Coordination Defect-Induced Frustrated Lewis Pairs in Polyoxo-metalate-Based Metal-Organic Frameworks for Efficient Catalytic Hydrogenation.

Precise control of the structure and spatial distance of Lewis acid (LA) and Lewis base (LB) sites in a porous system to construct efficient solid frustrated Lewis pair (FLP) catalyst is vital for industrial application but remains challenging. Herein, we constructed FLP sites in a polyoxometalate (POM)-based metal-organic framework (MOF) by introducing coordination-defect metal nodes (LA) and surface-basic POM with abundant oxygen (LB). The well-defined and unique spatial conformation of the defective POM-based MOF ensure that the distance between LA and LB is at ~4.3 Å, a suitable distance to activate H . This FLP catalyst can heterolytically dissociate H into active H , thus exhibiting high activity in hydrogenation, which is 55 and 2.7 times as high as that of defect-free POM-based MOF and defective MOF without POM, respectively. This work provides a new avenue toward precise design multi-site catalyst to achieve specific activation of target substrate for synergistic catalysis.