TiO2 films obtained by microwave-activated chemical-bath deposition used to improve TiO2-conducting glass contact

In traditional solar cells, metal-semiconductor contacts used to extract photogenerated carriers are very important. In dye-sensitized solar cells (DSSC) not much attention has been given to contact between the TiO₂ and the transparent conducting glass (TCO), which is used instead of a metal contact to extract electrons. TiO₂ layers obtained by microwave-activated chemical-bath deposition (MW-CBD) are proposed to improve TiO₂ contact to conducting glass. Spectra of incident photon to current conversion efficiency (IPCE) are obtained for two-photoelectrode TiO₂ photoelectrochemical cells. IPCE spectra show higher values when TiO₂ double layer photoelectrodes are used. In these, the first layer or contacting layer is made by MW-CBD. Best results are obtained for double layer photoelectrodes on FTO (SnO₂:F) as conducting oxide substrate. Modeling of IPCE spectra reveals the importance of electrical contact and electron extraction rate at the TiO₂/TCO interface.     

Tin-grafted TiO2 with enhanced activity for photocatalytic hydrogen generation from aqueous methanol solutions

A series of Sn-modified TiO₂ samples was prepared by an anhydrous grafting route and applied in the photocatalytic H₂ evolution from aqueous methanol solutions. The synthesized samples were characterized by N₂ physisorption, X-ray diffraction, Raman, UV–Vis reflectance and photoluminescence spectroscopy. The results revealed that the tin species were highly dispersed on the TiO₂ surface and did not alter its crystalline structure. Photocatalytic results showed that Sn-grafting led to a significant improvement in the activity compared to bare TiO₂ owing to the improved charge separation. The photocatalytic performance of samples was found to depend highly on the Sn content. Additionally, the influence of Rh co-modification on the photocatalytic activity of Sn-grafted TiO₂ was investigated, and a synergetic effect between Sn and Rh was identified, which is attributed to the assumed electron relay among TiO₂, tin species and photodeposited Rh nanoparticles.     

Ruthenium dye-sensitized SnO2/TiO2 coupled solar cells

The photoelectrochemical behaviors of RuL₂(NCS)₂ dye-sensitized SnO₂/TiO₂ coupled solar cell was studied and compared with TiO₂ single system. The coupled system shows higher incident photon-to-current conversion efficiency (IPCE) value than the single system. A maximum IPCE value in the coupled system with 3.5 μm-thick SnO₂ and 7 μm-thick TiO₂ attained 82.4% at 530 nm wavelength. The higher IPCE value in the coupled system is attributed to the charge separation by fast electron transfer process from the excited RuL₂(NCS)₂ dye to TiO₂ to SnO₂ in the system with different energy level.     

Effect of using betalain,anthocyanin and chlorophyll dyes together as a sensitizer on enhancing the efficiency of dye-sensitized solar cell

The paper explored the mechanism of working of dye sensitizers for the improvement of efficiency of environmentally benign dye-sensitized solar cells (DSSC). The identified natural dyes namely anthocyanin (A), betalain (B) and chlorophyll (C) were extracted from Roselle (Hibiscus sabdariffa L.), spinach (Spinacia oleracea) and beetroot (Beta vulgaris) respectively. Light absorption performance of dyes was recorded by ultraviolet-visible (UV-vis) spectroscopic analysis followed by direct and indirect band gap calculation. The effect of functional groups present in the dyes studied by Fourier transform infrared spectroscopy (FTIR) and binding of the dyes on TiO₂ through surface morphology of sheets was identified employing field emission scanning electron microscopy (FESEM). Photovoltage characteristics (I-V) and induced photon to current efficiency (IPCE) measurements were also noted followed by the stability studies. The N3 (synthetic dye chosen for the reference) dye-based cell showed the highest efficiency of 6.19% out of all of 11 cells fabricated using different sensitizers. The DSSC fabricated using the novel mixed dye (ABC) mixture gave the highest efficiency of 3.73%, however it showed similar drop (almost 22%) in efficiency as that with of N3 dye in stability studies. The mechanism for the increase in the overall power conversion efficiency of DSSC was also suggested.     

