Sea-Island-Like Morphology of CuNi Bimetallic Nanoparticles Uniformly Anchored on Single Layer Graphene Oxide as a Highly Efficient and Noble-Metal-Free Catalyst for Cyanation of Aryl Halides

Abstract

Aryl nitriles are versatile compounds that can be synthesized via transition-metal-mediated cyanation of aryl halides. Most of the supported-heterogeneous catalysts are noble-metals based and there are very limited numbers of efficient non-noble metal based catalysts demonstrated for the cyanation of aryl halides. Herein, bimetallic CuNi-oxide nanoparticles supported graphene oxide nanocatalyst (CuNi/GO-I and CuNi/GO-II) has been demonstrated as highly efficient system for the cyanation of aryl halides with K4[Fe(CN)6] as a cyanating agent. Metal-support interaction, defect ratio and synergistic effect with the bimetallic nanocatalyst were investigated. To our delight, the CuNi/GO-I system activity transformed a wide range of substrates such as aryl iodides, aryl bromides, aryl chlorides and heteroaryl compounds (Yields: 95–71%, TON/TOF: 50–38/2 h−1). Moreover, enhanced catalytic performance of CuNi/GO-I and CuNi/GO-II in reduction of 4-nitropehnol with NaBH4 was also confirmed (kapp = 18.2 × 10−3 s−1 with 0.1 mg of CuNi/GO-I). Possible mechanism has been proposed for the CuNi/GO-I catalyzed cyanation and reduction reactions. Reusability, heterogeneity and stability of the CuNi/GO-I are also found to be good.