纳米孔
分子
化学物理
吸附
红外光谱学
金属有机骨架
光谱学
氢键
化学
分子动力学
材料科学
纳米技术
计算化学
物理化学
有机化学
物理
量子力学
作者
Kelly Hunter,Jackson Wagner,Mark Kalaj,Seth M. Cohen,Wei Xiong,Francesco Paesani
标识
DOI:10.1021/acs.jpcc.1c03145
摘要
In nanoporous materials, host–guest interactions affect the properties and function of both adsorbent and adsorbate molecules. Because of their structural and chemical diversity, metal–organic frameworks (MOFs), a common class of nanoporous materials, have been shown to be able to efficiently and, often, selectively adsorb various types of guest molecules. In this study, we characterize the structure and dynamics of water confined in ZIF-90. Through the integration of experimental and computational infrared (IR) spectroscopy, we probe the structure of heavy water (D2O) adsorbed in the pores, disentangling the fundamental framework–water and water–water interactions. The experimental IR spectrum of D2O in ZIF-90 displays a blue-shifted OD-stretch band compared to that of liquid D2O. The analysis of the IR spectra simulated at both classical and quantum levels indicates that the D2O molecules preferentially interact with the carbonyl groups of the framework and highlights the importance of including nuclear quantum effects and taking into account Fermi resonances for a correct interpretation of the OD-stretch band in terms of the underlying hydrogen-bonding motifs. Through a systematic comparison with the experimental spectra, we demonstrate that computational spectroscopy can be used to gain quantitative, molecular-level insights into framework–water interactions that determine the water adsorption capacity of MOFs as well as the spatial arrangements of the water molecules inside the MOF pores which, in turn, are key to the design of MOF-based materials for water harvesting.
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