Engineering Supramolecular Binding Sites in an Ultrastable and Hydrophobic Metal–Organic Framework for C 2 H 6 /C 2 H 4 Separation

作者：Chenyi Yu, Keke Wang, Beiyu Zhao, Yiming Lin, Changjiang Zhou, Xianliang Huo, Bo Xie, Hui‐Min Wen, Yuanbin She, Jun Hu · 发表于：Inorganic Chemistry · 年份：2025 · DOI：10.1021/acs.inorgchem.5c00745 · 被引用次数：7 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Machine Learning in Materials Science、Catalytic Processes in Materials Science

The separation of ethane (C 2 H 6 ) from ethylene (C 2 H 4 ) is critical for obtaining polymer-grade C 2 H 4 . Adsorptive separation with C 2 H 6 -selective MOFs offers a viable alternative to energy-intensive cryogenic distillation, enabling the direct production of high-purity C 2 H 4 . In this study, we developed an ultrastable ethane-selective metal–organic framework, UiO-67-(CH 3 ) 2, which demonstrates enhanced C 2 H 6 adsorption (4.10 mmol g –1 at 1 bar and 298 K), higher C 2 H 6 /C 2 H 4 selectivity of 1.70, and an increased C 2 H 6 /C 2 H 4 adsorption ratio of 1.53 compared to unmodified UiO-67. GCMC simulations demonstrate that C 2 H 6 forms more C–H···π interactions with the surrounding benzene rings and more C–H···C interactions with methyl groups compared to C 2 H 4, highlighting the synergistic effects of supramolecular interactions. Furthermore, the hydrophobic pore environment also minimizes water interference, with exceptionally low water uptake (0.019 g g –1 at 60% RH), ensuring robust separation capacity under high humid conditions. The introduction of methyl groups not only significantly enhances C 2 H 6 adsorption performance and C 2 H 6 /C 2 H 4 separation selectivity but also improves material’s hydrophobicity.