Acid Gas Adsorption on Metal-Organic Framework Nanosheets as a Model of an "All-Surface" Material

J Chem Theory Comput. 2017 Mar 14;13(3):1341-1350. doi: 10.1021/acs.jctc.7b00041. Epub 2017 Mar 3.

Abstract

To establish a model of metal-organic framework (MOF) surfaces and build an understanding of surface-specific ligand adsorption phenomena in MOFs, we present a computational study exploring multiple models of a series of MOF-2 nanosheet materials, "M-BDCs", with M = Zn, Cu, and Co and BDC = benzene-1,4-dicarboxylate. We study and assess the appropriateness of a series of models ranging from small clusters (18 atoms) to fully periodic sheet models. We additionally study the interactions of these models with acid gases and energy-relevant small molecules (CO, CO2, H2O, SO2, NO2, and H2S). We employ computational methods ranging from DFT with various exchange-correlation functionals to perturbative and coupled-cluster methods. For these systems, we present binding energies and enthalpies with the various ligands studied as well as IR frequency shifts for the normal modes of these ligands upon complexation with the open-metal sites of these materials. Our calculations lead to an understanding of phenomena unique to MOF surfaces and the importance of the periodicity in these materials in capturing surface-specific adsorption behaviors.