Three orders of magnitude enhancement of proton conductivity of porous coordination polymers by incorporating ion-pairs into a framework.

A clathrate NH4Br@HKUST-1 has been prepared by means of soaking the metal-organic-framework, HKUST-1, in ammonium bromide saturated ethanol solution at ambient temperature. Both NH4Br@HKUST-1 and HKUST-1 show the same framework structure. The formula of the clathrate is approximately expressed as Cu3(BTC)2(NH4Br)1.15. The thermal stability of the metal-organic framework is not affected by incorporating ammonium bromide into its pores. The impedance spectra measurements were performed for both NH4Br@HKUST-1 and HKUST-1 in anhydrous and selected relative humidity environments, disclosing that the conductivity of NH4Br@HKUST-1 is enhanced by three/four orders of magnitude under the same conditions with respect to HKUST-1. This study provided an efficient strategy to achieve new high conductivity proton transport materials.