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A Review on Breathing Behaviors of Metal-Organic-Frameworks (MOFs) for Gas Adsorption

机译：金属有机骨架（MOFs）对气体吸附的呼吸行为研究进展

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Metal-organic frameworks (MOFs) are a new class of microporous materials that possess framework flexibility, large surface areas, “tailor-made” framework functionalities, and tunable pore sizes. These features empower MOFs superior performances and broader application spectra than those of zeolites and phosphine-based molecular sieves. In parallel with designing new structures and new chemistry of MOFs, the observation of unique breathing behaviors upon adsorption of gases or solvents stimulates their potential applications as host materials in gas storage for renewable energy. This has attracted intense research energy to understand the causes at the atomic level, using in situ X-ray diffraction, calorimetry, Fourier transform infrared spectroscopy, and molecular dynamics simulations. This article is developed in the following order: first to introduce the definition of MOFs and the observation of their framework flexibility. Second, synthesis routes of MOFs are summarized with the emphasis on the hydrothermal synthesis, owing to the environmental-benign and economically availability of water. Third, MOFs exhibiting breathing behaviors are summarized, followed by rationales from thermodynamic viewpoint. Subsequently, effects of various functionalities on breathing behaviors are appraised, including using post-synthetic modification routes. Finally, possible framework spatial requirements of MOFs for yielding breathing behaviors are highlighted as the design strategies for new syntheses.
机译：金属有机骨架（MOF）是一类新型的微孔材料，具有骨架柔韧性，较大的表面积，“量身定制”的骨架功能和可调的孔径。与沸石和膦基分子筛相比，这些功能赋予MOF优异的性能和更广阔的应用范围。在设计MOF的新结构和新化学物质的同时，观察到气体或溶剂吸附后独特的呼吸行为刺激了它们作为可再生能源储气中的主体材料的潜在应用。使用原位X射线衍射，量热法，傅里叶变换红外光谱法和分子动力学模拟，这吸引了巨大的研究精力来了解原子级的原因。本文按以下顺序开发：首先介绍MOF的定义以及对它们框架灵活性的观察。其次，由于水的环境友好性和经济可用性，总结了MOF的合成路线，重点是水热合成。第三，对表现出呼吸行为的MOF进行了总结，然后从热力学的角度提出了理论依据。随后，评估各种功能对呼吸行为的影响，包括使用合成后修饰途径。最后，强调了MOF产生呼吸行为的可能框架空间要求，作为新合成的设计策略。

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