23Na Nuclear Magnetic Resonance Spectroscopy Research Articles

Disrupting Na+ ion homeostasis and Na+/K+ ATPase activity in breast cancer cells directly modulates glycolysis in vitro and in vivo

BackgroundGlycolytic flux is regulated by the energy demands of the cell. Upregulated glycolysis in cancer cells may therefore result from increased demand for adenosine triphosphate (ATP), however it is unknown what this extra ATP turnover is used for. We hypothesise that an important contribution to the increased glycolytic flux in cancer cells results from the ATP demand of Na+/K+-ATPase (NKA) due to altered sodium ion homeostasis in cancer cells.MethodsLive whole-cell measurements of intracellular sodium [Na+]i were performed in three human breast cancer cells (MDA-MB-231, HCC1954, MCF-7), in murine breast cancer cells (4T1), and control human epithelial cells MCF-10A using triple quantum filtered 23Na nuclear magnetic resonance (NMR) spectroscopy. Glycolytic flux was measured by 2H NMR to monitor conversion of [6,6-2H2]d-glucose to [2H]-labelled l-lactate at baseline and in response to NKA inhibition with ouabain. Intracellular [Na+]i was titrated using isotonic buffers with varying [Na+] and [K+] and introducing an artificial Na+ plasma membrane leak using the ionophore gramicidin-A. Experiments were carried out in parallel with cell viability assays, 1H NMR metabolomics of intracellular and extracellular metabolites, extracellular flux analyses and in vivo measurements in a MDA-MB-231 human-xenograft mouse model using 2-deoxy-2-[18F]fluoroglucose (18F-FDG) positron emission tomography (PET).ResultsIntracellular [Na+]i was elevated in human and murine breast cancer cells compared to control MCF-10A cells. Acute inhibition of NKA by ouabain resulted in elevated [Na+]i and inhibition of glycolytic flux in all three human cancer cells which are ouabain sensitive, but not in the murine cells which are ouabain resistant. Permeabilization of cell membranes with gramicidin-A led to a titratable increase of [Na+]i in MDA-MB-231 and 4T1 cells and a Na+-dependent increase in glycolytic flux. This was attenuated with ouabain in the human cells but not in the murine cells. 18FDG PET imaging in an MDA-MB-231 human-xenograft mouse model recorded lower 18FDG tumour uptake when treated with ouabain while murine tissue uptake was unaffected.ConclusionsGlycolytic flux correlates with Na+-driven NKA activity in breast cancer cells, providing evidence for the ‘centrality of the [Na+]i-NKA nexus’ in the mechanistic basis of the Warburg effect.

The solid solution in the system NaMgAl(SO4)3–KMgAl(SO4)3

We synthesized six samples in the compositional field NaMgAl(SO4)3–KMgAl(SO4)3 in 20 mol% increments from pure Na to pure K compounds. We investigated them by Powder X-Ray diffraction, 23Na, and 27Al Nuclear Magnetic Resonance spectroscopy. The results confirm NaMgAl(SO4)3 as a unique phase identical to a presumed new mineral found in the fumaroles of Eldfell and Hekla volcanoes in Iceland. It tolerates less than 10 mol% K substitution for Na. There exists a compositional gap to approximately Na0.65K0.35MgAl(SO4)3 from where a solid solution extends to KMgAl(SO4)3. The mineral koryakite [NaKMg2Al2(SO4)6] is a member of the latter solid solution series. The crystal structures of all (Na,K)MgAl(SO4)3 phases are akin to NASICON (NA Super Ionic CONductor). NaMgAl(SO4)3 has R3¯c\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$R\\overline{3}c$$\\end{document} symmetry and a disordered distribution of Mg and Al among the octahedral sites with only one unique site for the alkali atom. The members of the solid solution have R3¯\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$R\\overline{3}$$\\end{document} symmetry with ordered Mg–Al distribution and two unique alkali sites with different preferences for Na and K. In the crystal structure, the coordination of Na and/or K is trigonal antiprismatic, and these share bases with two octahedral Mg (Na) or Al (K) coordinations. These polyhedra are arranged in columns parallel to [001] and interconnected by SO4 tetrahedral groups. The alkali atoms from a column lie in the same (001) layers as the octahedrally coordinated atoms from the three neighboring rows. On the same level, parallel to (001), there are gaps in the other three neighboring columns forming channels containing Na+ or K+ ions.

