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H2 interaction with divalent cations in isostructural MOFs: a key study for variable temperature infrared

Sachin M Chavan1, Olena Zavorotynska, Carlo Lamberti

  • 1Chemistry Department, NIS, Centre of Excellence and INSTM Università di Torino, via Pietro Giuria 7 and via Quarello 11, 10100, Torino, Italy. Sachin.chavan@kjemi.uio.no

Dalton Transactions (Cambridge, England : 2003)
|July 18, 2013
PubMed
Summary

Variable Temperature Infrared (VTIR) spectroscopy characterizes hydrogen storage materials by studying H2 adsorption. This research found a direct correlation between metal cation ionic radii and H2 interaction energy in isostructural Metal-Organic Frameworks (MOFs).

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Area of Science:

  • Materials Science
  • Spectroscopy
  • Physical Chemistry

Background:

  • Variable Temperature Infrared (VTIR) spectroscopy is valuable for characterizing hydrogen storage materials.
  • Metal-Organic Frameworks (MOFs) are promising candidates for hydrogen storage applications.

Purpose of the Study:

  • To report VTIR spectroscopy results of H2 adsorption at isostructural MOFs CPO-27-M (M = Mg, Mn, Co, Ni, Zn).
  • To investigate the correlation between metal cation properties and H2 interaction energy.
  • To validate VTIR spectroscopy as a method for determining energetic and entropic values for H2 adsorption.

Main Methods:

  • Variable Temperature Infrared (VTIR) spectroscopy was employed to study H2 adsorption.
  • Isostructural MOFs with varying metal cations (Mg, Mn, Co, Ni, Zn) were synthesized and characterized.
  • H2 vibrational frequency perturbations were analyzed to determine interaction energies.

Main Results:

  • The strongest perturbation of H2 vibrational frequency was observed due to interaction with open metal sites.
  • A direct correlation was found between the ionic radii of metal cations and H2 interaction energy in MOFs of the same topology.
  • The highest enthalpy of hydrogen adsorption (15 ± 1 kJ mol⁻¹) was recorded for Ni(2+).

Conclusions:

  • VTIR spectroscopy is a relevant approach for obtaining reliable energetic and entropic values for H2 adsorption.
  • The study highlights the importance of open metal sites and metal cation properties in H2 adsorption within MOFs.
  • Results provide a basis for comparing experimental data with computational predictions and isosteric heats.