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A bicarbonate-rich liquid condensed phase in non-saturated solutions in the absence of divalent cations
Bicarbonate (HCO 3 - ) and sodium (Na + )-containing solutions contain droplets of a separate, bicarbonate-rich liquid condensed phase (LCP) that have higher concentrations of HCO 3 - relative to the bulk solution in which they reside. The existence and composition of the LCP droplets has been investigated by nanoparticle tracking analysis, nuclear magnetic resonance spectroscopy, refractive index measurements and X-ray pair distribution function analysis. The bicarbonate-rich LCP species is a previously unaccounted-for, ionic phenomenon which occurs even in solutions with solely monovalent cations. Its existence requires re-evaluation of models used to describe and model aqueous solution physicochemistry, especially those used to describe and model carbonate mineral formation.
Radiation-induced reduction of divalent copper salts in solutions
Organic additives and concentration effects on radiation induced reduction of copper salts in aqueous solution
Moessbauer studies of lattice dynamics, fine and hyperfine structure of divalent Fe57 in FeF2
Isomer shift, Mossbauer recoil free fraction and nuclear quadrupole splitting for Fe57 in iron fluoride measured for lattice dynamics, fine and hyperfine structure
The catalysis of nucleotide polymerization by compounds of divalent lead
The nonenzymatic, nontemplate catalysis of nucleotide polymerization by Pb(2+) ions, a possible prebiotic catalyst, is reported. Adenosine and uridine phosphoimidazoles were reacted in buffered solutions of lead salts and products were analyzed by means of paper chromatography and electrophoresis. In the presence of Pb(2+) ion at pH 8.0 and 7.0 the reaction is found to progress rapidly with excellent yields of oligomers, with optimal yields observed at pH 8.0. Little temperature dependence in the range 0 to 30 C is observed, however hydrolysis of the reaction products is minimal when the reaction is carried out at 0 C. Results show that the yield of oligomers is insensitive to mixing or the source of lead ions, indicating that naturally occurring minerals or precipitates could be a source of Pb(2+) ions under prebiotic conditions.
Divalent Multilinking Bonds Control Growth and Morphology of Nanopolymers
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Facile, low-energy routes for the production of hydrated calcium and magnesium salts from alkaline industrial wastes
Divalent ions are extracted from solids by leaching to form a divalent ion-containing solution. The divalent ion-containing solution is subjected to concentration to form a concentrated divalent ion-containing solution. Precipitation of a divalent ion hydroxide salt is induced from the concentrated divalent ion-containing solution. In other cases, the concentrated divalent ion-containing solution is exposed to carbon dioxide to induce precipitation of a divalent ion carbonate salt.
Buffer-free process cycle for CO 2 sequestration and carbonate production from brine waste streams with high salinity
A method includes: (1) using a chelating agent, extracting divalent ions from a brine solution as complexes of the chelating agent and the divalent ions; (2) using a weak acid, regenerating the chelating agent and producing a divalent ion salt solution; and (3) introducing carbon dioxide to the divalent ion salt solution to induce precipitation of the divalent ions as a carbonate salt. Another method includes: (1) combining water with carbon dioxide to produce a carbon dioxide solution; (2) introducing an ion exchanger to the carbon dioxide solution to induce exchange of alkali metal cations included in the ion exchanger with protons included in the carbon dioxide solution and to produce a bicarbonate salt solution of the alkali metal cations; and (3) introducing a brine solution to the bicarbonate salt solution to induce precipitation of divalent ions from the brine solution as a carbonate salt.
Buffer-free process cycle for CO 2 sequestration and carbonate production from brine waste streams with high salinity
A method includes: (1) using a chelating agent, extracting divalent ions from a brine solution as complexes of the chelating agent and the divalent ions; (2) using a weak acid, regenerating the chelating agent and producing a divalent ion salt solution; and (3) introducing carbon dioxide to the divalent ion salt solution to induce precipitation of the divalent ions as a carbonate salt. Another method includes: (1) combining water with carbon dioxide to produce a carbon dioxide solution; (2) introducing an ion exchanger to the carbon dioxide solution to induce exchange of alkali metal cations included in the ion exchanger with protons included in the carbon dioxide solution and to produce a bicarbonate salt solution of the alkali metal cations; and (3) introducing a brine solution to the bicarbonate salt solution to induce precipitation of divalent ions from the brine solution as a carbonate salt.
