High‐Valence Metal‐Organic Framework Materials Constructed from Metal‐Oxo Clusters: Opportunities and Challenges

Abstract Metal‐organic framework (MOF), which possesses stable framework structure constructed by highly connected metal‐oxo cluster nodes and organic linkers, has shown great promise in gas storage, adsorption, and separation, owing to the high surface areas, tunable pore aperture, and rich functional groups. In this review article, we summarized recent progress made in synthesizing high‐valence MOF (e. g., UiO‐66, MIL‐125, PCN‐22, and MIP‐207) with metal‐oxo cluster as metal source. Of particular note, recent breakthroughs in the preparation of UiO‐66 and MIL‐125 membranes with the corresponding Zr6‐oxo and Ti8‐oxo cluster sources (e. g., Zr6O4(OH)4(OAc)12 and Ti8O8(OOCR)16 clusters) possessing superior separation performance were highlighted. In the end, an outlook on the preparation of versatile high‐valence MOF membranes with the corresponding metal‐oxo clusters as metal sources was highlighted.