Solvation Layer Research Articles

Energetic and durable all-polymer aqueous battery for sustainable, flexible power

All-polymer aqueous batteries, featuring electrodes and electrolytes made entirely from polymers, advance wearable electronics through their processing ease, inherent safety, and sustainability. Challenges persist with the instability of polymer electrode redox products in aqueous environments, which fail to achieve high performance in all-polymer aqueous batteries. Here, we report a polymer-aqueous electrolyte designed to stabilize polymer electrode redox products by modulating the solvation layers and forming a solid-electrolyte interphase. Polyaniline is selected as an example for its dual functionality as a cathode or anode working by p/n doping mechanisms. This approach pioneers the application of polyaniline as an anode and enhances the high-voltage stability of polyaniline cathode in an aqueous electrolyte. The resulting all-polymer aqueous sodium-ion battery with polyaniline as symmetric electrodes exhibits a high capacity of 139 mAh/g, energy density of 153 Wh/kg, and a retention of over 92% after 4800 cycles. Spectroscopic characterizations have elucidated the hydration structure, solid-electrolyte interphase, and dual-ion doping mechanism. Large-scale all-polymer flexible batteries are fabricated with excellent flexibility and recyclability, heralding a paradigmatic approach to sustainable, wearable energy storage.

Solvation of molecules from the family of "domain of unknown function" 3494 and their ability to bind to ice.

In 2012, the molecular structure of a new, broad class of ice-binding proteins, classified as "domain of unknown function" (DUF) 3494, was described for the first time. These proteins have a common tertiary structure and are characterized by a very wide spectrum of antifreeze activity (from weakly active to hyperactive). The ice-binding surface (IBS) region of these molecules differs significantly in its structure from the IBS of previously known antifreeze proteins (AFPs), showing a complete lack of regularity and high hydrophilicity. The presence of a regular, repeating structural motif in the IBS region of hitherto known AFP molecules, combined with the hydrophobic nature of this surface, promotes the formation of an ice-like ordering of the solvation water layer and, as a result, facilitates the process of transformation of this water layer into ice. It is, therefore, surprising that the newly discovered DUF3494 class of proteins clearly breaks out of this characteristic. In this paper, using molecular dynamics simulations, we analyze the solvation water structure of the IBS region of both DUF3494 family molecules and AFPs. As we show, although the IBS of DUF3494 molecules does not form an ice-like water structure in the solvation layer, this is compensated by the formation of the equivalent of "anchored clathrate water," in the form of a relatively large number of water molecules bound to the surface of the protein molecule and providing potential binding sites for it to the ice surface.

Effect of Inorganic Additive Strategy on the Stability of in Vanadium Redox Flow Battery Electrolyte by Molecular Dynamics.

Inorganic ions are considered to be effective additives to improve the temperature stability of all-vanadium redox flow batteries. In this study, molecular dynamics simulation has been performed to study the solvation structure and dynamic properties of VO2+ in the positive electrolyte by doping Na+, K+, and NH4+ in the presence of V2O5 precipitation. The results show that VO2+ ions aggregate into chainlike clusters in the electrolyte due to the induction of SO42-. The additives, which are stable in the solvation layers of VO2+, can work as protective shells to inhibit cluster growth. NH4+ is a superior dispersant compared with Na+ and K+ as it can stably exist in both the first solvation layer and the second solvation layer of VO2+. This work performed the molecular dynamics simulation of the electrolyte of vanadium redox flow batteries, and it gives some insights into the theoretical study of the modification of the cathode electrolyte.

Ion solvation modulating via Imidazolidinyl urea additive for stable Zn2+ deposition

