Synthesis of 3D-Ordered Macro/Microporous Yolk–Shelled Nanoreactor with Spatially Separated Functionalities for Cascade Reaction

Constructing three-dimensional (3D) hierarchical materials with spatial compartmentalization of multiple catalytic functionalities effectively facilitates the chemical processes’ intensification, especially for bulky-molecule-involved cascade reaction. Herein, a facile and novel core–shell colloidal crystal templating strategy was developed to synthesize highly ordered arrays of integrated yolk–shelled nanoreactor consisting of monolithically interconnected ZIF-8 shell and sulfonated polystyrene yolks decorated with rhodium nanoparticles. The obtained nanoreactor achieves efficient catalytic one-pot cascade Knoevenagel condensation-hydrogenation reactions for larger molecules, by taking advantage of the superior mass diffusion properties of the hierarchical macro/microporous metal–organic framework (MOF) skeleton, robust monolith nature, and spatially separated functionalities. This work offers an important strategy for preparing MOF-based composites with a hierarchical framework, accelerating various applications of MOFs, such as electrochemical applications, photothermal conversion, and heterogeneous catalysis.