A Funnel-Structured 12 × 10-Ring Zeolite Customized for Biomass Catalytic Pyrolysis

“Ab initio” synthesis of reaction-customized zeolites is essential for zeolite engineering. Catalytic fast pyrolysis (CFP) represents a promising reaction to directly convert biomass into drop-in hydrocarbon fuels, which necessitates zeolites with a gradient large-/medium-porosity. However, the synthesis of such a predefined zeolite is challenging. Herein, an in situ partial interzeolite transformation strategy is proposed to fabricate a core–shell HS-ZSM-5@Beta heterozeolite tailored for biomass CFP. HS-ZSM-5@Beta features a seamless core-to-shell interface and funnel-structured 12 × 10-membered ring (MR) channels, as revealed by atomic-level integrated differential phase contrast scanning transmission electron microscopy (iDPC-STEM). With the well-defined “core-to-shell” pathway and enhanced porosity synergy, HS-ZSM-5@Beta delivers a hydrocarbon selectivity of 57.4 area % during maize straw CFP, which is twice that of conventional ZSM-5. The robust catalytic activity is retained over eight pyrolysis-regeneration cycles. A structure–property relationship investigation underscores the kinetic advantages of this synthetic approach. This study advances the real rational design of zeolites for pre-established reactions.