Operando NMR electrochemical gating studies of ion dynamics in PEDOT:PSS

Although organic mixed ionic-electronic conductors are widely proposed for use in bioelectronics, energy generation/storage and neuromorphic computing, our fundamental understanding of the charge-compensating interactions between the ionic and electronic carriers and the dynamics of ions remains poor, particularly for hydrated devices and on electrochemical cycling. Here we show that operando 23Na and 1H nuclear magnetic resonance (NMR) spectroscopy can quantify cation and water movement during the doping/dedoping of films comprising the widely used mixed conductor poly(3,4-ethylene dioxythiophene) poly(styrene sulfonate) (PEDOT:PSS). A distinct 23Na quadrupolar splitting is observed due to the partial ordering of the PSS chains within the PEDOT:PSS-rich domains, with respect to the substrate. Operando 23Na NMR studies reveal a close-to-linear correlation between the quadrupolar splitting and the charge stored, which is quantitatively explained by a model in which the holes on the PEDOT backbone are bound to the PSS SO3- groups; an increase in hole concentration during doping inversely correlates with the number of Na+ ions bound to the PSS chains within the PEDOT-rich ordered domains, leading to a decrease in ions within the ordered regions and a decrease in quadrupolar splitting. The Na+-to-electron coupling efficiency, measured via 23Na NMR intensity changes, is close to 100% when using a 1 M NaCl electrolyte. Operando 1H NMR spectroscopy confirms that the Na+ ions injected into/extracted from the wet films are hydrated. These findings shed light on the working principles of organic mixed conductors and demonstrate the utility of operando NMR spectroscopy in revealing structure-property relationships in electroactive polymers.

SGLT2 inhibitor ertugliflozin decreases elevated intracellular sodium, and improves energetics and contractile function in diabetic cardiomyopathy

BackgroundElevated myocardial intracellular sodium ([Na+]i) was shown to decrease mitochondrial calcium ([Ca2+]MITO) via mitochondrial sodium/calcium exchanger (NCXMITO), resulting in decreased mitochondrial ATP synthesis. The sodium-glucose co-transporter 2 inhibitor (SGLT2i) ertugliflozin (ERTU) improved energetic deficit and contractile dysfunction in a mouse model of high fat, high sucrose (HFHS) diet-induced diabetic cardiomyopathy (DCMP). As SGLT2is were shown to lower [Na+]i in isolated cardiomyocytes, we hypothesized that energetic improvement in DCMP is at least partially mediated by a decrease in abnormally elevated myocardial [Na+]i. MethodsForty-two eight-week-old male C57BL/6J mice were fed a control or HFHS diet for six months. In the last month, a subgroup of HFHS-fed mice was treated with ERTU. At the end of the study, left ventricular contractile function and energetics were measured simultaneously in isolated beating hearts by 31P NMR (Nuclear Magnetic Resonance) spectroscopy. A subset of untreated HFHS hearts was perfused with vehicle vs. CGP 37157, an NCXMITO inhibitor. Myocardial [Na+]i was measured by 23Na NMR spectroscopy. ResultsHFHS hearts showed diastolic dysfunction, decreased contractile reserve, and impaired energetics as reflected by decreased phosphocreatine (PCr) and PCr/ATP ratio. Myocardial [Na+]i was elevated > 2-fold in HFHS (vs. control diet). ERTU reversed the impairments in HFHS hearts to levels similar to or better than control diet and decreased myocardial [Na+]i to control levels. CGP 37157 normalized the PCr/ATP ratio in HFHS hearts. ConclusionsElevated myocardial [Na+]i contributes to mitochondrial and contractile dysfunction in DCMP. Targeting myocardial [Na+]i and/or NCXMITO may be an effective strategy in DCMP and other forms of heart disease associated with elevated myocardial [Na+]i.

