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Metal hydroborates are versatile materials with interesting properties related to energy storage and cation conductivity. The hydrides containing B 3 H 8 - (triborane, or octahydrotriborate) ions have been at the center of attention for some time as reversible intermediates in the decomposition of BH 4 - (3BH 4 - ↔ B 3 H 8 - + 2H 2 ), and as conducting media in electrolytes based on boron-hydride cage clusters. We report here the first observation of two phase transitions in CsB 3 H 8 prior to its decomposition above 230 °C. The previously reported orthorhombic room temperature phase (here named α-CsB 3 H 8 ) with the space group Ama2 changes into a new phase with the space group Pnma at 73 °C (here named β-CsB 3 H 8 ), and then into a face-centered cubic phase, here named γ-CsB 3 H 8 , at 88 °C. These phases are not stable at room temperature thus requiring in situ measurements for their characterization. The phase transitions and decomposition pathway of CsB 3 H 8 were studied with in situ synchrotron powder X-ray diffraction (SR-PXD), in situ and ex situ vibrational spectroscopies (Raman and FTIR), and differential-scanning calorimetry combined with thermo-gravimetric analysis (DSC-TGA). The structure determination was validated by vibrational spectroscopy analysis and modeling of the periodic structures by density functional methods. In γ-CsB 3 H 8 , a significant disorder in B 3 H 8 - positions and orientations was found which can potentially benefit cation conducting properties through the paddle mechanism.

Rare earth (RE) metal borohydrides are receiving immense consideration as possible hydrogen storage materials and solid-state Li-ion conductors. In this study, halide free Er(BH4)3 and Pr(BH4)3 have been successfully synthesized for the first time by the combination of mechanochemical milling and/or wet chemistry. Rietveld refinement of Er(BH4)3 confirmed the formation of two different Er(BH4)3 polymorphs: α-Er(BH4)3 with space group Pa3[combining macron], a = 10.76796(5) Å, and β-Er(BH4)3 in Pm3[combining macron]m with a = 5.4664(1) Å. A variety of Pr(BH4)3 phases were found after extraction with diethyl ether: α-Pr(BH4)3 in Pa3[combining macron] with a = 11.2465(1) Å, β-Pr(BH4)3 in Pm3[combining macron]m with a = 5.716(2) Å and LiPr(BH4)3Cl in I4[combining macron]3m, a = 11.5468(3) Å. Almost phase pure α-Pr(BH4)3 in Pa3[combining macron] with a = 11.2473(2) Å was also synthesized. The thermal decomposition of Er(BH4)3 and Pr(BH4)3 proceeded without the formation of crystalline products. Rehydrogenation, as such, was not successful. However, addition of LiH promoted the rehydrogenation of RE hydride phases and LiBH4 from the decomposed RE(BH4)3 samples.

Mechanochemical reactions between KBH4 and KBF4 result in the formation of potassium fluoroborohydrides K(BH(x)F(4-x)) (x = 0-4), as determined by (11)B and (19)F solid state NMR. The materials maintain the cubic KBH4 structure. Thermogravimetric (TG) data for a ball-milled sample with KBH4 : KBF4 = 3 : 1 are consistent with only desorption of hydrogen.

Aluminum trihydride (alane) is one of the most promising among the prospective solid hydrogen-storage materials, with a high gravimetric and volumetric density of hydrogen. In the present work, the alane, crystallizing in the gamma-AlH3 polymorphic modification, was synthesized and then structurally characterized by means of synchrotron X-ray powder diffraction. This study revealed that gamma-AlH3 crystallizes with an orthorhombic unit cell (space group Pnnm, a = 5.3806(1) A, b = 7.3555(2) A, c = 5.77509(5) A). The crystal structure of gamma-AlH3 contains two types of AlH6 octahedra as the building blocks. The Al-H bond distances in the structure vary in the range of 1.66-1.79 A. A prominent feature of the crystal structure is the formation of the bifurcated double-bridge bonds, Al-2H-Al, in addition to the normal bridge bonds, Al-H-Al. This former feature has not been previously reported for Al-containing hydrides so far. The geometry of the double-bridge bond shows formation of short Al-Al (2.606 A) and Al-H (1.68-1.70 A) bonds compared to the Al-Al distances in Al metal (2.86 A) and Al-H distances for Al atoms involved in the formation of normal bridge bonds (1.769-1.784 A). The crystal structure of gamma-AlH3 contains large cavities between the AlH6 octahedra. As a consequence, the density is 11% less than for alpha-AlH3.

Pure and doped NaAlH(4) with 5 mol % Ti on the basis of Ti(13).6THF have been investigated by means of X-ray synchrotron radiation. The Rietveld method has been used to study the possible substitution of Ti inside the NaAlH(4) structure and/or the presence of vacancies. This study indicates that there is no significant variation of the lattice parameter once the Na Alanate is doped with the Ti cluster. From the refinement of the site occupation factors, the substitution of Ti on the Na site can be excluded. A slight improvement was found when Ti was substituted on the Al site, but it is not significant enough to say that Ti definitely substitutes for Al in the Alanate phase. Additionally, there is no evidence for vacancy formation in Ti-colloid-doped sodium Alanate.

Several ways to synthesize solvated and desolvated calcium tetrahydroaluminate by wet-chemical and mechanochemical methods are presented. The products were characterized by elemental analysis, X-ray diffraction (XRD), and infrared spectroscopy (FTIR). The crystal structure of Ca(AlH(4))(2).4THF was determined. After desolvation, an ultrafine powder was obtained. IR data and the mass balance suggest a compound with the composition Ca(AlH(4))(2), containing tetrahedral [AlH(4)] groups.

Surface-protected, air-stable nanoparticles of CoPt and CoPt3 were prepared by thermal decomposition/reduction of organometallic precursors with a long-chain aliphatic diol, also known as the polyol process. Particles 3 nm in diameter showed ferromagnetic behavior up to 350 K (Hc = 65 Oe at T = 300 K; Hc = 410 Oe at T = 5K) and underwent a disordering-ordering phase transformation after annealing that resulted in an increase in coercivity (Hc = 170 Oe at T = 300 K; Hc = 2000 Oe at T = 5 K).