Tailoring the Proximity of Metal‐Acid in Metal/zeolite Bifunctional Catalysts for Enhanced <i>n</i> ‐Hexane Hydroisomerization

The spatial arrangement between metal and acid sites critically influences the hydroisomerization efficiency of metal/zeolite catalysts in n-alkane conversion. Nevertheless, achieving precise control on metal-acid intimacy remains a significant challenge at the nanoscale. Herein, Pt nanoparticles are strategically tailored on TiO₂-modified ZSM-5 carriers via atomic layer deposition, leveraging the TiO₂ spacer thickness as a tunable parameter to modulate interfacial distances. In the hydroisomerization of n-hexane, the catalytic performance of the Pt-Ti/ZSM-5 with different TiO₂ thickness displayed a volcano-shaped trend with respect to the metal-acid distances, peaking at 67.5% iso-C6 yield under optimized proximity. This enhanced performance arose from the metal-acid distance-mediated diffusion confinement, resulting in the kinetically favorable reaction pathways. The established structure-property relationship provides a blueprint for rationally designing spatially optimized metal/zeolite catalysts, while advancing the fundamental understanding of bifunctional catalysis.