Different supports of modified heteropolyacid for ultra-deep oxidative desulfurization: A newly easy shaped catalyst and the DFT cluster model study.

Graphical abstract Highlights • Transition metal modified heteropolyacid was synthesized and calculated under DFT. • Fibre and MCM-41 were compared to the oxidative desulfurization behavior. • Under O 2 , L-Co-PMF exhibits excellent catalytic performance for deep desulfurization. • Desulfurization condition is mild with very low loss of desulfurization efficiency. • The catalyst can be easily recovered and reused more than 10 times. Abstract Heteroplyacid system exhibited a wide advantage as catalysts, mainly after the modification. In this paper, the density functional theory (DFT) calculations were used to evaluation the influence of electrochemical properties by the shape of the frontier molecular orbitals (MOs), proving the important role of the close relationship between the MOs of different metal modified heteropolyacid and the oxidative desulfurization performance. The obtained results showed that the Co2+ ion introduced into the PMo, as the position of the addenda atom presented a low gap of HOMO-LUMO, which was agreement with the desulfurization results. In addition, two different supports, Fibre and MCM-41, were used to synthesize the Co-PMo@MOF-199@ Supports, namely L-Co-PMF and L-Co-PMM, in which the modified heteropolyacid has been encapsulated into the pores with the mixture of metal-organic framework and the porous materials MCM-41/Fibre. The comparison results showed that the Fibre was an optimal, getting 100% desulfurization rate after 90 min under the chosen conditions. Moreover, the shaped catalyst could widely open the industrial application. [ABSTRACT FROM AUTHOR]