Atmospheric modulation of apparent electrical conductivity in a metal−organic framework

Abstract Combining high surface area and efficient charge transport, electrically conductive metal−organic frameworks (MOFs) find wide applications in energy storage, sensing, and electrocatalysis. Reliable characterization of electrical conductivity, the key metric for assessing this class of materials, remains challenging due to its high sensitivity to the atmosphere. Herein, through electrical characterization of an exemplary MOF, Cd2(TTFTB) (TTFTB4− = tetrathiafulvalene tetrabenzoate), under various controlled atmospheres, we show that adsorption of water in humid air or N2 improves the apparent room-temperature electrical conductivity by one to two orders of magnitude compared to the values observed in dry atmospheres. This observation in conjunction with spectroscopic characterization, structural analysis, and band structure calculations indicates significant contribution of water-mediated proton conductivity and/or proton-electron coupling to the apparent electrical conductivity. Thus, controlling and reporting atmospheres in electrical conductivity measurements of MOFs is critical to improve their reproducibility and to gain insights into electrical conduction mechanisms.