Abstract
The controlled elaboration of nanostructured chalcogenides with high specific area or functionalized surface is an interesting challenge. Breakthrough in various domains such as catalysis, gas separation, electrochemistry, photovoltaics or optics can be achieved by the production of chalcogenide materials with functionalized surface or high specific area coupled with high polarisability.The aim of the thesis was to develop new soft chemistry routes for the synthesis of germanium disulfide at room temperature and pressure. Two sulfur precursors, i.e. hydrogen sulfide (H2S) and thioacetamide, and a germanium precursor, the tetraethoxigermanium were used for the syntheses. The syntheses were carried out either in the presence or in the absence of a template, in most case an ionic liquid (IL).Syntheses without templating agent led to amorphous or nano-organized GeS2 nanoparticles of 20 to 35 nm in diameter and interesting specific areas (320 m2.g-1 with H2S, 270 m2.g-1 with thioacetamide). Hybrid materials comprising GeS2 and LI cation with a general formula 0.2GeS2-0.8 organic cation were obtained in the presence of IL. The obtained particles of nanometric sizes and with hardly any specific area have a morphology that depends on the nature of the organic cation present during the synthesis, i .e. spheres or gypsum rosette-like particles. XPS measurements indicate the presence of Ge-S- bonds in the hybrid material. The use of lithium de bis(trifluorométhanesulfonyl)imide led to the elaboration of a GeS2-Li material which conductivity of ~10-10 S.cm-1 is that of an ionic salt.A first iono-chalcogel which could lead after optimization to a porous chalcogenide has been elaborated when using the IL as both the solvent and the templating agent and in the absence of any other solvent. The use of hexadecilamine (HDA) above its critical micellar concentration, led to hybrid nanoparticles of 15 nm in size with interesting specific area (130 m2.g-1) but also intra-granular porosity.In conclusion, this exploratory work led to the elaboration of GeS2 either as naoparticles with high specific area or particles with intragranular porosity or finally hybrid materials with GeS2 interacting with an organic cation, the final product depending upon the chosen soft chemistry route.Keywords: chalcogenide, ionic liquid, organic-inorganic hybrid, morphology, soft chemistry