J Phys Chem C, v113, issue 1

Study of Aluminoborane Compound AlB4H11 for Hydrogen Storage
Ji-Cheng Zhao*†, Douglas A. Knight‡, Gilbert M. Brown‡, Chul Kim§, Son-Jong Hwang§, Joseph W. Reiter∥, Robert C. Bowman, Jr.∥, Jason A. Zan∥ and James G. Kulleck∥
J. Phys. Chem. C, 2009, 113 (1), pp 2–11

Aluminoborane compounds AlB4H11, AlB5H12, and AlB6H13 were reported by Himpsl and Bond in 1981, but they have eluded the attention of the worldwide hydrogen storage research community for more than a quarter of a century. These aluminoborane compounds have very attractive properties for hydrogen storage: high hydrogen capacity (i.e., 13.5, 12.9, and 12.4 wt % H, respectively) and attractive hydrogen desorption temperature (i.e., AlB4H11 decomposes at ∼125 °C). We have synthesized AlB4H11 and studied its thermal desorption behavior using temperature-programmed desorption with mass spectrometry, gas volumetric (Sieverts) measurement, infrared (IR) spectroscopy, and solid state nuclear magnetic resonance (NMR). Rehydrogenation of hydrogen-desorbed products was performed and encouraging evidence of at least partial reversibility for hydrogenation at relatively mild conditions is observed. Our chemical analysis indicates that the formula for the compound is closer to AlB4H12 than AlB4H11.



Solid-State 17O NMR Spectroscopy of Hydrous Magnesium Silicates: Evidence for Proton Dynamics
John M. Griffin†, Stephen Wimperis*‡, Andrew J. Berry§, Chris J. Pickard∥ and Sharon E. Ashbrook*†
J. Phys. Chem. C, 2009, 113 (1), pp 465–471
Abstract: First-principles calculations of 17O quadrupolar and chemical shift NMR parameters were performed using CASTEP, a density functional theory (DFT) code, to try and interpret high-resolution 17O NMR spectra of the humite group minerals hydroxyl-chondrodite (2Mg2SiO4·Mg(OH)2) and hydroxyl-clinohumite (4Mg2SiO4·Mg(OH)2), which are models for the incorporation of water within the Earth’s upper mantle. The structures of these humite minerals contain two possible crystallographically inequivalent H sites with 50% occupancy. Isotropic 17O multiple-quantum magic angle spinning (MQMAS) spectra were therefore simulated using the calculated 17O NMR parameters and assuming either a static or dynamic model for the positional disorder of the H atoms. Only the dynamic disorder model provided simulated spectra that agree with experimental 17O MQMAS spectra of hydroxyl-chondrodite and hydroxyl-clinohumite. Previously published 17O satellite-transition magic angle spinning (STMAS) spectra of these minerals showed significant dynamic line-broadenings in the isotropic frequency dimension. We were able to reproduce these line-broadenings with at least qualitative accuracy using a combination of the same dynamic model for the positional H disorder, calculated values for the change in 17O quadrupolar NMR parameters upon H exchange, and a simple analytical model for dynamic line-broadening in MAS NMR experiments. Overall, this study shows that a combination of state-of-the-art NMR methodology and first-principles calculations of NMR parameters is able to provide information on dynamic processes in solids with atomic-scale resolution that is unobtainable by any other method.