Ab initio and periodic DFT investigation of hydrogen storage on light metal-decorated MOF-5

Mudit Dixit, Tuhina Adit Maark, Sourav Pal

Research output: Contribution to journalArticlepeer-review

64 Scopus citations


The effect of light metal (M = Li, Be, Mg, and Al) decoration on the stability of metal organic framework MOF-5 and its hydrogen adsorption is investigated by ab initio and periodic density functional theory (DFT) calculations by employing models of the form BDC:M2:nH2 and MOF-5:M2:nH2, where BDC stands for the benzenedicarboxylate organic linker and MOF-5 represents the primitive unit cell. The suitability of the periodic DFT method employing the GGA-PBE functional is tested against MP2/6-311 + G (*) and MP2/cc-pVTZ molecular calculations. A correlation between the charge transfer and interaction energies is revealed. The metal-MOF-5 interactions are analyzed using the frontier molecular orbital approach. Difference charge density plots show that H 2 molecules get polarized due to the charge generated on the metal atom adsorbed over the BDC linker, resulting in electrostatic guest-host interactions. Our solid state results show that amongst the four metal atoms, Mg and Be decoration does not stabilize the MOF-5 to any significant extent. Li and Al decoration strengthened the H2-MOF-5 interactions relative to the pure MOF-5 exhibited by the enhanced binding energies. The hydrogen binding energies for the Li- and Al-decorated MOF-5 were found to be sensible for allowing reversible hydrogen storage at ambient temperatures. A high hydrogen uptake of 4.3 wt.% and 3.9 wt.% is also predicted for the Li- and Al-decorated MOF-5, respectively.

Original languageEnglish
Pages (from-to)10816-10827
Number of pages12
JournalInternational Journal of Hydrogen Energy
Issue number17
StatePublished - Aug 2011
Externally publishedYes

Bibliographical note

Funding Information:
The authors acknowledge the computational facilities of the Center of Excellence in Scientific Computing at National Chemical Laboratory, Pune. The authors also thank the FP7-NMP-EU-India-2 collaborative project HYPOMAP on “New materials for hydrogen powered mobile applications” for providing financial support. One of the authors (M.D.) thanks UGC, India for grant of Junior Research Fellowship and Bhakti Kulkarni for their help during the work. T.A.M. acknowledges the Swedish Institute for the scholarship for postdoctoral studies. S.P. acknowledges the J. C. Bose Fellowship grant of DST, India toward completion of this work.


  • Ab initio calculations
  • Density functional theory
  • Hydrogen binding energies
  • Hydrogen storage
  • Metal-Pi-Arene interactions


Dive into the research topics of 'Ab initio and periodic DFT investigation of hydrogen storage on light metal-decorated MOF-5'. Together they form a unique fingerprint.

Cite this