Ge‐Substituted Hierarchical Ferrierite for n‐Pentane Cracking to Light Olefins: Mechanistic Investigations via In‐situ DRIFTS Studies and DFT Calculations

The development of heterogeneous catalysts for light olefin production via a catalytic cracking has been crucially important due to the high demand of related products in industrial applications. Herein, we report the structural analysis of a germanium‐substituted hierarchical ferrierite zeolite obtained by one‐pot synthesis. This is the first report on an investigation of the synergistic effect of hierarchical structures and the one‐pot Ge‐substitution in a ferrierite framework on the catalytic cracking mechanism. Our findings exhibit that the existence of germanium in a hierarchical ferrierite framework can indeed reduce the Brønsted acid strength, facilitating a catalytic reaction with high light olefin selectivity (63 %) due to the elimination of side reactions, such as dimerization and aromatization, confirmed by in‐situ DRIFTS and DFT studies. This opens up the perspective of the development of metal substitution in an interconnected 8‐ and 10‐pore framework with hierarchical structures on the catalytic behaviors of light olefin production. The Ge‐substituted hierarchical ferrierite was used as a catalyst for catalytic cracking of n‐pentane to light olefins. This catalyst can indeed reduce Brønsted acid strength, leading to suppression of side reactions during n‐pentane cracking and a significant increase in light olefin selectivity. Moreover, this work provides evidence to observe the reaction mechanism and related intermediates by in‐situ DRIFTS and DFT studies.