Rational design of metal-acid bifunctional catalysts is crucial for steering selectivity in tandem catalysis, yet conventional metal/zeolite systems often suffer from diffusion-imposed limitations that hinder intermediate transport. Herein, we report a diethanolamine-assisted alkaline treatment (DEA-AT) strategy to reconstruct β zeolite into a hierarchical framework featuring radially aligned, exterior-connected mesoporous channels (β-DEA-AT). This architecture markedly improved the accessibility of intermediate cyclohexene to Brønsted acid sites and strengthened metal-acid cooperation in benzene hydroalkylation. As a result, Ru/β-DEA-AT catalysts delivered markedly enhanced performance, achieving a cyclohexylbenzene yield of 35.2%, benzene conversion of 62.1%, and a formation rate of 49.6 mmol_CHB·g_cat^-1·h^-1, surpassing both conventionally alkali-treated Ru/β-AT (30.6% conversion, 11.6% CHB yield, 31.0 mmol_CHB·g_cat^-1·h^-1) and pristine Ru/β catalysts (33.1% conversion, 21.6% CHB yield, 30.5 mmol_CHB·g_cat^-1·h^-1). Systematic investigations revealed that the DEA-induced hierarchical reconstruction facilitated the rapid migration of cyclohexene intermediates within the zeolite framework, as reflected by an increase in the apparent cyclohexene diffusion coefficient from 1.81 × 10⁻⁵ cm²·s⁻¹  for Ru/β₁₀₀ to 6.42 × 10⁻⁵ cm²·s⁻¹ for Ru/β₁₀₀-DEA-AT, where shortened diffusion pathways and enhanced accessibility of Brønsted acid sites promote intermediate transport and transformation. These findings establish pore-environment engineering as a generalizable strategy to regulate intermediate transformations through metal-acid synergy, providing guidance for the design of next-generation multifunctional tandem catalysts.

Precisely tuning the micro-nanoscale characteristics and synergistic effect of metal-acid sites to regulate the distribution of hydroconversion products are significant but challenging. The protonated carbocation intermediates triggered by tandem reaction on metal-acid region hinder target product formation due to their high reactivity and instability. Supported M/Zeolite hydroconversion catalysts, which often excel in simple synthesis, ease of separation and recyclability. However, they usually consist of sterically unconstrained metal centers which are isolated from acid sites, only providing limited coupling-selectivity to target product. Herein, metal nanoparticles enveloped in acidic zeolite frameworks were developed and used for investigating the process of hydroalkylation of benzene to cyclohexylbenzene. We show that appropriate metal encapsulation comprising adequate efficient metal-acid units successfully avoids the more thermodynamically favorable hydrogenation of cyclohexene to cyclohexane, but steers to alkylation of cyclohexene with benzene to cyclohexylbenzene. This resulted in the highest cyclohexylbenzene yield of 47.7% among the reported work, and surpassed the performance of all supported M/Zeolite catalysts. Experimental and theoretical results supported that the abundant bifunctional metal-acid units enhance the activation frequency and probability of intermediate cyclohexene. This work might provide insights for the integration strategy of dual active site and guidance for the construction of efficient “metal-acid balance” in tandem reactions.