Quantum‒Chemical Simulation of Molecular Hydrogen Abstraction from Magnesium Borohydride Diammoniate

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Abstract

Within the framework of the cluster approach using the 6‒31G* basis set and the hybrid density functional (B3LYP), we modeled successive abstraction of H2 from the complexes (Mg(BH4)2∙2NH3)2 and (Mg(BH4)2∙2NH3)4. It was found that the initial stage of dehydrogenation needs overcoming energy barriers ~ 1.5‒1.2 eV, which requires preheating, then the process can go on with energy release until about 10 wt % of H2 is extracted, for a higher degree of conversion, additional energy costs exceeding the combustion heat of H2 will be required when extracting more than 12.5 wt % of H2. Therefore, further dehydrogenation of this compound may turn out to be inexpedient from the energy point of view.

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About the authors

A. S. Zyubin

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Author for correspondence.
Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432

T. S. Zyubina

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432

O. V. Kravchenko

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432

M. V. Solov’ev

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432

V. P. Vasiliev

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432

A. A. Zaitsev

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432

A. V. Shikhovtsev

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences; Hydrogen energy center of AFK “Sistema”

Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432; Chernogolovka, 142432

Y. A. Dobrovol’sky

Federal Research Center for Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences; Hydrogen energy center of AFK “Sistema”

Email: zyubin@icp.ac.ru
Russian Federation, Chernogolovka, 142432; Chernogolovka, 142432

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Supplementary files

Supplementary Files
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2. Fig. 1. Configurations of the [Mg(BH4)22NH3]2 system that occur when up to three H2 molecules are removed. The number after the letter D indicates the number of H2 molecules removed.

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3. Fig. 2. Gibbs energies for the configurations of the [Mg(BH4)22NH3]2 system arising from the removal of up to four (D0‒D4) and up to nine (D4‒D9) H2 molecules.

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4. Fig. 3. Configurations of the [Mg(BH4)22NH3]2 system that occur when four to eight H2 molecules are removed.

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5. Fig. 4. Configurations of the [Mg(BH4)22NH3]2 system that occur when eight to ten H2 molecules are removed.

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6. Fig. 5. Gibbs energies for configurations of the Mg(BH4)22NH3]2 system that occur when nine to twelve (D9‒D12) H2 molecules are removed.

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7. Fig. 6. Configurations of the [Mg(BH4)22NH3]2 system arising from the removal of eleven and twelve H2 molecules, and complexes arising from the unification of D9‒D12 structures.

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8. Fig. 7. Configurations of the [Mg(BH4)22NH3]4 system that occur when eighteen to nineteen H2 molecules are removed.

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9. Fig. 8. Configurations of the [Mg(BH4)22NH3]4 system that occur when nineteen to twenty-three H2 molecules are removed.

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10. Fig. 9. Gibbs energies for the configurations of the [Mg(BH4)22NH3]4 system arising at a distance of eighteen to twenty-three H2 molecules.

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11. Supplement
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