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Indium tin oxide (ITO) glass substrates are widely used in electrochemical devices and as substrates for in situ spectro-electrochemical experiments owing to their interesting optical, electrical and electrochemical properties. In this work, we found ITO surfaces to undergo substantial changes in their properties on potentiodynamic stresses in the acidic pH range. The surface changes occurring during cathodic cycling of ITO were characterized by redox couples in cyclic voltammetry, and the resultant surfaces examined by scanning electron microscopy (SEM), atomic force microscopy (AFM), optical transmittance measurements, X-ray diffraction (XRD) and the compositional changes by X-ray fluorescence spectroscopy (XRF). The studies of electrical, optical and structural properties of ITO during cathodic cycling in the acidic pH range clearly point to a set of conditions that help retaining the stability of ITO substrates intact for electrochemical applications.

Polyol mediated synthesis for the preparation of tungsten trioxide and titanium doped tungsten trioxide has been reported. The reaction was carried out using chlorides of tungsten and titanium in diethylene glycol medium and water as the reagent for hydrolysis at 190 deg. C. Formation of a blue coloured dimensionally stable suspension of the precursor materials was observed during the course of the reaction. The particle sizes of the precursor materials were observed to be around 100 nm. The precursor materials were annealed to give tungsten trioxide and titanium doped tungsten trioxide. The precursor materials were characterised using TGA/DTA, FT-IR, optical spectra, SEM, TEM and powder XRD methods. It was observed that the doping of titanium could be effected at least up to 10% of Ti in WO{sub 3}. The TGA/DTA studies indicated that WO{sub 3-x}.H{sub 2}O is the dominant material that formed during the polyol mediated synthesis. The XRD data of the annealed samples revealed that the crystalline phase could be manipulated by varying the extent of titanium doping in the tungsten trioxide matrix.

Detection of dopamine (DA) in the presence of excess of ascorbic acid (AA) has been demonstrated using a conducting polymer matrix, poly (3,4-ethylenedioxythiophene) (PEDOT) film in neutral buffer (PBS 7.4) solution. The PEDOT film was deposited on a glassy carbon electrode by electropolymerization of EDOT from acetonitrile solution. Atomic force microscopy studies revealed that the electrodeposited film was found to be approximately 100 nm thick with a roughness factor of 2.6 nm. Voltammetric studies have shown catalytic oxidation of DA and AA on PEDOT modified electrode and can afford a peak potential separation of ∼0.2 V. It is speculated that the cationic PEDOT film interacts with the negatively charged ascorbate anion through favorable electrostatic interaction, which results in pre-concentration at a less anodic value. The positively charged DA tends to interact with the hydrophobic regions of PEDOT film through hydrophobic–hydrophobic interaction thus resulting in favorable adsorption on the polymer matrix. Further enhancement in sensitivity to micro molar level oxidation current for DA/AA oxidation was achieved by square wave voltammetry (SWV) which can detect DA at its low concentration of 1 μM in the presence of 1000 times higher concentration of AA (1 mM). Thus the PEDOT modified electrode exhibited a stable and sensitive response to DA in the presence of AA interference.

Self-assembled monolayers (SAMs) of thiols with carboxylic acid terminal groups were formed on gold substrates. The electron transfer characteristics of redox species on the above SAM-modified electrodes were studied in acid and neutral media with the help of voltammetry under two different conditions: (1) solution phase electron transfer and (2) bridge mediated electron transfer. Two redox systems, viz., [Fe(CN)6]4-/3− and Ru[(NH3)6]2+/3+ were chosen for the solution phase study. Investigations of bridge mediated electron transfer were carried out by functionalising the SAM with redox moieties and then studying their redox behaviour. For this study, ferrocene carboxylic acid and 1,4-diamino anthraquinone were used and they were linked to carboxylic acid terminated thiols by covalent linkage. The voltammetric results with mercaptoundecanoic acid SAM demonstrate the difference in behaviour between solution phase and bridge mediated electron transfer processes.

In this paper, the electrochemical current rectification phenomenon exhibited at an electrochemical interface constituted by a glassy carbon electrode covered with a bilayer of polymer films is discussed. The authors have shown that Methylene Blue (MB) redox species can be confined to a very thin insulating polymer film formed from orthophenylene diamine. The poly(opd) film exhibited excellent blocking properties to redox molecules in solution. On the other hand, the insulating poly(opd) film trapped with MB could mediate electron transfer between the redox molecules in solution and the electrode. Further, a second polymeric layer (Nafion film) trapped with ferrocene redox species was formed as the outer layer over the inner poly (opd) film containing MB. This bilayer-modified electrode, due to the significant difference in the redox potentials of the MB and ferrocene species immobilized in the inner and outer layers, respectively, exhibits unidirectional current flow and the results of the voltammetric investigations on the modified electrodes are described in this communication.

