Alkali Earth Metal Cations Research Articles

Pb2TeV2O10: A Lead Vanadate Tellurate with Wide Mid-IR Transparency and Large Birefringence Induced by Multiple Birefringence-Active Groups.

Birefringent materials as the key materials in laser science and technology have attracted continuous attention due to their ability to modulate polarized light. Herein, a new lead vanadate tellurate, Pb2TeV2O10, has been synthesized through the rational integration of different kinds of birefringence-active functional units. Pb2TeV2O10 features a unique two-dimensional (2D) [TeV2O10]∞ layered structure consisting of [VO6]7- and [TeO6]6- octahedra, and Pb2+ cations reside between the [TeV2O10]∞ layers. In addition, the rare edge-sharing mode of [VO6]7- and [TeO6]6- octahedra was found in this structure. Attributed to the high polarizability and appropriate arrangement of PbO8, VO6, and TeO6 units, Pb2TeV2O10 possesses a great theoretical birefringence of 0.275 at 532 nm, which is the largest among the vanadate tellurate family. The spectral tests also prove that Pb2TeV2O10 showcases a broad transparency window (439 nm-10 μm), covering an important mid-infrared (IR) atmospheric window (3-5 μm). In addition, in order to improve the transparency, alkali and alkaline earth metal cations were introduced by the substitution strategy, and then the compound K2Sr2Te2O9 was synthesized. It owns a shorter ultraviolet (UV) cutoff edge of 234 nm and a wider transparency window (234 nm-13.8 μm). The findings of Pb2TeV2O10 and K2Sr2Te2O9 enrich the structure chemistry of the tellurate family and provide new insights for designing new compounds with large optical anisotropy and wide spectral transparency.

Separation of CO2/N2 in Ion-Exchange binder-free beads of zeolite NaY for Post-Combustion CO2 capture

Ion-exchange on bare commercial zeolites can offer improved adsorption processes. In the context of CO2/N2 separation for post-combustion CO2 capture (PCC), here, we report, the effect of ion-exchange on commercial binder-free NaY zeolite with alkali (K+) and alkaline earth (Ca2+) metal cations, achieving exchange levels of 23 %, 58 %, and 95 % for K+ and 56 % and 71 % for Ca2+. Adsorption isotherms of CO2 and N2 were measured over a temperature range of 306–344 K and pressures up to 350 kPa. At low pressures, the CO2 adsorption capacity increases as Na+ ions are exchanged to a higher level of K+, while a reverse trend is observed for Ca2+ exchange. At 25 kPa and 306 K, the CO2 loading (mol∙kg−1) follows the order 2.01-Ca(71)Y < 2.63-Ca(56)Y < 4.05-NaY < 4.29-K(23)Y < 4.59-K(58)Y < 4.72-K(95)Y. The selectivities of CO2 (15 %)/N2 (85 %) at 306 K and 101.3 kPa range from 52 for Ca(71)Y to 101 for K(23)Y, compared to 89 in the bare NaY zeolite. The working capacities for the most promising exchanged sample (K(23)Y) exhibit superior values of 4.51, 2.98, and 2.41 mol∙kg−1 considering regeneration pressures of 3, 10, and 15 kPa, relative to a feed pressure of 101.3 kPa, respectively. Dynamic simulations were conducted using the Aspen Adsorption package to accurately predict both single- and binary-component breakthrough curves.

Regulation of acid/basic properties of Zr-Beta zeolite for efficient conversion of furfural to furfuryl alcohol

