A continuous interest exists in the development of efficient catalytic methods for the hydrolytic degradation of harmful organophosphates. Metal-organic frameworks (MOFs) have emerged as efficient catalyst materials for the degradation of toxic chemicals due to their high porosity and wide ranging chemistries. Recently, we have extended their relevance to degrade organophosphates in non-aqueous environments. There is a need to develop efficient methods to decontaminate sensitive electronics, incompatible with existing decontamination technologies.<br/>In this study we have explored the role of metal and linker functional groups in MOFs on the binding and degradation of a series of organophosphates. Material properties have been well-characterized using a blend of experimental and computational techniques. Degradation in non-aqueous solvent was monitored using <sup>31</sup>P NMR. Further, we investigated the most appropriate simulant that mimics the reactivity of Sarin in methanol and found that nitro and fluorophosphates are better suited surrogates than chlorophosphates. Binding energies and vibrational frequencies of host and guest modes have been explored using density functional theory calculations. Our results indicate a 2-fold increase in the binding energy at undercoordinated metal sites over their fully coordinated counterparts. A red shift in the infrared signature of the P=O stretch is observed which suggests that phosphates might be a viable probe for binding energies and geometries in MOFs.<br/>

Insights into the binding and degradation of organophosphates on MOFs from a complementary experimental-modeling study

256th National Meeting (2018)

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