Otto H. York Department of Chemical and Materials Engineering, New Jersey Institute of Technology, University Heights, Newark, New Jersey 07102, United States.
Universität Leipzig, Linnestraße 5, 04103 Leipzig, Germany.
ACS Appl Mater Interfaces. 2023 Apr 12;15(14):18559-18567. doi: 10.1021/acsami.3c02713. Epub 2023 Mar 28.
The development of effective protection against exposure to chemical warfare agents (CWAs), such as sarin, relies on studies of its adsorption on the capturing materials and seeking candidates capable of adsorbing large amounts of sarin gas. Many metal-organic frameworks (MOFs) are promising materials for the effective capture and degradation of sarin and simulant substances. Among the simulants capable of mimicking thermodynamic properties of the agent, not all of them have been investigated on the ability to act similarly in the adsorption process, in particular, whether the agent and a simulant have similar mechanisms of binding to the MOF surface. Molecular simulation studies not only provide a safe way to investigate the aforementioned processes but can also help reveal the mechanisms of interactions between the adsorbents and the adsorbing compounds at the molecular level. We performed Monte Carlo simulations of the adsorption of sarin and three simulants, dimethyl methylphosphonate (DMMP), diisopropyl methylphosphonate (DIMP), and diisopropyl fluorophosphate (DIFP), on selected MOFs that have previously shown strong capabilities to adsorb sarin. On the basis of the calculated adsorption isotherms, enthalpy of adsorption, and radial distribution functions, we revealed common mechanisms among the particularly efficient adsorbents as well as the ability of simulants to mimic them. The findings can help in selecting a suitable simulant compound to study CWA adsorption on MOFs and guide further synthesis of efficient MOFs for the capture of organophosphorus compounds.
开发针对化学战剂（CWA）暴露的有效防护措施，如沙林，依赖于对其在捕获材料上吸附的研究，并寻找能够吸附大量沙林气体的候选材料。许多金属有机骨架（MOFs）是有效捕获和降解沙林和模拟物质的有前途的材料。在能够模拟药剂热力学性质的模拟物中，并非所有模拟物都研究了其在吸附过程中具有相似作用的能力，特别是药剂和模拟物是否具有相似的与 MOF 表面结合的机制。分子模拟研究不仅提供了一种安全的方法来研究上述过程，而且还可以帮助揭示吸附剂与吸附化合物在分子水平上的相互作用机制。我们对沙林和三种模拟物，即二甲甲基膦酸酯（DMMP）、二异丙基甲基膦酸酯（DIMP）和二异丙基氟膦酸酯（DIFP）在先前表现出对沙林强吸附能力的选定 MOFs 上进行了蒙特卡罗模拟。基于计算得到的吸附等温线、吸附焓和径向分布函数，我们揭示了特别有效的吸附剂之间的共同机制，以及模拟物模拟它们的能力。这些发现有助于选择合适的模拟化合物来研究 MOFs 上的 CWA 吸附，并指导进一步合成用于捕获有机磷化合物的高效 MOFs。