Understanding fast ion dynamics in sodiated Li4Na x Ti5O12: from interfacial to extended Li+ and Na+ dynamics in its mixed-conducting solid solutions

Climate change and energy crises require the development of new sustainable materials to realise reliable electrochemical energy storage devices. Spinel-type Li4Ti5O12 (LTO) is one of the most promising anode materials not only for Li-based batteries, but also for those relying on sodium. While Li+ ion dynamics at the early stages of lithiation has been studied already previously, almost no data on the diffusion properties of Na+ ions can be found in the literature. Here, we used nucleus-specific 7Li and 23Na nuclear magnetic resonance (NMR) spectroscopy to quantify the motional processes in mixed-conducting Li4Na x Ti5O12 with x = 0.1, 0.5 and 1.5 on the angstrom length scale. Most importantly, our results reveal a strong increase in Li+ diffusivity in the early stages of chemical sodiation that is accompanied by a sharp decrease in activation energy when x reaches 0.5. The two-component 7Li NMR spectra point to the evolution of an interfacial solid solution at very low sodiation levels (x = 0.1). At x = 0.5, these regions emerge over almost the entire crystallite area, enabling rapid 8a-16c-8a Li+ exchange (0.4 eV), which leads to facile long-range ion transport. We direct the attention of the reader towards the initial formation of solid solutions in LTO-based anode materials and their capital impact on overall ion dynamics. In contrast to macroscopic electrochemical testing, NMR is uniquely positioned to detect and to resolve these exceptionally fast ion dynamics during the initial stages of sodiation. As these processes crucially determine the fast-charging performance of LTO-type batteries, our study lays the atomistic foundations to establish a general understanding of why two-phase materials such as LTO can act as an impressive insertion host for both Li and Na ions.

Isotopic Substitution Reveals the Importance of Aluminate Diffusion Dynamics in Gibbsite (Al(OH)3) Crystallization from Alkaline Aqueous Solution

Understanding molecular-scale factors governing the precipitation of aluminum hydroxides, such as gibbsite, under alkaline conditions is important for the formation of laterite deposits, as well as aluminum processing. However, mechanisms enabling tetrahedral aluminate ions to assemble into octahedral sites of the gibbsite lattice remain unclear. Formation of oligomeric complexes has been hypothesized as a critical intermediate step. Here, we report a study of gibbsite solubility in highly alkaline solutions using deuterium substitution to probe equilibrium and kinetic factors that could affect oligomeric intermediate formation, including the reactivity and the diffusivity of aluminate ions. When substituting sodium hydroxide with sodium deuteroxide, solution analysis shows a nearly 40% and 50% increase in gibbsite solubility in 2.4 and 3.3 mol·kg–1 total sodium solutions, respectively. Raman spectroscopy indicated that monomeric aluminate ions are the predominant species in solution irrespective of deuteration. However, both 27Al and 23Na nuclear magnetic resonance (NMR) spectroscopy revealed significant differences in chemical shifts in deuterated solutions, and analysis of 1H, 23Na, and 27Al diffusion coefficients with pulsed-field gradient, stimulated echo NMR spectroscopy shows a decrease in ion diffusivity with increasing total deuterium in solution, consistent with the notion of increasing strength in the hydrogen/deuterium bonding network. Because the relative change in 1H diffusion coefficients are commensurate with the difference in apparent solubility constants, there is evidence for an oligomeric intermediate whose steady-state concentration is maintained by the collision frequency of aluminate ions.

Structure and ionic conductivity of Na3+xSc2SixP3-xO12 (x=0.0, 0.2, 0.4, 0.8) NASICON materials: A combined neutron diffraction, MAS NMR and impedance study

