ABSTRACT
In this study, we investigated hollow AgAu nanoparticles with the goal of improving our understanding of the composition-dependent catalytic activity of these nanoparticles. AgAu nanoparticles were synthesized via the galvanic replacement method with controlled size and nanoparticle compositions. We studied extinction spectra with UV-Vis spectroscopy and simulations based on Mie theory and the boundary element method, and ultrafast spectroscopy measurements to characterize decay constants and the overall energy transfer dynamics as a function of AgAu composition. Electron-phonon coupling times for each composition were obtained from pump-power dependent pump-probe transients. These spectroscopic studies showed how nanoscale surface segregation, hollow interiors and porosity affect the surface plasmon resonance wavelength and fundamental electron-phonon coupling times. Analysis of the spectroscopic data was used to correlate electron-phonon coupling times to AgAu composition, and thus to surface segregation and catalytic activity. We have performed all-atom molecular dynamics simulations of model hollow AgAu core-shell nanoparticles to characterize nanoparticle stability and equilibrium structures, besides providing atomic level views of nanoparticle surface segregation. Overall, the basic atomistic and electron-lattice dynamics of core-shell AgAu nanoparticles characterized here thus aid the mechanistic understanding and performance optimization of AgAu nanoparticle catalysts.
ABSTRACT
The use of a model based on Langmuir's isotherm to evaluate the metal associated with separate geochemical phases of a sediment is proposed and its validity tested with sediments of certified composition. The model takes into account a standard procedure for a certified reference material (CRM601), which defines, experimentally, a set of sequential extractions that divide the sediment into four operational fractions. The derived equations allow the treatment of data from sediment of Flumendosa Lake, Italy, and certified material CRM601 and also allow the computation of corrected concentrations, i.e., the metal affinities for each fraction. Experimental values for Ni show its low sensitivity and an equal distribution among different phases, which suggests a similar adsorption mechanism in all cases. In the case of Cd, the corrected concentration in the Fe/Mn oxide phase is nine times higher than for the residual fraction. For sediment of the Bèsos River, Spain, results show the percentage distribution of Ni over different fractions. Affinity values for Ni on a Flumendosa Lake sediment have also been calculated. The present model is simple to apply and shows satisfactory agreement with experimental data.