Surface treated TiO2 nanorod arrays for the improvement of water splitting

Water splitting is widely employed for the hydrogen production for its abundant sources of water and sunlight. The TiO₂ nanostructures are the most promising materials because of their properties of the non-toxicity and relatively low cost. Surface treatments with TiCl₄ solution and titanium butoxide solution are applied on the TiO₂ nanorod arrays respectively. On the surface of the TiO₂ nanorods, TiO₂ nanoparticles are prepared through hydrolysis of TiCl₄ and homogeneous phase of TiO₂ synthesized with assist of second hydrothermal synthesis in titanium butoxide, resulting in the increase of the surface area of the TiO₂. Comparing with that of the original TiO₂ nanorod arrays, the incident photon-to-electron conversion efficiency (IPCE) of the TiO₂–TiCl₄ and TiO₂–H₂O samples is greatly enhanced by 25% and 250% in the ultraviolet region, respectively. The obviously enhanced activity is due to the larger surface structure after treatments, which could contribute to the improved performance in the water splitting. These surface treatments provide an efficient way to regulate the properties of the TiO₂ nanorod arrays for their extensive applications in the solar device for the hydrogen production.     

Photoelectric behavior of nanocrystalline TiO2 electrode with a novel terpyridyl ruthenium complex

The photoelectric behavior of a black dye, tris (isothiocyanato)-[N-(2,2′:6′,2″-terpyridine-4′-(4-carboxylic acid) phenyl)] ruthenium (II) complex, was examined under different conditions. The dye was adsorbed on nanocrystalline TiO₂ surface strongly and generated incident monochromatic photon-to-current conversion efficiency (IPCE) of about 90% at maximum absorption wavelength and greater than 20% in the near-IR region. A sandwich-type solar cell fabricated by this dye-sensitized nanocrystalline TiO₂ film generated 6.1 mAcm⁻² of short-circuit photocurrent, 0.58 V of open-circuit photovoltage and 2.9% of overall yield under irradiation of white light (78.0 mWcm⁻²) from a Xe lamp. Since the title dye shows better photoresponse than the N3 dye in the near-IR region, it would be a promising panchromatic sensitizer after optimization.     

Solvothermal synthesis ZnS–In2S3–Ag2S solid solution coupled with TiO2−xSx nanotubes film for photocatalytic hydrogen production

ZnS–In₂S₃–Ag₂S solid solution coupled with TiO_2-xS_x nanotubes film catalyst has been successfully prepared by a two-step process of anodization and solvothermal methods for the first time. The as-prepared photo-catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), UV–Visible diffuse reflectance spectra (UV–Vis DRS), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS), respectively. The results show that the ZnS–In₂S₃–Ag₂S solid solution are deposited on the surface of TiO₂NTs nanotubes under the solvothermal conditions, by which S atoms are incorporated into the lattice of TiO₂ through substituting the sites of oxygen atoms. Such ZnS–In₂S₃–Ag₂S@TiO_2-xS_x nanotubes composite presents the enhanced absorption in visible region and the efficient transfer of photoelectron between the solid solution and TiO_2-xS_x nanotubes, which determines the excellent photocatalytic activity for the photocatalytic hydrogen evolution from aqueous solutions containing the sacrificial reagents of Na₂S and Na₂SO₃ under 500 W Xe lamp irradiation.     

Design of high-efficiency solid-state dye-sensitized solar cells using coupled dye mixtures

A solid-state dye-sensitized solar cell comprising dye mixtures of [Ru(2,2-bpy-4,4′-dicarboxylic acid)(NCS)₂] and [Ru(4,4′,4″-tricarboxy-2,2;6,2″-terpy)(NCS)₃] on TiO₂ thin film was fabricated. The different optical properties of dyes results in increased photocurrent and incident photon to photocurrent efficiency (IPCE). The multiple dye system showed the short circuit current (I_sc) of 10.2 mA/cm² and a cell efficiency (η) of 2.8 while broadening the spectral sensitivity of the cell. When a single dye is used, I_sc of 6 and 5 mA/cm² and cell efficiency of 1.7 and 1.2 were observed for [Ru(4,4-bis(carboxy)-bpy)₂(NCS)₂] (dye 1) and [Ru(2,2′,2″-(COOH)₃-terpy)(NCS)₃] (dye 2), respectively. Additionally, the resulting IPCE for the solar cell consisting of dye mixture was 50% at wide wavelength range from 530 to 650 nm while for the dye 1, 32% IPCE was observed at 535 nm while for the dye 2, highest IPCE value observed was 20% at 620 nm.     

