Visible-Light-Responsive Polyoxometalate-Based Metal–Organic Frameworks for Photocatalytic Detoxification of Mustard Gas Simulant

Two [Ru(bpy)₃]²⁺ derivative-incorporated polyoxometalate-based metal-organic frameworks (POM@MOFs), {Cd(H₂O)₃Mn₃(H₂O)₉[Ru(dcbpy)₃][PMo₁₁^VIMo^VO₄₀]}·6H₂O (<b>Ru-CdMn-PMo</b>) and {Cd(H₂O)₃Cu₃(H₂O)₉[Ru(dcbpy)₃][PMo₁₁^VIMo^VO₄₀]}·6H₂O (<b>Ru-CdCu-PMo</b>), have been prepared through a conventional hydrothermal method. The introduction of Ru metalloligands enhanced the visible light absorption of POM@MOFs, and the photocatalytic detoxification reaction of mustard gas simulant 2-chloroethyl ethyl sulfide (CEES) confirmed their fascinating photocatalytic performances. Under visible light irradiation (λ > 400 nm), both <b>Ru-CdMn-PMo</b> and <b>Ru-CdCu-PMo</b> exhibited efficient photocatalytic properties for the detoxification of CEES into nontoxic CEESO in air, with a selectivity of 97% and a TOF of 26.6 min^-1. Besides, <b>Ru-CdMn-PMo</b> also exhibited commendable reusability and stability after three reaction cycles. In addition, EPR measurements and radical scavenging experiments were carried out to verify the generation of O₂^•- and ¹O₂, presenting reliable evidence for the detoxification mechanism.