title: The influence of organic-film morphology on the efficient electron transfer at passivated polymer-modified electrodes to which nanoparticles are attached.
abstract: The impact of polymer-film morphology on the electron-transfer process at electrode/organic insulator/nanomaterial architectures is studied. The experimental data are discussed in the context of the most recent theory modelling the nanoparticle-mediated electron-transfer process at electrode/insulator/nanomaterial architectures proposed by Chazalviel and Allongue [J. Am. Chem. Soc. 2011, 133, 762-764]. A previous report [Anal. Chem. 2013, 85, 1073-1080] by us qualitatively verified the theory and demonstrates a transition from thickness-independent to thickness-dependent electron transfer as the layer thickness exceeds a certain threshold. This follow-up study explores a different polymer, poly(phenylenediamine), and focuses on the effect of the uniformity of organic film on electron transfer at these hybrid structures. Electron-transfer kinetics of modified surfaces, which were assessed using the redox species Ru(NH3)6(3+) in aqueous solution, showed that a thickness-dependent electron-transfer regime is achieved with poly(phenylenediamine). This is attributed to the sufficiently thin films never being fabricated with this polymer. Rather, it is suggested that thin poly(phenylenediamine) layers have a globular structure with poor film homogeneity and pinhole defects.
authors.affiliation: School of Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia.
authors.forename: Abbas
authors.initials: A
authors.lastname: Barfidokht
authors.forename: Simone
authors.initials: S
authors.lastname: Ciampi
authors.forename: Erwann
authors.initials: E
authors.lastname: Luais
authors.forename: Nadim
authors.initials: N
authors.lastname: Darwish
authors.forename: J Justin
authors.initials: JJ
authors.lastname: Gooding
mesh_terms: D055664:Electrochemical Techniques; D004566:Electrodes; D004579:Electron Transport; D053758:Nanoparticles / Q000737:chemistry*; D009930:Organic Chemicals / Q000737:chemistry*; D010655:Phenylenediamines / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D013499:Surface Properties
chemical_list: D009930:Organic Chemicals; D010655:Phenylenediamines; D011108:Polymers
keywords: electron transfer; gold; nanoparticles; organic films; passivated electrodes