydrogen bond network (i.e., water-water) and ion hydration (i.e., ion-water) interactions of hydrated ion. For strongly hydrated (H2O)nCl- with more intense ion-water interactions, a higher salt concentration and coexisting ion competition led to a larger hydrated size and, thus, a higher ion rejection by the NF membrane, whereas weakly hydrated (H2O)nNO3- takes the reverse under the same conditions. Stronger OH--anion hydration competition resulted in a smaller hydrated size of (H2O)nCl- and (H2O)nNO3-, showing a lower observed average hydration number at pH 10.5. This study deepens the long-overlooked understanding of NF separation mechanisms, concerning the hydration structure.

An ab-initio deep neural network potential for accurate large-scale simulations of the muscovite mica-water interface

Mineral-water interfaces play a critical role in several geochemical processes relevant to the habitability of our planet. These processes are often underpinned by the hydration of the ions covering the mineral surface and the resultant ion exchange with the aqueous environment. Muscovite mica, whose surface is nominally covered by K + ions, has long been considered an ideal system for probing some of these processes. However, despite several decades of both experimental and computational work, there still remains a lack of consensus on ion hydration and exchange at the mica-water interface. To obtain a detailed microscopic picture of these processes, we have developed an ab-initio based deep neural network potential (DP) describing the potential energy surface (PES) of the mica(001)-water interface. Our training dataset consisted of bulk mica, bulk liquid water, the mica(001) surface in vacuum and the explicit mica(001)-water interface, both with different surface K + arrangements. The trained model is able to reproduce the energies and forces derived from Density functional theory (DFT) based on the SCAN exchange correlation functional with good accuracy. For the surface in vacuum, K + ions located in the ditrigonal cavities composed of 2 Al atoms are predicted to be energetically more favourable, while the specific surface arrangement of K + ions does not affect the water density profile at the mica-water interface. The developed model sets the stage for estimating the energetics of the ion-exchange process at affordable computational cost without compromising the accuracy of first-principles methods.

The Determination of Free Energy of Hydration of Water Ions from First Principles.

We model the autoionization of water by determining the free energy of hydration of the major intermediate species of water ions. We represent the smallest ions─the hydroxide ion OH-, the hydronium ion H3O+, and the Zundel ion H5O2+─by bonded models and the more extended ionic structures by strong nonbonded interactions (e.g., the Eigen H9O4+ = H3O+ + 3(H2O) and the Stoyanov H13O6+ = H5O2+ + 4(H2O)). Our models are faithful to the precise QM energies and their components to within 1% or less. Using the calculated free energies and atomization energies, we compute the pKa of pure water from first principles as a consistency check and arrive at a value within 1.3 log units of the experimental one. From these calculations, we conclude that the hydronium ion, and its hydrated state, the Eigen cation, are the dominant species in the water autoionization process.

Achieving Exceptional Volumetric Desalination Capacity Using Compact MoS2 Nanolaminates.

Capacitive deionization (CDI) has emerged as a promising technology for freshwater recovery from low-salinity brackish water. It is still inapplicable in specific scenarios (e.g., households, islands, or offshore platforms) due to too low volumetric adsorption capacities. In this study, a high-density semi-metallic molybdenum disulfide (1T'-MoS2) electrode with compact architecture obtained by restacking of exfoliated nanosheets, which achieve high capacitance up to ≈277.5Fcm-3 under an ultrahigh scan rate of 1000mVs-1 with a lower charge-transfer resistance and nearly tenfold higher electrochemical active surface area than the 2H-MoS2 electrode, is reported. Furthermore, 1T'-MoS2 electrode demonstrates exceptional volumetric desalination capacity of 65.1mgNaClcm-3 in CDI experiments. Ex situ X-ray diffraction (XRD) reveal that the cation storage mechanism with the dynamic expansion of 1T'-MoS2 interlayer to accommodate cations such as Na+, K+, Ca2+, and Mg2+, which in turn enhances the capacity. Theoretical analysis unveils that 1T' phase is thermodynamically preferable over 2H phase, the ion hydration and channel confinement also play critical role in enhancing ion adsorption. Overall, this work provides a new method to design compact 2D-layered nanolaminates with high-volumetric performance for CDI desalination.

