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.

中文翻译：

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柔性金属有机骨架分子筛分离甲醇/苯共沸物

甲醇/苯共沸混合物的分离无论是通过传统蒸馏技术还是通过吸附剂都非常具有挑战性。在这项工作中，我们设计并合成了一种由廉价原材料组成的柔性钙基金属有机骨架MAF-58。 MAF-58 显示出选择性甲醇诱导的开孔灵活性。尽管开孔足够大，可以容纳苯分子，但 MAF-58 表现出具有超高实验选择性的甲醇/苯分子筛，可得到 5.1 mmol g ^–1高纯度（99.99%+）甲醇和 2.0 mmol g ^–1高纯度甲醇(99.97%+) 苯在单个吸附/解吸循环中。计算模拟表明，优先吸附的配位甲醇分子作为门控组分，选择性地阻止苯的扩散，提供了一种新的门控吸附机制。