Zirconium metal–organic frameworks (Zr-MOFs) are promising catalysts for the hydrolytic degradation of organophosphate nerve agents and their simulants, yet the influence of topology on their stability and reactivity remains underexplored. Here, we report two (4,8)-connected Zr-MOFs featuring sqc and csq topologies, specifically Zr-sTPEex-BA and Zr-sTPEex-TFA, constructed from a flexible, custom-designed tetratopic carboxylate linker (H4-sTPEex) and 8-connected Zr6 clusters, with topology directed by benzoic acid (BA) or trifluoroacetic acid (TFA) as modulators. The csq-type Zr-sTPEex-TFA exhibits enhanced stability, increased porosity and superior catalytic efficiency compared to the sqc-type Zr-sTPEex-BA, achieving a half-life of 5.4 min for the hydrolysis of the nerve agent simulant dimethyl 4-nitrophenyl phosphate (DMNP). This study underscores the pivotal role of topology in governing the stability and catalytic activity of Zr-MOFs, offering valuable insights for their rational design in decontamination applications.
Zhang et al. (Mon,) studied this question.