Abstract
New materials for hydrogen storage of Li-doped fullerene (C20, C28, C36, C50, C60, C70)-intercalated hexagonal boron nitrogen (h-BN) frameworks were designed by using density functional theory (DFT) calculations. First-principles molecular dynamics (MD) simulations showed that the structures of the C n -BN (n = 20, 28, 36, 50, 60, and 70) frameworks were stable at room temperature. The interlayer distance of the h-BN layers was expanded to 9.96–13.59 Å by the intercalated fullerenes. The hydrogen storage capacities of these three-dimensional (3D) frameworks were studied using grand canonical Monte Carlo (GCMC) simulations. The GCMC results revealed that at 77 K and 100 bar (10 MPa), the C50-BN framework exhibited the highest gravimetric hydrogen uptake of 6.86 wt% and volumetric hydrogen uptake of 58.01 g/L. Thus, the hydrogen uptake of the Li-doped C n -intercalated h-BN frameworks was nearly double that of the non-doped framework at room temperature. Furthermore, the isosteric heats of adsorption were in the range of 10–21 kJ/mol, values that are suitable for adsorbing/desorbing the hydrogen molecules at room temperature. At 193 K (–80 °C) and 100 bar for the Li-doped C50-BN framework, the gravimetric and volumetric uptakes of H2 reached 3.72 wt% and 30.08 g/L, respectively.
Similar content being viewed by others
References
L. Schlapbach and A. Züttel, Hydrogen-storage materials for mobile applications, Nature 414(6861), 353 (2001)
J. A. Turner, A realizable renewable energy future, Science 285(5428), 687 (1999)
J. A. Turner, Sustainable hydrogen production, Science 305(5686), 972 (2004)
A. W. C. van den Berg, and C. O. Arean, Materials for hydrogen storage: Current research trends and perspectives, Chem. Commun. 669(6), 668 (2008)
M. Felderhoff, C. Weidenthaler, R. von Helmolt, and U. Eberle, Hydrogen storage: The remaining scientific and technological challenges, Phys. Chem. Chem. Phys. 9(21), 2643 (2007)
H. M. El-Kaderi, J. R. Hunt, J. L. Mendoza-Cortes, A. P. Côté, R. E. Taylor, M. O’Keeffe, and O. M. Yaghi, Designed synthesis of 3D covalent organic frameworks, Science 316(5822), 268 (2007)
J. L. Belof, A. C. Stern, M. Eddaoudi, and B. Space, On the mechanism of hydrogen storage in a metal-organic framework material, J. Am. Chem. Soc. 129(49), 15202 (2007)
S. S. Han, H. Furukawa, O. M. Yaghi, and W. A. Goddard, Covalent organic frameworks as exceptional hydrogen storage materials, J. Am. Chem. Soc. 130(35), 11580 (2008)
Z. Y. Zhong, Z. T. Xiong, L. F. Sun, J. Z. Luo, P. Chen, X. Wu, J. Lin, and K. L. Tan, Nanosized nickel (or cobalt)/graphite composites for hydrogen storage, J. Phys. Chem. B 106(37), 9507 (2002)
J. Jiang, R. Babarao, and Z. Hu, Molecular simulations for energy, environmental and pharmaceutical applications of nanoporous materials: From zeolites, metal–organic frameworks to protein crystals, Chem. Soc. Rev. 40(7), 3599 (2011)
K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, and S. V. Dubonos, Electric field effect in atomically thin carbon films, Science 306(5696), 666 (2004)
M. D. Stoller, S. Park, Y. Zhu, J. An, and R. S. Ruoff, Graphene-based ultracapacitors, Nano Lett. 8(10), 3498 (2008)
J. Zhou, Q. Wang, Q. Sun, P. Jena, and X. S. Chen, Electric field enhanced hydrogen storage on polarizable materials substrates, Proc. Natl. Acad. Sci. USA 107(7), 2801 (2010)
M. Khazaei, M. S. Bahramy, N. S. Venkataramanan, H. Mizuseki, and Y. Kawazoe, Chemical engineering of prehydrogenated C and BN-sheets by Li: Application in hydrogen storage, J. Appl. Phys. 106(9), 094303 (2009)
L. P. Zhang, P. Wu, and M. B. Sullivan, Hydrogen adsorption on Rh, Ni, and Pd functionalized single-walled boron nitride nanotubes, J. Phys. Chem. C 115(10), 4289 (2011)
M. Corso, W. Auwärter, M. Muntwiler, A. Tamai, T. Greber, and J. Osterwalder, Boron nitride nanomesh, Science 303(5655), 217 (2004)
