Helium expansion revisited: Effects of accessible volume on excess adsorption in kerogen matrices

Liu, Bo; Babaei, Saeed; Kanduč, Matej; Tian, Shansi; Bai, Longhui; Xu, Yaohui; Ostadhassan, Mehdi

doi:10.1016/j.cej.2024.152690

Cited by 3 publications

(1 citation statement)

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“…Specifically, the electrophilic region (blue) is primarily located at the NN bond, while the nucleophilic regions (red) are at the ends of the N 2 molecule. Therefore, the N 2 molecule was modeled using the transferable potentials for phase equilibria force field with an additional point charge site, , which has been successfully applied in other N 2 -related studies. − The complete set of Lennard–Jones parameters and charges for the N 2 molecule and fluoroalkylfluorophosphate anions (i.e., [PF y (C m F n ) x ] − , abbreviated as [PyCm] − ) are given in Table S2. Figure S22 compares the solubility for N 2 force fields at 300 K with and without point charge, where the latter results in smaller values.…”

Section: Computational Models and Methodsmentioning

confidence: 99%

Fluorine Domains Induced Ultrahigh Nitrogen Solubility in Ionic Liquids

Li,

Wang,

Wang

et al. 2024

J. Am. Chem. Soc.

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Fluorinated ionic liquids (ILs) are well-known as electrolytes in the nitrogen (N 2 ) electroreduction reaction due to their exceptional gas solubility. However, the influence of fluorinated functional group on N 2 solvation and solubility enhancement remains unclear. Massive molecular dynamics simulations and free energy perturbation methods are conducted to investigate the N 2 solubility in 11 traditional and 9 fluorinated ILs. It shows that the fluorinated IL of 1-Ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate ([Emim]FAP) exhibits ultrahigh solubility, 4.844 × 10 −3 , approximately 118 times higher than that of traditional IL 1-Ethyl-3-methylimidazolium nitrate ([Emim]NO 3 ). Moreover, fluorinated ILs with more than 10 C−F bonds possess higher N 2 solubility than others and show an exothermic nature during solvation. As the C−F bonds number in ILs decreases, the N 2 solubility decreases significantly and displays the opposite endothermic behavior. To understand the ultrahigh N 2 solubility in fluorinated ILs, we propose a concept of fluorine densification energy (FDE), referring to the average strength of interaction between atoms per unit volume in ILs with fluorine domains, demonstrating a linear relationship with C−F bonds. Physically, lower FDE results in lower N 2 −anion pair dissociation energy and higher free volume, finally enhancing the N 2 solubility. Consequently, medium to long alkyl fluorine tails within a polar environment defines a distinct fluorine domain, emphasizing FDE's role in enhancing N 2 solubility. Overall, these quantitative results will not only deepen the understanding of N 2 solvation in ILs but may also shed light on the rational design of IL-based high-performance N 2 capture and conversion technologies.

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