Hydroxyl radical scavenging-based method for evaluation of TiO2 photocatalytic activity.

A novel hydroxyl radical scavenging method was developed to establish the photocatalytic activity of TiO2 thin films. Transparent TiO2 thin films were prepared on soda-lime glass substrates using the sol-gel method and characterized using X-ray diffraction. During photoirradiation in aqueous buffered solutions, activity of the films was followed using the substituted nitrobenzene N,N'-(5-nitro-1,3-phenylene)bisglutaramide as a hydroxyl radical scavenger and its hydroxylated products were quantified using HPLC. The yield of hydroxyl radicals was evaluated at various pH of the reaction media, and reflected the dependence of the rate of the hydroxylation reaction on the experimental conditions and on the different qualities of the TiO2 thin films. The proposed method allows for direct assessment of hydroxyl radical production, it is straightforward and is proposed for routine use.

Microplate-based assays for the evaluation of antibacterial effects of photocatalytic coatings.

Three microplate-based viability assays for assessing the antibacterial effects of photocatalytic coatings were compared to the conventional colony count method. In the experimental design, cultured Escherichia coli were exposed to photocatalysis on various TiO(2) films in the presence of either UVA or visible light. The photocatalytic effects on the bacterial physiology were determined by real-time measurements of metabolic activity (XTT assay), biomass formation in the liquid medium (growth assay), and by assessing membrane integrity (with propidium iodide and SYTO 9 fluorescent nucleic acid binding dyes-BacLight assay). All three methods proved to be more sensitive and reproducible than colony count for the evaluation of the bactericidal effect of photocatalysis, XTT, and growth assay succeeded in detecting differences in both UVA and visible light-activated photocatalytic coatings. BacLight could efficiently detect the visible light-dependent photocatalytic effect on bacteria and identify membrane damage, but resulted inadequate for evaluating the UVA-dependent antibacterial effects. The described microplate-based evaluation methods proved being more effective and rapid than the colony count assay for assessing the antibacterial effect of various photocatalytic coatings.

Enhanced photo-degradation of N-methyl-2-pyrrolidone (NMP): Influence of matrix components, kinetic study and artificial neural network modelling.

This study investigates the degradation of N-methyl-2-pyrrolidone (NMP) by UV-C and UV-C/PMS-treatment processes. The degradation of NMP was less than 2% by UV-C photolysis. To enhance the degradation, PMS was used as a source of sulphate (SO4• -) and hydroxyl (HO•) radicals in the UV-C photolysis treatment system. The operational parameters such as initial pH and concentration of NMP and PMS and water matrix elements were studied to understand their effects on degradation. At pH = 6.3, λ = 260 nm, initial concentration of NMP = 10 mg/L, PMS = 300 mg/L and carbonate ion = 150 mg/L, the degradation of NMP was found to be 97.5%, along with 26.86% of TOC removal. The bicarbonate ions, nitrate ions, and chloride ions showed the inhibitory effect on the degradation of NMP. The NMP degradation was governed by pseudo first order kinetics. SO4• - was found to be the dominating degradation species through the radical quenching studies. The intermediates formed during the degradation were identified through LC-MS analysis, and a degradation pathway was proposed. The experimental data was successfully validated through the application of the developed ANN model. The R2 between expected and experimental outcomes was 0.97. The developed ANN model was successful in predicting the degradation of NMP in the given reaction conditions with the prediction accuracy of 90.91% and RMSE of 3.54.

Highly active and efficient Cu-based hydrotalcite-like structured materials as reusable heterogeneous catalysts used for transcarbonation reaction.