Mechanistic Insights into Adsorptive and Catalytic Reactions from Controllable Distributions of Metal Cations (Pd, Pt, Ni, Cr, Cu) as [M‐OH] +1 /1Al or M +2 /2Al in Zeolites
Anchoring divalent metal ions in the same zeolite framework with similar Si/Al ratio selectively as zeolite-bound M +2 or [M +2 -OH] +1 cationic species enables critical comparison of the species’ intrinsic reactivity for industrially and fundamentally relevant reactions. H-BEA zeolites with similar Si/Al ratios but differing framework Al siting were used to anchored multiple divalent metal cations (Ni, Pd, Pt, Cr, Cu) in the zeolite micropores. State-of-the-art infrared (IR) spectroscopy, electron paramagnetic resonance (EPR) measurements, including two-dimensional pulsed HYSCORE EPR, extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT) calculations together provide unambiguous evidence for the selective formation of divalent metal cations as M +2 /2Al species (for H-BEA prepared in the conventional hydroxide media), and [M +2 OH] +1 /1Al species for H-BEA prepared in HF. Solid-state proton-decoupled triple-quantum magic-angle spinning (3Q MAS) NMR measurements confirmed contrasting Al distributions in the two H-BEA zeolites, which led to a contrasting divalent cation speciation. The reactivities of the two cationic species were explored for catalytic and adsorptive applications in both organometallic homogeneous and heterogeneous catalysis. This work demonstrates their divergent reactivity in ethylene dimerization, ethylene oxidation (Wacker process), selective catalytic reduction (SCR) of NO, NO adsorption, and methane oxidation. Both M +2 /2Al and [M +2 OH] +1 /1Al cations are both active for ethylene dimerization, but [M +2 OH] +1 /1Al species show higher reaction rates for each Pd, Ni, Pt. [M +2 OH] +1 /1Al is active for acetaldehyde formation in Wacker ethylene oxidation. A new active site for ethylene oligomerization is proposed that possesses a terminal OH group (Cr-OH) in Phillips catalysts evident by a nearly inactive isolated Cr +2 /2Al species that contrast an active Cr─OH motif.
Techno-economic analysis of converting oil & gas produced water into valuable resources
Managing produced water from oil and gas wells constitutes a significant portion of the costs of operating a well. Here, in this work, we have designed two different centralized water treatment facilities capable of managing produced water from oil and gas wells in Texas and Louisiana, both of which convert the produced water into the following valuable resources: ten-pound brine and fresh water. The two main designs each use commercially available technology with varying levels of establishment in treating produced water. Both treatment processes remove oil and grease and suspended solids, reduce the divalent ion concentrations, and concentrate the brines to a near-saturation state. The baseline design uses chemical precipitation to remove the divalent ions to meet the reuse specifications, whereas the advanced design uses nanofiltration (NF) membranes to separate divalent ions and uses reverse osmosis (RO) membranes to partially concentrate the brine. Both models use mechanical vapor recompression to concentrate the brine up to NaCl saturation. The baseline process is shown to be cost-effective for low-hardness brines. In the case of high hardness, the chemical precipitation step is cost-prohibitive. We find that NF membranes are a promising alternative to chemical precipitation as a means of separating monovalent and divalent ions.
