Accurate Prediction of Hydrogen Adsorption in Metal-Organic Frameworks with Unsaturated Metal Sites via a Combined Density-Functional Theory and Molecular Mechanics Approach
Accurate Prediction of Hydrogen Adsorption in Metal-Organic Frameworks with Unsaturated Metal Sites via a Combined Density-Functional Theory and Molecular Mechanics Approach
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通过结合密度泛函理论和分子力学方法准确预测具有不饱和金属位点的金属有机框架中的氢吸附
DOI：
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发表时间：
2010
期刊：
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通讯作者：
M. Fröba
中科院分区：
文献类型：
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作者：
M. Fischer;B. Kuchta;L. Firlej;F. Hoffmann;M. Fröba
在微孔金属有机骨架（MOFs）中引入配位不饱和金属位点已成为开发潜在室温储氢材料的重要合成策略，因为氢与金属中心的相对较强的局部相互作用引起氢吸附的电子等排热增加。以前的建模研究表明，这些相互作用没有充分建模时，使用文献力场参数。巨正则蒙特卡罗（GCMC）模拟的典型结果表现出明显低估的氢吸收在低压和低温。在这项研究中，它表明，这一缺点可以得到解决，通过推导出一组新的潜在的参数来表示从从头计算的分子模型系统的金属-二氢相互作用。该方法计算效率高，适用于金属中心的任何配位环境。T...
The incorporation of coordinatively unsaturated metal sites in microporous metal−organic frameworks (MOFs) has emerged as an important synthetic strategy for the development of potential room-temperature hydrogen storage materials, because the relatively strong, localized interaction of hydrogen with the metal centers induces an increase of the isosteric heat of hydrogen adsorption. Previous modeling studies have shown that these interactions are not adequately modeled when literature force-field parameters are used. Typical results of grand-canonical Monte Carlo (GCMC) simulations exhibit a pronounced underestimation of the hydrogen uptake at low pressures and low temperatures. In this study, it is shown that this shortcoming can be resolved by deriving a new set of potential parameters to represent the metal−dihydrogen interaction from ab initio calculations for molecular model systems. The approach is computationally efficient and could be applied for any coordination environment of the metal center. T...