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Templated interfacial synthesis of metal-organic framework (MOF) nano- and micro-structures with precisely controlled shapes and sizes
Communications Chemistry ( IF 5.9 ) Pub Date : 2021-06-03 , DOI: 10.1038/s42004-021-00522-1
Lingyao Meng 1 , Binyu Yu 2 , Yang Qin 1, 2
Affiliation  

Metal-organic frameworks (MOF) are an emerging class of microporous materials with promising applications. MOF nanocrystals, and their assembled super-structures, can display unique properties and reactivities when compared with their bulk analogues. MOF nanostructures of 0-D, 2-D, and 3-D dimensions can be routinely obtained by controlling reaction conditions and ligand additives, while formation of 1-D MOF nanocrystals (nanowires and nanorods) and super-structures has been relatively rare. We report here a facile templated interfacial synthesis methodology for the preparation of a series of 1-D MOF nano- and micro-structures with precisely controlled shapes and sizes. Specifically, by applying track-etched polycarbonate (PCTE) membranes as the templates and at the oil/water interface, we rapidly and reproducibly synthesize zeolitic imidazolate framework-8 (ZIF-8) and ZIF-67 nano- and micro structures of sizes ranging from 10 nm to 20 μm. We also identify a size confinement effect on MOF crystal growth, which leads to single crystals under the most restricted conditions and inter-grown polycrystals at larger template pore sizes, as well as surface directing effects that influence the crystallographic preferred orientation. Our findings provide a potentially generalizable method for controlling the size, morphology, and crystal orientations of MOF nanomaterials, as well as offering fundamental understanding into MOF crystal growth mechanisms.



中文翻译:

具有精确控制形状和尺寸的金属有机骨架 (MOF) 纳米和微米结构的模板化界面合成

金属有机框架 (MOF) 是一类新兴的微孔材料,具有广阔的应用前景。与块状类似物相比,MOF 纳米晶体及其组装的超结构可以显示出独特的特性和反应性。0-D、2-D 和 3-D 尺寸的 MOF 纳米结构通常可以通过控制反应条件和配体添加剂获得,而 1-D MOF 纳米晶体(纳米线和纳米棒)和超结构的形成相对较少。我们在这里报告了一种简便的模板化界面合成方法,用于制备一系列具有精确控制的形状和尺寸的一维 MOF 纳米和微观结构。具体来说,通过在油/水界面应用径迹蚀刻聚碳酸酯 (PCTE) 膜作为模板,我们快速且可重复地合成沸石咪唑酯框架 8 (ZIF-8) 和 ZIF-67 纳米和微米结构,尺寸范围为 10 nm 至 20 μm。我们还确定了对 MOF 晶体生长的尺寸限制效应,这会导致在最受限制的条件下形成单晶,并在较大的模板孔径下形成相互生长的多晶,以及影响晶体择优取向的表面定向效应。我们的研究结果为控制 MOF 纳米材料的尺寸、形态和晶体取向提供了一种潜在的通用方法,并提供了对 MOF 晶体生长机制的基本理解。这导致在最受限制的条件下形成单晶,在较大的模板孔径下形成相互生长的多晶,以及影响晶体择优取向的表面定向效应。我们的研究结果为控制 MOF 纳米材料的尺寸、形态和晶体取向提供了一种潜在的通用方法,并提供了对 MOF 晶体生长机制的基本理解。这导致在最受限制的条件下形成单晶,在较大的模板孔径下形成相互生长的多晶,以及影响晶体择优取向的表面定向效应。我们的研究结果为控制 MOF 纳米材料的尺寸、形态和晶体取向提供了一种潜在的通用方法,并提供了对 MOF 晶体生长机制的基本理解。

更新日期:2021-06-03
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