Construction of Novel Polyoxometalate/Perylenediimide Hybrid Heterostructures for Enhanced Photocatalytic Oxidation of Mustard Gas Simulants

Abstract

Developing and designing novel materials for effective sulfur mustard detoxification are of great importance given their threat to human health. Crystalline donor–acceptor (D–A) hybrid heterostructures as an emerging class of materials are composed of semiconducting organic and inorganic components with enhanced charge-separated properties and thus promising applications in photocatalysis and photovoltaic cells. Herein, we demonstrated that the combination of three perylene diimide derivatives (PDIs) as electron-deficient acceptors with polyoxometalate (POM) anion [SiW12O40]4– as electron-rich donors resulted in three crystalline D–A hybrid heterostructures, namely, (Me4-PDI)2·SiW12O40 (1), (Me4-Br2-PDI)1.5·(HSiW12O40) (2), and (Me4-Cl4-PDI)2·SiW12O40 (3). Due to the considerable electrostatically assisted noncovalent interactions (lone pair−π, π–π, anion−π, and hydrogen-bonding interactions) between electron donors and acceptors, POMs, and PDIs, these hybrids displayed a significant enhancement in the photochemical stability and selective photocatalytic oxidation of the sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES).