Ab-Initio Fully Periodic Characterization of MOF-74-M (M = Mg, Mn, Ni, Zn): Structures and Enthalpies of Adsorption

As a part of a systematic study on cation-exchanged MOF-74-M, we report a partial snapshot of our recent work achieved via a fully periodic first principle approach. Structures are reported for bulk MOF-74-Mg, Mn, Ni, and Zn as computed at DFT-B3LYP level of theory; enthalpies of adsorption for CO and CO2 in interaction with MOF-74-Ni, and Zn are also investigated as obtained at B3LYP+D* level, which is able to take into account the long-range dispersion interaction between adsorbate and adsorbant, through an a-posteriori scheme. Results are discussed and compared with available experimental data. To the authors’ knowledge this represents the first description of MOF-74-Mn structure and of the interaction of the mentioned molecules with MOF-74-Zn.