Ni/Pd core/shell nanoparticles supported on graphene as a highly active and reusable catalyst for Suzuki-Miyaura cross-coupling reaction

Metin O., Ho S. F. , ALP C., CAN H., Mankin M. N. , GÜLTEKİN M. S. , ...More

NANO RESEARCH, vol.6, no.1, pp.10-18, 2013 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 6 Issue: 1
  • Publication Date: 2013
  • Doi Number: 10.1007/s12274-012-0276-4
  • Journal Name: NANO RESEARCH
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.10-18
  • Erzincan Binali Yildirim University Affiliated: Yes


Monodisperse Ni/Pd core/shell nanoparticles (NPs) have been synthesized by sequential reduction of nickel(II) acetate and palladium(II) bromide in oleylamine (OAm) and trioctylphosphine (TOP). The Ni/Pd NPs have a narrow size distribution with a mean particle size of 10 nm and a standard deviation of 5% with respect to the particle diameter. Mechanistic studies showed that the presence of TOP was essential to control the reductive decomposition of Ni-TOP and Pd-TOP, and the formation of Ni/Pd core/shell NPs. Using the current synthetic protocol, the composition of the Ni/Pd within the core/shell structure can be readily tuned by simply controlling the initial molar ratio of the Ni and Pd salts. The as-synthesized Ni/Pd core/shell NPs were supported on graphene (G) and used as catalyst in Suzuki-Miyaura cross-coupling reactions. Among three different kinds of Ni/Pd NPs tested, the Ni/Pd (Ni/Pd = 3/2) NPs were found to be the most active catalyst for the Suzuki-Miyaura cross-coupling of arylboronic acids with aryl iodides, bromides and even chlorides in a dimethylformamide/water mixture by using K2CO3 as a base at 110 A degrees C. The G-Ni/Pd was also stable and reusable, providing 98% conversion after the 5(th) catalytic run without showing any noticeable Ni/Pd composition change. The G-Ni/Pd structure reported in this paper combines both the efficiency of a homogeneous catalyst and the durability of a heterogeneous catalyst, and is promising catalyst candidate for various Pd-based catalytic applications.