期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 135, 期 48, 页码 18183-18190出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja408972f
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资金
- Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0001015]
- Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-AC02-05CH11231]
We explore the local electronic signatures of molecular adsorption at coordinatively unsaturated binding sites in the metal organic framework Mg-MOF-74 using X-ray spectroscopy and first-principles calculations. In situ measurements at the Mg K-edge reveal distinct pre-edge absorption features associated with the unique, open coordination of the Mg sites which are suppressed upon adsorption of CO2 and N,N'-dimethylformamide. Density functional theory shows that these spectral changes arise from modifications of local symmetry around the Mg sites upon gas uptake and are strongly dependent on the metal-adsorbate binding strength. The expanded MOP Mg-2(dobpdc) displays the same behavior upon adsorption of CO2 and N,N'-dimethylethylenediamine. Similar sensitivity to local symmetry is expected for any open metal site, making X-ray spectroscopy an ideal tool for examining adsorption in such MOFs. Qualitative agreement between ambient-temperature experimental and 0 K theoretical spectra is good, with minor discrepancies thought to result from framework vibrational motion.
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