Influence of atoms of nitrogen and boron atoms inserted into graphene-like matrix on molecular hydrogen adsorption

  • E. M. Demyanenko O.O.Chuiko Institute of Surface Chemistry of the National Academy of Sciences of Ukraine
  • V. V. Lobanov O.O.Chuiko Institute of Surface Chemistry of the National Academy of Sciences of Ukraine
  • A. G. Grebenyuk O.O.Chuiko Institute of Surface Chemistry of the National Academy of Sciences of Ukraine
  • O. S. Karpenko O.O.Chuiko Institute of Surface Chemistry of the National Academy of Sciences of Ukraine
  • M. T. Kartel O.O.Chuiko Institute of Surface Chemistry of the National Academy of Sciences of Ukraine
Keywords: molecular hydrogen, adsorption, graphene-like cluster, density functional theory method, cluster approach, activation energy, energy effect of reaction, dissociative chemisorption, polyaromatic molecules, nitrogen- and boron-containing aromatics

Abstract

The features of the interaction of hydrogen molecules with graphene-like planes in which two carbon atoms are replaced by nitrogen or boron atoms are investigated by methods of quantum chemistry (DFT, B3LYP, 6-31G**). To take into account the dispersion contributions to the energy of the formation of intermolecular complexes that arise in the formation of adsorption supramolecular structures, the dispersion correction Grimme-D3 is used.

To study the influence of the size of the graphene-like cluster on the molecular hydrogen chemisorption energy in the model of graphene nanoparticles, polyaromatic molecules (PAM) pyrene, coronene (Cor) and that of 54 carbon atoms, as well as their nitrogen and boron-containing analogues, in which the atoms of nitrogen and boron are placed in a para-position in relation to one another, in the so-called piperazine configuration of the atoms of nitrogen or boron.

Equilibrium spatial structures of reagent molecules, formed complexes and products of dissociative chemisorption of hydrogen molecules were found by minimizing the norm of a gradient of total energy. An important stage in the transformation of physically sorbed H2 molecules on the surface of the most carbon materials is its decomposition into two hydrogen atoms that can bind to different carbon atoms of model molecules. In this case, a significant number of different reaction products of the same gross composition is formed. The lowest energy among them is related to one where the atoms of the hydrogen are bound to carbon atoms that are adjacent to the nitrogen or boron atoms. It has been found that, regardless of the size of the carbon PAM, the value of the chemisorption energy in all cases has a positive value and is greater than 100 kJ/mol. The chemisorption energy of the hydrogen molecule by PAM with heteroatoms depends on the size of the model, the position of the atoms of nitrogen and boron and, for the most part, has a small negative value (up to -35 kJ/mole), which indicates the spontaneity of the corresponding process. Calculations have shown that the lowest activation energy of the reaction of the H2 molecule with boron PAM, and the most - for pure carbon PAM, regardless of the size of the models. The nature of the heteroatom changes the structure of the transition state and the mechanism of chemisorption.

Analysis of the results of quantum chemical calculations showed the highest exothermicity of dissociative adsorption of H2 molecule on boron-containing graphene-like molecules. For nitrogen-containing surfactants, the reaction is slightly less exothermic, as well as the possibility of desorption of atomic hydrogen from the surface of the latter with subsequent recombination in the gas phase. At the same time, for the models of pure graphene-like layer, these data indicate that chemosorption of molecular hydrogen is impossible. Without a total analysis of the results of all possible placements of a pair of hydrogen atoms (formed by the dissociation of the H2 molecule) when they are bound to nitrogen-containing polyaromatic molecules, it can be noted that the dissociation chemisorption of the H2 molecule, regardless of the nature of the heteroatom in the PAM, is thermodynamically more probable at the periphery of the model molecules than in their center.

References

1. Niaz S., Manzoor T., Pandith A.H. Hydrogen storage: Materials, methods and perspectives. Renewable Sustainable Energy Rev. 2015. 50: 457. https://doi.org/10.1016/j.rser.2015.05.011

2. Uyar T.S.D. Beşikci Integration of hydrogen energy systems into renewable energy systems for better design of 100% renewable energy communities. Int. J. Hydrogen Energ. 2017. 42(4): 2453. https://doi.org/10.1016/j.ijhydene.2016.09.086

3. Qi J., Zhang W., Cao R. Solar to Hydrogen Energy Conversion Based on Water Splitting. Adv. Energy Mater. 2018. 8(5): 1701620. https://doi.org/10.1002/aenm.201701620

4. Ross D.K. Hydrogen storage: The major technological barrier to the development of hydrogen fuel cell cars. Vacuum. 2006. 80(10): 1084. https://doi.org/10.1016/j.vacuum.2006.03.030

5. Nagar R., Vinayan B.P., Samantaray S.S., Ramaprabhu S. Recent advances in hydrogen storage using catalytically and chemically modified graphene nanocomposites. J. Mater. Chem. A. 2017. 5(44): 22897. https://doi.org/10.1039/C7TA05068B

6. Rajaura R.S., Srivastava S., Sharma P.K., Mathur Sh., Shrivastava R., Sharma S.S., Vijay Y.K. Structural and surface modification of carbon nanotubes for enhanced hydrogen storage density. Nano-Structures & Nano-Objects. 2018. 14: 57. https://doi.org/10.1016/j.nanoso.2018.01.005