Effect of mono- and multi-valent ionic environments on the in-lattice nanoparticle-grafted single-stranded DNA
The polyelectrolyte (PE) chains respond in a complex manner to the multivalent salt environments, and this behavior depends on pH, temperature, and the presence of specific counter ions. Although much work was done to understand the behaviour of free PE chains, it is important to reveal their behaviour on nanoparticle's surface, where surface constraints, particle geometry, and multi-chain environment can affect their behaviour and contribute to particles assembly states. Our work investigates, using in-situ small-angle x-ray scattering (SAXS), the morphology of PEs (single-stranded DNA) chains grafted onto a surface of spherical gold nanoparticles assembled in a lattice in the presence of monovalent, divalent and trivalent salts. For divalent salts, the DNA brush length was found to decrease at a faster rate with salt concentration than in the monovalent salt environment, while trivalent salt lead to a chain collapse. Using a power law analysis and modified Daoud-Cotton model, we have obtained insight into the mechanism of nanoparticle-grafted chain's response to ionic environments. Our analysis suggests that the decrease in a brush length is due to the conventional electrostatic screening for monovalent systems, whereas for divalent systems both, electrostatic screening and divalent ion bridging must be considered.
Cation valency in water-in-salt electrolytes alters the short- and long-range structure of the electrical double layer
Highly concentrated aqueous electrolytes (termed water-in-salt electrolytes, WiSEs) at solid-liquid interfaces are ubiquitous in myriad applications including biological signaling, electrosynthesis, and energy storage. This interface, known as the electrical double layer (EDL), has a different structure in WiSEs than in dilute electrolytes. Here, we investigate how divalent salts [zinc bis(trifluoromethylsulfonyl)imide, Zn(TFSI) 2 ], as well as mixtures of mono- and divalent salts [lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) mixed with Zn(TFSI) 2 ], affect the short- and long-range structure of the EDL under confinement using a multimodal combination of scattering, spectroscopy, and surface forces measurements. Raman spectroscopy of bulk electrolytes suggests that the cation is closely associated with the anion regardless of valency. Wide-angle X-ray scattering reveals that all bulk electrolytes form ion clusters; however, the clusters are suppressed with increasing concentration of the divalent ion. To probe the EDL under confinement, we use a Surface Forces Apparatus and demonstrate that the thickness of the adsorbed layer of ions at the interface grows with increasing divalent ion concentration. Multiple interfacial layers form following this adlayer; their thicknesses appear dependent on anion size, rather than cation. Importantly, all electrolytes exhibit very long electrostatic decay lengths that are insensitive to valency. It is likely that in the WiSE regime, electrostatic screening is mediated by the formation of ion clusters rather than individual well-solvated ions. This work contributes to understanding the structure and charge-neutralization mechanism in this class of electrolytes and the interfacial behavior of mixed-electrolyte systems encountered in electrochemistry and biology.
The effect of ion pairing on speciation and transport in ion exchange membranes at varying hydration levels: A four-state model
Understanding ion pairing in ion exchange membranes (IEMs) is essential for advancing IEM applications in energy and environmental technologies. Here, this study introduces a four-state molecular dynamics model to quantify speciation and transport within Nafion-117, specifically examining the role of ion pairing in monovalent and divalent counterions (NaCl, Na 2 SO 4 , and MgSO 4 ). By analyzing radial distribution functions (RDFs) and molecular snapshots, we distinguish ion pairing modes and classify counterions into four states: condensed counterion, condensed ion pair, free ion pair, and free counterion. A key finding is that while divalent counterions (e. g., Mg 2+ ) maintain stable speciation across hydration levels, monovalent counterions (e.g., Na + ) show notable speciation shifts with hydration. Both monovalent and divalent counterions are not diffusive when condensed onto the polymer (sorbed to membrane functional groups). In contrast, free counterions are diffusive across all hydration levels. To evaluate the overall diffusivity of counterions, four-state fractions and diffusivities are computed, each contributing to counterion transport. The condensed/free ion speciation for multivalent sulfate salts aligns with previous revisions to the Donnan-Manning framework that include ion pairing, thereby validating its relevance to established membrane theories. The four-state model's diffusivity results support several current ion exchange assumptions, including that the condensed counterions are immobile, while uncondensed counterions are mobile. The four-state model offers insights into contact ion pairing within IEMs, highlighting its potential even when undetected in aqueous solution experiments. This work advances the theoretical understanding of counterion speciation in IEMs while identifying model limitations that suggest avenues for refinement, such as distinguishing water-mediated ion pairs between fully hydrated ions.
