Kinetics of Solute Partitioning into Ultrathin Nafion Films on Electrode Surfaces: Theory and Experimental Measurement Paolo Bertoncello,* ,² Ilenia Ciani, ² Davide Marenduzzo, ‡ and Patrick R. Unwin* ,² Department of Chemistry, UniVersity of Warwick, CoVentry CV4 7AL, United Kingdom and School of Physics, UniVersity of Edinburgh, Edinburgh EH9 3JZ, United Kingdom ReceiVed: August 21, 2006; In Final Form: October 16, 2006 A simple voltammetric procedure for measuring the kinetics of slow partitioning processes into thin films is described and applied to determine the transport of trimethylammonium ferrocinium, FA + , into ultrathin Nafion Langmuir-Schaefer films. By recording cyclic voltammograms for the oxidation of FA + as a function of time of a Nafion modified electrode placed in a dilute solution containing FA + , one can readily measure the uptake of FA + into a film. An analytical model for the charge accumulated in the film has been derived for the cases of (i) transport-controlled partitioning; (ii) transport with a kinetic barrier at the film/solution (f/s) interface; and (iii) pure kinetic control. Analysis of experimental data indicates that, in contrast to dropcast Nafion films, there is a significant kinetic barrier at the f/s interface to FA + partitioning. The methodology and theory described are generic and could be applied to other chemical systems and detection methods. Introduction Nafion is one of the most common membrane materials used in polymer electrolyte fuel cells and has been the subject of extensive investigations since the 1970s. 1-5 Current applications of Nafion membranes include its use as a membrane separator in fuel cells, 6,7 batteries, 8,9 and water electrolizers. 10,11 Nafion is a polymer comprising a polytetrafluoroethylene-like backbone and perfluorinated side chains with terminating sulfonic acid groups. 2 The perfluorination confers excellent chemical, thermal, and electrochemical stability, while the sulfonic acid groups provide superacidity properties 2 as well as very good ion- exchange and permselectivity characteristics. 12 These properties and the availability of Nafion as a hydroalcoholic solution have inspired electrochemists to utilize Nafion to modify electrode surfaces so as to produce chemically modified electrodes 12-15 and voltammetric sensors. 16-18 In general, the practical applications of Nafion require a detailed understanding of the transport properties of water and ions within this material. 2,3,10 Measurements of ion transport, particularly of redox-active ions within Nafion films, have been extensive 19-28 given the implications for the operation of electrocatalytic and biosensing systems. Ion-exchange coef- ficients for electroactive cations have been evaluated, which show a preference of Nafion for hydrophobic cations. 29-31 White et al. 12 and Anson and co-workers 14,19,21,24-26 reported detailed investigations on the mechanisms of charge transport within Nafion-coated electrodes using voltammetric methods; they were able to evaluate the contributions of physical diffusion and electron hopping to the apparent diffusion coefficient of different organic cations. In general, the transport properties of redox species within Nafion have been evaluated on macroelectrodes using films having thicknesses from hundreds of nanometers to a few micrometers via cyclic voltammetry 13,26,29-31 and chronoamper- ometry. 12,22,31,32 However, the rate of charge transport in Nafion film has also been investigated using ultramicroelectrodes 22 and scanning electrochemical microscopy (SECM) approaches. 33,34 New procedures have recently been developed for obtaining ultrathin films of Nafion with thicknesses of the order of tens of nanometers: Heineman 35 and Seliskar 36 fabricated Nafion films using a spin coating, and recently, one of the authors developed a novel procedure based on the Langmuir-Schaefer (LS) technique. 37-40 The apparent diffusion coefficients for the Ru[(bpy) 3 ] 2+ (bpy ) 2,2′-bipyridine) and trimethylammoniom- ethylferrocene (FA + ) incorporated within the latter type of the Nafion film which were determined using a novel SECM approach were in the range of 10 -11 to 10 -10 cm 2 s -1 . 40 These atypically low values of the apparent diffusion coefficients appear to be intrinsically linked to the LS technique which results in ordered molecular and polymeric film structures that show high compactness. 41 In this paper, we report a detailed investigation of the partitioning properties of FA + into Nafion LS films using cyclic voltammetry. Analytical theory and a numerical model are developed to interpret the experimental data. An outcome of the studies herein is that there is a significant kinetic barrier to the partitioning process at the film/solution (f/s) interface, which is not apparent in studies of dropcast films where partitioning is generally assumed to be diffusion-limited. 12,30,36 The studies herein are of further significance because the preconcentration of cationic chromophores into ultrathin Nafion films has been proposed as an analytical procedure for trace-level detec- tions; 35,36,42-44 clearly, knowledge of the partitioning kinetics is important for the effective application of these methods. Moreover, the theoretical treatment presented here is general, and the method could be applied to other thin film partitioning processes. Theory We consider the natural diffusion of an electroactive species (FA + ) from an infinitely thick solution into an ultrathin (tens * Corresponding author. Phone: +44 (0) 2476 523264. Fax: +44 (0) 2476 524112. E-mail: p.r.unwin@warwick.ac.uk (P.R.U.); p.bertoncello@ warwick.ac.uk (P.B.). ² University of Warwick. ‡ University of Edinburgh. 294 J. Phys. Chem. C 2007, 111, 294-302 10.1021/jp065398l CCC: $37.00 © 2007 American Chemical Society Published on Web 12/02/2006