Diffusion is an extremely critical step in zeolite catalysis which determines the catalytic performance, in particular for the conversion of bulky molecules. Introducing interconnected mesopores and macropores into a single microporous zeolite with the rationalized pore size at each level is an effective strategy to suppress the diffusion limitations, but remains highly challenging due to the lack of rational design principles. Herein, we demonstrate the first example of boosting molecular diffusion by constructing hierarchical Murray zeolites with highly ordered and fully interconnected macro-meso-microporous structure on the basis of the generalized Murray's Law. Such hierarchical Murray zeolite with a refined quantitative relationship between pore size at each length scale exhibited 9 and 5 times higher effective diffusion rate, leading to 2.5 and 1.5 times higher catalytic performance in the bulky 1,3,5-triisopropylbenzene cracking reaction than those of microporous ZSM-5 and ZSM-5 nanocrystals, respectively. The concept of hierarchical Murray zeolites with optimized structural feature and their design principles could be applied to other catalytic reactions for maximized performance.

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The epoxidation reaction over titanium silicalite-1 (TS-1) zeolites is a green way to produce epoxides that are important intermediates for chemicals. Nevertheless, the conventional microporous TS-1 zeolite shows limited diffusion ability for bulky molecules, leading to poor activity and low selectivity. Constructing hierarchical porosity in microporous materials is an effective strategy to enhance the diffusion properties of catalysts. However, there are few reports on the design and synthesis of TS-1 zeolites with hierarchical structure featuring multilevels, interconnectivity, and regularity for efficient diffusion and epoxidations. Herein, hierarchical TS-1 zeolites with ordered macro–meso–microporosity (OMMM-TS-1) are obtained by a method combining a templated effect of ordered macro–mesoporous matrices and a confined in situ crystallization process. The OMMM-TS-1 possesses ordered macropores with tunable size (∼200–600 nm), ordered mesopores (∼8 nm), and intact micropores (∼0.5 nm). The OMMM-TS-1 achieves a cyclooctene conversion as 3.6 times and 1.8 times and a selectivity to epoxy product as 1.6 times and 1.3 times higher than the conventional TS-1 (C-TS-1) and nanosized TS-1 (Nano-TS-1) zeolites, respectively. The OMMM-TS-1 also outperforms the C-TS-1 and Nano-TS-1 zeolites in epoxidations of a series of alkenes. Such a novel hierarchical structure can be applied in the design and synthesis of many other catalysts.