Electrochromic switching and nanoscale electrical properties of a poly(5-cyano indole)-poly(3,4-ethylenedioxypyrrole) device with a free standing ionic liquid electrolyte

Poly(5-cyano indole) or PCIND and poly(3,4-ethylenedioxy pyrrole) or PEDOP films have been electro-synthesized for the first time in a hydrophobic ionic liquid: trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate. PCIND, is an anodically coloring electrochrome, and exhibited a reversible switching between a transmissive yellow and a saturated green hue, with an absorption maximum at 650 nm in the fully oxidized state. Conducting atomic force microscopy studies revealed the PCIND film to be composed of an ensemble of segregated high current islands with a nanoscale electronic conductivity of 0.1 S cm⁻¹ and a band gap of 1.41 eV. The cathodically coloring PEDOP film comprised of uniformly distributed and inter-connected high current carrying domains with a band gap of 1.82 eV and a conductivity of 5.4 S cm⁻¹. Prototype electrochromic devices were fabricated using PEDOP and PCIND as cathode and anode with a thermally stable ionic liquid based, free standing polymeric gel film with a high ionic conductivity of 1.19 × 10⁻³ S cm⁻¹ as the electrolyte. The device showed large coloration efficiencies of 480 and 796 cm² C⁻¹ at visible and NIR wavelengths of 475 and 1100 nm respectively which far exceeded the coloration efficiencies of the individual electrochromes, thereby demonstrating the synergy between the two colorants. The performance attributes of the device, which switched reversibly between red, green and blue hues, are an outcome of an interplay between the high nanolevel electron conduction capabilities (enable fast charge transport) and high ion storage capacities (increase optical contrast as more number of electrochemically addressable sites are accessed by the electrolyte ions) of the PEDOP and PCIND films. Our studies demonstrate the applicability of PCIND films as anodic electrochromes in energy efficient windows.     

Electrochemical characterization of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with sulfonated thiophenes

Sulfonated thiophenes, sodium 2-(3-thienyloxy)ethanesulfonate (C₆H₇S₂O₄Na) and sodium 6-(3-thienyloxy)hexanesulfonate (C₁₀H₁₅S₂O₄Na), were synthesized and used in the fabrication of ion-selective electrodes (ISEs) sensitive and selective to Ag⁺. The Ag⁺-ISEs were prepared by galvanostatic electropolymerization of 3,4-ethylenedioxythiophene (EDOT) on glassy carbon (GC) electrodes, with either C₆H₇S₂O₄⁻ or C₁₀H₁₅S₂O₄⁻ as the charge compensator (doping ion) for p-doped poly(3,4-ethylenedioxythiophene) (PEDOT). Potentiometric measurements were carried out with these sensors, GC/PEDOT(C₆H₇S₂O₄⁻) and GC/PEDOT(C₁₀H₁₅S₂O₄⁻), to study and compare their sensitivity and selectivity to silver ions. PEDOT(C₆H₇S₂O₄⁻) and PEDOT(C₁₀H₁₅S₂O₄⁻) films were also studied by using other techniques such as cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), electrochemical quartz crystal microbalance (EQCM) and Fourier transform infrared spectroscopy (FTIR).Results from the potentiometric measurements showed that the difference in length of the alkyl chain of the doping ions C₆H₇S₂O₄⁻ and C₁₀H₁₅S₂O₄⁻ has no significant effect on the sensitivity or selectivity of GC/PEDOT(C₆H₇S₂O₄⁻) and GC/PEDOT(C₁₀H₁₅S₂O₄⁻) sensors to Ag⁺. More differences can be seen in the cyclic voltammograms and EIS spectra of the sensors. FTIR spectra confirmed that both C₆H₇S₂O₄⁻ and C₁₀H₁₅S₂O₄⁻ act as doping ions in the electrosynthesis of PEDOT-based films and they are not irreversibly immobilized in the polymer backbone.     

Electrocatalytic reduction of nitrite using ferricyanide; Application for its simple and selective determination

The electrocatalytic reduction of nitrite has been studied by ferricyanide at the surface of carbon paste electrode. Cyclic voltammetry and chronoamperometry techniques were used to investigate the suitability of ferricyanide as a mediator for the electrocatalytic nitrite reduction in aqueous solution with various pH. Results showed that pH 0.00 is the most suitable for this purpose. In the optimum pH, the electrocatalytic ability about 700 mV can be seen and the homogeneous second-order rate constant (k_s) for nitrite coupled catalytically to ferricyanide was calculated 2.75 × 10³ M⁻¹ s⁻¹ by Nicholson-Shain method. Also, electron transfer coefficients (α) for ferricyanide was determined by using various electrochemical approaches such as Tafel plot in the absence and presence of nitrite 0.556 and 0.760, respectively. The catalytic reduction peak current was linearly dependent on the nitrite concentration and the linearity range obtained was 5.00 × 10⁻⁵ to 1.00 × 10⁻³ M. Detection limit has been found to be 2.63 × 10⁻⁵ M (2σ). This method has been applied as a selective, simple and precise method for determination of nitrite in real sample.     

