Tuning Catalytic Sites on Zr₆O₈ Metal-Organic Framework Nodes via Ligand and Defect Chemistry Probed with tert-Butyl Alcohol Dehydration to Isobutylene

Metal-organic frameworks (MOFs) have drawn wide attention as candidate catalysts, but some essential questions about their nature and performance have barely been addressed. (1) How do OH groups on MOF nodes act as catalytic sites (2) What are the relationships among these groups, node defects, and MOF stability, and how do reaction conditions influence them (3) What are the interplays between catalytic properties and transport limitations To address these questions, we report an experimental and theoretical investigation of the catalytic dehydration of tert-butyl alcohol (TBA) used to probe the activities of OH groups of Zr₆O₈ nodes in the MOFs UiO-66 and MOF-808, which have different densities of vacancy sites and different pore sizes. The results show that (1) terminal node OH groups are formed as formate and/or acetate ligands present initially on the nodes react with TBA to form esters, (2) these OH groups act as catalytic sites for TBA dehydration to isobutylene, and (3) TBA also reacts to break node-linker bonds to form esters and thereby unzip the MOFs. The small pores of UiO-66 limit the access of TBA and the reaction with the formate/acetate ligands bound within the pores, whereas the larger pores of MOF-808 facilitate transport and favor reaction in the MOF interior. However, after removal of the formate and acetate ligands by reaction with methanol to form esters, interior active sites in UiO-66 become accessible for the reaction of TBA, with the activity depending on the density of defect sites with terminal OH groups. The number of vacancies on the nodes is important in determining a tradeoff between the catalytic activity of a MOF and its resistance to unzipping. Computations at the level of density functional theory show how the terminal OH groups on node vacancies act as Brønsted bases, facilitating TBA dehydration via a carbocation intermediate in an E1 mechanism; the calculations further illuminate the comparable chemistry of the unzipping.