Enhanced heterogeneous ferrioxalate photo-fenton degradation of reactive orange 4 by solar light

A combined homogeneous and heterogeneous photocatalytic decolourisation and degradation of a chlorotriazine Reactive azo dye Reactive Orange 4 (RO4) have been carried out using ferrous sulphate/ ferrioxalate with H₂O₂ and TiO₂-P25 particles. Solar/ferrous/H₂O₂/TiO₂-P25 and solar/ferrioxalate/H₂O₂/TiO₂-P25 processes are found to be more efficient than the individual photo-Fenton and solar/TiO₂-P25 processes. A comparison of these two processes with UV/ferrous/H₂O₂/TiO₂-P25 and UV/ferrioxalate/H₂O₂/TiO₂-P25 reveals that ferrioxalate is more efficient in solar light whereas ferrous ion is more efficient in UV light. The experimental parameters such as pH, initial H₂O₂, Fe²⁺, ferrioxalate and TiO₂-P25 concentration strongly influenced the dye removal rate in solar processes. The optimum operating conditions of these two combined processes are reported.     

Electrospun TiO2/SnO2 nanofibers with innovative structure and chemical properties for highly efficient photocatalytic H2 generation

Innovative TiO₂/SnO₂ nanofibers were fabricated via electrospinning an innovated precursor solution and used for photocatalytic H₂ generation. The nanofibers exhibited greatly enhanced H₂ evolution rate compared to bare TiO₂ nanofiber and P25. The enhanced efficiency of the TiO₂/SnO₂ nanofibers was attributed to its excellent synergistic properties: (1) its good mesoporosity; (2) the red-shift of absorbance spectra to enhance light absorbance capability; (3) its long nanofibrous structure and (4) anatase TiO₂ – rutile TiO₂ – rutile SnO₂ ternary junctions favorable for the separation of electrons and holes. Based on our experimental results, the optimum ratio of TiO₂/SnO₂ nanofibers with 3% Sn demonstrated the highest efficiency in H₂ generation.     

Photocatalytic hydrogen production using Fe2O3-based core shell nano particles with ZnS and CdS

Stability and efficiency of photocatalysts are important to realize the practical applications of them for photocatalytic hydrogen production from industrial sulfide effluent. Novel, magnetically separable core–shell nano photocatalysts viz., CdS/Fe₂O₃, ZnS/Fe₂O₃ and (CdS + ZnS)/Fe₂O₃ were prepared and their hydrogen evolution activity under visible light was examined. The XRD result shows that CdS and ZnS were very well coated on the surface of the iron oxide core shell particles. The HR-TEM result also confirms the core shell formation. (CdS + ZnS)/Fe₂O₃ evolved higher volume of hydrogen than the other catalysts. It is ascribed to rapid migration of excited electrons from (CdS + ZnS) toward Fe₂O₃ suppressing electron hole annihilation compared to other catalysts. The catalysts can be easily recovered from the reaction medium using external magnetic bar and so the photocatalyst can be reused without any mass loss. Hence, it can be a potential catalyst for recovery of hydrogen from industrial sulfide containing waste streams.     

Ab initio study of electronic structures and absorption properties of pure and Fedoped anatase TiO2

Using the first-principles calculations, the band structure, total and partial density of states (DOS) and absorption properties of anatase TiO₂, Fe³⁺ doped TiO₂ and FeTiO₃ were calculated by a plane-wave pseudopotential method based on density functional theory (DFT). From the calculated results, the band gaps of anatase TiO₂, Fe³⁺ doped TiO₂ and FeTiO₃ are about 2.4, 0.32 and 0.28 eV, respectively. The states of the valence bands and conduction bands of undoped and Fe³⁺ doped TiO₂ with anatase structure were calculated. As shown in the absorption spectra, the FeTiO₃ has the strongest absorption and the Fe-TiO₂ has the weakest absorption. Effect of Fe³⁺ dopant on the absorption property of the anatase TiO₂ is explained in detail based on the calculations using the first-principles. The Fe³⁺ doped anatase TiO₂ could be a potential candidate for photocatalyst because of the absorption ability of visible light.     

