Metal Organic Frameworks (MOFs) are a class of porous materials of high interest for applications in the natural gas industry, in particular to store and separate methane in an energy efficient manner. To date, Cu-HKUST-1 is among the best performing materials for methane storage. In this work, we seek to improve upon this framework by varying the metal and ligand functional groups. This framework contains a paddlewheel compound with two square planar Cu atoms and weak Cu-Cu interactions. Replacing Cu with other transition metals, including Cr, Mo, and Ni has been achieved experimentally and results in very different metal-metal bonding interactions. Periodic density functional theory was employed to explore the effects upon methane binding for the various metals and for the yet unsynthesized frameworks with bromine and methyl group functionalized ligands. Additionally, neutron diffraction studies indicate a change in the Cr-Cr bond distance with methane loading; therefore, high-level wavefunction based methods (the complete active space self-consistent field approach with corrections from second order perturbation theory (CASSCF/CASPT2)) have been employed on cluster models to probe the nature of the metal-metal bonds.

Electronic structure of methane binding in M-HKUST-1 metal organic frameworks

248th National Meeting (2014)

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