Mechanistic Insights into the Formation of Dodecanethiolate-Stabilized Magnetic Iridium Nanoparticles: Thiosulfate vs Thiol Ligands (vol 118, pg 14548, 2014)
JOURNAL OF PHYSICAL CHEMISTRY C(2014)
摘要
The synthesis of stable and isolable iridium nanopartides with an average core size of similar to 1.2 +/- 0.3 nm was achieved by employing sodium S-dodecylthiosulfate as a ligand precursor during the modified Brust-Schiffrin reaction. Transmission electron microscopy (TEM) of the isolated Ir nanopartides revealed a high degree of monodispersity. Further characterizations with H-1 NMR, FT-IR, UV-vis spectroscopy, thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) confirmed that the synthesized Ir nanopartides are stabilized by dodecanethiolate ligands produced upon the adsorption/cleavage of S-dodecylthiosulfate on the growing Ir nanoparticle surface. By comparison, synthetic attempts employing dodecanethiol as a stabilizing ligand led to the formation of Ir-thiolate species (Ir(SR)(3)) as an intermediate and Ir-hydroxide species at the completion of reaction. Mechanistic investigations of these two reactions using S-dodecylthiosulfate and dodecanethiol provided deeper understandings on the novelty of thiosulfate ligands, which allow the successful formation of stable thiolate-capped Ir nanopartides. Moreover, these Ir nanopartides were shown to have strong magnetic properties.
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