Palladium-Rhenium Catalysts for Selective Hydrogenation of Furfural: Influence of Catalyst Preparation on Structure and Performance

Abstract

PdRe/Al2O3 catalysts are highly selective for hydrogenation of furfural to furfuryl alcohol (FAL). Moreover, the synergy between the metals can result in greater specific activity (higher turnover frequency, TOF) than exhibited by either metal alone. Bimetallic catalyst structure depends strongly on the metal precursors employed and their addition sequence to the support. In this work, PdRe/Al2O3 catalysts were prepared by: (i) co-impregnation (CI) and sequential impregnation (SI) of γ-Al2O3 using HReO4 and Pd(NO3)2, (ii) SI using NH4ReO4 and [Pd(NH3)4(NO3)2], (iii) HReO4 addition to a reduced and passivated Pd/Al2O3 catalyst, and (iv) impregnation with the double complex salt (DCS), [Pd(NH3)4(ReO4)2]. Raman spectroscopy and temperature-programmed reduction (TPR) evidence larger supported PdO crystallites in catalysts prepared using Pd(NO3)2 than [Pd(NH3)4(NO3)2]. Surface [ReO4]− species detected by Raman exhibit TPR peak temperatures from ranging 85 to 260 °C (versus 375 °C for Re/Al2O3). After H2 reduction at 400 °C, the catalysts were characterized by chemisorption, temperature-programmed hydride decomposition (TPHD), CO diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and scanning transmission electron microscopy (STEM) with energy-dispersive x-ray (EDX) spectroscopy. The CI catalyst containing supported Pd–Re alloy crystallites had a TOF similar to Pd/Al2O3 but higher (61%) FAL selectivity. In contrast, catalysts prepared by methods (ii–iv) containing supported Pd-Re nanoparticles exhibit higher TOFs and up to 78% FAL selectivity.