Tuning the catalytic acidity in Al₂O₃ nanofibers with mordenite nanocrystals for dehydration reactions

Alumina (Al₂O₃) is one of the most used supports in the chemical industry due to its exceptional thermal stability, surface area, and acidic properties. Mesoscopic structured alumina with adequate acidic properties is important in catalysis to enhance the selectivity and conversion of certain reactions and processes. This study introduces a synthetic method based on electrospinning to produce Al₂O₃ nanofibers (ANFs) with zeolite mordenite (MOR) nanocrystals (hereafter, hybrid ANFs) to tune the textural and surface acidity properties. The hybrid ANFs with electrospinning form a non-woven network with macropores. ANF-HMOR, i.e., ANFs containing protonated mordenite (HMOR), shows the highest total acidity of ca. 276 μmol g^-1 as determined with infrared spectroscopy using pyridine as a molecular probe (IR-Py). IR-Py results reveal that Lewis acid sites are prominently present in the hybrid ANFs. Brønsted acid sites are also observed in the hybrid ANFs and are associated with the HMOR presence. The functionality of hybrid ANFs is evaluated during methanol dehydration to dimethyl ether (DME). The proof of concept reaction reveals that ANF-HMOR is the more active and selective catalyst with 87% conversion and nearly 100% selectivity to DME at 573 K. The results demonstrate that the textural properties and the acid site type and content can be modulated in hybrid ANF structures, synergistically improving the selectivity and conversion during the methanol dehydration reaction. From a broader perspective, our results promote the utilization of hybrid structural materials as a means to tune chemical reactions selectively.