A series of robust and efficient Cu-Al hydrotalcite-like compounds (HTLc) as catalysts were prepared by the simple precipitation method with different Cu/Al molar ratios and investigated for the transcarbonation of glycerol with dimethyl carbonate (DMC) for glycerol carbonate (GC) synthesis in a batch reactor. The structural and textural properties of the Cu-Al (HTLc) catalysts were analyzed by several methods like N2-sorption, SEM-EDX/TEM, XRD, FTIR, CO2-TPD, TGA/DTA and ICP-OES. It was found that the transcarbonation of glycerol is directly dependent on the strong basic sites of the catalysts. The Cu/Al molar ratio has easily tuned the glycerol conversion and the GC yield. Among all synthesized catalysts, the Copper-Aluminum (3Cu-Al@500) catalyst showed excellent catalytic activity for a glycerol conversion (96%) and a GC yield (86%) with reaction rate (irrespective to glycerol) of approximately 0.106 mol L-1 h-1. Furthermore, the optimization of the reaction conditions (i.e. molar ratio of the reactants, catalyst mass, reaction time and temperature) and the reusability of the 3Cu-Al@500 catalyst for glycerol conversion and GC yield with TOF value were studied. In addition, the effect of stirring speed and particle size on the minimization of external and internal mass transfer resistance, respectively, was investigated.

Optimization Method of the Solvothermal Parameters Using Box-Behnken Experimental Design-The Case Study of ZnO Structural and Catalytic Tailoring.

ZnO photocatalysts were synthesized via solvothermal method and a reduced experimental design (Box-Behnken) was applied to investigate the influence of four parameters (temperature, duration, composition of the reaction mixture) upon the photocatalytic activity and the crystal structure of ZnO. The four parameters were correlated with photocatalytic degradation of methyl orange and the ratio of two crystallographic facets ((002) and (100)) using a quadratic model. The quadratic model shows good fit for both responses. The optimization experimental results validated the models. The ratio of the crystal facets shows similar variation as the photocatalytic activity of the samples. The water content of the solvent is the primary factor, which predominantly influence both responses. An explanation was proposed for the effect of the parameters and how the ratio of (002) and (100) crystal facets is influenced and its relation to the photocatalytic activity. The present research laconically describes a case study for an original experimental work, in order to serve as guideline to deal with such complicated subjects as quantifying influence of synthesis parameters upon the catalytic activity of the obtained ZnO.

Infrared spectroscopic and conductivity studies of ureasil-based proton conducting membranes for medium temperature fuel cell applications.

Proton conducting membranes for fuel cells were prepared by the sol-gel process from two different ureasil organic-inorganic hybrid precursors: bis[(N-(3-triethoxysilylpropyl)ureido]-terminated poly(propylene glycol) 4000 (PPGU) and bis[3-(N-(3-triethoxysilylpropyl)ureido)propyl]-terminated poly(dimethylsiloxane) 1000 (PDMSU). Heteropoly silicotungstic acid was added to actuate the reactions of hydrolysis and condensation and to introduce proton conductivity. XRD measurements of membranes revealed the presence of a diffraction peak at 6.3°, which could be ascribed to gradual formation of R-(SiO3/2) silsesquioxane clusters, i.e. arrangement of the Si-O-Si skeleton on the nano-scale. TG and DSC measurements showed thermal stability of the membranes above 120 °C. Proton conductivities at room temperature were of the order of 10-4 to 10-3 S/cm, classifying the membranes in the group of super ionic conductors. At elevated temperatures up to 160 °C and at conditions of autogenous pressure, conductivities increased up to values acceptable for fuel cells of 10-1 S/cm, which could be the result of the presence of H3O+ ions. The protonation of the urea groups and the formation of amidonium ions [C(OH)=NH+] were followed using IR ATR spectroscopy.

One-Pot Synthesis of Sulfur-Doped TiO2/Reduced Graphene Oxide Composite (S-TiO2/rGO) With Improved Photocatalytic Activity for the Removal of Diclofenac From Water.

Sulfur-doped TiO2 (S-TiO2) composites with reduced graphene oxide (rGO), wt. % of rGO equal to 0.5%, 2.75%, and 5.0%, were prepared by a one-pot solvothermal procedure. The aim was to improve photocatalytic performance in comparison to TiO2 under simulated solar irradiation for the treatment of diclofenac (DCF) in aqueous medium. The obtained composites were characterized for physical-chemical properties using thermogravimetric analysis (TGA), X-ray diffractograms (XRD), Raman, scanning electron microscopy (SEM)/energy dispersive X-ray (EDX), Brauner Emmett Teller (BET), and photoluminescence (PL) analyses, indicating successful sulfur doping and inclusion of rGO. Sulfur doping and rGO have successfully led to a decrease in photogenerated charge recombination. However, both antagonistic and synergistic effects toward DCF treatment were observed, with the latter being brought forward by higher wt.% rGO. The composite with 5.0 wt.% rGO has shown the highest DCF conversion at pH 4 compared to that obtained by pristine TiO2, despite lower DCF adsorption during the initial dark period. The expected positive effects of both sulfur doping and rGO on charge recombination were found to be limited because of the subpar interphase contact with the composite and incomplete reduction of the GO precursor. Consequent unfavorable interactions between rGO and DCF negatively influenced the activity of the studied S-TiO2/rGO photocatalyst under simulated solar irradiation.

