期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 24, 页码 9408-9413出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202002705
关键词
bromine intercalation; lamellar morphology; ligand diffusion; metal-organic frameworks; modulated bi-phases
资金
- NSF [DMR 1552220, DMR 1933214, CMMI-1825594, DMR-1955889]
- Army Research Office [W911NF1810381]
- [NNCI-ECCS-1542160]
- U.S. Department of Defense (DOD) [W911NF1810381] Funding Source: U.S. Department of Defense (DOD)
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.
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