The development of energy conversion and storage equipment is a necessary guarantee for social development, and aqueous Zn-ion batteries have become a promising alternative to Li-ion batteries due to its high safety, environmental friendliness, and low cost. However, aqueous Zn-ion batteries suffer from the dendrite growth and parasitic reactions, which hinder the wide application of the batteries. In this paper, imidazolidinyl urea (IDU) is added to aqueous electrolytes because of the special structural properties of IDU. The effects of IDU as an additive on battery stability are elucidated through theoretical modelling, calculations, and experimental validation. Firstly, the effect of concentration on the ion transport properties of the electrolyte was obtained by modelling and calculating the Zn2+ diffusion coefficient and ionic conductivity of electrolytes with different concentrations of IDU added. In addition, the optimal IDU addition concentration was achieved by verification of cycling experiments in Zn symmetric cells. Moreover, it was confirmed using in situ deposition experiments that the addition of IDU could participate in the coordination of Zn2+ into the solvated layer of Zn2+, thereby accelerating the desolvation process of Zn2+, and further improving the uneven deposition of Zn on the negative electrode surface and the growth of dendrites. Finally, it was verified that the IDU addition could enhance the cycle life and stability of the battery, maintaining an efficiency of about 95% and a specific capacity of discharge of 90 mAh·g-1 after more than 1000 cycles in a full cell assembled from Zn flakes and improved iodine electrodes.

Two-Step Macromolecule Separation Process with Acid Pretreatment and High-Shear-Assisted Extraction for Microalgae-Based Biorefinery

A simple two-stage extraction and recovery method for macromolecules from microalgae biomass, termed CASS (concentrating the microalgae solution, acid pretreatment, high-shear-assisted lipid extraction, and separation), was developed. This method effectively processed the wet biomass of Chlorella sp. ABC-001 at a moderately low biomass concentration (50 g/L). The optimal conditions were acid pretreatment with 5 wt.% H2SO4 at 100 °C for 1 h, followed by high-shear extraction using hexane at 3000 rpm for 30 min. The acid pretreatment hydrolyzed carbohydrates and phospholipids, disrupting the cell wall and membrane, while high-shear mixing enhanced mass transfer rates between solvents and lipids, overcoming the hydraulic barrier at the cell surface. Within 10 min after completing the process, the extraction mixture achieved natural phase separation into water, solvent, and biomass residue layers, each enriched with carbohydrates, lipids, and proteins, respectively. The CASS process demonstrated high esterifiable lipid yields (91%), along with substantial recovery of glucose (90%) and proteins (100%). The stable phase separation prevented emulsion formation, simplifying downstream processing. This study presents the results on cell disruption, optimal acid treatment concentration, and high-shear mixing to achieve macromolecule separation, expanding the lipid-centric microalgal process to a comprehensive biorefinery concept.

Impact of mobile and stationary phases on siRNA duplex stability in liquid chromatography

Nucleic acid duplexes are typically analyzed in non-denaturing conditions. Melting temperature (Tm) is the property used to measure duplex stability; however, it is not known how the chromatographic conditions and mobile phase composition affect the duplex stability. We employed differential scanning calorimetry (DSC) method to measure the melting temperature of chemically modified silencing RNA duplex (21 base pairs, 0.15 mM duplex concentration) in mobile phases commonly used in reversed-phase, ion-pair reversed-phase, size exclusion and hydrophilic interaction chromatography. We investigated mobile phases consisting of ammonium acetate, alkylammonium ion-pairing reagents, alkali-ion chlorides, magnesium chloride, and additives including methanol, ethanol, acetonitrile and hexafluoroisopropanol. Increasing buffer concentration enhanced the duplex stability (Tm was 67.1 – 78.2 °C for 10–100 mM [Na+] concentration). The melting temperature decreases with the increase in cation size (70.2 °C in 10 mM [Li+], 68.1 °C in 10 mM [NH4+], 65.6 °C in 10 mM [Cs+], and 56.6 °C in 10 mM [triethylammonium+] solutions). Inclusion of 20 % of organic solvent in buffer reduced the melting temperature by 1–3 °C, and denaturation power increases in the order MeOH<EtOH<MeCN. Next, we investigated the RNA duplex melting using selected chromatographic techniques and within the 10–90 °C column temperature range. Melting temperature obtained with size exclusion chromatography in 25 mM sodium phosphate buffer was ∼ 70 °C, about 5 °C lower compared to DSC values. The apparent melting temperature for a reversed-phase chromatography experiment was < 10 °C for 10 mM ammonium acetate mobile phase with acetonitrile eluent. Ion-pair reversed-phase with 10 mM triethylamine, 100 mM hexafluoroisopropanol and MeCN as eluent yielded Tm 49.3–54.9 °C. Hydrophilic interaction chromatography experiments with 10 mM ammonium acetate and ∼ 50 % acetonitrile mobile phase showed high duplex stability (Tm ∼ 80 °C). The observed chromatographic Tm values suggest that the formation of an organic/aqueous solvent layer on the chromatographic sorbent surface affects the duplex stability more significantly than the composition of the mobile phase alone.