Rational design of Ag/TiO2 nanosystems by a combined RF-sputtering/sol-gel approach.

The present work is devoted to the preparation of Ag/TiO(2) nanosystems by an original synthetic strategy, based on the radio-frequency (RF) sputtering of silver particles on titania-based xerogels prepared by the sol-gel (SG) route. This approach takes advantage of the synergy between the microporous xerogel structure and the infiltration power characterizing RF-sputtering, whose combination enables the obtainment of a tailored dispersion of Ag-containing particles into the titania matrix. In addition, the system's chemico-physical features can be tuned further through proper ex situ thermal treatments in air at 400 and 600 degrees C. The synthesized composites are extensively characterized by the joint use of complementary techniques, that is, X-ray photoelectron and X-ray excited Auger electron spectroscopies (XPS, XE-AES), secondary ion mass spectrometry (SIMS), glancing incidence X-ray diffraction (GIXRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), electron diffraction (ED), high-angle annular dark field scanning TEM (HAADF-STEM), energy-filtered TEM (EF-TEM) and optical absorption spectroscopy. Finally, the photocatalytic performances of selected samples in the decomposition of the azo-dye Plasmocorinth B are preliminarily investigated. The obtained results highlight the possibility of tailoring the system characteristics over a broad range, directly influencing their eventual functional properties.

Surface Functionalization of Grown-on-Tip ZnO Nanopyramids: From Fabrication to Light-Triggered Applications.

We report on a combined chemical vapor deposition (CVD)/radio frequency (RF) sputtering synthetic strategy for the controlled surface modification of ZnO nanostructures by Ti-containing species. Specifically, the proposed approach consists in the CVD of grown-on-tip ZnO nanopyramids, followed by titanium RF sputtering under mild conditions. The results obtained by a thorough characterization demonstrate the successful ZnO surface functionalization with dispersed Ti-containing species in low amounts. This phenomenon, in turn, yields a remarkable enhancement of photoactivated superhydrophilic behavior, self-cleaning ability, and photocatalytic performances in comparison to bare ZnO. The reasons accounting for such an improvement are unravelled by a multitechnique analysis, elucidating the interplay between material chemico-physical properties and the corresponding functional behavior. Overall, the proposed strategy stands as an amenable tool for the mastering of semiconductor-based functional nanoarchitectures through ad hoc engineering of the system surface.

Design and evaluation of a compact photocatalytic reactor for water treatment.

A compact reactor for photocatalytic oxidation and photocatalytic ozonation water treatment was developed and evaluated by using four model pollutants. Additionally, combinations of pollutants were evaluated. Specially produced Al2O3 porous reticulated monolith foams served as TiO2 carriers, offering a high surface area support. UV lamps were placed in the interior to achieve reduced dimensions of the reactor (12 cm in diameter × 20 cm in height). Despite its small size, the overall photocatalytic cleaning capacity was substantial. It was evaluated by measuring the degradation of LAS + PBIS and RB19 as representatives of surfactants and textile dyes, respectively. These contaminants are commonly found in household grey wastewater with phenol as a trace contaminant. Three different commercial photocatalysts and one mixture of photocatalysts (P25, P90, PC500 and P25 + PC500) were introduced in the sol-gel processing and immobilized on foamed Al2O3 monoliths. RB19 and phenol were easily degradable, while LAS and PBIS were more resistant. The experiments were conducted at neutral-acidic pH because alkaline pH negatively influences both photocatalyic ozonation (PCOZ) and photocatalysis. The synergistic effect of PCOZ was generally much more expressed in mineralization reactions. Total organic carbon TOC half lives were in the range of between 13 and 43 min in the case of individual pollutants in double-deionized water. However, for the mixed pollutants in tap water, the TOC half-life only increased to 53 min with the most efficient catalyst (P90). In comparison to photocatalysis, the PCOZ process is more suitable for treating wastewater with a high loading of organic pollutants due to its higher cleaning capacity. Therefore, PCOZ may prove more effective in industrial applications.

