Reduced polyoxomolybdate immobilized on reduced graphene oxide for rapid catalytic decontamination of a sulfur mustard simulant.

Keggin-type polyoxometalates (POMs) were immobilized on poly(diallyldimethylammonium chloride) (PDDA) functionalized reduced graphene oxide (rGO) by a facile and broad-spectrum hydrothermal method. The prepared POMs@PDDA-rGO composites (POM = H3PMo12O40, H3PW12O40, H5PMo10V2O40) have been thoroughly characterized using a series of techniques. The three composites can catalyze the oxidative decontamination of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES) in the order of PMo12@PDDA-rGO > PMo10V2@PDDA-rGO > PW12@PDDA-rGO. Notably, under ambient conditions PMo12@PDDA-rGO can convert 99% of CEES within 30 min in the presence of nearly stoichiometric aqueous H2O2 (3 wt%) and its catalytic activity is significantly higher than that of homogeneous H3PMo12O40. XPS spectral analysis and control experiments indicate that the Mo center of POM is reduced from +6 to +5 during the hydrothermal process, and the excellent catalytic performance is related to the reduction of Mo. Moreover, the PMo12@PDDA-rGO composite is stable during the decontamination process and it can be used for at least five cycles without loss of activity.