K. S. Novoselov, D. Jiang, F. Schedin, T. J. Booth, V. V. Khotkevich, S. V. Morozov, and A. K. Geim, Twodimensional atomic crystals, Proc. Natl. Acad. Sci. USA 102(30), 10451 (2005)
A. Nag, K. Raidongia, K. P. S. S. Hembram, R. Datta, U. V. Waghmare, and C. N. R. Rao, Graphene analogues of BN: Novel synthesis and properties, ACS Nano 4(3), 1539 (2010)
J. D. Bernal, The structure of graphite, Proc. R. Soc. Lond. A 106(740), 749 (1924)
D. Chung, Review graphite, J. Mater. Sci. 37(8), 1475 (2002)
Y. Baskin and L. Meyer, Lattice constants of graphite at low temperatures, Phys. Rev. 100(2), 544 (1955)
V. L. Solozhenko, G. Will, and F. Elf, Isothermal compression of hexagonal graphite-like boron nitride up to 12 GPa, Solid State Commun. 96(1), 1 (1995)
W. Paszkowicz, J. B. Pelka, M. Knapp, T. Szyszko, and S. Podsiadlo, Lattice parameters and anisotropic thermal expansion of hexagonal boron nitride in the 10–297.5 K temperature range, Appl. Phys. A 75(3), 431 (2002)
A. Marini, P. Garcia-Gonzalez, and A. Rubio, Firstprinciples description of correlation effects in layered materials, Phys. Rev. Lett. 96(13), 136404 (2006)
G. Kern, G. Kresse, and J. Hafner, Ab initio calculation of the lattice dynamics and phase diagram of boron nitride, Phys. Rev. B 59(13), 8551 (1999)
R. Pease, An X-ray study of boron nitride, Acta Crystallogr. 5(3), 356 (1952)
Y. Shi, C. Hamsen, X. Jia, K. K. Kim, A. Reina, M. Hofmann, A. L. Hsu, K. Zhang, H. Li, Z.Y. Juang, M. S. Dresselhaus, L. J. Li, and J. Kong, Synthesis of few-layer hexagonal boron nitride thin film by chemical vapor deposition, Nano Lett. 10(10), 4134 (2010)
S. S. Han, H. S. Kim, K. S. Han, J. Y. Lee, H. M. Lee, J. K. Kang, S. I. Woo, A. C. T. van Duin, and W. A. Goddard, Nanopores of carbon nanotubes as practical hydrogen storage media, Appl. Phys. Lett. 87(21), 213113 (2005)
S. Patchkovskii, J. S. Tse, S. N. Yurchenko, L. Zhechkov, T. Heine, and G. Seifert, Graphene nanostructures as tunable storage media for molecular hydrogen, Proc. Natl. Acad. Sci. USA 102(30), 10439 (2005)
W. Q. Deng, X. Xu, and N. Goddard, New alkali doped pillared carbon materials designed to achieve practical reversible hydrogen storage for transportation, Phys. Rev. Lett. 92(16), 166103 (2004)
M. S. Fuhrer, J. G. Hou, X. D. Xiang, and A. Zettl, C60 intercalated graphite: Predictions and experiments, Solid State Commun. 90(6), 357 (1994)
V. Gupta, P. Scharff, K. Risch, H. Romanus, and R. Müller, Synthesis of C60 intercalated graphite, Solid State Commun. 131(3–4), 153 (2004)
A. Kuc, L. Zhechkov, S. Patchkovskii, G. Seifert, and T. Heine, Hydrogen sieving and storage in fullerene intercalated graphite, Nano Lett. 7(1), 1 (2007)
Y. Gogotsi, R. K. Dash, G. Yushin, T. Yildirim, G. Laudisio, and J. E. Fischer, Tailoring of nanoscale porosity in carbide-derived carbons for hydrogen storage, J. Am. Chem. Soc. 127(46), 16006 (2005)
S. S. Han and S. S. Jang, A hydrogen storage nanotank: Lithium-organic pillared graphite, Chem. Commun. 36(36), 5427 (2009)
J. H. Guo, H. Zhang, and Y. Miyamoto, New Lidoped fullerene-intercalated phthalocyanine covalent organic frameworks designed for hydrogen storage, Phys. Chem. Chem. Phys. 15(21), 8199 (2013)
J. Ren, H. Zhang, and X. L. Cheng, Grand canonical Monte Carlo simulation of isotherm for hydrogen adsorption on nanoporous LiBH4, Comput. Mater. Sci. 71, 109 (2013)
J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Pederson, D. J. Singh, and C. Fiolhais, Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation, Phys. Rev. B 46(11), 6671 (1992)
P. E. Blöchl, Projector augmented-wave method, Phys. Rev. B 50(24), 17953 (1994)
G. Kresse and J. Hafner, Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements, J. Phys. Condens. Matter 6(40), 8245 (1994)
G. Kresse and D. Joubert, From ultrasoft pseudopotentials to the projector augmented-wave method, Phys. Rev. B 59(3), 1758 (1999)
S. Nosé, A molecular dynamics method for simulations in the canonical ensemble, Mol. Phys. 52(2), 255 (1984)
