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.

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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: aszyubin@bk.ru
Russian Federation, Chernogolovka, Moscow region, 142432

T. S. Zyubina

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

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

O. V. Kravchenko

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

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

M. V. Solovev

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

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

V. P. Vasiliev

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

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

A. A. Zaitsev

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

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

A. V. Shikhovtsev

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

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

Yu. A. Dobrovol’sky

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

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

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Supplementary files

Supplementary Files
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2. Fig. 1. Configurations of the MgZn(BH4)4 4NH3 system that arise upon removal of up to four H2 molecules. The number after the letter D denotes the number of H2 molecules removed.

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3. Fig. 2. Gibbs energies for configurations of the ZnMg(BH4)4 4NH3 system that arise upon removal of up to four (D0–D4) and six (D4–D6) H2 molecules.

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4. Fig. 3. Configurations of the MgZn(BH4)4 4NH3 system that arise upon removal of four to six H2 molecules.

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5. Fig. 4. Configurations of the MgZn(BH4)4 4NH3 system that arise upon removal of six to nine H2 molecules.

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6. Fig. 5. Gibbs energies for configurations of the ZnMg(BH4)4 4NH3 system arising upon removal of six to nine (D6–D9) H2 molecules.

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7. Fig. 6. Configurations of the Mg2Zn2(BH4)8 8NH3 system arising upon removal of sixteen to seventeen H2 molecules.

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8. Fig. 7. Gibbs energies for configurations of the Zn2Mg2(BH4)8 8NH3 system arising upon removal of sixteen to nineteen (Q16–Q19) H2 molecules.

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9. Fig. 8. Configurations of the Mg2Zn2(BH4)8 8NH3 system arising upon removal of seventeen to eighteen H2 molecules.

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10. Fig. 9. Configurations of the Mg2Zn2(BH4)8 · 8NH3 system arising upon removal of nineteen to twenty-one H2 molecules.

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11. Fig. 10. Gibbs energies for configurations of the Zn2Mg2(BH4)8 · 8NH3 system arising upon removal of nineteen to twenty-three (Q19–Q23) H2 molecules.

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12. Fig. 11. Configurations of the Mg2Zn2(BH4)8 · 8NH3 system arising upon removal of twenty-one to twenty-three H2 molecules.

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13. Fig. 12. Configurations of the Mg2Zn2(BH4)8 · 8NH3 system arising upon removal of twenty-three to twenty-five H2 molecules.

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14. Fig. 13. Gibbs energies for configurations of the Zn2Mg2(BH4)8 · 8NH3 system arising upon removal of twenty-three to twenty-five (Q23–Q25) H2 molecules.

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15. Fig. 14. Configurations of the Mg2Zn2(BH4)8 · 8NH3 system arising upon removal of twenty-four to twenty-six H2 molecules.

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