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Gold Nanoparticles with Different Capping Systems: An Electronic and Structural XAS Analysis

AuthorsLópez-Cartes, C.; Rojas, T. Cristina; Litrán-Ramos, Rocío; Martínez-Martínez, D. ; Martínez de la Fuente, Jesús; Penadés, Soledad; Fernández-Camacho, A.
X-ray absortion spectroscopy
Issue Date5-Apr-2005
PublisherAmerican Chemical Society
CitationJournal of Physical Chemistry B 109(18): 8761-8766 (2005)
AbstractGold nanoparticles (NPs) have been prepared with three different capping systems: a tetralkylammonium salt, an alkanethiol, and a thiol-derivatized neoglycoconjugate. Also gold NPs supported on a porous TiO(2) substrate have been investigated. X-ray absorption spectroscopy (XAS) has been used to determine the electronic behavior of the different capped/supported systems regarding the electron/hole density of d states. Surface and size effects, as well as the role of the microstructure, have been also studied through an exhaustive analysis of the EXAFS (extended X-ray absorption fine structure) data. Very small gold NPs functionalized with thiol-derivatized molecules show an increase in d-hole density at the gold site due to Au-S charge transfer. This effect is overcoming size effects (which lead to a slightly increase of the d-electron density) for high S:Au atomic ratios and core-shell microstructures where an atomically abrupt Au-S interface likely does not exist. It has been also shown that thiol functionalization of very small gold NPs is introducing a strong distortion as compared to fcc order. To the contrary, electron transfer from reduced support oxides to gold NPs can produce a higher increase in d-electron density at the gold site, as compared to naked gold clusters.
Description6 páginas, 6 figuras, 2 tablas, 1 esquema.
Publisher version (URL)http://dx.doi.org/10.1021/jp050184+
Appears in Collections:(ICMS) Artículos
(IIQ) Artículos
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