Zirconium-based metal−organic frameworks (MOFs) have been reported as promising catalysts for the hydrolytic destruction of chemical warfare agents (CWAs) that contain phosphate ester bonds. We used density functional theory (DFT) calculations to study the hydrolysis of CWAs and their simulants on Zr-based MOFs. To combat product inhibition resulting from strong bidentate binding of the hydrolysis products to the Zr nodes in gas-phase reactions, we analyzed single-atom catalysts that could be deposited on the nodes. Using DFT, we calculated the complete reaction pathways for sarin on M−NU-1000 systems and discovered that the highest reaction barrier varies between catalysts, highlighting the need to consider more than a single reaction step when screening a large number of diverse materials. The single-metal catalysts are predicted to exhibit lower product desorption energies than unfunctionalized NU-1000. By comparing their relative turnover frequencies using the energetic span model, we identified several catalysts that are predicted to be more active than the parent MOF for this reaction. The effect of adsorbed water molecules from the air on the reaction will also be discussed.

Computational modeling of metal−organic frameworks for hydrolysis of nerve agents

ACS Spring Meeting 2021

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