A knowledge of structural parameters that play a role in influencing ionic conduction is the key to the design of improved NASICON materials which have attracted significant attention in recent years as potential solid electrolytes for sodium ion batteries. In this article, we report the results of our study on a series of scandium-based NASICON compounds, namely Na3+xSc2SixP3-xO12 (x= 0.0, 0.2, 0.4, 0.8) that have been prepared by the ceramic route. These materials have been characterized by powder X-ray and neutron diffraction, as well as solid-state 23Na, 45Sc, 31P, and 29Si nuclear magnetic resonance (NMR) spectroscopy at room temperature (RT). The electrical conductivity of the compounds in the temperature range of RT ̶400 °C has been determined by impedance spectroscopy. Rietveld refinement of the diffraction patterns confirms monoclinic C2/c unit cell for the Na3Sc2P3O12 but indicates a rhombohedral R3‾c unit cell for Na3+xSc2SixP3-xO12 compounds. The local environments surrounding sodium, scandium, phosphorus and silicon atoms have been deduced from solid-state NMR. 23Na NMR results gave evidence of Na-ion mobility at RT. AC impedance measurements show that the total conductivity of the sample increases with increasing substitution of P with Si. However, it is much reduced for x = 0.8 composition. Na-ion conductivity of 2.4×10-3 S cm−1 at 30 °C has been measured in Na3.4Sc2Si0·4P2·6O12 compound, which is comparable to the best-performing polycrystalline NASICONs. Parameters such as the area of the bottleneck region, Na–Na hopping distances, and the activation energy for Na-ion conduction have been determined from the structural data. A correlation has been found between the conductivity and the ratio of Na site vacancy to Na site occupancy. Possible reasons for the significant variation of the Na-ion conductivity with x are also discussed in the context of the structure and Na site occupancy.

(A04 Best Poster Award Winner) Magnetic Resonance Imaging of Sodium-Ion Batteries - The Quest for Quasimetallic Nanoparticles

An increase in the demand for clean energy generation has brought about a need for improved energy storage devices to distribute the power generated by renewable sources. Sodium-ion batteries have been proposed as a lower cost and more sustainable solution. In order to commercialise this emerging technology, new materials and characterisation techniques are required. Magnetic resonance imaging (MRI) is able to characterise both the electrode and electrolyte materials non-invasively, providing a more holistic view of battery chemistry. Furthermore, MRI can spatially resolve electrochemical processes, in real-time, within cells.(1-4) In this study, 23Na and 1H nuclear magnetic resonance (NMR) spectroscopy and MRI experiments have been performed, in operando, on sodium metal cells. At high cycle rates, the growth of dendrites is observed during galvanostatic plating. Operando 23Na NMR experiments on sodium full cells have also been performed, which provide unprecedented insight into the sodiation mechanisms within a hard carbon anode. The formation of metallic and quasimetallic sodium species are observed during the first charge cycle.(5) M. M. Britton, Prog. Nucl. Magn. Reson. Spectrosc., 101, 51 (2017). M. M. Britton, ChemPhysChem, 15, 1731 (2014). A. J. Davenport, M. Forsyth and M. M. Britton, Electrochem. Commun., 12, 44 (2010). J. M. Stratford, P. K. Allan, O. Pecher, P. A. Chater and C. P. Grey, Chem. Commun. (Cambridge, U.K.), 52, 12430 (2016). J. M. Bray, C. L. Doswell, G. E. Pavlovskaya, L. Chen, B. Kishore, H. Au, H. Alptekin, E. Kendrick, M. M. Titirici, T. Meersmann and M. M. Britton, Nat. Commun., 11, 2083 (2020). Figure 1

Study of thermal transformations in Na,Ca-based catalysts supported on activated carbon and their application in the synthesis of biodiesel from soybean oil

Abstract Catalysts containing Na and Ca compounds dispersed in a porous carbon support were prepared by a wet chemical route followed by heat treatments and their catalytic performance in the transesterification reaction of soybean oil with methanol was investigated. The chemical composition and the structural properties of the Na,Ca-based catalysts were modified by means of heat treatments at temperatures ranging from 500 to 800 °C. The chemical nature of the Na,Ca-containing phases was studied by X-ray diffraction and solid-state 23Na nuclear magnetic resonance (NMR) spectroscopy, among other methods. The as-prepared material was found to be composed of a mixture of Ca(OH)2 and Na2CO3; the heat treatment at 500 °C led to the formation of the double carbonate, Na2CO3.CaCO3, whereas at high temperatures the dominant phases were CaO and Na2CO3. The best catalytic efficiency was achieved for the catalysts prepared at 700 and 800 °C. An important advantage of the prepared catalysts was the low concentration of Ca and Na leached into the produced biodiesel samples. It was found that the best heat treatment temperatures to prevent metal leaching were 700 and 800 °C. These results show that the simple method of wet impregnation followed by heat treatments is an efficient route for the production of carbon-supported Na,Ca-based catalysts with high porosity, good catalytic efficiency and that allow the synthesis of biodiesel samples with low metal contents.

