Zhou Xianlong, Jin Huanyu, Xia Bao Yu, Davey Kenneth, Zheng Yao, Qiao Shi-Zhang
School of Chemical Engineering and Advanced Materials, The University of Adelaide, Adelaide, SA, 5005, Australia.
Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, Wuhan, 430074, China.
Adv Mater. 2021 Dec;33(51):e2104341. doi: 10.1002/adma.202104341. Epub 2021 Oct 4.
The physicochemical properties of metal-organic frameworks (MOFs) significantly depend on composition, topology, and porosity, which can be tuned via synthesis. In addition to a classic direct synthesis, postsynthesis modulations of MOFs, including ion exchange, installation, and destruction, can significantly expand the application. Because of a limitation of the qualitative hard and soft acids and bases (HSAB) theory, posttreatment permits regulation of MOF structure by cleaving chemical bonds at the molecular level. Here, methods of coordination bond scission to tailor the structure are critically appraised and the application to energy storage and conversion is assessed. MOF structures synthesized by molecular-level coordination bond cleavage are described and the corresponding MOFs for electrocatalysis and renewable battery applications are evaluated. Significant emphasis is placed on various coordination bond cleavage to tune properties, including chemical groups, electronic structures, and morphologies. The review concludes with a critical perspective on practical application, together with challenges and future outlook for this emerging field.
金属有机框架材料（MOFs）的物理化学性质很大程度上取决于其组成、拓扑结构和孔隙率，这些可通过合成进行调节。除了经典的直接合成法外，MOFs的后合成调控，包括离子交换、官能团引入和结构破坏等，能够显著拓展其应用范围。由于定性的软硬酸碱（HSAB）理论存在局限性，后处理允许在分子水平上通过切断化学键来调控MOF结构。在此，对通过切断配位键来定制结构的方法进行了批判性评估，并对其在能量存储和转换方面的应用进行了评估。描述了通过分子水平切断配位键合成的MOF结构，并对用于电催化和可再生电池应用的相应MOFs进行了评估。重点强调了通过各种配位键切断来调节性质，包括化学基团、电子结构和形态等。综述最后对实际应用进行了批判性展望，并探讨了这一新兴领域面临的挑战和未来前景。
