Vervoorts Pia, Schneemann Andreas, Hante Inke, Pirillo Jenny, Hijikata Yuh, Toyao Takashi, Kon Kenichi, Shimizu Ken-Ichi, Nakamura Takayoshi, Noro Shin-Ichiro, Fischer Roland A
Inorganic and Metal-Organic Chemistry , Technical University of Munich , Lichtenbergstrasse 4 , 85748 Garching , Germany.
Inorganic Chemistry II , Ruhr-University Bochum , Universitätsstrasse 150 , 44801 Bochum , Germany.
ACS Appl Mater Interfaces. 2020 Feb 26;12(8):9448-9456. doi: 10.1021/acsami.9b21261. Epub 2020 Feb 12.
Metal-organic frameworks with open metal sites are promising materials for gas separations. Particularly, the M(dobdc) (dobdc = 2,5-dioxidobenzenedicarboxylate, M = Co, Mn, Fe, ...) framework has been the of this research field and has delivered groundbreaking results in terms of sorption selectivity. However, many studies focus on perfect two-component mixtures and use theoretical models, e.g., the ideal adsorbed solution theory, to calculate selectivities. Within this work, we shed light on the comparability of these selectivities with values obtained from propane/propene multicomponent measurements on the prototypical Co(dobdc) framework, and we study the impact of impurities like water on the selectivity. Despite the expected capacity loss, the presence of water does not necessarily lead to a decreased selectivity. Density functional theory calculations of the binding energies prove that the water molecules adsorbed to the metal centers introduce new binding sites for the adsorbates.
具有开放金属位点的金属有机框架是用于气体分离的有前景的材料。特别是，M(dobdc)（dobdc = 2,5 - 二氧代苯二甲酸酯，M = Co、Mn、Fe等）框架一直是该研究领域的焦点，并在吸附选择性方面取得了开创性的成果。然而，许多研究集中在理想的二元混合物上，并使用理论模型，例如理想吸附溶液理论，来计算选择性。在这项工作中，我们揭示了这些选择性与在典型的Co(dobdc)框架上进行丙烷/丙烯多组分测量所获得的值之间的可比性，并且我们研究了诸如水等杂质对选择性的影响。尽管预期会有容量损失，但水的存在并不一定会导致选择性降低。结合能的密度泛函理论计算证明，吸附到金属中心的水分子为吸附质引入了新的结合位点。
