Anisotropic Water-Mediated Proton Conductivity in Large Iron(II) Metal-Organic Framework Single Crystals for Proton-Exchange Membrane Fuel Cells

Herein we present a new proton-conducting iron(II) metal-organic framework (MOF) of an unusual structure formed by chains of alternating bistriazolate-pbenzoquinone anions and iron(II) cations with four axially coordinated water molecules. These chains assemble via pi-pi stacking between the aromatic units to form a three-dimensional grid-like network with channel pores filled with water molecules. The material was structurally characterized by single-crystal XRD analysis, and its water and thermal stability was investigated. The proton conductivity was studied by impedance measurements on needle-like single crystals. A simple but efficient measurement setup consisting of interdigital electrodes was used. The influence of the crystal orientation, temperature, and humidity was investigated. The iron(II)-MOF showed the highest proton conductivity of 3.3-10(-3) S cm(-1) at 22 degrees C and 94% relative humidity. Contrary to most known structures, the conductivity in this material is controlled by chemical properties of the pore system rather than by grain boundaries. The presented material is the starting point for further tailoring the proton-conducting properties, independent of morphological features which could find potential applications as membrane materials in proton-exchange membrane fuel cells.