Deciphering the structure and potassium-ion transport mechanism of potassium borate glass.

Potassium borate glass has great potential as an ion transport material. The ion transport rate is closely related to the microstructure of the glass. However, the disorder and variations in boron and oxygen atom types in the glass structure pose challenges in the analysis of this complex glass structure. In this work, the structure of potassium borate glass was unveiled through the neutron diffraction method and ab initio molecular dynamics (AIMD) simulations. The B-O, K-O, and O-O atomic interactions, bond lengths, coordination numbers, cavity distribution, ring structure distributions and other detailed information in the microstructure of potassium borate glass were obtained. By comparing the structure and properties of potassium borate glass with those of crystals of similar components, it is found that the bond lengths of 3B-BO (BO, bridging oxygen), 4B-BO and 3B-NBO (NBO, non-bridging oxygen) are longer than those of corresponding crystals, so the structure of the boron-oxygen network is looser and the density is smaller than that of similar crystals. Moreover, we found a rule that in both borate glass and crystal, the increase of NBO shortened the length of the B-O bond, and the increase of 4B increased the length of the B-O bond. The key structures affecting the transport rate of K+ were NBO, chain structure units and cavities. This work will provide reference data for designing and developing electrically conductive amorphous materials with faster potassium-ion transport rates.

Hydrolysis mechanism of the cyclohexaborate anion: Unraveling the intricacies.

B 6 O 7 OH 6 2 - is a highly polymerized borate anion of three six-membered rings. Limited research on the B 6 O 7 OH 6 2 - hydrolysis mechanism under neutral solution conditions exists. Calculations based on density functional theory show that B 6 O 7 OH 6 2 - undergoes five steps of hydrolysis to form H3BO3 and B OH 4 - . At the same time, there are a small number of borate ions with different degrees of polymerization during the hydrolysis process, such as triborate, tetraborate, and pentaborate anions. The structure of the borate anion and the coordination environment of the bridging oxygen atoms control the hydrolysis process. Finally, this work explains that in existing experimental studies, the reason for the low B 6 O 7 OH 6 2 - content in solution environments with low total boron concentrations is that it depolymerizes into other types of borate ions and clarifies the borate species. The conversion relationship provides a basis for identifying the possibility of various borate ions existing in the solution. This work also provides a certain degree of theoretical support for the cause of the "dilution to salt" phenomenon.

Alkali Metal Ion Recognition by 18-Crown-6 in Aqueous Solutions: Evidence from Local Structures.

The underlying recognition mechanisms of alkali metal ions by crown ethers in aqueous solutions are yet to be fully understood at the molecular level. We report direct experimental and theoretical evidence for the structure and recognition sequence of alkali metal ions (Li+, Na+, K+, Rb+, and Cs+) by 18-crown-6 in aqueous solutions by wide-angle X-ray scattering combined with an empirical potential structure refinement modeling and ab initio molecular dynamics simulation. Li+, Na+, and K+ are located in the negative potential cavity of 18-crown-6, with Li+ and Na+ deviating from the centroid of 18-crown-6 by 0.95 and 0.35 Å, respectively. Rb+ and Cs+ lie outside the 18-crown-6 ring and deviate from the centroid of 18-crown-6 by 0.05 and 1.35 Å, respectively. The formation of the 18-crown-6/alkali metal ion complexes is dominated by electrostatic attraction between the cations and the oxygen atoms (Oc) of 18-crown-6. Li+, Na+, K+, and Rb+ form the H2O···18-crown-6/cation···H2O "sandwich" hydrates, while water molecules only hydrate with Cs+ of the 18-crown-6/Cs+ complex on the same side of Cs+. Based on the local structure, the recognition sequence of 18-crown-6 for alkali metal ions in an aqueous solution follows K+ > Rb+ >Na+ >Li+, which is completely different from that (Li+ > Na+ > K+ > Rb+ > Cs+) in the gas phase, confirming that the solvation medium seriously affects the cation recognition of crown ethers. This work provides atomic insights into understanding the host-guest recognition and solvation behavior of crown ether/cation complexes.

Structural analysis of potassium borate solutions.

