The ruthenium-nickel bimetallic nanoparticles supported on carbon black (Ru-Ni/C) with various Ru and Ni loadings, while keeping a constant Ru/Ni atomic ratio (51/49), were synthesized at ambient temperature by liquid reduction with hydrazine hydrate as reducing agent and galvanic replacement reaction approaches. Different Ru-Ni interfaces (Ru-Ni-NiO with 1.250 wt% or 0.630 wt% Ru, and RuO2-NiO with 0.160 wt% Ru) were formed after being annealed in N-2 at 380 degrees C for 3 h. Several techniques, including powder X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution TEM (HRTEM) and synchrotron radiation X-ray absorption spectroscopy (XAS) and in-situ XAS (in hydrogen) have been employed for structural characterization. It was found that most Ru atoms and a small amount of Ni atoms at the Ru-Ni-NiO interface were reduced, leading to the occurrence of hydrogen spillover and hence synergy effect of Ru, Ni and NiO active sites. However, such a synergy was not observed at the RuO2-NiO interface. The catalytic properties of the Ru-Ni/C nanocatalysts in the hydrogenation of benzene reaction were significantly improved due to the presence of particular Ru-Ni-NiO interface. (C) 2019 Elsevier Inc. All rights reserved.