Sizable dynamics in small pores: CO₂ location and motion in the α-Mg formate metal-organic framework

Metal-organic frameworks (MOFs) are promising materials for carbon dioxide (CO₂) adsorption and storage; however, many details regarding CO₂ dynamics and specific adsorption site locations within MOFs remain unknown, restricting the practical uses of MOFs for CO₂ capture. The intriguing α-magnesium formate (α-Mg₃(HCOO)₆) MOF can adsorb CO₂ and features a small pore size. Using an intertwined approach of ¹³C solid-state NMR (SSNMR) spectroscopy, ¹H-¹³C cross-polarization SSNMR, and computational molecular dynamics (MD) simulations, new physical insights and a rich variety of information have been uncovered regarding CO₂ adsorption in this MOF, including the surprising suggestion that CO₂ motion is restricted at elevated temperatures. Guest CO₂ molecules undergo a combined localized rotational wobbling and non-localized twofold jumping between adsorption sites. MD simulations and SSNMR experiments accurately locate the CO₂ adsorption sites; the mechanism behind CO₂ adsorption is the distant interaction between the hydrogen atom of the MOF formate linker and a guest CO₂ oxygen atom, which are ca. 3.2 Å apart.