The preparation of TiO2–nitrogen doped by calcination of TiO2·xH2O under ammonia atmosphere for visible light photocatalysis

The investigation on incorporating nitrogen group into titanium dioxide in order to obtain powdered visible light-active photocatalysts is presented. The industrial hydrated amorphous titanium dioxide (TiO₂·xH₂O) obtained directly from sulphate technology installation was modified by heat treatment at temperatures of 100–800 °C for 4 h in an ammonia atmosphere. The photocatalysts were characterized by UV–VIS–DR and XRD techniques. The UV–VIS–DR spectra of the modified catalysts exhibited an additional maximum in the VIS region (, ) which may be due to the presence of nitrogen in TiO₂ structure. On the basis of XRD analysis it can be supposed that the presence of nitrogen does not have any influence on the transformation temperature of anatase to rutile. The photocatalytic activity of the modified photocatalysts was determined on the basis of decomposition rate of phenol and azo-dye (Reactive Red 198) under visible light irradiation. The highest rate of phenol degradation was obtained for catalysts calcinated at 700 °C (6.55%), and the highest rate of dye decomposition was found for catalysts calcinated at 500 and 600 °C (ca. 40–45%). The nitrogen doping during calcination under ammonia atmosphere is a very promising way of preparation of photocatalysts which could have a practical application in water treatment system under broader solar light spectrum.     

Facile synthesis of titanium dioxide‐cadmium sulfide nanocomposite using pulsed laser ablation in liquid and its performance in photovoltaic and photocatalytic applications

Narrow band gap semiconductors like cadmium sulfide (CdS) are being applied as an agent to reduce the band gap of metal oxide semiconductors like titanium dioxide (TiO₂). In order to obtain a TiO₂/CdS nanocomposite with reduced electron‐hole recombination and improved stability, we coupled 10%, 20%, and 40% by weight of CdS with TiO₂ in this work using pulsed laser ablation in liquid technique. Here, 532 nm wavelength generated from neodymium‐doped yttrium aluminum garnet laser was directed into the TiO₂/CdS mixture prepared in a colloid form to produce the TiO₂/CdS nanocomposites. The effect of the CdS concentration on the performance of the obtained nanocomposite in a dye‐sensitized solar cell and photocatalytic degradation of methyl orange in water was studied in detail. However, the nanocomposite with 10% percentage weight of CdS in anatase TiO₂ showed the best performance as compared with pure TiO₂, and the photoconversion efficiency of the dye‐sensitized solar cell was improved from 0.6% to 4.3%, while the percentage of methyl orange degraded was enhanced from 58% to 82% after 36 min irradiation using ultraviolet–visible light. This improvement in photovoltaic and photodegradation properties is due to limited electron hole recombination rate, higher conduction of charge carriers, their longer lifetime during the photocatalytic process, improved ultraviolet–visible light activity, reduced photocorrosion, and improved pore size. Copyright © 2017 John Wiley & Sons, Ltd.     

Photocatalytic hydrogen production from aqueous methanol solution with CuO/Al2O3/TiO2 nanocomposite

The photocatalytic hydrogen production from aqueous methanol solution was investigated with ZnO/TiO₂, SnO/TiO₂, CuO/TiO₂, Al₂O₃/TiO₂ and CuO/Al₂O₃/TiO₂ nanocomposites. A mechanical mixing method, followed by the solid-state reaction at elevated temperature, was used for the preparation of nanocomposite photocatalyst. Among these nanocomposite photocatalysts, the maximal photocatalytic hydrogen production was observed with CuO/Al₂O₃/TiO₂ nanocomposites. A variety of components of CuO/Al₂O₃/TiO₂ photocatalysts were tested for the enhancement of H₂ formation. The optimal component was 0.2 wt% CuO/0.3 wt% Al₂O₃/TiO₂. The activity exhibited approximately tenfold enhancement at the optimum loading, compared with that with pure P-25 TiO₂. Nano-sized TiO₂ photocatalytic hydrogen technology has great potential for low-cost, environmentally friendly solar-hydrogen production to support the future hydrogen economy.     

Photoelectrochemical study on charge transfer properties of nanostructured Fe2O3 modified by g-C3N4

Novel photocatalysts, which consist of two visible light responsive semiconductors including graphite-like carbon nitride (g-C₃N₄) and Fe₂O₃, were successfully synthesized via electrodeposition followed by chemical vapor deposition. The morphology of the g-C₃N₄/Fe₂O₃ can be tuned from regular nanosheets to porous cross-linked nanostructures. Remarkably, the optimum activity of the g-C₃N₄/Fe₂O₃ is almost 70 times higher than that of individual Fe₂O₃ for photoelectrochemical water splitting. The enhancement of photoelectrochemical activity could be assigned to the morphology change of the photocatalysts and the effective separation and transfer of photogenerated electrons and holes originated from the intimately contacted interfaces. The g-C₃N₄/Fe₂O₃ composites could be developed as high performance photocatalysts for water splitting and other optoelectric devices.     

