Computational investigation of hysteresis and phase equilibria of n-alkanes in a metal-organic framework with both micropores and mesopores

Li, Zhao; Turner, Jake; Snurr, Randall Q.

doi:10.1038/s42004-023-00889-3

Title: Computational investigation of hysteresis and phase equilibria of n-alkanes in a metal-organic framework with both micropores and mesopores

Journal Article · 08 May 2023 · Communications Chemistry

DOI: https://doi.org/10.1038/s42004-023-00889-3 · OSTI ID:1972876

^[1]; Turner, Jake ^[1];

^[1]

Northwestern University, Evanston, IL (United States)

Adsorption hysteresis is a phenomenon related to phase transitions that can impact applications such as gas storage and separations in porous materials. Computational approaches can greatly facilitate the understanding of phase transitions and phase equilibria in porous materials. In this work, adsorption isotherms for methane, ethane, propane, and n-hexane were calculated from atomistic grand canonical Monte Carlo (GCMC) simulations in a metal-organic framework having both micropores and mesopores to better understand hysteresis and phase equilibria between connected pores of different size and the external bulk fluid. At low temperatures, the calculated isotherms exhibit sharp steps accompanied by hysteresis. As a complementary simulation method, canonical (NVT) ensemble simulations with Widom test particle insertions are demonstrated to provide additional information about these systems. The NVT+Widom simulations provide the full van der Waals loop associated with the sharp steps and hysteresis, including the locations of the spinodal points and points within the metastable and unstable regions that are inaccessible to GCMC simulations. The simulations provide molecular-level insight into pore filling and equilibria between high- and low-density states within individual pores. The effect of framework flexibility on adsorption hysteresis is also investigated for methane in IRMOF-1.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE

Grant/Contract Number:: SC0023454; AC02-05CH11231

OSTI ID:: 1972876

Alternate ID(s):: OSTI ID: 1993514

Journal Information:: Communications Chemistry, Vol. 6, Issue 1; ISSN 2399-3669

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
Nanoporous materials
Adsorption
Computational methods
Metal–organic frameworks
Organic–inorganic nanostructures
Porous materials

Title: Computational investigation of hysteresis and phase equilibria of n-alkanes in a metal-organic framework with both micropores and mesopores

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