In this work, we examine the electrocatalytic activity of electrodeposited Platinum (Pt)-Nickel (Ni) alloy layers on an inert substrate electrode for methanol oxidation reaction. Analyses using energy-dispersive fluorescent X-ray analysis and powder X-ray diffractometry confirm alloying of Pt with Ni in a range of compositions. Steady-state polarisation measurements in 0.5 M methanol+0.5 M H2SO4 solutions clearly show that the onset of electro-oxidation shifts to less anodic potential values (approximately 160 mV), while also exhibiting current enhancements up to ~15 times the currents obtained for the pure Pt electrodeposit. A linear relationship between the cyclic voltammetric peak (oxidation) current and [MeOH] is observed at a scan rate of 50 mVs−1, thus indicating reduced influence of adsorbed CO (COads) surface poison. A critical composition, Pt (92%)/Ni (8%) [denoted Pt-Ni(3) alloy] is found to exhibit maximum electrocatalytic activity, beyond which the activity drops, whereas pure Ni does not catalyse the reaction. While the promotion of electro-oxidation is understood to be largely due to the alloy catalyst, surface redox species of Ni oxide formed during the electro-oxidation process may also contribute to the oxygenation of COads, thereby enhancing the oxidation current. Plausible mechanisms of methanol oxidation on Pt/ transition metal alloy electrocatalysts are discussed in terms of electron transfer (in the alloy) and the role of Ni oxide species.

Electrochemical sensing of glucose on a gold electrode modified by the sequential incorporation of the mediator, 1,4-diaminoanthraquinone (DAAQ) and the enzyme, glucose oxidase (GOD), through covalent linkage onto a self-assembled monolayer configuration is described in this paper. It has been shown that two alternate layers of enzyme and mediator could be formed on the surface. The modified electrode is catalytic towards glucose oxidation. The catalytic response becomes more well behaved with the two-layer configuration and it is demonstrated by the amperometric experiments. The results also indicated that the mediator catalyzes the oxidation of H2O2, and also it establishes a weak electrical communication between the enzyme and the electrode surface. The results present the scope for the fabrication of membrane-free biosensors of ultra-thin dimensions.

A potentiometric hydrogen peroxide (H2O2) sensing scheme was developed using arylboronic acid as the electrode modifier. It is well-known that both aliphatic and aryl boronic acid undergo electrophilic displacement reaction with H2O2. This reaction involves replacement of boronic acid by the hydroxyl group of peroxide resulting in a change in pKa value that can be exploited for sensing of H2O2. Vinylphenylboronic acid (VPBA) ink was prepared using Nafion as the binder and it was drop cast on an electrode surface. Morphology of the modified electrode was analysed using scanning electron microscopy (SEM). The present modifier exhibited a linear relationship between the difference in electrode potential (∆Ep) vs. [H2O2] with a Nernstian slope of 26 ± 2 mV in the concentration range of 10− 1–10− 5 M. Application of the VPBA modified electrode for hydrogen peroxide sensing was studied in an industrial dye-bleach effluent.

The formation of metal monolayers through underpotential deposition (UPD) depends on the interactions between the electrode surface and the depositing species. Other adsorbable species, if present in the solution, will influence the formation of UPD metal films through their adsorption on the electrode surface, taking place simultaneously. Copper UPD formation on polycrystalline gold surfaces has been investigated in the presence of small amounts of urea, thiourea (TU) and N-substituted thioureas using cyclic voltammetry. The results show that the UPD of copper on gold is significantly influenced by the presence of thiourea in solution. The charge corresponding to the stripping peak obtained in the presence of both Cu2+ and TU in solution is always larger than the sum of the charges resulting when either of them is present alone. Again, the charge observed during stripping in the presence of both Cu2+ and TU is believed to arise from (i) stripping of the UPD Cu, (ii) adsorption–desorption of TU and (iii) oxidation of Cu(TU)n+ complexes. The addition of N-substituted TUs is found to influence the UPD of Cu to different extents. This is tentatively explained in terms of the structure of the organic molecules.

In this work, conducting polymer incorporated gold nanoparticles are synthesized through a sequence of chemical and electrochemical routes. These materials are characterized using TEM and FE-SEM techniques. The advantages of these films are demonstrated for sensing biologically important compounds such as dopamine and uric acid in presence of excess ascorbic acid. The PEDOT matrix is recognized to be responsible for the peak separation (selectivity) while also favouring catalytic oxidation of the above compounds and the nanometer-sized gold particles allow nanomolar sensing of DA and UA (sensitivity). Thus, it is possible to detect nanomolar levels of DA and UA in presence of excess of AA.

