Synthesis of hierarchical ZSM-12 nanolayers for levulinic acid esterification with ethanol to ethyl levulinate

Hierarchical ZSM-12 nanolayers have been successfully synthesized via a one-pot hydrothermal process using dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride (TPOAC) as a secondary organic structure-directing agent (OSDA). The as-synthesized ZSM-12 samples were characterized by means of XRD, SEM, TEM, N₂ physisorption, and NH₃-TPD. This clearly demonstrates that the TPOAC content and the crystallization time are crucial parameters for the formation of nanolayered structures. The presence of such a structure significantly improves the mesoporosity of ZSM-12 by generating interstitial mesopores between nanolayers, eventually resulting in enhancing external surface areas and mesopore volumes, and subsequently promoting the molecular diffusion inside a zeolite framework. To illustrate its advantages as a heterogeneous catalyst, hierarchical ZSM-12 nanolayers were applied in the catalytic application of an esterification of levulinic acid with ethanol to ethyl levulinate. Interestingly, hierarchical ZSM-12 nanolayers exhibit an improvement of catalytic activity in terms of levulinic acid conversion (78.5%) and ethyl levulinate selectivity (98.7%) compared with other frameworks of hierarchical zeolite nanosheets, such as ZSM-5 and FAU. The example reported herein demonstrates an efficient way to synthesize a unidimensional pore zeolite with hierarchical nanolayered structure via a dual template method and also opens up perspectives for the application of different hierarchical porous systems of zeolites in the bulky-molecule reactions such as in the case of levulinic acid esterification with ethanol.