Leilei Cheng, Xueru Chen, Jing Gu, Xiaowei Liu, Ruizhe Chen, Jialiang Yang, Haoran Yuan, Yong Chen
Abstract Hydrodeoxygenation (HDO) of high‐carbon‐number phenolic compounds (e.g., bisphenol A, BPA) to polycyclic alkanes enhances fuel energy density, yet faces challenges in suppressing C─C bond cleavage and catalyst coking. Conventional microporous zeolites exhibit limited mass transfer for bulky molecules, promoting intrapore secondary reactions. To address this, a 3Ru/s‐ZSM‐5 catalyst with short mesoporous nanosheets is engineered, significantly enhancing accessibility to Ru/acid sites and accelerating bulky phenolic diffusion. This structure and suitable Brønsted acidity achieve a 96.30% yield of propane‐2,2‐diyldicyclohexane from BPA, while effectively suppressing C─C cleavage and coking. Furthermore, in situ environmental transmission electron microscopy captures the instantaneous atomic‐scale changes of Ru metal, combined with DFT calculations revealing its dynamic evolution during different hydrogenation reaction stages. The HDO strategy and mechanistic understanding provide promising insights into coking‐resistant catalyst design and avoidance of C─C cleavage during the high‐carbon‐number phenolic compounds HDO process, applicable to waste plastics and biomass conversion.