Direct anodic growth of thick WO3 mesosponge layers and characterization of their photoelectrochemical response

Thick mesoporous tungsten oxide (WO₃) layers can be formed by anodization of tungsten in a 10 wt% K₂HPO₄/glycerol electrolyte, if the electrolyte temperature is around 80-100 °C. At 90 °C, a regular mesoporous WO₃ layer was grown up to a thickness of approximately 9 μm. This WO₃ mesosponge layer consists of typical feature sizes of 20-30 nm and pore widths of 10-30 nm. The photoresponse of different layer thicknesses and different annealing treatments was characterized in a photoelectrochemical cell. The highest photocurrents were observed with a 2.5 μm thick WO₃ layer annealed at 550 °C consisting of a mixture of orthorhombic, triclinic and monoclinic phases. Incident photon to current efficiencies (IPCEs) of the samples were 73.4% in a 1 M HClO₄ electrolyte and 167.5% for methanol photo-oxidation in 0.1 M CH₃OH/1 M HClO₄ electrolyte, at 1 V vs. Ag/AgCl under illumination at a wavelength of 420 nm.     

Anodic formation of low-aspect-ratio porous alumina films for metal-oxide sensor application

Thin nanoporous anodic alumina films, of low aspect ratio (1:1), with two distinctive pore sizes and morphologies were prepared by two-step constant-current anodising of aluminium layers on SiO₂/Si substrates in 0.4 mol dm⁻³ tartaric (TA) and malonic acid (MA) electrolytes and then modified by open-circuit dissolution. The anodic films were employed as a support material for sputtering-deposition of thin WO₃ layers in view of exploiting their gas sensing properties. The films and deposits were characterized by scanning electron microscopy, X-ray diffraction and electric resistance measurements at fixed temperatures in the range of 100-300 °C upon NH₃ and CO gas exposures. Test sensors prepared from the annealed and stabilized alumina-supported WO₃ active layers were insensitive to CO but showed considerably enhanced responses to NH₃ at 300 °C, the sensitivity depending upon the anodic film nature, the pore size and the surface morphology. The increased sensor sensitivity is due to the substantially enlarged film surface area of the TA-supported WO₃ films and the nanostructured, camomile-like morphology of the MA-supported WO₃ films. Sensing mechanisms in the alumina-supported WO₃ active layers are discussed.     

Enhanced electrochromic performance of macroporous WO3 films formed by anodic oxidation of DC-sputtered tungsten layers

Self-organized macroporous tungsten trioxide (WO₃) films are obtained by anodic oxidation of DC-sputtered tungsten (W) layers on 10 mm × 25 mm indium tin oxide (ITO)-coated glass. Under optimized experimental conditions, uniformly macroporous WO₃ films with a thickness of ca. 350 nm are formed. The film shows a connected network with average pore size of 100 nm and a pore wall thickness of approximately 30 nm. The anodized film becomes transparent after annealing without significant change in macroporous structure. In 0.1 M H₂SO₄, the macroporous WO₃ films show enhanced electrochromic properties with a coloration efficiency of 58 cm² C⁻¹. Large modulation of transmittance (∼50% at 632.8 nm) and a switching speed of about 8 s are also achieved with this macroporous film.     

Role of surface state on the electron flow in modified TiO2 film incorporating carbon powder for a dye-sensitized solar cell

