Yang Dong, Gates Bruce C
Department of Chemical Engineering, University of California, Davis, Davis, California 95616, United States.
J Phys Chem C Nanomater Interfaces. 2024 May 15;128(21):8551-8559. doi: 10.1021/acs.jpcc.4c02105. eCollection 2024 May 30.
Among the important properties of metal-organic frameworks (MOFs) is stability, which may limit applications, for example, in separations and catalysis. Many MOFs consist of metal oxo cluster nodes connected by carboxylate linkers. Addressing MOF stability, we highlight connections between metal oxo cluster chemistry and MOF node chemistry, including results characterizing Keggin ions and biological clusters. MOF syntheses yield diverse metal oxo cluster node structures, with varying numbers of metal atoms (3-13) and the tendency to form chains. MOF stabilities reflect a balance between the number of node-linker connections and the degree of node hydrolysis. We summarize literature results showing how MOF stability (the temperature of decomposition in air) depends on the degree of hydrolysis/condensation of the node metals, which is correlated to their degree of substitution with linkers. We suggest that this correlation may help guide the discovery of stable new MOFs, and we foresee opportunities for progress in MOF chemistry emerging from progress in metal oxo cluster chemistry.
金属有机框架材料（MOF）的重要特性之一是稳定性，而这一特性可能会限制其应用，例如在分离和催化领域的应用。许多MOF由通过羧酸盐连接体相连的金属氧簇节点组成。为了解决MOF的稳定性问题，我们着重强调金属氧簇化学与MOF节点化学之间的联系，包括对表征凯金离子和生物簇的研究结果。MOF的合成产生了多样的金属氧簇节点结构，其金属原子数量不同（3 - 13个）且有形成链状的趋势。MOF的稳定性反映了节点 - 连接体连接数量与节点水解程度之间的平衡。我们总结了文献结果，展示了MOF稳定性（在空气中的分解温度）如何取决于节点金属的水解/缩合程度，这与它们被连接体取代的程度相关。我们认为这种相关性可能有助于指导新型稳定MOF的发现，并且我们预见随着金属氧簇化学的进展，MOF化学将有取得进展的机会。
