Jae-Hyuk Her

Ammine Magnesium Borohydride Complex as a New Material for Hydrogen Storage: Structure and Properties of Mg(BH4)2·2NH3

The ammonia complex of magnesium borohydride Mg(BH4)2.2NH3 (I), which contains 16.0 wt % hydrogen, is a potentially promising material for hydrogen storage. This complex was synthesized by thermal decomposition of a hexaaammine complex Mg(BH4)2.6NH3 (II), which crystallizes in the cubic space group Fm3 m with unit cell parameter a=10.82(1) A and is isostructural to Mg(NH3) 6Cl2. We solved the structure of I that crystallizes in the orthorhombic space group Pcab with unit cell parameters a=17.4872(4) A, b=9.4132(2) A, c=8.7304(2) A, and Z=8. This structure is built from individual pseudotetrahedral molecules Mg(BH4)2.2NH3 containing one bidentate BH4 group and one tridentate BH4 group that pack into a layered crystal structure mediated by N-H...H-B dihydrogen bonds. Complex I decomposes endothermically starting at 150 degrees C, with a maximum hydrogen release rate at 205 degrees C, which makes it competitive with ammonia borane BH 3NH3 as a hydrogen storage material.

Structure of Unsolvated Magnesium Borohydride Mg(BH4)2

We have determined the structures of two phases of unsolvated Mg(BH(4))(2), a material of interest for hydrogen storage. One or both phases can be obtained depending on the synthesis conditions. The first, a hexagonal phase with space group P6(1), is stable below 453 K. Upon heating above that temperature it transforms to an orthorhombic phase, with space group Fddd, stable to 613 K at which point it decomposes with hydrogen release. Both phases consist of complex networks of corner-sharing tetrahedra consisting of a central Mg atom and four BH(4) units. The high-temperature orthorhombic phase has a strong antisite disorder in the a lattice direction, which can be understood on the basis of atomic structure.

Crystal Structure of Li2B12H12: a Possible Intermediate Species in the Decomposition of LiBH4

The crystal structure of solvent-free Li2B12H12 has been determined by powder X-ray diffraction and confirmed by a combination of neutron vibrational spectroscopy and first-principles calculations. This compound is a possible intermediate in the dehydrogenation of LiBH4, and its structural characterization is crucial for understanding the decomposition and regeneration of LiBH4. Our results reveal that the structure of Li2B12H12 differs from other known alkali-metal (K, Rb, and Cs) derivatives.

Porous Mg formation upon dehydrogenation of MgH2 thin films

The hydrogenation and dehydrogenation of a thin film of Mg with a Pd cap layer was measured using neutron reflectometry. Upon hydrogenation, (at 373 K and 0.2 MPa H2), the Mg film swelled in the surface normal direction by an amount roughly equal to the difference in volume between MgH2 and Mg. After dehydrogenation (at 343–423 K), the Mg film returned to a composition of Mg but retained the swelled thickness by incorporating voids. The presence of the voids is confirmed by SEM micrographs. The voids may explain some of the changes in absorption kinetics after full cycling of Mg films.

High Throughput Quantitative Phase Mapping Using Synchrotron X-Ray Diffraction

The X-Ray diffraction (XRD) technique has been used to characterize crystalline phases in mixtures ever since its discovery. In contrast to the spectroscopy, it can provide quantitative phase information via Rietveld refinement [1]. While spectroscopy is commonly used to map surface elemental distributions, XRD has not been popular for such mapping applications – likely due to the lack of suitable instruments and analysis software. Nowadays, high brilliance and high energy synchrotron Xrays are available, that can penetrate relatively thick bulk materials. And with highly collimated micronsize beams, the technique can generate tens of thousands diffraction patterns in a few hours – which can cover a few cm 2 surface with sub-mm resolution. Quantitative analysis of such big data sets remains a challenge since most Rietveld refinement programs were not developed with such applications in mind.