Nickel-palladium bimetallic nanoparticles supported on multi-walled carbon nanotubes; versatile catalyst for...

We have developed an efficient method to generate highly active nickel-palladium bimetallic nanoparticles supported on multi-walled carbon nanotubes (Ni-Pd/MWCNTs) by dry mixing of the nickel and palladium salts utilizing the mechanical energy of a ball-mill. These nanoparticles were successfully employed in Sonogashira cross-coupling reactions with a wide array of functionalized aryl halides and terminal alkynes under ligand and copper free conditions using a Monowave 50 heating reactor. Notably, the concentration of palladium can be lowered to a minimum amount of 0.81% and replaced by more abundant and less expensive nickel nanoparticles while effectively catalyzing the reaction. The remarkable reactivity of the Ni-Pd/MWCNTs catalyst toward Sonogashira cross-coupling reactions is attributed to the high degree of the dispersion of Ni-Pd nanoparticles with small particle size of 5-10 nm due to an efficient grinding method. The catalyst was easily removed from the reaction mixture by centrifugation and reused several times with minimal loss of catalytic activity. Furthermore, the concentration of catalyst in Sonogashira reactions can be reduced to a minimum amount of 0.01 mol% while still providing a high conversion of the Sonogashira product with a remarkable turnover number (TON) of 7200 and turnover frequency (TOF) of 21 600 h^-1. The catalyst was fully characterized by a variety of spectroscopic techniques including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS).