Department of Chemistry , Yonsei University , 50 Yonsei-ro , Seodaemun-gu, Seoul 03722 , Republic of Korea.
J Am Chem Soc. 2020 Feb 12;142(6):3042-3049. doi: 10.1021/jacs.9b12193. Epub 2020 Feb 3.
Well-organized construction of hybrid metal-organic frameworks (MOFs) with complicated structures or components is a great importance because of their potential usefulness. In this regard, the conjugation of more than two MOFs, which have dissimilar components and/or structures, is a smart strategy for the production of hybrid MOFs. MOF-on-MOF growth is fundamental for the conjugation of two MOFs and should be deeply understood for the finely controlled conjugation and for the formation of well-organized hybrid MOFs. Herein, we report an interesting MOF growth process for the construction of hybrid MOF particles containing heterogeneous components and cell lattices. Interestingly, even though a newly grown MOF and an MOF template have mismatched cell lattices, the anisotropic growth results in unexpectedly well-defined core-shell-type hybrid MOFs. Comprehensive monitoring of the growth process revealed a tip-to-middle MOF-on-MOF growth, which elucidates the uncommon formation of a well-defined core-shell hybrid despite the anisotropic growth. A tip-to-middle anisotropic growth process is accompanied by self-adjustment of MOF cell lattices to anchor on the template surface having mismatched cell lattices in the early reaction stage and self-reversion of cell lattices to the original comfortable configuration in the middle stage of the reaction.
有序构建具有复杂结构或组成的杂化金属有机骨架(MOFs)非常重要,因为它们具有潜在的用途。在这方面,将具有不同组成和/或结构的两种以上 MOF 连接起来是制备杂化 MOF 的一种明智策略。MOF 之间的生长是连接两种 MOF 的基础,应该深入了解这种生长,以便对连接进行精细控制,并形成组织良好的杂化 MOF。在此,我们报告了一种有趣的 MOF 生长过程,用于构建含有异质成分和细胞晶格的杂化 MOF 颗粒。有趣的是,即使新生长的 MOF 和 MOF 模板具有不匹配的晶格,各向异性生长也会导致出乎意料的具有明确核壳结构的杂化 MOF。对生长过程的全面监测揭示了一种尖端到中间的 MOF 之间的生长,这阐明了尽管存在各向异性生长,但仍能形成明确的核壳杂化。尖端到中间的各向异性生长过程伴随着 MOF 晶格的自我调整,以在早期反应阶段锚定在具有不匹配晶格的模板表面上,并在反应的中间阶段将晶格自我反转回原始的舒适构型。