Reactivation and reuse of TiO2-SnS2 composite catalyst for solar-driven water treatment.

One of the most important features of photocatalytic materials intended to be used for water treatment is their long-term stability. The study is focused on the application of thermal and chemical treatments for the reactivation of TiO2-SnS2 composite photocatalyst, prepared by hydrothermal synthesis and immobilized on the glass support using titania/silica binder. Such a catalytic system was applied in solar-driven treatment, solar/TiO2-SnS2/H2O2, for the purification of water contaminated with diclofenac (DCF). The effectiveness of studied reactivation methods for retaining TiO2-SnS2 activity in consecutive cycles was evaluated on basis of DCF removal and conversion, and TOC removal and mineralization of organic content. Besides these water quality parameters, biodegradability changes in DCF aqueous solution treated by solar/TiO2-SnS2/H2O2 process using simply reused (air-dried) and thermally and chemically reactivated composite photocatalyst through six consecutive cycles were monitored. It was established that both thermal and chemical reactivation retain TiO2-SnS2 activity in the second cycle of its reuse. However, both treatments caused the alteration in the TiO2-SnS2 morphology due to the partial transformation of visible-active SnS2 into non-active SnO2. Such alteration, repeated through consecutive reactivation and reuse, was reflected through gradual activity loss of TiO2-SnS2 composite in applied solar-driven water treatment.

TiO2-SnS2 nanocomposites: solar-active photocatalytic materials for water treatment.

The study is aimed at evaluating TiO2-SnS2 composites as effective solar-active photocatalysts for water treatment. Two strategies for the preparation of TiO2-SnS2 composites were examined: (i) in-situ chemical synthesis followed by immobilization on glass plates and (ii) binding of two components (TiO2 and SnS2) within the immobilization step. The as-prepared TiO2-SnS2 composites and their sole components (TiO2 or SnS2) were inspected for composition, crystallinity, and morphology using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analyses. Diffuse reflectance spectroscopy (DRS) was used to determine band gaps of immobilized TiO2-SnS2 and to establish the changes in comparison to respective sole components. The activity of immobilized TiO2-SnS2 composites was tested for the removal of diclofenac (DCF) in aqueous solution under simulated solar irradiation and compared with that of single component photocatalysts. In situ chemical synthesis yielded materials of high crystallinity, while their morphology and composition strongly depended on synthesis conditions applied. TiO2-SnS2 composites exhibited higher activity toward DCF removal and conversion in comparison to their sole components at acidic pH, while only in situ synthesized TiO2-SnS2 composites showed higher activity at neutral pH.

Novel two-step vapor-phase synthesis of UV-Vis light active Fe2O3/WO3 nanocomposites for phenol degradation.

Supported Fe2O3/WO3 nanocomposites were fabricated by an original vapor phase approach, involving the chemical vapor deposition (CVD) of Fe2O3 on Ti sheets and the subsequent radio frequency (RF)-sputtering of WO3. Particular attention was dedicated to the control of the W/Fe ratio, in order to tailor the composition of the resulting materials. The target systems were analyzed by the joint use of complementary techniques, that is, X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), energy dispersive X-ray spectroscopy (EDXS), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), and optical absorption spectroscopy. The results showed the uniform decoration of α-Fe2O3 (hematite) globular particles by tiny WO3 aggregates, whose content could be controlled by modulations of the sole sputtering time. The photocatalytic degradation of phenol in the liquid phase was selected as a test reaction for a preliminary investigation of the system behavior in wastewater treatment applications. The system activity under both UV and Vis light illumination may open doors for further material optimization in view of real-world end-uses.

Solar-driven photocatalytic treatment of diclofenac using immobilized TiO2-based zeolite composites.

