Destabilizing the Dehydrogenation Thermodynamics of Magnesium Hydride by Utilizing the Immiscibility of Mn with Mg.

Hydrogen storage is a key technology for the advancement of hydrogen and fuel cell power technologies in stationary and portable applications. MgH2, an example of a high-capacity hydrogen storage material, has two major material challenges for practical applications: slow hydrogen desorption kinetics and high hydrogen desorption temperature. Numerous studies have reported enhancements in kinetics but only a few in thermodynamics. Here, we present a simple but effective way to improve upon both the kinetic and thermodynamic aspects of desorption by utilizing the immiscibility of Mn, a non-hydrogen absorbing metal, with Mg. Mg0.25Mn0.75, prepared through ball milling MgH2 and Mn powders, is a nanocomposite where the nanometer-sized MgH2 domains are randomly embedded in a Mn matrix. This sample readily and reversibly absorbs and desorbs deuterium even at a temperature of 200 °C without the addition of any catalysts. This is nearly 180 °C lower than the typical operating temperature of conventional bulk Mg. Furthermore, at a given temperature, its deuterium desorption pressure is clearly elevated compared to that of pure Mg, indicating the destabilization of MgD2. The average crystallite size of MgD2 in deuterated Mg0.25Mn0.75 determined from X-ray diffraction data is around 9 nm. Nuclear magnetic resonance spectroscopy studies show that MgD2 domains are heavily strained and some of the D atoms are coordinated by a few Mn atoms, suggesting that a large number of lattice defects, including the partial substitution of Mg with Mn, are introduced during ball milling. Furthermore, the Mn matrix firmly locks nanosized MgD2, preventing the agglomeration of MgD2 below 250 °C. Our study suggests that a synergistic effect created by nanosizing, large lattice distortions, and robust interfaces between MgD2 and the Mn matrix can effectively and concurrently improve the kinetics and thermodynamics of MgD2 in Mg0.25Mn0.75. Our work demonstrates the possibility of utilizing the immiscibility of metals with Mg to synthesize a robust nanostructure that can alter the kinetics and stability of MgH2.

Structural Variation of Self-Organized Mg Hydride Nanoclusters in Immiscible Ti Matrix by Hydrogenation.

Hydrogenation of nonequilibrium alloys may form nanometer-sized metal hydride clusters, depending on the alloy compositions and hydrogenation conditions. Here in the Ti-rich compositions of the immiscible Mg-Ti system MgH2 clusters are embedded in a Ti-H matrix. Our previous works have indicated that the interface energy between the two metal hydrides reduces the stability of MgH2. The aim of our study is to obtain the structural information on the nanometer-sized clusters. Indeed, MgD2 clusters embedded in a face-centered-cubic (FCC) Ti-D matrix is found in Mg0.25Ti0.75D1.65 by means of 2H magic angle spinning nuclear magnetic resonance (MAS NMR). The atomic pair distribution function (PDF) analysis of neutron total scattering data suggests that the MgD2 clusters have an orthorhombic structure, which is different from a rutile-type body-centered-tetragonal (BCT) structure of α-MgD2 observed in the Mg-rich compositions. Our results suggest that we can tune the thermodynamics of hydrogen absorption and desorption in Mg-H using the interface energy effect and accompanying stress-induced structural change, which contributes to the substantial development of lightweight and inexpensive hydrogen storage materials.

Spin diffusion and 1H spin-lattice relaxation in Cs2(HSO4)(H2PO4) containing a small amount of ammonium ions.

Inorganic solid acid salts with hydrogen bond networks frequently show very long spin-lattice relaxation times even for 1H because the hydrogen bonds suppress motions. In the present work, the 1H spin-lattice relaxation in Cs2(HSO4)(H2PO4) containing a small amount of ammonium ions were studied in detail by use of the effect of magic angle spinning (MAS) on the relaxation. The 1H spin-lattice relaxation times of the acid protons decrease with increase in the content of ammonium ions. Reorientation of the NH4 group fluctuates the dipole-dipole interaction and relaxes the ammonium protons as well as the acid protons. The 1H relaxation times of the acid protons are a little bit longer than those of the ammonium protons at the MAS rate of 8 kHz. The spinning at 50 kHz makes the relaxation times of the acid protons longer and those of the ammonium protons shorter. Spin diffusion between the acid and the ammonium protons averages partially the 1H relaxation of the acid and the ammonium protons at the MAS rate of 8 kHz. The spin diffusion is suppressed completely at the MAS rate of 50 kHz. Spin diffusion between the acid protons is not suppressed at the MAS rate of 50 kHz. The acid protons always show the same relaxation times. The intrinsic relaxation times not affected by spin diffusion are evaluated quantitatively for both the acid and the ammonium protons. Those values are independent of the ammonium content. Contribution of the spin diffusion between the acid and the ammonium protons to the relaxation is estimated quantitatively. Using those parameters, the effect of ammonium ions on the 1H spin-lattice relaxation can be predicted. The 1H spin-lattice relaxation is a sensitive tool to study the distribution of ammonium ions in solids.

