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Ni/Pd core/shell nanoparticles supported on graphene as a highly active and reusable catalyst for Suzuki-Miyaura cross-coupling reaction |
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| Authors: | Önder Metin Sally Fae Ho Cemalettin Alp Hasan Can Max N Mankin Mehmet Serdar Gültekin Miaofang Chi Shouheng Sun | |
| Affiliation: | 1. Department of Chemistry, Brown University, Providence, Rhode Island, 02912, USA 2. Department of Chemistry, Faculty of Science, Atatürk University, 25240, Erzurum, Turkey 4. ?ay?rl? Vocational School, Erzincan University, Erzincan, Turkey 3. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, 37831, USA |
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| Abstract: | 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 °C. The G-Ni/Pd was also stable and reusable, providing 98% conversion after the 5th 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.  | |
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