A Computational Assessment of Actinide Dioxide Cations AnO 2 2+ for An = U to Lr: The Limited Stability Range of the Hexavalent Actinyl Moiety, [O=An=O] 2+
The isolated gas-phase actinide dioxide dications, AnO 2 2+ , were evaluated by DFT and coupled cluster CCSD(T) calculations for 12 actinides, An = U–Lr. CASSCF calculations were used to define the orbitals for the CCSD(T) calculations. The characteristic linear [O$=$An$=$O] 2+ hexavalent actinyl(VI) was found to be the lowest energy structure for An = U, Np, and Pu, which also form stable actinyl(VI) species in solution and possibly for Am when spin–orbit effects are included. For Am, there is a divalent [An II (O 2 )] 2+ structure where the dioxygen is an end-on physisorbed η 1 - 3 O 2 2 kcal/mol above the actinyl when spin–orbit effects are included which lower the energy of the actinyl structure. For An = Cm, Bk, and Lr, the lowest energy structure is trivalent [An III (O 2 – )] 2+ where the dioxygen is a side-on superoxide, η 2 -O 2 – . For Cm, the actinyl is close in energy to the ground state when spin–orbit effects are included. For An = Cf, Es, Fm, Md, and No, the lowest energy structure is divalent [An II (O 2 )] 2+ where the dioxygen is an end-on physisorbed η 1 - 3 O 2 . The relative energies suggest that curyl(VI) and berkelyl(VI), like well-known americyl(VI), might be stabilized by coordinating ligands in condensed phases. The results further indicate that for californyl and beyond, the actinyl(VI) moieties will probably be elusive even using strong donor ligands. The prevalence of low oxidation states (OSs) An(II) and An(III) for transplutonium actinides reflects stabilization of the 5f orbitals and validates established trends, including the remarkably high stability of divalent No. Finally, bond distances and other parameters suggest maximum bond covalency around plutonyl(VI), with a particularly substantial decrease in bond strength between americyl(VI) and curyl(VI).
Impact of Ligands on the Ion–Ion Selectivity of Ligand-Appended-Pillar[ n ]arene Channels
Ligand-appended pillar[5]arene (LAP) channels are emerging as a promising platform for ion-selective membranes. In this study, we investigated the ion selectivities of three LAP channels functionalized with distinct ligands: diglycolamine, carbamoylmethyl phosphine oxide, and propionamide phosphonic acid. These ligands were chosen based on their demonstrated affinities for lanthanides in solvent extraction studies. We examined the selectivity of each channel toward a series of monovalent, divalent, and trivalent ions: Li + , Na + , K + , Mg 2+ , Ca 2+ , La 3+ , Eu 3+ , and Yb 3+ . To quantify ion-channel interactions and the energetics of translocation, we computed the potential of mean force (PMF) profiles for each ion. These PMFs were subsequently recast into permeability coefficients, enabling a direct evaluation of ion permselectivity. Our results reveal distinct selectivity patterns governed by the chemical nature of the appended ligands. The diglycolamine-functionalized channel exhibits strong interactions with monovalent ions, leading to replication of the Li + bulk hydration shell within the channel. This promotes preferential transport Li + ions while effectively excluding divalent and trivalent species. In contrast, the carbamoylmethyl phosphine oxide-functionalized channel displays a reduced selectivity between monovalent ions while similarly exhibiting an effective rejection of divalent and trivalent ions. This arises from steric hindrance around channel-lining oxygens imposed by the ligand's bulky phenyl groups which limits heavy ion coordination and promotes retention of hydration shells effectively increasing effective ion size. The propionamide phosphonic acid-functionalized channel exhibits a different trend, favoring ions with lower hydration free energies, with K + ions showing enhanced permeation. These findings highlight the critical role of ligand-ion interactions in modulating ion selectivity within LAP channels. In particular, the strong coordination exhibited by diglycolamine and propionamide phosphonic acid ligands significantly influences the ion transport energetics and selectivity profiles.
