Vitrification-Enabled Enhancement of Proton Conductivity in Hydrogen-Bonded Organic Frameworks

Hydrogen-bonded organic frameworks (HOFs) are versatile materials with potential applications in proton conduction. Traditional approaches involve incorporating humidity control to address grain boundary challenges for proton conduction. This study finds vitrification as an alternative strategy to eliminate grain boundary effect in HOFs by rapidly melt quenching the kinetically stable to glassy state HOF-SXU-8-g . Notably, a remarkable enhancement in proton conductivity without humidity was achieved after vitrification, from 1.31 × 10 -7 S cm -1 to 5.62 × 10 -2 S cm -1 at 100°C. Long term stability test showed negligible performance degradation, and even at 30°C, the proton conductivity remained at high level of 1.2 × 10 -2 S cm -1 . Molecule dynamics (MD) simulations and X-ray total scattering experiments reveal the HOF-SXU-8-g system is consisted of three kinds of clusters, i.e., 1,5-Naphthalenedisulfonic acid (1,5-NSA) anion clusters, N,N-dimethylformamide molecule clusters, and H + -H 2 O clusters. In which, the H + plays an important role to bridge these clusters and the high conductivity is mainly related to the H+ on H 3 O + . 1 H magic angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) revealed that the H + mobility was increased significantly after the transformation. These findings provide valuable insights for optimizing HOFs, enabling efficient proton conduction, and advancing energy conversion and storage devices.