How Domain Segregation in Ionic Liquids Stabilizes Nanoparticles and Establishes Long-Range Ordering─A Computational Study.

Due to their physical properties including high thermal stability, very low vapor pressure, and high microwave absorption, ionic liquids have attracted great attention as solvents for the synthesis of nanomaterials, being considered as greener alternatives to traditional solvents. While usual solvents often need additives like surfactants, polymers, or other ligands to avoid nanoparticle coalescence, some ionic liquids can stabilize nanoparticles in dispersion without any additive. In order to quantify how the ionic liquids can affect both the aggregation thermodynamics and kinetics, molecular dynamics simulations were performed to simulate the evolution of concentrated dispersions and to compute the potential of mean force between nanoparticles of both hydrophilic and hydrophobic natures in two imidazolium-based ionic liquids, which differ from each other by the length of the cation alkyl group. Depending on the nature of the nanoparticle, structured layers of the polar and apolar regions of the ionic liquid can be formed close to its surface, and those layers lead to activation barriers for dispersed particles to get in contact. If the alkyl group of the ionic liquid is long enough to lead to domain segregation between the ionic and apolar portions of the solvent, the layered structure around the particle becomes more structured and propagates several nanometers away from its surface. This leads to stronger barriers close to the contact and also multiple barriers at larger distances that result from the unfavorable superposition of solvent layers of opposing nature when the nanoparticles approach each other. Those long-range solvent-mediated forces not only provide kinetic stability to dispersions but also affect their dynamics and lead to a long-range ordering between dispersed particles that can be explored as a template for the synthesis of complex materials.

Reaction Center Shifting in Partially Fluorinated Electrolytes for Robust Lithium Metal Battery.

The strategic formulation of a compatible electrolyte plays a pivotal role in extending the longevity of lithium-metal batteries (LMBs). Here, we present findings on a partially fluorinated electrolyte distinguished by a subdued solvation affinity towards Li+ ions and a concentrated anion presence within the primary solvation layer. This distinctive solvation arrangement redirects the focal points of reactions from solvent molecules to anions, facilitating the predominant involvement of anions in the creation of a LiF-enriched solid-electrolyte interphase (SEI). Electrochemical assessments showcase effective Li+ transport kinetics, diminished overpotential polarization for Li nucleation, and prolonged cycling durability in Li||Li cells employing the partially fluorinated electrolyte. When tested in Li||NCM811 cells, the designed electrolyte delivers a capacity retention of 89.30% and exhibits a high average Coulombic efficiency of 99.80% over 100 cycles with a charge-potential cut-off of 4.6 V vs. Li/Li+ under the current density of 0.4 C. Furthermore, even at a current density of 1C, the cells maintain 81.90% capacity retention and a high average Coulombic efficiency of 99.40% after 180 cycles. This work underscores the significance of weak-solvation interaction in partially fluorinated electrolytes and highlights the crucial role of solvent structure in enabling the long-term stability and high-energy density of LMBs.

