Molecular Promoting of Aluminum Metal-Organic Framework Topology MIL-101 by N,N-Dimethylformamide
Molecular Promoting of Aluminum Metal-Organic Framework Topology MIL-101 by N,N-Dimethylformamide
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DOI：
10.1021/ic402198a
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发表时间：
2014-01-20
影响因子：
4.6
通讯作者：
Gascon, Jorge
中科院分区：
文献类型：
--
作者：
Goesten, Maarten G.;Magusin, Pieter C. M. M.;Gascon, Jorge
原位NMR和DFT模拟表明，N，N-二甲基甲酰胺（DMF）促进了金属有机骨架NH 2-MIL-101（Al）的形成。原位NMR研究表明，在NH 2-MOF-235（Al）中铝配位的水配体解离后，DMF在合成期间形成H-Cl-DMF络合物。该反应诱导从M0 F-235拓扑结构到MIL-101拓扑结构的转化。电子结构密度泛函理论（DFT）计算表明，使用DMF代替水作为合成溶剂减小了动力学上有利的MIL-101和化学上有利的MIL-53产物之间的能隙。因此，DMF促进MIL-101拓扑结构的动力学和化学。
In situ NMR and DFT modeling demonstrate that N,N-dimethylformamide (DMF) promotes the formation of metal-organic framework NH2-MIL-101(Al). In situ NMR studies show that upon dissociation of an aluminum-coordinated aqua ligand in NH2-MOF-235(Al), DMF forms a H-Cl-DMF complex during synthesis. This reaction induces a transformation from the MOF-235 topology into the MIL-101 topology. Electronic structure density functional theory (DFT) calculations show that the use of DMF instead of water as the synthesis solvent decreases the energy gap between the kinetically favored MIL-101 and thermodynamically favored MIL-53 products. DMF therefore promotes MIL-101 topology both kinetically and thermodynamically.