Hydrogen-fluorine exchange in NaBH4-NaBF4.

Hydrogen-fluorine exchange in the NaBH4-NaBF4 system is investigated using a range of experimental methods combined with DFT calculations and a possible mechanism for the reactions is proposed. Fluorine substitution is observed using in situ synchrotron radiation powder X-ray diffraction (SR-PXD) as a new Rock salt type compound with idealized composition NaBF2H2 in the temperature range T = 200 to 215 °C. Combined use of solid-state (19)F MAS NMR, FT-IR and DFT calculations supports the formation of a BF2H2(-) complex ion, reproducing the observation of a (19)F chemical shift at -144.2 ppm, which is different from that of NaBF4 at -159.2 ppm, along with the new absorption bands observed in the IR spectra. After further heating, the fluorine substituted compound becomes X-ray amorphous and decomposes to NaF at ~310 °C. This work shows that fluorine-substituted borohydrides tend to decompose to more stable compounds, e.g. NaF and BF3 or amorphous products such as closo-boranes, e.g. Na2B12H12. The NaBH4-NaBF4 composite decomposes at lower temperatures (300 °C) compared to NaBH4 (476 °C), as observed by thermogravimetric analysis. NaBH4-NaBF4 (1:0.5) preserves 30% of the hydrogen storage capacity after three hydrogen release and uptake cycles compared to 8% for NaBH4 as measured using Sievert's method under identical conditions, but more than 50% using prolonged hydrogen absorption time. The reversible hydrogen storage capacity tends to decrease possibly due to the formation of NaF and Na2B12H12. On the other hand, the additive sodium fluoride appears to facilitate hydrogen uptake, prevent foaming, phase segregation and loss of material from the sample container for samples of NaBH4-NaF.

The formation mechanism and structural characterization of the mixed transition-metal complex hydride Mg2(FeH6)0.5(CoH5)0.5 obtained by reactive milling.

Mg2(Fe0.5Co0.5) elemental powder mixtures were processed by reactive ball milling in a H2 (orD2) atmosphere at about 50 bar. The changes of pressure were monitored during milling and hydrogen absorption was detected within the first 10 h of milling. X-ray and neutron powder diffraction analysis, followed by Rietveld refinement, suggests an almost complete conversion of the starting metals into the quaternary hydride Mg2(FeH6)0.5(CoH5)0.5. The latter has a cubic K2PtCl6-type structure (space group Fm3m) with a cell parameter a approximately 6.42 A degrees. Fe and Co atoms are disorderly distributed in the 4a position. Hydrogen desorption upon heating was investigated by both in situ x-ray diffraction and temperature programmed desorption analysis.Hydrogen is released in a one-step desorption reaction at temperatures between 500 and 600 K,with Mg and a FeCo solid solution as desorption products. Finally, Mg2(FeH6)0.5(CoH5)0.5 was also synthesized by ball milling equi-molar mixtures of Mg2FeH6 and Mg2CoH5 in Ar.

The crystal structure of Zr2NiD4.5.

The crystal structure of Zr2NiD4.5 has been determined by a combination of synchrotron radiation powder X-ray diffraction, electron diffraction and powder neutron diffraction data. Deuterium ordering results in a triclinic supercell given by asuper=6.81560 (7), bsuper=8.85137 (9), csuper=8.88007 (10) A, alphasuper=79.8337 (8), betasuper=90.0987 (9), gammasuper=90.3634 (9) degrees, which relates to the non-super unit cell as asuper=-a, bsuper=-b-c, csuper=-b+c. The centrosymmetric and fully ordered deuterium sublattice was determined by simulated annealing and Rietveld refinement. Deuterium was found to occupy three types of tetrahedral sites: two that are coordinated by four Zr atoms and one that is coordinated by three Zr atoms and one Ni atom. All D-D distances are longer than 2 A. The feasibility of the crystal structure was supported by density functional theory calculations.

Physical estimation of triplet phases--effects of different radiation sources and modes for profile scans.

A comparative study has been made of the intensity profiles from three-beam experiments to estimate triplet phases using radiation from a conventional sealed-tube X-ray source and two different synchrotron sources. Synchrotron radiation, with its much smaller angular divergence, narrower spectral bandwidth and higher flux, distinctly improves the experimental conditions for physical phase estimation. Pure psi scans about the primary diffraction vector, such as can be made with a six-circle diffractometer, further improve the conditions compared with combined omega/psi scans with a four-circle instrument, where the rotation in psi is accomplished by combining rotations about the three axes omega, chi and varphi. Interference profiles collected by pure psi scans and unfocused synchrotron radiation have FWHM values reduced by factors in the range 20-35 relative to those obtained with combined omega-2theta/psi scans and radiation from a conventional source. As a consequence of these changes, which also involve greatly increased peak amplitudes, the 0/pi-type asymmetry of the profiles is exposed much more pronounced closer to the three-beam point, enabling unambiguous phase assignment for all triplets that were studied. The superiority of the pure psi scan will be even more important in studies of general phases for which the phase information lies also in the relative heights of the (sharp) interference maxima for a triplet and the Friedel-related triplet.

Application of known X-ray phases in the crystallographic study of a small protein.

Phase information, assumed known from three-beam diffraction experiments, has been used successfully as input to direct methods to re-determine the crystal structure of rubredoxin. With data at 1.54 A resolution, starting sets containing 26 single phases, or alternatively 45 triplet phases, in both cases known with a mean error of +/-22.5 degrees, were sufficient to initiate solution of the structure. Conventional figures of merit were employed in the early stages to reject the majority of the incorrect phase models. The presence of a FeS(4) cluster in the structure was used in the interpretation of the initial maps. Phase sets including 2500 E's with a mean single phase error approximately 70 degrees or a mean triplet phase error approximately 80 degrees, both relative to the model from the crystallographic refinement, could be refined and expanded by Fourier recycling using the SAYTAN formalism. Several parameters have been varied to study their influence on phase expansion and refinement.