Molecular hydrogen "pairing" interaction in a metal organic framework system with unsaturated metel centers (MOF-74)

Nour Nijem, Jean François Veyan, Lingzhu Kong, Haohan Wu, Yonggang Zhao, Jing Li, David C. Langreth, Yves J. Chabal

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63 Scopus citations


Infrared (IR) absorption spectroscopy measurements of molecular hydrogen in MOF-74-M (M = metal center) are performed as a function of temperature and pressure [to 45 kTorr (60 bar) at 300 K, and at lower pressures in the 20-200 K range] to investigate the nature of H2 interactions with the unsaturated metal centers. A small shift (∼ -30 cm-1 with respect to the unperturbed H2 molecule) is observed for the internal stretch frequency of H2 molecules adsorbed on the metal site at low loading. This finding is in contrast to much larger shifts (∼ -70 cm-1) observed in previous studies of MOFs with unsaturated metal centers (including MOF-74) and the general assumption that H2 stretch shifts depend on adsorption energies (FitzGerald et al., Phys. Rev. B 2010, 81, 104305). We show that larger shifts (∼ -70 cm-1) do occur, but only when the next available site ("oxygen" site) is occupied. This larger shift originates from H2-H2 interactions on neighboring sites of the same pore, consistent with the short distance between H2 in these two sites ∼2.6 Å derived from an analysis of neutron diffraction experiments of D2-D2 at 4 K (Liu et al., Langmuir 2008, 24, 4772-4777). Our results at 77 K and low loading can be explained by a diffusion barrier against pair disruption, which should be enhanced by this interaction. Calculations indicate that the vibrational shifts do not correlate with binding energies and are instead very sensitive to the environment (interaction potential and H2-H2 interactions), which complicates the use of variable temperature IR methods to calculate adsorption energies of specific adsorption sites.

Original languageEnglish (US)
Pages (from-to)14834-14848
Number of pages15
JournalJournal of the American Chemical Society
Issue number42
StatePublished - Oct 27 2010

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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