Inversed Benzene/Cyclohexene/Cyclohexane Adsorption Selectivities for One-Step Purification of Cyclohexene and Beyond

作者：Dong‐Dong Zhou, Xi Ping Feng, Ding-Yi Hu, Xiaotong Lu, Fang-Di Dong, Zijun Fang, Rui‐Biao Lin, Jie‐Peng Zhang, Xiao‐Ming Chen · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c03564 · 被引用次数：20 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Membrane Separation and Gas Transport、Carbon Dioxide Capture Technologies

Separation of benzene/cyclohexene/cyclohexane (Bz/Cye/Cya) mixtures, especially purification of Cye, is crucial but challenging in the petrochemical industry. Here, we report two new metal–organic frameworks with opposite adsorption selectivities for on-demand separation/purification of Bz/Cye/Cya mixtures. Although they possess similar frameworks and pore structures, their pore surfaces are functionalized by hydrophobic ethyl and hydrophilic hydroxymethyl groups, which interact conversely with Bz/Cye/Cya, giving a record-high Bz selectivity (129) and the first example of Cya/Cye/Bz selectivity (18.6), respectively. Equimolar ternary mixture breakthrough experiments showed that they could directly produce high-purity Cya (99.5%+, 0.39 mmol g –1 ) or Bz (99.5%+, 0.25 mmol g –1 ), and the tandem connection of two adsorbents enabled direct production of high-purity Cye (99.5%+, 0.37 mmol g –1 ) in a one-step adsorption process. Further, a bypass-tandem strategy is proposed to not only greatly improve Cye productivity (99.5%+, 0.57 mmol g –1 ) but also simultaneously produce high-purity Cya (99.5%+, 0.36 mmol g –1 ).