Continuous flow photochemical reactor for solar decontamination of water using immobilized TiO2

A photochemical reactor is designed for solar decontamination of organic pollutants in water, where the nanocrystalline photocatalyst TiO₂ is immobilized on glass. The reactor modules could be connected in series and/or parallel to achieve desired flow rates under different conditions of illumination and degree of contamination. Methyl violet and phenol was found to completely degrade under solor irradiation and flow rates of 102–138 ml/h.     

On the impact evaluation of various chemical treatments of support on the photocatalytic properties and hydrogen evolution of sonochemically synthesized TiO2/Clinoptilolite

The water splitting process for hydrogen production was investigated over a series of TiO₂-deposited Clinoptilolite photocatalysts assessing the individual and synergistic effects of acid/alkaline and ion exchange treatments of Clinoptilolite as a support on the physicochemical properties and photocatalytic performance. The as-synthesized photocatalysts were characterized by XRD, BET, FESEM, EDX, FTIR, PL, and UV–vis techniques. Based on the FESEM, EDX and BET techniques, higher dispersion of Ti species and an increased accessibility of the micro-channels could be achieved using modified Clinoptilolite supports due to their better textural properties. The fine dispersion of TiO₂ particles reflects higher surface density of active sites and separation efficiency of electron–hole pairs, which accounts for their better photocatalytic performance. The characterization results generally indicated the remarkable synergetic effect of alkaline treatment on the surface morphology and TiO₂ dispersion, especially when it is coupled with NH₄NO₃ treatment. The photocatalytic tests illustrated that employing the treated Clinoptilolite supports increases the photocatalytic activity up to 12–57%. It was found that TiO₂ supported on the alkaline Clinoptilolite followed by NH₄NO₃ treatment effectively splitted water to hydrogen by $896\text{.}8\text{μmol}{\text{g}}_{{\text{TiO}}_2}^{\mathrm{?}1}{\text{h}}^{\mathrm{?}1}$ hydrogen production rate. The results indicate that the ion exchange-alkaline treatment of Clinoptilolite could provide strong basic sites and mesopore structure (average pore diameter of 21.65 nm) with high surface area (73.43 m² g^?1) and well dispersion ability to improve the photocatalytic activity of TiO₂/Clinoptilolite composite for hydrogen evolution.     

A 2D/1D TiO2 nanosheet/CdS nanorods heterostructure with enhanced photocatalytic water splitting performance for H2 evolution

TiO₂ with exposed (001) facets were composited with CdS nanorods to construct 2D/1D heterojunction. As comparison, P25 with mainly exposed (101) facets were employed to combine with CdS nanorods. The 2D/1D heterojunction of TiO₂ nanosheets and CdS nanorod displayed 3.7 times higher hydrogen generation than that of P25/CdS composites. The results indicated that TiO₂ with exposed (001) facets were favorable for enhancing the photocatalytic activity of CdS via optimizing the heterojunction between TiO₂ and CdS. Photoluminescence and photoelectrochemical characteristics results demonstrated that the 2D-TiO₂/1D-CdS heterojunction exhibits higher separation efficiency of photoinduced carriers and superior electron transfer ability. This work exemplifies that heterojunction modification is an effective strategy to improve the efficiency of the photocatalyst composites.     

Remarkable promotion of photocatalytic hydrogen evolution from water on TiO2-pillared titanoniobate

TiO₂-pillared titanoniobate TiO₂/HTiNbO₅ as an efficient photocatalyst was prepared via an exfoliation–restacking route. The as-prepared nanohybrid is mesoporous with a high specific surface area of 171 m²/g and a gallery height of 1.55 nm. Under a 300 W Xe lamp irradiation, the nanohybrid exhibited a high photocatalytic activity of 219 μmol/h/(g cat) in splitting water into hydrogen, which is 12 times as high as its parent HTiNbO₅ (18 μmol/h/g) and 24 times as TiO₂ (9 μmol/h/g). Enlarged surface area and effective electronic coupling between the host and the guest components contribute to the high photocatalytic activity of TiO₂/HTiNbO₅. Its photocatalytic activity was further improved through platinizing, and 5 wt% Pt-loaded TiO₂/HTiNbO₅ gave a remarkable hydrogen evolution rate of 4735 μmol/h/g. A photoexcitation model of the semiconductor–semiconductor pillared photocatalyst was proposed based on the results of XPS and UV–vis.     

