Syntheses and High Proton Conductivities of Two 3D Zr(IV)/Hf(IV)-MOFs from Furandicarboxylic Acid.

With the gradual progress of research on proton-conducting metal-organic framework (MOFs), it has become a challenging task to find MOF materials that are easy to prepare and have low toxicity, high stability, and splendid proton conductivity. With the abovementioned objectives in mind, we selected the non-toxic organic ligand 2,5-furandicarboxylic acid and the low toxic quadrivalent metals zirconium(IV) or hafnium(IV) as starting materials and successfully obtained 2 three-dimensional porous MOFs, [M6O4(OH)4(FDC)4(OH)4(H2O)4] [M = ZrIV (1) and HfIV (2)], with ultrahigh water stability using a rapid and green synthesis approach. Their proton conductive ability is remarkable, thanks to the large number of Lewis acidic sites contained in their porous frameworks and the abundant H-bonding network, hydroxyl groups, as well as coordination and crystalline water molecules. The positive correlation of their proton conductivity with relative humidity (RH) and the temperature was observed. Notably, their optimized proton conductivities are 2.80 × 10-3 S·cm-1 of 1 and 3.38 × 10-3 S·cm-1 of 2 under 100 °C/98% RH, which are at the forefront of Zr(IV)/Hf(IV) MOFs with prominent proton conductivity. Logically, their framework features, nitrogen/water adsorption/desorption data, and activation energy values are integrated to deduce their proton conductivity and conducting mechanism differences.