Zr-Beta zeolites with different acid/basic properties were prepared by hydrothermal and post-synthesis methods and subsequent alkaline treatment. The acid/basic properties of Zr-Beta zeolites were characterized by FT-IR spectra of hydroxyl region and probe molecule adsorption (CD3CN, pyridine and CHCl3). The effects of the acid/basic properties of Zr-Beta zeolites on the conversion of furfural (FUR) to furfuryl alcohol (FAL) via Meerwein-Ponndorf-Verley reduction were investigated and discussed. The results indicate that both Brønsted acid sites, including strong and weak Brønsted acid sites, and Lewis acid sites are effective for conversion of FUR, but high yield of FAL can only be obtained over Zr-Beta with sole Lewis acid sites of framework Zr due to the further conversion of FAL to furfuryl ether, angelica lactone and levulinate ester over Brønsted acid sites. Therefore, Al-free Zr-Beta(h) synthesized in fluoride media is more active and selective than the post-synthesized counterpart. Alkali (earth) metal cations modified Zr-Beta(h) can further eliminate weak Brønsted acid sites of silanols and at the same time generate basic sites. Thus, the activity and selectivity of Zr-Beta(h) are further enhanced. 99.5 % of FAL yield was obtained over Na-Zr-Beta(h) with 99.8 % of FUR conversion at 120 °C for 4 h.

Molecular geochemistry of radium: A key to understanding cation adsorption reaction on clay minerals

Adsorption reactions of various cations on clay minerals have different effects on their environmental behaviors depending on the molecular-scale adsorption structure. Some cations form outer-sphere complexes via hydration, while others create inner-sphere complexes through dehydration. This preference dictates their environmental impact. However, the factors controlling these complex formations remain unclear. Furthermore, research on the adsorption preferences of radium (Ra) is lacking. Thus, this study conducted the first EXAFS study of Ra2+ adsorbed on clay minerals and showed that Ra2+ forms inner-sphere complexes on vermiculite, which can be surprising because Ra2+ is a divalent cation and prefers to be hydrated. In order to investigate the factors controlling the complex formations, this study conducted systematic EXAFS measurements and DFT calculations for alkali and alkaline earth metal cations. The results showed the importance of the size-matching effect between the adsorbed cation and the cavity of the tetrahedral sheets and that the complex formation can be estimated by the combination of the ionic radius and hydration enthalpy of the adsorbed cation. Furthermore, this study also analyzed environmental core samples. Their results showed the fixation of Ra2+ by clay minerals and the controlling factors can effectively predict cation environmental behavior.

Common Cations Are Not Polarizable: Effects of Dispersion Correction on Hydration Structures from Ab Initio Molecular Dynamics.

We employed density functional theory-based ab initio molecular dynamics simulations to examine the hydration structure of several common alkali and alkali earth metal cations. We found that the commonly used atom pairwise dispersion correction scheme D3, which assigns dispersion coefficients based on the neutral form of the atom rather than its actual oxidation state, leads to inaccuracies in the hydration structures of these cations. We evaluated this effect for lithium, sodium, potassium, and calcium and found that the inaccuracies are particularly pronounced for sodium and potassium compared to the experiment. To remedy this issue, we propose disabling the D3 correction specifically for all cation-including pairs, which leads to a much better agreement with experimental data.

ЭЛЕКТРОХИМИЧЕСКОЕ ПОВЕДЕНИЕ ТИТАНА В ХЛОРИДНО-ФТОРИДНЫХ РАСПЛАВАХ РАЗЛИЧНОГО СОСТАВА В ПРИСУТСТВИИ КАТИОНОВ ЩЕЛОЧНОЗЕМЕЛЬНЫХ МЕТАЛЛОВ

The electrochemical behavior of titanium and the influence of alkali earth metal cations (Mg2+, Ca2+, Sr2+ and Ва2+) on the charge transfer kinetics of the Ti(IV)/Ti(III) redox couple were studied by cyclic voltammetry method in chloride-fluoride melts of different composition. Standard rate constants of charge transfer and the activation energies of the charge transfer process were calculated.

Design and Synthesis of Covalently Tethered "IsoG-Star" as Recyclable Host for Selective Cesium Separation.

