Landfill leachate treatment by solar-driven AOPs

Sanitary landfill leachate resulting from the rainwater percolation through the landfill layers and waste material decomposition is a complex mixture of high-strength organic and inorganic compounds which constitutes serious environmental problems. In this study, different heterogeneous (TiO₂/UV, TiO₂/H₂O₂/UV) and homogenous (H₂O₂/UV, Fe²⁺/H₂O₂/UV) photocatalytic processes were investigated as an alternative for the treatment of a mature landfill leachate. The addition of H₂O₂ to TiO₂/UV system increased the reduction of the aromatic compounds from 15% to 61%, although mineralization was almost the same. The DOC and aromatic content abatement is similar for the H₂O₂/UV and TiO₂/H₂O₂/UV processes, although the H₂O₂ consumption is three times higher in the H₂O₂/UV system. The low efficiency of TiO₂/H₂O₂/UV system is presumably due to the alkaline leachate solution, for which the H₂O₂ becomes highly unstable and self-decomposition of H₂O₂ occurs. The efficiency of the TiO₂/H₂O₂/UV system increased 10 times after a preliminary pH correction to 4. The photo-Fenton process is much more efficient than heterogeneous (TiO₂, TiO₂/H₂O₂/UV) or homogeneous (H₂O₂/UV) photocatalysis, showing an initial reaction rate more than 20 times higher, and leading to almost complete mineralization of the wastewater. However, when compared with TiO₂/H₂O₂/UV with acidification, the photo-Fenton reaction is only two times faster.The optimal initial iron dose for the photo-Fenton treatment of the leachate is 60 mg Fe²⁺ L⁻¹, which is in agreement with path length of 5 cm in the photoreactor. The kinetic behaviour of the process (60 mg Fe²⁺ L⁻¹) comprises a slow initial reaction, followed by a first-order kinetics (k = 0.020 , r₀ = 12.5 mg ), with H₂O₂ consumption rate of k_H2O2 = 3.0 mmol H₂O₂, and finally, the third reaction period, characterized by a lower DOC degradation and H₂O₂ consumption until the end of the experiment, presumably due to the formation of low-molecular-weight carboxylic groups. A total of 306 mM of H₂O₂ was consumed for achieving 86% mineralization (DOC_final = 134 mg L⁻¹) and 94% aromatic content reduction after 110 kJ_UV L⁻¹, using an initial iron concentration of 60 mg Fe²⁺ L⁻¹.     

Solar photocatalytic degradation of a reactive azo dye in TiO2-suspension

The photocatalytic decolourisation and degradation of an azo dye reactive orange 4 (RO4) in aqueous solution with TiO₂-P25 (Degussa) as photocatalyst in slurry form have been investigated using solarlight. There is a significant difference in adsorption of dye on TiO₂ surface with the change in solution pH. The effect of various photocatalysts such as TiO₂-P25, TiO₂ (anatase), ZnO, CdS, Fe₂O₃, SnO₂ on the decolourisation and degradation has been studied. The order of reactivity of photocatalysts is TiO₂-P25>ZnO>TiO₂ (anatase). CdS, Fe₂O₃ and SnO₂ have negligible activity on RO4 decolourisation and degradation. The effects of various parameters such as catalyst loading, pH and initial concentration of the dye on decolourisation and degradation have been determined. The degradation was strongly enhanced in the presence of electron acceptors such as H₂O₂, (NH₄)₂S₂O₈ and KBrO₃. The effects of dye-assisting chemicals such as Na₂CO₃, NaCl have been carried out. Addition of these chemicals inhibits the removal rate. The photodecolourisation and degradation kinetics are discussed in terms of Langmuir–Hinshelwood kinetic model.     

Visible-light sensitive hydrogen evolution photocatalyst ZnRh2O4

We investigated the ability of the oxide ZnRh₂O₄ to serve as a solar H₂-evolution photocatalyst due to the predicted potential of its conduction band bottom, which may allow thermodynamically favorable H₂ evolution in spite of its small band-gap of 1.2 eV. ZnRh₂O₄ produced H₂ in the presence of HCHO, but only scarcely in the presence of CH₃OH, indicating that the potential of the valence band top of ZnRh₂O₄ lies at ∼0.1 V (vs. SHE). Thus, the conduction band bottom potential (∼−1.1 V) lies much more negative than the potential of H⁺/H₂, allowing thermodynamically favorable H₂ evolution. In addition, the irradiated-light-wavelength dependence of the quantum efficiency (QE) for H₂ evolution was consistent with the solar spectrum, and the QE was quite high (∼27%), even at a wavelength of 770 ± 25 nm. Taken together, our findings indicate that ZnRh₂O₄ can utilize solar light effectively, not only the entire range of UV and visible light, but is also sensitive to infrared light.     