Hexacyanoferrate modification of gold electrode has been achieved by immobilizing the species in a self-assembled monolayer of 3,3‘-thiodipropionic acid anchored to the gold surface. The surface coverage of hexacyanoferrate is estimated from the voltammetric data point to be about one monolayer, and the modified electrode exhibits excellent surface redox behavior. Further, it shows good electrocatalytic influence on the oxidation of hydrazine and ascorbic acid.

The formation and characterization of self-assembled monolayers of organosulfur compounds like alkanethiols and dialkyl (di)sulfides on metal surfaces such as gold are areas of current research interest. The presence of an aromatic ring in a thiol molecule can enhance the binding between Au and the thiol, resulting in the formation of compact and impervious self-assembled monolayers. The formation of a monolayer of 2-mercaptobenzothiazole (MBT), containing an aromatic group with a fused thiazole ring but no long alkyl chain, is achieved on a gold electrode surface. Voltammetric investigations of ferro/ferricyanide and ferrous/ferric redox systems carried out on this Au|MBT electrode are reported. Further, the possibility of using such an Au|MBT electrode to distinguish between inner and outer sphere electron transfer reactions is indicated.

In this work, gold-incorporated polyethylenedioxythiophene nanocomposite material has been synthesized chemically, employing reverse emulsion polymerization method. Infrared and Raman spectroscopic studies revealed that the polymerization of ethylenedioxythiophene leads to the formation of polymer polyethylenedioxythiophene incorporating gold nanoparticles. Scanning electron microscope studies showed the formation of polymer nanorods of 50–100 nm diameter and the X-ray diffraction analysis clearly indicates the presence of gold nanoparticles of 50 nm in size.

Formation of self assembled monolayers on gold surface by thiols and disulphides is a well known phenomenon and extensive research work has been carried out in this area with envisaged applications in the area of sensors, molecular electronics, lithography, device fabrication using bottom-up approach, etc. Recently, it has been established that thiophene molecules can self assemble on gold surface due to Au-S interactions. 3-(3-thienyl) acrylic acid, a bifunctional ligand is used in this work to form self-assembled monolayers on planar gold surfaces (two dimensional assemblies) and to prepare monolayer protected gold nano clusters (three-dimensional assemblies). The electron transfer blocking properties of the two-dimensional monolayers were evaluated by using standard redox probes like ferrocyanide anions and Ruthenium hexamine cations. The functionalisation of the two-dimensional and three-dimensional assemblies has been carried out with ferrocene carboxylic acid and the functionalised monolayers were characterized by Cyclic voltammetry. The formation of thienyl acrylic acid protected nanoclusters has been verified by TEM and surface plasmon resonance absorption. It has been observed that when thiophene based ligands are used as stabilizers for the formation of metal nanoparticles, they tend to aggregate as a result of pi-pi interactions between adjacent thiophene ligands. In this case it is found that aggregation is prevented. The substituent at the thiophene ring hinders pi-pi interactions. The quantised nature of electrochemical charging of these nanoparticles has been demonstrated by differential pulse voltammetry (DPV), which exhibit peak like features (coulomb's staircase). This work also explores the possibility of using 3-(3-thienyl) acrylic acid as building blocks or spacers on planar and colloidal gold surfaces for potential applications in the field of sensors and devices.

In this work, conducting polymer impregnated gold nanoparticles are synthesized through a sequence of chemical and electrochemical routes. The nanocomposite film is characterized using UV-vis, FTIR spectroscopy, and SEM techniques to study the formation of oxidized PEDOT and Au0. The advantages of these films are demonstrated for sensing biologically important compounds such as dopamine and uric acid in presence of excess ascorbic acid, one of the major interferants in the detection of DA and UA (mimicking the physiological conditions), with superior selectivity and sensitivity when compared to the polymer film alone. Simultaneous determination is realized at 115 mV and 246 mV for DA and UA, respectively. The PEDOT matrix is recognized to be responsible for the peak separation (selectivity) while also favouring catalytic oxidation of the above compounds and the nanometer-sized gold particles allow nanomolar sensing of DA and UA (sensitivity). Thus, it is possible to detect nanomolar levels of DA and UA in presence of excess of AA. The combined effect of Au nanoparticles and the PEDOT matrix is rationalized that the Aunano surrounded by a "hydrophobic sheath (PEDOT)" tending to reside within these hydrophobic regions of PEDOT, thus favouring the selectivity and sensitivity of the DA/UA detection. This new generation of nanocomposites is expected to enhance the value of electroanalytical techniques, as it is possible to tune their properties suiting the analytical needs.

A gold electrode surface has been modified with a monolayer of 3,3'-thiodipropionic acid (TPA) by self-assembly. The pH-sensitive TPA monolayer is further derivatized to form a monolayer of nickel hexacyanoferrate. This electrode shows molecular discrimination between potassium and sodium ions and exhibits a near-Nernstian response, with a slope of 55 mV/decade to potassium ions in the range from 10 -2 to 1 M.