Immobilization of Metal–Organic Framework Nanocrystals for Advanced Design of Supported Nanocatalysts

In recent years, metal-organic frameworks (MOFs) have been employed as heterogeneous catalysts or precursors for synthesis of catalytic materials. However, conventional MOFs and their derivatives usually exhibit limited mass transfer and modest catalytic activities owing to a lengthy diffusion path and less exposed active sites. In contrast, it has been generally conceived that nanoscale MOFs are beneficial to materials utilization and mass transport, but their instability poses a serious issue to practical application. To tackle above challenges, herein we develop a novel and facile approach to the design and synthesis of nanocomposites through in situ growth and directed immobilization of nanoscale MOFs onto layered double hydroxides (LDH). The resulting supported nano-MOFs inherit advantages of pristine MOF nanocrystals and meanwhile gain enhanced stability and workability under reactive environments. A series of uniform nanometer-sized MOFs, including monometallic (ZIF-8, ZIF-67, and Cu-BTC) and bimetallic (CoZn-ZIF), can be readily synthesized onto hierarchically structured flowerlike MgAl-LDH supports with high dispersion and precision. Additionally, the resultant MgAl-LDH/MOFs can serve as a generic platform to prepare integrated nanocatalysts via controlled thermolysis. Knoevenagel condensation and reduction of 4-nitrophenol (4-NP) are used as model reactions for demonstrating the technological merits of these nanocatalysts. Therefore, this work elucidates that the synthetic immobilization of nanoscale MOFs onto conventional catalyst supports is a viable route to develop integrated nanocatalysts with high controllability over structural architecture and chemical composition.