Paul-Henri Haumesser

Ruthenium Nanoparticles in Ionic Liquids – A Saga

Ionic liquids (ILs) are excellent media for the generation and stabilisation of metallic nanoparticles (NPs). Their ionic character coupled with 3-D structural pre-organisation in the liquid state, serves to direct the growth of transition metal NPs generated in situ, and to subsequently protect and stabilise them. Until now, many different NPs have been successfully synthesised within these media, however much attention has been paid to Ru-NPs. These have been prepared with small sizes and narrow size distributions by reduction of organometallic compounds with molecular hydrogen as well as decomposition of transition-metal complexes in the zero-valent state. These stable Ru-NPs immobilised in the ILs have proven to be efficient green catalysts for several reactions in multiphase conditions, including important energy-related processes such as biomass refinement. Furthermore, they present potential novel materials for use in the production of smarter electronic devices. In this review, the synthesis, stabilisation and size-control of Ru-NPs via various methods in different ILs is discussed, followed by their varied application in catalysis and potential in new fields.

Impact of Surface Chemistry on Copper Deposition in Mesoporous Silicon

An easy, efficient, and safe process is developed to metallize mesoporous silicon (PSi) with Cu from the decomposition of a solution of mesitylcopper (CuMes) in an imidazolium-based ionic liquid (IL), [C1C4Im][NTf2]. The impregnation of a solution of CuMes in IL affords the deposition of metallic islands not only on the surface but also deep within the pores of a mesoporous Si layer with small pores below 10 nm. Therefore, this process is well suited to efficiently and completely metallize PSi layers. An in-depth mechanistic study shows that metal deposition is due to the reduction of CuMes by surface silane groups rather than by Si oxidation as observed in aqueous or water-containing media. This could open a new route to the chemical metallization of PSi by less-noble metals difficult to attain by a conventional displacement reaction.

Magnetic, Structural, and Chemical Properties of Cobalt Nanoparticles Synthesized in Ionic Liquids

Cobalt nanoparticles (CoNPs) exhibit quite unique magnetic, catalytic, and optical properties. In this work, imidazolium-based ionic liquids (ILs) are successfully used to elaborate magnetically responsive suspensions of quite monodisperse CoNPs with diameters below 5 nm. The as-synthesized CoNPs adopt the noncompact and metastable structure of ϵ-Co that progressively evolves at room temperature toward the stable hexagonal close-packed allotrope of Co. Accordingly, magnetization curves are consistent with zero-valent Co. As expected in this size range, the CoNPs are superparamagnetic at room temperature. Their blocking temperature is found to depend on the size of the IL cation. The CoNPs produced in an IL with a large cation exhibit a very high anisotropy, attributed to an enhanced dipolar coupling of the NPs, even though a larger interparticle distance is observed in this IL. Finally, the presence of surface hydrides on the CoNPs is assessed and paves the way toward the synthesis for Co-based bimetallic NPs.

An Efficient, Versatile, and Safe Access to Supported Metallic Nanoparticles on Porous Silicon with Ionic Liquids.

The metallization of porous silicon (PSi) is generally realized through physical vapor deposition (PVD) or electrochemical processes using aqueous solutions. The former uses a strong vacuum and does not allow for a conformal deposition into the pores. In the latter, the water used as solvent causes oxidation of the silicon during the reduction of the salt precursors. Moreover, as PSi is hydrophobic, the metal penetration into the pores is restricted to the near-surface region. Using a solution of organometallic (OM) precursors in ionic liquid (IL), we have developed an easy and efficient way to fully metallize the pores throughout the several-µm-thick porous Si. This process affords supported metallic nanoparticles characterized by a narrow size distribution. This process is demonstrated for different metals (Pt, Pd, Cu, and Ru) and can probably be extended to other metals. Moreover, as no reducing agent is necessary (the decomposition in an argon atmosphere at 50 °C is fostered by surface silicon hydride groups borne by PSi), the safety and the cost of the process are improved.