Inorganic oxide materials are used in semiconductor electronics, ion exchange, catalysis, coatings, gas sensors and as separation materials. Although their synthesis is well understood, the scope for new materials is reduced because of the stability limits imposed by high-temperature processing and top-down synthetic approaches. In this Review, we describe the derivatization of polyoxometalate (POM) clusters, which enables their assembly into a range of frameworks by use of organic or inorganic linkers. Additionally, bottom-up synthetic approaches can be used to make metal oxide framework materials, and the features of the molecular POM precursors are retained in these structures. Highly robust all-inorganic frameworks can be made using metal-ion linkers, which combine molecular synthetic control without the need for organic components. The resulting frameworks have high stability, and high catalytic, photochemical and electrochemical activity. Conceptually, these inorganic oxide materials bridge the gap between zeolites and metal–organic frameworks (MOFs) and establish a new class of all-inorganic POM frameworks that can be designed using topological and reactivity principles similar to MOFs.

无机氧化物材料可用于半导体电子，离子交换，催化，涂层，气体传感器以及用作分离材料。尽管已经很好地理解了它们的合成，但是由于高温处理和自上而下的合成方法所施加的稳定性限制，新材料的范围有所减少。在这篇综述中，我们描述了多金属氧酸盐（POM）簇的衍生化，这使得它们可以通过使用有机或无机连接基组装成一系列框架。另外，自下而上的合成方法可用于制造金属氧化物骨架材料，并且分子POM前体的特征保留在这些结构中。可以使用金属离子接头制备高度坚固的全无机骨架，该接头结合了分子合成控制而无需有机成分。所得框架具有高稳定性，以及高催化，光化学和电化学活性。从概念上讲，这些无机氧化物材料弥合了沸石和金属有机骨架（MOF）之间的鸿沟，并建立了一种新的全无机POM骨架，可以使用类似于MOF的拓扑和反应原理进行设计。