Metal-Specific Interactions of H2 Adsorbed within Isostructural Metal–Organic Frameworks
Diffuse reflectance infrared (IR) spectroscopy performed over a wide temperature range (35–298 K) is used to study the dynamics of H2 adsorbed within the isostructural metal–organic frameworks M2L (M = Mg, Mn, Co, Ni and Zn; L = 2,5-dioxidobenzene-1,4-dicarboxylate) referred to as MOF-74 and CPO-27. Spectra collected at H2 concentrations ranging from 0.1 to 3.0 H2 per metal cation reveal that strongly red-shifted vibrational modes arise from isolated H2 bound to the available metal coordination site. The red shift of the bands associated with this site correlate with reported isosteric enthalpies of adsorption (at small surface coverage), which in turn depend on the identity of M. In contrast, the bands assigned to H2 adsorbed at positions >3 Å from the metal site exhibit only minor differences among the five materials. Our results are consistent with previous models based on neutron diffraction data and independent IR studies, but they do not support a recently proposed adsorption mechanism that invokes strong H2···H2 interactions (Nijem et al. J. Am. Chem. Soc.2010, 132, 14834–14848). Room temperature IR spectra comparable to those on which the recently proposed adsorption mechanism was based were only reproduced after contaminating the adsorbent with ambient air. Our interpretation that the uncontaminated spectral features result from stepwise adsorption at discrete framework sites is reinforced by systematic red shifts of adsorbed H2 isotopologues and consistencies among overtone bands that are well-described by the Buckingham model of molecular interactions in vibrational spectroscopy.
FitzGerald, S.A., B. Burkholder, M. Friedman, et al. 2011. "Metal-Specific Interactions of H2 Adsorbed within Isostructural Metal–Organic Frameworks." Journal of the American Chemical Society 133(50): 20310-20318.
American Chemical Society
Journal of the American Chemical Society
Chemistry and Biochemistry
Record for J.L.C. Rowsell. Additional record for S. FitzGerald: https://digitalcommons.oberlin.edu/faculty_schol/3222/