Effect of Ionic Liquid Impurities on the Synthesis of Silver Nanoparticles

Imidazolium-based ionic liquids have been widely utilized as versatile solvents for metal nanoparticle synthesis; however, reactions to synthesize silver nanoparticles that are performed identically in different commercially obtained lots of 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF₄) give divergent results. This suggests that impurities in these nominally identical solvents play an important role in the resulting silver nanoparticle quality. To test the effect that impurities have on the quality of silver nanoparticles synthesized in BMIM-BF₄, silver nanoparticles were synthesized in carefully prepared and purified BMIM-BF₄ and compared against silver nanoparticles that were synthesized in the purified BMIM-BF₄ that had been spiked with trace amounts of water, chloride, and 1-methylimidazole. It was clearly demonstrated that trace amounts of these common ionic liquid impurities cause significant deviation in size and shape (creating polydisperse and irregularly shaped ensembles of both large and small particles), and also negatively impact the stabilization of the resulting silver nanoparticles

Two-Phase Microfluidic Droplet Flows of Ionic Liquids for the Synthesis of Gold and Silver Nanoparticles

Droplet-based microfluidic platforms have the potential to provide superior control over mixing as compared to traditional batch reactions. Ionic liquids have advantageous properties for metal nanoparticle synthesis as a result of their low interfacial tension and complexing ability; however, droplet formation of ionic liquids within microfluidic channels in a two-phase system has not yet been attained because of their complex interfacial properties and high viscosities. Here, breakup of an imidazolium-based ionic liquid into droplets in a simple two-phase system has for the first time been achieved and characterized by using a microchannel modified with a thin film fluoropolymer. This microfluidic/ionic liquid droplet system was used to produce small, spherical gold (4.28 ± 0.84 nm) and silver (3.73 ± 0.77 nm) nanoparticles

Chalcogenol Ligand Toolbox for CdSe Nanocrystals and Their Influence on Exciton Relaxation Pathways

We have employed a simple modular approach to install small chalcogenol ligands on the surface of CdSe nanocrystals. This versatile modification strategy provides access to thiol, selenol, and tellurol ligand sets <i>via</i> the <i>in situ</i> reduction of R₂E₂ (R = ^<i>t</i>Bu, Bn, Ph; E = S, Se, Te) by diphenylphosphine (Ph₂PH). The ligand exchange chemistry was analyzed by solution NMR spectroscopy, which reveals that reduction of the R₂E₂ precursors by Ph₂PH directly yields active chalcogenol ligands that subsequently bind to the surface of the CdSe nanocrystals. Thermogravimetric analysis, FT-IR spectroscopy, and energy dispersive X-ray spectroscopy provide further evidence for chalcogenol addition to the CdSe surface with a concomitant reduction in overall organic content from the displacement of native ligands. Time-resolved and low temperature photoluminescence measurements showed that all of the phenylchalcogenol ligands rapidly quench the photoluminescence by hole localization onto the ligand. Selenol and tellurol ligands exhibit a larger driving force for hole transfer than thiol ligands and therefore quench the photoluminescence more efficiently. The hole transfer process could lead to engineering long-lived, partially separated excited states