Semiconductor-catalyzed degradation of phenols with sunlight

With natural sunlight TiO₂ (anatase), Fe₂O₃, CuO, ZnO, ZnS, ZrO₂, CdO, HgO, PbO, PbO₂ and Al₂O₃ catalyze the degradation of phenol but MoO₃, Co₃O₄, CdS, SnO₂, Sb₂O₃, La₂O₃, CeO₂, Sm₂O₃, Eu₂O₃, Pb₂O₃ and Bi₂O₃ do not. The degradation rates increase linearly with phenol-concentration and area of the catalyst bed but decrease linearly with pH. Air is essential for degradation and the catalysts show sustainable photocatalysis. Pre-sonication fails to enhance the photocatalysis. The system does not respond to application of a potential bias for enhancement of the photocatalysis. o-Cresol, m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-nitrophenol, p-nitrophenol, o-aminophenol, m-aminophenol, p-aminophenol, catechol, resorcinol and quinol degrade much slower than phenol. The ease of degradation correlates neither with the electron-releasing or withdrawing capacity of the substituent nor with its position in the phenyl ring. Also, the photocatalytic efficiency of the semiconductor is not in accordance with its band-gap energy.     

Photooxidation of iodide ion on immobilized semiconductor powders

MoO₃ particles immobilized on an organic polymer, fixed on a glass plate, effectively catalyze the oxidation of iodide ion in air-saturated solution under illumination at 365 nm; the catalytic efficiency is higher than that of ZnO and anatase TiO₂. Immobilized ZrO₂, Fe₂O₃, Al₂O₃, Bi₂O₃, Y₂O₃, CeO₂ and Nd₂O₃ particles also photocatalyze the oxidation. Except ZnO, all the listed metal oxides show sustainable photocatalytic activity at least up to 2 h; ZnO photocatalysis slackens after half-an-hour. Immobilized particulate CuO, ZnS, CdO, CdS, PbO and Sb₂O₃ fail to catalyze the photooxidation of iodide ion whereas SnO₂ oxidizes iodide ion in dark itself; V₂O₅ dissolves. All the stated photocatalysis depend linearly on iodide ion concentration and enhance with the photon flux. The mechanistic detail of the photocatalysis is presented.     

Solar photocatalytic degradation of azo dye: comparison of photocatalytic efficiency of ZnO and TiO2

The photocatalytic activity of commercial ZnO powder has been investigated and compared with that of Degussa P25 TiO₂. Laboratory experiments with acid brown 14 as the model pollutant have been carried out to evaluate the performance of both ZnO and TiO₂ catalysts. Solar light was used as the energy source for the photocatalytic experiments. These catalysts were examined for surface area, particle size and crystallinity. The effect of initial dye concentration, catalyst loading, irradiation time, pH, adsorption of acid brown 14 on ZnO and TiO₂, intensity of light and comparison of photocatalytic activity with different commercial catalysts were studied. The progress of photocatalytic degradation of the acid brown 14 has been observed by monitoring the change in substrate concentration of the model compound employing HPLC and measuring the absorbance in UV–Visible spectrophotometer for decolourisation. The photodegradation rate was determined for each experiment and the highest values were observed for ZnO suggesting that it absorbs large fraction of the solar spectrum and absorption of more light quanta than TiO₂. The complete mineralisation was confirmed by total organic carbon (TOC) analysis, COD measurement and estimation of the formation of inorganic ions such as NH₄⁺, NO₃⁻, Cl⁻ and SO₄²⁻.     

