摘要: Separation of ternary cyclic C6 hydrocarbons, i.e., the mixture of benzene (Bz), cyclohexene (Cye), and cyclohexane (Cya), is one of the critical chemical processes but challenging in the petrochemical industry. Here, we design and synthesize a stable Al-based metal‒organic framework with high-quality single crystals, which exhibits excellent thermal stability (up to 300 °C), acid-base stability (within a pH range of 2–12) and boiling-water stability. Interestingly, by virtue of multiple gates controlled by organic fragments and/or inorganic clusters in the quasi-three-dimensional pores, the framework exhibits not only the ultrahigh Bz/Cya (180) and Bz/Cye (66) selectivities, but also ultrahigh Bz selectivity (118) from the ternary Bz/Cye/Cya mixtures. Notably, all the above selectivities rank in the top three in all porous materials, and the Bz/Cye selectivity is the highest value to date. Single-crystal X-ray diffraction analyses and computational simulations revealed that the multiple types of gating play the crucial role in the adsorption and separation of Bz/Cye/Cya mixture.