Factors Influencing Preferential Anion Interactions during Solvation of Multivalent Cations in Ethereal Solvents
Most multivalent secondary batteries have employed electrolytes composed of cyclic ether solvents such as tetrahydrofuran or linear glycol ether solvents (glymes) such as 1,2-dimethoxyethane (G1). A robust understanding of multivalent cation solvation tendencies in these classes of solvents provides insight into corresponding structure–property relationships which, in turn, promotes the design and discovery of improved electrolytes. In this work, our goal is to systematically address how electrolyte constituent properties, namely, ether solvent structure and dication size, direct the solvation interactions of divalent electrolytes and their resultant properties. This study utilizes pulsed-field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy in conjunction with Raman spectroscopy and ionic conductivity measurements to elucidate the preferential interactions between multivalent cations, anions, and solvent molecules along with their correlated ion dynamics. These investigations incorporate two representative divalent cations (Ca 2+ and Zn 2+ ) as well as two ethereal solvent representatives from both the cyclic ether and glyme structural classes. The results reveal that anions coordinate more readily with divalent cations in cyclic ethers than in glymes. Furthermore, the coordination of the anions with Ca 2+ , i.e., contact-ion pair (CIP) formation is more pronounced than with Zn 2+ in a glyme solvent of limited chain length (G1), providing insight into cation size effects that are important for translating solvation behavior across various multivalent electrolytes. Importantly, we find that specific anion coordination is more strongly controlled by solvent structure than by salt concentration in the practical range of 0.1–0.5 M. However, simply reducing these inner-sphere inter-ionic interactions by changing solvent structure does not necessarily de-correlate ionic motion. Instead, concentration-dependent changes in molar ionic conductivity suggest that second-shell interactions, i.e., solvent separated ion pairs (SSIPs), are prevalent in these electrolytes and that the solution dielectric constant, which is increased by the presence of dipolar ion pairs, is critical for controlling these interactions. These findings thus provide a basis for understanding the physical chemistry of multivalent battery electrolytes.
Relativistic Douglas–Kroll–Hess calculations of hyperfine interactions within first-principles multireference methods
A relativistic magnetic hyperfine interaction Hamiltonian based on the Douglas–Kroll–Hess (DKH) theory up to the second order is implemented within the ab initio multireference methods, including spin–orbit coupling in the Molcas/OpenMolcas package. This implementation is applied to calculate relativistic hyperfine coupling (HFC) parameters for atomic systems and diatomic radicals with valence s or d orbitals by systematically varying active space size in the restricted active space self-consistent field formalism with restricted active space state interaction for spin–orbit coupling. The DKH relativistic treatment of the hyperfine interaction reduces the Fermi contact contribution to the HFC due to the presence of kinetic factors that regularize the singularity of the Dirac delta function in the nonrelativistic Fermi contact operator. This effect is more prominent for heavier nuclei. As the active space size increases, the relativistic correction of the Fermi contact contribution converges well to the experimental data for light and moderately heavy nuclei. The relativistic correction, however, does not significantly affect the spin-dipole contribution to the hyperfine interaction. In addition to the atomic and molecular systems, the implementation is applied to calculate the relativistic HFC parameters for large trivalent and divalent Tb-based single-molecule magnets (SMMs), such as Tb(III)Pc2 and Tb(II)(CpiPr5)2 without ligand truncation using well-converged basis sets. In particular, for the divalent SMM, which has an unpaired valence 6s/5d hybrid orbital, the relativistic treatment of HFC is crucial for a proper description of the Fermi contact contribution. Even with the relativistic hyperfine Hamiltonian, the divalent SMM is shown to exhibit strong tunability of HFC via an external electric field (i.e., strong hyperfine Stark effect).