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

Abstract

Hydrogen adsorption by the metal organic framework (MOF) structure Zn2(BDC)2(TED) is investigated using a combination of experimental and theoretical methods. By use of the nonempirical van der Waals density-functional (vdW-DF) 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.

4 pages, 4 figures

References in corpus (5)

• Van der Waals Density Functional for General Geometries
• Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond
• Direct Observation of Hydrogen Adsorption Sites and Nano-Cage Formation in Metal-Organic Frameworks (MOF)
• Towards a working density-functional theory for polymers: First-principles determination of the polyethylene crystal structure
• Lattice Dynamics of Metal-Organic Frameworks (MOFs): Neutron Inelastic Scattering and First-Principles Calculations

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