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Organometallic Ruthenium Nanoparticles and Catalysis

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Ruthenium in Catalysis

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 48))

Abstract

Due to a high number of possible applications in various domains, metal nanoparticles are nowadays the subject of an extensive development. This interest in metal nanoparticles is related to their electronic properties at the frontier between those of molecular species and bulk compounds which are induced by their nanometric size. Regarding the field of catalysis, the growing attention for metal nanoparticles also results from the high proportion of surface atoms present in the upper layer of the metallic core which gives rise to numerous potential active sites. Thus, nanocatalysis (which involves the use of catalysts with at least one dimension at the nanoscale) has emerged in the field of modern catalysis as a domain on the borderline between homogeneous and heterogeneous catalysis. Present developments aim at multifunctionality which can be achieved by the proper design of complex nanostructures also named nanohybrids. In nanohybrid the term “hybrid” refers to the appropriate association between a metal core and a stabilizing shell such as a polymer, a ligand, an ionic liquid, or even a support (inorganic materials, carbon black, carbon nanotubes, etc.…). This association can be considered as crucial to tune the surface properties of nanostructures and consequently their catalytic performance. The main expectation for the scientific community is that precisely designed nanoparticles (in terms of size, shape, and composition including surface ligands) should offer the benefits of both homogeneous and heterogeneous catalysts, namely high efficiency and better selectivity.

In that context, we have been developing an efficient and versatile synthesis method using common tools from organometallic chemistry to produce well-controlled nanostructures which have been proved to be of interest for application in catalysis. A high number of studies have been focused on ruthenium nanosystems due to the use of a very convenient organometallic precursor, namely [Ru(COD)(COT)], as the metal source. This Ru complex is easily decomposed under dihydrogen atmosphere at room temperature. In addition, it is a complex of choice to prepare “naked” ruthenium nanostructures since the olefinic ligands present in the coordination sphere of ruthenium are hydrogenated into alkanes which exhibit no interaction with the metal surface. As a consequence, the metallic surface of the obtained nanoparticles is only covered by hydrides and the stabilizer which was deliberately added. This is highly convenient for studying the influence of the stabilizer on the morphology of the nanoparticles as well as their surface chemistry and related catalytic performance.

This chapter gives an overview of our experience in the preparation of ruthenium nanoparticles of controlled size and surface state. Insights are given on the study of their surface chemistry by using simple techniques, mainly IR and NMR, both in solution and in solid state, as well as model hydrogenation reactions. We also discuss the performances of the Ru nanoparticles in catalysis which have been investigated both in solution (in organic or aqueous phases) and after their deposition on a support (alumina, silica, or carbon supports).

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Acknowledgments

All our collaborators are greatly acknowledged for their fruitful contributions. We also thank CNRS, University Paul Sabatier at Toulouse University, Institut des Sciences Appliquées at Toulouse (INSA), the Midi-Pyrénées region (including CTP program), ANR (SIDERUS-ANR-08-BLAN-0010-03; SUPRANANO-ANR-09-BLAN-0194), ANR-DFG (MOCA-NANO-ANR-11-INTB-1011 and DFG-911/19-1), INTERREG SUDOE (TRAIN 2 project), EU (ARTIZYMES STREP-FP6-2003-NEST-B3-0151471; SYNFLOW FP7-NMP2-Large program 2010–246461; NANOSONWINGS ERC Advanced Grant-2009-246763), CAPES-COFECUB, CONACyt, ANRT and Sasol for financial supports.

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Authors and Affiliations

  1. Laboratoire de Chimie de Coordination, CNRS, LCC, 205 Route de Narbonne, 31077, Toulouse, France

    Karine Philippot & Pascal Lignier

  2. Université de Toulouse, UPS, INPT, LCC, 31077, Toulouse, France

    Karine Philippot & Pascal Lignier

  3. Laboratoire de Physique et Chimie des Nano-Objets (LPCNO), UMR5215 INSA-CNRS-UPS, Institut des Sciences appliquées, 135, Avenue de Rangueil, 31077, Toulouse, France

    Bruno Chaudret

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  1. Karine Philippot
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Correspondence to Karine Philippot .

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  1. Inst. des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université Rennes1, Rennes, France

    Pierre H. Dixneuf

  2. Inst. des Sciences Chimiques de Rennes, UMR 6226-CNRS-Université de Rennes1, Rennes, France

    Christian Bruneau

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Philippot, K., Lignier, P., Chaudret, B. (2014). Organometallic Ruthenium Nanoparticles and Catalysis. In: Dixneuf, P., Bruneau, C. (eds) Ruthenium in Catalysis. Topics in Organometallic Chemistry, vol 48. Springer, Cham. https://doi.org/10.1007/3418_2014_83

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