D. Frenkel and B. Smit, Understanding Molecular Simulation, Computational Science Series, San Diego: Academic Press, 2002
A. Gupta, S. Chempath, M. J. Sanborn, L. A. Clark, and R. Q. Snurr, Object-oriented programming paradigms for molecular modeling, Mol. Simul. 29(1), 29 (2003)
S. L. Mayo, B. D. Olafson, and Goddard A, Dreiding: A generic force field for molecular simulations, J. Phys. Chem. 94(26), 8897 (1990)
Q. Y. Yang and C. L. Zhong, Molecular simulation of adsorption and diffusion of hydrogen in metal-organic frameworks, J. Phys. Chem. B 109(24), 11862 (2005)
G. Garberoglio, A. I. Skoulidas, and J. K. Johnson, Adsorption of gases in metal organic materials: Comparison of simulations and experiments, J. Phys. Chem. B 109(27), 13094 (2005)
T. Düren, L. Sarkisov, O. M. Yaghi, and R. Q. Snurr, Design of new materials for methane storage, Langmuir 20(7), 2683 (2004)
B. Assfour and G. Seifert, Adsorption of hydrogen in covalent organic frameworks: Comparison of simulations and experiments, Microporous Mesoporous Mater. 133(1–3), 59 (2010)
O. Talu and A. L. Myers, Molecular simulation of adsorption: Gibbs dividing surface and comparison with experiment, AIChE J. 47(5), 1160 (2001)
H. Frost, T. Düren, and R. Q. Snurr, Effects of surface area, free volume, and heat of adsorption on hydrogen uptake in metal-organic frameworks, J. Phys. Chem. B 110(19), 9565 (2006)
R. Q. Snurr, A. T. Bell, and D. N. Theodorou, Prediction of adsorption of aromatic hydrocarbons in silicalite from grand canonical Monte Carlo simulations with biased insertions, J. Phys. Chem. 97(51), 13742 (1993)
H. Tanaka, J. Fan, H. Kanoh, H. Yudasaka, S. Iijima, and K. Kaneko, Quantum nature of adsorbed hydrogen on singlewall carbon nanohorns, Mol. Simul. 31(6–7), 465 (2005)
D. Levesque, A. Gicquel, F. L. Darkrim, and S. B. Kayiran, Monte Carlo simulations of hydrogen storage in carbon nanotubes, J. Phys. Condens. Matter 14(40), 9285 (2002)
P. Kowalczyk, H. Tanaka, R. Holyst, K. Kaneko, T. Ohmori, and J. Miyamoto, Storage of hydrogen at 303 K in graphite slitlike pores from grand canonical Monte Carlo simulation, J. Phys. Chem. B 109(36), 17174 (2005)
B. Panella, M. Hirscher, H. Pütter, and U. Müller, Hydrogen adsorption in metal–organic frameworks: Cu-MOFs and Zn-MOFs compared, Adv. Funct. Mater. 16(4), 520 (2006)
Y. W. Li and R. T. Yang, Hydrogen storage in metal-organic frameworks by bridged hydrogen spillover, J. Am. Chem. Soc. 128(25), 8136 (2006)
L. J. Murray, M. Dinca, and J. R. Long, Hydrogen storage in metal–organic frameworks, Chem. Soc. Rev. 38(5), 1294 (2009)
S. K. Bhatia and A. L. Myers, Optimum conditions for adsorptive storage, Langmuir 22(4), 1688 (2006)
K. Srinivasu, K. R. S. Chandrakumar, and S. K. Ghosh, Quantum chemical studies on hydrogen adsorption in carbon-based model systems: Role of charged surface and the electronic induction effect, Phys. Chem. Chem. Phys. 10(38), 5832 (2008)
Q. Sun, Q. Wang, P. Jena, and Y. Kawazoe, Clustering of Ti on a C60 surface and its effect on hydrogen storage, J. Am. Chem. Soc. 127(42), 14582 (2005)
K. L. Mulfort and J. T. Hupp, Chemical reduction of metalorganic framework materials as a method to enhance gas uptake and binding, J. Am. Chem. Soc. 129(31), 9604 (2007)
D. Himsl, D. Wallacher, and M. Hartmann, Improving the hydrogen-adsorption properties of a hydroxy-modified MIL-53 (Al) structural analogue by lithium doping, Angew. Chem. Int. Ed. 48(25), 4639 (2009)
Z. H. Xiang, Z. Hu, W. T. Yang, and D. P. Cao, Lithium doping on metal-organic frameworks for enhancing H2 storage, Int. J. Hydrogen Energy 37(1), 946 (2012)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Cheng, YH., Zhang, CY., Ren, J. et al. Hydrogen storage in Li-doped fullerene-intercalated hexagonal boron nitrogen layers. Front. Phys. 11, 113101 (2016). https://doi.org/10.1007/s11467-016-0559-4
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11467-016-0559-4