An investigation of surface-related traps in nanostructured TiO₂ films modified by the incorporation of carbon powder was conducted by the potential-step chronoamperometric method. For the modification of the morphology and surface state of the nanoporous TiO₂ electrode, the incorporation of carbon into the white TiO₂ powder was accomplished. In the chronoamperometric data, all of the transients showed an initial fast phase (<1 s) followed by a slower phase which is related to the trap filling process. The trap-filling period of the carbon incorporated TiO₂ film becomes longer, as the applied negative potential increases, due to the widely distributed traps induced by the increased surface area. Furthermore, the film capacitance was derived as a function of the applied bias by integrating the current to time curves of the chronoamperometric data. The accumulated charge of the carbon incorporated TiO₂ film increases prominently in two regions. The dominant increase shown in the positive region (−0.7 to −0.9 V vs. Ag/AgCl at pH 13) of the flat band potential implies that the electron occupancy in the surface-related traps is increased. At a more negative potential (below −1.2 V vs. Ag/AgCl), electrons from the conduction band of the TiO₂ film substantially influence the total current, thereby inducing an exponential increase in the current. Therefore, it is found that most of the traps are located in the positive region of the flat band potential, since the Fermi level of the nanostructured TiO₂ film is positioned at −1.14 V vs. Ag/AgCl at pH 13. The trap sites in the sub-bandgap region of the TiO₂ film are important in the electron transport of photoinjected electrons from dye molecules and partially charge recombination with redox electrolyte in operating dye-sensitized solar cell. The influence of charge trap formed by increased surface states on the electron transport and electron transfer was investigated by photovoltage and photocurrent transient measurements.     

An investigation on room temperature synthesis of vertically oriented arrays of iron oxide nanotubes by anodization of iron

Formation of iron oxide nanotubes on to pure iron substrate by an electrochemical anodization method was investigated in fluoride containing electrolytes. Anodization of iron foil in fluoride containing borate solution resulted in stacked nano-ring type oxide morphology. Nanoporous oxide layer was observed at low pH and a granular oxide layer was formed at higher pH of phosphate + fluoride solutions. Formation of either nanoporous or nanotubular oxide layer was observed in ethylene glycol (EG) solution containing 0.05-0.1 M fluoride + 1.5-3.0 vol.% water. Transition from nanoporous structure to nanotubular structure was critically controlled by anodization potential, water addition and fluoride concentration of the EG solution. The potential required for this transition decreased with increase in the water content up to 7 vol.% beyond which enhanced dissolution occurred. Annealing of the nanotubes at 500 °C resulted in predominantly α-Fe₂O₃ crystal structure. The annealed Fe₂O₃ samples consisting of a single layer of nanotubular structure showed a photo current density of 0.4 mA/cm² at 0.5 V Ag/AgCl in 1 M KOH solution under simulated solar light illumination.     

Electrochemical activity of Geobacter sulfurreducens biofilms on stainless steel anodes

Stainless steel was studied as anode for the biocatalysis of acetate oxidation by biofilms of Geobacter sulfurreducens. Electrodes were individually polarized at different potential in the range −0.20 V to +0.20 V vs. Ag/AgCl either in the same reactor or in different reactors containing acetate as electron donor and no electron acceptor except the working electrode. At +0.20 V vs. Ag/AgCl, the current increased after a 2-day lag period up to maximum current densities around 0.7 A m⁻² and 2.4 A m⁻² with 5 mM and 10 mM acetate, respectively. No current was obtained during chronoamperometry (CA) at potential values lower than 0.00 V vs. Ag/AgCl, while the cyclic voltammetries (CV) that were performed periodically always detected a fast electron transfer, with the oxidation starting around −0.25 V vs. Ag/AgCl. Epifluorescent microscopy showed that the current recorded by chronoamperometry was linked to the biofilm growth on the electrode surface, while CVs were more likely linked to the cells initially adsorbed from the inoculum. A model was proposed to explain the electrochemical behaviour of the biofilm, which appeared to be controlled by the pioneering adherent cells playing the role of “electrochemical gate” between the biofilm and the electrode surface.     

Electrodeposition of bismuth telluride films from a nonaqueous solvent

The author examines Bi₂Te₃ deposition from a DMSO solution containing TeCl₄ and Bi(NO₃)₃ × 5H₂O by means of cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM). Accumulated charges and related mass changes for Bi₂Te₃ deposition on working electrodes are measured in situ. The deposit composition is more dependent on Te⁴⁺ concentrations in DMSO solution than on the potential. In a DMSO solution containing 0.01 M Te⁴⁺ and 0.0075 M Bi³⁺, Bi₂Te₃ deposits were obtained in the potential range between −0.2 and −0.8 V vs. Ag/AgCl. In a DMSO solution containing 0.05 M Te⁴⁺ and 0.0375 M Bi³⁺, Te-rich deposits were formed from −0.2 to −0.8 V vs. Ag/AgCl.     

