Straightforward Loading of Imidazole Molecules into Metal–Organic Framework for High Proton Conduction

A one-step straightforward strategy
has been developed to incorporate
free imidazole molecules into a highly stable metal–organic
framework (NENU-3, ([Cu12(BTC)8(H2O)12]­[HPW12O40])·Guest).
The resulting material Im@(NENU-3) exhibits a very high
proton conductivity of 1.82 × 10–2 S cm–1 at 90% RH and 70 °C, which is significantly
higher than 3.16 × 10–4 S cm–1 for Im-Cu@(NENU-3a) synthesized through a two-step
approach with mainly terminal bound imidazole molecules inside pores.
Single crystal structure reveals that imidazole molecules in Im-Cu@(NENU-3a) isolate lattice water molecules and then block
proton transport pathway, whereas high concentration of free imidazole
molecules within Im@(NENU-3) significantly facilitate
successive proton-hopping pathways through formation of hydrogen bonded
networks.