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 ℃. 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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Monodisperse Ni nanoparticles (NPs) have been synthesized by the reduction of nickel(Ⅱ) acetylacetonate with the borane-tributylamine complex in a mixture of oleylamine and oleic acid. These Ni NPs are an active catalyst for the hydrolysis of the ammonia-borane (AB, H3N·BH3) complex under ambient conditions and their activities are dependent on the chemical nature of the oxide support that they were deposited on. Among various oxides (SiO2, Al2O3, and CeO2) tested, SiO2 was found to enhance Ni NP catalytic activity due to the etching of the 3.2 nm Ni NPs giving Ni(Ⅱ) ions and the subsequent reduction of Ni(Ⅱ) that led to the formation of 1.6 nm Ni NPs on the SiO2 surface. The kinetics of the hydrolysis of AB catalyzed by Ni/SiO2 was shown to be dependent on catalyst and substrate concentration as well as temperature. The Ni/SiO2 catalyst has a turnover frequency (TOF) of 13.2 mol H2·(mol Ni)-1·min-1—the best ever reported for the hydrolysis of AB using a nickel catalyst, an activation energy of 34 kJ/mol ± 2 kJ/mol and a total turnover number of 15, 400 in the hydrolysis of AB. It is a promising candidate to replace noble metals for catalyzing AB hydrolysis and for hydrogen generation under ambient conditions.
We report the synthesis of high magnetic moment CoFe nanoparticles via the diffusion of Co and Fe in core/shell structured Co/Fe nanoparticles. In an organic solution, Co nanoparticles were coated with a layer of Fe to form a Co/Fe core/shell structure. Further raising the solution temperature led to inter-diffusion of Co and Fe and formation of CoFe alloy nanoparticles. These nanoparticles have high saturation magnetization of up to 192 emu/g CoFe and can be further stabilized by thermal annealing at 600 ℃.
Monodisperse Au nanoparticles (NPs) have been synthesized at room temperature via a burst nucleation of Au upon injection of the reducing agent t-butylamine-borane complex into a 1, 2, 3, 4-tetrahydronaphthalene solution of HAuCl4·3H2O in the presence of oleylamine. The as-synthesized Au NPs show size-dependent surface plasmonic properties between 520 and 530 nm. They adopt an icosahedral shape and are polycrystalline with multiple-twinned structures. When deposited on a graphitized porous carbon support, the NPs are highly active for CO oxidation, showing 100% CO conversion at −45 ℃.