TiO2 nanosheets loaded with Cu: A low-cost efficient photocatalytic system for hydrogen evolution from water

Rutile TiO₂ nanosheets were prepared by a simple solvothermal process, and Cu was loaded on the surface of TiO₂ nanosheets using the in situ photo-deposition method. Meanwhile, photocatalytic H₂ evolution from water over the as-prepared TiO₂ nanosheets loaded with Cu was explored using methanol as a sacrificial reagent. The results indicate that the TiO₂ nanosheets loaded with Cu is an efficient photocatalyst under UV irradiation. During the first 5 h, a rate of H₂ evolution of approximately 22.1 mmol g⁻¹ h⁻¹ was achieved under optimal conditions. Furthermore, for practical purposes, the photocatalytic hydrogen evolution was studied as a function of content of Cu, pH of solution, concentration of methanol and dosage of photocatalyst, respectively. At last, the photocatalytic mechanism was preliminarily discussed.     

Solar photocatalysis for detoxification and disinfection of water: Different types of suspended and fixed TiO2 catalysts study

Photocatalysis by titanium dioxide (TiO₂), operational in the UV-A domain with a potential use of solar radiation, could be an alternative to conventional water detoxification and disinfection technologies. However, employing the photocatalyst as a suspension or slurry makes the scaling-up of the process difficult, as the TiO₂ has to be removed from the decontaminated water to be reused several times. In this work the photocatalytic activity of different types of TiO₂ catalyst (Degussa P-25, Millennium PC-100 and PC-500, Tayca AMT-100 and AMT-600) in suspension or coated on fibrous web were studied in both decontamination and disinfection experiments at laboratory scale. Gallic acid was chosen as the model pollutant for detoxification experiments and Escherichia coli as the model microorganism for disinfection experiments. The influence of the surface area and other characteristics of TiO₂ are discussed concerning the photocatalytic properties of TiO₂. The role of adsorption is suggested, indicating that the reaction occurs at the TiO₂ surface and not in the solution. Gallic acid degradation kinetics were found to be of the same extent for both TiO₂ suspended and fixed, whereas for the bacterial inactivation efficiency was significantly less important with coated than with suspended TiO₂.     

Efficiency in the disinfection of water for human consumption in rural communities using solar radiation

The efficiency of solar disinfection for the inactivation of Total Coliforms (TC) and Escherichia coli (EC) in drinking water was tested in rural communities of the Guachochi Municipality, in the Tarahumara Sierra, State of Chihuahua, Mexico.The study zone was selected mostly because it lacks formal water supply systems and the population is forced to consume untreated water directly from rivers and shallow or artesian wells without treatment.To determine the bacteriological quality of the water consumed by the population, the amount of TC and EC in the water supplies of 23 communities in the studied municipality was determined.The efficiency of the solar energy based water disinfection process was determined for several months of the humid and dry seasons with water from the most contaminated sources of the study zone. The performed tests consisted in studying the effect of disinfecting water by direct exposure to sunlight during the whole day, with and without solar concentrators, in plastic bottles of commercial beverages. The three types of bottles used were transparent, partially painted black (one half of the bottle, along the longitudinal axis), and totally black.The study shows that, in this geographic zone, the available water must be disinfected before consumption and disinfection efficiency can reach 100% through the use of solar radiation. It was found that, since more than 6 h of daily solar radiation are available during most of the year in this zone, no solar concentrators are really necessary to ensure the complete elimination of bacteria. A complete disinfection takes place by simply placing water bottles in the sunlight during the whole day.Nevertheless, the use of solar concentrators and bottles partially painted black increases the TC and EC inactivation efficiency, reducing the solar exposure time required for a total disinfection to just 2 h. With the use of solar concentrators and partially blackened bottles, the water temperature reached 65 °C, while only 50 °C were achieved when using the same concentrators and completely transparent bottles.     