A technique to compare polythiophene solid-state dye sensitized TiO2 solar cells to liquid junction devices

In this communication, we report on a technique to fabricate solid-state polythiophene-based dye sensitized solar cells (DSSCs) that can be directly compared to analogous liquid junction devices. The device configuration is based on non-porous TiO₂ thin films and one of the three undoped polythiophene hole conductors: poly[3-(11 diethylphosphorylundecyl) thiophene], P3PUT, poly(4-undecyl-2,2′-bithiophene), P4UBT, or poly(3-undecyl-2,2′-bithiophene), P3UBT. These polymers were spin coated and cast from organic solutions onto the TiO₂ films. The dense TiO₂ thin films (ca. 30 nm) were deposited on conductive glass via facile spray pyrolysis and sol–gel techniques. After that, cis-(SCN)₂ Bis(2,2′ bipyridyl-4,4′-dicarboxylate) ruthenium(II) (a.k.a. Ru N3 dye) was adsorbed on the TiO₂ surface, and the polythiophenes were utilized as hole conductors in a simplified solar cell geometry. The results were compared to the control DSSC device made with dense TiO₂ and a liquid electrolyte, or 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene (a.k.a. Spiro-MeOTAD). The polythiophenes exhibited bandgaps in the range 1.9–2.0 eV, and HOMO energy levels of approximately 5 eV (vs. vacuum). The P3PUT DSSC device exhibited an AM1.5 V_OC=0.8 V, a J_SC=0.1 mA/cm², as well as an IPCE=0.5–1%. The AM1.5 short-circuit photocurrents and quantum efficiencies for DSSCs made with the polythiophenes, the Spiro-MeOTAD and the standard liquid electrolyte (I⁻/I₃⁻) were found to be identical within the limits of experimental uncertainty and reproducibility. Our results indicate that a solid-state replacement to the liquid junction is not necessarily limited by the fundamental aspect of hole transfer, one of the three fundamental aspects that must be met for an efficient DSSC. Rather than suggest that P3UBT or P4UBT could be used to create efficient “organic solar cells” with the exclusion of the Ru dye, we suggest that transparent thiophene compounds could be attractive candidates for high-surface area solid-state DSSCs, and that the technique presented can be applied to other hole conductors. It can allow a verification of one of the things necessary for the DSSC, so that parallel studies using high-surface area materials can proceed with confidence.     

Photocatalytic hydrogen production with aid of simultaneous metal deposition using titanium dioxide from aqueous glucose solution

The photocatalytic hydrogen production with aid of simultaneous metal deposition using TiO₂ was investigated in biomass glucose solution. Because the hydrogen production was very trace with pure TiO₂, the simultaneous metal deposition was applied into the glucose solution. The photocatalytic H₂ production activity with TiO₂ was significantly enhanced by simultaneous metal deposition for Au and Pd. The experimental factors such as glucose concentration, metal ion concentration and reaction temperature were investigated. The photocatalytic hydrogen production increased with increasing the concentration of glucose, and it followed Langmuir–Hinshelwood mechanism. Under the optimal conditions, the photocatalytic hydrogen generations from aqueous glucose solution with in-situ Au and Pd deposited TiO₂ were about 203 and 362 times larger compared with those observed with pure TiO₂. The enhanced photocatalytic activity could be explained in terms of reduced electron hole recombination via electron transfer from conductance band of TiO₂ to metal.     

Photoelectrochemical properties of ruthenium dye-sensitized nanocrystalline SnO2:TiO2 solar cells

The photoelectrochemical properties of RuL₂(NCS)₂ dye-sensitized nanocrystalline SnO₂:TiO₂ coupled and composite solar cells are reported. The coupled (bilayer) system shows higher incident photon-to-current conversion efficiency (IPCE) value than the composite (mixture) system. A maximum IPCE value attained 82.4% at 530 nm wavelength in the coupled system with 3.5 μm-thick SnO₂ and 7 μm-thick TiO₂. The higher IPCE value in the coupled system is attributed to the promotion of the charge separation by fast electron transfer process in the SnO₂/TiO₂/RuL₂(NCS)₂ system with different energy levels, different conduction band edge energy positions.     

