Recent experimental studies on ZrIV-based metal-organic frameworks (MOFs) have shown the extraordinary effectiveness of these porous materials for the detoxification of phosphorus-based chemical warfare agents (CWAs). However, pressing challenges remain with respect to characterizing these catalytic processes both at the molecular and crystalline levels. We here use theory to compare the reactivity of different zirconium-based MOFs for the catalytic hydrolysis of the CWA sarin, using both periodic and cluster modeling. We consider both hydrated and dehydrated secondary building units, as well as linker functionalized MOFs, to more fully understand and rationalize available experimental findings as well as to enable concrete predictions for achieving higher activities for the decomposition of CWAs.
Bibliographical noteFunding Information:
The authors gratefully acknowledge the Defense Threat Reduction Agency (HDTRA1-18-1-0003) for financial support. The authors also acknowledge the Minnesota Supercomputing Institute (MSI) for providing resources that contributed to the research results reported within this paper. M.R.M. is grateful for helpful discussions with Omar Farha, Timur Islamoglu, Manuel Ortuño, Dale Pahls, Hung Pham, and Debmalya Ray.
- chemical warfare agent
- functionalized MOFs
- heterogeneous catalysis
- metal-organic framework (MOF)