Influences of Deprotonation and Modulation on Nucleation and Growth of UiO-66: Intergrowth and Orientation
Influences of Deprotonation and Modulation on Nucleation and Growth of UiO-66: Intergrowth and Orientation
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DOI：
10.1021/acs.jpcc.7b11012
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发表时间：
2018-01
影响因子：
3.7
通讯作者：
Bohan Shan;J. James;Mitchell Armstrong;E. C. Close;P. A. Letham;Kassandra Nikkhah;Jerry Y. S. Lin
中科院分区：
文献类型：
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作者：
Bohan Shan;J. James;Mitchell Armstrong;E. C. Close;P. A. Letham;Kassandra Nikkhah;Jerry Y. S. Lin
合成锆基金属有机骨架材料 (ZrMOF) 时最常见的产品是细粉末。典型的ZrMOF UiO-66的粒径首次被报道为200 nm左右，因此由于单晶XRD无法解析这种结晶度较差的小晶体，因此只能通过粉末XRD结合Rietveld精修来解析原始晶体结构。有人可能会问，为什么UiO-66的粒径与其他常见MOF相比如此之小，以及终止UiO-66生长的关键因素是什么。在这项工作中，我们试图通过提出一个假设来回答这个问题：反应溶液中积累的质子引起的配体部分去质子化是阻止UiO-66晶体连续生长的关键因素。该假设通过在原位双相溶剂热反应中添加去质子剂的生长再激活得到验证。只要质子与去质子充分协调......
The most common products obtained in the synthesis of zirconium-based metal–organic frameworks (ZrMOFs) are fine powders. The particle size of a typical ZrMOF UiO-66 was first reported to be around 200 nm, so the original crystal structure was only solved by powder XRD coupled with Rietveld refinement due to the incapability of single crystal XRD to solve such small crystals with poor crystallinity. One may ask the reason why the particle size of UiO-66 is so small compared to that of other common MOFs and what the key factor terminating the growth of UiO-66 is. In this work, we try to answer this question by proposing a hypothesis that the partially deprotonated ligand caused by the accumulated protons in the reaction solution is the key factor preventing the continuous growth of the UiO-66 crystal. The hypothesis is verified by growth reactivation with the addition of a deprotonating agent in an in situ biphase solvothermal reaction. As long as the protons were sufficiently coordinated by the deprotonat...