ASESSMENT OF THE EFFECTIVENESS OF CAVITATION PROCESSING OF DARK OIL PRODUCTS

The paper presents experimental results of the influence of the conditions of cavitation treatment of dark petroleum products in the hydrodynamic regime on the yield of fractions boiling up to 400 °C. Straight-run products (fuel oils, vacuum gas oils), as well as catalytic cracking gas oils, were considered as raw materials. The influence of raw material characteristics (density, fractional and group hydrocarbon composition) and its processing conditions (pressure, at five cycles of exposure) on the yield of the target fraction is considered. The linear dependence of the yield of the target fractions on the processing pressure is revealed. The constructed regression models are adequate, informative, and all their coefficients are significant. Taking into account the density of the feedstock did not improved models. The best model constructed was tested using the cross-validation method. The average forecast error was 11%, the maximum was 22%. For a small number of samples, such an error is acceptable. The possibility of assessing the effectiveness of cavitation treatment of crude oil based on data on its fractional and group hydrocarbon composition is shown. It was possible to build several regression models linking the increase in yield with pressure during processing and the content of resins and oils in the raw materials. All of them are adequate and informative, and their coefficients are significant. The increase in the yield of fractions boiling up to 400 °C is associated with the transformations of hydrocarbons during cavitation. The possibility of evaluating the effectiveness of cavitation treatment of petroleum raw materials based on data on its group hydrocarbon composition has been established. Several regression models have been constructed linking the increase in yield with the pressure during processing and the content of resins and oils in the raw materials. All of them are adequate and informative, and their coefficients are significant. Based on the constructed models, it is assumed that the change in the fractional composition of petroleum products during cavitation treatment is more associated with the destruction of the transition and solvate layers of complex structural units of the oil dispersed system than with the course of cracking reactions. For citation: Peshnev B.V., Burlyaeva E.V., Nikishin D.V., Nikolaev A.I., Kuznetsov A.S. Asessment of the effectiveness of cavitation processing of dark oil products. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 7. P. 103-110. DOI: 10.6060/ivkkt.20246707.7006.

Fast interfacial electrocatalytic desolvation enabling low‐temperature and long‐cycle‐life aqueous Zn batteries

AbstractLow‐temperature zinc batteries (LT‐ZIBs) based on aqueous electrolytes show great promise for practical applications owing to their natural resource abundance and low cost. However, they suffer from sluggish kinetics with elevated energy barriers due to the dissociation of bulky Zn(H2O)62+ solvation structure and free Zn2+ diffusion, resulting in unsatisfactory lifespan and performance. Herein, dissimilar to solvation shell tuning or layer spacing enlargement engineering, delocalized electrons in cathode through constructing intrinsic defect engineering is proposed to achieve a rapid electrocatalytic desolvation to obtain free Zn2+ for insertion/extraction. As revealed by density functional theory calculations and interfacial spectroscopic characterizations, the intrinsic delocalized electron distribution propels the Zn(H2O)62+ dissociation, forming a reversible interphase and facilitating Zn2+ diffusion across the electrolyte/cathode interface. The as‐fabricated oxygen defect‐rich V2O5 on hierarchical porous carbon (ODVO@HPC) electrode exhibits high capacity robustness from 25 to −20°C. Operating at −20°C, the ODVO@HPC delivers 191 mAh g−1 at 50 A g−1 and lasts for 50 000 cycles at 10 A g−1, significantly enhancing the power density and lifespan under low‐temperature environments in comparison to previous reports. Even with areal mass loading of ~13 mg cm−2, both coin cells and pouch batteries maintain excellent stability and areal capacities, realizing practical high‐performance LT‐ZIBs.

Electrolyte solvents as architects: How solvents guide the spontaneous formation of 3D porous nanostructures in Alloy- and Conversion-type battery anodes

During battery cycling, fragmented anode materials following alloying, conversion, and conversion-alloying reactions spontaneously form three-dimensional (3D) porous nanostructures, influenced by the electrolyte solvent. While it is known that various solvents can enhance anode energy capacity, rate performance, and cycling stability by promoting this 3D structure, the specific solvent property responsible for this transformation was unclear. Our study investigates the role of 48 commercial solvents in Sn nanoparticle self-assembly, using both experimental and simulation methods. We discovered that solvent electrophilicity is crucial in initiating a solvation layer, guiding the development of the 3D nanostructure. This finding is significant in addressing anode fragmentation issues in alloying, conversion, and conversion-alloying processes. The resulting 3D nanostructures show enhanced mechanical and chemical resilience, offering a cost-effective and robust method to improve battery performance. Our research provides new insights into nanostructured anode design, paving the way for advanced battery technologies and enhancing our understanding of nanostructure formation in batteries.

