Fluoride Product\nInhibition: New Insight into the\nDegradation of Nerve Agents by Zr-MOFs

Zirconium-based metal–organic frameworks (Zr-MOFs)\nhave\nshown remarkable efficacy in catalytically degrading neurotoxic agents\nin recent years. However, the catalytic activity of Zr-MOFs can be\ninhibited due to the binding of phosphate degradation products to\nthe Zr nodes. Here, we reported the inhibition effect of a nonphosphate\nsubstance, fluoride, which can deactivate Zr-MOF nodes for the degradation\nof GD and VX and simulate DEPPT. The experimental and theoretical\ncalculation results reveal that the fluoride product during GD degradation\nshows much more significant suppression than phosphate. The phosphate\nproducts can depart from the Zr nodes completely by adding H<sub>2</sub>O molecules on the Zr nodes to reduce the energy barrier. However,\nthe fluoride can replace the bridged μ<sub>3</sub>-OH groups\nand terminal −OH groups on Zr-oxo clusters irreversibly, changing\nthe electric density of Zr nodes and eliminating the terminal −OH.\nWithout the terminal −OH, the five-coordinate phosphorus intermediate\ncannot be formed, resulting in the inactivation of Zr–O–Zr\nsites. This study provides new insights into Zr-MOF catalyst deactivation\nmechanisms and may help to develop a new strategy to design MOFs with\nhigh anti-inhibition efficiency for the degradation of nerve agents.