Annealing induced structural evolution in feldspar dental glass-ceramics investigated by solid-state NMR spectroscopy

Glass-ceramics are an attractive oxide-based material routinely used for biomineral repair such as porcelain veneers in dental crown applications. The short- and long-range structure of a commercial glass-ceramic feldspar material, VITA VM9, has been investigated as a function of annealing temperature. The relative amounts of amorphous and crystalline components were monitored using a combination of powder X-ray diffraction and solid-state 23Na, 27Al, and 29Si nuclear magnetic resonance spectroscopy. The insight gained from this study was then applied to analyze a series of synthetic lab-grade ceramics Na0.5K0.5Al1–xMxSi3O8 (x ​= ​0.1; M ​= ​B, Al, Ga), whose onset of crystallization was found to resemble that of the commercial ceramic material.

Operando visualisation of battery chemistry in a sodium-ion battery by 23Na magnetic resonance imaging

Sodium-ion batteries are a promising battery technology for their cost and sustainability. This has led to increasing interest in the development of new sodium-ion batteries and new analytical methods to non-invasively, directly visualise battery chemistry. Here we report operando 1H and 23Na nuclear magnetic resonance spectroscopy and imaging experiments to observe the speciation and distribution of sodium in the electrode and electrolyte during sodiation and desodiation of hard carbon in a sodium metal cell and a sodium-ion full-cell configuration. The evolution of the hard carbon sodiation and subsequent formation and evolution of sodium dendrites, upon over-sodiation of the hard carbon, are observed and mapped by 23Na nuclear magnetic resonance spectroscopy and imaging, and their three-dimensional microstructure visualised by 1H magnetic resonance imaging. We also observe, for the first time, the formation of metallic sodium species on hard carbon upon first charge (formation) in a full-cell configuration.

Solid-state 23Na NMR spectroscopy studies of ordered and disordered cellulose nanocrystal films

Cellulose nanocrystal films with either disordered or chiral nematic structures of varying helical pitch were investigated using 23Na solid-state nuclear magnetic resonance (NMR) spectroscopy. Spin lattice relaxation of 1H correlated with 23Na analyzed by indirect observation using polarization transfer from 1H nuclei to 23Na nuclei showed that the Na+ cations are well hydrated in the cellulose nanocrystal films. Linewidth analysis in solid-state 23Na NMR showed that the Na+ cations move in confined spaces, and that the Na+ cations in the film having disordered structure are more dynamic than in the films having ordered structure. From lineshape analysis of the 23Na 2D nutation NMR spectra, we can distinguish the Na+ environments within the ordered and disordered films, and find trends in anisotropic interaction parameters between ordered samples with different pitches. These are the first detailed 23Na NMR spectroscopic studies of CNC-Na+ films, and they show that this technique may be a powerful probe for characterizing the extent of order in nanocellulose samples.

Vacancy-Driven Na+ Superionic Conduction in New Ca-Doped Na3PS4 for All-Solid-State Na-Ion Batteries

Mechanically sinterable sulfide Na+ superionic conductors are key to enabling room-temperature-operable all-solid-state Na-ion batteries (ASNBs) for large-scale energy storage applications. To date, few candidates can fulfill the requirement of a high ionic conductivity of ≥1 mS cm–1 using abundant, cost-effective, and nontoxic elements. Herein, the development of a new Na+ superionic conductor, Ca-doped cubic Na3PS4, showing a maximum conductivity of ∼1 mS cm–1 at 25 °C is described. Complementary analyses using conductivity measurement by the AC impedance method, 23Na nuclear magnetic resonance spectroscopy, and density functional theory calculations reveal that the aliovalent substitution of Na+ in Na3PS4 with Ca2+ renders a cubic phase with Na vacancies, which increases the activation barriers but drastically enhances Na-ion diffusion. It is demonstrated that TiS2/Na–Sn ASNBs employing Ca-doped Na3PS4 exhibit a high charge capacity of 200 mA h g–1 at 0.06C, good cycling performance, and higher rate ca...

