Computational Analysis of Sarin, Soman, and Their Water Mixtures in NU-1000: Interaction Mechanisms, Distribution Patterns, and Pairing Effects

Due to their extraordinary structural stability under humid conditions, zirconium-based metal-organic frameworks (Zr-MOFs) have been widely investigated for the hydrolytic degradation of nerve agents. That said, mechanisms of hydrolysis in the solid state and the participation of environmental water are not well understood. This work utilizes computational techniques to evaluate the behavior of water and two organophosphorus nerve agents (sarin and soman) in NU-1000, a Zr-MOF with the characteristic attributes for hydrolytic efficiency under humid conditions. Density functional theory (DFT) calculations reveal that soman binds more favorably to NU-1000 active sites than sarin, resulting in different preferential locations of each nerve agent within the framework. The strength of nerve agent binding is also found to vary depending on the site environment, with more favorable binding of both nerve agents occurring in the c-pores of NU-1000 than in the mesopores. Molecular dynamics (MD) simulation results further illustrate that free water molecules in NU-1000 prioritize interactions with nerve agents. Given the variation in their affinity for active site interactions, the introduction of different nerve agents to the framework results in substantial differences in water distribution and behavior. The results give insight into potential variances in the functionality of NU-1000 toward the hydrolysis of each nerve agent. More importantly, they emphasize the significance of considering the role of environmental water in hydrolysis and the possibility of diverse reaction variables based on the type of nerve agent and the properties of the MOF.