Achieving Morphological Control over Lamellar Manganese Metal-Organic Framework through Modulated Bi-Phase Growth.,Angewandte Chemie International Edition

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Achieving Morphological Control over Lamellar Manganese Metal-Organic Framework through Modulated Bi-Phase Growth.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-03-11 , DOI: 10.1002/anie.202002705
Yuxia Shen ₁ , Bohan Shan ₁ , Bin Mu ₁ , Sefaattin Tongay ₁

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A modulated bi‐phase synthesis towards large‐scale manganese 1,4‐benzenedicarboxylate (MnBDC) MOFs with a precise control over their morphology (bulk vs. layered) is presented. Metal precursors and organic ligands are separated to reduce the kinetic reaction rates for better control over the crystallization process. Based on scanning electron microscopy (SEM), X‐ray diffraction (XRD), energy‐dispersive X‐ray spectroscopy (EDS), and Raman spectroscopy studies, the continuous ligand supply along with the presence of pyridine capping agent are highly effective in promoting the layer‐by‐layer growth and achieving large crystal sizes. Once layered MnBDC is stabilized, topotactic intercalation chemistry was used to demonstrate the feasibility of bromine intercalation on these layered materials. Bromine intercalation is possible between the MOFs layers for the first time. Bromine intercalation causes colossal reduction in layered MnBDC band gap while it has no observable effect on bulk MOFs.

中文翻译：

通过调节双相生长实现对层状锰金属有机骨架的形态控制。

提出了一种针对大规模1,4-苯二甲酸锰（MnBDC）MOF的调制双相合成方法，可精确控制其形态（本体与分层）。分离金属前体和有机配体以降低动力学反应速率，以更好地控制结晶过程。基于扫描电子显微镜（SEM），X射线衍射（XRD），能量色散X射线光谱（EDS）和拉曼光谱研究，连续配体供应以及吡啶封端剂的存在对促进逐层生长并实现大晶体尺寸。一旦层状MnBDC稳定，就可以使用全位插层化学方法来证明在这些层状材料上进行溴插层的可行性。首次可能在MOF层之间插入溴。溴嵌入会导致层状MnBDC带隙的整体减小，而对整体MOF则没有明显影响。

更新日期：2020-03-11

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