Molecular-Sieving Separation of Methanol/Benzene Azeotrope by a Flexible Metal–Organic Framework

作者：Mu‐Yang Zhou, Xuewen Zhang, Yi Heng, Zhi‐Shuo Wang, Dong‐Dong Zhou, Rui‐Biao Lin, Jie‐Peng Zhang, Xiao‐Ming Chen · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.3c13480 · 被引用次数：48 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Covalent Organic Framework Applications、Mesoporous Materials and Catalysis

Separation of methanol/benzene azeotrope mixtures is very challenging not only by the conventional distillation technique but also by adsorbents. In this work, we design and synthesize a flexible Ca-based metal–organic framework MAF-58 consisting of cheap raw materials. MAF-58 shows selective methanol-induced pore-opening flexibility. Although the opened pores are large enough to accommodate benzene molecules, MAF-58 shows methanol/benzene molecular sieving with ultrahigh experimental selectivity, giving 5.1 mmol g –1 high-purity (99.99%+) methanol and 2.0 mmol g –1 high-purity (99.97%+) benzene in a single adsorption/desorption cycle. Computational simulations reveal that the preferentially adsorbed, coordinated methanol molecules act as the gating component to selectively block the diffusion of benzene, offering a new gating adsorption mechanism.