All Title Author
Keywords Abstract

First Principles Calculations of Hydrogen Storage on Calcium-Decorated, Boron-Doped Bilayer Graphene

DOI: 10.4236/msce.2018.611001, PP. 1-12

Keywords: Hydrogen Storage, Calcium-Decorated, Boron-Doped, Bilayer Graphene, Interlayer, Outerlayer

Full-Text   Cite this paper   Add to My Lib


In this paper, the adsorption and storage of hydrogen on calcium-decorated, boron-doped bilayer graphene was investigated using first principles calculation. The calcium-decorated bilayer graphene was investigated and it was shown that the binding energy of H2 molecule adsorbed on the calcium-decorated bilayer graphene is 0.02 eV and the energy does not belong to reversible usage range of 0.2 - 0.6 eV. Substitutional boron doping can improve the adsorption energy of Ca to bilayer graphene with the empty pz orbital of boron atoms. Our calculations show that calcium atoms can be solidly adsorbed on the interlayer (Ca/B/Graphene) and outerlayer (2Ca/B/Graphene and 3Ca/B/Graphene) of B-doped bilayer graphene. Hydrogen molecule binds with Ca/B/Graphene, 2Ca/B/Graphene and 3Ca/B/Graphene system with an energy that belongs to reversible usage range of 0.2 - 0.6 eV. The overlap between Ca 3d and H2σ orbitals just below the Fermi energy demonstrates the charge transfer between the Ca atom and the H atom and the role of hybridization of the 3d orbita of Ca with the σ orbitals of H2 in efficient adsorption of hydrogen molecules. The charge from hydrogen bonding orbital transfers to empty 3d orbitals of the Ca atom, and then from the 3d orbitals of the Ca atom donated to H2σ* antibonding orbital. Hydrogen moleculars can be adsorbed on the interlayer and outerlayer of Ca-decorated B-doped bilayer graphene.


[1]  Schlapbach, L. and Züttel. A. (2001) Hydrogen-Storage Materials for Mobile Applications. Nature, 414, 353-358.
[2]  Ahluwalia, R.K., Hua, T.Q., Peng, J.K., Lasher, S., McKenney, K., Sinha, J., et al. (2010) Technical Assessment of Cryo-Compressed Hydrogen Storage Tank Systems for Automotive Applications. International Journal of Hydrogen Energy, 35, 4171-4184.
[3]  Schoof, T., Groth, S., Vorberger, J., et al. (2015) Ab Initio Thermodynamic Results for the Degenerate Electron Gas at Finite Temperature. Physical Review Letters, 115, 130402.
[4]  Sure, R. and Grimme, S. (2013) Corrected Small Basis set Hartree-Fock Method for Large Systems. Journal of Computational Chemistry, 34, 1672-1685.
[5]  Momen, G., Hermosilla, G., Michau, A., Pons, M., Firdaouss, M. and Hassouni, K. (2009) Hydrogen Storage in an Activated Carbon Bed: Effect of Energy Release on Storage Capacity of the Tank. International Journal of Hydrogen Energy, 34, 3799-3809.
[6]  Bhatia, S.K. and Myers A.L. (2006) Optimum Conditions for Adsorptive Storage. Langmuir, 22, 1688-1700.
[7]  Lochan, R.C. and Head-Gordon, M. (2006) Computational Studies of Molecular Hydrogen Binding Affinities: The Role of Dispersion Forces, Electrostatics, and Orbital Interactions. Physical Chemistry Chemical Physics, 8, 1357-1370.
[8]  Pierson, H.O. (1993) Handbook of Carbon, Graphite, Diamond and Fullerenes. Noyes, NJ, USA.
[9]  Castro, E.V., Novoselov, K.S., Morozov, S.V., et al. (2007) Biased Bilayer Graphene: Semiconductor with a Gap Tunable by the Electric Field Effect. Physical Review Letters, 99, 216802.
[10]  Cai, L., Fan, J., Lin, L., et al. (2017) Influence of Donor and Acceptor Groups on the ST Energy Gap for Thermally Activated Delayed Fluorescence Emitters. Molecular Physics, 115, 809-814.
[11]  Skone, J.H., Govoni, M. and Galli, G. (2014) Self-Consistent Hybrid Functional for Condensed Systems. Physical Review B, 89, 195112.
[12]  Butler, K.T., Hendon, C.H. and Walsh, A. (2014) Electronic Chemical Potentials of Porous Metal-Organic Frameworks. Journal of the American Chemical Society, 136, 2703-2706.
[13]  Berland, K. and Hyldgaard, P. (2014) Exchange Functional that Tests the Robustness of the Plasmon Description of the van der Waals Density Functional. Physical Review B, 89, 035412.
[14]  Yoon, M., Yang, S., Hicke, C., Wang, E., Geohegan, D. and Zhang, Z. (2008) Calcium as the Superior Coating Metal in Functionalization of Carbon Fullerenes for High-Capacity Hydrogen Storage. Physical Review Letters, 100, 206806.
[15]  Li, M., Li, Y.F., Zhou, Z., Shen, P.W. and Chen, Z.F. (2009) Ca-Coated Boron Fullerenes and Nanotubes as Superior Hydrogen Storage Materials. Nano Letters, 9, 1944-1948.
[16]  Lee, H., Ihm, J., Cohen, M.L. and Louie, S.G. (2009) Calcium-Decorated Carbon Nanotubes for High-Capacity Hydrogen Storage: First-Principles Calculations. Physical Review B, 80, Article ID: 115412.
[17]  Ataca, C., Aktürk, E. and Ciraci, S. (2009) Hydrogen Storage of Calcium Atoms Adsorbed on Graphene: First-Principles Plane Wave Calculations. Physical Review B, 79, Article ID: 041406.
[18]  Lee, H., Ihm, G., Cohen, M.L. and Louie, S.G. (2010) Calcium-Decorated Graphene-Based Nanostructures for Hydrogen Storage. Nano Letters, 10, 793-798.
[19]  Monkhorst, H.J. and Pack, J.D. (1976) Special Points for Brillouin-Zone Integrations. Physical Review B, 13, 5188-5191.
[20]  Yu, H.S., He, X. and Truhlar, D.G. (2016) MN15-L: A New Local Exchange-Correlation Functional for Kohn-Sham Density Functional Theory with Broad Accuracy for atoms, Molecules, and Solids. Journal of Chemical Theory and Computation, 12, 1280-1293.
[21]  Omata, Y., Yamagami, Y., Tadano, K., Miyake, T. and Saito, S. (2005) Nanotube Nanoscience: A Molecular-Dynamics Study. Physica E, 29, 454-468.
[22]  Fujimoto, Y. and Saito, S. (2015) Electronic Structures and Stabilities of Bilayer Graphene Doped with Boron and Nitrogen. Surface Science, 634, 57-61.
[23]  Dai, J., Yuan, J. and Giannozzi, P. (2009) Gas Adsorption on Graphene Doped with B, N, Al, and S: A Theoretical Study. Applied Physics Letters, 95, Article ID: 232105.


comments powered by Disqus