Ultrafine Nanoparticle-Supported Ru Nanoclusters with Ultrahigh Catalytic Activity

The design of an ideal heterogeneous catalyst for hydrogenation reaction is to impart the catalyst with synergetic surface sites active cooperatively toward different reaction species. Herein a new strategy is presented for the creation of such a catalyst with dual active sites by decorating metal and metal oxide nanoparticles with ultrafine nanoclusters at atomic level. This strategy is exemplified by the design and synthesis of Ru nanoclusters supported on Ni/NiO nanoparticles. This Ru‐nanocluster/Ni/NiO‐nanoparticle catalyst is shown to exhibit ultrahigh catalytic activity for benzene hydrogenation reaction, which is 55 times higher than Ru–Ni alloy or Ru on Ni catalysts. The nanoclusters‐on‐nanoparticles are characterized by high‐resolution transmission electron microscope, Cs‐corrected high angle annular dark field‐scanning transmission electron microscopy, elemental mapping, high‐sensitivity low‐energy ion scattering, and X‐ray absorption spectra. The atomic‐scale nanocluster–nanoparticle structural characteristics constitute the basis for creating the catalytic synergy of the surface sites, where Ru provides hydrogen adsorption and dissociation site, Ni acts as a “bridge” for transferring H species to benzene adsorbed and activated at NiO site, which has significant implications to multifunctional nanocatalysts design for wide ranges of catalytic reactions. Ru nanocluster‐decorated Ni/NiO nanoparticles (Ru–Ni/NiO) supported on carbon are designed and prepared for benzene hydrogenation. The ultrahigh activity of the Ru–Ni/NiO/C catalyst is attributed to synergetic multifunction of catalytic sites where the Ru sites activate molecular hydrogen, NiO sites activate benzene, and Ni sites function as a “bridge” for transferring the activated H species to the activated benzene.