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.     

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.     

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⁻.     

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.     

Enhanced hydrogen generation using ZrO2-modified coupled ZnO/TiO2 nanocomposites in the absence of noble metal co-catalyst

Mesoporous ZrO₂-modified coupled ZnO/TiO₂ nanocomposites were prepared by a surfactant assisted sol–gel method. The photocatalytic performance of these materials was investigated for H₂ evolution without noble metal co-catalyst using aqueous methanol media under AM1.5 simulated light. The H₂ evolution was compared with coupled ZnO/TiO₂, TiO₂, ZnO and Degussa P25. The ZrO₂-modified nanocomposites exhibited higher H₂ generation, specifically 0.5 wt.% ZrO₂ loading produced 30.78 mmol H₂ g⁻¹ compared to 3.55 mmol H₂ g⁻¹ obtained with coupled ZnO/TiO₂. A multiple absorbance thresholds at 435 nm and 417 nm were observed with 0.5 wt.% ZrO₂ loading, corresponding to 2.85 eV and 2.97 eV band gap energies. The high surface area, large pore volume, uniform crystallite sizes and enhanced light harvesting observed in ZrO₂-modified nanocomposites were contributing factors for effective charge separation and higher H₂ production. The possible mechanism of H₂ generation from aqueous methanol solution over ZrO₂-modified nanocomposite is presented.     

Au/TiO2 catalysts prepared by photo-deposition method for selective CO oxidation in H2 stream

A series of Au/TiO₂ catalysts were prepared by photo-deposition (PD) method. Various preparation parameters, such as pH value, power of UV light and irradiation time on the characteristics of the catalysts were investigated. The catalysts were characterized by inductively-coupled plasma-mass spectrometry, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy. The preferential oxidation of CO in H₂ stream (PROX) on these catalysts was carried out in a fixed-bed micro reactor with a feed of CO: O₂: H₂: He = 1: 1: 49: 49 (volume ratios) and a space velocity of 30,000 ml/g h. Limited amount of O₂ was used to investigate the selectivity of O₂ reacting with CO or H₂. Au/TiO₂ catalysts prepared by PD method showed narrow particle size distribution of gold particles within few nanometers and were found to be 1.5 nm. The particle size of gold nanoparticles deposited on the support depends on irradiation time, UV light source and pH value of preparation. The electronic structure of Au was a function of particle size. The smaller the Au particle size was, the higher the concentration of Au cation was. Using weak power of UV light, appropriate irradiation time and suitable pH value, very fine gold particles on the support could be obtained even in the powder form. The samples prepared with PD method did not need heat treatment to reduce Au cation, UV irradiation could reduce it. Therefore it is easier to have smaller particle size. Au/TiO₂ catalysts prepared by PD method were very active and selective in PROX reaction. In long time test, the catalysts were stable at 80 °C for more than 60 h.     

Al2O3-coated nanoporous TiO2 electrode for solid-state dye-sensitized solar cell

This paper reports the preparation of a core-shell nanoporous electrode consisting of an inner TiO₂ porous matrix and a thin overlayer of Al₂O₃, and its application for solid-state dye-sensitized solar cell using p-CuI as hole conductor. Al₂O₃ overlayer was coated onto TiO₂ porous film by the surface sol–gel process. The role of Al₂O₃ layer thickness on the cell performance was investigated. The solar cells fabricated from Al₂O₃-coated electrodes showed superior performance to the bare TiO₂ electrode. Under illumination of AM 1.5 simulated sunlight (89 mW/cm²), a ca. 0.19 nm Al₂O₃ overlayer increased the photo-to-electric conversion efficiency from 1.94% to 2.59%.     

Synthesis of reduced graphene oxide–TiO2 nanoparticle composite systems and its application in hydrogen production

The utilization of solar energy for the conversion of water to hydrogen and oxygen has been considered to be an efficient strategy to solve crisis of energy and environment. Here, we report the synthesis of reduced graphene oxide–TiO₂ nanoparticle composite system through the photocatalytic reduction of graphite oxide using TiO₂ nanoparticles. Photoelectrochemical characterizations and hydrogen evolution measurements of these nanocomposites reveal that the presence of graphene enhances the photocurrent density and hydrogen generation rate. The optimum photocurrent density and hydrogen generation rate has been found to be 3.4 mA cm⁻² and 127.5 μmole cm⁻²h⁻¹ in 0.5 M Na₂SO₄ electrolyte solution under 1.5AM solar irradiance of white light with illumination intensity of 100 mW cm⁻². In graphene–TiO₂ nanocomposite, photogenerated electrons in TiO₂ are scavenged by graphene sheets and percolate to counter electrode to reduce H⁺ to molecular hydrogen thus increasing the performance of water-splitting reaction.     

