Comparison of Two Types of Overoxidized PEDOT Films and Their Application in Sensor Fabrication

Poly(3,4-ethylenedioxythiophene) (PEDOT) films were prepared by electro-oxidation on Au microelectrodes in an aqueous solution. Electrolyte solutions and polymerization parameters were optimized prior to overoxidation. The effect of overoxidation time has been optimized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), which results in the film overoxidized for 45 s at 1.35 V presenting a strong adsorption. The other one-step overoxidation film prepared by direct CV ranging from −0.6 V to 1.35 V was polymerized for comparison. Scanning electron microscope (SEM) analysis and Fourier transform infrared (FTIR) spectroscopy were used for monitoring morphological changes and the evolution of functional groups. Both of them indicate increased abundant oxygen functional groups and roughness, yet the products exhibit dendritic morphology and piles of spherical protrusions, respectively. Moreover, double-step overoxidized film showed better electrochemical performance toward lead ion sensing. These characterizations highlight some novel properties that may be beneficial for specific sensing applications.

[1]  Shanhong Xia,et al.  Determination of trace mercury in water based on N-octylpyridinium ionic liquids preconcentration and stripping voltammetry. , 2016, Journal of hazardous materials.

[2]  Peng Wang,et al.  PEDOT/Nafion composite thin films supported on Pt electrodes: Facile fabrication and electrochemical activities , 2010 .

[3]  G. Láng,et al.  The Electrochemical Degradation of Poly(3,4-ethylenedioxythiophene) Films Electrodeposited from Aqueous Solutions , 2016 .

[4]  Vilma Ratautaite,et al.  Electrochemical stability and repulsion of polypyrrole film , 2013 .

[5]  Fritz Beck,et al.  Anodic overoxidation of polythiophenes in wet acetonitrile electrolytes , 1996 .

[6]  Asha Chaubey,et al.  Application of conducting polymers to biosensors. , 2002, Biosensors & bioelectronics.

[7]  Arunas Ramanavicius,et al.  Electrochemical determination of Cu(II) ions using glassy carbon electrode modified by some nanomaterials and 3-nitroaniline , 2015 .

[8]  Magnus Berggren,et al.  The effect of pH on the electrochemical over-oxidation in PEDOT:PSS films , 2007 .

[9]  Mária Ujvári,et al.  Morphological changes in electrochemically deposited poly(3,4-ethylenedioxythiophene) films during overoxidation , 2015, Journal of Solid State Electrochemistry.

[10]  César Fernández-Sánchez,et al.  Electrochemical impedance spectroscopy studies of polymer degradation: application to biosensor development , 2005 .

[11]  A. Pron,et al.  Electrochemical oxidation of poly(3,4-ethylenedioxythiophene) — “in situ” conductivity and spectroscopic investigations , 2000 .

[12]  Jing Li,et al.  Electrodeposition of gold nanoclusters on overoxidized polypyrrole film modified glassy carbon electrode and its application for the simultaneous determination of epinephrine and uric acid under coexistence of ascorbic acid. , 2007, Analytica chimica acta.

[13]  Wei-Ting Chang,et al.  Strong adsorption characteristics of a novel overoxidized poly(3,4-ethylenedioxythiophene) film and application for dopamine sensing , 2014 .

[14]  Mincheol Chang,et al.  Chemical Sensors Based on Highly Conductive Poly(3,4‐ethylenedioxythiophene) Nanorods , 2005 .

[15]  Gang Wang,et al.  Application of impedance spectroscopy for monitoring colloid Au-enhanced antibody immobilization and antibody-antigen reactions. , 2004, Biosensors & bioelectronics.

[16]  Dong Hwan Kim,et al.  Ordered surfactant-templated poly(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer on microfabricated neural probes. , 2005, Acta biomaterialia.

[17]  Ying Liu,et al.  Sensitive square wave anodic stripping voltammetric determination of Cd2+ and Pb2+ ions at Bi/Nafion/overoxidized 2-mercaptoethanesulfonate-tethered polypyrrole/glassy carbon electrode , 2014 .

[18]  Xin Yang,et al.  Conducting polymers in environmental analysis , 2012 .

[19]  P. Manisankar,et al.  Differential pulse stripping voltammetric determination of heavy metals simultaneously using new polymer modified glassy carbon electrodes , 2008 .

[20]  P. Jasiński,et al.  Influence of electropolymerization conditions on the morphological and electrical properties of PEDOT film , 2015 .

[21]  M. D. Rooij,et al.  Electrochemical Methods: Fundamentals and Applications , 2003 .

[22]  David C. Martin,et al.  Structural, chemical and electrochemical characterization of poly(3,4-ethylenedioxythiophene) (PEDOT) prepared with various counter-ions and heat treatments. , 2011, Polymer.

[23]  Ali Özcan,et al.  Preparation of poly(3,4-ethylenedioxythiophene) nanofibers modified pencil graphite electrode and investigation of over-oxidation conditions for the selective and sensitive determination of uric acid in body fluids. , 2015, Analytica chimica acta.

[24]  V. Yegnaraman,et al.  Chemical Synthesis of PEDOT–Au Nanocomposite , 2007, Nanoscale Research Letters.

[25]  David J. Gates,et al.  The response of some nucleation/growth processes to triangular scans of potential , 1983 .

[26]  Jeff Moulton,et al.  Electrical and mechanical properties of oriented poly(3-alkylthiophenes): 2. Effect of side-chain length , 1992 .

[27]  Thierry Noguer,et al.  Chronoamperometric determination of lead ions using PEDOT:PSS modified carbon electrodes. , 2011, Talanta.

[28]  Ruo Yuan,et al.  Simultaneous determination of ascorbic acid, dopamine, uric acid and tryptophan on gold nanoparticles/overoxidized-polyimidazole composite modified glassy carbon electrode. , 2012, Analytica chimica acta.

[29]  Liu Dongqing Research Progress in Electrochromic Conducting Polymer PEDOT , 2010 .

[30]  Arunas Ramanavicius,et al.  Electrochemical Impedance Spectroscopy Based Evaluation of 1,10-Phenanthroline-5,6-dione and Glucose Oxidase Modified Graphite Electrode , 2014 .

[31]  Noemi Rozlosnik,et al.  New directions in medical biosensors employing poly(3,4-ethylenedioxy thiophene) derivative-based electrodes , 2009, Analytical and bioanalytical chemistry.

[32]  G. Gopu,et al.  Electrochemical, electrochromic behaviour and effects of supporting electrolyte on nano-thin film of poly (3,4-ethylenedioxy thiophene) , 2013 .

[33]  Wojciech Domagala,et al.  Electrochemical overoxidation of poly(3,4-ethylenedioxythiophene)—PEDOT studied by means of in situ ESR spectroelectrochemistry , 2005 .

[34]  Hitoshi Yamato,et al.  Stability of polypyrrole and poly(3,4-ethylenedioxythiophene) for biosensor application , 1995 .

[35]  Yang Li,et al.  A single-layer structured microbial sensor for fast detection of biochemical oxygen demand , 2016 .

[36]  Gang Zhang,et al.  Adsorption of Cu(II), Pb(II), Co(II), Ni(II), and Cd(II) from aqueous solution by poly(aryl ether ketone) containing pendant carboxyl groups (PEK-L): Equilibrium, kinetics, and thermodynamics , 2011 .

[37]  Ferenc Ujhelyi,et al.  Monitoring of the electrochemical degradation of PEDOT films on gold using the bending beam method , 2011 .