Solvent-assisted linker exchange (SALE) is a powerful tool to increase the structural complexity of metal–organic frameworks (MOF) and expand their functionality, while amounts of organic solvent and energy-intensive heating are needed in this process. In this work, we propose a solvent-free and environment-friendly mechanochemistry-assisted linker exchange strategy (MALE) for MOF post-synthetic modification in a green and sustainable manner at room temperature, which is demonstrated by the efficient linker exchange in ZIF-8 (ZIF = Zeolitic imidazolate frameworks) with imidazole-2-formaldehyde (Im-CHO) ligand. Importantly, contrast experiments show that the linker exchange reaction rate of the MALE method is much faster and more efficient than the conventional SALE method. In addition, the versatility of the MALE method is certified by successfully extending to robust UiO-66 (UiO = University of Oslo) and other functional ZIF-8 analogues, including ZIF-8/Br, ZIF-8/CF₃, ZIF-8/CH₂OH, ZIF-8/Cl, and ZIF-8/Et. Besides, the obtained ZIF-8/CF₃ shows a boosting kinetic separation performance for C₃H₆/C₃H₈ gas mixtures compared with pristine ZIF-8. This work not only proposes a green, efficient, and solvent-free linker exchange method of MOF, but also develops a potential adsorbent for efficient kinetic separation of C₃H₆/C₃H₈ mixtures.

溶剂辅助连接子交换 (SALE) 是增加金属有机框架 (MOF) 结构复杂性和扩展其功能的有力工具，而在此过程中需要大量的有机溶剂和能源密集型加热。在这项工作中，我们提出了一种无溶剂和环境友好的机械化学辅助接头交换策略（MALE），用于在室温下以绿色和可持续的方式进行 MOF 后合成修饰，这通过 ZIF 中的高效接头交换得到证明- 8（ZIF = 沸石咪唑酯骨架）与咪唑-2-甲醛 (Im-CHO) 配体。重要的是，对比实验表明，MALE 方法的接头交换反应速率比传统的 SALE 方法更快、更有效。此外，₃、ZIF-8/CH ₂ OH、ZIF-8/Cl和ZIF-8/Et。此外，与原始 ZIF-8 相比，所得 ZIF-8/CF ₃对 C ₃ H ₆ /C ₃ H ₈气体混合物的动力学分离性能有所提高。该工作不仅提出了一种绿色、高效、无溶剂的 MOF 接头交换方法，而且还开发了一种潜在的吸附剂，用于 C ₃ H ₆ /C ₃ H ₈混合物的高效动力学分离。