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

Abstract

AbstractPrecise 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 H2. This FLP catalyst can heterolytically dissociate H2 into active Hδ−, 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.