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

Gopiraman Mayakrishnan,Ick Soo Kim,Vijayakumar Elayappan,Ill-Min Chung

doi:10.1038/s41598-020-57483-z

Gopiraman Mayakrishnan, Ick Soo Kim + Show 2 more

Open Access

https://doi.org/10.1038/s41598-020-57483-z

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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.

Highlights

Aryl nitriles are versatile compounds that can be synthesized via transition-metal-mediated cyanation of aryl halides
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
The surface morphology of CuNi/GO-II showed no such difference in the particle size, the size of CuNioxide was found to be quite uniform (Fig. 3a–c)

Summary

Introduction

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. 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. Number of cost-effective Cu and Ni mediated catalytic system are developed, to the best of our knowledge, there is no efficient and stable non-noble metals based heterogeneous catalyst reported for the cyanation reaction to date. Nanostructured transition metals (such as Cu, Ni, Ag, Au, Pd and Pt) supported graphene nanocomposites have found to be highly efficient candidates for a number of industrially important catalytic processes[14,15].

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