Study on the adsorption/desorption characteristics and dynamic diffusion mechanism of rare earth hydrated ions on the kaolinite (001) surface

Coal gangue (CG) contains abundant rare earth elements (REEs), which is a potential REE resource. REEs are mainly present in clay minerals as hydrates. The adsorption, desorption, and diffusion of REEs-hydrates on the surface of clay minerals are the key to regulating the leaching effect of REEs. The paper focuses on the typical clay minerals kaolinite and REEs-hydrates and combines quantum mechanics and molecular dynamics methods to systematically study the adsorption, desorption, and dynamic diffusion behavior of REEs-hydrates in acid solution. The research results indicate that stable REEs-hydrates La(H2O)9 and Y(H2O)7 are formed, with ion bonds between REEs and water molecules. La(H2O)9 and Y(H2O)7 mainly interact with the kaolinite (001) surface through hydrogen bonding. Competitive adsorption is formed between water molecules, hydrated hydrogen ions, and REEs-hydrates. Water molecules and hydrated hydrogen ions occupy the adsorption active sites of REEs-hydrates and form a dense water molecular layer on the surface. The distance between H3O+ and REEs-hydrates and the number of H3O+ in the solvent layer affect the desorption and diffusion behavior of hydrates. The bonding law, dynamic desorption, and diffusion mechanism of REEs-hydrates can provide meaningful references for selective leaching of REEs from CG.

Study on the mechanism of interaction between cations and the surface of nano-SiO2 particle in the salt solution by using molecular dynamics simulation

Nano-SiO2 solution has great potential for application in the field of oil and gas exploration and development. However, its application is restricted due to the aggregation of nano-SiO2 in stratum water. This paper studies the process of interaction between nano-SiO2 particles and salt solutions by using the molecular dynamics simulation experiments, including the characteristics of transportation and diffusion of cations around the nano SiO2, the effect of cations on the recombination and destruction of hydrogen bonds, the interaction energy between cations and nano SiO2. The main results are as follows. During the transportation and diffusion of cations in the solution, the hydrogen bonds of water molecules are broken, so that the hydrogen bonds can be rearranged, and a stable solvated layer can be formed. In the solvated layer, the repulsive force of solvation can prevent the charge exchange between cation and the charged surface of nano SiO2 particle. Compared with the monovalent salt solution, more divalent cations can break through the solvation layer to generate the charge exchange on the surface of nano-SiO2 particle. More divalent cations can conduct small amplitude oscillation movement near the surface of nano-SiO2 particle due to the strong electrostatic effect. When the concentration of salt solution is increased (3000 mg/L → 7000 mg/L) and the valence of cations is increased (monovalent → bivalent), the hydrogen bond is easier to break through the solvation layer to gather on the surface of nano SiO2 particles, which is unfavorable to the stability of nano SiO2 particles. When the cations transport to the position of 7 Å away from the surface of nano-SiO2 particles, the short-range force (including hydrogen bond force, van der Waals force, and electrostatic force) begins to affect the movement of cations. When the cations transport to the position of 2 ∼ 3 Å away from the surface of nano-SiO2 particles, the charge exchange occurs between cations and the surface of nano SiO2 particle, so that the local energy is increased and the cation continues to oscillate. In summary, with the increasing of concentration of salt solution and the valence state, more cations can break through the solvation layer to be adsorbed on the surface of nano SiO2 particle, showing that the ability of transportation and diffusion of cations is weakened, the interaction energy between nano SiO2 particle and salt solution molecules is enhanced. The electrostatic force is the main force to destroy the stability of nano SiO2 particle. The conclusions can provide a certain theoretical basis for the efficient application of nano-SiO2 materials in the field of oil and gas exploration and development and other interrelated industry.

Application of the CL&P-Pol polarizable force field in the determination of the excess chemical potential of thiophene within the [C4mim] [BF4, Cl, Br, CH3COO] ionic liquids

The combustion of fossil fuels is an important source of air pollution due to the presence of sulfur-based compounds. In this regard, a reliable atomistic forcefield is required in order to provide insights on solute-solvent interactions, and in designing high aromatic sulfur extracting solvents. In the present work, the excess chemical potentials of thiophene within four 1-butyl-3-methylimidazolium-based ionic liquids were evaluated through the free energy perturbation with replica exchange molecular dynamics methodology by using the CL&Pol polarizable force fields based on Drude oscillators. First, in order to validate the accuracy of the polarizable force fields, a series of thermodynamic properties of pure ionic liquids such as diffusion coefficient, liquid density, dielectric constant, and heat of vaporization were computed using the CL&Pol force field and compared against experimental values. The results from the calculated thiophene excess chemical potential values, indicated that the [C4mim][CH3COO] ionic liquid presents the more favorable excess chemical potential (higher solubility) with respect to the thiophene molecule at both 300 K and 343 K in comparison to the other ionic liquids studied. The structural analysis revealed that the ionic liquid anion interacts more closely and with well-defined RDF peaks with the thiophene molecule, the larger anions present higher surrounding particle densities with the thiophene molecules (solvation shell), while the monoatomic anions interact preferentially with the hydrogens close to the sulfur thiophene atom; In contrast no marked solvation layers were observed with the ionic liquid cations.

