Manganese Single Atom Modification of MOF-808 for Catalytic Nerve Agent and Simulant Degradation

Abstract

The extreme toxicity of nerve agents highlights the urgent need for catalytic materials that can operate under realistic, dry conditions. Zirconium-based MOF-808 is effective for aqueous-phase hydrolysis of these agents, but its performance drops sharply in solid-phase environments due to poisoning by tightly bound bidentate products. Here, we introduce a manganese (Mn) single-atom modified version of MOF-808 that overcomes this limitation. Unlike the native framework, Mn@MOF-808 achieves catalytic turnover (turnover number or TON>1) for nerve agent simulant degradation under ambient, unbuffered, and solvent-free conditions. The Mn sites help avoid product inhibition by favoring monodentate interactions over bidentate coordination. Experimental results show sustained reactivity during degradation of sarin and its simulants, and DFT calculations support reduced desorption energies of bound products. This work marks the first example of a MOF-based catalyst demonstrating turnover in solid-phase nerve agent degradation and moves a step closer to practical chemical threat mitigation.