RESUMEN
A variety of methods are employed to synthesize amorphous silica-alumina (ASA) to resolve the role of Al speciation and surface area in the catalytic performance in the Diels-Alder cycloaddition reaction of 2,5-dimethylfuran and ethylene to p-xylene. ASA was prepared by homogeneous deposition-precipitation (HDP) of Al3+ on ordered mesoporous silica, i.e., SBA-15 and OMS prepared under hydrothermal synthesis conditions using an imidazole-based template, and one-step flame spray pyrolysis (FSP). IR spectroscopy and 27Al MAS NMR showed that the resulting ASA represented a set of materials with distinct textural and acidic properties. ASA prepared by grafting Al to ordered mesoporous silica led to a much higher concentration of Brønsted acid sites (BAS). These samples performed much better in the DAC reaction, with p-xylene yields higher than those obtained with a HBeta zeolite benchmark. Materials with Al partially in the bulk of silica (OMS, FSP) and containing significant alumina domains are less acidic and exhibit much lower p-xylene yields. These findings point to the importance of Brønsted acidity for p-xylene formation. This study shows that careful design of the Al speciation can lead to amorphous silica-alumina with similar DAC performance to microporous zeolites.
RESUMEN
Non-oxidative coupling of methane is a promising route to obtain ethylene directly from natural gas. We synthesized siliceous [Fe]zeolites with MFI and CHA topologies and found that they display high selectivity (>90 % for MFI and >99 % for CHA) to ethylene and ethane among gas-phase products. Deactivated [Fe]zeolites can be regenerated by burning coke in air. In situ X-ray absorption spectroscopy demonstrates that the isolated Fe3+ centers in zeolite framework of fresh catalysts are reduced during the reaction to the active sites, including Fe2+ species and Fe (oxy)carbides dispersed in zeolite pores. Photoelectron photoion coincidence spectroscopy results show that methyl radicals are the reaction intermediates formed upon methane activation. Ethane is formed by methyl radical coupling, followed by its dehydrogenation to ethylene. Based on the observation of intermediates including allene, vinylacetylene, 1,3-butadiene, 2-butyne, and cyclopentadiene over [Fe]MFI, a reaction network is proposed leading to polyaromatic species. Such reaction intermediates are not observed over the small-pore [Fe]CHA, where ethylene and ethane are the only gas-phase products.
RESUMEN
A methanethiol-to-olefins (MtTO) equivalent of methanol-to-olefins (MTO) chemistry is demonstrated. CH3SH can be converted to ethylene and propylene in a similar manner as CH3OH over SSZ-13 zeolite involving a hydrocarbon pool mechansim. Methylated aromatic intermediates were identified by 13C NMR analysis. Comparison of MtTO and MTO chemistry provides clues about the mechanism of C-C bond formation and catalyst deactivation.
RESUMEN
In this work, we developed a novel strategy to synthesize porous (alumino)silicate materials using a single structure-directing agent composed of an imidazole unit with a hydrophobic tail, namely, 1,2-dimethyl-3-hexadecyl-1H-imidazol-3-ium bromide (C16dMImz). A wide range of products such as ordered mesoporous silicas, layered silica-alumina, and hierarchically porous mordenite zeolite were obtained by varying synthesis parameters such as temperature and aluminum concentration. By changing crystallization temperature, we could control the degree of silica condensation and tune the textural and morphological properties of the final materials. By varying the aluminum concentration in the gel, we can obtain mesoporous amorphous silica-alumina or crystalline mordenite zeolite with, respectively, weak and strong Brønsted acid sites. Obtained acidic silica-alumina materials displayed promising performance in catalytic reactions of linear paraffin hydroisomerization and Friedel-Crafts alkylation of benzene with benzyl alcohol.