Thermal degradation of PAN fibers modified with hydrazine hydrate and strontium ions

Thermal degradation of PAN fibers modified with hydrazine hydrate and strontium ions

Step-wise ion hydration modeling of aqueous solutions of 1:1 acid neutral electrolytes at different temperatures

In a previous work, we showed that the current stepwise ion hydration framework was promising for modeling electrolyte activities at 298.15 K. Briefly, the model assumes that (1) ions are hydrated in solution and this hydration is governed by an equilibrium between the bound and free water, (2) the mean spherical approximation (MSA) models the long range electrostatic interactions in the solution sufficiently well, and (3) this solution behaves ideally. In this work, we continue developing this model by exploring its temperature dependence. MSA has no temperature-dependent adjustable parameters. The hydration equilibrium constants are temperature dependent due to non-zero enthalpy and specific heat of the hydration equilibrium. Their values were adjusted. The calculated osmotic coefficients from the model are in good agreement with measured values.

Novel flow-electrode capacitive deionization system employing modified MOF-derived carbon electrodes for metal ion removal

Activated carbon (AC) as an electrode for capacitive deionization (CDI) is constrained by its low specific surface area and specific capacitance, leading to electrical double layer overlap (EDL). To address this issue, a flow electrode capacitive deionization system (MDC-FCDI) was developed, which used modified MOFs-derived carbon (MDC) as the electrode. The MDC electrode exhibited enhanced specific capacitance (145.78 F/g) and specific surface area (2458.44 m2/g). Compared to conventional FCDI, the MDC-FCDI system demonstrated a 35–39 % improvement in heavy metal removal efficiency from wastewater containing Pb2+, Cu2+, Cd2+, and Zn2+. The selectivity of MDC-FCDI for heavy metals exhibited a unique “two-step phenomenon” that differed from what was observed in conventional CDI systems. In the MDC-FCDI system, high-valent ions experienced stronger electric field forces and preferentially occupied active sites on the electrode surface prior to the adsorption of ions with lower valence. The selectivity of the MDC-FCDI system for heavy metal ions is determined by three factors in the following order of priority: ionic charge, hydration radius, and ion feed concentration. This study offers a practical approach for expanding the range of MDC-FCDI applications.

Terahertz fingerprint reveals the effect of alcohols on sodium ions hydration shell.

Ion hydration plays a crucial role in numerous fundamental processes. Various spectroscopic methods are employed to investigate the slowing down of hydration bond dynamics in the proximity of both anions and cations. To date, most of these studies have primarily focused on the properties of binary systems. However, in comparison to ion-water binary systems, ternary systems that involve ions, water, and organic matter are more prevalent in nature and provide more realistic insights into biological processes. This study focuses on ion hydration in water and alcohol mixture using terahertz spectroscopy and x-ray diffraction (XRD). The results reveal a distinct behavior depending on the type of alcohol used. Specifically, the presence of both methanol and ethanol results in the disappearance of absorption peaks associated with NaCl hydrate at low temperatures. In contrast, tert-butanol does not exhibit such an effect, and isopropanol demonstrates a more complex response. By combining these terahertz spectroscopic findings with low-temperature XRD data, we gain insights into the formation, or lack thereof, of NaCl · 2H2O hydrate crystals. Crucially, our observations suggest a dominant correlation between the polarity of the alcohol molecules and its impact on the Na+ hydration. Strongly polar alcohols preferentially solvating the Na+ ion lead to the failure of hydrate formation, while weakly polar alcohols do not have this effect.

