Superhydrophobic carbon nanotube electrode produces a near-symmetrical alternating current from photosynthetic protein-based photoelectrochemical cells

The construction of protein-based photoelectrochemical cells that produce a variety of alternating currents in response to discontinuous illumination is reported. The photovoltaic component is a protein complex from the purple photosynthetic bacterium Rhodobacter sphaeroides which catalyses photochemical charge separation with a high quantum yield. Photoelectrochemical cells formed from this protein, a mobile redox mediator and a counter electrode formed from cobalt disilicide, titanium nitride, platinum, or multi-walled carbon nanotubes (MWCNT) generate a direct current during continuous illumination and an alternating current with different characteristics during discontinuous illumination. In particular, the use of superhydrophobic MWCNT as the back electrode results in a near symmetrical forward and reverse current upon light on and light off, respectively. The symmetry of the AC output of these cells is correlated with the wettability of the counter electrode. Potential applications of a hybrid biological/synthetic solar cell capable of generating an approximately symmetrical alternating current are discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design of Narrow-Gap TiO2: A Passivated Codoping Approach for Enhanced Photoelectrochemical Activity

To improve the photoelectrochemical activity of TiO2 for hydrogen production through water splitting, the band edges of TiO2 should be tailored to match with visible light absorption and the hydrogen or oxygen production levels. By analyzing the band structure of TiO2 and the chemical potentials of the dopants, we propose that the band edges of TiO2 can be modified by passivated codopants such as (Mo+C) to shift the valence band edge up significantly, while leaving the conduction band edge almost unchanged, thus satisfying the stringent requirements. The design principle for the band-edge modification should be applicable to other wide-band-gap semiconductors.

Photoelectrochemical behavior of a novel composite In0.15Ga0.85As/GaAs vertical bar GaAs/Al0.3Ga0.7As multiple quantum well electrode

A novel composite InxGa1-xAs/GaAs/GaAs/AlxGa1-xAs multiple quantum well material with different well widths was studied as a new kind of photoelectrode in a photoelectrochemical cell. The photocurrent spectrum and photocurrent-electrode potential curve were measured in ferrocene nonaqueous solution. Pronounced quantization effects and strong exciton absorption were observed in the photocurrent spectrum. The effects of surface states and interfacial states on the photocurrent-electrode potential curve are discussed. (C) 2000 Elsevier Science S.A. All rights reserved.

PHOTOELECTROCHEMICAL BEHAVIOR OF THE GAAS/ALXGA1-XAS SUPERLATTICE ELECTRODE/ELECTROLYTE INTERFACE

Single and multiple quantum wells of lattice-matched superlattices material GaAs/AlxGa1-xAs have been studied as photoelectrodes in photoelectrochemical cells containing nonaqueous electrolyte. Structural photocurrent spectra in the potential range of -1.8 to 1.0 V (vs standard calomel electrode) were obtained. The quantum yields for both superlattice electrodes were estimated and compared.

Photoelectrochemical reduction of CO2 mediated with methylviologen at roughened silver electrodes

The photoelectrocatalytic effect for the reduction of CO2 mediated with methylviologen (MV) was studied at mercury, polished silver and roughened silver electrodes using electrochemical and surface-enhanced Raman scattering (SERS) techniques. A large photoelectrocatalytic effect for the reduction of CO2 in the presence of MV was observed at the roughened silver electrode, whereas there was only a very small photoelectrocatalytic current at a more negative potential on mercury and polished silver electrodes. The SERS spectra of MV in the presence and absence of CO2, along with the electrochemical results, demonstrate that the surface adsorbed complexes, MV+ -Ag and MV0-Ag, played a role as the mediator for photoinduced electron transfer to CO2 in the solution. The results also suggest that the surface plasmon resonance of the nanoscale silver particle contributes to the overall photoelectrocatalytic effect on a roughened silver electrode.

Surface photovoltage spectra and photoelectrochemical properties of semiconductor-sensitized nanostructured TiO2 electrodes

Three kinds of TiO2 nanostructured thin films and their CdS-sensitized films, consisting of different sizes of TiO2 nanoparticles prepared with different methods, have been investigated. The surface photovoltage spectra (SPS) measurements indicate that the density of surface states on TiO2 is likely dependent upon the details of prepared methods. TiO2 particles prepared from basic sol have more surface states than that prepared from acidic sol. When the TiO2 thin films prepared using the TiO2 sols were sensitized by CdS particles, the SPS responses relative to the surface states on TiO2 from 350 to 800 nm were decreased. The photoelectrochemical properties of nanostructured TiO2 electrodes suggest that the fewer the surface states and the smaller the particle sizes of TiO2, the larger the photocurrent response. For CdS sensitized TiO2 thin film electrode, it is shown that the semiconductor sensitization is an efficient way to decrease the influence of surface states on the charge separation, and can improve the intensity of photocurrent response. (C) 2001 Elsevier Science B.V. All rights reserved.