TiO2 nanotubes incorporated with CdS for photocatalytic hydrogen production from splitting water under visible light irradiation

The CdS/TiO₂ composites were synthesized using titanate nanotubes (TiO₂NTs) with different pore diameters as the precursor by simple ion change and followed by sulfurization process at a moderate temperature. Some of results obtained from XRD, TEM, BET, UV–vis and PL analysis confirmed that cadmium sulfide nanoparticles (CdSNPs) incorporated into the titanium dioxide nanotubes. The photocatalytic production of H₂ was remarkably enhanced when CdS nanoparticles was incorporated into TiO₂NTs. The apparent quantum yield for hydrogen production reached about 43.4% under visible light around λ = 420 nm. The high activity might be attributed to the following reasons: (1) the quantum size effect and homogeneous distribution of CdSNPs; (2) the synergetic effects between CdS particles and TiO₂NTs, viz., the potential gradient at the interface between CdSNPs and TiO₂NTs.     

Chemical bath deposition synthesis of TiO2/Cu2O core/shell nanowire arrays with enhanced photoelectrochemical water splitting for H2 evolution and photostability

In this study, we have developed a facile chemical bath deposition (CBD) method to grow p-type Cu₂O nanoparticles on n-type TiO₂ nanowire arrays (TiO₂ NWAs) to fabricate TiO₂/Cu₂O core/shell heterojunction nanowire arrays (TiO₂/Cu₂O core/shell NWAs). When used as photoelectrode, the fabricated TiO₂/Cu₂O core/shell NWAs show improved photoelectrochemical (PEC) water splitting activity to pure TiO₂ NWAs. The effects of the CBD cycle times on the PEC activities have been studied. The TiO₂/Cu₂O core/shell heterojunction nanowire array photoelectrode prepared by cycling 5 times in the CBD process achieves the highest photocurrent of 2.5 mA cm^?2, which is 2.5 times higher than that of pure TiO₂ NWAs. In addition, the H₂ generation rate of this photoelectrode reaches to 32 μmol h^?1 cm^?2, 1.7 times higher than that of pure TiO₂ NWAs. Furthermore, the TiO₂/Cu₂O core/shell heterojunction nanowire array photoelectrode shows excellent photostability and achieves a stable photocurrent of over 2.3 mA cm^?2 during long light illumination time of 5 h. The enhanced photocatalytic activity of TiO₂/Cu₂O core/shell heterojunction nanowire array photoelectrode is attributed to the synergistic actions of TiO₂ and Cu₂O for improving visible light harvesting, and efficient transfer and separation of photogenerated electrons and holes.     

The role of CuO in promoting photocatalytic hydrogen production over TiO2

Low cost semiconductor photocatalysts that can efficiently harvest solar energy to generate H₂ from water or biofuels will be critical to future hydrogen economies. In this study, low cost CuO/TiO₂ photocatalysts (CuO loadings 0–15 wt.%) were prepared, characterized and evaluated for H₂ production from ethanol–water mixtures (80 vol.% ethanol, 20 vol.% H₂O) under UV excitation. TEM, XRF, EDAX, EPR, Raman, TGA, XPS and Cu L-edge NEXAFS data showed that at CuO loadings <5 wt.%, Cu(II) was highly dispersed over the TiO₂ support, possibly as a sub-monolayer CuO species. At higher loadings, CuO crystallites of diameter 1–2 nm were identified. The photocatalytic activity of CuO/TiO₂ photocatalysts was highly dependent on the CuO loading, with 1.25 wt.% CuO being optimal (H₂ production rate = 20.3 mmol g⁻¹ h⁻¹). Results suggest that sub-monolayer coverages of Cu(II) or CuO on TiO₂ are highly beneficial for H₂ generation from ethanol–water mixtures and support the development of a sustainable H₂ economy.     

