Metal–organic frameworks (MOFs) have diverse applications involving the storage, separation and sensing of weakly interacting, high-purity gases. Exposure to impure gas streams and interactions with corrosive and coordinating gases raises the question of chemical robustness; however, the factors that determine the stability of MOFs are not fully understood. Framework materials have been previously categorized as either thermodynamically or kinetically stable, but recent work has elucidated an energetic penalty for porosity for all these materials with respect to a dense phase, which has implications for the design of materials for gas storage, heterogeneous catalysis and electronic applications. In this Review, we focus on two main strategies for stabilization of the porous phase — using inert metal ions or increasing the heterolytic metal–ligand bond strength. We review the progress in designing robust materials for the capture of coordinating and corrosive gases such as H₂O vapour, NH₃, H₂S, SO₂, nitrogen oxides (NO_x) and elemental halogens. We envision that the pursuit of strategies for kinetic stabilization of MOFs will yield increasing numbers of robust frameworks suited to harsh conditions and that short-term stability towards these challenging gases will be predictive of long-term stability for applications in less demanding environments.

金属有机框架（MOF）具有多种应用程序，包括弱相互作用的高纯度气体的存储，分离和检测。暴露于不纯净的气流中以及与腐蚀性和配位气体的相互作用提出了化学稳定性的问题。但是，尚未完全了解确定MOF稳定性的因素。先前已经将框架材料归类为热力学或动力学稳定的材料，但是最近的工作阐明了所有这些材料在致密相方面对孔隙率的高能损失，这对气体存储，非均相催化和电子材料的设计有重要意义。应用程序。在这篇评论中，我们专注于稳定多孔相的两种主要策略-使用惰性金属离子或提高杂化金属-配体的结合强度。我们回顾了设计用于捕获配位和腐蚀性气体（例如H）的坚固材料的进展₂ O蒸气，NH ₃，H ₂ S，SO ₂，氮氧化物（NO _x）和元素卤素。我们设想，追求MOF动力学稳定化的策略将产生越来越多的适用于苛刻条件的坚固框架，而对这些挑战性气体的短期稳定性将预示着在要求不高的环境中应用的长期稳定性。