Selectivity Descriptors of Glycerol Valorization over 10‐Member Ring Zeolites

The shift to renewable feedstocks is essential for developing "smart drop-in" technologies to produce synthetic fuels and chemicals, playing a crucial role in industrial decarbonization. Herein, zeolite-catalyzed glycerol valorization offers a mature way to create higher-value chemicals. This study aims to identify the key factors influencing process efficiency by examining the reaction mechanisms of glycerol valorization using 10-membered ring zeolites: ZSM-5 (MFI, 3D), MCM-22 (MWW, 2D), and ZSM-22 (TON, 1D), each with unique topologies and channel structures. Strategic integration of catalytic studies with advanced characterization techniques, such as in situ UV-vis and solid-state NMR spectroscopy, reveals that zeolite topology plays a key role in determining catalytic performance and product selectivity. Zeolites with cages or intersectional voids (e.g., ZSM-5, MCM-22) promote the production of aromatic compounds, whereas the cage/void-free ZSM-22 favors acrolein formation. Simultaneously, zeolite channels balance the dual cycle mechanism by mediating between diffusion-friendly straight channels (i.e., in ZSM-5 and ZSM-22) and diffusion-restrictive sinusoidal channels (i.e., in ZSM-5 and MCM-22), affecting efficiency and selectivity. This study underscores the critical role of zeolite architecture in determining catalytic outcomes, providing mechanistic insights that bridge the structure-performance gap.