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溶液加工型导电 MOF 纳米晶体的尺寸依赖性性质。

Size-Dependent Properties of Solution-Processable Conductive MOF Nanocrystals.

机构信息

Department of Chemistry and Biochemistry, Material Science Institute, University of Oregon, Eugene, Oregon 97403, United States.

Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409, United States.

出版信息

J Am Chem Soc. 2022 Apr 6;144(13):5784-5794. doi: 10.1021/jacs.1c10800. Epub 2022 Mar 28.

Abstract

The diverse optical, magnetic, and electronic behaviors of most colloidal semiconductor nanocrystals emerge from materials with limited structural and elemental compositions. Conductive metal-organic frameworks (MOFs) possess rich compositions with complex architectures but remain unexplored as nanocrystals, hindering their incorporation into scalable devices. Here, we report the controllable synthesis of conductive MOF nanoparticles based on Fe(1,2,3-triazolate). Sizes can be tuned to as small as 5.5 nm, ensuring indefinite colloidal stability. These solution-processable MOFs can be analyzed by solution-state spectroscopy and electrochemistry and cast into conductive thin films with excellent uniformity. This unprecedented analysis of MOF materials reveals a strong size dependence in optical and electronic behaviors sensitive to the intrinsic porosity and guest-host interactions of MOFs. These results provide a radical departure from typical MOF characterization, enabling insights into physical properties otherwise impossible with bulk analogues while offering a roadmap for the future of MOF nanoparticle synthesis and device fabrication.

摘要

大多数胶体半导体纳米晶体的多样光学、磁性和电子行为源自结构和元素组成有限的材料。具有复杂结构的导电金属-有机骨架(MOF)具有丰富的组成,但作为纳米晶体仍未被探索,这阻碍了它们在可扩展器件中的应用。在这里,我们报告了基于 Fe(1,2,3-三氮唑)的可控合成导电 MOF 纳米粒子。尺寸可以调小至 5.5nm,确保了无限期的胶体稳定性。这些溶液可加工的 MOF 可以通过溶液状态光谱法和电化学进行分析,并铸造成具有优异均匀性的导电薄膜。这种对 MOF 材料的前所未有的分析揭示了光学和电子行为的强烈尺寸依赖性,对 MOF 的固有孔隙率和主客体相互作用敏感。这些结果与典型的 MOF 特性有根本的不同,使人们能够深入了解物理特性,而这些特性是使用块状类似物不可能实现的,同时为 MOF 纳米粒子合成和器件制造的未来提供了一条途径。

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