7. Arjunan A., Viswanathan B., Nandhakumar V. Nitrogen-incorporated carbon nanotube derived from polystyrene and polypyrrole as hydrogen storage material. Int. J. Hydrogen Energ. 2018. 43(10): 5077. https://doi.org/10.1016/j.ijhydene.2018.01.110

8. Chambers A, Park C, Baker R.T.K., Rodriguez N.M. Hydrogen storage in graphite nanofibers. J. Phys. Chem. B. 1998. 102(22): 4253. https://doi.org/10.1021/jp980114l

9. Murata K.K., Kaneko K., Kanoh H., Kasuya D., Takahashi K., Kokai F., Yudasaka M., Iijima S. Adsorption mechanism of supercritical hydrogen in internal and interstitial nanospaces of single-wall carbon nanohorn assembly. J. Phys. Chem. B. 2002. 106(43): 1132. https://doi.org/10.1021/jp020583u

10. Gayathri V., Geetha R. Hydrogen adsorption in defect carbon nanotubes. Adsorption. 2007. 13(1): 53. https://doi.org/10.1007/s10450-007-9002-z

11. Dillon A.C., Jones K.M., Bekkedalh T.A., C.-H. Kiang Storage of hydrogen in single-walled carbon nanotubes. Nature. 1997. 386(6623): 377. https://doi.org/10.1038/386377a0

12. McKay H., Wales D.J., Jenkins S.J., Verges J.A., de Andres P.L. Hydrogen on graphene under stress: Molecular dissociation and gap opening. Phys. Rev. B. 2010. 81: 075425. https://doi.org/10.1103/PhysRevB.81.075425

13. Lee H., Ihm J., Cohen M.L. Calcium decorated carbon nanotubes for high capacity hydrogen storage: First principles calculations. Nano Lett. 2010. 10: 793. https://doi.org/10.1021/nl902822s

14. Ao Z.M., Peeters F.M. High-capacity hydrogen storage in Al-adsorbed graphene. Phys. Rev. B. 2010. 81(20): 205406. https://doi.org/10.1103/PhysRevB.81.205406

15. Schmidt M.W., Baldridge K.K., Boatz J.A., Elbert S.T., Gordon M.S., Jensen J.H., Koseki Sh., Matsunaga N., Nguyen K.A., Su Sh., Windus T.L., Dupuis M., Montgomery J.A. General atomic and molecular electronic structure system. J. Comput. Chem. 1993. 14(11): 1347. https://doi.org/10.1002/jcc.540141112

16. Becke A.D. Density functional thermo-chemistry. III. The role of exact exchange. J. Chem. Phys. 1993. 98(7): 5648. https://doi.org/10.1063/1.464913

17. Lee C., Yang W., Parr R.G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B. 1988. 37(2): 785. https://doi.org/10.1103/PhysRevB.37.785

18. Jackson K., Jaffar S. K., Paton R.S. Computational Organic Chemistry. Annu. Rep. Prog. Chem., Sect. B: Org. Chem. 2013. 109: 235.

19. Hutchison G.R., Ratner M.A., Marks T.J. Intermolecular Charge Transfer between Heterocyclic Oligomers. Effects of Heteroatom and Molecular Packing on Hopping Transport in Organic Semiconductors. J. Am. Chem. Soc. 2005. 127(48): 16866. https://doi.org/10.1021/ja0533996

20. Grimme S., Ehrlich S., Goerigk L. Effect of the Damping Function in Dispersion Corrected Density Functional Theory. J. Comput. Chem. 2011. 32(7): 1456. https://doi.org/10.1002/jcc.21759

21. Grimme S. Density functional theory with London dispersion corrections. Wires Comput. Mol. Sci. 2011. 1(2): 211. https://doi.org/10.1002/wcms.30

22. Alrawashdeh A.I., Lagowski J.B. The role of the solvent and the size of the nanotube in the non-covalent dispersion of carbon nanotubes with short organic oligomers – a DFT study. RSC Adv. 2018. 8(53): 30520. https://doi.org/10.1039/C8RA02460J

23. Wales D.J., Berry R.S. Limitations of the Murrell-Laidler theorem. J. Chem. Soc. Faraday Trans. 1992. 88(4): 543. https://doi.org/10.1039/FT9928800543

24. Fukui K. The path of chemical reactions – the IRC approach. Acc. Chem. Res. 1981. 14(12): 363. https://doi.org/10.1021/ar00072a001

25. Dreyer D.R., Park S., Bielawski C.W., Ruoff R.S. The chemistry of graphene oxide. Chem. Soc. Rev. 2010. 39(1): 228. https://doi.org/10.1039/B917103G

26. Koopmans T. Über die Zuordnung von Wellenfunktionen und Eigenwerten zu den einzelnen Elektronen eines Atoms. Physica. 1934. 1: 104. https://doi.org/10.1016/S0031-8914(34)90011-2

27. Bellafont N.P., Illas F., Bagus P.S. Validation of Koopmans' theorem for density functional theory binding energies. Phys. Chem. Chem. Phys. 2015. 17(6): 4015. https://doi.org/10.1039/C4CP05434B

Published
2019-01-11
How to Cite
Demyanenko, E. M., Lobanov, V. V., Grebenyuk, A. G., Karpenko, O. S., & Kartel, M. T. (2019). Influence of atoms of nitrogen and boron atoms inserted into graphene-like matrix on molecular hydrogen adsorption. Surface, (10(25), 19-36. https://doi.org/10.15407/Surface.2018.10.019
Section
Theory of surface chemical structure and reactivity.