The isoguanosine self-assembled pentamer (isoG-star) has exhibited remarkable selectivity for Cs+ binding over competing alkali and alkali earth metal cation, rendering it a promising extractor for radioactive waste 137Cs separation. However, to make isoG-star a pracrtical material for Cs+ isolation, the development of recyclable isoG-star material is required. In this study, a systematic screening of functional isoG derivatives was performed. By employing well-defined complex formation and post-assembly modification, a covalently tethered isoG5-star was prepared through olefin metathesis, utilizing a designed isoG monomer. The application of this newly developed covalently linked isoG-star enabled selective Cs+ extraction, followed by controled solvent-induced H-bond dessociation. This resulted in the creation of a recyclable Cs+ extractor, demonstrating excellent cation selectivity and good reusability (over seven cycles) the first time. Consequently, this new supramolecular macrocycle offers a practical new platform for the treatment of radiocesium (134Cs and 137Cs) in an environmentally friendly and highly effective manner.

Adsorption of the hydrophobic organic pollutant hexachlorobenzene to phyllosilicate minerals

Hexachlorobenzene (HCB), a representative of hydrophobic organic chemicals (HOC), belongs to the group of persistent organic pollutants (POPs) that can have harmful effects on humans and other biota. Sorption processes in soils and sediments largely determine the fate of HCB and the risks arising from the compound in the environment. In this context, especially HOC–organic matter interactions are intensively studied, whereas knowledge of HOC adsorption to mineral phases (e.g., clay minerals) is comparatively limited. In this work, we performed batch adsorption experiments of HCB on a set of twelve phyllosilicate mineral sorbents that comprised several smectites, kaolinite, hectorite, chlorite, vermiculite, and illite. The effect of charge and size of exchangeable cations on HCB adsorption was studied using the source clay montmorillonite STx-1b after treatment with nine types of alkali (M+: Li, K, Na, Rb, Cs) and alkaline earth metal cations (M2+: Mg, Ca, Sr, Ba). Molecular modeling simulations based on density functional theory (DFT) calculations to reveal the effect of different cations on the adsorption energy in a selected HCB-clay mineral system accompanied this study. Results for HCB adsorption to minerals showed a large variation of solid–liquid adsorption constants Kd over four orders of magnitude (log Kd 0.9–3.3). Experiments with cation-modified montmorillonite resulted in increasing HCB adsorption with decreasing hydrated radii of exchangeable cations (log Kd 1.3–3.8 for M+ and 1.3–1.4 for M2+). DFT calculations predicted (gas phase) adsorption energies (− 76 to − 24 kJ mol−1 for M+ and − 96 to − 71 kJ mol−1 for M2+) showing a good correlation with Kd values for M2+-modified montmorillonite, whereas a discrepancy was observed for M+-modified montmorillonite. Supported by further calculations, this indicated that the solvent effect plays a relevant role in the adsorption process. Our results provide insight into the influence of minerals on HOC adsorption using HCB as an example and support the relevance of minerals for the environmental fate of HOCs such as for long-term source/sink phenomena in soils and sediments.

Insight into Hofmeister effects on aggregation of 2:1 and 1:1 type clay minerals

Abstract2:1 and 1:1 types of clay minerals are ubiquitous in soil, and their different surface properties result in distinct environmental behaviours. In this study, dynamic light scattering (DLS) technology was adopted to determine the aggregation kinetics of 2:1 type (Montmorillonite [Mt]) and 1:1 type (Kaolinite [Ka]) clay minerals in different electrolytes. Hofmeister effects on their aggregation characteristics and mechanisms were explored. The results showed that the activation energy and critical coagulation concentration (CCC) for Mt and Ka aggregation followed Hofmeister sequences of Na+ &gt; K+ &gt; Cs+, Mg2+ &gt; Ca2+ &gt; Zn2+ ≈ Cd2+ &gt; Cu2+&gt; Pb2+. The analyses of physical insights into those differences revealed that the observed Hofmeister sequence was produced from the different non‐classical polarisation of cations and surface O atoms in the strong electric field of clay, which led to non‐electrostatic force adsorption of cations at the surface (or in the Stern layer). In this study, the effective charge coefficient γ was employed to characterise the intensity of the non‐electrostatic adsorption forces of cations arising from the non‐classical polarisation, and the γ values followed Na+ &lt; K+ &lt; Cs+, Mg2+ &lt; Ca2+ &lt; Zn2+ = Cd2+ &lt; Cu2+ &lt; Pb2+. For alkali and alkali earth metal cations with same valence, the more the electron layers, the ‘softer’ the electron cloud, the stronger the non‐classical polarisation effects in the electric field and the stronger ability to shield the electric field around the particle, which finally lead to the larger γ and lower CCC for clay minerals aggregation. For heavy metal cations, different s/p/d empty orbitals provided the basis for the difference in polarisation‐induced coordination between heavy metal cations with surface O atoms on clay. The results also showed that, the Hofmeister effects on Mt/Ka aggregation were different, it was from the differences in Hamaker constant and surface charge density for the two clay minerals.Highlights Mt and Ka aggregations exhibited different Hofmeister effects. Repulsive force among Mt particles was much larger than Ka. Cationic polarisation played critical role in particle interactions of Mt. Polarisation‐induced covalent adsorption of cations was observed at Mt surface.

