Structure, activity, and selectivity of bimetallic Pd-Fe/SiO2 and Pd-Fe/γ-Al2O3 catalysts for the conversion of furfural

[Display omitted] •Over Pd/SiO2 dominant furfural reaction is decarbonylation to furan.•Over bimetallic Pd-Fe/SiO2 O-hydrogenation and CO hydrogenolysis dominate.•Pd-Fe/γ-Al2O3 behaves more like monometallic Pd than bimetallic Pd-Fe.•Characterization indicates that while Pd-Fe alloy is formed on SiO2 is not formed on γ-Al2O3.•DFT suggests the presence of Fe weakens surface binding of the furan ring compared to pure Pd. The conversion of furfural has been investigated in vapor and liquid phases over a series of supported monometallic Pd and bimetallic Pd-Fe catalysts. Over the monometallic Pd/SiO2 catalyst, the decarbonylation reaction dominates, yielding furan as the main product. By contrast, over the bimetallic Pd-Fe/SiO2 catalyst a high yield of 2-methylfuran is obtained with much lower yield to furan. Interestingly, changing the catalyst support affects the product distribution. For instance, using γ-Al2O3 instead of SiO2 as support of the bimetallic catalyst changed the dominant product from 2-methylfuran to furan. That is, Pd-Fe/γ-Al2O3 behaves more like monometallic Pd/SiO2 than bimetallic Pd-Fe/SiO2. A detailed characterization of the catalysts via XPS, XRD, and TEM indicated that a Pd-Fe alloy is formed on the SiO2 support but not on the γ-Al2O3 support. Theoretical density functional theory calculations suggest that on the Pd-Fe alloy binding of the furan ring to the surface is weakened compared to on pure Pd. This weakening disfavors the ring hydrogenation and decarbonylation paths, while the oxophilic nature of Fe atoms enhances the interaction of the CO and the OH groups with the metal surface, which favors the CO hydrogenation and CO bond cleavage paths. The presence of the solvent has a less pronounced effect, but clearly has a stronger inhibition on CC bond cleavage (decarbonylation to furan) than on CO bond cleavage (hydrogenolysis to methylfuran).