Interfacial Confinement Enables Dual Hosting of Sulfur Mustard and Mustard Sulfoxide in NU-1000.
- 1School of Sustainable Chemical, Biological and Materials Engineering, University of Oklahoma, Norman, Oklahoma73019, United States.
- 2Materials Science and Engineering Program, University of Oklahoma, Norman, Oklahoma73019, United States.
Abstract
Zirconium-based metal-organic frameworks have emerged as promising materials for the capture and detoxification of chemical warfare agents, but the molecular mechanism by which a hierarchical MOF differentiates a hydrophobic reactant from its oxidized product remains incompletely understood. Here, we use molecular dynamics simulations, grand-canonical Monte Carlo adsorption calculations, and periodic density functional theory to examine the dual-hosting behavior of NU-1000 toward sulfur mustard (HD) and mustard sulfoxide (HDO). Rather than treating NU-1000 only as an adsorbent or oxidation catalyst, we resolve how its internal micropore, mesopore, and c-pore interfaces impose distinct confinement environments on reactant and product species. Density functional theory (DFT) calculations show that HD binds most favorably in the c-pore region, with a binding energy of approximately -12.5 kcal/mol, and similarly favorable stabilization in confined micropore environments, whereas substantially weaker binding is observed in the mesopore. Molecular dynamics simulations also reveal sharply different pore residence patterns: HD localizes predominantly in micropores, occupying this region for ∼80% of the trajectory, while HDO samples larger pore environments more broadly, with ∼45% mesopore and ∼34% c-pore occupancy. This pore-selective behavior persists under mixed HD/HDO coadsorption conditions, demonstrating that reactant-product differentiation is intrinsic to the NU-1000 pore network rather than an artifact of isolated single-component simulations. Radial distribution functions further show that HD is stabilized by dispersion-dominated confinement and weak halogen-hydrogen contacts, whereas HDO is governed by more localized, orientation-dependent interactions with hydrated zirconium node sites. These interaction differences produce a pronounced transport asymmetry, with HDO exhibiting a self-diffusion coefficient of 10.6 ± 2.11 × 10-10 m2/s compared with 0.5 ± 0.09 × 10-10 m2/s for HD at comparable loading. The results identify NU-1000 as a dual-function molecular host that couples reactant retention with product mobility, providing an interface-level mechanism relevant to selective CWA detoxification and confined transport in hierarchical porous catalysts.
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BibTeX
@article{mccormick2026interfacial,
title = {{Interfacial Confinement Enables Dual Hosting of Sulfur Mustard and Mustard Sulfoxide in NU-1000.}},
author = {Farrah S McCormick and Liangliang Huang},
journal = {Langmuir : the ACS journal of surfaces and colloids},
year = {2026},
month = oct,
doi = {10.1021/acs.langmuir.6c04057},
url = {https://europepmc.org/article/MED/42899887},
note = {CC BY},
}
RIS
TY - JOUR
TI - Interfacial Confinement Enables Dual Hosting of Sulfur Mustard and Mustard Sulfoxide in NU-1000.
AU - Farrah S McCormick
AU - Liangliang Huang
PY - 2026
DA - 2026/10/01
JO - Langmuir : the ACS journal of surfaces and colloids
DO - 10.1021/acs.langmuir.6c04057
UR - https://europepmc.org/article/MED/42899887
AB - Zirconium-based metal-organic frameworks have emerged as promising materials for the capture and detoxification of chemical warfare agents, but the molecular mechanism by which a hierarchical MOF differentiates a hydrophobic reactant from its oxidized product remains incompletely understood. Here, we use molecular dynamics simulations, grand-canonical Monte Carlo adsorption calculations, and periodic density functional theory to examine the dual-hosting behavior of NU-1000 toward sulfur mustard (HD) and mustard sulfoxide (HDO). Rather than treating NU-1000 only as an adsorbent or oxidation catalyst, we resolve how its internal micropore, mesopore, and c-pore interfaces impose distinct confinement environments on reactant and product species. Density functional theory (DFT) calculations show that HD binds most favorably in the c-pore region, with a binding energy of approximately -12.5 kcal/mol, and similarly favorable stabilization in confined micropore environments, whereas substantially weaker binding is observed in the mesopore. Molecular dynamics simulations also reveal sharply different pore residence patterns: HD localizes predominantly in micropores, occupying this region for ∼80% of the trajectory, while HDO samples larger pore environments more broadly, with ∼45% mesopore and ∼34% c-pore occupancy. This pore-selective behavior persists under mixed HD/HDO coadsorption conditions, demonstrating that reactant-product differentiation is intrinsic to the NU-1000 pore network rather than an artifact of isolated single-component simulations. Radial distribution functions further show that HD is stabilized by dispersion-dominated confinement and weak halogen-hydrogen contacts, whereas HDO is governed by more localized, orientation-dependent interactions with hydrated zirconium node sites. These interaction differences produce a pronounced transport asymmetry, with HDO exhibiting a self-diffusion coefficient of 10.6 ± 2.11 × 10-10 m2/s compared with 0.5 ± 0.09 × 10-10 m2/s for HD at comparable loading. The results identify NU-1000 as a dual-function molecular host that couples reactant retention with product mobility, providing an interface-level mechanism relevant to selective CWA detoxification and confined transport in hierarchical porous catalysts.
SN - 0743-7463
SN - 1520-5827
ER -