Quantum-chemical simulation of molecular hydrogen abstraction from the ZnMg(BH4)4 ⋅ 4NH3 bicationic complex

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Abstract

Within the framework of the cluster approach using the 6-31G* basis set and the hybrid density functional (B3LYP), was modeled successive abstraction of H2 from the [ZnMg(BH4)4 4NH3] and [Zn2Mg2(BH4)8⋅8NH3] complexes. It was found that to start the dehydrogenation process, it is necessary to overcome the energy barrier of ~1.25 eV, then the process proceeds with the release of energy until about 70% of the available H2 is extracted, for a higher degree of conversion additional energy costs will be required. The cleavage of H2 molecules occurs through a number of intermediate structures of varying complexity with the significant participation of metal cations and the formation of fragments of chains based on B-N bonds containing fragments of N-H and B-H, which can be detected by IR spectroscopy, when dehydrogenation is stopped.

About the authors

A. S. Zyubin

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry

Email: aszyubin@bk.ru
Chernogolovka, Moscow region, 142432 Russia

T. S. Zyubina

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry

Email: aszyubin@bk.ru
Chernogolovka, Moscow region, 142432 Russia

O. V. Kravchenko

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry; Center of Hydrogen Energy (Sistema PJSFC)

Email: aszyubin@bk.ru
Chernogolovka, Moscow region, 142432 Russia; Chernogolovka, Moscow region, 142432 Russia

M. V. Solovev

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry

Email: aszyubin@bk.ru
Chernogolovka, Moscow region, 142432 Russia

V. P. Vasiliev

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry; Center of Hydrogen Energy (Sistema PJSFC)

Email: aszyubin@bk.ru
Chernogolovka, Moscow region, 142432 Russia; Chernogolovka, Moscow region, 142432 Russia

A. A. Zaitsev

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry

Email: aszyubin@bk.ru
Chernogolovka, Moscow region, 142432 Russia

A. V. Shikhovtsev

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry; Center of Hydrogen Energy (Sistema PJSFC)

Email: aszyubin@bk.ru
Chernogolovka, Moscow region, 142432 Russia; Chernogolovka, Moscow region, 142432 Russia

Y. A. Dobrovol'sky

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry; Center of Hydrogen Energy (Sistema PJSFC)

Author for correspondence.
Email: aszyubin@bk.ru
Chernogolovka, Moscow region, 142432 Russia; Chernogolovka, Moscow region, 142432 Russia

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