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%).     

Metalloid Ni2P and its behavior for boosting the photocatalytic hydrogen evolution of CaIn2S4

The development of high-efficiency and low-cost photocatalysts in photocatalytic H₂ evolution systems from water remains challenging. The substitution of a noble metal as the co-catalyst is still one of the important and meaningful issues in this field. Herein, we report a series of CaIn₂S₄ catalysts combined with Ni₂P, which acts as the co-catalyst, for boosting photocatalytic hydrogen evolution under visible light. The integrated system of the Ni₂P/CaIn₂S₄ composite exhibited high efficiency and durability, which were even higher than those of Pt decorated catalysts. The promoting effect of Ni₂P can be ascribed to its excellent reductive ability and analogous metallic character, which can accelerate the transfer and consumption of the photo-generated electrons. Moreover, based on the surface photo-voltage technique and electrochemical tests, the unique mechanism of Ni₂P for the movement of photo-generated charges during the photocatalysis process is proposed for the first time.     

A novel UV-mediated low-temperature sintering of TiO2 for dye-sensitized solar cells

Titania pastes were fired at 450 °C in oxygen to give white titania that was used to prepare dye-sensitized solar cells (DSSC). Titania fired at lower temperature and/or under inert atmosphere have brown stripes and cells made from these stripes had no measurable efficiency. When the titania paste was screen printed and then heated and simultaneously irradiated with UV light, white stripes were obtained. Improved efficiency was noted for PV cells made from pastes heated at lower temperature under irradiation vs. cells made from low-temperature heated paste but without irradiation. UV irradiation appears to facilitate clean oxidation of residual organic materials in the titania precursor pastes. The best cells in our study made with our titania paste treated at 450 °C in oxygen had the following characteristics: efficiency=3.45%; V_oc=630 mV; J_sc=8.5 mA/cm²; and a fill factor=0.64.     

Controllable O2 oxidization graphene in TiO2/graphene composite and its effect on photocatalytic hydrogen evolution

TiO₂/reduced graphene oxide composite (T-rGO) was synthesized and its performance was evaluated with photocatalytic hydrogen evolution. It was found that the hydrogen evolution rate of T-rGO increased significantly after injecting small amount of air into the vacuum pumped and UV irradiated sealed reaction cell. The IR, XPS, Raman and ESR spectra analysis indicated that the O₂^•−, which generated from the reaction of photoinduced electrons and the injected O₂ can moderately and controllably increase the oxygen groups on graphene planar of T-rGO at ambient condition. The amount of oxygen groups on graphene planar of T-rGO will affect the p-doping concentration of graphene, thus affect the p–n junction and the performance of T-rGO for photocatalytic hydrogen evolution.     

High photocatalytic hydrogen production over the band gap-tuned urchin-like Bi2S3-loaded TiO2 composites system

A new system using Bi₂S₃-loaded TiO₂ photocatalysts (Bi₂S₃/TiO₂) was developed to enhance the production of hydrogen. The Bi₂S₃ (5, 10, 15 wt%) particles in an urchin-like morphology with a length of about 2∼3 μm and a diameter of 15–20 nm, which can absorb all wavelengths in UV–visible radiation, were prepared by solvothermal method and loaded onto nano-sized TiO₂ (10∼15 nm) for photocatalysis on hydrogen production. The evolution of H₂ from methanol/water (1:1) photo splitting over the Bi₂S₃/TiO₂ composite in the liquid system was enhanced, compared with that over pure TiO₂ and Bi₂S₃. In particular, 14.2 ml of H₂ gas was produced after 12 h when 0.5 g of a 10 wt% Bi₂S₃/TiO₂ composite was used. On the basis of cyclic voltammetry (CV) results, the high photoactivity was attributed to the increase of band gap in the Bi₂S₃/TiO₂ composite, due to the decreased recombination between the excited electrons and holes.     

