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Photoelectrochemical Evidence of Cu2O/TiO2 Nanotubes Hetero-Junctions formation and their Physicochemical Characterization
2014
Cu2O/TiO2 nanotubes heterojunctions were fabricated by electrochemical deposition of cuprous oxide on TiO2 nanotubes arrays grown by anodizing. X-ray diffraction and Raman Spectroscopy analysis allows for identification of Cu2O, whose morphological features were studied by Scanning Electron Microscopy as a function of the charge circulated during the electrodeposition step. Photoelectrochemical measurements in aqueous solutions evidenced a red shift of the light absorption threshold of TiO2 nanotubes due to the presence of cuprous oxide even for very low circulated charges, while electrochemical impedance measurements proved a significant reduction of the electrode impedance due the presenc…
A Simple Model for the Photoelectrochemical Behavior of Corrosion Layers with Variable Hydration Degree
2002
Abstract With the goal of quantitatively applying photocurrent spectroscopy to corrosion studies, the photoelectrochemical behavior of layered passive films having a decreasing hydration/hydroxylation degree, from the solution interface toward the metal interface, has been modeled. The model makes use of the correlations between optical gap and electronegativity of the constituents previously proposed for surface oxides and hydroxides. In this paper, the model was tested successfully against the experimental data pertaining to three high band gap insulating oxide-forming metals, like Zr, Al, and Y. In the first case, the fitting of the experimental spectra was compatible with the occurrence…
Influences of Structure and Composition on the Photoelectrochemical Behaviour of Anodic Films on Zr and Zr-20at.%Ti
2008
Abstract A photoelectrochemical investigation on anodic films of different thickness grown on sputter-deposited Zr and Zr–20 at.%Ti was carried out. The estimated optical band gap and flat band potential of thick ( U F ≥ 50 V) anodic films were related to their crystalline structure and compared with those obtained for thinner ( U F ≤ 8 V/SCE) anodic oxides having undetermined crystalline structure. The E g values obtained by photocurrent spectroscopy were also compared with the experimental band gap estimated by other optical ex situ techniques and with the available theoretical estimates of the zirconia electronic structures in an attempt to reconcile the wide range of band gap data rep…
Photocurrent Spectroscopy in Corrosion and Passivity Studies. A Critical Assessment
2016
Photocurrent Spectroscopy (PCS) is currently employed for the characterization of solid-state properties of semiconducting and insulating materials, since the knowledge of their band gap is a prerequisite to any possible application in different fields such as: solar energy conversion (photoelectrochemical and photovoltaic solar cells, photocatalysis) and microelectronics (high-k, high band-gap materials) (1-2). In the last 20-30 years an increasing number of scientists working in the area of corrosion has been attracted by this technique owing to its versatility and ability to scrutinize in situ corrosion layers and passive films having semiconducting or insulating behaviour. In previous w…
Photoelectrochemical characterization of amorphous anodic films on Ti-6at.%Si
2013
Abstract The solid state properties of anodic films grown galvanostatically on sputtering-deposited Ti–6at.%Si alloys were studied as a function of the formation voltage (5–40 V). From the photocurrent spectra a band gap of ∼3.4 eV was estimated for all the investigated thicknesses, which is almost coincident with the value measured for amorphous TiO 2 . The photocharacteristics allowed to estimate the flat band potential of the films, which resulted to be more anodic for thicker layers and allowed to evidence a change from n-type semiconducting material to insulator by increasing the formation voltage. A dielectric constant of ∼31 was estimated by differential capacitance measurements. The…
Band gap narrowing and dielectric constant enhancement of (NbxTa(1-x))2O5 by electrochemical nitrogen doping
2018
Abstract Anodic films were grown to 5 V and 50 V on Nb, Ta and Ta-Nb sputtering deposited alloys in 0.1 M ammonium biborate solutions in order to induce N incorporation. Their properties were compared to those of N free anodic films grown to the same formation voltages in 0.1 M NaOH. Photoelectrochemical measurements evidenced the presence of optical transitions at energy lower than the band gap of the oxides, attributed to localized states located close to the valence band mobility edge of the films, generated by N 2p orbitals, with consequent narrowing of the band gap. Since N incorporation occurs in the outer 70% of the anodic films, the dependence of the measured photocurrent as a funct…
Erroneous p-type assignment by Hall effect measurements in annealed ZnO films grown on InP substrate
2013
We report on incorrect carrier type identification achieved by Hall effect measurements performed on ZnO films grown by pulsed laser deposition on InP substrates and subsequently annealed for 1 h at 600 C in air. While Hall measurements, after post-growth annealing, reveal a change in the electrical properties of the films, from n-type to p-type, both photocurrent-based and standard C V measurements performed on the same samples show no change in the native n-type doping of the ZnO films. A possible interpretation of the two results is reported. In particular, p-type conductivity observed by Hall effect may be ascribed to a highly conductive thin layer formed during the annealing process at…
In situ characterization of passive films on al-ti alloy by photocurrent and impedance spectroscopy
1998
Abstract The anodic behaviour of an Al-Ti alloy (Ti-48Al-1V, atomic %) was investigated in different aqueous electrolytes. In all cases the alloy was passive owing to the growth of a barrier-like oxide film according to the high field mechanism. The study of the growth curves suggests partial dissolution of the film during the formation process in acidic solution. The kinetic parameters for film formation have been estimated in neutral solutions and the dielectric constant of the passive layer was roughly estimated. The in-situ characterization of the passive film revealed a n-type behaviour only for very low thicknesses, whilst thicker films showed insulator-like characteristics. The analy…
A photoelectrochemical characterization of passive films on stainless steels
1986
Abstract Passive films on stainless steels for sea water service have been studied by means of photocurrent measurements. Four experimental ELI (Extra Low Interstitital) ferritic stainless steels (types 25Cr-4Ni-4Mo) and a commercial superaustenitic stainless steel (type 20Cr-18Ni-6Mo-N) have been investigated. Differences in the photoelectrochemical behaviour have been attributed to the different nature of the passive films grown on ferritic or superaustenitic stainless steels. An interpretation is provided to explain the complex dependence of the photocurrent transients on the applied potential. Manuscript received 27 February 1986; in amended form 19 June 1986.
Plasmonic versus catalytic effect of gold nanoparticles on mesoporous TiO2 electrodes for water splitting
2014
a b s t r a c t Solar water splitting with metal oxide semiconductors constitutes a promising approach to the conversion of solar energy into chemical energy stored in the atomic bonds of hydrogen molecules. In the present study, we evaluate the effect of the presence of Au nanoparticles on the photoelectrochemical behaviour of mesoporous TiO2 to photo-oxidize water. We observe that the presence of Au nanoparticles leads to enhanced photocurrents for water oxidation and we explore the origin of this enhancement by optical and electrochemical characterization techniques. Our results indicate that although the Au nanoparticles are responsible for a localized surface plasmonic resonance effect…