Synergistic effect of a catechin-immobilized poly(3,4-ethylenedioxythiophene)-modified electrode on electrocatalysis of NADH in the presence of ascorbic acid and uric acid

Catechin is a polyphenolic flavonoid that can be isolated from a variety of natural sources, including tea leaves, grape seeds, and the wood and bark of trees such as acacia and mahogany. In our experiments, catechin was immobilized on PEDOT/GC (poly(3,4-ethylenedioxythiophene)/glassy carbon)-modified electrodes and used as a mediator for NADH (nicotinamide adenine dinucleotide) oxidation. The effect of the PEDOT thickness on the surface coverage of the catechin molecules was studied using cyclic voltammetry. The electrochemical properties and the effect of pH on the redox properties of the immobilized catechin molecules were studied by cyclic voltammetry in phosphate solution. The electrocatalytic oxidation of NADH at different electrode surfaces such as the bare GC-, the PEDOT/GC-, the catechin/GC- and the catechin/PEDOT/GC-modified electrodes was explored in phosphate solution at pH 7. In the catechin/PEDOT/GC-modified electrode, the PEDOT film plays an important role in resolving the oxidation potentials of ascorbic acid and NADH into two peaks that occur at the same potential for the catechin/GC-modified electrode surface. The heterogeneous electron transfer rate constant for NADH oxidation at the catechin/PEDOT/GC-modified electrode was determined using the rotating disk electrode technique and found to be 9.88 × 10³ M⁻¹ s⁻¹. The amperometric determination of NADH at the catechin/PEDOT/GC electrode was tested. The sensitivity of the electrode was 19 nA/μM.     

Electrochemical preparation of epinephrine/Nafion chemically modified electrodes and their electrocatalytic oxidation of ascorbic acid and dopamine

Two types of epinephrine and cyclized epinephrine quinone films have been prepared using cyclic voltammetry from the epinephrine in the strong acidic solutions and neutral aqueous solutions over different scanning potential ranges. The cyclic voltammogram of the epinephrine film is characterized by one redox couple at about +0.5 V (versus Ag|AgCl) and cyclized epinephrine quinone film exhibits one redox couples at about −0.15 V (versus Ag|AgCl) .In addition to cyclic voltammetry and an electrochemical quartz crystal microbalance (EQCM) were used to study the growth mechanism of the epinephrine and cyclized epinephrine quinone molecules. The electrocatalytic oxidation of catecholamines (dopamine and norepinephrine) and also ascorbic acid were investigated in acidic aqueous solutions using epinephrine films. The rotating ring-disk electrode technique was used to investigate the mechanism of electrochemical oxidation of dopamine and ascorbic acid.     

Synthesis, characterization and photoelectrochemical properties of poly(3,4-dioctyloxythiophene)-CdS hybrid electrodes

CdS-poly(3,4-dioctyloxythiophene) (CdS-PDOT) hybrid electrode has been prepared by electrosynthesis of PDOT on Au substrate followed by electrodeposition of Cd and its chemical transformation into CdS. The polymer and semiconductor obtained by this method form hemispherical structures dispersed on the substrate. The synthesized composites were characterized by UV-vis absorption spectra and energy dispersive X-ray spectra (EDS). The AFM images of the electrodes covered with different amounts of each component were correlated with photoactivity of the hybrid electrodes. Photoresponses of Au/PDOT-CdS electrodes under illumination in aqueous solution of Na₂S were also compared with those of CdS without polymer. Enhancement of the photocurrent achieved for some polymer-to-semiconductor ratio is discussed in terms of the hybrid electrode morphology and hole-mediating properties of PDOT. The power conversion efficiency of the device based on CdS-PDOT hybrid electrode was determined from photocurrent-potential behavior of two electrode system, Au/CdS-PDOT/0.1 M Na₂S/Pt with a variable resistance in series in the external circuit.     

