A Correlated Multimodal Approach Reveals Key Details of Nerve-Agent Decomposition by Single Site Zr-Based Polyoxometalates

Development of technologies for protection against chemical warfareagents (CWAs) is critically important. Recently, polyoxometalateshave attracted attention as potential catalysts for nerve-agentdecomposition. The improvement of their effectiveness in real operating conditions requires an atomic-level understanding of CWA decomposition at the gas-solid interface. We investigated decomposition of the nerve agent Sarinand its simulant, dimethyl chlorophosphate (DMCP), by a zirconium polytungstate. Using a multimodal approach, we showed that, upon DMCP and Sarinexposure, the dimeric tungstateundergoes monomerization, making coordinatively unsaturated Zr(IV)-centers available, which activate nucleophilic hydrolysis. Further, DMCP is shown to be a good model system of reduced toxicity for studies of CWA deactivation at the gas-solid interface.