Highly efficient and magnetically recyclable graphene-supported Pd/Fe3O4 nanoparticle catalysts for Suzuki and Heck cross-coupling reactions

Abstract

Herein, we report a facile and efficient one-step method for the synthesis of highly active, Pd/Fe3O4 nanoparticles supported on graphene nanosheets (Pd/Fe3O4/G) that exhibit excellent catalytic activity for Suzuki and Heck coupling reactions and that can be magnetically separated from the reaction mixture and recycled multiple times without loss of catalytic activity. The synthesis approach is based on the Microwave (MW)-assisted reduction of palladium and ferric nitrates in the presence of graphene oxide (GO) nanosheets using hydrazine hydrate as the reducing agent. The results provide a fundamental understanding of the system variables by comparing the catalytic activity and recyclability of four different catalysts with different properties. The most active and recyclable catalyst contains 7.6wt% Pd nanoparticles with 4-6nm diameters in Pd(0) oxidation state well-dispersed with 30wt% Fe3O4 nanoparticles with 12–16nm diameters on highly reduced GO containing a C/O ratio of 8.1. These combined properties produce remarkable catalytic activity for Suzuki cross coupling reactions under MW reaction conditions with an extremely high turnover number (TON) of 9250 and turn over frequency (TOF) of 111,000h−1 at 80°C. The magnetic properties imparted by the Fe3O4 component of the catalyst enables the catalyst to be easily isolated and recycled, thus greatly simplifying the ability to purify the reaction products and increasing the economic value of the catalyst. The utility of these magnetic catalysts towards Suzuki and Heck cross coupling reactions with a variety of functionalized substrates was also demonstrated.