Theoretical and experimental analysis of H₂ binding in a prototypical metal-organic framework material

Hydrogen adsorption by the metal-organic framework (MOF) structure Zn₂(BDC)₂(TED) is investigated using a combination of experimental and theoretical methods. By using the nonempirical van der Waals density-functional approach, it is found that the locus of deepest H₂ binding positions lies within two types of narrow channel. The energies of the most stable binding sites, as well as the number of such binding sites, are consistent with the values obtained from experimental adsorption isotherms and heat of adsorption data. Calculations of the shift of the H-H stretch frequency when adsorbed in the MOF give a value of approximately −30 cm⁻¹ at the strongest binding point in each of the two channels. Ambient temperature infrared-absorption spectroscopy measurements give a hydrogen peak centered at 4120 cm⁻¹, implying a shift consistent with the theoretical calculations.