Characterization of electrodeposited WO3 films and its application to electrochemical wastewater treatment

WO₃ films have been prepared on to IrO₂-coated Ti substrate by cathodic deposition, and as-deposited and annealed films have been characterized using XRD, TEM, Raman and FT-IR spectroscopy. The as-deposited film consists of nanocrystalline, orthorhombic WO₃·H₂O and this phase transforms to amorphous WO₃ by annealing at 250 °C and to monoclinic WO₃ by annealing at and above 350 °C. The as-deposited and annealed films have been used as anodes for electrochemical decomposition of phenol in aqueous solutions with and without chloride ions. The monoclinic WO₃ anodes prepared by annealing at 350 and 400 °C show relatively high electrochemical activity in the chloride-containing solution. In addition, the anodes possess high chemical and physical stabilities: very low dissolution rate of WO₃ during the electrolysis and good adhesion to the substrate. Thus, WO₃ anodes may be promising materials for anodic oxidation of bio-refractory organics in wastewater, although further improvement of electrochemical activity is needed for more effective decrease in total organic carbons in wastewater.     

Atomic emission spectroelectrochemistry applied to dealloying phenomena II. Selective dissolution of iron and chromium during active-passive cycles of an austenitic stainless steel

Atomic emission spectroelectrochemistry was used to investigate selective dissolution of a 304 austenitic stainless steel sample in 2 M H₂SO₄. The partial dissolution rates of Fe, Cr, Ni, Mn, Mo, and Cu were measured as function of time during a series of potentiostatic triggered activation/passivation cycles. When first exposed to sulfuric acid solution, the steel sample was in a passive state with a total steady state ionic dissolution rate expressed as an equivalent current density of 10 μA cm⁻². A transition into the active and passive state could be triggered by cathodic (−700 mV vs. Ag/AgCl) and anodic (+400 to +700 mV vs. Ag/AgCl) potentiostatic pulses respectively of variable time. Excess Cr dissolution was observed during the activation cycle as compared to Fe and a depletion of Cr dissolution was observed during the passivation cycle. These results are interpreted in terms of the dissolution of a Cr rich passive layer during activation and selective dissolution of Fe, Mn, Ni and other elements to form a Cr rich passive layer during passivation. Quantitative analysis of the excess Cr showed that the residual film contained approximately 0.38 μg Cr/cm². Fe does not appear to be incorporated into the film at this early stage of passive film growth. Residual films of metallic nickel and copper were formed on the surface during the active period that subsequently dissolved during passivation.     

Electrochemical and optical properties of new soluble dithienylpyrroles based on azo dyes

Two dithienylpyrroles based on azo dyes, namely 2,5′-dimethyl-[4-(2,5-di-thiophen-2-yl-pyrrol-1-yl)-phenyl]azobenzene (SNS-AB2) and 2,5′-dimethyloxy-[4-(2,5-di-thiophen-2-yl-pyrrol-1-yl)-phenyl]azobenzene (SNS-AB3), were synthesized and their corresponding polymers (PSNS-AB2 and PSNS-AB3) were successfully obtained via electropolymerization. The monomers have lower oxidation potentials (0.75 V and 0.80 V vs. Ag/AgCl for SNS-AB2 and SNS-AB3, respectively) when compared to their analogous. Both monomers exhibited photoisomerism properties under irradiation at 360 nm. During the irradiation process, for example, the color of SNS-AB3 changes from yellow to greenish yellow. The electroactive polymer films have well defined and reversible redox couples with a good cycle stability in both aqueous and organic solutions. The polymer films also exhibited electrochromic behaviors; color changes from yellowish green to dark green for the PSNS-AB2 (λ_max = 435 nm and E_g = 2.31 eV) and from mustard color to green for PSNS-AB3 (λ_max = 430 nm and E_g = 2.34 eV). Furthermore, the soluble polymers demonstrated different hues of yellow and green colors.     