Ionic hydration at ambient and higher pressures: Computed chemical potentials from simulations and finite-size effects

For the chemical potential of a hydrated mono-atomic ion, finite- size effects on simulation results obtained using molecular potential truncation are investigated. Free energy perturbation (FEP) calculations were carried out by scaling in two processes the Lennard-Jones (LJ) ion-water parameters and the ion-charge (q) for Br−, K+ and Ca2+ interacting with TIP4P water. Corrections which scale with q2 enable us to reduce finite-size effects. However, at ambient conditions, discrepancies which depend on q are shown by the corrected values when comparison is made with the experimental data of the Marcus compilation. Similar behavior was observed by extrapolating the original FEP results to an infinitely large system. Hence, these errors were assumed to depend on water density and corrected at high pressures. Consistency, within statistical uncertainties, is shown when comparing with results derived from computed volumetric quantities. Results are also compared with those derived from experimental values of excess volumes at ambient conditions.

ZnO sintering additive without negative impact on proton-conducting SrHf0.8Sc0.2O3-δ electrolyte

Many proton-conducting oxides are refractory, making it difficult to fabricate dense electrolyte membranes for electrochemical devices. The use of a sintering additive is a common strategy, although it often has a negative effect on proton transport. We found that the addition of ZnO (2 and 4 mol%) successfully contributes to densification of SrHf0.8Sc0.2O3-δ ceramics at 1450 °C without negative consequences for the ionic transport. The chemical stability of the materials, high levels of hydration and proton conductivity were confirmed. ZnO is partially (less than 0.3 mol%) incorporated into the crystal lattice of the perovskite and partially accumulates at grain boundaries gradually volatilizing during high-temperature treatments. As a result, ZnO sintering additive does not influence the bulk and specific grain-boundary conductivities, ionic transference numbers and hydration ability, maintaining the excellent electrolytic properties of SrHf0.8Sc0.2O3-δ ceramics.

Modification mechanism of calcium lignosulfonate on cementing cement

During the construction of coalbed methane extraction wells, cementing cement sheath is crucial for the stability and sealing of surface wells. One effective method to enhance these properties is the addition of lignosulfonate. However, the mechanism of the effect of calcium lignosulfonate on the whole process of cement hydration is still unclear. In this paper, the water distribution and variation characteristics of calcium lignosulfonate modified cement paste were revealed by low-field nuclear magnetic resonance technology, and the hydration ion experiment of modified cement was carried out to obtain the variation characteristics of hydration ions of modified cementing cement. Finally, the formation mechanism of hydration products was clarified by analyzing the phase change of modified cement stone. The results indicate that the cement paste’s hydration process can be divided into four stages: dissolution, crystallization, acceleration, and decline. During the dissolution stage, calcium lignosulfonate’s air entraining effect maintains the cement paste in a stable suspension state. In the crystallization stage, calcium lignosulfonate’s electro-repulsion delays the formation of hydration products and the hydration process. During the acceleration stage, the addition of calcium lignosulfonate reduces bound water formation in the cement slurry’s flocculation structure, and the released filled water participates more in the hydration reaction, reducing the total relaxation signal’s increasing trend. In the decline stage, the cement paste has solidified, and the system’s water is primarily in the porous medium. The research results have practical guiding significance for the addition of calcium lignosulfonate in cementing operations.

Immobilization mechanisms of Sr(II), Ni(II), and Cd(II) on glomalin-related soil protein in mangrove sediments at the microscopic scale

Glomalin-related soil protein (GRSP) is a significant component in the sequestration of heavy metal in soils, but its mechanisms for metal adsorption are poorly known. This study combined spectroscopic data with molecular docking simulations to reveal metal adsorption onto GRSP's surface functional groups at the molecular level. The EXAFS combined with FTIR and XPS analyses indicated that the adsorption of Cd(II), Sr(II), and Ni(II) by GRSP occurred mainly through the coordination of –OH and –COOH groups with the metal. The –COOH and –OH groups bound to the metal as electron donors and the electron density of the oxygen atom decreased, suggesting that electrostatic attraction might be involved in the adsorption process. Two-dimensional correlation spectroscopy revealed that preferential adsorption occurred on GRSP for the metal in sequential order of –COOH groups followed by –OH groups. The presence of the Ni–C shell in the Ni EXAFS spectrum suggested that Ni formed organometallic complexes with the GRSP surface. However, Sr–C and Cd–C were absent in the second shell of the Sr and Cd spectra, which was attributed to the adsorption of Sr and Cd ions with large hydration ion radius by GRSP to form outer-sphere complexes. Through molecular docking simulations, negatively charged residues such as ASP151 and ASP472 in GRSP were found to provide electrostatic attraction and ligand combination for the metal adsorption, which was consistent with the spectroscopic analyses. Overall, these findings provided new insights into the interaction mechanisms between GRSP and metals, which will help deepen our understanding of the ecological functions of GRSP in metal sequestration.

