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Solketal, a widely used glycerol-derived solvent, can be efficiently synthesized through heterogeneous catalysis, thus avoiding the significant product losses typically encountered with aqueous work-up in homogeneous catalysis. This study explores the catalytic synthesis of solketal using solid acid catalysts derived from recovered carbon blacks (rCBs), which are obtained through the pyrolysis of end-of-life tires. This was further converted into solid acid catalysts through the introduction of acidic functional groups using concentrated H2SO4 or 4-benzenediazonium sulfonate (BDS) as sulfonating agents. Additionally, post-pyrolytic rCB treated with glucose and subsequently sulfonated with sulfuric acid was also prepared. Comprehensive characterization of the initial and modified rCBs was performed using techniques such as elemental analysis, powder X-ray diffraction, thermogravimetric analysis, a back titration method, and both scanning and transmission electron microscopy, along with X-ray photoelectron spectroscopy. The catalytic performance of these samples was evaluated through the batch mode glycerol acetalization to produce solketal. The modified rCBs exhibited substantial catalytic activity, achieving high glycerol conversions (approximately 90%) and high solketal selectivity (around 95%) within 30 min at 40 °C. This notable activity was attributed to the presence of -SO3H groups on the surface of the functionalized rCBs. Reusability tests indicated that only rCBs modified with glucose demonstrated acceptable catalytic stability in subsequent acetalization cycles. The findings underscore the potential of utilizing end-of-life tires to produce effective acid catalysts for glycerol valorization processes. [ABSTRACT FROM AUTHOR]

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]

The present work concerns proton-conducting composites obtained by replacing the water molecules present in aluminophosphate and silicoaluminophosphate AFI-type molecular sieves (AlPO-5 and SAPO-5) with azole molecules (imidazole or 1,2,4-triazole). Both the introduction of azoles and the generation of Brønsted acid centers by isomorphous substitution in aluminophosphate materials were aimed at improving the proton conductivity of the materials and its stability. In the presented study, AlPO-5 and several SAPO-5 materials differing in silicon content were synthesized. The obtained porous matrices were studied using PXRD, low-temperature nitrogen sorption, TPD-NH3, FTIR, and SEM. The proton conductivity of composites was measured using impedance spectroscopy. The results show that the increase in silicon content of the porous matrices is accompanied by an increase in their acidity. However, this does not translate into an increase in the conductivity of the azole composites. Triazole composites show lower conductivity and significantly higher activation energies than imidazole composites; however, most triazole composites show much higher stability. The different conductivity values for imidazole and triazole composites may be due to differences in chemical properties of the azoles. [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]

Ordered mesoporous tin oxide and tin phosphate were successfully synthesized via two-step nanocasting route. The SBA-15 silica and CMK-3 carbon were used as hard templates. Powder X-ray diffraction, nitrogen adsorption and transmission electron microscopy confirmed hexagonal mesoporous structure of resulted products. Mesoporous tin oxide indicated crystalline walls (cassiterite). The mesoporous products showed considerable catalytic activity in propan-2-ol decomposition. The tin oxide led the dehydrogenation towards acetone, while mesoporous tin phosphate exhibited activity of acid sites resulting in dehydration to propene. [ABSTRACT FROM AUTHOR]

The metallosilicalites (MFI) containing copper ([Cu,Si]), zinc ([Zn,Si]) or both elements ([Cu,Zn,Si]) were prepared and modified as potential catalysts for the NO reduction with propene. The H-[Cu,Si] samples showed the highest activity, which was initially comparable to that of Cu-ZSM-5, but contrary to the latter, it increased with time. The framework Cu or Cu released from the framework probably act as active sites. [ABSTRACT FROM AUTHOR]

The metallosilicalites (MFI) containing copper ([Cu,Si]), zinc ([Zn,Si]) or both elements ([Cu,Zn,Si]) were prepared and modified as potential catalysts for the NO reduction with propene. The H-[Cu,Si] samples showed the highest activity, which was initially comparable to that of Cu-ZSM-5, but contrary to the latter, it increased with time. The framework Cu or Cu released from the framework probably act as active sites. [ABSTRACT FROM AUTHOR]