飞秒时间分辨红外光谱探测金属有机骨架中超快的水 H 键重排。
Ultrafast Water H-Bond Rearrangement in a Metal-Organic Framework Probed by Femtosecond Time-Resolved Infrared Spectroscopy.
机构信息
Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, California 92093, United States.
Materials Science and Engineering Program, University of California San Diego, La Jolla, California 92093, United States.
出版信息
J Am Chem Soc. 2023 May 31;145(21):11482-11487. doi: 10.1021/jacs.3c01728. Epub 2023 May 18.
We investigated the water H-bond network and its dynamics in NiClBTDD, a prototypical MOF for atmospheric water harvesting, using linear and ultrafast IR spectroscopy. Utilizing isotopic labeling and infrared spectroscopy, we found that water forms an extensive H-bonding network in NiClBTDD. Further investigation with ultrafast spectroscopy revealed that water can reorient in a confined cone up to ∼50° within 1.3 ps. This large angle reorientation indicates H-bond rearrangement, similar to bulk water. Thus, although the water H-bond network is confined in NiClBTDD, different from other confined systems, H-bond rearrangement is not hindered. The picosecond H-bond rearrangement in NiClBTDD corroborates its reversibility with minimal hysteresis in water sorption.
我们使用线性和超快红外光谱研究了 NiClBTDD（一种用于大气水收集的典型 MOF）中的水氢键网络及其动力学。利用同位素标记和红外光谱，我们发现水在 NiClBTDD 中形成了广泛的氢键网络。进一步的超快光谱研究表明，水可以在 1.3 ps 内以受限的锥形重新取向高达约 50°。这种大角度重新取向表明氢键发生了重排，类似于体相水。因此，尽管 NiClBTDD 中的水氢键网络受到限制，但与其他受限体系不同，氢键重排不受阻碍。NiClBTDD 中皮秒级的氢键重排证实了其在水吸附过程中具有极小滞后的可逆性。
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