In this work, H/D isotopic substitution neutron diffraction was combined with empirical potential structure refinement (EPSR) and DFT-based quantum calculations to study the interactions between B(OH)3 boric acid molecules, B(OH)4- metaborate ions, water molecules, and potassium cations in borate solutions. The results show that the solute ions and molecules have a marked effect on the second coordination shell of the water molecules, causing a greater deviation from a tetrahedral structure than is observed for pure water. Potassium ions and trans-B(OH)3 tend to form a monodentate contact ion pair (MCIP) with a K-B distance ∼3.8 Å, which remains constant upon changing the solution concentration. Potassium ions and cis-B(OH)3 form both a MCIP at K-B ∼3.8 Å and a bidentate contact ion pair (BCIP) at K-B ∼3.4 Å. As the solution concentration increases, there is a BCIP to MCIP transformation. Boric acid molecules can undergo hydration in one of three ways: direct hydration, interstitial hydration, and axial hydration. The energetic hydration preference is direct hydration → interstitial hydration → axial hydration. Nine water molecules are required when all water molecules directly interact with the -OH groups of B(OH)4-, and a tenth water molecule is located at an interstitial position. The hydrogen bonding between boric acid molecule/metaborate ion and water molecules is stronger than that between water molecules in the hydration layer.

Structure of choline chloride-carboxylic acid deep eutectic solvents by wide-angle X-ray scattering and DFT calculations.

Choline chloride (ChCl)-carboxylic acid deep eutectic solvents (DESs) are promising green solvents for lignocellulose pretreatment, de-aromatization of gasoline, battery recycling, etc. Micro interactions determine the physical properties of DESs, such as melting point, viscosity, and solubility. In the present work, the structures of choline chloride/formic acid (FA) and choline chloride/acetic acid (AA) with a 1 : 2 molar ratio were investigated by wide-angle X-ray scattering, empirical potential structure refinement (EPSR) and density functional theory (DFT) calculations. Reduced density gradient (RDG) and atoms in molecules (AIM) show that hydrogen bonds and carbon-hydrogen bonds exist in choline chloride-carboxylic acid DESs. EPSR modelling based on the gauche choline cation model reveals the interactions between DES components. Cl- plays an important role in maintaining the structural stability of choline chloride-carboxylic acid DESs, by participating in the formation of hydrogen bonds, carbon-hydrogen bonds, and acting as a bridge for indirect interaction, including between choline cations and carboxylic acid molecules. Molecular size and steric hindrance elucidate the formation of different sizes of clusters (≤10 molecules) and chains (≤5 molecules) in DESs. Spatial density functions show that formic acid and acetic acid have a strong orientational preference. The strong interaction between Ch+ and FA and the existence of the Cl- bridge significantly destroyed the lattice structure of ChCl, resulting in the melting point of ChClFA (<-90 °C) being lower than that of ChClAA (-8.98 °C). This fundamental understanding of the structure will enable the development of green, economical, and nontoxic choline chloride-carboxylic acid DESs.

The hydration of Li+ and Mg2+ in subnano carbon nanotubes using a multiscale theoretical approach.

The separation of brines with high Mg/Li mass ratios is a huge challenge. To provide a theoretical basis for the design of separation materials, the hydration of Li+ and Mg2+ in confinement using carbon nanotubes (CNTs) as the 1-D nanopore model was investigated using a multiscale theoretical approach. According to the analysis of the first coordination layer of cations, we determined that the coordination shells of two cations exist inside CNTs, while the second coordination shells of the cations are unstable. Moreover, the results of the structure analysis indicate that the hydration layer of Li+ is not complete in CNTs with diameters of 0.73, 0.87, and 1.00 nm. However, this does not occur in the 0.60 nm CNT, which is explained by the formation of contact ion pairs (CIP) between Li+ and Cl- that go through a unstable solvent-shared ion pair [Li(H2O)4]+, and this research was further extended by 400 ns in the 0.60 nm CNT to address the aforementioned results. However, the hydration layer of Mg2+ is complete and not sensitive to the diameter of CNTs using molecular dynamics simulation and an ab initio molecular dynamics (AIMD) method. Furthermore, the results of the orientation distribution of Li+ and Mg2+ indicate that the water molecules around Mg2+ are more ordered than water molecules around Li+ in the CNTs and are more analogous to the bulk solution. We conclude that it is energetically unfavorable to confine Li+ inside the 0.60-nm diameter CNT, while it is favorable for confining Li+ inside the other four CNTs and Mg2+ in all CNTs, which is driven by the strong electrostatic interaction between cations and Cl-. In addition, the interaction between cations and water molecules in the five CNTs was also analyzed from the non-covalent interaction (NCI) perspective by AIMD.

