期刊
CHEMISTRY OF MATERIALS
卷 -, 期 -, 页码 -出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemmater.1c04132
关键词
-
资金
- European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme [772204, 2017 ERC-COG, MISOTOP]
- GENCI- IDRIS [2020-A0090807394, DMR-1644779]
- National Science Foundation [FR 3050]
- State of Florida
- IR-RMN-THC
- CNRS
- European Research Council (ERC) [772204] Funding Source: European Research Council (ERC)
This study successfully observed the formation process of different zinc terephthalate compounds by using mechanochemistry and operando Raman spectroscopy. The crystal structures of these compounds were accurately described using solid-state NMR and density functional theory calculations. The O-17 NMR analysis was particularly notable in detecting structural defects and hydrogen bonding networks. Additionally, the possibility of using deuterated precursors for operando Raman spectroscopy studies was introduced.
The description of the formation, structure, and reactivity of coordination networks and metal-organic frameworks (MOFs) remains a real challenge in a number of cases. This is notably true for compounds composed of Zn2+ ions and terephthalate ligands (benzene-1,4-dicarboxylate, BDC) because of the difficulties in isolating them as pure phases and/or because of the presence of structural defects. Here, using mechanochemistry in combination with operando Raman spectroscopy, the observation of the formation of various zinc terephthalate compounds was rendered possible, allowing the distinction and isolation of three intermediates during the ball-milling synthesis of Zn-3(OH)(4)(BDC). An NMR crystallography approach was then used, combining solid-state NMR (H-1, C-13, and O-17) and density functional theory (DFT) calculations to refine the poorly described crystallographic structures of these phases. Particularly noteworthy are the high-resolution O-17 NMR analyses, which were made possible in a highly efficient and cost-effective way, thanks to the selective O-17-enrichment of either hydroxyl or terephthalate groups by ball-milling. This allowed the presence of defect sites to be identified for the first time in one of the phases, and the nature of the H-bonding network of the hydroxyls to be established in another. Lastly, the possibility of using deuterated precursors (e.g., D2O and d(4)-BDC) during ball-milling is also introduced as a means for observing specific transformations during operando Raman spectroscopy studies, which would not have been possible with hydrogenated equivalents. Overall, the synthetic and spectroscopic approaches developed herein are expected to push forward the understanding of the structure and reactivity of other complex coordination networks and MOFs.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据