Characterization of the Coordination and Solvation Dynamics of Solvated Systems─Implications for the Analysis of Molecular Interactions in Solutions and Pure H2O.

The characterization of solvation shells of atoms, ions, and molecules in solution is essential to relate solvation properties to chemical phenomena such as complex formation and reactivity. Different definitions of the first-shell coordination sphere from simulation data can lead to potentially conflicting data on the structural properties and associated ligand exchange dynamics. The definition of a solvation shell is typically based on a given threshold distance determined from the respective solute-solvent pair distribution function g(r) (i.e., GC). Alternatively, a nearest neighbor (NN) assignment based on geometric properties of the coordination complex without the need for a predetermined cutoff criterion, such as the relative angular distance (RAD) or the modified Voronoi (MV) tessellation, can be applied. In this study, the effect of different NN algorithms on the coordination number and ligand exchange dynamics evaluated for a series of monatomic ions in aqueous solution, carbon dioxide in aqueous and dichloromethane solutions, and pure liquid water has been investigated. In the case of the monatomic ions, the RAD approach is superior in achieving a well separated definition of the first solvation layer. In contrast, the MV algorithm provides a better separation of the NNs from a molecular point of view, leading to better results in the case of solvated CO2. When analyzing the coordination environment in pure water, the cutoff-based GC framework was found to be the most reliable approach. By comparison of the number of ligand exchange reactions and the associated mean ligand residence times (MRTs) with the properties of the coordination number autocorrelation functions, it is shown that although the average coordination numbers are sensitive to the different definitions of the first solvation shell, highly consistent estimates for the associated MRT of the solvated system are obtained in the majority of cases.

Studying the Collective Functional Response of a Receptor in Alchemical Ligand Binding Free Energy Simulations with Accelerated Solvation Layer Dynamics.

Ligand binding free energy simulations (LB-FES) that involve sampling of protein functional conformations have been longstanding challenges in research on molecular recognition. Particularly, modeling of the conformational transition pathway and design of the heuristic biasing mechanism are severe bottlenecks for the existing enhanced configurational sampling (ECS) methods. Inspired by the key role of hydration in regulating conformational dynamics of macromolecules, this report proposes a novel ECS approach that facilitates binding-associated structural dynamics by accelerated hydration transitions in combination with the λ-exchange of free energy perturbation (FEP). Two challenging protein-ligand binding processes involving large configurational transitions of the receptor are studied, with hydration transitions at binding sites accelerated by Hamiltonian-simulated annealing of the hydration layer. Without the need for pathway analysis or ad hoc barrier flattening potential, LB-FES were performed with FEP/λ-exchange molecular dynamics simulation at a minor overhead for annealing of the hydration layer. The LB-FES studies showed that the accelerated rehydration significantly enhances the collective conformational transitions of the receptor, and convergence of binding affinity calculations is obtained at a sweet-spot simulation time scale. Alchemical LB-FES with the proposed ECS strategy is free from the effort of trial and error for the setup and realizes efficient on-the-fly sampling for the collective functional response of the receptor and bound water and therefore presents a practical approach to high-throughput screening in drug discovery.

Dinuclear Copper Sulfate-Based Square Lattice Topology Network with High Alkyne Selectivity.