Changes in Porous Parameters of the Ion Exchanged X Zeolite and Their Effect on CO2 Adsorption.

Zeolite 13X (NaX) was modified through ion-exchange with alkali and alkaline earth metal cations. The degree of ion exchange was thoroughly characterized with ICP, EDS and XRF methods. The new method of EDS data evaluation for zeolites was presented. It delivers the same reliable results as more complicated, expensive, time consuming and hazardous ICP approach. The highest adsorption capacities at 273 K and 0.95 bar were achieved for materials containing the alkali metals in the following order K < Na < Li, respectively, 4.54, 5.55 and 5.94 mmol/g. It was found that it is associated with the porous parameters of the ion-exchanged samples. The Li0.61Na0.39X form of zeolite exhibited the highest specific surface area of 624 m2/g and micropore volume of 0.35 cm3/g compared to sodium form 569 m2/g and 0.30 cm3/g, respectively. The increase of CO2 uptake is not related with deterioration of CO2 selectivity. At room temperature, the CO2 vs. N2 selectivity remains at a very high stable level prior and after ion exchange in co-adsorption process (XCO2 during adsorption 0.15; XCO2 during desorption 0.95) within measurement uncertainty. Additionally, the Li0.61Na0.39X sample was proven to be stable in the aging adsorption-desorption tests (200 sorption-desorption cycles; circa 11 days of continuous process) exhibiting the CO2 uptake decrease of about 6%. The exchange with alkaline earth metals (Mg, Ca) led to a significant decrease of SSA and micropore volume which correlated with lower CO2 adsorption capacities. Interestingly, the divalent cations cause formation of mesopores, due to the relaxation of lattice strains.

Interplay of Alkali, Transition Metals, Nitrogen, and Hydrogen in Ammonia Synthesis and Decomposition Reactions.

ConspectusThe fixation of dinitrogen to ammonia is critically important for the biogeochemical cycle on earth. Ammonia also holds promise as a sustainable energy carrier. Tremendous effort has been devoted to the development of green processes and advanced materials for ammonia synthesis and decomposition under milder conditions, and encouraging progress has been made.The reduction of dinitrogen to ammonia needs electrons and protons, which hydridic hydrogen H- could supply. Polarized, electron-rich NxHy intermediates, on the other hand, can be stabilized by alkali or alkaline earth metal cations to lower kinetic barriers in the transformation. The inherent properties of alkali/alkaline earth metal hydrides (denoted as AH) endow them with a unique function in ammonia synthesis.In this Account, recent efforts in the exploration of alkali or alkaline earth metal hydrides (denoted as AH), amides, and imides (denoted as ANH hereafter) for ammonia synthesis and decomposition reactions will be summarized and discussed. We begin with an introduction to the chemistry of A with N2, NH3, and H2, highlighting the interconversion between AH and ANH that has profound implications on the formation and decomposition of NH3. We then present our finding on the strong synergistic effect between ANH and transition metals (TM) in ammonia decomposition catalysis, which stimulated our subsequent research on AH for ammonia synthesis. We discuss the effect and function mechanism of AH in the thermocatalytic and chemical looping ammonia synthesis processes. In the thermocatalytic process, AH cooperates with both early and late TM forming either composite catalysts with two active centers or complex metal hydride catalysts with electron- and hydrogen-rich ionic centers facilitating ammonia synthesis with high activities at lower temperatures. Very interestingly, AH levels the catalytic performances of TMs and intervenes in the energy-scaling relations of TM-only catalysts. Moreover, ANH serves as a new type nitrogen carrier effectively mediating ammonia synthesis via a low-temperature chemical looping process, in which N2 is fixed by AH forming ANH. Subsequently, ANH is hydrogenated to ammonia and AH. Late TMs have a strong catalytic effect on the chemical looping process. The unique interplay of A, N, TM, and H- offers plenty of opportunities for achieving dinitrogen conversion under mild conditions, while further efforts are needed to address the challenges in the fundamental understanding and practical application.

