Synthesis, characterization and chemistry of platinum and iridium nanoparticles in solution and nanoporous silicas.

摘要

This project focuses on the synthesis of catalytically-active, transition-metal nanoparticles, their adsorption into porous Vycor glass (PVG), the removal of the poly(vinylpyrrolidone) (PVP) surfactant employed in their synthesis and their chemistry with Ru(II) diimine complexes. Platinum and iridium nanoparticles with a narrow size distribution were prepared by the alcohol reduction method with poly(vinylpyrrolidone) (PVP) as the size limiting surfactant. PVP/Pt nanoparticles adsorb into PVG and as much as 46 ± 4% of the PVP can be removed without further nanoparticle aggregation. XANES spectra show that removal of the PVP surfactant occurs without oxidation of the Pt nanoparticle. EXAFS of the adsorbed Pt nanoparticles after removal of the PVP yield a Pt-Pt bond length of 2.74 ± 0.01 Å which is slightly shorter than the Pt-Pt bond length measured in Pt foil, 2.78 Å. We have shown that the Pt nanoparticles, both the stripped and the unstripped of PVP in porous Vycor glass, does not influence their reactivity with either the [Ru(bpy)2 dpp]2+ or the [Ru(bpy)2ppz]2+ complexes.;The addition of PVP/Pt or PVP/Ir nanoparticles to aqueous-ethanol solutions of [Ru(bpy)2ppz]2+ (ppz denotes 4,7-phenanthro-lino-5:6,5'6'pyrazine) leads to the spontaneous aggregation of the nanoparticles about the complex. A comparison of the aggregation about different Ru(II) diimines indicates aggregation initiates at the heteroleptic ligand. Although initiating at the ppz ligand, continued aggregation of the nanoparticles about the complex dilutes the specificity of the initial interaction leading to larger aggregates of differing shape. TEM analyses of the aggregates indicate the volume occupied by the individual nanoparticles is a small fraction of the total volume of the aggregate suggesting a somewhat open structure interlaced with the solvent. Correlating TEM analyses of the aggregation with the electronic spectra of the solutions reveals a new absorption assigned to the formation of the [Ru(bpy)2(ppz)2+-PVP/Pt] and [Ru(bpy) 2(ppz)2+-PVP/Ir] aggregates. Analysis of the latter absorption as a function of the concentration of PVP/Pt nanoparticles indicates step-wise formation of the [Ru(bpy)2(ppz)2+-PVP/Pt] aggregates. Consistent with the self-assembly of the aggregates, intensity and lifetime quenching of the complex by the PVP/Pt nanoparticles shows that ≥ 80% of the quenching occurs by a static mechanism, i.e., the self-assembly of the [Ru(bpy)2(ppz)2+-PVP/Pt] aggregates.