Porous Frustrated Lewis Pairs Catalyst Constructed on Defective Zirconium-Based Metal–Organic Frameworks for Hydrogenation Reactions with H2

A porous metal–organic framework (MOF)-based frustrated Lewis pairs (FLPs) were prepared via a ligand replacement strategy to generate organic linker defects in zirconium-based MOF (MOF-808), thereby exposing Zr sites as Lewis acid. Due to the rigid features of the MOF skeleton, the unsaturated metal cluster and the adjacent lattice oxygen (Lewis bases) are in sterically hindered positions, which formed FLP sites with efficient H2 activation ability. This porous heterogeneous FLP catalyst [MOF-808-OH (15%)] exhibits high performance styrene hydrogenation to ethylbenzene with 99% yield. The high structural stability and reusability enabled the catalyst to maintain an over 98% activity after five cycles. This work provides a defect modulation strategy to prepare MOF-based solid FLP catalysts.