Issue 6, 2007
From the journal:

Physical Chemistry Chemical Physics

Electronic properties of Ag nanoparticle arrays. A Kelvin probe and high resolution XPS study†

Mathias Schnippering,a   Michel Carrara,ab   Annette Foelske,c   Rüdiger Kötzc  and  David J. Fermín*ab  

* Corresponding authors

a Departement für Chemie und Biochemie, Universität Bern, Freiestrasse 3, Bern, Switzerland
E-mail: david.fermin@iac.unibe.ch
Fax: +41 31631 3994
Tel: +41 31631 4317

b Laboratoire d’Electrochimie Physique et Analytique, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, Lausanne, Switzerland

c Electrochemistry Laboratory, Paul Scherrer Institute, Villigen PSI, Switzerland

Abstract

The electronic properties of citrate stabilised Ag nanoparticles with sizes ranging from 4 to 35 nm were investigated by the Kelvin probe method and high resolution XPS. Two and three dimensional assemblies of the particles were prepared by electrostatic adsorption from aqueous solution onto poly-L-lysine modified surfaces. The work function of the Ag particles increased from 5.29 ± 0.05 to 5.53 ± 0.05 eV as the particle size decreased. These values are approximately 0.8 eV higher than for clean polycrystalline Ag surfaces. The origin of these remarkable high work functions cannot be explained in terms of either citrate induced changes in the surface dipole or image forces in the confined metallic domains. High resolution XPS spectra of the Ag 3d5/2 core level were characterised by broad bands and a 0.4 eV shift towards lower binding energies for the smallest particles. Comparisons with reported studies on extended Ag surfaces indicate that as-grown particles exhibit partially oxidised surfaces. The behaviour of the work function further suggests that the strength of the Ag–O bonding increases with decreasing particle sizes. These findings are highly relevant to the interpretation of the catalytic properties of Ag nanoparticles.

Graphical abstract: Electronic properties of Ag nanoparticle arrays. A Kelvin probe and high resolution XPS study

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Article information

DOI
https://doi.org/10.1039/B611496B
Article type
Paper
Submitted
09 Aug 2006
Accepted
27 Nov 2006
First published
15 Dec 2006

Phys. Chem. Chem. Phys., 2007,9, 725-730

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Electronic properties of Ag nanoparticle arrays. A Kelvin probe and high resolution XPS study

M. Schnippering, M. Carrara, A. Foelske, R. Kötz and D. J. Fermín, Phys. Chem. Chem. Phys., 2007, 9, 725 DOI: 10.1039/B611496B

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