Proton-Conductive Cerium-Based Metal–Organic Frameworks

In this study, proton-conducting behaviors of a cerium-based metal–organic framework (MOF), Ce-MOF-808, its zirconium-based isostructural MOF, and bimetallic MOFs with various Zr-to-Ce ratios are investigated. The significantly increased proton conductivity (σ) and decreased activation energy (E_a) are obtained by substituting Zr with Ce in the nodes of MOF-808. Ce-MOF-808 achieves a σ of 4.4 × 10^–3 S/cm at 25 °C under 99% relative humidity and an E_a of 0.14 eV; this value is among the lowest-reported E_a of proton-conductive MOFs. Density functional theory calculations are utilized to probe the proton affinities of these MOFs. As the first study reporting the proton conduction in cerium-based MOFs, the finding here suggests that cerium-based MOFs should be a better platform for the design of proton conductors compared to the commonly reported zirconium-based MOFs in future studies on energy-related applications.