Synergistic effects of advanced oxidization reactions in a combination of TiO2 photocatalysis for hydrogen production and wastewater treatment applications

In this paper, the synergistic effects of advanced oxidization reactions in a combination of TiO₂ photocatalysis are comparatively investigated for hydrogen production and wastewater treatment applications. An experimental study is conducted with a photoelectrochemical reactor under a UV-light source. TiO₂ is selected as the photocatalyst due to the high corrosion resistant nature and ability to form hydroxyl radicals with the interaction with photons. The synergetic effects of advanced oxidization processes (AOPs) such as Fenton, Fenton-like, photocatalysis (TiO₂/UV) and UV photolysis (H₂O₂/UV) are investigated individually and in a combination of each other. The Fenton type reagent in the reactor is formed by anodic sacrificial of stainless-steel electrode with the presence of H₂O₂. The influences of various parameters, including pH level, type of the electrode and electrolyte and the UV light, on the performance of the combined system are also investigated experimentally. The highest chemical oxygen demand (COD) removal efficiency is observed as 97.9% for the experimental condition which combines UV/TiO₂, UV/H₂O₂ and photo-electro Fenton type processes. The maximum hydrogen production rate from the photoelectrolysis of wastewater is obtained as 7.0 mg/Wh for the experimental condition which has the highest rate of photo-electro Fenton type processes. The average enhancement with the presence of UV light on hydrogen production rates and COD removal efficiencies are further calculated to be 3% and 20%, respectively.     

Field solar E. coli inactivation in the absence and presence of TiO2: is UV solar dose an appropriate parameter for standardization of water solar disinfection?

Evaluation of solar treatment in the absence and presence of TiO₂ has been made to assess its effectiveness in reducing bacterial load with respect to drinking water standards.Field experiments under direct solar radiation were carried out using a compound parabolic collector (CPC) placed at the Swiss Federal Institute of Technology (EPFL), Lausanne, Switzerland. Water contaminated with E. coli K12 was exposed to sunlight in different seasons. The obtained results indicate that the presence of TiO₂ accelerates the detrimental action of light. Total photocatalytic disinfection was obtained in both periods of year and no bacterial recovery was observed during 24 h after stopping sunlight exposure. In the absence of TiO₂, total disinfection was not always reached; and bacterial recovery was observed, especially when inactivation was not complete. Bacterial decay was mainly dependent on light intensity. It was also demonstrated that solar UV dose is not a pertinent parameter to standardize solar disinfection. The influence of the following topics on solar water disinfection is also studied in this paper: (a) UV and total solar spectra characteristics (b) volume of phototreated water (c) post-irradiation events.     

Treatment of textile wastewaters by solar-driven advanced oxidation processes

Heterogeneous (TiO₂/UV, TiO₂/H₂O₂/UV) and homogenous (H₂O₂/UV, Fe²⁺/H₂O₂/UV) solar advanced oxidation processes (AOPs) are proposed for the treatment of recalcitrant textile wastewater at pilot-plant scale with compound parabolic collectors (CPCs). The textile wastewater presents a lilac colour, with a maximum absorbance peak at 516 nm, high pH (pH = 11), moderate organic content (DOC = 382 mg C L⁻¹, COD = 1020 mg O₂ L⁻¹) and high conductivity (13.6 mS cm⁻¹), associated with a high concentration of chloride (4.7 g Cl⁻ L⁻¹). The DOC abatement is similar for the H₂O₂/UV and TiO₂/UV processes, corresponding only to 30% and 36% mineralization after 190 kJ_UV L⁻¹. The addition of H₂O₂ to TiO₂/UV system increased the initial degradation rate more than seven times, leading to 90% mineralization after exposure to 100 kJ_UV L⁻¹. All the processes using H₂O₂ contributed to an effective decolourisation, but the most efficient process for decolourisation and mineralization was the solar-photo-Fenton with an optimum catalyst concentration of 100 mg Fe²⁺ L⁻¹, leading to 98% decolourisation and 89% mineralization after 7.2 and 49.1 kJ_UV L⁻¹, respectively. According to the Zahn-Wellens test, the energy dose necessary to achieve a biodegradable effluent after the solar-photo-Fenton process with 100 mg Fe²⁺ L⁻¹ is 12 kJ_UV L⁻¹.     

