Macro-Meso-Microporous Metal–Organic Frameworks: Template-Assisted Spray Drying Synthesis and Enhanced Catalysis

Hierarchically porous metal–organic frameworks (HP-MOFs) are promising in many applications. However, most previous studies focus on HP-MOFs with two kinds of pore structures. Herein, a strategy for efficient construction of HP-MOFs possessing macro-meso-micropores using template-assisted spray drying followed by etching process is proposed. Taking ZIF-8 as an example, using polystyrene (PS) templates, the complete HP-ZIF-8 with all the three categories of pores can be easily fabricated. The close arrangement of intrinsic microporous nanosized ZIF-8 (N-ZIF-8) in the spray drying process results in the creation of mesopores, while the macropores are further generated after the removal of PS templates. The structures of macropores and mesopores can be easily adjusted by altering the size and proportion of PS and the size of N-ZIF-8, respectively. Furthermore, this method is extended to the preparation of HP-HKUST-1. As a proof-of-concept, HP-ZIF-8 displays excellent catalytic properties in Knoevenagel reaction owing to its unique pore features. Compared with conventional microsized ZIF-8 (M-ZIF-8) with similar size, HP-ZIF-8 achieves the significantly increased conversion of benzaldehyde from 55% to 100% within 3 h, and shows better recycling performance than N-ZIF-8.