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.