Gas capture and sequestration are valuable properties of metal–organic frameworks (MOFs) driving tremendous interest in their use as filtration materials for chemical warfare agents. Recently, the Zr-based MOF UiO-67 was shown to effectively adsorb and decompose the nerve-agent simulant, dimethyl methylphosphonate (DMMP). Understanding mechanisms of MOF-agent interaction is challenging due to the need to distinguish between the roles of the MOF framework and its particular sites for the activation and sequestration process. Here, we demonstrate the quantitative tracking of both framework and binding component structures using in situ X-ray total scattering measurements of UiO-67 under DMMP exposure, pair distribution function analysis, and theoretical calculations. The sorption and desorption of DMMP within the pores, association with linker-deficient Zr6 cores, and decomposition to irreversibly bound methyl methylphosphonate were directly observed and analyzed with atomic resolution.

气体捕获和封存是金属有机框架 (MOF) 的宝贵特性，这促使人们对其用作化学战剂的过滤材料产生了极大的兴趣。最近，基于 Zr 的 MOF UiO-67 被证明可以有效吸附和分解神经毒剂模拟物甲基膦酸二甲酯 (DMMP)。由于需要区分 MOF 框架的作用及其在激活和隔离过程中的特定位点，因此了解 MOF-代理相互作用的机制具有挑战性。在这里，我们展示了在 DMMP 曝光、对分布函数分析和理论计算下使用 UiO-67 的原位 X 射线总散射测量对框架和结合组件结构的定量跟踪。DMMP在孔隙内的吸附和解吸，