Mechanochemical Synthesis of Phosphonate-Based Proton Conducting Metal-Organic Frameworks

Water-stable metal-organic frameworks (MOFs) with proton-conducting behavior have attracted great attention as promising materials for proton-exchange membrane fuel cells. Herein, we report the mechanochemical gram-scale synthesis of three new mixed-ligand phosphonate-based MOFs, {Co(H₂PhDPA)(4,4'-bipy)(H₂O)·2H₂O} (BAM-1), {Fe(H₂PhDPA)(4,4'-bipy) (H₂O)·2H₂O} (BAM-2), and {Cu(H₂PhDPA)(dpe)₂(H₂O)₂·2H₂O} (BAM-3) [where H₂PhDPA = phenylene diphosphonate, 4,4'-bipy = 4,4'-bipyridine, and dpe = 1,2-di(4-pyridyl)ethylene]. Single-crystal X-ray diffraction measurements revealed that BAM-1 and BAM-2 are isostructural and possess a three-dimensional (3D) network structure comprising one-dimensional (1D) channels filled with guest water molecules. Instead, BAM-3 displays a 1D network structure extended into a 3D supramolecular structure through hydrogen-bonding and π-π interactions. In all three structures, guest water molecules are interconnected with the uncoordinated acidic hydroxyl groups of the phosphonate moieties and coordinated water molecules by means of extended hydrogen-bonding interactions. BAM-1 and BAM-2 showed a gradual increase in proton conductivity with increasing temperature and reached 4.9 × 10^-5 and 4.4 × 10^-5 S cm^-1 at 90 °C and 98% relative humidity (RH). The highest proton conductivity recorded for BAM-3 was 1.4 × 10^-5 S cm^-1 at 50 °C and 98% RH. Upon further heating, BAM-3 undergoes dehydration followed by a phase transition to another crystalline form which largely affects its performance. All compounds exhibited a proton hopping (Grotthuss model) mechanism, as suggested by their low activation energy.