Grand canonical Monte Carlo (GCMC) simulations of H2 sorption were performed in different members of the M-MOF-74 series (M = Mg, Ni, Co, Zn, Cu), a family of isostructural metal–organic frameworks (MOFs) that consists of M2+ ions coordinated to 2,5-dioxido-1,4-benzenedicarboxylate (dobdc) ligands. The simulations were performed using four different H2 potentials of increasing complexity, with the most realistic potential including induced dipole parameters to account for explicit many-body polarization interactions. Explicit polarization effects were implemented in classical GCMC simulation using a Thole-Applequist type model. The experimental H2 adsorption isotherms and isosteric heat of adsorption (Qst) values for all five M-MOF-74 analogues were closely reproduced in simulation using only the polarizable H2 potential. Simulations using potentials that include only explicit repulsion and dispersion and/or permanent electrostatic interactions failed to reproduce such measurements. Utilizing the polarizable H2 model in classical GCMC simulation also resulted in M2+–H2 distances that are comparable to those obtained through neutron powder diffraction measurements for the individual variants. Consistent with experimental measurements, the simulations reproduced the following trend for the H2−metal interaction strength: Ni-MOF-74 &gt; Co-MOF-74 &gt; Mg-MOF-74 &gt; Zn-MOF-74 &gt; Cu-MOF-74. The simulations revealed that stronger H2−metal interactions within the M-MOF-74 series corresponds to shorter H2−metal distances and higher induced dipoles on the metal-adsorbed H2 molecules. The observed H2 adsorption trend within this series were potentially rationalized by analyzing the calculated partial charges of the MOF atoms, the polarizability of the metal ions, and steric interactions within the crystal structures.

Capturing the H2–metal interaction in the M-MOF-74 series using classical polarization

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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