Tailoring the morphology of WO₃films with substitutional cation doping: Effect on the photoelectrochemical properties

With the aim of improving the performance and extending the range of applications of mesoporous WO₃films, which were initially developed for the photoelectrochemical oxidation of water, we investigated the effect of a number of dopants (lithium, silicon, ruthenium, molybdenum and tin) upon the transparency, crystallinity, porosity and conductivity of the modified films. Tin, molybdenum and silicon were shown to improve the electrochromic behaviour of the layers whereas ruthenium enhanced considerably the electronic conductivity of the WO₃films. Interestingly, most of the dopants also affected the film morphology and the size of WO₃nanocrystals. X-ray photoelectron spectra revealed absence of significant segregation of doping elements within the film. Raman analyses confirmed that the monoclinic structure of WO₃films does not change upon substitutional cation doping; thus, the crystallinity of WO₃films is maintained.

METHYL-ORANGE AS A PROBE OF PHOTOELECTROCHEMICAL REACTIONS SENSITIZED BY COLLOIDAL CDS

The kinetics of photoreduction of methyl orange by ethylenediaminetetraacetic acid (EDTA) sensitized by colloidal CdS are reported as a function of [methyl orange], [O2] and [EDTA]. The results are interpreted using a reaction scheme which was proposed in an earlier paper for the same reaction sensitized by a powdered dispersion of highly crystalline CdS. An analysis of the results for the CdS colloid based on this reaction scheme shows that the rate of dye reduction by photogenerated electrons is approximately 50 times greater than the rate of oxygen reduction and the rate of scavenging of the photogenerated holes is approximately 7000 times greater than the rate of recombination. These findings are discussed in the light of similar observations reported for powdered CdS.

Factors affecting the photoelectrochemical fixation of carbon dioxide with semiconductor colloids

Carbon dioxide was reduced photocatalytically using aqueous CdS or ZnS colloids containing tetramethylammonium chloride to give the dimeric and tetrameric products namely, oxalate, glyoxylate, glycolate and tartrate. A model is presented to explain the role of the tetramethylammonium ions. Studies were also performed using ZnO, SiC, BaTiO₃ and Sr TiO₃, which in the absence of tetramethylammonium ions produced formate and formaldehyde. The relative quantum efficiencies of the six semiconductors were related to their band gaps and conduction band potentials. The role and effectiveness of several 'hole acceptor' (electron donor) compounds in this process is shown to be related to their redox potentials.

High Optical Quality Nanoporous GaN Prepared by Photoelectrochemical Etching

Nanoporous GaN films are prepared by UV assisted electrochemical etching using HF solution as an electrolyte. To assess the optical quality and morphology of these nanoporous films, micro-photoluminescence (PL), micro-Raman scattering, scanning electron microscopy (SEM), and atomic force microscopy (AFM) techniques have been employed. SEM and AFM measurements revealed an average pore size of about 85-90 nm with a transverse dimension of 70-75 nm. As compared to the as-grown GaN film, the porous layer exhibits a substantial photoluminescence intensity enhancement with a partial relaxation of compressive stress. Such a stress relaxation is further confirmed by the red shifted E₂(TO) phonon peak in the Raman spectrum of porous GaN.

Analytical Methods in Photoelectrochemical Treatment of Phenol

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Photoelectrochemical properties of sol-gel Nb2O5 films

Structural, optical, electro and photoelectrochemical properties of amorphous and crystalline sol-gel Nb2O5 coatings have been determined. The coatings are n-type semiconductor with indirect allowed transition and present an overall low quantum efficiency (phi < 4%) for UV light to electric conversion. The photoconducting behavior of the coatings is discussed within the framework of the Gartner and Sodergren models. Improvement can be foreseen if Nb2O5 coatings can be made of 10-20 nm size nanoparticles.

Photocatalytic and photoelectrochemical treatment effects on the killing of escherichia coli cells

In this study, we report the efficiency of photocatalytic and photoelectrochemical treatment using titanium dioxide as semiconductor and its applications in water disinfection. It was compared the efficiency of the two methods on the killing of E.coli cells. The photoelectrochemical treatment with electric field enhancement showed a good result and could be a new technology to water treatment.

Photoelectrochemical properties of FTO/m-BiVO4 electrode in different electrolytes solutions under visible light irradiation

Photoelectrochemical properties of FTO/BiVO4 electrode were investigated in different electrolytic solutions, potassium chloride (KCl) and sodium sulphate (Na2SO4), and under visible light irradiation condition. In order to accomplish that, an FTO/BiVO4 electrode was built by combining the solution combustion synthesis technique with the dip-coating deposition process. The morphology and structure of the BiVO4 electrode were investigated through X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. Photoelectrochemical properties were analyzed through chronoamperometry measurements. Results have shown that the FTO/BiVO4 electrode presents higher electroactivity in the electrolyte Na2SO4, leading to better current stabilization, response time, and photoinduced current density, when compared to KCl electrolyte. Besides, this electrode shows excellent performance for methylene blue degradation under visible light irradiation condition. In Na2SO4, the electrode has shown higher degradation rate, 51 %, in contrast to 44 % in KCl, plus higher rate constant, 174 × 10-4 min-1 compared to 150 × 10-4 min-1 in KCl. Results presented in this communication leads to the indication of BiVO4 thin films as alternate materials to use in heterogeneous photoelectrocatalysis, more specifically in decontamination of surface water. © 2013 Springer-Verlag Berlin Heidelberg.