A Porous Sulfonated 2D Zirconium Metal-Organic Framework as a Robust Platform for Proton Conduction

By using the strategy of pre-assembly chlorosulfonation applied to a linker precursor, the first sulfonated zirconium metal-organic framework (JUK-14) with two-dimensional (2D) structure, was synthesized. Single-crystal X-ray diffraction reveals that the material is built of Zr₆ O₄ (OH)₄ (COO)₈ oxoclusters, doubly 4-connected by angular dicarboxylates, and stacked in layers spaced 1.5 nm apart by the presence of sulfonic groups. JUK-14 exhibits excellent hydrothermal stability, permanent porosity confirmed by gas adsorption studies, and shows high (>10^-4  S/cm) and low (<10^-8  S/cm) proton conductivity under humidified and anhydrous conditions, respectively. Post-synthesis inclusion of imidazole improves the overall conductivity increasing it to 1.7×10^-3  S/cm at 60 °C and 90 % relative humidity, and by 3 orders of magnitude at 160 °C. The combination of 2D porous nature with robustness of zirconium MOFs offers new opportunities for exploration of the material towards energy and environmental applications.