Sr-LSX zeolite for air separation

Due to the surging demand of lithium for lithium-ion batteries, the price of lithium has seen a steep rise and is projected to maintain the trend for the foreseeable future. With Li-LSX being the sorbent of choice in pressure swing adsorption systems for air separation, it is imperative to develop efficient adsorbents with significantly lower lithium content (mixed-cations zeolites) or completely replace it with abundant and low-cost alkali-earth metal cations such as Sr2+. This article presents promising results for pure Sr-LSX zeolite for O2 productivity performance via PSA and the possibility of completely replacing Li-LSX with Sr-LSX.

The effect of uronic acid moieties on xylan pyrolysis

The 4-O-methyl-D-glucuronic acid groups attached to xylose chains in wood xylan can form uronate salts with alkali and alkaline earth metal cations. These uronic acid and metal uronate moieties may act as acid and base catalysts, respectively, during xylan pyrolysis. In this study, commercial beechwood xylan (in which most uronic acids were present as sodium salts) and a demineralized version of the same material containing free uronic acid groups were pyrolyzed at 220–340 °C under N2 and the decomposition behaviors of the uronic acid and xylose units were determined. In the case of the original xylan, differential thermogravimetric (DTG) peaks were assigned to the degradation of sodium uronate and some xylose units (at lower temperatures) and to the decomposition of the remaining xylose units (at higher temperatures). In contrast, the demineralized xylan generated only one DTG peak in the intermediate temperature range, corresponding to the simultaneous decomposition of both uronic acid and xylose units. Thus, the effect of sodium uronate on the pyrolysis of the original xylan was only regional, whereas the free uronic acid affected the demineralized xylan in a more homogeneous manner. Additional data from pyrolysis-gas chromatography-mass spectrometry revealed that the compositions of the pyrolysis products were also different for these two xylan samples. The results of this work provide an improved understanding of wood pyrolysis mechanisms.

Removal of A-Site Alkali and Alkaline Earth Metal Cations in KBe2BO3F2-Type Layered Structures To Enhance the Deep-Ultraviolet Nonlinear Optical Capability.

In order to generate deep-ultraviolet (DUV, λ < 200 nm) coherent light, many DUV-transparent nonlinear optical (NLO) compounds have been synthesized experimentally over the past few decades, most of which contain alkali or/and alkaline earth metal cations. However, to date, practical DUV NLO materials beyond KBe2BO3F2 (KBBF) are still very scarce. In this work, based on analysis of the DUV NLO effect induced by the A-site alkali and alkaline earth metal cations, we attempt to expand the options for DUV NLO compounds from a molecular engineering point of view. Accordingly, a useful strategy is proposed to design densely stacked layered structures without A-site cations as new and promising DUV NLO materials. Along with the available experimental and first-principles calculation results, it is demonstrated that layered structures in which the A-site cations are removed, such as Be2BO3F, Be2CO3F2, AlCO3F, SiCO3F2, AlNO3F2, PBO3F2, and PB3O6F2, whether real or hypothetical, exhibit excellent DUV NLO performances. Based on the findings, our strategy may open up new opportunities for the design and exploration of high-performance DUV NLO materials beyond KBBF.