Anion Competition at Positively Charged Surfactant Monolayers.

Interactions of anions with hydrophobic surfaces of proteins and water-soluble polymers depend on the ability of the ions to shed their hydration shells. At positively charged surfactant monolayers, the interactions of anions are less well understood. Due to the interplay of electrostatic surface forces, hydration effects, and ion-ion interactions in the electrostatic double layer, a comprehensive microscopic picture remains elusive. Herein, we study the interactions of chloride, bromide, and a mixture of these two anions at the aqueous interface of dihexadecyldimethylammonium (DHDA+) and dioctadecyldimethylammonium (DODA+) cationic monolayers. Using molecular dynamics simulations and three surface-sensitive X-ray scattering techniques, we demonstrate that bromide interacts preferentially over chloride with both monolayers. The structure of the two monolayers and their interfacial electron density profiles obtained from the simulations quantitatively reproduce the experimental data. We observe that chloride and bromide form contact ion pairs with the quaternary ammonium groups on both monolayers. However, ion pairing with bromide leads to a greater reduction in the number of water molecules hydrating the anion, resulting in more energetically stable ion pairs. This leads to long-range (>3 nm) lateral correlations between bromide ions on the structured DODA+ monolayer. These observations indicate that ion hydration is the dominant factor determining the interfacial electrolyte structure.

Rational design on hierarchically porous Cu/ZSM-5 zeolite for promoting low-temperature NH3-SCR performance based on protectively alkali-etching strategy

In this study, organic structure-directing agents (OSDA) of TPA+ are used as templating agents to synthesize zeolites with different topologies, and are also served as protectants for alkali treatment to inhibit the severe silicon extraction from zeolite skeleton. The TPA+ cations could be bound to the negatively charged Al sites in the framework, so we prepared a series of Cu-based ZSM-5 catalysts with mesoporous/microporous composite structure by using TPA+ cation as a protectant for alkali treatment and evaluated the pore structures by using the hierarchy factor (HF). The results show the hierarchically mesoporous/microporous structure of the alkali-etched catalyst with the maximal HF (0.115) effectively improved the low-temperature activity on selective catalytic reduction (SCR) of NO by ammonia, achieving a complete NOx to N2 conversion at 225–400 ºC. It was shown that the TPA+ cation played an important role on protecting the crystallinity, long-range order, and pore connectivity of zeolites, and substantially widened the mesopore volume with the loss of a small portion of micropores. In addition, the alkali treatment strategy involving protectant was systematically studied, including the corresponding effect on the pore structure, redox ability, acidity, and copper ion dispersion. The N2 adsorption-desorption experiments revealed that the maximization of the HF can be obtained by adjusting the ratio of protectant to etchant (TPA+/OH-). Among them, the Cu/ZSM-5 catalyst associated with the ratio of TPA+/OH-=0.4 and the best activity has a maximum surface area of 515 m2/g, which enhances the mesopore volume (0.325 cm3/g) by approximately three times simultaneously with only a 16.9% loss of the micropore volume (0.154 cm3/g). The hierarchically porous zeolites not only enhance the diffusion of mobile hydrated copper ions and ammonia-solvated copper complexes, but also facilitate the dispersion of copper ions. This work provides a feasible strategy to rapidly enhance the low-temperature deNOx efficiency on the zeolite catalysts.