The study is aimed at evaluating the potential of immobilized TiO2-based zeolite composite for solar-driven photocatalytic water treatment. In that purpose, TiO2-iron-exchanged zeolite (FeZ) composite was prepared using commercial Aeroxide TiO2 P25 and iron-exchanged zeolite of ZSM5 type, FeZ. The activity of TiO2-FeZ, immobilized on glass support, was evaluated under solar irradiation for removal of diclofenac (DCF) in water. TiO2-FeZ immobilized in a form of thin film was characterized for its morphology, structure, and composition using scanning electron microscopy/energy-dispersive x-ray spectroscopy (SEM/EDX). Diffuse reflectance spectroscopy (DRS) was used to determine potential changes in band gaps of prepared TiO2-FeZ in comparison to pure TiO2. The influence of pH, concentration of hydrogen peroxide, FeZ wt% within the composite, and photocatalyst dosage on DCF removal and conversion efficiency by solar/TiO2-FeZ/H2O2 process was investigated. TiO2-FeZ demonstrated higher photocatalytic activity than pure TiO2 under solar irradiation in acidic conditions and presence of H2O2.

Properties and Application Perspective of Hybrid Titania-Silica Patterns Fabricated by Inkjet Printing.

A hybrid titania-silica cold-setting sol has been developed that can be deposited onto a wide variety of surfaces without the need for high-temperature fixing and that is suitable for material printing deposition. Thin hybrid titania-silica coatings were patterned onto glass and PET substrates by inkjet printing. Well-defined hybrid titania-silica patterns, with thicknesses ranging from 40 to 400 nm, were fabricated by overprinting 1 to 10 layers. Excellent mechanical, optical, and photocatalytic properties were observed, making the reported material well suited for the fabrication of transparent self-cleaning coatings both on mineral and organic substrates. The printed patterns exhibit photoelectrochemical activity that can be further improved by thermal or photonic curing. A concept of fully printed interdigitated photoelectrochemical cells on flexible PET substrates utilizing the reported hybrid photocatalyst is disclosed as well.

Highly active photocatalytic coatings prepared by a low-temperature method.

Photocatalytic properties of titanium (IV) oxide (TiO2) in anatase form can be used for various purposes, including photocatalytic purification of water. For such an application, suspended or fixed photocatalytic reactors are used. Those with fixed phase seem to be preferred due to some advantages, one of which is the avoidance of photocatalyst filtration. To avoid leaching and exfoliation of the fixed phase, an immobilization procedure leading to a good adhesion of a catalyst to a substrate is crucial. Within this work, we present physical and photocatalytic characterization results of five commercially available TiO2 photocatalysts (P25, P90, PC500, KRONOClean 7000, VPC-10) and one pigment (Hombitan LO-CR-S-M), which were successfully immobilized on glass slides by a "sol suspension" procedure. Different mechanical tests and characterization methods were used to evaluate the stability and morphology of the layers. Evaluation of photocatalytic activity was done by tests under UVA and UV-vis irradiation, using a method based on the detection of the fluorescent oxidation product of terephthalic acid (TPA), i.e., hydroxyterephthalic acid (HTPA). Aeroxide® P90 incorporated into the silica-titania binder was the most photocatalytically active layer and, unlike the others, showed significant increase of photocatalytic activity through the entire range of tested UVA irradiation intensities (2.3 mW/cm(2)-6.1 mW/cm(2)). The high mechanical stability of some photocatalytic layers allows using them in water photocatalytic purification reactions.

Synthesis of BiVO4/TiO2 composites and evaluation of their photocatalytic activity under indoor illumination.

BiVO4/TiO2 composites with different weight ratios have been prepared by coprecipitation-based reactions followed by either thermal or hydrothermal treatment with the aim of evaluating the TiO2 photosensitization by BiVO4. The obtained materials present in all cases the desired monoclinic phase of BiVO4 and anatase phase of TiO2. Visible light absorption increased with increasing amount of bismuth vanadate. XPS results reveal the surface enrichment of Ti with respect to the bulk composition in samples characterised by a higher content of BiVO4. The photocatalytic activity of the prepared materials was tested for the degradation of isopropanol in the gas phase under indoor illumination conditions. Although none of the composites was able to improve the activity of TiO2, the low BiVO4 containing samples appear as more suitable for further synthesis tuning.