Study on ionic association behavior in sodium nitrate solution.

Raman spectroscopy combined with component analysis and molecular dynamics simulation were used to study chemical species and their transformation in aqueous sodium solutions. Study shows that the characteristic vibrational frequency of nitrate ions (ν1-NO3-) blue-shifted from 1043.9 to 1046.9 cm-1, and the full width at half maximum increased from 6.8 to 10.8 cm-1 as the concentration increasing. When water/salt molar ratio (WSR) > 30, the relative concentration (RC) of free hydrated ions and solvent shared ion pair accounts for the vast majority, and there is almost no contact ion pair in solution. When WSR less than 30, due to the continuous reduction of the number of water molecules, the hydrated water molecules around the sodium ions and nitrate ions begin to decrease, and solvent shared ion pair or contact ion pair gradually forms. Sodium ions and nitrate ions mainly exist in a monodentate coordination. When WSR > 160, both the relative concentration of contact ion pair and complex structure is close to 0. This work proves that a lower RC of complex structure in solution, a smaller supersaturation of the solution is achieved, meaning aqueous sodium nitrate solution is easier to nucleate crystals.

Unveiling the structure of aqueous magnesium nitrate solutions by combining X-ray diffraction and theoretical calculations.

The structure of aqueous magnesium nitrate solution is gaining significant interest among researchers, especially whether contact ion pairs exist in concentrated solutions. Here, combining X-ray diffraction experiments, quantum chemical calculations and ab initio molecular dynamics simulations, we report that the [Mg(NO3)2] molecular structure in solution from the coexistence of a free [Mg(H2O)6]2+ octahedral supramolecular structure with a free [NO3(H2O)n]- (n = 11-13) supramolecular structure to an [Mg2+(H2O)n(NO3-)m] (n = 3, 4, 5; m = 3, 2, 1) associated structure with increasing concentration. Interestingly, two hydration modes of NO3--the nearest neighbor hydration with a hydration distance less than 3.9 Å and the next nearest neighbor hydration with hydration distance ranging from 3.9 to 4.3 Å-were distinguished. With an increase in the solution concentration, the hydrated NO3- ions lost outer layer water molecules, and the hexagonal octahedral hydration structure of [Mg(H2O)62+] was destroyed, resulting in direct contact between Mg2+ and NO3- ions in a monodentate way. As the concentration of the solution further increased, NO3- ions replaced water molecules in the hydration layer of Mg2+ to form three-ion clusters and even more complex chains or linear ion clusters.

Structure of Aqueous KNO3 Solutions by Wide-Angle X-ray Scattering and Density Functional Theory.

The structure of aqueous KNO3 solutions was studied by wide-angle X-ray scattering (WAXS) and density functional theory (DFT). The interference functions were subjected to empirical potential structure refinement (EPSR) modeling to extract the detailed hydration structure information. In aqueous KNO3 solutions with a concentration from 0.50 to 2.72 mol·dm-3, water molecules coordinate K+ with a mean coordination number (CN) from 6.6 ± 0.9 to 5.8 ± 1.2, respectively, and a K-OW(H2O) distance of 2.82 Å. To further describe the hydration properties of K+, a hydration factor (fh) was defined based on the orientational angle between the water O-H vector and the ion-oxygen vector. The fh value obtained for K+ is 0.792, 0.787, 0.766, and 0.765, and the corresponding average hydration numbers (HN) are 5.2, 5.1, 4.8, and 4.5. The reduced HN is compensated by the direct binding of oxygen atoms of NO3- with the average CN from 0.3 ± 0.7 to 2.6 ± 1.7, respectively, and the K-ON(NO3-) distance of 2.82 Å. The average number of water molecules around NO3- slightly reduces from 10.5 ± 1.5 to 9.6 ± 1.7 with rN-OW = 3.63 Å. K+-NO3- ion association is characterized by K-ON and K-N pair correlation functions (PCFs). A K-N peak is observed at 3.81 Å as the main peak with a shoulder at 3.42 Å in gK-N(r). This finding indicates that two occupancy sites are available for K+, i.e., the edge-shared bidentate (BCIP) and the corner-shared monodentate (MCIP) contact ion pairs. The structure and stability of the KNO3(H2O)10 cluster were investigated by a DFT method and cross-checked with the results from WAXS.