Synthesis and characterization of highly stable optically passive CeO2-ZrO2 counter electrode

Transparent and adherent CeO₂-ZrO₂ thin films having film thicknesses ∼543-598 nm were spray deposited onto the conducting (fluorine doped tin oxide coated glass) substrates from a blend of equimolar concentrations of cerium nitrate hexahydrate and zirconium nitrate having different volumetric proportions (0-6 vol.% of Zr) in methanol. CeO₂-ZrO₂ films were polycrystalline with cubic fluorite crystal structure and the crystallinity was improved with increasing ZrO₂ content. Films were highly transparent (T ∼ 92%), showing decrease in band gap energy from 3.45 eV for pristine CeO₂ to 3.08-3.14 eV for CeO₂-ZrO₂ films. The different morphological features of the film obtained at various CeO₂-ZrO₂ compositions had pronounced effect on the ion storage capacity and electrochemical stability. CeO₂-ZrO₂ film prepared at 5 vol.% Zr concentration exhibited higher ion storage capacity of 24 mC cm⁻² and electrochemical stability of 10,000 cycles in 0.5 M LiClO₄ + PC electrolyte due to its film thickness (584 nm) coupled with relatively larger porosity (8%). The optically passive behavior of such CeO₂-ZrO₂ film (with 5 vol.% Zr) is affirmed by its negligible transmission modulation irrespective of repeated Li⁺ and electron insertion/extraction. The coloration efficiency of spray deposited WO₃ thin film is found to enhance from 47 to 107 cm² C⁻¹ when CeO₂-ZrO₂ is coupled as a counter electrode with WO₃ in an electrochromic device (ECD). These films can be used as stable ‘passive’ counter electrodes in electrochromic smart windows as they retain full transparency in both the oxidized and reduced states and ever-reported longevity.     

Electrochemical synthesis and characterization of mixed molybdenum-rhenium oxides

The electrodeposition of Mo_xRe_1−xO_y films (0.6 ≤ x ≤ 1) on indium-tin oxide (ITO) coated glass substrates from acidic peroxo-polymolybdo-perrhenate solutions is described. Trends in film growth were established as a function of potential from +0.4 V to −0.7 V vs Ag/AgCl by analyzing the composition and stoichiometry of the deposit using inductively coupled plasma mass spectrometry (ICPMS) and X-ray photoelectron spectroscopy (XPS). These experiments show that the concentration of rhenium increases linearly with the deposition potential and that the deposits are mixed-valent containing up to five different metal oxidation states (i.e., Mo^IV, Mo^V, Mo^VI, Re⁰, Re^IV). Electroanalytical techniques were used to explore the deposition mechanism, including chronocoulometry, cyclic voltammetry, spectroelectrochemistry, and electrochemical quartz crystal nanogravimetry (EQCN). At potentials positive to −0.26 V, perrhenate (Re^VIIO₄⁻) behaves as a redox mediator to accelerate the deposition of a mixed-valent molybdenum oxide, but at more negative potentials mixed molybdenum-rhenium oxides are produced.     

Poly(3‐chlorothiophene) films prepared by the direct electrochemical oxidation of 3‐chlorothiophene in mixed electrolytes of boron trifluoride diethyl etherate and sulfuric acid

3‐Chlorothiophene (CT) was electrochemically polymerized in mixed electrolytes of a boron trifluoride diethyl etherate solution containing 0–20% (by volume) sulfuric acid. The oxidation potentials of the monomer in these media were measured to be only 1.06–1.31 V (vs Ag/AgCl). These values were much lower than that of CT in acetonitrile and 0.1 mol/L (Bu)₄NBF₄ (1.92 V vs Ag/AgCl). Poly(3‐chlorothiophene) (PCT) films with conductivities of 0.1–2 S cm^?1 were obtained. The structure, morphology, and electrochemical behavior of the PCT films also were investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 502–509, 2003     

Electrochromic WO3−x films with reduced lattice deformation stress and fast response time

