Uncovering the Role of Metal–Organic Framework Topology on the Capture and Reactivity of Chemical Warfare Agents

Chemical warfare agents (CWAs), such as sarin and sulfur mustard, continue to be a threat due to their high toxicity coupled with worldwide usage. Metal–organic frameworks (MOFs) are efficient materials for the adsorption and detoxification of CWAs because of their high porosity and tunable reactivity. MOFs can be utilized as adsorbents designed to have high uptake of these compounds, allowing time for the degradation of the CWAs into benign moieties. In this study, ten Zr MOFs differing in surface area/pore volume, secondary building unit (SBU) connectivity, pore functionalization, and open metal sites were examined for the adsorption of sarin gas and 2-chloroethyl ethyl sulfide, a sulfur mustard simulant. We observed the CWA loading across the series of MOFs to elucidate the significance of each factor on the capture of the substrates. High surface areas/pore volumes and increased hydrogen-bonding interactions were influential toward the increased uptake of both GB and CEES. Because of the presence of more active sites per unit volume, UiO-66, defective UiO-66, and MOF-808 were found to have the highest reactivities toward GB. With the results obtained from this study, different topologies can be utilized based on the targeted application.