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

封面

如何引用文章

全文:

开放存取 开放存取
受限制的访问 ##reader.subscriptionAccessGranted##
受限制的访问 订阅或者付费存取

详细

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.

全文:

受限制的访问

作者简介

A. Zyubin

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

编辑信件的主要联系方式.
Email: aszyubin@bk.ru
俄罗斯联邦, 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
俄罗斯联邦, 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
俄罗斯联邦, 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
俄罗斯联邦, 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
俄罗斯联邦, 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
俄罗斯联邦, 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
俄罗斯联邦, 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
俄罗斯联邦, Chernogolovka, Moscow region, 142432; Chernogolovka, Moscow region, 142432

参考

  1. Ritter A., Ebner A.D., Wang J., Zidan R. // Mater. Today. 2003. V. 6. P. 18.
  2. Schlapbach L., Zuttel A. // Nature. 2001. V. 414. P. 353.
  3. Züttel A. // Mater. Today. 2003. V. 6. P. 24.
  4. Orimo S.-I., Nakamori Y., Eliseo J.R. et al. // Chem. Rev. 2007. V. 107. P. 4111.
  5. Ouyang L., Chen K., Jiang J. et al. // J. Alloys Compd. 2020. V. 829. P. 154597.
  6. Sakintuna B., Lamari-Darkrim F., Hirscher M. // Int. J. Hydrogen Energy. 2007. V. 32. P. 1121.
  7. Diwan M., Diakov V., Shafirovich E., Varma A. // Int. J. Hydrogen Energy. 2008. V. 33. P. 1135.
  8. Guo Y., Yu X., Sun W. et al. // Angew. Chem. Int. Ed. 2011. V. 50. P. 1087.
  9. Richter B., Ravnsbæk D.B., Tumanov N. et al. // Dalton Trans. 2015. V. 44. P. 3988.
  10. Paskevicius M., Jepsen L.H., Schouwink P. et al. // Chem. Soc. Rev. 2017. V. 46. P. 1565.
  11. Wu R., Ren Z., Zhang X. et al. // J. Phys. Chem. Lett. 2019. V. 10. P. 1872.
  12. Kravchenko O.V., Kravchenko S.E., Semenenko K.N. // J. Gen. Chem. USSR. 1990. V. 60. P. 2641.
  13. Johnson S.R., David W.I.F., Royse D.M. et al. // Chem. Asian J. 2009. V. 4. P. 849.
  14. Zhao S., Xu B., Sun N. et al. // Int. J. Hydrogen Energy. 2015. V. 40. P. 8721.
  15. Zavorotynska O., El-Kharbachi A., Deledda S. et al. // Int. J. Hydrogen Energy. 2016. V. 41. P. 14387. http://dx.doi.org/10.1016/j.ijhydene.2016.02.015
  16. Zyubin A.S., Zyubina T.S., Kravchenko O.V. et al. // Russ. J. Inorg. Chem. 2016. V. 61. P. 731. https://doi.org/10.1134/S0036023616060231
  17. Zyubin A.S., Zyubina T.S., Kravchenko O.V. et al. // Russ. J. Inorg. Chem. 2018. V. 63. P. 201. https://doi.org/10.1134/S0036023618020237
  18. Solovev M.V., Chashchikhin O.V., Dorovatovskii P.V. et al. // J. Power Sources. 2018. V. 377. P. 93. https://doi.org/10.1016/j.jpowsour.2017.11.090
  19. Guo Y., Xia G., Zhu Y. et al. // Chem. Commun. 2010. V. 46. P. 2599. https://doi.org/10.1039/B924057H
  20. Chu H., Wu G., Xiong Z. et al. // Chem. Mater. 2010. V. 22. P. 6021. https://doi.org/10.1021/cm1023234.
  21. Guo Y., Yu X., Sun W. et al. // Angew. Chem. Int. Ed. 2011. V. 50. P. 1087. https://doi.org/10.1002/anie.201006188.
  22. Vasiliev V.P., Kravchenko O.V., Soloviev M.V. et al. // Int. J. Hydrogen Energy. 2022. V. 47. P. 35320. https://doi.org/10.1016/j.ijhydene.2022.08.100.
  23. Zhu Y., Shen S., Yang X-S. et al. // ACS Sustainable Chem. Eng. 2023. V. 11. P. 8931. https://doi.org/10.1021/acssuschemeng.3c01073.
  24. Solovev M.V., Vasiliev V.P., Shilov G.V. et al. // Russ. Chem. Bull. 2024. V. 73. P. 906. https://doi.org/10.1007/s11172-024-4204-z.
  25. Yang Y., Liu Y., Zhang Y. et al. // J. Alloys Compd. 2014. V. 585. P. 674. http://dx.doi.org/10.1016/j.jallcom.2013.09.208
  26. Soloveichik G., Her J.-H., Stephens P.W. et al. // Inorg. Chem. 2008. V. 47. P. 4290. https://doi.org/10.1021/ic7023633
  27. Guo Y., Wu H., Zhou W., Yu X. // J. Amer. Chem. Soc. 2011. V. 133. P. 4690. http://dx.doi.org/10.1021/ja1105893
  28. Yang Y., Liu Y., Li Y. et al. // Chem. Asian J. 2013. V. 8. P. 476. https://doi.org/10.1002/asia.201200970
  29. Yang Y., Liu Y., Li Y. et al. // J. Phys. Chem. C. 2013. V. 117. P. 16326. http://dx.doi.org/10.1021/jp404424m
  30. Jepsen L.H., Ley M.B. et al. // Chem-Sus Chem. 2015. V. 8. P. 1452. https://doi.org/10.1002/cssc.201500029
  31. Yan Y., Dononelli W., Jorgensen M. et al. // Phys. Chem. Chem. Phys. 2020. V. 22. P. 9204. https://doi.org/10.1039/d0cp00158a
  32. Chen X., Yu X. // J. Phys. Chem. C. 2012. V. 116. P. 11900. http://dx.doi.org/10.1021/jp301986k
  33. Yuan P.-F., Wang F., Sun Q. et al. // Int. J. Hydrogen Energy. 2013. V. 38. P. 2836. http://dx.doi.org/10.1016/j.ijhydene.2012.12.075
  34. Wang K., Zhang J.-G., Lang X.-Q. // Phys. Chem. Chem. Phys. 2016. V. 18. P. 7015. https://doi.org/10.1039/C5CP06808H
  35. Chen X., Li R., Xia G. et al. // RSC Adv. 2017. V. 7. P. 31027. https://doi.org/10.1039/c7ra05322c
  36. Chen X., Zou W., Li R. et al. // J. Phys. Chem. C. 2018. V. 122. P. 4241. https://doi.org/10.1021/acs.jpcc.8b00455
  37. Vasiliev V.P., Solovev M.V., Kravchenko O.V. et al. // J. Alloys Compd. 2024. V. 1008. P. 176732. https://doi.org/10.1016/j.jallcom.2024.176738.
  38. Nickels E.A., Jones M.O., David W.I.F. et al. // Angew. Chem. Int. Ed. 2008. V. 47. P. 2817. https://doi.org/10.1002/anie.200704949.
  39. Ravnsbæk D., Filinchuk Y., Cerenius Y. et al. // Angew. Chem. Int. Ed. 2009. V. 48. P. 6659. https://doi.org/10.1002/anie.200903030.
  40. Lindemann I., Ferrer R.D., Dunsch L. et al. // Chem. Eur. J. 2010. V. 16. P. 8707. https://doi.org/10.1002/chem.201000831.
  41. Černy R., Kim K.C., Penin N. et al. // J. Phys. Chem. C. 2010. V. 114. P. 19127. https://doi.org/10.1021/jp105957r.
  42. Fang Z.Z., Kang X.D., Wang P. et al. // J. Alloys Compd. 2010. V. 491. P. L1. https://doi.org/10.1016/j.jallcom.2009.10.149.
  43. Fang Z.Z., Kang X.D., Luo J.H. et al. // J. Phys. Chem. C. 2010. V. 114. P. 22736. https://doi.org/10.1021/jp109260g.
  44. Aidhy D.S., Wolverton C. // Phys. Rev. B. 2011. V. 83. P. 144111. https://doi.org/10.1103/PhysRevB.83.144111.
  45. Zyubin A.S., Zyubina T.S., Kravchenko O.V. et al. // Russ. J. Inorg. Chem. 2024. V. 69. P. 867. https://doi.org/10.1134/S0036023624600874
  46. Zyubin A.S., Zyubina T.S., Kravchenko O.V. et al. // Russ. J. Inorg. Chem. 2022. V. 67. P. 1591.
  47. Becke A.D. // J. Chem. Phys. 1993. V. 98. P. 5648. https://doi.org/10.1063/1.464913
  48. Johnson B.J., Gill P.M.W., Pople J.A. // J. Chem. Phys. 1993. V. 98. P. 5612. https://doi.org/10.1063/1.464906
  49. Gaussian 09, Revision B.01. Gaussian, Inc., Wallingford CT, 2010. https://doi.org/10.1063/1.464906