Structure analysis of aqueous Mg(NO3)2 solutions.

An increasing amount of research has investigated whether direct contact ion pairs (CIP) exist in magnesium nitrate solutions. In this work, the relationship between the concentration and microstructure, as well as the details of the ion pair structure in magnesium nitrate solutions were studied by Raman spectroscopy, molecular dynamics (MD) simulations, and density functional theory (DFT) calculations. Component analysis showed that solvent-shared ion pairs (SIPs) and free hydrated ions were the dominant species in dilute solution. SIPs gradually transformed into contact ion pairs as the concentration increased. Complex structures and CIPs were the main species when WSR < 10, and as the concentration further increased, the CIP content gradually decreased, while the number of complex structures gradually increased. MD simulations and DFT calculations provide a new understanding of the structural units of ion pairs in magnesium nitrate solutions. The SIPs and CIPs were mainly composed of cationic triple ion clusters with two magnesium ions and one nitrate ion. The nitrate ion mainly existed as monodentate ligand to form a CIP with the magnesium ion. As the solution concentration increased, triple ion clusters gradually transformed into more complex chain structures. The structural complexity of magnesium nitrate solutions deserves further attention.

The structural elucidation of aqueous H3BO3 solutions by DFT and neutron scattering studies.

The micro-structure of aqueous boric acid (H3BO3) solutions is of broad interest in earth sciences, geochemistry, material science, as well as chemical engineering. In the present study, the structure of aqueous H3BO3 solutions was studied via neutron scattering with 2H and 11B isotope labelling combined with empirical potential structure refinement (EPSR) modelling. In aqueous H3BO3 solutions, B(OH)3 is the dominant borate species. Density function theory (DFT) calculations show that the boron hydroxyl has a lower electrostatic potential (ESP), which makes B(OH)3 a relatively weakly hydrated, compared with the bulk water. In the 0.95 mol L-1 H3BO3 solution at 298 K (saturated), ∼18 water molecules enter the hydration sphere of B(OH)3 with the hydration distance (B-O(W)) of 3.75 Å, while only 4.23 of them hydrate with H3BO3 as the hydrogen bond (H-bond) acceptor or H-bond donor. Both neutron scattering and DFT calculations for 2B(OH)3·6H2O clusters at the ωB97XD/6-311++g(3df,3pd) basis level show that B(OH)3 forms molecular clusters in bidentate contact molecular pairs (BCMP), mono-dentate molecular pairs (MCMP), solvent-shared molecular pairs (SMP), and parallel solvent-shared molecular pairs (PSMP) in aqueous solutions. Their relative contents are both concentration- and temperature-sensitive. BCMP with the B-B distance of ∼4.1 Å is the dominant molecular pair in the aqueous solutions. Relatively less content and van der Waals interactions stabilized PSMP, with a B-B distance of ∼3.6 Å between the two parallel layers, which is a crucial species for the crystallization of H3BO3 from aqueous solution.

Dihydrogen Bonds in Aqueous NaBD4 Solution by Neutron and X-ray Diffraction.

Neutron diffraction, X-ray diffraction, and empirical potential structure refinement modeling were employed to study the structure of alkaline aqueous NaBD4 solutions at different NaBD4 concentrations and temperatures. In 1.0 mol·dm-3 NaBD4 aqueous solutions, about 5.6 ± 1.6 water molecules bond to BD4- via tetrahedral edges or tetrahedral corners without a very specific hydration geometry; that is, each hydrogen atom of BD4- bonds to 2.2 ± 1.0 water molecules through dihydrogen bonds with the D(B)···D(W) distance of 1.95 Å. The number of dihydrogen bonds decreases with increasing concentration and increases with temperature. Dihydrogen bonding is a predominantly electrostatic interaction which shows relatively lower directionality and saturability in comparison with the regular hydrogen bonds between water molecules. The water orientation around BD4- shows that the proportion of tetrahedral-edge dihydrogen bonds increases with temperature and decreases with concentration.

Ion hydration and association in aqueous potassium tetrahydroxyborate solutions.