Photocatalytic properties of redox-treated Pt/TiO2 photocatalysts for H2 production from an aqueous methanol solution

The influence of redox-treated Pt/TiO₂ photocatalysts on H₂ production is investigated. Catalyst characterizations are performed by TEM, XPS, XRD, BET, and UV–vis/DR spectroscopy techniques. In terms of production rate, the oxidation treatment shows higher reactivity than the reduction treatment. The reduction treatment allows the formation of metallic Pt(0), which more easily catalyzes the transition of TiO₂ from the anatase to the rutile phases. Reduction-treated Pt/TiO₂ photocatalysts have lower S_BET values than oxidation-treated Pt/TiO₂ photocatalysts due to the higher percentage of TiO₂ in the rutile phase. Combining the results of XPS and optical analyses, PtO/TiO₂ shows a higher energy band gap than metallic Pt(0)/TiO₂, indicating that oxidation-treated Pt/TiO₂ is more capable of achieving water splitting for H₂ production. According to the results of this study, the oxidation treatment of Pt/TiO₂ photocatalysts can significantly enhance the reactivity of photocatalytic H₂ production because of their homogenous distribution, lower phase transition, higher S_BET, and higher energy band gap.     

Studies on ferric oxide electrodes for the photo-assisted electrolysis of water

Results of the photoelectrochemical studies carried out with sintered discs of pure Fe₂O₃ and of Fe₂O₃ doped with TiO₂, SnO₂, ZrO₂ and Ta₂O₅ are compared and discussed. Flat band potential, saturation current and minority charge carrier diffusion length are higher for TiO₂-doped Fe₂O₃ samples than for other doped specimens. Ta₂O₅-doped Fe₂O₃ samples and SrFe₂O₄ have been found to be photo-inactive. The results are analysed in terms of depletion layer theory.     

Stability of the SnO2/MgO dye-sensitized photoelectrochemical solar cell

Dye-sensitized solar cells made of TiO₂ are extensively studied as a cheap alternative to conventional photovoltaic cells. The other familiar stable oxide material of similar band gap suitable for dye sensitization is SnO₂. Although cells based only of SnO₂ are prone to severe recombination losses, the cells made of SnO₂/MgO films where the SnO₂ crystallite is surface covered with an ultra-thin shell of MgO, deliver reasonably high efficiencies. It is found that SnO₂/MgO cells resist dye and electrolyte degradation better than TiO₂ cells. Furthermore, the ultra-thin barrier of MgO on SnO₂ remains intact during prolonged usage or storage of the cell.     

Hydrothermally stabilized Fe(III) doped titania active under visible light for water splitting reaction

Fe³⁺ doped TiO₂ photocatalysts were prepared by hydrothermal treatment for the photocatalytic water splitting to produce stoichiometric hydrogen and oxygen under visible light irradiation. It was found that hydrothermal treatment at 110 °C for 10 h was essential for the synthesis of highly stabilized Fe³⁺ doped TiO₂ photocatalysts. The synthesized photocatalysts were characterized by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS) and BET surface area techniques. The doping of highly stabilized Fe³⁺ in the titania matrix leads to significant red shift of optical response towards visible light owing to the reduced band gap energy. Optimum amount of Fe³⁺ doped TiO₂, 1.0 wt% Fe/TiO₂, showed drastically improved hydrogen production performance of 12.5 μmol-H₂/h in aqueous methanol and 1.8 μmol-H₂/h in pure water, respectively. This Fe/TiO₂ photocatalyst was stable for 36 h without significant deactivation in the water splitting reaction.     

Low cost photovoltaic modules based on dye sensitized nanocrystalline titanium dioxide and carbon powder

A new type of photovoltaic module based on monolithically series connected dye sensitized photoelectrochemical cells is described. Each solar cell element consists of three porous layers on a transparent conducting substrate, namely a photoelectrode of dye sensitized nanocrystalline TiO₂ (anatase), a spacer of electrically insulating, light reflecting particles of TiO₂ (rutile), and a counterelectrode of graphite powder and carbon black. The pores of these layers are filled with a redox electrolyte containing iodide for hole transport between photo- and counterelectrode. The monolithic series connection on the transparent conducting substrate, e.g., SnO₂ coated glass, is achieved by simple overlap of each carbon counterelectrode with the back contact of the adjacent photoelectrode. Such modules may be produced in a continuous non-vacuum process by simple printing techniques. In this paper we present the first results on energy conversion efficiency and long term stability obtained with this new type of solar cell.     

