Lv Zirui, Lin Runfeng, Yang Yi, Lan Kun, Hung Chin-Te, Zhang Pengfei, Wang Jinxiu, Zhou Wanhai, Zhao Zaiwang, Wang Zhongyao, Zou Jiawen, Wang Taoyang, Zhao Tiancong, Xu Yifei, Chao Dongliang, Tan Weimin, Yan Bo, Li Qiaowei, Zhao Dongyuan, Li Xiaomin
Laboratory of Advanced Materials, Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, State Key Laboratory of Molecular Engineering of Polymers, Collaborative Innovation Center of Chemistry for Energy Materials (2011-iChEM), College of Chemistry and Materials, Fudan University, Shanghai, P. R. China.
College of Energy Materials and Chemistry, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, P. R. China.
Nat Chem. 2025 Feb;17(2):177-185. doi: 10.1038/s41557-024-01693-9. Epub 2025 Jan 6.
The synthesis of mesoporous metal-organic frameworks (meso-MOFs) is desirable as these materials can be used in various applications. However, owing to the imbalance in structural tension at the micro-scale (MOF crystallization) and the meso-scales (assembly of micelles with MOF subunits), the formation of single-crystal meso-MOFs is challenging. Here we report the preparation of uniform single-crystal meso-MOF nanoparticles with ordered mesopore channels in microporous frameworks with definite arrangements, through a cooperative assembly method co-mediated by strong and weak acids. These nanoparticles feature a truncated octahedron shape with variable size and well-defined two-dimensional hexagonally structured (p6mm) columnar mesopores. Notably, the match between the crystallization kinetics of MOFs and the assembly kinetics of micelles is critical for forming the single-crystal meso-MOFs. On the basis of this strategy, we have constructed a library of meso-MOFs with tunable large pore sizes, controllable mesophases, various morphologies and multivariate components.
介孔金属有机框架材料（介孔MOF）的合成备受关注，因为这些材料可用于各种应用。然而，由于在微观尺度（MOF结晶）和介观尺度（胶束与MOF亚基的组装）上结构张力的不平衡，单晶介孔MOF的形成具有挑战性。在此，我们报告了通过强酸和弱酸共同介导的协同组装方法，制备出具有有序介孔通道的均匀单晶介孔MOF纳米颗粒，其微孔框架具有确定的排列。这些纳米颗粒具有截顶八面体形状，尺寸可变，且具有明确的二维六方结构（p6mm）柱状介孔。值得注意的是，MOF的结晶动力学与胶束的组装动力学之间的匹配对于形成单晶介孔MOF至关重要。基于这一策略，我们构建了一个具有可调大孔径、可控介相、各种形态和多变量组分的介孔MOF库。