Potassium tetrahydroxyborate solution is a significant material in the borate solution family, but there is limited knowledge about hydration structures and interactions of K+, [B(OH)4-], and water. In this study, the X-ray diffraction measurements of potassium tetrahydroxyborate solutions have been made. The experimental structure factors are subjected to Empirical Potential Structure Refinement (EPSR) modeling to reveal the details of ion hydration and association in the aqueous solutions. This study shows that the O(W)-O(W) distance of water in the studied solutions ranges from 2.82 to 2.76 Å with a coordination number that ranges from 4.7 ± 1.4 to 3.1 ± 1.3 when the value of the water-salt molar ratio (WSR) is decreased from 30 to 6. The addition of ions slightly affects the tetrahedral structure of water even when the concentration of ions is high. The first hydration distance of K+ remained at ∼2.67 Å, whereas the value of the coordination number (CN) decreased from 5.4 ± 1.3 to 3.9 ± 1.5 when the concentration of the borate solution was increased. The hydration ability of K+ was weak and almost did not have a fixed local hydration structure. The pair distribution function (PDF) of gB-O(W)(r) shows that [B(OH)4-] has a broad hydration distance from 2.9 to 5.4 Å because of the complex interactive relationship between K+, [B(OH)4-] and water. There is a competitive hydration between K+ and [B(OH)4-]. Both the X-ray diffraction and DFT-based calculations confirm that the main species is monodentate contact ion pairs when WSR = 30, bidentate contact ion pairs when WSR = 14, and triple contact ion pairs when WSR = 6. These results will provide a new understanding about potassium tetrahydroxyborate solution.

Raman and ab initio analyses of ion pairs in concentrated K[B(OH)4] droplets.

In this study, microscopic Raman spectroscopy and Ab initio quantum chemical calculation were used to determine the structural details of ion pairs and their transformation in concentrated K[B(OH)4] droplets. The Raman experiment shows that the vsym-B(OH)4- undergoes a downward shift with the decrease of WSR. The contact ion pairs (CIPs) change to solvent shared ion pairs when the molar water-to-solute ratio (WSR) is bigger than 6; CIPs are the dominant species when 1.33 < WSR < 6, where K+ bonds to [B(OH)4-] in bidentate form (CIP-II); the CIPs quickly dehydrate and associate to triple ion pairs (TIPs) when WSR < 5. Raman experiment and ab initio quantum chemical calculation show that TIPs are mainly present in "anionic" type such as {[B(OH)4-]K+[B(OH)4-](H2O)n}, where K+ bonds to two [B(OH)4-] in bidentate or/and tridentate form (TIP-a-II or/and TIP-a-III). When WSR <1.33, most TIPs convert to complex clusters such as chain-like structure. The remaining TIPs associate to six-membered ring structure [B3O3(OH)4-] and the relative content increases from 0 to 20% when the WSR ranges from 1.33 to 0.55.

Micro-Raman and density functional theory analyses of ion pairs in concentrated sodium tetrahydroxyborate droplets.

In this study, ion pairs in a single sodium tetrahydroxyborate [Na [B(OH)4] droplet were analyzed using an "in-situ strategy" in which a sample-droplet of nanogram mass was deposited on a hydrophobic substrate and droplet was forced to enter into a supersaturated state by decreasing the relative humidity (RH) of the environment. The structure of the solvated [B(OH)4-] ionic moiety with various molar water-to-solute ratios (WSR) was analyzed using Raman spectroscopy. To confirm the structural changes in the droplet, electronic structure calculations were carried out using density functional theory (DFT). The frequencies calculated for the totally symmetric BO stretching vibration (vsym(BO)) of the [B(OH)4-] moiety were compared with those of the fundamental bands observed in the Raman spectra recorded of the droplets. The following results have been obtained: (i) when WSR is reduced from 9 to 0.1, the frequency of the band that corresponds to vsym(BO) shifts from 745 to 746 cm-1, and its full-width at half-maximum value increases from 19.7 to 20.5 cm-1; (ii) when WSR ≥7, the solvent-shared ion pair (SIP) is predominantly present in the solution, whereas in the case of WSR < 7, SIP transforms into a contact ion pair (CIP) formed by Na+ and [B(OH)4-] in bidentate coordination; (iii) when WSR = 3, most of the CIPs transform into a cationic type of triple ion pair (TIP) composed of two Na+ and one [B(OH)4-] in bidentate coordination; (iv) when WSR is further reduced, most TIP continually associate to form a more complex structure and with a small amount of six-membered ring complex also formed. These results will help us understand the ion association mechanism during dehydration process of Na[B(OH)4] droplets.

