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Polyoxomolybdate based ionic-liquids as active catalysts for oxidative desulfurization of simulated diesel

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This work compares the stability and the catalytic efficiency of different ionic liquid phosphomolybdates ([BPy]3[PMo12O40] and [BMIM]3[PMo12O40]) with a cationic (propylpyridinium) functionalized mesoporous silica nanoparticle composite (PMo12O40@PPy-MSN). These were used as solid catalysts for the oxidative desulfurization of a multicomponent model diesel using hydrogen peroxide as oxidant and a polar immiscible extraction solvent. Ionic liquid ([BMIM][PF6] was successfully used as solvent to extract sulfur compounds from model diesel. The ionic liquid phosphomolybdates showed partial solubility in the ionic liquid phase, occurring some decomposition of their Keggin structure in the soluble reaction media, probably caused by their interaction with oxidant. On the other hand, the phosphomolybdate composite PMo12O40@PPy-MSN presented high structural stability and only negligible leaching occurrence after various consecutive reaction cycles. The model diesel was near complete desulfurized after 3 h and consecutive desulfurization cycles were performed without loss of activity. Therefore, the immobilization of Keggin phosphomolybdate structure [PMo12O40]3− using cationic propylpyridinium silica nanoparticle is an assertive strategy to produce stable and active heterogeneous catalysts.

Descrição

This work was partly funded through the Associate Laboratory for Green Chemistry- LAQV which is financed by national funds from FCT/MCTES (POCI-01-0145-FEDER-007265, UID/QUI/50006/2019) and CENIMAT, I3N (POCI-01-0145-FEDER-007688, UID/CTM/50025/2013), also financed by national funds through the FCT/MCTES, and when appropriate co-financed by the Fundo Europeu de Desenvolvimento Regional (FEDER) under the PT2020 Partnership Agreement. This work is funded by national funds (OE), through FCT – Fundação para a Ciência e a Tecnologia. European Social Fund through the program POPH of QREN. The authors also acknowledge the Portuguese Nuclear Magnetic Resonance Network (PTNMR).

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Fuels Heterogeneous catalysis Mesoporous silica nanoparticles Oxidative desulfurization Polyoxomolybdate Physical and Theoretical Chemistry Inorganic Chemistry Materials Chemistry

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