H<sub>2</sub>, N<sub>2</sub>, and CH<sub>4</sub> Gas
Adsorption in Zeolitic Imidazolate Framework-95 and -100: Ab Initio
Based Grand Canonical Monte Carlo Simulations
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Abstract
A multiscale approach
based on ab initio and grand canonical Monte
Carlo (GCMC) simulations is used to report the H<sub>2</sub>, N<sub>2</sub>, and CH<sub>4</sub> uptake behaviors of two zeolitic imidazolate
frameworks (ZIFs), ZIF-95 and -100, with exceptionally large and complex
colossal cages. The force fields describing the weak interactions
between the gas molecules and ZIFs in GCMC simulations are based on
ab initio MP2 level of theory aimed at accurately describing the London
dispersions. We report the total and excess gas uptakes up to 100
bar at 77 and 300 K. Our results unravel the interplay between the
uptake amount, pore volume, guest molecule size, temperature, chlorine
functional group, and isosteric heat of adsorption in ZIFs. We found
that while the uptake capacity of ZIF-100 outperforms ZIF-95 for small
molecules (H<sub>2</sub>), ZIF-95 offers a superior adsorption capacity
for large molecules (CH<sub>4</sub>). Moderately sized molecules (N<sub>2</sub>) exhibit a more complex uptake behavior depending on the
temperature. Furthermore, we show that the induced dipole interactions,
such as those caused by −Cl functional groups, play a vital
role on gas adsorption behaviors. This work provides the first report
on the N<sub>2</sub> and CH<sub>4</sub> uptake of ZIF-95 and -100
using ab initio based GCMC simulations