Role of exposed metal sites in hydrogen storage in MOFs

Jenny G. Vitillo, Laura Regli, Sachin Chavan, Gabriele Ricchiardi, Giuseppe Spoto, Pascal D.C. Dietzel, Silvia Bordiga, Adriano Zecchina

Research output: Contribution to journalArticlepeer-review

339 Scopus citations

Abstract

The role of exposed metal sites in increasing the H2 storage performances in metal-organic frameworks (MOFs) has been investigated by means of IR spectrometry. Three MOFs have been considered: MOF-5, with unexposed metal sites, and HKUST-1 and CPO-27-Ni, with exposed Cu2+ and Ni 2+, respectively. The onset temperature of spectroscopic features associated with adsorbed H2 correlates with the adsorption enthalpy obtained by the VTIR method and with the shift experienced by the H-H stretching frequency. This relationship can be ascribed to the different nature and accessibility of the metal sites. On the basis of a pure energetic evaluation, it was observed that the best performance was shown by CPO-27-Ni that exhibits also an initial adsorption enthalpy of -13.5 kJ mol-1, the highest yet observed for a MOF. Unfortunately, upon comparison of the hydrogen amounts stored at high pressure, the hydrogen capacities in these conditions are mostly dependent on the surface area and total pore volume of the material. This means that if control of MOF surface area can benefit the total stored amounts, only the presence of a great number of strong adsorption sites can make the (P, T) storage conditions more economically favorable. These observations lead to the prediction that efficient H2 storage by physisorption can be obtained by increasing the surface density of strong adsorption sites.

Original languageEnglish (US)
Pages (from-to)8386-8396
Number of pages11
JournalJournal of the American Chemical Society
Volume130
Issue number26
DOIs
StatePublished - Jul 2 2008

Fingerprint Dive into the research topics of 'Role of exposed metal sites in hydrogen storage in MOFs'. Together they form a unique fingerprint.

Cite this