Pair Sites on Nodes of Metal-Organic Framework hcp UiO-66 Catalyze tert-Butyl Alcohol Dehydration.

On metal oxide cluster nodes of metal-organic frameworks (MOFs), sites not bonded to linkers (e.g., defects and structural vacancies) control reactivity and catalysis. Attention has been focused on isolated, individual sites, but pair sites have been largely overlooked. We now show that the MOF hcp UiO-66, which incorporates dimeric Zr6O8 nodes bridged by μ2-OH groups, is an excellent platform for identifying and controlling adjacent sites consisting of OH groups and Zr4+ sites, which catalyze tert-butyl alcohol dehydration much more rapidly than isolated single sites.