Designing UiO-66-Based Superprotonic Conductor with the Highest Metal-Organic Framework Based Proton Conductivity

Metal-organic framework (MOF) based proton conductors have received immense importance recently. The present study endeavors to design two post synthetically modified UiO-66-based MOFs and examines the effects of their structural differences on their proton conductivity. UiO-66-NH₂ is modified by reaction with sultones to prepare two homologous compounds, that is, PSM 1 and PSM 2, with SO₃H functionalization in comparable extent (Zr:S = 2:1) in both. However, the pendant alkyl chain holding the -SO₃H group is of different length. PSM 2 has longer alkyl chain attachment than PSM 1. This difference in the length of side arms results in a huge difference in proton conductivity of the two compounds. PSM 1 is observed to have the highest MOF-based proton conductivity (1.64 × 10^-1 S cm^-1) at 80 °C, which is comparable to commercially available Nafion, while PSM 2 shows significantly lower conductivity (4.6 × 10^-3 S cm^-1). Again, the activation energy for proton conduction is one of the lowest among all MOF-based proton conductors in the case of PSM 1, while PSM 2 requires larger activation energy (almost 3 times). This profound effect of variation of the chain length of the side arm by one carbon atom in the case of PSM 1 and PSM 2 was rather surprising and never documented before. This effect of the length of the side arm can be very useful to understand the proton conduction mechanism of MOF-based compounds and also to design better proton conductors. Besides, PSM 1 showed proton conductivity as high as 1.64 × 10^-1 S cm^-1 at 80 °C, which is the highest reported value to date among all MOF-based systems. The lability of the -SO₃H proton of the post synthetically modified UiO-66 MOFs has theoretically been determined by molecular electrostatic potential analysis and theoretical p K_a calculation of models of functional sites along with relevant NBO analyses.