Ab-initio investigation on ion-associated species and association process in Li[B(OH)4] solution.

In this paper, the factors determining the spectroscopic characteristics of vsym-B(OH)4- band including coupling effect, hydrogen bonding effect, and direct contact effect in Li[B(OH)4] solutions are investigated by using ab initio calculation. The coupling effect between the liberations of water and [B(OH)4-] has a larger effect on vsym-B(OH)4- in solvent-shared ion pair (SIP) and monodentate contact ion pair (MCIP), but the smaller effect in bidentate contact ion pair (BCIP). Water molecule tends to hydrate to the middle position between the first sphere of B(OH)4- and outer-sphere of [Li(H2O)4+] and has a different effect on vsym-B(OH)4- in ion pairs. The direct contact effect and polarization effect lead to 19.7 cm-1 red shift of vsym-B(OH)4- in MCIP, and 0.4 cm-1 blue shift in BCIP. The association process in Li[B(OH)4] solution was also introduced by using Raman spectral evolution of vsym -B(OH)4- in the dehydration process.

Solution structure of energy stored system I: aqua-B(OH)4(-): a DFT, Car-Parrinello molecular dynamics, and Raman study.

A systematic study on the structure, stability, and Raman spectra of the metaborate anion hydrated clusters, B(OH)4(-)(H2O)n, (n = 1-15) was carried out by DFT in both gaseous and aqueous phase at the B3LYP/aug-cc-pVDZ level; all of these stable configurations were described, and the most stable hydrated clusters were chosen. The hydrogen bonds in those hydrated clusters were described in three different items: symmetrical double hydrogen bonding (DHB), single hydrogen bonding (SHB), and interwater hydrogen bonding (WHB). The distance of SHB is shorter than that of DHB, and multiple SHBs are more stable than a single DHB. In small size clusters (n ≤ 5), a structure with more DHBs is more stable than other arrangements. With continued increase in size, more SHBs were found in the first hydration sphere: when n ≥ 9, only SHBs can be found, and when n ≥ 12, a full hydration structure is formed with 12 SHBs and a hydration number of 10-12. The Car-Parrinello molecular dynamics simulation shows that only the first hydration sphere can be found, and the hydration number of B(OH)4(-) is 9.2 and the hydration distance is 3.68. The total symmetrical stretching vibration of B(OH)4(-) in hydrated B(OH)4(-)(H2O)n is blue shifted with increasing cluster size. After consideration of hydration, the calculated characteristic frequencies are in accord with the experiment characteristic frequency of B(OH)4(-).

Polyborates in aqueous borate solution: a Raman and DFT theory investigation.

The geometries, energies and vibrational frequencies of various polyborates in both gaseous and aqueous phase were calculated at the B3LYP/aug-cc-pVDZ level. The calculated total symmetrical stretching Raman shifts of B(OH)(3), B(OH)(4)(-), B(2)O(OH)(4), B(2)O(OH)(5)(-), B(2)O(OH)(6)(2-), B(3)O(3)(OH)(3), B(3)O(3)(OH)(4)(-), B(3)O(3)(OH)(5)(2-), B(3)O(3)(OH)(6)(3-), B(4)O(5)(OH)(4)(2-) and B(5)O(6)(OH)(4)(-) were assigned to 877.40, 735.33, 785.22, 792.90, 696.79, 587.72, 599.06, 740.16, 705.01, 551.67 and 521.04cm(-1), respectively. The results can be used as the characteristic frequency for polyborates in aqueous phase at room temperature. At least six types of polyborates B(OH)(3), B(OH)(4)(-), B(3)O(3)(OH)(4)(-), B(3)O(3)(OH)(5)(2-), B(4)O(5)(OH)(4)(2-) and B(5)O(6)(OH)(4)(-), occur in aqueous solutions at ambient temperature. The chemical species distribution and the relevant interaction mechanisms among polyborates in the solutions were also suggested.