Investigation on Mn3O4 Coated Ru Nanoparticles for Partial Hydrogenation of Benzene towards Cyclohexene Production Using ZnSO4, MnSO4 and FeSO4 as Reaction Additives.

Mn3O4 coated Ru nanoparticles (Ru@Mn3O4) were synthesized via a precipitation-reduction-gel method. The prepared catalysts were evaluated for partial hydrogenation of benzene towards cyclohexene generation by applying ZnSO4, MnSO4 and FeSO4 as reaction additives. The fresh and spent catalysts were thoroughly characterized by XRD, X ray fluorescence (XRF), XPS, TEM and N2-physicalsorption in order to understand the promotion effect of Mn3O4 as the modifier as well as ZnSO4, MnSO4 and FeSO4 as reaction additives. It was found that 72.0% of benzene conversion and 79.2% of cyclohexene selectivity was achieved after 25 min of reaction time over Ru@Mn3O4 with a molar ratio of Mn/Ru being 0.46. This can be rationalized in terms of the formed (Zn(OH)2)3(ZnSO4)(H2O)3 on the Ru surface from the reaction between Mn3O4 and the added ZnSO4. Furthermore, Fe2+ and Fe3+ compounds could be generated and adsorbed on the surface of Ru@Mn3O4 when FeSO4 is applied as a reaction additive. The most electrons were transferred from Ru to Fe, resulting in that lowest benzene conversion of 1.5% and the highest cyclohexene selectivity of 92.2% after 25 min of catalytic experiment. On the other hand, by utilizing MnSO4 as an additive, no electrons transfer was observed between Ru and Mn, which lead to the complete hydrogenation of benzene towards cyclohexane within 5 min. In comparison, moderate amount of electrons were transferred from Ru to Zn2+ in (Zn(OH)2)3(ZnSO4)(H2O)3 when ZnSO4 is used as a reaction additive, and the highest cyclohexene yield of 57.0% was obtained within 25 min of reaction time.