Direct synthesis of mesoporous silica containing cobalt: A new strategy using a cobalt soap as a co-template

A novel approach to incorporate transition metals into porous structures is presented, which makes use of a cobalt soap in combination with the templating agent C16TMABr. An ordered mesoporous silica MCM-41 type material doped with Co is obtained after removal of the organic part by calcination. The a unit cell parameter of the cobalt containing mesoporous matrices is larger than that of pure MCM-41 and increases with the amount of cobalt present in the sample as well as the diameter of the pores. This is not observed when e.g. cobalt acetate is employed instead of the metal soap. The procedure presented establishes a new route for the incorporation of a transition metal into MCM-41 together with a tuning of the porous structure

On the nature of metallic nanoparticles obtained from molecular Co3Ru–carbonyl clusters in mesoporous silica matrices

We report on the impregnation of THF solutions of the low-valent heterometallic cluster NEt4[Co3Ru(CO)12] into two mesoporous silica matrices, amorphous xerogels and ordered MCM-41, and a study of its thermal decomposition into metallic nanoparticles by X-ray diffraction, transmission electron microscopy and in situ magnetic measurements under controlled atmospheres. The decomposition of the cluster was monitored as a function of temperature by examining the chemical composition of the particles, their size distributions and their structures as well as their magnetic properties. Treatment under inert atmosphere (i.e. argon) at temperatures below 200 °C resulted in the formation of segregated spherical particles of hcp-ruthenium (2.3 ± 1.0 nm) and hcp-cobalt (3.1 ± 0.9 nm). The latter is transformed to fcc-cobalt (3.2 ± 1.0 nm) above 270 °C. At higher temperatures, Co–Ru alloying takes place and the Ru content of the particles increases with increasing temperature to reach the nominal composition of the molecular precursor, Co3Ru. The particles are more evenly distributed in the MCM-41 framework compared to the disordered xerogel and also show a narrower size distribution. Owing to the different magnetic anisotropy of hcp- and fcc-cobalt, which results in different blocking temperatures, we were able to clearly identify the products formed at the early stages of the thermal decomposition procedure