Selective hydrocracking of bicyclic aromatics to benzene, toluene, and xylenes (BTX) requires close coordination of hydrogenation on metal sites, conversion at acid sites, and intermediate transport. However, the combined effects of functional organization, transport connectivity, and the properties of the metal and acid functions remain poorly resolved. Here, hydrangea-like Beta/Al2O3 (HBA) micro-mesoporous supports were prepared by seed-assisted compartmentalized assembly and loaded with NiMo. The architecture embeds acidic regions containing Beta within an open three-dimensional Al2O3 nanosheet framework that supports the metal phase. Varying the Beta/Al2O3 ratio simultaneously changed acidic domain density, molecular transport, acid properties, and the structure of the sulfided NiMo phase. NiMo/HBA4 provided the best overall balance and achieved a 63.8% BTX yield at 64.5% selectivity and 99.0% 1-methylnaphthalene (1-MN) conversion. NiMo/HBA5 showed the highest apparent rate constant (k) and apparent turnover frequency (TOF) at low conversion, yet produced less BTX. Thus, high 1-MN conversion activity alone did not ensure selective BTX formation. At a common LHSV of 7.5 h−1, NiMo/HBA4 gave a BTX-forming-to-competing pathway ratio of 6.04, compared with 4.29 for mechanically mixed NiMo/MBA(40) with the same composition and nominal NiMo loading. These results support a role for the compartmentalized architecture in promoting metal–acid cooperation. Pore connectivity, acidity, and sulfided-phase properties may jointly facilitate intermediate transfer and selective BTX formation.
