The double complex salt [Pd(NH3)(4)](ReO4)(2) was employed as precursor of supported bimetallic catalysts for selective hydrogenation of furfural. Direct reduction of [Pd(NH3)(4)](ReO4)(2) on gamma-Al2O3 in flowing H-2 at 400 degrees C yields bimetallic nanoparticles 1-2 nm in size that exhibit significant interaction between the metals, as evidenced by temperature-programmed hydride decomposition (complete suppression of beta-PdHx formation), extended X-ray absorption fine structure spectroscopy at the Pd K and Re L-III edges (Pd Re distance = 2.72 angstrom), and scanning transmission electron microscopy with energy dispersive X-ray analysis. In contrast, calcination of [Pd(NH3)(4)](ReO4)(2) on gamma-Al2O3 at 350 degrees C in air and subsequent reduction in H-2 at 400 degrees C results in metal segregation and formation of large (>50 nm) supported Pd particles; Re species cover the Pd particles and gamma-Al2O3 support. A PdRe 1:2 catalyst prepared by sequential impregnation and calcination using HReO4 and [Pd(NH3)(4)](NO3)(2) has a similar morphology. The catalyst derived by direct reduction of [Pd(NH3)(4)](ReO4)(2) on gamma-Al2O3 exhibits remarkably high activity for selective hydrogenation of furfural to furfuryl alcohol (FAL) at 150 degrees C and 1 atm. Suppression of H-2 chemisorption via elimination of Pd threefold sites, as evidenced by CO diffuse-reflectance infrared Fourier transform spectroscopy, correlates with increased FAL selectivity. (C) 2017 Elsevier Inc. All rights reserved.