The Surface Chemistry of Metal Oxide Clusters: From Metal–Organic Frameworks to Minerals

[Image: see text] Many metal–organic frameworks (MOFs) incorporate nodes that are small metal oxide clusters. Some of these MOFs are stable at high temperatures, offering good prospects as catalysts—prospects that focus attention on their defect sites and reactivities—all part of a broader subject: the surface chemistry of metal oxide clusters, illustrated here for MOF nodes and for polyoxocations and polyoxoanions. Ligands on MOF defect sites form during synthesis and are central to the understanding and control of MOF reactivity. Reactions of alcohols are illustrative probes of Zr(6)O(8) node defects in UiO-66, characterized by the interconversions of formate, methoxy, hydroxy, and linker carboxylate ligands and by catalysis of alcohol dehydration reactions. We posit that new reactivities of MOF nodes will emerge from incorporation of a wide range of groups on their surfaces and from targeted substitutions of metals within them.