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

Мұқаба

Дәйексөз келтіру

Толық мәтін

Ашық рұқсат Ашық рұқсат
Рұқсат жабық Рұқсат берілді
Рұқсат жабық Рұқсат ақылы немесе тек жазылушылар үшін

Аннотация

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.

Толық мәтін

Рұқсат жабық

Авторлар туралы

A. Zyubin

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

Хат алмасуға жауапты Автор.
Email: aszyubin@bk.ru
Ресей, Chernogolovka, Moscow region, 142432

T. Zyubina

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

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

O. 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
Ресей, Chernogolovka, Moscow region, 142432; Chernogolovka, Moscow region, 142432

M. Solovev

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

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

V. 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
Ресей, Chernogolovka, Moscow region, 142432; Chernogolovka, Moscow region, 142432

A. Zaitsev

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

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

A. 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
Ресей, Chernogolovka, Moscow region, 142432; Chernogolovka, Moscow region, 142432

Yu. 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
Ресей, Chernogolovka, Moscow region, 142432; Chernogolovka, Moscow region, 142432

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Жүктеу
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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