Hydrolysis of Mg(BH4)2 and its coordination compounds as a way to obtain hydrogen

Three ligand-stabilized Mg(BH4)2–based complexes have been synthesized and evaluated as potential hydrogen storage media for portable fuel cell applications. The new borohydrides: Mg(BH4)2 × 0.5Et2O and Mg(BH4)2 × diglyme (diglyme – CH3O(CH2)2O(CH2)2OCH3) have been synthesized and examined by X-ray single crystal diffraction method. Hydrolysis reactions of the compounds liberate hydrogen in quantities ranging from 46 to 96% of the theoretical yield. The hydrolysis of Mg(BH4)2 and other borohydrides is also accompanied by the diborane formation. The amount of liberated diborane depends on the Mg-coordination environment. To explain this fact quantum-chemical calculations have been performed. It is shown that formation of Mg-O-Mg-bridges enables the side process of diborane generation. It means that the size and denticity of the ligand directly affects the amount of released diborane. In general, the larger the ligand and the higher its denticity, the smaller is amount of diborane produced. The new compound Mg(BH4)2 × diglyme decomposes without diborane formation that allows one to be considered as a new promising chemical hydrogen storage compound for the practical usage. © 2017 Elsevier B.V

Role of non-covalent interactions at the oxidation of 2,5-di-Me-pyrazine-di-N-oxide at glassy carbon, single-walled and multi-walled carbon nanotube paper electrodes

Recently in our work it was shown that the catalytic efficiency of organic compound oxidation in the presence of electrochemically generated radical cations of aromatic di-N-oxides was increased several times using single-walled (SWCNT) or multi-walled (MWCNT) carbon nanotube paper electrodes instead of glassy carbon (GC) electrode. It was found that, in the absence of substrate, the oxidation currents of di-N-oxides at SWCNT or MWCNT paper electrodes, in contrast to the GC electrode, exceeded the oxidation current of the ferrocene (Fc) reference several times. In this work, the study of 2,5-di-Me-pyrazine-di-N-oxide (Pyr1) and Fc oxidation in 0.1 M Bu4NClO4 solutions in acetonitrile (MeCN) at GC, SWCNT and MWCNT paper electrodes was performed by methods of cyclic voltammetry, electron paramagnetic resonance (EPR) electrolysis, and differential capacitance. Quantum chemical modeling of adsorption of Pyr1, Fc, and MeСN on CNT surface was carried out using a cluster model describing the surface of conducting and non-conducting carbon nanotubes. The adsorption energies, equilibrium distances for molecular location and orientation on CNT surface were obtained. The observed effects were explained on the basis of quantum chemical modeling of the non-covalent interaction of the components of the studied system with CNT surface

Hydrolysis of Mg(BH4)2 and its coordination compounds as a way to obtain hydrogen

Three ligand-stabilized Mg(BH4)2–based complexes have been synthesized and evaluated as potential hydrogen storage media for portable fuel cell applications. The new borohydrides: Mg(BH4)2 × 0.5Et2O and Mg(BH4)2 × diglyme (diglyme – CH3O(CH2)2O(CH2)2OCH3) have been synthesized and examined by X-ray single crystal diffraction method. Hydrolysis reactions of the compounds liberate hydrogen in quantities ranging from 46 to 96% of the theoretical yield. The hydrolysis of Mg(BH4)2 and other borohydrides is also accompanied by the diborane formation. The amount of liberated diborane depends on the Mg-coordination environment. To explain this fact quantum-chemical calculations have been performed. It is shown that formation of Mg-O-Mg-bridges enables the side process of diborane generation. It means that the size and denticity of the ligand directly affects the amount of released diborane. In general, the larger the ligand and the higher its denticity, the smaller is amount of diborane produced. The new compound Mg(BH4)2 × diglyme decomposes without diborane formation that allows one to be considered as a new promising chemical hydrogen storage compound for the practical usage. © 2017 Elsevier B.V

Effect of lattice relaxation on spin density of nitrogen-vacancy centers in diamond and oscillator strength calculations

Using a generalized Hubbard Hamiltonian, many-electron wavefunctions of negatively charged (NV−) and neutral nitrogen-vacancy (NV0) centers in diamond were calculated. We report the effect of symmetric relaxation of surrounding atoms on the spin density, calculated from the many electron wavefunctions in the ground and excited states. We evaluated the error, that, arises in estimation of spin density when lattice relaxation effect is neglected in Electron Paramagnetic Resonance experiment and showed that the ground state spin density distribution is accessible in outward relaxations. The computed oscillator strengths give a higher efficiency for the 1.945 eV photoluminescence (PL) line of NV− with respect to 2.156 eV PL line of NV0 which agrees well with experiment. This result is explained based on the largest the ground state spin among available values for the NV− with respect to NV0. The transition probability between degenerate ground and excited states slightly depends on the Sz value. Finally, we report on the electronic configurations which contribute to the ground and excited states and discuss the population variation of electronic configurations with relaxation