Scorpionate complexes of aza-18-crown-6 containing fluoronitrophenyl substituents as studied by electrospray ionization mass spectrometry.

Coordination of a metal cation by a nitro group is rare and the interaction between them is usually weak. Examples of complexes in which such an interaction takes place are metal complexes of cyclams containing nitrophenyl or nitrobenzyl substituents. It seemed to be interesting to check if in the complexes of the respective crown ether conjugates the interaction can also take place. We synthesized the respective conjugates of aza-18-crown-6, namely fluoro-substituted N-nitrophenylaza-18C6 conjugates. Their complexes with alkali and alkali earth metal cations were generated in the gas phase by electrospray ionization mass spectrometry (ESI-MS). Both collision-induced dissociation 'in-source' and collision-induced dissociation tandem mass spectrometry (ESI-CID-'in-source' and ESI-CID-MS/MS) were used to study the gas-phase stabilities of the generated complexes. The gas-phase decomposition of the studied complexes indicated that the complexes formed by the conjugates containing a nitro group at the ortho position are more stable than those formed by the conjugates with a nitro group at the para position. This indicates that a metal cation complexed by crown ether ring is additionally coordinated by a nitro group in the scorpionate mode. To the best of our knowledge, our finding provide the first example of a complex in which a metal cation complexed by a crown ether ring is additionally coordinated by a nitro group.

Complexes and salts of the nitrogen-rich triazole–tetrazole hybrid ligand with alkali and alkaline earth metal cations: experimental and theoretical findings

A series of the triazole–tetrazole based compounds with Li+, Na+, K+, Mg2+, Ca2+ and Ba2+ was obtained and fully characterised.

Effect of the cation on the stability of cation-glyme complexes and their interactions with the [TFSA]- anion.

The interactions of glymes with alkali or alkaline earth metal cations depend strongly on the metal cations. For example, the stabilization energies (Eform) calculated for the formation of cation-triglyme (G3) complexes with Li+, Na+, K+, Mg2+, and Ca2+ at the MP2/6-311G** level were -95.6, -66.4, -52.5, -255.0, and -185.0 kcal mol-1, respectively, and those for the cation-tetraglyme (G4) complexes were -107.7, -76.3, -60.9, -288.3 and -215.0 kcal mol-1, respectively. The electrostatic and induction interactions are the major source of the attraction in the complexes; the contribution of the induction interactions to the attraction is especially significant in the divalent cation-glyme complexes. The binding energies of the cation-G3 complexes with Li+, Na+, K+, Mg2+, and Ca2+ and the bis(trifluoromethylsulfonyl)amide anion ([TFSA]-) were -83.9, -86.6, -80.0, -196.1, and -189.5 kcal mol-1, respectively, and they are larger than the binding energies of the corresponding cation-G4 complexes (-73.6, -75.0, -77.4, -172.1, and -177.2 kcal mol-1, respectively). The binding energies and conformational flexibility of the cation-glyme complexes also affect the melting points of equimolar mixtures of glyme and TFSA salts. Furthermore, the interactions of the metal cations with the oxygen atoms of glymes significantly decrease the HOMO energy levels of glymes. The HOMO energy levels of glymes in the cation-glyme-TFSA complexes are lower than those of isolated glymes, although they are higher than those of the cation-glyme complexes.

