Pal Arun, Chand Santanu, Madden David G, Franz Douglas, Ritter Logan, Johnson Alexis, Space Brian, Curtin Teresa, Das Madhab C
Department of Chemistry , Indian Institute of Technology Kharagpur , Kharagpur - 721302 , WB , India.
Bernal Institute , University of Limerick , V94 T9PX , Limerick , Ireland.
Inorg Chem. 2019 Sep 3;58(17):11553-11560. doi: 10.1021/acs.inorgchem.9b01402. Epub 2019 Aug 9.
In the context of porous crystalline materials toward CO separation and capture, a new 2-fold interpenetrated 3D microporous Co-MOF, IITKGP-11 (IITKGP denotes Indian Institute of Technology Kharagpur), has been synthesized consisting of a 1D channel of ∼3.6 × 5.0 Å along the [101] direction with a cavity volume of 35.20%. This microporous framework with a BET surface area of 253 mg shows higher uptake of CO (under 1 bar, 3.35 and 2.70 mmol g at 273 and 295 K, respectively), with high separation selectivities for CO/N and CO/CH gas mixtures under ambient conditions as estimated through IAST calculation. Moreover, real time dynamic breakthrough studies reveal the high adsorption selectivity toward CO for these binary mixed gases at 295 K and 1 bar. Besides high gas separation selectivity, capacity considerations in mixed gas phases are also important to check the performance of a given adsorbent. CO loading amounts in mixed gas phases are quite high as predicted through IAST calculation and experimentally determined from dynamic breakthrough studies. In order to get insight into the phenomena, GCMC simulation was performed demonstrating that the CO molecules are electrostatically trapped via interactions between oxygen on CO and hydrogen on pyridyl moieties of the spacers.
在多孔晶体材料用于CO分离和捕获的背景下，一种新型的具有2重穿插结构的三维微孔钴基金属有机框架材料IITKGP-11（IITKGP代表印度理工学院卡拉格布尔分校）已被合成，它沿着[101]方向具有一个约3.6×5.0 Å的一维通道，空腔体积为35.20%。这种比表面积为253 m²/g的微孔骨架材料对CO具有更高的吸附量（在1 bar下，273 K和295 K时分别为3.35和2.70 mmol/g），通过理想吸附溶液理论（IAST）计算估计，在环境条件下对CO/N₂和CO/CH₄气体混合物具有高分离选择性。此外，实时动态突破研究表明，在295 K和1 bar下，该材料对这些二元混合气体中的CO具有高吸附选择性。除了高气体分离选择性外，混合气相中的容量考量对于检验给定吸附剂的性能也很重要。通过IAST计算预测并从动态突破研究中实验测定，混合气相中的CO负载量相当高。为了深入了解这些现象，进行了巨正则蒙特卡罗（GCMC）模拟，结果表明CO分子通过CO上的氧与间隔基吡啶部分上的氢之间的相互作用被静电捕获。