A study on the electron transport properties of TiO2 electrodes in dye-sensitized solar cells

The influences of annealing temperature and different poly (ethylene glycol) (PEG) contents in nano-crystalline TiO₂ electrodes with and without N3 dye on the electron transfer in a dye-sensitized solar cell (DSSC) were investigated. It is found that the power conversion efficiency increases with the increase in annealing temperature and becomes saturated at 400–500 °C, and further increase lowers the performance which is consistent with the enhancement of the crystalline TiO₂ particles observed in X-ray diffraction (XRD) patterns and scanning electron microscopy (SEM) images. Electrochemical impedance spectroscopy (EIS) also confirms this behavior. These results have been further verified by studying the electron lifetimes (τ_e) and electron diffusion coefficients (D_e) of a bare TiO₂ and a dye-sensitized TiO₂ film using a pulsed laser spectrometer. It is noted that both the electron lifetime and the electron diffusion coefficient increase with the increase in annealing temperature. However, the evolution of rutile TiO₂ begins beyond 600 °C and this lowers the dye absorbance and the electron diffusion coefficients of TiO₂ electrodes. A similar study was made by varying the content of the PEG in the TiO₂ films. It is found that with the increase in the PEG content, a decrease in the electron lifetimes and a little hike in the electron diffusion coefficients are noted, where the cell performance remains almost the same. In addition, the dye adsorption decreases the electron lifetime and increases the electron diffusion coefficient of the TiO₂ films regardless of the PEG content and the annealing temperature.     

Direct Z-scheme anatase/rutile bi-phase nanocomposite TiO2 nanofiber photocatalyst with enhanced photocatalytic H2-production activity

Design and preparation of direct Z-scheme anatase/rutile TiO₂ nanofiber photocatalyst to enhance photocatalytic H₂-production activity via water splitting is of great importance from both theoretical and practical viewpoints. Herein, we develop a facile method for preparing anatase and rutile bi-phase TiO₂ nanofibers with changing rutile content via a slow and rapid cooling of calcined electrospun TiO₂ nanofibers. The phase structure and composition, surface morphology, specific surface area, surface chemical composition and element chemical states of TiO₂ nanofibers were analyzed by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). By a rapid cooling of 500 °C-calcined electrospun TiO₂ precursor, anatase/rutile bi-phase TiO₂ nanofibers with a roughly equal weight ratio of 55 wt.% anatase and 45 wt.% rutile were prepared. The enhanced H₂ production performance was observed in the above obtained anatase/rutile composite TiO₂ nanofibers. A Z-scheme photocatalytic mechanism is first proposed to explain the enhanced photocatalytic H₂-production activity of anatase/rutile bi-phase TiO₂ nanofibers, which is different from the traditional heterojunction electron–hole separation mechanism. This report highlights the importance of phase structure and composition on optimizing photocatalytic activity of TiO₂-based material.     

Investigation on the electron transfer between anatase and rutile in nano-sized TiO2 by means of surface photovoltage technique and its effects on the photocatalytic activity

Photoinduced electron transfer between anatase and rutile in nanosized TiO₂, prepared by a sol–gel method, was revealed by means of the surface photovoltage technique, and its effects on the photocatalytic performance in the degradation of a phenol solution were investigated. Also, the role of the surface states during the processes of photo-physics and photochemical reactions was discussed. In the as-prepared TiO₂ sample consisting of anatase and rutile, the photoinduced electrons can easily transfer from anatase surface states to rutile, as well as from anatase conduction band to rutile. These factors are responsible for the strong surface photovoltage response and high photocatalytic activity. Moreover, the surface states related to oxygen vacancies can induce photocatalytic reactions under visible irradiation, especially in the resulting biphase TiO₂, due to the electron transfer from anatase surface states to rutile.     

The influence of surface morphology of TiO2 coating on the performance of dye-sensitized solar cells

The optimization of solar energy conversion efficiency of dye-sensitized solar cells (DSSCs) was investigated by the tuning of TiO₂ photoelectrode's surface morphology. Double-layered TiO₂ photoelectrodes with four different structures were designed by the coating of TiO₂ suspension, incorporated with low and high molecular weight poly(ethylene glycol) as a binder. Among these four systems, P2P1, where P1 and P2 correspond to the molecular weight of 20,000 and 200,000, respectively, showed the highest efficiency under the conditions of identical film thickness and constant irradiation. This can be explained by the larger pore size and higher surface area of P2P1 TiO₂ electrode than the other materials as revealed by scanning electron microscopic (SEM) and Brunauer–Emmett–Teller (BET) analyses. Electrochemical Impedance Spectroscopy (EIS) analysis shows that P2P1 formulation displayed a smaller resistance than the others at the TiO₂/electrolyte interface. The best efficiency (η) of 9.04% with the short-circuit photocurrent density (J_sc) and open-circuit voltage (V_oc) of 18.9 mA/cm² and 0.74 V, respectively, was obtained for a solar cell by introducing the light-scattering particles to the TiO₂ nanoparticles matrix coated on FTO electrode having the sheet resistivity of 8 Ω/sq.     