Multifunctional Octamethyltetrasila[2.2]cyclophanes: Conformational Variations, Circularly Polarized Luminescence, and Organic Electroluminescence.

Both symmetrical and unsymmetrical cyclophanes containing disilane units, tetrasila[2.2]cyclophanes 1-9, were synthesized. The syn and anti conformations and the kinetics of inversion between two anti-isomers were investigated by X-ray diffraction and variable-temperature NMR analysis, respectively. The flipping motion of two aromatic rings was affected by the bulkiness of the aromatic moiety (1 vs 6), the phase (solid vs solution), and the inclusion by host molecules (1 vs 1⊂[Ag2L]2+). The photophysical, electrochemical, and structural properties of the compounds were thoroughly investigated. Unsymmetrical tetrasila[2.2]cyclophanes 5-8 displayed blue-green emission arising from intramolecular charge transfer. Compound 6 emitted a brilliant green light in the solid state under 365 nm irradiation and showed a higher fluorescence quantum yield in the solid state (Φ = 0.49) than in solution (Φ = 0.05). We also obtained planar chiral tetrasila[2.2]cyclophane 9, which showed interesting chiroptical properties, such as a circularly polarized luminescence (CPL) with a dissymmetry factor of |glum| = ca. 2 × 10-3 at 500 nm. Moreover, an organic green light-emitting diode that showed a maximum external quantum efficiency (ηext) of ca. 0.4% was fabricated by doping 4,4'-bis(2,2'-diphenylvinyl)-1,1'-biphenyl with 6.

Detailed mechanisms of 1H spin-lattice relaxation in ammonium dihydrogen phosphate confirmed by magic angle spinning.

Mechanisms of the 1H spin-lattice relaxation in NH4H2PO4 were studied in detail by use of the effect of magic angle spinning on the relaxation. The acid and the ammonium protons have different relaxation times at the spinning rates higher than 10 kHz due to suppression of spin diffusion between the two kinds of protons. The intrinsic relaxation times not affected by the spin diffusion and the spin-diffusion assisted relaxation times were evaluated separately, taking into consideration temperature dependence. Both mechanisms contribute to the 1H relaxation of the acid protons comparatively. The spin-diffusion assisted relaxation mechanism was suppressed to the level lower than the experimental errors at the spinning rate of 30 kHz.

Structural changes of layered alkylsiloxanes during the reversible melting-solidification process.

Through various in situ analyses, we have revealed the structural changes that occur during the reversible melting-solidification process of layered alkylsiloxanes (CnLSiloxanes) with carbon numbers (n) of 18 and 16. In situ high-resolution solid-state (13)C nuclear magnetic resonance (NMR) analysis at controlled temperatures indicates drastic conformational changes of the long alkyl chains during the melting-solidification process. A (13)C NMR signal at 33 ppm, which shows the highest intensity at room temperature (RT), is assigned to an inner methylene group with an all-trans conformation. As the temperature increases, the 33-ppm signal intensity decreases while the signal intensity at 30.5 ppm simultaneously increases. The 30.5 ppm signal is assigned to an inner methylene group with a trans-gauche conformation. Subsequently, upon cooling, the signal at 33 ppm recovers, even after CnLSiloxanes have melted. In situ X-ray diffraction measurements at controlled temperatures reveal that the ordered arrangement of the long alkyl chains becomes disordered with elevating temperatures and reordered upon cooling to RT. In situ high-resolution solid-state (29)Si NMR analysis shows that the melting-solidification process progresses without any structural change in siloxane sheets of the CnLSiloxanes. Thus, the in situ analyses show that disordering of the long alkyl chains causes the CnLSiloxanes to melt. Because the majority of long alkyl chains are packed again in the ordered arrangement with the all-trans conformation upon cooling, the CnLSiloxanes are reversibly solidified and the CnLSiloxane structure is recovered.