This study reports the development of a quantitative microscale dynamic column breakthrough instrument to measure the competitive equilibrium loadings of CO₂ and H₂O isotherms on small quantities (≈150 mg) of metal–organic framework (MOF) samples. The binary CO₂ and H₂O equilibria were measured on CALF-20, Al-Fumarate and CAU-10-H, three MOFs of interest for postcombustion CO₂ capture at 30 °C and specifically since they show an S-shaped water isotherm. For Al-Fumarate and CAU-10-H, pure CO₂ and H₂O competition was measured at 30 °C. For CALF-20, extensive mapping of the impact of CO₂ concentration and various water concentrations was performed at 30 °C. In all three MOFs, the CO₂ capacity is generally retained toward the left of the inflection point of the H₂O isotherm. However CO₂ capacity drops toward the right of the inflection point, and the magnitude of the drop depends on the sharpness of the H₂O isotherm. On the one hand, for Al-Fumarate and CAU-10-H the H₂O isotherm was unaffected by CO₂. On the other hand, for CALF-20, the presence of CO₂ impacts the H₂O water isotherm, extending the relative humidity range over which the CO₂ capacity is retained. Using the ideal adsorbed solution theory to predict the binary equilibria revealed deviations from ideality for all three MOFs.

中文翻译：

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使用微量动态色谱柱突破对 CO2 捕获金属-有机框架 CALF-20、Al-Fumarate 和 CAU-10-H 进行二元 CO2/H2O 吸附


本研究报告了一种定量微量动态色谱柱穿透仪器的开发，用于测量 CO₂ 和 H₂O 等温线在少量 （≈150 mg） 金属有机框架 （MOF） 样品上的竞争性平衡负载。在 CALF-20、Al-Fumarate 和 CAU-10-H 上测量二元 CO₂ 和 H₂O 平衡，这三种 MOF 在 30 °C 下捕获燃烧后 CO₂ 感兴趣，特别是因为它们显示出 S 形水等温线。对于富马酸铝和 CAU-10-H，在 30 °C 下测量纯 CO₂ 和 H₂O 竞争。 对于 CALF-20，在 30 °C 下对 CO₂ 浓度和各种水浓度的影响进行了广泛的绘图分析。 在所有三种 MOF 中，CO₂ 容量通常保持在 H₂O 等温线拐点的左侧。然而，CO₂ 容量向拐点右侧下降，下降的大小取决于 H₂O 等温线的锐度。一方面，对于富马酸铝和 CAU-10-H，H₂O 等温线不受 CO₂ 的影响。另一方面，对于 CALF-20，CO₂ 的存在会影响 H₂O 水等温线，从而扩大了保持 CO₂ 容量的相对湿度范围。使用理想吸附解理论预测二元平衡揭示了所有三种 MOF 与理想的偏差。