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C. R.

Chimie 6 (2003) 1019–1034

Nanoparticles

Organometallic approach to the synthesis and surface reactivity


of noble metal nanoparticles
Karine Philippot, Bruno Chaudret *
Laboratoire de chimie de coordination du CNRS, 205, route de Narbonne, 31077 Toulouse cedex 04, France

Received 25 April 2003; accepted 22 July 2003

Abstract

The use of organometallic precursors allows the synthesis in mild conditions of nanoparticles of uniform small size (1–3 nm)
and of clean surface, which can be stabilized by polymers or ligands. These nano-objects display an interesting surface chemistry
comparable to that of molecular species. This involves classical elementary steps of organometallic chemistry such as
substitution and oxidative addition as well as ligand fluxionality. An overview of recent work in this field from our group will be
presented including stabilization of metal nanoparticles by asymmetric ligands and preliminary catalytic attempts. To cite this
article: K. Philippot, B. Chaudret, C. R. Chimie 6 (2003).
© 2003 Académie des sciences. Published by Éditions scientifiques et médicales Elsevier SAS. All rights reserved.

1. Introduction methods to produce in solution particles of either pure


metal or metal oxides, and more generally chalco-
The recent period has evidenced an ever-increasing genides have been reported in the literature since then
interest for chemical species of nanometric size [1]. [1]. These species have recently attracted a renewed
This size corresponds to proteins, to organic macro- interest, mainly because of their real or expected physi-
molecules such as polymers or dendrimers or to rela- cal properties resulting from their ‘quantum size’. This
tively small molecules which self-organize into differ- concerns the fields of optics, magnetism and electron-
ent sorts of objects such as micelles or vesicles. ics [5]. Nevertheless, the recent renewed interest in the
Inorganic molecular clusters [2] may also reach this properties of these objects has evidenced the need for
size and display interesting physical properties [3]. the control of the particles monodispersity, of their
Compared to this new approach of nanometric com- size, their shape, their organization and the nature of
pounds, the inorganic particles in solution (colloids) the chemical species present at their surface. In this
may appear as outdated species. In fact, coloured solu- respect, the well-known reduction methods [6] display
tions of noble metal, essentially gold, have been known limitations due to their lack of variability. The use of
for ages and the first rational synthesis of gold colloids reverse micelles as ‘nanoreactors’ inside which salt
has been described by Faraday in 1857 [4]. Many reduction and particle growth occurs has allowed to
obtain monodisperse nano-objects which may display
a define shape (spheres, rods, wires...) and which may
* Corresponding author.
E-mail address: chaudret@lcc-toulouse.fr (B. Chaudret). self-assemble on various substrates [7]. In these pro-

© 2003 Académie des sciences. Published by Éditions scientifiques et médicales Elsevier SAS. All rights reserved.
doi:10.1016/j.crci.2003.07.010
K. Philippot, B. Chaudret / C. R. Chimie 6 (2003) 1019–1034 1031

Scheme 3. Colloids synthesis with ligand structures.

Fig. 22. TEM micrographs of oxazoline stabilised platinum particles showing the platinum nanowires and their assemblies in bundles (the inset
of (a) is presented at a higher magnification in (b)).

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