Function–Topology Relationship in the Catalytic Hydrolysis of a Chemical Warfare Simulant in Two Zr‐MOFs

Abstract Owing to their high surface area, high concentration of active metal sites, and water stability, zirconium(VI)‐based metal–organic frameworks (Zr‐MOFs) have shown excellent activity in the hydrolysis of organophosphorus nerve agents (OPNs). In this regard, for the first time, two topologically different Zr‐MOFs (Zr‐fcu‐tmuc and Zr‐bcu‐tmuc, constructed from the same organic and inorganic building blocks; fcu=face‐centered cubic, bcu=body‐centered cubic) have been rationally chosen to investigate the effect of network topology on the catalytic hydrolysis of the nerve agent simulant, dimethyl 4‐nitrophenyl phosphate (DMNP). A remarkable enhancement in the hydrolysis rate of DMNP was observed with Zr‐bcu‐tmuc, reducing the half‐life more than three‐fold compared with Zr‐fcu‐tmuc. Greater accessibility of the active Zr VI sites in the 8‐connected bcu net compared with the 12‐connected fcu leads to a faster hydrolysis of DMNP on Zr‐bcu‐tmuc. Interestingly, the higher activity of Zr‐bcu‐tmuc was also confirmed by its higher fluorescence sensitivity towards DMNP (limit of detection (LOD)=0.557 μ m ) compared with Zr‐fcu‐tmuc (LOD=1.09 μ m ). The results show that controlling the desired topology of Zr‐MOFs is a useful strategy for improving their performance in the detection and catalytic detoxification of OPNs.