Metal-Organic Frameworks with Precisely Designed Interior for Carbon Dioxide Capture in the Presence of Water
Metal-Organic Frameworks with Precisely Designed Interior for Carbon Dioxide Capture in the Presence of Water
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DOI：
10.1021/ja503296c
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发表时间：
2014-06-25
影响因子：
15
通讯作者：
Yaghi, Omar M.
中科院分区：
文献类型：
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作者：
Fracaroli, Alejandro M.;Furukawa, Hiroyasu;Yaghi, Omar M.
在有水存在的情况下选择性捕获二氧化碳是一项重大挑战。在此，我们表明IRMOF - 74 - III的内部可以用伯胺（IRMOF - 74 - III - CH₂NH₂）进行共价官能化，并用于在65 - 96%相对湿度下选择性捕获CO₂。这项研究涵盖了各种官能化的IRMOF - 74 - III化合物（IRMOF - 74 - III - CH₃、- NH₂、- CH₂NHBoc、- CH₂NMeBoc、- CH₂NH₂和 - CH₂NHMe）的合成、结构表征、气体吸附以及CO₂捕获性能。交叉极化魔角旋转C - 13核磁共振谱表明，CO₂与IRMOF - 74 - III - CH₂NH₂和 - CH₂NHMe发生化学结合形成氨基甲酸类物质。二氧化碳等温线和穿透实验表明，IRMOF - 74 - III - CH₂NH₂在吸收CO₂方面特别高效（在800托时每克可吸收3.2毫摩尔CO₂），更重要的是，它能从湿氮气流中去除CO₂，穿透时间为610 ± 10秒/克，并且IRMOF结构完全保留。
The selective capture of carbon dioxide in the presence of water is an outstanding challenge. Here, we show that the interior of IRMOF-74-III can be covalently functionalized with primary amine (IRMOF-74-III-CH2NH2) and used for the selective capture of CO2 in 6596 relative humidity. This study encompasses the synthesis, structural characterization, gas adsorption, and CO2 capture properties of variously functionalized IRMOF-74-III compounds (IRMOF-74-III-CH3, -NH2, -CH(2)NHBoc, -CH(2)NMeBoc, -CH2NH2, and -CH2NHMe). Cross-polarization magic angle spinning C-13 NMR spectra showed that CO2 binds chemically to IRMOF-74-III-CH2NH2 and -CH2NHMe to make carbamic species. Carbon dioxide isotherms and breakthrough experiments show that IRMOF-74-III-CH2NH2 is especially efficient at taking up CO2 (3.2 mmol of CO2 per gram at 800 Torr) and, more significantly, removing CO2 from wet nitrogen gas streams with breakthrough time of 610 +/- 10 s g(-1) and full preservation of the IRMOF structure.