Tandem hydrogenation/hydrogenolysis of furfural to 2-methylfuran over a Fe/Mg/O catalyst: Structure–activity relationship

The hydrodeoxygenation of furfural (FU) was investigated over Fe-containing MgO catalysts, on a continuous gas flow reactor, using methanol as a hydrogen donor. Catalysts were prepared either by coprecipitation or impregnation methods, with different Fe/Mg atomic ratios. The main product was 2-methylfuran (MFU), an important highly added value chemical, up to 92% selectivity. The catalyst design helped our understanding of the impact of acid/base properties and the nature of iron species in terms of catalytic performance. In particular, the addition of iron on the surface of the basic oxide led to (i) the increase of Lewis acid sites, (ii) the increase of the dehydrogenation capacity of the presented catalytic system, and (iii) to the significant enhancement of the FU conversion to MFU. FTIR studies, using methanol as the chosen probe molecule, indicated that, at the low temperature regime, the process follows the typical hydrogen transfer reduction, but at the high temperature regime, methanol dehydrogenation and methanol disproportionation were both presented, whereas iron oxide promoted methanol transfer. FTIR studies were performed using furfural and furfuryl alcohol as probe molecules. These studies indicated that furfuryl alcohol activation is the rate-determining step for methyl furan formation. Our experimental results clearly demonstrate that the nature of iron oxide is critical in the efficient hydrodeoxygenation of furfural to methyl furan and provides insights toward the rational design of catalysts toward C–O bonds’ hydrodeoxygenation in the production of fuel components.