Metalation of metal–organic frameworks (MOFs) has been developed as a prominent strategy for materials functionalization for pore chemistry modulation and property optimization. By introducing exotic metal ions/complexes/nanoparticles onto/into the parent framework, many metallized MOFs have exhibited significantly improved performance in a wide range of applications. In this review, we focus on the research progress in the metalation of metal–organic frameworks during the last five years, spanning the design principles, synthetic strategies, and potential applications. Based on the crystal engineering principles, a minor change in the MOF composition through metalation would lead to leveraged variation of properties. This review starts from the general strategies established for the incorporation of metal species within MOFs, followed by the design principles to graft the desired functionality while maintaining the porosity of frameworks. Facile metalation has contributed a great number of bespoke materials with excellent performance, and we summarize their applications in gas adsorption and separation, heterogeneous catalysis, detection and sensing, and energy storage and conversion. The underlying mechanisms are also investigated by state-of-the-art techniques and analyzed for gaining insight into the structure–property relationships, which would in turn facilitate the further development of design principles. Finally, the current challenges and opportunities in MOF metalation have been discussed, and the promising future directions for customizing the next-generation advanced materials have been outlined as well.

中文翻译：

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金属有机框架的金属化：基础知识和应用

金属有机框架（MOF）的金属化已被开发为用于孔隙化学调节和性能优化的材料功能化的重要策略。通过将外来金属离子/复合物/纳米颗粒引入到母体框架上，许多金属化 MOF 在广泛的应用中表现出显着改善的性能。在这篇综述中，我们重点关注过去五年金属有机框架金属化的研究进展，涵盖设计原理、合成策略和潜在应用。根据晶体工程原理，金属化对 MOF 成分的微小改变将导致性能的杠杆变化。本综述从在 MOF 中掺入金属物质的一般策略开始，然后是在保持框架孔隙率的同时接枝所需功能的设计原则。简便的金属化提供了大量性能优异的定制材料，我们总结了它们在气体吸附与分离、多相催化、检测与传感、能量存储与转换等方面的应用。还通过最先进的技术研究了潜在的机制，并进行了分析，以深入了解结构-性能关系，从而促进设计原则的进一步发展。最后，讨论了 MOF 金属化当前的挑战和机遇，并概述了定制下一代先进材料的有前景的未来方向。