Computational Insights into Dual Hosting of Sarin and Mustard Gas in MOF-808: Distinct Binding and Interaction Mechanisms

FS McCormick and MC Oliver and LL Huang, JOURNAL OF PHYSICAL CHEMISTRY C, 129, 19824-19835 (2025).

DOI: 10.1021/acs.jpcc.5c06023

Zirconium-based metal-organic frameworks (Zr-MOF) are promising candidates for the capture and catalytic degradation of chemical warfare agents (CWAs), owing to their tunable porosity, robust stability, and versatile catalytic properties. However, few studies have explicitly addressed how multiple distinct CWAs coexist and competitively interact within these frameworks under realistic environmental conditions. In this work, we provide computational insights into the simultaneous hosting and interactions of two chemically distinct CWAs within the pristine MOF-808, namely, sarin, a nerve agent, and mustard gas, a blister agent. By combining molecular dynamics (MD) simulations, Monte Carlo (MC) adsorption studies, and density functional theory (DFT) calculations, we identify distinct binding preferences and interaction mechanisms of GB and HD within the MOF-808 framework. Our results reveal that sarin closely binds to the Zr metal nodes, while mustard gas exhibits comparatively more spatially distinct interactions, even in the presence of capping agents. Furthermore, we demonstrate that environmental species, particularly water and oxygen, can modulate the spatial distribution, binding competition, and diffusional behaviors of these CWAs. These findings provide critical molecular-level insights into the competitive and cooperative interactions among multiple CWAs and coadsorbed environmental species in Zr-MOFs, underscoring the need to consider these complex interactions when designing materials for efficient CWA remediation under practical conditions.

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