Understanding Pore Filling Processes and Adsorption/Desorption Hysteresis in Nanoporous Metal–Organic Frameworks: Insights from Grand Canonical Monte Carlo Simulations and Free Energy Calculations
- Northwestern University, Evanston, IL (United States)
- University of Minnesota, Minneapolis, MN (United States)
Grand canonical Monte Carlo (GCMC) simulations were used to investigate pore filling and hysteresis in nanoporous metal-organic frameworks (MOFs). Adsorption and desorption isotherms were calculated for argon at 87 K in 1866 MOFs from the CoRE MOF database and for short n-alkanes in selected MOFs, keeping the adsorbent structure rigid. Analysis of the molecular configurations showed two different mechanisms and origins of hysteresis: one involving a transition of the adsorbate arrangement in the pores similar to a gas-to-liquid transition associated with a large change in the loading and one more similar to a liquid-to-solid transition associated with a relatively small change in the loading. Our GCMC simulations in MOFs with diverse pore topologies indicate exceptions to an empirical relationship for the minimum diameter of a cylindical pore required for hysteresis as a function of the adsorbate diameter and reduced temperature. The simulations reveal some structures where isotherms exhibit two steps in the adsorption branch and only one step in the desorption branch. Hysteresis loops with a different number of adsorption and desorption steps are not common. Here, to better understand why hysteresis is observed in the GCMC simulations, the concept of the transition probability for observing a step in the adsorption isotherm at a given pressure in a GCMC simulation is introduced. We used two different methods to calculate the transition probabilities and find that these yield comparable results. Furthermore, the transition probability provides a measure for the length of GCMC simulations to yield reliable results.
- Research Organization:
- University of Minnesota, Minneapolis, MN (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); National Energy Research Scientific Computing Center (NERSC)
- Grant/Contract Number:
- SC0023454; AC02-05CH11231
- OSTI ID:
- 3010678
- Alternate ID(s):
- OSTI ID: 2587666
- Journal Information:
- Langmuir, Journal Name: Langmuir Journal Issue: 25 Vol. 41; ISSN 0743-7463; ISSN 1520-5827
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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