Dye-sensitized nanocrystalline TiO2 solar cells based on novel coumarin dyes

We have developed dye-sensitized nanocrystalline TiO₂ solar cells (DSSCs) based on novel coumarin-dye photosensitizers. The absorption spectra of these novel dyes are red-shifted remarkably in the visible region relative to the spectrum of C343, a conventional coumarin dye. Introduction of a methine unit (–CH=CH–) connecting the cyano (–CN) and carboxyl (–COOH) groups into the coumarin framework expanded the π-conjugation in the dye and thus resulted in a wide absorption in the visible region. These novel dyes performed as efficient photosensitizers for DSSCs. A DSSC based on 2-cyano-5-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-penta-2,4-dienoic acid (NKX-2311), produced a 6.0% solar energy-to-electricity conversion efficiency (η), the highest performance among DSSCs based on organic-dye photosensitizers, under AM 1.5 irradiation (100 mW cm^–2) with a short-circuit current density (J_sc) of 14.0 mA cm^–2, an open-circuit voltage (V_oc) of 0.60 V, and a fill factor of 0.71. Our results suggests that the structure of NKX-2311 whose carboxyl group is directly connected to the –CH=CH– unit, is advantageous for effective electron injection from the dye into the conduction band of TiO₂. In addition, the cyano group, owing to its strong electron-withdrawing ability, might play an important role in electron injection in addition to a red shift in the absorption region. On a long-term stability test under continuous irradiation with white light (80 mW cm^–2), stable performance was attained with a solar cell based on the NKX-2311 dye with a turnover number of 2.6×10⁷ per one molecule.     

Facile fabrication of mesoporous TiO2 electrodes for dye solar cells: chemical modification and repetitive coating

A chemical dispersing technique for preparing a coating paste of TiO₂ nanoparticles is disclosed to fabricate mesoporous electrodes for dye-sensitized TiO₂ solar cells. The suspension of TiO₂ (P-25) powder was stirred in aqueous nitric acid at 80°C, and then evaporated to dryness, giving the nitric acid-adsorbed P-25 powder. The coating paste was obtained by mixing the nitric acid-adsorbed P-25 with PEG (M_w 20,000) as a porosity-controlling agent and cellulosic polymer as a thickener. The mesoporous TiO₂ films were fabricated on conducting glasses by repetitive coating and calcined at 500°C (30 min). The TiO₂ film obtained by the five times repetitive coating (20 μm thickness) resulted in the 1.4 times higher energy conversion efficiency of the dye-sensitized solar cells than that of the one time coating TiO₂ film (V_oc=690 mV, J_sc=12.2 mA/cm², the fill FACTOR=0.71 and η=6.0%).     

Ferrioxalate-mediated solar degradation of organic contaminants in water

The capture and use of solar energy for the destruction of organic pollutants in aqueous media has been studied. The sunlight is captured by ferrioxalate which, in the presence of hydrogen peroxide, generates hydroxyl radicals. The latter reacts with and oxidizes organic molecules present in aqueous media. The efficiency of this new process for the destruction of organic molecules in tap water is at least 25 times greater than sunlight/TiO₂/H₂O₂, which is a known process for solar detoxification.     

Morphological, optical and photocatalytic properties of TiO2–Fe2O3 multilayers

Morphological, optical and photocatalytic properties of TiO₂, Fe₂O₃ and TiO₂–Fe₂O₃ samples (formed by 1, 3 and 5 coatings) were studied. The layers were deposited on glass substrate by the sol–gel method. The catalytic activity of the samples was studied by the photodecomposition of methylene blue (MB) under visible light illumination. The FTIR results indicate that all samples present surface OH radicals that are bound either to the Ti or Fe atoms. This effect is better visualized at larger number of coatings in the TiO₂–Fe₂O₃/glass systems. Also, two mechanisms are observed during the photodecomposition of the MB.     

CuCr2O4/TiO2 heterojunction for photocatalytic H2 evolution under simulated sunlight irradiation

CuCr₂O₄/TiO₂ heterojunction has been successfully synthesized via a facile citric acid (CA)-assisted sol-gel method. Techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectrum (UV-vis DRS) have been employed to characterize the as-synthesized nanocomposites. Furthermore, photocatalytic activities of the as-obtained nanocomposites have been evaluated based on the H₂ evolution from oxalic acid solution under simulated sunlight irradiation. Factors such as CuCr₂O₄ to TiO₂ molar ratio in the composites, calcination temperature, photocatalyst mass concentration, and initial oxalic acid concentration affecting the photocatalytic hydrogen producing have been studied in detail. The results showed that the nanocomposite of CuCr₂O₄/TiO₂ is more efficient than their single part of CuCr₂O₄ or TiO₂ in producing hydrogen. The optimized composition of the nanocomposites has been found to be CuCr₂O₄·0.7TiO₂. And the optimized calcination temperature and photocatalyst mass concentration are 500 °C and 0.8 g l⁻¹, respectively. The influence of initial oxalic acid concentration is consistent with the Langmuir model.