On the p-doping of PEDOT layers in various ionic liquids studied by EQCM and acoustic impedance

Poly(3,4-ethylenedioxythiophene) (PEDOT) films have been polymerized in several ionic liquids on the polycrystalline gold electrode of an electrochemical quartz crystal microbalance (EQCM) at 25 °C and 85 °C. Under cyclic potential variation, the EQCM resonance frequency decreased in the anodic potential region, indicating that the p-doping process is accompanied by the incorporation of anions. Elastic shear moduli G′, G″ - calculated from acoustic impedance measurements - were about 10⁷ Pa, values that are 2 orders of magnitude higher than for PEDOT polymerized in acetonitrile solutions. This difference is explained by the stiffening of the film by incorporated charged species because of the absence of a neutral molecular solvent plasticizing the film.     

Preparation, characterization and electrocatalytic behavior of zinc oxide/zinchexacyanoferrate and ruthenium oxide hexacyanoferrate hybrid film-modified electrodes

Polynuclear mixed-valent hybrid films of zinc oxide/zinchexacyanoferrate and ruthenium oxide hexacyanoferrate (ZnO/ZnHCF-RuOHCF) have been deposited on electrode surfaces from H₂SO₄ solution containing Zn(NO₃)₂, RuCl₃ and K₃[Fe(CN)₆] by potentiodynamic cycling method. Simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM) measurements demonstrate the steady growth of hybrid film. Surface morphology of hybrid film was investigated using scanning electron microscopy (SEM). Energy dispersive spectrometer (EDS) data confirm existence of zinc oxide and ruthenium oxide hexacyanoferrate (RuOHCF) in the hybrid film. The effect of type of monovalent cations on the redox behavior of hybrid film was investigated. In pure supporting electrolyte, electrochemical responses of Ru^II/III redox transition occurring at negative potential region resemble with that of a surface immobilized redox couple. The electrocatalytic activity of ZnO/ZnHCF-RuOHCF hybrid film was investigated towards oxidation of epinephrine, dopamine and l-cysteine, and reduction of S₂O₈²⁻ and SO₅²⁻ as well as IO₃⁻ using cyclic voltammetry and rotating ring disc electrode (RRDE) techniques.     

Poly(3,4-ethylenedioxythiophene)/Au-nanoparticles composite as electrode coating suitable for electrocatalytic oxidation

Composite materials consisting of poly(3,4-ethylenedioxythiophene) including Au nanoparticles, encapsulated by citrate anions, have been firmly deposited on an electrode surface through a simple method, taking advantage of the interaction between Au metal and thiophene polymeric backbone. A series of similar electrode coatings, also including different amounts of nanoparticles inside, has been characterised in terms of thickness and surface morphology, through different microscopic techniques. The electrocatalytic properties have been studied with respect to the oxidation of glucose in alkaline media, which is prevented from occurring on the pure organic material.     

Fabrication of conducting polymer-gold nanoparticles film on electrodes using monolayer protected gold nanoparticles and its electrocatalytic application

We wish to report a simple and new strategy for the fabrication of gold nanoparticles-conducting polymer film on glassy carbon (GC) and indium tin oxide (ITO) surfaces using 5-amino-2-mercapto-1,3,4-thiadiazole capped gold nanoparticles (AMT-AuNPs) in 0.01 M H₂SO₄ by electropolymerization. The presence of amine groups on the surface of the AuNPs was responsible for the deposition of the AMT-AuNPs film on the electrode surface. The atomic force microscopy (AFM) studies reveal that the fabricated p-AMT-AuNPs film showed homogeneously distributed AuNPs with a spherical shape of ∼8 nm diameter. The XPS spectrum shows the binding energies at 83.8 and 87.5 eV in the Au 4f region corresponding to 4f_7/2 and 4f_5/2, respectively. The position and difference between these two peaks (3.7 eV) exactly match the value reported for Au⁰. The N1s XPS showed three binding energies at 396.7, 399.6 and 403.3 eV, corresponding to the NH, –NH– and –N⁺H–, respectively, confirming that the electropolymerization proceeded through the oxidation of –NH₂ groups present on the periphery of the AMT-AuNPs. The application of the present p-AMT-AuNPs modified electrode was demonstrated by studying the electro reduction of oxygen at pH 7.2. The p-AMT-AuNPs film enhanced the oxygen reduction current more than three times than that of p-AMT film prepared under identical conditions.     