Electrochromic properties of electrochemically deposited and etched (EDE) WO_3−x films have been investigated using voltammetry and nanogravimetry to elucidate the amount of residual stress associated with lattice polarization and deformation in WO_3−x nanoparticles. The cathodic WO_3−x deposition from pertungstic acid solution and unusual properties of the cathodic electroetching of the oxide in tetraethyl ammonium chloride solution are reported and elucidated on the basis of Electrochemical Quartz Crystal Nanogravimetry (EQCN) measurements. The stress enhanced resonant frequency shift was observed upon WO_3−x film coloration. However, the stress enhancement appeared to be much lower (up to 4-6 times) than that measured for films synthesized by other methods. The stress reduction in WO_3−x films under study has been attributed to the stress relaxing propensity of EDE film to suppress the compressive stress wave. A considerable isotopic effect has been observed in nanogravimetry of the H⁺ and D⁺ ion intercalation into WO_3−x films. We have found that the isotopic effect is primarily due to the true mass loading difference between hydrogen and deuterium ions, for the same concentration of color centers (2.65 × 10²¹ cm⁻³), since EQCN frequency shifts associated with stress in the film for H⁺ and D⁺ are very close to each other.     

Synergic effect of benzotriazole and chloride ion on Cu passivation in a phosphate electrochemical mechanical planarization electrolyte

In this study, the effect of chloride ion (Cl⁻) in phosphate electrolytes of pH 2 containing benzotriazole (BTAH) developed for use in electrochemical mechanical planarization (ECMP) was investigated at various anodic potentials. According to D.C. and A.C. electrochemical analyses, the inhibition effect of the BTAH passive film formed in phosphate electrolyte containing both BTAH and Cl⁻ was superior to that formed in phosphate electrolytes containing BTAH alone, even at high anodic potential. The effective window for BTAH passivation reached ∼1.3 V vs. Ag/AgCl nearly three times that of the ∼0.5 V vs. Ag/AgCl recorded for electrolyte containing BTAH alone. According to analyses conducted by atomic force microscopy (AFM) and secondary ion mass spectrometer (SIMS), the thickness of the passive film grown from the BTAH-only electrolyte at 0.3 V vs. Ag/AgCl was ∼52 ± 7 nm and ∼55 nm, respectively. As for the passive film grown from the BTAH and Cl⁻ electrolyte, the thickness increased to ∼104 ± 18 nm and ∼106 nm, respectively. The mechanism for the enhanced inhibition capability was that the passive film grown from the BTAH and Cl⁻ electrolyte was thicker compared to that formed from the BTAH-only electrolyte due to the incorporation of Cl⁻ into the BTAH passive film. The ECMP polishing results also demonstrated an obvious step height reduction of ∼1000 nm in a patterned structure for only 60 s polishing at a high potential of 1.0 V vs. Ag/AgCl under a low downward pressure (∼0.5 psi). Subsequently, this study proposes that the control of Cl⁻ in a phosphate ECMP electrolyte of pH 2 may be useful in enhancing the passivation capability of BTAH passive film, thus expanding the operating potential window.     

Electrodeposition of tungsten from ZnCl2-NaCl-KCl-KF-WO3 melt and investigation on tungsten species in the melt

The electrodeposition of tungsten in ZnCl₂-NaCl-KCl-KF-WO₃ melt at 250 °C was further studied to obtain a thicker deposit. In the ordinary electrolysis at 0.08 V vs. Zn(II)/Zn, the current density decreased from 1.2 mA cm⁻² to 0.3 mA cm⁻² in 6 h. A thickness of the obtained tungsten layer was 2.1 μm and the estimated current efficiency was 93%. A supernatant salt and a bottom salt were sampled after 6 h from the melting and were analyzed by ICP-AES and XRD. It was found that the soluble tungsten species slowly changes to insoluble ones in the melt. The soluble species was suggested to be WO₃F⁻ anion. One of the insoluble species was confirmed to be ZnWO₄ and the other one was suggested to be K₂WO₂F₄. Electrodeposition was carried out under the same condition as above except for the intermittent addition of WO₃ every 2 h. The current density was kept at the initial value and the thickness was 4.2 μm. The intermittent addition of WO₃ was confirmed to be effective to obtain a thicker tungsten film.     

