, Volume 56, Issue 13-14, pp 1228-1238
Date: 20 Jun 2013

Screening of Soluble Rhodium Nanoparticles as Precursor for Highly Active Hydrogenation Catalysts: The Effect of the Stabilizing Agents

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Abstract

We report the preparation of rhodium nanoparticles (NPs) stabilized by 1-octadecanethiol (ODT), polyvinyl alcohol (PVA), and tetraoctylammonium bromide (TOAB), and their application for hydrogenation catalysis. The three metal–ligand systems correspond to different mechanism of NPs stabilization via strong covalent linkage, chemisorbed atoms and electrostatic interactions, respectively. We found a strong effect of the interaction between the stabilizer and the surface of the metal nanoparticle on the catalytic activity. The Rh NPs were studied as soluble nanoparticle catalysts and as precursors for the synthesis of supported catalysts. All catalysts were tested in the hydrogenation of cyclohexene under similar conditions as a model reaction. Generally, RhODT NPs were inactive, RhPVA NPs exhibited distinct activities in solution (aqueous biphasic catalysis) and as a supported catalyst, and RhTOAB NPs exhibited similar activities in solution and after immobilization. This last result opens the opportunity for the preparation of highly active Rh NP catalysts both in solution and as a heterogeneous catalyst. Additionally, the stability of the nanoparticles depends on the choice of ligand and on the functionalization of the support surface before immobilization. By optimizing the catalyst synthesis and reaction conditions, turnover frequencies as high as 700,000 h−1 where observed for stable and recyclable catalyst.