TiO2-containing cement pastes and mortars: Measurements of the photocatalytic efficiency using a rhodamine B-based colourimetric test

The photocatalytic activities of cement pastes and mortars, containing various amounts of titanium dioxide (TiO₂) in the anatase form, were evaluated and compared. The density, total porosity and pore size distribution of the materials were measured, and the amount of TiO₂ being at their surfaces was estimated. The photocatalytic efficiency was evaluated by monitoring the discolouration of rhodamine B applied to the surface of the materials which were then exposed to artificial sun light; this evaluation was based on the use of a dimensionless specific activity coefficient. For TiO₂ contents higher than 1 wt% (up to 5 wt%), cement pastes exhibited a photocatalytic activity higher than that of mortars because their activity was roughly proportional to the TiO₂ content, whereas the activity of mortars levelled off. On the other hand, the type of cement used to prepare the materials had a low effect on the photocatalytic performances.     

The size and valence state effect of Pt on photocatalytic H2 evolution over platinized TiO2 photocatalyst

Photocatalytic hydrogen production from water or organic compounds is a promising way to resolve our energy crisis and environmental problems in the near future. Over the past decades, many photocatalysts have been developed for solar water splitting. However, most of these photocatalysts require cocatalyst to facilitate H₂ evolution reaction and noble metals as key cocatalysts are widely used. Consequently, the condition of noble metal cocatalyst including the size and valence state etc plays the key role in such photocatalytic system. Here, the size and valence state effect of Pt on photocatalytic H₂ evolution over platinized TiO₂ photocatalyst were studied for the first time. Surprisingly, it was found that Pt particle size does not affect the photoreaction rate with the size range of several nanometers in this work, while it is mainly depended on the valence state of Pt particles. Typically, TOFs of TiO₂ photodeposited with 0.1–0.2 wt% Pt can exceed 3000 h⁻¹.     

Physically and chemically synthesized TiO2 composite thin films for hydrogen production by photocatalytic water splitting

TiO₂ thin films have been synthesized by radio-frequency magnetron sputtering and sol–gel method to study the hydrogen generation by photocatalytic water splitting under visible light irradiation. Photoelectrochemical cell with chemical bias, involving photo-anode in form of TiO₂ film deposited on conducting indium tin oxide (ITO) film and Pt as cathode, is developed. The effect of conducting ITO layer on photo-voltage is studied by varying the thickness of ITO films. Constant H₂ generation rate is obtained for long period of time by both the TiO₂ films because of the separated evolution of H₂ and O₂ gas, thus eliminating the back-reaction effect. Sputter-deposited film as compared to sol–gel-synthesized film showed better H₂ generation rate, mainly explained in terms of the higher visible light absorption achieved by oxygen vacancies created in the TiO₂ film by the energetic target ions during deposition in pure Ar gas pressure.     

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.     

Modification of the photocatalytic properties of self doped TiO2 nanoparticles for hydrogen generation using sunlight type radiation

Synthetic approaches/methodologies can change the properties of nanoparticles significantly. In this study, the photocatalytic property of self (Ti³⁺) doped TiO₂ nanoparticles was modified by synthesizing through different routes. Solvothermal (T-Sol), sonochemical (T-Son) and polyol (T-Pol) methods were employed to prepare TiO₂ nanoparticles and the photocatalytic activities of these samples were compared with that of the sample prepared by precipitation using ammonia solution (T-Ppt). All samples had particle size below 30 nm except T-Son, where small nanoparticles existed as large spherical agglomerates with size around 500 nm. Surface area and porosity measurements of these different TiO₂ samples showed a significant dependency on the synthesis method. UV–Visible absorption spectra showed the onset of absorption at ∼440 nm for all samples due to the presence of defect levels originating from anion vacancies. Photocatalytic activity for hydrogen generation decreased in the order T-Sol > T-Son > T-Pol > T-Ppt and the observed activity is correlated with their physical properties such as surface area and crystallinity. The hydrogen yield was highly enhanced by the addition of Pd metal as co-catalyst on the surface of TiO₂ photocatalysts. Present experiments clearly demonstrate the importance of synthesis route to improve the photocatalytic activity of TiO₂.