Crystal Structures, Local Atomic Environments, and Ion Diffusion Mechanisms of Scandium-Substituted Sodium Superionic Conductor (NASICON) Solid Electrolytes

The importance of exploring new solid electrolytes for all-solid-state batteries has led to significant interest in NASICON-type materials. Here, the Sc3+-substituted NASICON compositions Na3ScxZr2–x(SiO4)2–x(PO4)1+x (termed N3) and Na2ScyZr2–y(SiO4)1–y(PO4)2+y (termed N2) (x, y = 0–1) are studied as model Na+-ion conducting electrolytes for solid-state batteries. The influence of Sc3+ substitution on the crystal structures and local atomic environments has been characterized by powder X-ray diffraction (XRD) and neutron powder diffraction (NPD), as well as solid-state 23Na, 31P, and 29Si nuclear magnetic resonance (NMR) spectroscopy. A phase transition between 295 and 473 K from monoclinic C2/c to rhombohedral R3̅c is observed for the N3 compositions, while N2 compositions crystallize in a rhombohedral R3̅c unit cell in this temperature range. Alternating current (AC) impedance spectroscopy, molecular dynamics (MD), and high temperature 23Na NMR studies are in good agreement, showing that, with a higher Sc3+ concentration, the ionic conductivity (of about 10–4 S/cm at 473 K) decreases and the activation energy for ion diffusion increases. 23Na NMR experiments indicate that the nature of the Na+-ion motion is two-dimensional on the local atomic scale of NMR although the long-range diffusion pathways are three-dimensional. In addition, a combination of MD, bond valence, maximum entropy/Rietveld, and van Hove correlation methods has been used to reveal that the Na+-ion diffusion in these NASICON materials is three-dimensional and that there is a continuous exchange of sodium ions between Na(1) and Na(2) sites.

Elementary Steps of Faujasite Formation Followed by in Situ Spectroscopy

Ex situ and in situ spectroscopy was used to identify the kinetics of processes during the formation of the faujasite (FAU) zeolite lattice from a hydrous gel. Using solid-state 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR), the autocatalytic transformation from the amorphous gel into the crystalline material was monitored. Al X-ray absorption near-edge structure shows that most Al already adopts a tetrahedral coordination in the X-ray-amorphous aluminosilicate at the beginning of the induction period, which hardly changes throughout the rest of the synthesis. Using 23Na NMR spectroscopy, environments in the growing zeolite crystal were identified and used to define the processes in the stepwise formation of the zeolite lattice. The end of the induction period was accompanied by a narrowing of the 27Al and 23Na MAS NMR peak widths, indicating the increased level of long-range order. The experiments show conclusively that the formation of faujasite occurs via the continuous formation and...

Structural modifications induced by Na+/K+ ion exchange in silicate glasses: A multinuclear NMR spectroscopic study

The structural mechanisms of stress relaxation during Na+/K+ ion exchange is studied in a variety of Na silicate glasses with and without alkaline-earth modifiers, using one and two-dimensional 23Na and 29Si nuclear magnetic resonance (NMR) spectroscopy. The results suggest that significant structural modifications accompany the Na+/K+ ion exchange process in the form of a shortening of the average NaO and SiNBO distances and an opening of the SiOSi angles without any detectable change in the Qn speciation. These trends are similar to those observed in analogous mixed Na,K glasses derived via the melt-quench route, with increasing K:Na ratio. Consequently, the ion-exchange-induced reorganization of the glass network is accompanied by a partial relaxation of the stress generated by the exchange of smaller Na+ by the larger K+ and better accommodation of the latter ion as a modifier.

Structure and short time degradation studies of sodium zirconium phosphate ceramics loaded with simulated fast breeder (FBR) waste

Sodium zirconium phosphate (NZP) ceramics have been prepared using conventional sintering and hot isostatic pressing (HIP) routes. The structure of NZP ceramics, prepared using the HIP route, has been compared with conventionally sintered NZP using a combination of X-ray diffraction (XRD) and (31P and 23Na) nuclear magnetic resonance (NMR) spectroscopy techniques. It is observed that NZP with no waste loading is aggressive toward the steel HIP-can during hot isostatic compaction and significant fraction of cations from the steel enter the ceramic material. Waste loaded NZP samples (10 wt% simulated FBR waste) show significantly low can-interaction and primary NZP phase is evident in this material. Upon exposure of can-interacted and waste loaded NZP to boiling water and steam, 31P NMR does not detect any major modifications in the network structure. However, the 23Na NMR spectra indicate migration of Na+ ions from the surface and possible re-crystallization. This is corroborated by Small-Angle Neutron Scattering (SANS) data and Scanning Electron Microscopy (SEM) measurements carried out on these samples.

