Dual Role of Water in Heterogeneous Catalytic Hydrolysis of Sarin by Zirconium-Based Metal–Organic Frameworks

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.