Controlling Guest Diffusion by Local Dynamic Motion in Soft Porous Crystals to Separate Water Isotopologues and Similar Gases

作者：Yanjing Su, Jia‐Jia Zheng, Ken‐ichi Otake, Nobuhiko Hosono, Susumu Kitagawa, Cheng Gu · 发表于：Accounts of Chemical Research · 年份：2024 · DOI：10.1021/acs.accounts.4c00325 · 被引用次数：37 · 研究领域：Lattice Boltzmann Simulation Studies、Methane Hydrates and Related Phenomena、Metal-Organic Frameworks: Synthesis and Applications

Conspectus The precise and effective separation of similar mixtures is one of the fundamental issues and essential tasks in chemical research. In the field of gas/vapor separation, the size difference among the molecular pairs/isomers of light hydrocarbons and aromatic compounds is generally 0.3–0.5 Å, and the boiling-point difference is generally 6–15 K. These are necessary industrial raw materials and have great separation demands. Still, their separation mainly relies on energy-intensive distillation technology. On the other hand, remarkably similar substances such as oxygen/argon and isotopologues usually exhibit size differences of only 0–0.07 Å and boiling-point differences of only 1–3 K. Although their industrial separation can be realized, their efficiency is considerably low. Therefore, effectively separating remarkably similar mixtures is crucial in fundamental chemistry and industry, but it remains a significant challenge. Porous coordination polymers (PCPs) or metal–organic frameworks (MOFs) are emerging materials platforms for designing adsorbents for separating similar mixtures. However, the reported PCPs did not work well for separating remarkably similar substances. The framework structures of the mainstream PCPs remain unchanged (rigid) or significantly change (globally flexible) upon adsorption. However, rigid and globally flexible PCPs find controlling the pore aperture in subangstrom precision challenging, a prerequisite for distinguishing remarkably simil...