Ultrahigh Proton Conductivities of Postmodified Hf(IV) Metal-Organic Frameworks and Related Chitosan-Based Composite Membranes.

Recently, researchers have focused on preparing and studying proton exchange membranes. Metal-organic frameworks (MOFs) are candidates for composite membrane fillers due to their high crystallinity and structural characteristics, and Hf-based MOFs have attracted our attention with their high porosity and high stability. Therefore, in this study, Hf-based MOFs were doped into a cost-effective chitosan matrix as fillers to fabricate composite films having excellent proton conductivity (σ). First, the nanoscale MOFs Hf-UiO-66-(OH)2 (1) and Hf-UiO-66-NH2 (2) were chemically modified by a ligand design strategy to obtain SA-1 and CBD-2 bearing free -COOH units. The proton conductivities of SA-1 and CBD-2 under optimal test conditions reached 1.23 × 10-2 and 0.71 × 10-2 S cm-1. After that, we prepared composite membranes CS/SA-1 and CS/CBD-2 by the casting method; tests revealed that the introduction of MOFs improved the stabilities and σ values of the membranes, and their best σ could reach above 10-2 S cm-1 under 100 °C/98% RH. Further structural characterization and activation energy calculation revealed the conductive mechanism of the composite films. This investigation not only proposes a novel chemical modification method for optimizing the σ of MOFs but also promotes the development of MOF-doped composite membranes and provides a basis for future applications of MOFs in fuel cells.