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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. [ABSTRACT FROM AUTHOR]

X-band electron spin resonance (ESR) spectra of S3- radicals in ultramarine analog (pigment) prepared from zeolite A and maintaining the original structure of parent zeolite were recorded in the temperature range of 4.2–380 K. Electron spin echo experiments (echo detected ESR, electron spin-lattice relaxation, and spin echo dephasing) were performed in the temperature range of 4.2–50 K. The rigid lattice g factors are gx=2.0016, gy=2.0505, and gz=2.0355, and they are gradually averaged with temperature to the final collapse into a single line with g=2.028 above 300 K. This is due to reorientations of S3- molecule between 12 possible orientations in the sodalite cage through the energy barrier of 2.4 kJ/mol. The low-lying orbital states of the open form of S3- molecule having C2v symmetry are considered and molecular orbital (MO) theory of the g factors is presented. The orbital mixing coefficients were calculated from experimental g factors and available theoretical orbital splitting. They indicate that the unpaired electron spin density in the ground state is localized mainly (about 50%) on the central sulfur atom of S3- anion radical, whereas in the excited electronic state the density is localized mainly on the lateral sulfur atoms (90%). A strong broadening of the ESR lines in directions around the twofold symmetry axis of the radical S3- molecule (z-axis) is discovered below 10 K. It is due to a distribution of the S–S–S bond angle value influencing mainly the energy of the 2B2-symmetry MO. This effect is smeared out by molecular dynamics at higher temperatures. A distribution of the g factors is confirmed by the recovery of the spin system magnetization during spin-lattice relaxation measurements, which is described by a stretched exponential function. Both the spin-lattice relaxation and electron spin echo dephasing are governed by localized phonon mode of energy of about 40 cm-1. Thus, the anion-radical S3- molecules are weakly bonded to the zeolite framework, and they do not participate in the phonon motion of the host lattice because of their own local dynamics. [ABSTRACT FROM AUTHOR]