Electrochemical synthesis of WO3/PANI composite for electrocatalytic reduction of iodate

Composite film of polyaniline (PANI) and tungsten oxide (WO₃) was electrodeposited by cyclic voltammetric technique from a solution of aniline and tungstic acid. The obtained WO₃/PANI film displayed a significant enhancement of electrocatalytic activity for iodate reduction and a better stability than that of pure WO₃ and PANI films. Result of amperometric experiment revealed a good linear relationship with concentration of IO₃⁻ from 20 to 500 μM, with a high sensitivity of 0.54 μA/μM and a detection limit of 2.7 μM for the determination of iodate. This composite film was also successfully applied in determination of iodate in commercial table salt.     

Strategy for the syntheses of isolated fine silver nanoparticles and polypyrrole/silver nanocomposites on gold substrates

In this work, isolated fine silver nanoparticles and polypyrrole/silver nanocomposites with diameters of about 10 nm on gold substrates were first prepared by electrochemical methods. First, an Ag substrate was cycled in a deoxygenated aqueous solution containing 0.1 M HCl from −0.30 to +0.30 V versus Ag/AgCl at 5 mV/s with 30 scans. Subsequently the Ag working electrode was immediately replaced by an Au electrode and a cathodic overpotential of 0.2 V was applied under controlled sonication to synthesize Ag nanoparticles on the Au electrode. Then pyrrole monomers were encouragingly found to be polymerized on the deposited Ag nanoparticles. This polymerization is distinguishable from the known chemical or electrochemical one, due to the electrochemical activity of unreduced species of Ag_n⁺ clusters inside the nanoparticles. Also, this polymerization may be ascribed to the oxidizing agent of AuCl₄⁻, which is present on the Au electrode.     

Hydrophilic carbon nanoparticle-laccase thin film electrode for mediatorless dioxygen reduction: SECM activity mapping and application in zinc-dioxygen battery

Laccase from Cerrena unicolor was adsorbed on hydrophilic carbon nanoparticles (diameter = ca. 7.8 nm) modified with phenyl sulfonate groups and immobilized on an ITO electrode surface in a sol-gel processed silicate film. As shown by scanning electron and atomic force microscopies, the nanoparticles are evenly distributed on the electrode surface forming small aggregates of tens of nanometers in size. The mediator-free electrode exhibits significant and pH-dependent electrocatalytic activity towards dioxygen reduction. The maximum catalytic current density (95 μA cm⁻²) is obtained at pH 4.8 corresponding to maximum activity of the enzyme. Under these conditions dioxygen electroreduction commences at 0.575 V vs. Ag|AgCl_sat, a value close to the formal potential of the T1 redox centre of the laccase. The scanning electrochemical microscopy images obtained in redox competition mode exploiting mediatorless electrocatalysis show that the laccase is evenly distributed in the composite film. The obtained electrode was applied as biocathode in a zinc-dioxygen battery operating in 0.1 M McIlvaine buffer (pH 4.8). It provides 1.48 V at open circuit and a maximum power density 17.4 μW cm⁻² at 0.7 V.     

Thermal treatment effect on nanostructured TiO2 films deposited using diethanolamine stabilized precursor sol

A clear ethanol based precursor sol obtained using diethanolamine has been utilized for the deposition of TiO₂ films annealed at different temperatures. The influence of annealing temperature on the structural, optical and electrochemical properties of TiO₂ thin films has been examined. Diethanolamine stabilizes the precursor sol due to its chelate forming ability with the alkoxides. It reacts as a tridentate ligand with the titanium isopropoxide. The threshold for the onset of crystallization in the films is identified at a temperature of 300 °C. The SEM study on the films elucidates segregation of irregularly shaped features into finer round clusters as a function of annealing temperature. As determined from the AFM study, the roughness parameter in the films has shown an increase with the annealing temperature. Photoluminescence measurements have given an indirect evidence for the presence of stoichiometric titanium oxide in the films. An optimum crystallite size and high ion storage capacity in the 300 °C annealed film has led to its superior electrochromic activity with the transmission modulation and coloration efficiency of the same film being 42% and 8.1 cm² C⁻¹, respectively at 550 nm. The highest degree of porosity in the 300 °C annealed film as established from the SEM study is also the reason behind its best electrochromic performance. In addition, the 300 °C annealed film also exhibits the fastest coloration switching kinetics.