Imidazole molecules entrapped in porous materials can exhibit high and stable proton conductivity suitable for elevated temperature (>373 K) fuel cell applications. In this study, new anhydrous proton conductors based on imidazole and mesoporous KIT-6 were prepared. To explore the impact of the acidic nature of the porous matrix on proton conduction, a series of KIT-6 materials with varying Si/Al ratios and pure silica materials were synthesized. These materials were additionally modified with cerium atoms to enhance their Brønsted acidity. TPD-NH3 and esterification model reaction confirmed that incorporating aluminum into the silica framework and subsequent modification with cerium atoms generated additional acidic sites. UV-Vis and XPS identified the presence of Ce3+ and Ce4+ in the KIT-6 materials, indicating that high-temperature treatment after cerium introduction may lead to partial cerium incorporation into the framework. EIS studies demonstrated that dispersing imidazole within the KIT-6 matrices resulted in composites showing high proton conductivity over a wide temperature range (300-393 K). The presence of weak acidic centers, particularly Brønsted sites, was found to be beneficial for achieving high conductivity. Cerium-modified composites exhibited conductivity surpassing that of molten imidazole, with the highest conductivity (1.13 × 10-3 S/cm at 393 K) recorded under anhydrous conditions for Ce-KIT-6. Furthermore, all tested composites maintained high stability over multiple heating and cooling cycles.
Keywords: Brønsted acid centers; KIT-6 porous materials; cerium modification; imidazole; proton conductivity.