Solar photocatalytic decomposition of Probenazole in water with TiO2 in the presence of H2O2

The photocatalytic decomposition of Probenazole in water using TiO₂/H₂O₂ under sunlight illumination is studied. The addition of H₂O₂ is effective for the improvement of photocatalytic decomposition of Probenazole with TiO₂. Furthermore, the operating conditions, such as photocatalyst dosage, temperature, pH, sunlight intensity and illumination time are also optimized. The kinetics of photocatalytic decomposition follow a pseudo–first–order kinetic law, and the rate constant is 0.129 min^?1. The activation energy (E_a) is 11.34 kJ/mol. The photocatalytic decomposition mechanism is discussed on the basis of molecular orbital (MO) simulation for frontier electron density.     

Improvement in dye-sensitized solar cells employing TiO2 electrodes coated with Al2O3 by reactive direct current magnetron sputtering

A novel surface modification method was carried out by reactive dc magnetron sputtering to fabricate TiO₂ electrodes coated with Al₂O₃ for improving the performance of dye-sensitized solar cells (DSSCs). The Al₂O₃-coated TiO₂ electrodes had been characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV–vis spectrophotometer, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The study results revealed that the modification to TiO₂ increases dye absorption amount, reduces trap sites on TiO₂, and suppresses interfacial recombination. The impact of sputtering time on photoelectric performance of DSSCs was investigated. Sputtering Al₂O₃ for 4 min on 5-μm thick TiO₂ greatly improves all cell parameters, resulting in enhancing the conversion efficiency from 3.93% to 5.91%. Further increasing sputtering time decreases conversion efficiency.     

Photo-catalytic conversion of oxygenated hydrocarbons to hydrogen over heteroatom-doped TiO2 catalysts

Here we report a sustainable process for photo-induced hydrogen production from aqueous solutions of oxygenated hydrocarbons. Doping N and B into TiO₂ noticeably improves its activity for hydrogen production. The addition of oxygenated hydrocarbons into water serves both as a hydrogen source and as an electron donor, which substantially enhances hydrogen production as compared with that for the photo-catalytic splitting of pure water. Other biomass-derived compounds such as glucose and sucrose are also shown to have potential for hydrogen production by this photo-catalytic conversion.     

Designing and fabrication of phenothiazine and carbazole based sensitizers for photocatalytic water splitting application

In the present work, we have designed and synthesized two carbazole and phenothiazine donor moieties based metal-free organic sensitizers and their codes are WCBZ2 and WPTZ2 respectively. These sensitizers have been used for photocatalytic hydrogen (H₂) evaluation application. The sensitizers exhibit good light absorption capability and electrochemical properties as well. For increasing water splitting capacity, incorporate platinum salt on TiO₂ semiconductor photoanode was performed and compared hydrogen evolution with pure TiO₂ photoanode. We have also studied the influence of the sensitizer's concentration and the effect of pH of the medium was explored. Using a theoretical measurement optimized both the synthesized dimer dyes structure geometry and the calculated their HOMO-LUMO energy level. Here also reported optimized pH and concentration of sensitizers in the reaction medium and found that the high hydrogen generation efficiency from water splitting is 138.3 μmol (348 TONs) by the WPTZ2 dye.     

Surface modification of TiO2 electrode by various over-layer coatings and O2 plasma treatment for dye sensitized solar cells

The anti-recombination property and the surface area of TiO₂ influence the efficiency of dye-sensitized solar cells (DSSCs). The effects of various over-layers and O₂ plasma treatment on TiO₂ electrodes have been investigated. Over-layers were coated by dip coating in a solution of saturated Ba(NO₃)₂, Mg(NO₃)₂ and N₂O₆Sr, which reduced the recombination of electrons from the photo excited state of Ru dye. O₂ plasma treatment was applied to improve both the contact ability with the dye and the electron takeover capability by reducing oxygen vacancies on both the TiO₂ and the over-layer surface. The photo conversion efficiency of DSSC was improved by both over-layer coating and O₂ plasma treatment. In particular, dipping in saturated Ba(NO₃)₂ solution and O₂ plasma treatment (BP), the photo conversion efficiency was greatly improved from 5.27% to 6.76%. The reason was that the over-layers and O₂ plasma treatment decreased electron recombination. The energy barrier of the modified over-layers blocks the electron transfer from TiO₂ to the electrolyte, and consequently increases electron density by extending the electron lifetime. O₂ plasma treatment also increased the Ru dye absorption.