Bimetallic MOFs With Enzyme‐Mimetic Active Sites for Nerve Agent Detoxification: Synergistic Insights Into Impeccable Performance From Experiment and Theory

ABSTRACT Nerve agents pose severe risks to human health, underscoring the need for efficient decontamination strategies. This study explores metal–organic frameworks (MOFs) as catalytic platforms owing to their structural tunability, redox‐active metal centers, and abundance of Lewis acidic sites. Single‐ and bimetallic UiO‐series MOFs incorporating Ce(IV) and Zr(IV) (confirmed by inductively coupled plasma mass spectrometry) were synthesized using different approaches, including ligand exchange and controlled crystal growth, with four ligands: BDC, BDC–NH 2 , BDC–NO 2 , and BDC–(OH) 2 . These frameworks were systematically evaluated for the hydrolysis of p ‐nitrophenyl phosphate (PNPP), a simulant for G‐ and V‐type nerve agents (e.g., sarin, VX). The design strategy leverages the redox activity and cooperativity of Ce/Zr nodes, alongside the caging effect of the MOF architecture, to enhance catalytic efficacy. Density functional theory (DFT) calculations provided mechanistic insights into sarin degradation, revealing how metal composition and linker functionality govern substrate binding and activation. Experimental results demonstrated that bimetallic Ce/Zr‐MOFs with electron‐withdrawing functional groups exhibit significantly accelerated hydrolysis under basic aqueous conditions. Notably, a Ce/Zr‐MOF with –NO 2 functionality achieved the shortest half‐life of 1.16 min. These findings highlight Ce/Zr‐UiO frameworks as promising candidates for real‐world nerve agent decontamination technologies.