Porous coordination networks (PCNs) sustained by inorganic anions that serve as linker ligands can offer high selectivity toward specific gases or vapors in gas mixtures. Such inorganic anions are best exemplified by electron-rich fluorinated anions, e.g., SiF62-, TiF62-, and NbOF52-, although sulfate anions have recently been highlighted as inexpensive and earth-friendly alternatives. Herein, we report the use of a rare copper sulfate dimer molecular building block to generate two square lattice, sql, coordination networks which can be prepared via solvent layering or slurrying, CuSO4(1,4-bib)1.5, 1, (1,4-bib = 1,4-bisimidazole benzene) and CuSO4(1,4-bin)1.5, 2, (1,4-bin = 1,4-bisimidazole naphthalene). Variable-temperature SCXRD and PXRD experiments revealed that both sql networks underwent reversible structural transformations due to linker rotations or internetwork displacements. Gas sorption studies conducted upon the narrow-pore phase of CuSO4(1,4-bin)1.5, 2np, found a high calculated 1:99 selectivity for C2H2 over C2H4 (33.01) and CO2 (15.18), as well as strong breakthrough performance. Across-the-board, C3H4 selectivity vs C3H6, CO2, and C3H8 was also observed. Sulfate-based PCNs, although still understudied, appear increasingly likely to offer utility in gas and vapor separations.

Ca-dimers, solvent layering, and dominant electrochemically active species in Ca(BH4)2 in THF

Divalent ions (Mg, Ca, and Zn) are being considered as competitive, safe, and earth-abundant alternatives to Li-ion electrochemistry, but present challenges for stable cycling due to undesirable interfacial phenomena. We explore the formation of electroactive species in the electrolyte Ca(BH4)2∣THF using molecular dynamics coupled with a continuum model of bulk and interfacial speciation. Free-energy analysis and unsupervised learning indicate a majority population of neutral Ca dimers and monomers with diverse molecular conformations and an order of magnitude lower concentration of the primary electroactive charged species – the monocation, CaBH4+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\rm{CaBH}}_{4}^{+}$$\\end{document} – produced via disproportionation of neutral complexes. Dense layering of THF molecules within ~1 nm of the electrode surface strongly modulates local electrolyte species populations. A dramatic increase in monocation population in this interfacial zone is induced at negative bias. We see no evidence for electrochemical activity of fully-solvated Ca2+. The consequences for performance are discussed in light of this molecular-scale insight.

Isostructural behaviour in ammonium and potassium salt forms of sulfonated azo dyes.

The structures of five ammonium salt forms of monosulfonated azo dyes, derivatives of 4-(2-phenyldiazen-1-yl)benzenesulfonate, with the general formula [NH4][O3S(C6H4)NN(C6H3)RR']·XH2O [R = OH, NH2 or N(C2H4OH)2; R' = H or OH] are presented. All form simple layered structures with alternating hydrophobic (organic) and hydrophilic (cation, solvent and polar groups) layers. To assess for isostructural behaviour of the ammonium cation with M+ ions, the packing of these structures is compared with literature examples. To aid this comparison, the corresponding structures of four potassium salt forms of the monosulfonated azo dyes are also presented herein. Of the five ammonium salts it is found that three have isostructural equivalents. In two cases this equivalent is a potassium salt form and in one case it is a rubidium salt form. The isostructurality of ion packing and of unit-cell symmetry and dimensions tolerates cases where the ammonium ions form somewhat different interaction types with coformer species than do the potassium or rubidium ions. No sodium salt forms are found to be isostructural with any ammonium equivalent. However, similarities in the anion packing within a single hydrophobic layer are found for a group that consists of the ammonium and rubidium salt forms of one azo anion species and the sodium and silver salt forms of a different azo species.

Constant Potential Thermodynamic Integration for Obtaining the Free Energy Profile of Electrochemical Reaction.

In this work, we advanced an efficient free energy sampling method based on constrained ab initio molecular dynamics (cAIMD) with a fully explicit solvent layer to depict the electrochemical reaction process at constant surface charge density, named the "Constant-Potential Thermodynamic Integration (CPTI)" method. For automatically adjusting surface charge density at different states, we built an "on-the-fly" procedure which is capable of managing all the necessary steps during cAIMD simulations, including the system pre-equilibrium, surface charge density updating, and force sampling. We applied it to predict the potential-dependent free energy profiles of CO2 adsorption on a single-atom catalyst. The results show that our method can not only account for changes in electrostatic potential energy associated with potential but also consider the potential-induced solvation effects. Our approach enables the accurate simulation of electrochemical environment by presenting the complete solid-liquid interface and efficient computation of electrocatalytic reaction energetics based on a robust potential descriptor.