title: Electrodeposition of palladium onto a pyridine-terminated self-assembled monolayer.
abstract: The electrodeposition of Pd onto self-assembled monolayers (SAMs) of 3-(4-pyridine-4-ylphenyl)propane-1-thiol on Au(111) has been investigated by scanning tunneling microscopy. Two schemes are compared: One involves an established two-step procedure where Pd(2+) ions are first coordinated to the pyridine moieties and subsequently reduced in Pd(2+)-free electrolyte. The second deposition routine involves electroreduction in an electrolyte containing low concentration of Pd(2+) which merges both steps and, thus, significantly simplifies metal deposition onto pyridine-terminated SAMs. Both strategies produce identical Pd nanoparticles (NPs) which exhibit a narrow size distribution and an apparent STM height of ∼2.4 nm. The observation of a Coulomb blockade and easy displacement of the nanoparticles in STM experiments evidence deposition on top of the SAM. The NPs are concluded to be essentially spherical. Growth of the NPs is found to be self-limiting since repeating the complexation-deposition cycle increases the density of the nanoparticles rather than their size but only close to full coverage. At high concentration of the Pd(2+) electrolyte, deposition on top of the SAM is impeded by a competitive mushroom-type growth.
authors.affiliation: EaStCHEM School of Chemistry, University of St. Andrews , Scotland, U.K.
authors.forename: Christophe
authors.initials: C
authors.lastname: Silien
authors.forename: Dorothée
authors.initials: D
authors.lastname: Lahaye
authors.forename: Marco
authors.initials: M
authors.lastname: Caffio
authors.forename: Renald
authors.initials: R
authors.lastname: Schaub
authors.forename: Neil R
authors.initials: NR
authors.lastname: Champness
authors.forename: Manfred
authors.initials: M
authors.lastname: Buck