New insights into the chemistry of thiolate-protected palladium nanoparticles

Authors

Gaston Corthey, National University Of La Plata -Conicet
Aldo Rubert, National University Of La Plata-Conicet
A. Lorena Picone, National University Of La Plata-Conicet
Gilberto Casillas, University of Texas at SanAntonioFollow
Lisandro J. Giovanetti, National University Of La Plata-Conicet
Jose M. Ramallo-Lopez, National University Of La Plata-Conicet
Eugenia Zelaya, National Atomic Energy Commission Conicet
Guillermo A. Benitez, National University Of La Plata-Conicet
Felix Requejo, National University Of La Plata-Conicet
Miguel Jose-Yacaman, University of Texas at San Antonio
Roberto Salvarezza, National University Of La Plata-Conicet
Mariano H. Fonticelli, National University Of La Plata-Conicet

RIS ID

81298

Publication Details

Corthey, G., Rubert, A. A., Picone, A. L., Casillas, G., Giovanetti, L. J., Ramallo-Lopez, J. M., Zelaya, E., Benitez, G. A., Requejo, F. G., Jose-Yacaman, M., Salvarezza, R. C. & Fonticelli, M. H. (2012). New insights into the chemistry of thiolate-protected palladium nanoparticles. The Journal of Physical Chemistry C, 116 (17), 9830-9837.

Abstract

This paper establishes the chemical nature of Pd nanoparticles protected by alkanethiolates that were prepared through a ligand placeexchange approach and the two-phase method, first developed for Au nanoparticles by Brust and Schiffrin. After 10 years since the first study on this kind of Pd nanoparticles was published, the surface composition of the particles is a matter of debate in the literature and it has not been unambiguously assessed. The nanoparticles were studied by means of several techniques: UV−visible spectroscopy, scanning transmission electron microscopy, Fourier-transform infrared spectroscopy, extended X-ray absorption fine structure, and X-ray photoelectron spectroscopy. The experimental data, obtained for the 3 nm diameter Pd particles, prepared by both synthetic routes, are consistent with nanoparticles composed by Pd(0) cores surrounded by a submonolayer of sulfide species, which are protected by alkanethiolates. Also, we unambiguously demonstrate that the chemical nature of these particles is very similar to that experimentally found for alkanethiolate-modified bulk Pd. The results from this paper are important not only for handling thiolate-protected Pd nanoparticles in catalysis and sensing, but also for the basic comprehension of metallic nanoparticles and the relation of their surface structure with the synthesis method.