Issue 18, 2008
From the journal:

Journal of Materials Chemistry

Unique properties of a perfluoroalkyl-modified 2,2′-bipyridyl ruthenium complex in a Nafion™ membrane: attenuated leaching of a potential biofuel cell redox mediator†

Paul A. Jelliss,*a   Shelley D. Minteer,a   Mitesh Patel,a   Aleksander Siemiarczuk,b   Michelle Watta  and  Rudolph E. K. Winterc  

* Corresponding authors

a Department of Chemistry, Saint Louis University, St. Louis, MO 63103, USA
E-mail: jellisp@slu.edu
Fax: +1(314)977-2521
Tel: +1(314)977-2834

b Fast Kinetics Application Laboratory, Photon Technology International (Canada) Inc., 347 Consortium Court, London, Ontario, Canada

c Department of Chemistry and Biochemistry, University of Missouri – St. Louis, St. Louis, USA

Abstract

The synthesis and characterization are described for the complex salt [Ru(κ2-2,2′-N2C10H6{(CH2)3(CF2)5CF3}2-4,4′)(κ2-2,2′-N2C10H8)2][PF6]2, where one of the 2,2′-bipyridyl ligands bears terminal bis(perfluoralkyl) chains, the purpose of which is to exploit ‘like-dissolves-like’ intermolecular forces as an anchoring mechanism for the complex in Nafion™ membranes. TBAB-modified-Nafion™ thin films (sulfonic acid protons exchanged for NBun4+ cations) were cast or spin-coated onto electrodes and glass microscope slips, exposed to CH2Cl2 solutions of the complex and then examined by fluorimetry and cyclic voltammetry. Steady state and time-resolved luminescence analysis revealed quite different behavior in comparison with tris-2,2′-bipyridyl ruthenium in unmodified Nafion™ films. Exposure to methanol solutions indicated mitigation of the swelling effect of this solvent along with sustained structural integrity of the mediator complex among the various microenvironmental domains of the TBAB-modified-Nafion™ polymer. The dramatic leaching evident for samples of regular tris-2,2′-bipyridyl ruthenium dications in unmodified and modified Nafion™ films is not apparent for the new [Ru(κ2-2,2′-N2C10H6{(CH2)3(CF2)5CF3}2-4,4′)(κ2-2,2′-N2C10H8)2]2+/TBAB-modified-Nafion™-coated electrodes. Thus CVs of the latter show sustained peak current densities in excess of 1.0 mA cm−2 for the Ru3+/2+ couple and thus decent mediator retention over multiple potential cycles when exposed to mixed methanol–phosphate buffer solutions.

Graphical abstract: Unique properties of a perfluoroalkyl-modified 2,2′-bipyridyl ruthenium complex in a Nafion™ membrane: attenuated leaching of a potential biofuel cell redox mediator

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Article information

DOI
https://doi.org/10.1039/B717741K
Article type
Paper
Submitted
16 Nov 2007
Accepted
25 Feb 2008
First published
13 Mar 2008

J. Mater. Chem., 2008,18, 2104-2111

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Unique properties of a perfluoroalkyl-modified 2,2′-bipyridyl ruthenium complex in a Nafion™ membrane: attenuated leaching of a potential biofuel cell redox mediator

P. A. Jelliss, S. D. Minteer, M. Patel, A. Siemiarczuk, M. Watt and R. E. K. Winter, J. Mater. Chem., 2008, 18, 2104 DOI: 10.1039/B717741K

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