Surface functionalization of nanostructured Fe2O3 polymorphs: from design to light-activated applications.

Nanostructured iron(III) oxide deposits are grown by chemical vapor deposition (CVD) at 400-500 °C on Si(100) substrates from Fe(hfa)2TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N',N'-tetramethylethylenediamine), yielding the selective formation of α-Fe2O3 or the scarcely studied ε-Fe2O3 polymorphs under suitably optimized preparative conditions. By using Ti(OPr(i))4 (OPr(i) = iso-propoxy) and water as atomic layer deposition (ALD) precursors, we subsequently functionalized the obtained materials at moderate temperatures (<300 °C) by an ultrathin titanomagnetite (Fe3-xTixO4) overlayer. An extensive multitechnique characterization, aimed at elucidating the system structure, morphology, composition and optical properties, evidenced that the photoactivated hydrophilic and photocatalytic behavior of the synthesized materials is dependent both on iron oxide phase composition and ALD surface modification. The proposed CVD/ALD hybrid synthetic approach candidates itself as a powerful tool for a variety of applications where semiconductor-based nanoarchitectures can benefit from the coupling with an ad hoc surface layer.

Photocatalytic degradation of gaseous toluene by using immobilized titania/silica on aluminum sheets.

PURPOSE: The aim of this study was to prepare a highly active immobilized titania/silica photocatalyst and to test its performance in situ toward degradation of toluene as one of the major toxic indoor contaminants. METHODS: In this work, two different titania layers immobilized on Al sheets were synthesized via low temperature sol-gel method employing presynthesized highly active titania powders (Degussa P25 and Millennium PC500, mass ratio 1:1): (a) with a silica/titania binder and a protective layer and (b) without the binder. The photocatalysts were characterized by X-ray diffraction, nitrogen sorption measurements, scanning electron microscopy (SEM), infrared spectroscopy, and UV-vis diffuse reflectance spectroscopy (DRS). The in situ photocatalytic degradation of gaseous toluene was selected as a probe reaction to test photocatalytic activity and to verify the potential application of these materials for air remediation. RESULTS: Results show that nontransparent highly photocatalytically active coatings based on the silica/titania binder and homogeneously dispersed TiO(2) powders were obtained on the Al sheets. The crystalline structure of titania was not altered upon addition of the binder, which also prevented inhomogeneous agglomeration of particles on the photocatalyst surface. The photoactivity results indicate that the adsorption properties and photocatalytic activity of immobilized photocatalysts with the silica/titania binder and an underlying protective layer were very effective and additionally, they exhibited considerably improved adhesion and uniformity. CONCLUSION: We present a new highly photocatalytically active immobilized catalyst on a convenient metallic support, which has a potential application in an air cleaning device.

Effect of dissolved ozone or ferric ions on photodegradation of thiacloprid in presence of different TiO2 catalysts.

Combining TiO(2) photocatalysis with inorganic oxidants (such as O(3) and H(2)O(2)) or transition metal ions (Fe(3+), Cu(2+) and Ag(+)) often leads to a synergic effect. Electron transfer between TiO(2) and the oxidant is usually involved. Accordingly, the degree of synergy could be influenced by TiO(2) surface area. With this in mind, the disappearance of thiacloprid, a neonicotinoid insecticide, was studied applying various photochemical AOPs and different TiO(2) photocatalysts. In photocatalytic ozonation experiments, synergic effect of three different TiO(2) photocatalysts was quantified. Higher surface area resulted in a more pronounced synergic effect but an increasing amount of TiO(2) did not influence the degree of the synergy. This supports the theory that the synergy is a consequence of adsorption of ozone on the TiO(2) surface. No synergy was observed in photocatalytic degradation of thiacloprid in the presence of dissolved iron(III) species performed under varied experimental conditions (concentration, age of iron(III) solution, different TiO(2) films, usage of TiO(2) slurries). This goes against the literature for different organic compounds (i.e., monuron). It indicates different roles of iron(III) in the photodegradation of different organic molecules. Moreover, TiO(2) surface area did not affect photodegradation efficiency in iron(III)-based experiments which could confirm absence of electron transfer between TiO(2) photocatalyst and iron(III).