Probing the sites on metal oxide cluster nodes of metal organic framework MIL-96, MIL-100 and MIL-110

Metal oxide cluster MOF nodes are a good platform to understand the reactivities and catalysis. MIL-96, MIL-100 and MIL-110 are drastically different in their node structures. Following our previous reported results for MIL-100, we report the modified synthesis and characterization of the node sites of MIL-110 and MIL-96 and their catalytic sites by using methanol dehydration as probe reaction. We show that these MOFs can be synthesized from the same solution by adding various amounts of formic acid as modulator. Herein, the chemistry of hydroxyl, formate and methoxy groups were used to probe the three MOFs' node sites. IR data show the bonding structures of these ligands are highly diverse, with reactivities and flexibility depending on node sites. We identified terminal OH group and various µ2-OH groups in single, paired or hydrogen bonded modes on the MOF nodes. Formate ligands were introduced to the node sites during the synthesis or by a post treatment in formic acid/DMF solution. Surprisingly, the bonding modes of formate ligands on Al3(OH)3 node structure of MIL-96 can be reversibly switched between monodentate and bidentate through a process induced by water molecules. Further, methoxy ligands—likely to be the intermediate for catalytic reaction—were also observed on the node sites under methanol dehydration conditions at 250 ℃. The activities of MIL-100 and MIL-96 for methanol dehydration determined by TOF per node are similar, both approximately 3-fold higher than that of MIL-110. The data suggests that catalytic sites incorporate adjacent vacancy and defect node sites, which constitute a minority among observed MOF node sites. We foresee the opportunities in expanding the chemistry and understanding into other MOFs with metal oxide cluster nodes.