Cellulose nanocrystal shelled with poly(ionic liquid)/polyoxometalate hybrid as efficient catalyst for aerobic oxidative desulfurization.

Immobilization of polyoxometalates (POMs) plays significant roles in their industrial applications. In this work, POM-supported catalyst has been developed with cellulose nanocrystal (CNC) as a sustainable carrier and employed in the aerobic oxidative desulfurization (AODS) of fuels. The catalyst was constructed by grafting a poly(ionic liquid) (PIL) onto CNCs and subsequently exchanging the counterions of the PIL into [Co(OH)6Mo6O18]3-, a kind of POM anionic clusters. The resulting CNC@PIL@POM was systematically characterized and utilized as a catalyst in the AODS of thiophenic compounds including benzothiophene (BT), dibenzothiophene (DBT), and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT), with oxygen contained in air as oxidizing agent. The catalyst could achieve complete conversion of DBT in model diesel under mild condition and be reused five times without apparent losing of activity. As for the desulfurization of a real diesel, it was demonstrated that almost all of the original sulfides were completely converted. Based on these results, it is expected that the core-shell POM-supported catalyst may serve as an efficient, separable and sustainable catalyst for AODS of fuels.