ABSTRACT
The first bimetallic imidazolates containing alkali and alkaline earth metals, NaMgIm3 and KMgIm3, respectively, are prepared by mechanochemical synthesis and are reported in this paper. NaMgIm3 has been prepared by the reaction between NaIm and Mg(BH4)2 as well as directly from NaIm and MgIm2. Structural evolution and thermal stability were followed by an in situ high-temperature X-ray powder diffraction experiment utilizing synchrotron radiation. In both compounds, the imidazolate ligand is connected to four metal cations forming a complex three-dimensional network with channels running along the c-direction. NaMgIm3 and KMgIm3 are the first members of a new family of imidazolate frameworks with stp topology. The formation of mixed-alkali-metal imidazolate compounds is thermodynamically controlled. LiIm and MgIm2 have not yielded a mixed-metal compound, while KIm reacts swiftly and forms KMgIm3.
ABSTRACT
To investigate the dynamical properties of the novel hybrid compound, lithium benzimidazolate-borohydride Li2(bIm)BH4 (where bIm denotes a benzimidazolate anion, C7N2H5 -), we have used a set of complementary techniques: neutron powder diffraction, ab initio density functional theory calculations, neutron vibrational spectroscopy, nuclear magnetic resonance, neutron spin echo, and quasi-elastic neutron scattering. Our measurements performed over the temperature range from 1.5 to 385 K have revealed the exceptionally fast low-temperature reorientational motion of BH4 - anions. This motion is facilitated by the unusual coordination of tetrahedral BH4 - anions in Li2(bIm)BH4: each anion has one of its H atoms anchored within a nearly square hollow formed by four coplanar Li+ cations, while the remaining -BH3 fragment extends into a relatively open space, being only loosely coordinated to other atoms. As a result, the energy barriers for reorientations of this fragment around the anchored B-H bond axis are very small, and at low temperatures, this motion can be described as rotational tunneling. The tunnel splitting derived from the neutron spin echo measurements at 3.6 K is 0.43(2) µeV. With increasing temperature, we have observed a gradual transition from the regime of low-temperature quantum dynamics to the regime of classical thermally activated jump reorientations. The jump rate of the uniaxial 3-fold reorientations reaches 5 × 1011 s-1 at 80 K. Nearer room temperature and above, both nuclear magnetic resonance and quasielastic neutron scattering measurements have revealed the second process of BH4 - reorientations characterized by the activation energy of 261 meV. This process is several orders of magnitude slower than the uniaxial 3-fold reorientations; the corresponding jump rate reaches ~7 × 108 s-1 at 300 K.
ABSTRACT
Metal borohydrides are intensively researched as high-capacity hydrogen storage materials. Aluminum is a cheap, light, and abundant element and Al3+ can serve as a template for reversible dehydrogenation. However, Al(BH4 )3 , containing 16.9â wt % of hydrogen, has a low boiling point, is explosive on air and has poor storage stability. A new family of mixed-cation borohydrides M[Al(BH4 )4 ], which are all solid under ambient conditions, show diverse thermal decomposition behaviors: Al(BH4 )3 is released for M=Li+ or Na+ , whereas heavier derivatives evolve hydrogen and diborane. NH4 [Al(BH4 )4 ], containing both protic and hydridic hydrogen, has the lowest decomposition temperature of 35 °C and yields Al(BH4 )3 â NHBH and hydrogen. The decomposition temperatures, correlated with the cations' ionic potential, show that M[Al(BH4 )4 ] species are in the most practical stability window. This family of solids, with convenient and versatile properties, puts aluminum borohydride chemistry in the mainstream of hydrogen storage research, for example, for the development of reactive hydride composites with increased hydrogen content.
