Isoreticular Curves: A Theory of Capillary Condensation To Model Water Sorption within Microporous Sorbents

化学 微型多孔材料 吸附 毛细管冷凝 冷凝 毛细管作用 化学工程 色谱法 热力学 多孔性 有机化学 吸附 物理 工程类
作者
Julius J. Oppenheim,Mircea Dincă
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:146 (30): 20615-20626 被引量:13
标识
DOI:10.1021/jacs.4c02743
摘要

Metal-organic frameworks have gained traction as leading materials for water sorption applications due to precise chemical tunability of their well-ordered pores. These applications include atmospheric water capture, heat pumps, desiccation, desalination, humidity control, and thermal batteries. However, the relationships between the framework pore structure and the measurable water sorption properties, namely critical relative humidity for condensation, maximal capacity, and pore size or temperature for the onset of hysteresis, have not been clearly delineated. Herein, we precisely formulate these relationships by application of the theory of capillary condensation and macroscopic thermodynamic models to a large data set of MOF water isotherms. These relationships include a concept termed isoreticular curves that relates the critical pressure for pore condensation (α), gravimetric capacity (Qmax), and hydrophilicity (the Gibbs free energy for binding water, ΔG) as Qmax = a1(ΔG/ln α)2 + a2(ΔG/ln α), with constants a1 and a2 dependent upon the density and volume occupied by the linker and secondary building unit, and framework topology. Through this analysis, we propose guidelines for the maximization of sorption capacity at a given relative humidity with minimal hysteresis and discuss the theoretical limits for capacity at low relative humidity. This model provides an explanation for the lack of high-capacity frameworks at low relative humidity, as increasing pore size also causes an increase in relative humidity. We propose a loose upper bound of Qmax = -0.25(1/ln α)2 - 1.75(1/ln α) for the limit of maximal capacity at a given relative humidity in the dry regime. These guidelines are consequential for the design of new materials for water sorption applications.
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