The Role of Tris(2-carboxyethyl)phosphine Reducing Agent in the Controlled Formation of α,ω-Alkanedithiols Monolayers on Au(111) with Monocoordinated and Bicoordinated Configurations.

The addition of the reducing agent tris(2-carboxyethyl) phosphine (TCEP) during the formation of α,ω-alkanedithiols monolayers on Au(111) using the immersion method produces the assembly of monolayers with bicoordinated molecules (both S-terminal groups bound to the surface) that have a reductive desorption potential that is more positive than for monolayers with monocoordinated molecules in a standing up configuration. We show that the use of TCEP either during formation of the monolayer or as a post treatment procedure allows the controlled formation of monolayers with bicoordinated or monocoordinated configurations. Density functional theory (DFT) calculations were performed to elucidate the role of TCEP in the formation of the bicoordinated configuration. We investigated the TCEP-dithiol interaction in ethanol solvent as well as the coadsorption of trimethylphosphine with 1,2-ethanedithiol on Au(111). The Brønsted base character of the phosphine facilitates the H exchange from the -SH groups of the dithiol to the phosphorus atom of TCEP with very low activation energy barriers, thus allowing the thiolate groups to bind to the Au(111) surface, thus yielding the bicoordinated configuration. Dithiol lifting mechanisms such as H exchange between S atoms and the formation of intra/inter layer disulfide bonds have much higher energy barriers.

One-step/one-pot decoration of oxide microparticles with silver nanoparticles.

HYPOTHESIS: Heterogeneous nucleation of silver oxide (Ag2O) onto oxide microparticles (OMPs) followed by spontaneous thermal decomposition produce nanostructures made of OMPs decorated with silver nanoparticles (OMP|AgNPs). EXPERIMENTS: Colloidal chemistry methods have been used to produce the decoration of OMPs with silver nanoparticles (AgNPs), by carrying out the Ag2O precipitation/thermal decomposition. The process is driven in water enriched acetone medium containing NaOH, NH3, AgNO3 and SiO2MPs as substrate. Optical and morphological properties of OMP|AgNPs were characterized by using STEM, EDS, HRTEM and Raman spectroscopy. FINDINGS: A new synthetic method to decorate OMPs (TiO2, SiO2) with metallic AgNPs in a single step/single pot reaction is proven effective to produce OMP|AgNPs either in aqueous or water enriched media.