复旦大学李晓民研究团队解锁了单晶金属有机框架的先进架构。相关研究成果于2025年1月22日发表在国际顶尖学术期刊《德国应用化学》。

具有不同几何形状的金属有机框架（MOFs）的合成因其表现出新颖和非凡的性能而引起了人们的极大兴趣。虽然在塑造规则多面体单晶MOFs方面取得了很大进展，但创建更复杂、拓扑结构更复杂的纳米结构仍然是一个很大程度上未被探索的前沿。

该文中，研究人员提出了一种精细的位点特异性各向异性组装和蚀刻共中介方法，用于制造一系列分级MOFs纳米杂化物和单晶MOFs。这种方法这边了具有不同拓扑结构的ZIF-8和mSiO₂纳米杂化物，以及具有复杂形态的衍生单晶MOFs纳米颗粒，如六足、嵌套纳米笼和八足。该方法涉及在ZIF-8纳米立方体的{100}面上选择性生长六个mSiO₂纳米板，形成立方体形状的ZIF-8和mSiO₂纳米杂化物，同时蚀刻初始ZIF-8纳米管的{110}面。

通过微调生长和蚀刻之间的平衡，实现了精确的形态控制，将立方体纳米杂化物转化为复杂的六足纳米杂化物。此外，在这些杂化材料上，同质或异质MOFs的二次外延生长导致了具有六个mSiO2嵌体的ZIF-8、mSiO₂和MOFs复合材料。最后，对mSiO₂腔室的选择性碱性蚀刻，导致单晶MOFs纳米颗粒具有前所未有的复杂形态，如六足、嵌套纳米笼、八足。

附：英文原文

Title: Unlocking Advanced Architectures of Single-Crystal Metal-Organic Frameworks

Author: Minchao Liu, Zirui Lv, Yao Peng, Yufang Kou, Tiancong Zhao, Hongyue Yu, Jia Jia, Lifei Gao, Cheng Shang, Fan Zhang, Dongyuan Zhao, Xiaomin Li

Issue&Volume: 2025-01-22

Abstract: The synthesis of metal-organic frameworks (MOFs) with diverse geometries has captivated considerable interest due to their manifestation of novel and extraordinary properties. While much progress has been made in shaping regular polyhedral single-crystal MOFs, the creation of more complex, topologically intricate nanostructures remains a largely unexplored frontier. Here, we present a refined site-specific anisotropic assembly and etching co-mediation approach to fabricate a series of hierarchical MOF nanohybrids and single-crystal MOFs. This approach yields ZIF-8&mSiO2 nanohybrids with diverse topologies, alongside derived single-crystal MOF nanoparticles exhibiting intricate morphologies such as hexapods, nested nanocages, and octopods. Our method involves the selective growth of six mSiO2 nanoplates on the {100} facets of ZIF-8 nanocubes, forming the cubic-shaped ZIF-8&mSiO2 nanohybrids, with the concurrent etching of the {110} facets of initial ZIF-8 nanocubes. By fine-tuning this balance between the growth and etching, we achieved precise morphological control, transforming cubic nanohybrids into intricate hexapods nanohybrids. Additionally, secondary epitaxial growth of homo- or hetero-MOFs on these hybrids led to ZIF-8&mSiO2&MOF composites with six mSiO2 inlays. Finally, selective alkaline etching of the mSiO2 compartments result in single-crystal MOF nanoparticles with unprecedented and sophisticated morphologies, such as hexapods, nested nanocages, octopods.

DOI: 10.1002/anie.202423939

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202423939