Bimetallic Nickel-Palladium Nanoparticles Supported on Multiwalled Carbon Nanotubes for Suzuki Cross-Coupling Reactions in Continuous Flow.

An efficient Suzuki cross-coupling reaction under continuous flow conditions was developed utilizing an immobilized solid supported catalyst consisting of bimetallic nickel-palladium nanoparticles (Ni-Pd/MWCNTs). In this process, the reactants can be continuously pumped into a catalyst bed at a high flow rate of 0.6 mL/min and the temperature of 130 °C while the Suzuki products are recovered in high steady-state yields for prolonged continuous processing. The catalyst was prepared by mechanical shaking of the appropriate nickel and palladium salts using ball-mill energy without the requirement of any solvent or reducing agent. This straightforward, facile, and simple method allows for bulk production of Ni-Pd/MWCNTs nanoparticles with a small particle size ideal for application in continuous flow cross-coupling catalysis. The as-prepared catalyst mostly contains nickel (7.9%) with a very small amount of palladium (0.81%) according to ICP-OES analysis. This remarkable immobilized catalyst can be used several times for different Suzuki reactions with a minimum loss of reactivity and no detectable leaching of the metal nanoparticles. Notably, by modifying the groups on both aryl halides and phenylboronic acids, the method provides access to a diverse array of the Suzuki products in flow with high steady-state yield, making it suitable for applications in industrial and pharmaceutical scales. Moreover, several spectroscopic techniques were employed to identify the structure and composition of the as-prepared Ni-Pd/MWCNTs nanoparticles before and after the reaction in flow such as transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), BET surface area (physisorption), and FTIR spectroscopy.