补充文件

附件文件
动作
1. JATS XML
下载
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.

下载 (97KB)
索引源数据
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.

下载 (39KB)
索引源数据
4. Fig. 3. Configurations of the MgZn(BH4)4 4NH3 system that arise upon removal of four to six H2 molecules.

下载 (88KB)
索引源数据
5. Fig. 4. Configurations of the MgZn(BH4)4 4NH3 system that arise upon removal of six to nine H2 molecules.

下载 (88KB)
索引源数据
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.

下载 (19KB)
索引源数据
7. Fig. 6. Configurations of the Mg2Zn2(BH4)8 8NH3 system arising upon removal of sixteen to seventeen H2 molecules.

下载 (108KB)
索引源数据
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.

下载 (39KB)
索引源数据
9. Fig. 8. Configurations of the Mg2Zn2(BH4)8 8NH3 system arising upon removal of seventeen to eighteen H2 molecules.

下载 (99KB)
索引源数据
10. Fig. 9. Configurations of the Mg2Zn2(BH4)8 · 8NH3 system arising upon removal of nineteen to twenty-one H2 molecules.

下载 (104KB)
索引源数据
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.

下载 (45KB)
索引源数据
12. Fig. 11. Configurations of the Mg2Zn2(BH4)8 · 8NH3 system arising upon removal of twenty-one to twenty-three H2 molecules.

下载 (103KB)
索引源数据
13. Fig. 12. Configurations of the Mg2Zn2(BH4)8 · 8NH3 system arising upon removal of twenty-three to twenty-five H2 molecules.

下载 (92KB)
索引源数据
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.

下载 (25KB)
索引源数据
15. Fig. 14. Configurations of the Mg2Zn2(BH4)8 · 8NH3 system arising upon removal of twenty-four to twenty-six H2 molecules.

下载 (63KB)
索引源数据

版权所有 © Russian Academy of Sciences, 2025