Self-Adjusting Binding Pockets Enhance H₂ and CH₄ Adsorption in a Uranium-Based Metal–Organic Framework

17 April 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

A new, air-stable, permanently porous uranium(IV) metal–organic framework U(bdc)2 (1, bdc2− = 1,4-benzenedicarboxylate) was synthesized and its H2 and CH4 adsorption properties were investigated. Low temperature adsorption isotherms confirm strong adsorption of both gases in the framework at low pressures. In situ gas-dosed neutron diffraction experiments with different D2 loadings revealed a rare example of cooperative framework contraction (ΔV = −7.8%), triggered by D2 adsorption at low pressures. This deformation creates two optimized binding pockets for hydrogen (Qst = −8.6 kJ/mol) per pore, in agreement with H2 adsorption data. Analogous experiments with CD4 (Qst = −24.8 kJ/mol) and N,N-dimethylformamide as guests revealed that the binding pockets in 1 adjust by selective framework contractions that are unique for each adsorbent, augmenting individual host-guest interactions. Our results suggest that the strategic combination of binding pockets and structural flexibility in metal–organic frameworks holds great potential for the development of new adsorbents with an enhanced substrate affinity.

Keywords

metal-organic frameworks (MOFs)
Flexible MOFs
self-adjusting adsorption pocket
Uranium
hydrogen storage
methane storage

Supplementary materials

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Halter Long U(bdc)2 ChemRxiv Supporting Information
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