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γ-Al2O3 supported Ni-Pd catalysts with different Ni:Pd ratios were studied in the hydrogenation of two industrially-relevant platform molecules derived from biomass, namely levulinic acid and hydroxymethylfurfural. The bimetallic catalysts showed better performances in both processes in comparison to the monometallic counterparts, for which a too strong interaction with the alumina support reduced the activity. The behavior of the bimetallic catalysts was dependent on the Ni:Pd ratio, and interestingly also on the targeted hydrogenation reaction. The Pd-modified Ni-rich system behaves like pure Ni catalyst, but with a strongly boosted activity due to a higher number of Ni active sites available, Pd being considered as a spectator. This high activity was manifested in the levulinic acid hydrogenation with formic acid used as an internal hydrogen source. This behavior differs from the case of the Pd-rich system modified by Ni, which displayed a much higher Pd dispersion on the support compared to the monometallic Pd catalyst. The higher availability of the Pd active sites while maintaining a high surface acidity allows the catalyst to push the HMF hydrodeoxygenation reaction forward towards the green biopolymer precursor 2,5-bis(hydroxymethyl)-tetrahydrofuran, and in consequence to strongly modify the selectivity of the reaction. In that case, residual chlorine was proposed to play a significant role, while Ni was considered as a spectator.

Ni-Pd/γ-Al2O3 Catalysts in the Hydrogenation of Levulinic Acid and Hydroxymethylfurfural towards Value Added Chemicals