Additive Effects of Rare-Earth Ions in Sodium Aluminoborate Glasses Using <sup>23</sup>Na and <sup>27</sup>Al Magic Angle Spinning Nuclear Magnetic Resonance

We conducted structural analysis of xNa2O-yY2O3-5B2O3-3Al2O3 and xNa2O-yLa2O3-5B2O3-3Al2O3 glasses to elucidate the additive effects of rare-earth ions in these sodium aluminoborate glasses, and investigated the local environment surrounding Na+ in them by using 23Na and 27Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The amount of higher-coordinated Al species ([5]Al and [6]Al) gradually increased in response to an increase in the ratios of Y2O3 to Al2O3 and La2O3 to Al2O3 in each type of glass, respectively. Moreover, the difference in the cation field strength (CFS) between Y3+ and La3+ was observed to affect the generation of [5]Al and [6]Al, especially when the amount of these ions in the glasses increased. In addition to the above, the coordination number of Na+ ions increased with an increase in the number of rare earth ions, confirmed by comparing results with NMR spectra of crystalline Na2Al2B2O7. The latter possibly occurred due to the oxygen concentration on Al[5] and Al[6]. Finally, it was confirmed that the formation of [5]Al and [6]Al decreases molar volume in oxide glasses, which might be partially due to better atomic packing of [5]Al and [6]Al.

Mechanisms of Sodium Insertion/Extraction on the Surface of Defective Graphenes.

Two chemically synthesized defective graphene materials with distinctly contrasting extended structures and surface chemistry are used to prepare sodium-ion battery electrodes. The difference in electrode performance between the chemically prepared graphene materials is qualified based on correlations with intrinsic structural and chemical dissimilarities. The overall effects of the materials' physical and chemical discrepancies are quantified by measuring the electrode capacities after repeated charge/discharge cycles. Solvothermal synthesized graphene (STSG) electrodes produce capacities of 92 mAh/g in sodium-ion batteries after 50 cycles at 10 mA/g, while thermally exfoliated graphite oxide (TEGO) electrodes produce capacities of 248 mAh/g after 50 cycles at 100 mA/g. Solid-state 23Na nuclear magnetic resonance spectroscopy is employed to locally probe distinct sodium environments on and between the surface of the graphene layers after charge/discharge cycles that are responsible for the variations in electrode capacities. Multiple distinct sodium environments of which at least 3 are mobile during the charge-discharge cycle are found in both cases, but the majority of Na is predominantly located in an immobile site, assigned to the solid electrolyte interface (SEI) layer. Mechanisms of sodium insertion and extraction on and between the defective graphene surfaces are proposed and discussed in relation to electrode performance. This work provides a direct account of the chemical and structural environments on the surface of graphene that govern the feasibility of graphene materials for use as sodium-ion battery electrodes.

Local structure of alkalis in mixed-alkali borate glass to elucidate the origin of mixed-alkali effect

We report the structural analysis of Na+ and Cs+ in sodium cesium borate crystals and glasses using 23Na and 133Cs magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The composition dependence of NMR spectra of the borate was similar to that of the silicate: (1) the peak position of cesium borate crystals shifted to upfield for structures with larger Cs+ coordination numbers, (2) the MAS NMR spectra of xNa2O-yCs2O-3B2O3 (x = 0, 0.25, 0.5, 0.75, 1.0, x + y = 1) glass showed that the average coordination number (CN) of both the alkali cations decreases with increasing Cs+/(Na+ + Cs+) ratio. However, the degree of decrement in borates is much smaller than that in silicates. We have considered that the small difference in CN is due to 4-coordinated B, because it is electrically compensated by the alkali metal ions resulting in the restriction of having various coordinations of O to alkali metal.