Nanoengineering Multilength-Scale Porous Hierarchy in Mesoporous Metal–Organic Framework Single Crystals
Yingji Zhao, Liyang Zhu, Yunqing Kang, Cheng‐Hui Shen, Xiangyang Liu, Dong Jiang, Lei Fu, Olga Guselnikova, Lijin Huang, Xiaokai Song, Toru Asahi, Yusuke Yamauchi
Abstract
Developing a reliable method for constructing mesoporous metal–organic frameworks (MOFs) with single-crystalline forms remains a challenging task despite numerous efforts. This study presents a solvent-mediated assembly method for fabricating zeolitic imidazolate framework (ZIF) single-crystal nanoparticles with a well-defined micro–mesoporous structure using polystyrene- block -poly(ethylene oxide) diblock copolymer micelles as a soft-template. The precise control of particle sizes, ranging from 85 to 1200 nm, is achieved by regulating nucleation and crystal growth rates while maintaining consistent pore diameters in mesoporous nanoparticles and a rhombohedral dodecahedron morphology. Furthermore, this study presents a robust platform for nanoarchitecturing to prepare hierarchically porous materials (e.g., core–shell and hollow structures), including microporous ZIF@mesoporous ZIF, hollow mesoporous ZIF, and mesoporous ZIF@mesoporous ZIF. Such a multimodal pore design, ranging from microporous to microporous/mesoporous and further micro-/meso-/macroporous, provides significant evidence for the future possibility of the structural design of MOFs.