Poly-phenothiazine derivative-modified glassy carbon electrode for NADH electrocatalytic oxidation

Electropolymerization of a new phenothiazine derivative (bis-phenothiazin-3-yl methane; BPhM) on glassy carbon (GC) electrode generates a conducting film of poly-BPhM, in stable contact with the electrode surface. The heterogeneous electron-transfer process corresponding to the modified electrode is characterized by a high rate constant (50.4 s⁻¹, pH 7). The GC/poly-BPhM electrode shows excellent electrocatalytic activity toward NADH oxidation. The rate constant for catalytic NADH oxidation, estimated from rotating disk electrode (RDE) measurements and extrapolated to zero concentration of NADH, was found to be 9.4 × 10⁴ M⁻¹ s⁻¹ (pH 7). The amperometric detection of NADH, at +200 mV vs. SCE, is described by the following electroanalytical parameters: a sensitivity of 1.82 mA M⁻¹, a detection limit of 2 μM and a linear domain up to 0.1 mM NADH.     

Electrochemical and spectroelectrochemical study on bilayer films composed of C60 and poly(3,4-ethylenedioxythiophene) PEDOT

Bilayers of drop casted C₆₀ fullerene films and electrochemically synthesized poly(3,4-ethylenedioxythiophene) (PEDOT) films have been studied. The PEDOT film was polymerised by cyclic voltammetry on top of the drop casted C₆₀ fullerene film. The bilayer films were produced and characterized in three different electrolytes; tetrabutylammoniumhexafluorophosphate (TBAPF₆) and lithium hexafluorophosphate (LiPF₆) in acetonitrile (ACN) and in the ionic liquid 1-butyl-3-methyl-imidazolium tetrafluoroborate (BMIMBF₄). The bilayers were studied by cyclic voltammetry and in situ Fourier transform infrared attenuated total reflection (FTIR-ATR) spectroscopy. Both p- and n-doping of the bilayer films were studied and compared with PEDOT films prepared in organic media.     

Electrochemical determination of cysteine based on conducting polymers/gold nanoparticles hybrid nanocomposites

In this study, a hybrid nanocomposite consisting of a conducting polymer and gold nanoparticles (AuNPs) is fabricated onto a screen-printed carbon electrode (SPCE). A thin layer of poly(3,4-ethylenedioxythiophene) (PEDOT) is coated electrochemically on a bare SPCE; then, the nano-sized AuNPs are embedded by electrochemical deposition. The resultant SPCE/PEDOT/AuNPs-modified electrode is characterized by electrochemical methods, field emission scanning electron microscopy (FE-SEM) and X-ray photoelectron spectroscopy (XPS). The SPCE/PEDOT/AuNPs-modified electrode possesses great catalytic activity for the oxidation of cysteine in various pH buffer solutions (pH 2.0–8.0). The selectivity of the method is demonstrated by the separation of the oxidation peaks at up to 240 mV for cysteine and glutathione in pH 6.0 buffer solutions. The effects of the oxidizable interferences are also investigated. Flow-injection amperometry is performed for 0.5–200 μM of cysteine in pH 4.0 buffer solutions, and a linear calibration plot with a slope of 0.115 μA/μM is obtained. The detection limit (S/N = 3) is 0.05 μM. Additionally, the proposed methods obtain satisfactory results in the detection of cysteine-containing medicine samples.     

High conductivity PEDOT resulting from glycol/oxidant complex and glycol/polymer intercalation during vacuum vapour phase polymerisation

Vacuum vapour phase polymerisation (V-VPP) was used to synthesis high conductivity poly(3,4-ethylenedioxythiophene) (PEDOT) on glycol/oxidant coated substrates. Thermo gravimetric analysis (TGA) indicated that up to 15 wt.-% glycol was able to complex with the Fe(Tos)₃ oxidant solution and that this loading produced PEDOT with the highest conductivity, namely 1487 S cm⁻¹. Further addition beyond 15 wt.-% resulted in an unbounded excess of glycol which appeared to inhibit the polymerisation process, resulting in reduced doping levels and conductivity. XPS data showed that glycol was incorporated within the PEDOT matrix after polymer synthesis, and that this may contribute to the high conductivity achieved using the V-VPP technique. XPS data also confirmed that the highest conductivity coincided with the highest recorded doping level, d = 28.4%.     

Electrochemical preparation and kinetic study of poly(o-tolidine) in aqueous medium

Poly(o-tolidine), PoT, film was prepared by electrochemical oxidation of the monomer, oT, in 0.1 M HCl + 0.1 M KClO₄. The presence of KClO₄ in the formation medium was found to be essential for the electropolymerization process to proceed. Increasing the upper potential limit up to +1.5 V, instead of +1.0 V, leads to appearance of a new anodic peak at +1.36 V and enhancement of the polymer formation of PoT without changing the film structure. The electrochemical behavior of the formed polymer films was investigated in 1.0 M HClO₄. The kinetic parameters were calculated from the values of the charge consumed during the electropolymerization process. The rate of the polymerization reaction was found to depend on the concentration of the monomer rather than the electrolyte. The polymerization rate is first order with respect to the monomer concentration and zero order with respect to the electrolyte. The electrolyte plays no active role in the kinetics of the electropolymerization process and its role is most likely limited to polymer doping.     

