Bunching and Immobilization of Ionic Liquids in Nanoporous Metal–Organic Framework
Kanj, A.B. / Verma, R. / Liu, M. / Helfferich, J. / Wenzel, W. / Heinke, L. (2019)
Nano Lett., 2019, 19, 3, 2114–2120, DOI: 10.1021/acs.nanolett.8b04694
- Datum: März 2019
Room-temperature ionic liquids (ILs) are a unique, novel class of designer solvents and materials with exclusive properties, attracting substantial attention in fields like energy storage and supercapacitors as well as in ion-based signal processing and electronics. For most applications, ILs need to be incorporated or embedded in solid materials like porous hosts. We investigate the dynamic structure of ILs embedded in well-defined pores of metal–organic frameworks (MOFs). The experimental data combined with molecular dynamics simulations unveil astonishing dynamic properties of the IL in the MOF nanoconfinement. At low IL loadings, the ions drift in the pores along the electric field, whereas at high IL loadings, collective field-induced interactions of the cations and anions lead to blocking the transport, thus suppressing the ionic mobility and tremendously decreasing the conductivity. The mutual pore blockage causes immobilized ions in the pores, resulting in a highly inhomogeneous IL density and bunched-up ions at the clogged pores. These results provide novel molecular-level insights into the dynamics of ILs in nanoconfinement, significantly enhancing the tunability of IL material properties.