Transportation and Accumulation of Redox Active Species at the Buried Interfaces of Plasticized Membrane Electrodes.
The transportation and accumulation of redox active species at the buried interface between glassy carbon electrodes and plasticized polymeric membranes have been studied using synchrotron radiation X-ray photoelectron spectroscopy (SR-XPS), near edge X-ray absorption fine structure (NEXAFS), in situ electrochemical Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy, cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). Ferrocene tagged poly(vinyl chloride) [FcPVC], ferrocene (Fc), and its derivatives together with tetracyanoquinodimethane (TCNQ) doped plasticized polymeric membrane electrodes have been investigated, so as to extend the study of the mechanism of this reaction chemistry to different time scales (both small and large molecules with variable diffusion coefficients) using a range of complementary electrochemical and surface analysis techniques. This study also provides direct spectroscopic evidence for the transportation and electrochemical reactivity of redox active species, regardless of the size of the electrochemically reactive molecule, at the buried interface of the substrate electrode. With all redox dopants, when CA electrolysis was performed, redox active species were undetectable (<1 wt % of signature elements or below the detection limit of SR-XPS and NEXAFS) in the outermost surface layers of the membrane, while a high concentration of redox species was located at the electrode substrate as a consequence of the deposition of the reaction product (Fc(+)-anion complex) at the buried interface between the electrode and the membrane. This reaction chemistry for redox active species within plasticized polymeric membranes may be useful in the fashioning of multilayered polymeric devices (e.g., chemical sensors, organic electronic devices, protective laminates, etc.) based on an electrochemical tunable deposition of redox molecules at the buried substrate electrode beneath the membrane.
Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast , 90 Sippy Downs Drive, Sippy Downs, Queensland 4556, Australia.
Manzar
M
Sohail
Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast , 90 Sippy Downs Drive, Sippy Downs, Queensland 4556, Australia.|School of Chemistry and Molecular Biosciences, The University of Queensland , Brisbane, Queensland 4072, Australia.|Department of Chemistry, Curtin University , GPO Box U1987, Perth, Western Australia 6109, Australia.
Roland
R
De Marco
Department of Inorganic and Analytical Chemistry, University of Geneva , Quai Ernest-Ansermet 30, CH-1211 Geneva, Switzerland.
Zdeňka
Z
Jarolímová
Department of Inorganic and Analytical Chemistry, University of Geneva , Quai Ernest-Ansermet 30, CH-1211 Geneva, Switzerland.
Marcin
M
Pawlak
Department of Inorganic and Analytical Chemistry, University of Geneva , Quai Ernest-Ansermet 30, CH-1211 Geneva, Switzerland.
Eric
E
Bakker
Johan Gadolin Process Chemistry Centre, c/o Laboratory of Analytical Chemistry, Åbo Akademi University , Biskopsgatan 8, FI-20500 Turku-Åbo, Finland.
Ning
N
He
Johan Gadolin Process Chemistry Centre, c/o Laboratory of Analytical Chemistry, Åbo Akademi University , Biskopsgatan 8, FI-20500 Turku-Åbo, Finland.
Rose-Marie
RM
Latonen
Johan Gadolin Process Chemistry Centre, c/o Laboratory of Analytical Chemistry, Åbo Akademi University , Biskopsgatan 8, FI-20500 Turku-Åbo, Finland.
Tom
T
Lindfors
Johan Gadolin Process Chemistry Centre, c/o Laboratory of Analytical Chemistry, Åbo Akademi University , Biskopsgatan 8, FI-20500 Turku-Åbo, Finland.
Johan
J
Bobacka
D002244:Carbon / Q000737:chemistry*; D004566:Electrodes; D010084:Oxidation-Reduction; D010968:Plasticizers / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D013499:Surface Properties
D010968:Plasticizers; D011108:Polymers; D002244:Carbon