Influence of the Alkaline Earth Metal Cations on the Standard Rate Constants of Charge Transfer for the Redox Couple Ti(IV)/Ti(III) in Chloride-Fluoride Melts

The aim of the present investigation was study of charge transfer kinetics for the redox couple Ti(IV)/Ti(III) in the (NaCl-KCl)equimol.-NaF(10 wt.%)-K2TiF6 melt and the estimation of the alkali earth metal cations influence on the standard rate constants of charge transfer (ks ) for this redox couple. Method of cyclic voltammetry was employed for the determination of the standard rate constants of charge transfer. The electrochemical redox process: Ti(IV) + e-↔ Ti(III) (1) was classified as quasi-reversible in the range of scan rate 0.75 V s-1≤ν≤2.0 V s-1. The standard rate constants of charge transfer for the reaction (1) were calculated based on the Nicholson’s equation. It was shown, that k s increase with increasing temperature and the temperature dependence of k swas described by the following empirical equation: log k s=(1.505±0,32)–(3364±675)/Т (2) The activation energy of charge transfer calculated from (2) was found equal to (64.41±13) kJ mol-1. Influence of strongly polarizing cations of Mg2+, Ca2+, Sr2+ and Ba2+on the standard rate constants of charge transfer for the redox couple Ti(IV)/Ti(III) was studied. It was determined that addition of alkali earth metal cations resulted in increasing of ks up to the certain mole ratio of Me2+/Ti(IV), which was inversely proportional to ionic potential of cations. Further addition brought some decreasing of the standard rate constants. Increase of ks is connected with substitution of Na+ and K+ cations by strongly polarizing cations in the second coordination sphere of titanium complexes that led to increasing of the bond distance between Ti and F- ligands and decreasing of titanium fluoride complexes strength. Decrease of ks at the definite ratio of components can be explained by increasing of the viscosity melts, which brings to decreasing of the diffusion coefficients. It was established the linear dependence of ks on ionic potential of alkali earth metal cations and the maximum value was obtained for complexes with outer sphere cations of magnesium. The temperature dependences for the maximum values of ks in the melts containing strongly polarizing cations were fitted by empirical equations and the activation energies of charge transfer were calculated. Values of activation energy for systems with strongly polarizing cations are considerably less than activation energy for initial system. Acknowledgments The work was financially supported by Russian Foundation for Basic Research (15-03-02290_a).

Force Fields for Carbohydrate-Divalent Cation Interactions.

We report molecular dynamics simulations to study intermolecular interactions for carbohydrate-divalent cation complexes. We observed that common force fields from literature with standard Lorentz-Berthelot combining rules are unable to reproduce the experimental stability constants for model carbohydrate monomer (α-d-Allopyranose) and alkali earth metal cation (Mg(2+), Ca(2+), Sr(2+), or Ba(2+)) complexes. A modified combining rule with rescaled effective cross-interaction radius between cations and the hydroxyl oxygens on the carbohydrates was introduced to reproduce the experimental stability constants, which the preferential carbohydrate-cation complexing structures through the ax-eq-ax sequence of O-1, O-2, and O-3 on α-d-Allopyranose were also observed. The effective radius scaling factor obtained from (α-d-Allopyranose)-Ca(2+) complexes was directly transferrable to the similar six-membered ring (α-d-Ribopyranose)-Ca(2+) complexes; however, reparameterization for the scaling factor may be necessary for the five-membered ring (α-d-Ribofuranose)-Ca(2+) complexes.

Inhibition of corrosion driven delamination on iron by smart-release bentonite cation-exchange pigments studied using a scanning Kelvin probe technique

Abstract Low-cost, environmentally friendly, cation exchange pigments derived from naturally occurring bentonite clay are shown to significantly enhance resistance to corrosion-driven cathodic delamination in organic coatings adherent to iron surfaces. A scanning Kelvin probe (SKP) is used to study the delamination kinetics of pigmented and unpigmented poly-vinyl-butyral (PVB)-based coatings applied to polished iron substrates. The bentonite clay is used both in its native form and exhaustively exchanged with a range of divalent alkali earth and trivalent rare earth metal cations. For the best performing divalent cation-exchanged pigment, the dependence of coating delamination rate on pigment volume fraction is determined and compared with that of a conventional strontium chromate (SrCrO 4 ) inhibitor. An inhibition mechanism is proposed for the bentonite pigments whereby underfilm cation release and subsequent precipitation of sparingly soluble hydroxides reduces the conductivity of the underfilm electrolyte.