Electrochemical sensors based on platinum electrodes modified with hybrid inorganic-organic coatings for determination of 4-nitrophenol and dopamine

New electrochemical sensors for dopamine (DA) and phenol derivative, based on hybrid inorganic redox material-organic conducting polymers, were developed. Hybrid inorganic-organic coatings based on Prussian blue, polyazulene, poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3-[(E)-2-azulene-1-yl)vinyl]thiophene) have been prepared by electrochemical methods in various configurations onto Pt substrate. Dopamine and 4-nitrophenol (4-NP) have been determined by square wave voltammetry using both mono and bilayer modified electrodes. The modified electrodes exhibited a linear response over wide range of 4-nitrophenol concentrations from 30 to 90 μM, with a detection limit of 8.23 μM (s/n = 3). A linear trend for the responses for dopamine concentrations ranging from 2 to 100 μM, with a sensitivity of 0.116 μA/μM, has been also obtained.     

In-situ QCM-D analysis reveals four distinct stages during vapour phase polymerisation of PEDOT thin films

Gaining a deeper understanding of the growth of poly(3,4-ethylenedioxythiophene) (PEDOT) films by vapour phase polymerisation (VPP) is essential for the rational design and optimization of such films. The VPP process was used to synthesise films of PEDOT on oxidant-coated substrates. Atomic force microscopy images showed that the morphology of the films changed considerably with time. Utilising a quartz crystal microbalance with dissipation measurement (QCM-D), we found that the kinetics of polymerisation and the viscoelastic properties of the films varied. The data reveal four distinct stages in film growth. Each stage produces a layer having different conductivity values, from a low of 276 S cm⁻¹ to a high of 1196 S cm⁻¹. Conductivity and electrochromic optical contrast, Δ%Tx, can thus be maximized by appropriate termination of the polymerisation reaction. Factors determining the polymerisation rate and changes in conductivity and optical performance are discussed.     

Electrosynthesis and efficient electrocatalytic performance of poly(neutral red)/ordered mesoporous carbon composite

A novel composite film which contains ordered mesoporous carbon (OMC) along with the incorporation of poly(neutral red) (PNR) has been synthesized on glassy carbon electrode by potentiostatic method. This composite film was characterized by scanning electron microscope (SEM) and cyclic voltammetry (CV). Two pairs of the redox peaks appear at formal potential E^0′ = +0.045 V (peak I) and E^0′ = −0.49 V (peak II) at the PNR/OMC/GC electrode. And it is found that only the redox waves (peak I) exhibits good electrocatalytic activity towards nicotinamide adenine dinucleotide (NADH) and 2-mercaptoethanol (2-ME). Under a lower operation potential of +0.07 V, amperometry method was used to determine the concentration of NADH and 2-ME, respectively. In pH 7.0, sensors for two molecules under their corresponding optimized conditions were developed with acceptable sensitivity and low detection limits in large determination ranges. In addition, these sensors have good reproducibility and stability.     

Electrochemical and electrocatalytic properties of α-substituted manganese and titanium phthalocyanines

This work reports on the synthesis of manganese and titanium phthalocyanine complexes that are tetra-substituted at four non-peripheral positions with amino ligands. The complexes are investigated for the first time for their electrochemical properties using cyclic voltammetry, rotating disc electrode voltammetry and spectroelectrochemistry. Electropolymerisation on a glassy carbon electrode was performed with ease and the modified electrodes were investigated for electrocatalysis of nitrite oxidation. Nitrite oxidation to nitrate is confirmed from the transfer of a total of two electrons.     

Electrochemical synthesis of Pd particles on poly(vinylferrocenium)

Electrochemical synthesis of Pd particles on poly(vinylferrocenium) (PVF⁺) support was described. K₂PdCl₄ was used as the metal particle precursor. Pd particles were incorporated into the polymer matrix electrochemically either by cyclic voltammetric scans (between +1.0 V and −0.8 V vs. SCE) or by reduction at constant potential (at −0.8 V vs. SCE) from aqueous solution of K₂PdCl₄. Scanning electron microscopy (SEM) studies showed that the Pd particles were well dispersed in the polymer matrix. Experimental parameters such as polymer film thickness, number of cycles during cyclic voltammetric scans in K₂PdCl₄ and electrolysis time in K₂PdCl₄ were studied. The Pd/PVF⁺ system showed catalytic activity towards hydrazine oxidation and appreciable results were obtained when compared with the related studies.