Performance of nano photocatalysts for the recovery of hydrogen and sulphur from sulphide containing wastewater

Stability of photocatalyst plays an important role in efficient hydrogen recovery from sulphide waste streams. This research focuses on the stability and efficiency of visible light active photocatalysts viz., RuO₂/CuGa_1.6Fe_0.4O₄, ZnFe₂O₃, (CdS + ZnS)/Fe₂O₃ and Ce/TiO₂ for H₂ production. RuO₂/CuGa_1.6Fe_0.4O₄ photocatalyst was found to give maximum hydrogen production of 8370 μmol/h. The reusability of the photocatalysts was tested by multiple cycles of catalyst regeneration along with H₂ production. The result shows that (CdS + ZnS) coated iron oxide core shell particles were found to be stable than other prepared nano photocatalysts. It is also demonstrated that H₂S can be split into hydrogen and sulphur under visible light irradiation using sulphide and sulphite reaction media at room temperature. This research paper will help in search of stable photocatalysts in recovering hydrogen from sulphide wastewater along with sulphur separation.     

Fabrication and electrochemical properties of three-dimensional net architectures of anatase TiO2 and spinel Li4Ti5O12 nanofibers

As a new type of electrodes engineering method with three-dimensional (3D) architecture for 3D rechargeable lithium ion batteries, an electrospinning has been successfully employed to prepare 3D net architectures of anatase TiO₂ and spinel Li₄Ti₅O₁₂ nanofibers. Scanning electron microscopy, X-ray diffraction, cyclic voltammetry and the discharge/charge measurements were used to characterize their structures and electrochemical properties. Our results demonstrated that 3D architectures stacked from a cross-bar array of electrospun anatase TiO₂ nanofibers could be accomplished but were destroyed after the insertion of Li ion. Significantly, spinel Li₄Ti₅O₁₂ could be selected as one of promise candidates for the realization of 3D batteries considering its structure stability of 3D spinel Li₄Ti₅O₁₂ nanofibers associated with well cyclability.     

In2O3:Sn/TiO2/CdS heterojunction nanowire array photoanode in photoelectrochemical cells

The design of photoanode with highly efficient light harvesting and charge collection properties is important in photoelectrochemical (PEC) cell performance for hydrogen production. Here, we report the hierarchical In₂O₃:Sn/TiO₂/CdS heterojunction nanowire array photoanode (ITO/TiO₂/CdS-nanowire array photoanode) as it provides a short travel distance for charge carrier and long light absorption pathway by scattering effect. In addition, optical properties and device performance of the ITO/TiO₂/CdS-nanowire array photoanode were compared with the TiO₂ nanoparticle/CdS photoanode. The photocatalytic properties for water splitting were measured in the presence of sacrificial agent such as SO₃²⁻ and S²⁻ ions. Under illumination (AM 1.5G, 100 mW/cm²), ITO/TiO₂/CdS-nanowire array photoanode exhibits a photocurrent density of 8.36 mA/cm² at 0 V versus Ag/AgCl, which is four times higher than the TiO₂ nanoparticle/CdS photoanode. The maximum applied bias photon-to-current efficiency for the ITO/TiO₂/CdS-nanowire array and the TiO₂ nanoparticle/CdS photoanode were 3.33% and 2.09%, respectively. The improved light harvesting and the charge collection properties due to the increased light absorption pathway and reduced electron travel distance by ITO nanowire lead to enhancement of PEC performance.     

Single crystalline TiO2 nanorods with enhanced visible light activity for solar hydrogen generation

Single crystalline TiO₂ nanorods and polycrystalline nanotubes were fabricated with same length to investigate the effects of their nanostructures on photocatalytic properties for splitting water. In order to enhance the visible light absorbance, TiO₂ nanorods and nanotubes were sensitized with semiconductor nanoparticles such as CdS, CdSe, and CdS/CdSe, and compared in viewpoint of solar hydrogen generation. It was observed that single-crystalline nanorods showed superior photocatalytic properties to polycrystalline nanotubes, and also the potential level of the nanorods with rutile phase was measured as lower than that of the nanotubes with mixture of anatase and rutile. Further improvement of photo-conversion efficiency was obtained by subsequent heat treatments of the sensitized photoelectrodes. It turns out that the improvement is attributed to the improved crystallinity and the increased size of the nanoparticles during the post-annealing treatments. It was demonstrated that TiO₂ nanorods with lower potential level and a single crystalline phase on FTO glass were advantageous for effective charge injection from the sensitized nanoparticles and transport without recombination lost at grain boundaries.