Mehdi Ghaffari Moghaddam - Department of Chemistry, Faculty of Science, University of Abhar, Zanjan, Iran

We study trends in the binding between CO2 and MIL-47(V) (see bottom figure) as anopen-metal site (OMS) metal-organic framework (MOF) using van der Waals-corrected densityfunctional theory. The latter method is same Grimme s functional including dispersion onperiodic boundary DFT that call usually DFT-D2.We find that the OMS-MOF based on vanadium (V) with terephthalic acid as its linkerhas large CO2 binding energies and show that for these cation, the CO2 binding energies aretwice the value expected based on pure electrostatics. We associate this adsorption behavior withthe specific electronic configuration of the divalent cations and symmetry of the Zn and Fe site insame organic linker upon CO2 binding. In the last investigations, the grand canonical Monte-Carlo (GCMC) and molecular dynamics (MD) simulations based on REPEAT electrostaticcharges are presented to demonstrate that physical bond and electrostatic interactions can be usedto predict trends of CO2 binding affinities to OMS-MOFs with transition-metal cations which arefiling their d orbitals.

MOF, MD Simulation, Adsorption, DFT, GCMC Simulation