Short time deposition of TiO2 nanoparticles on SiC as photocatalysts for the degradation of organic dyes

The deposition of TiO₂ nanoparticles on SiC was carried out by mechanical milling under different conditions. SiC–TiO₂ samples were used as photocatalysts for the degradation of organic dyes such as methylene blue and rhodamine B. A short time deposition of TiO₂ nanoparticles was observed during mechanical milling (2 min at 200 rpm) to cover the SiC particles. The presence of SiC and TiO₂ (anatase and rutile) was confirmed by means of X-ray diffraction after thermal treatment at 450 °C. The deposition of TiO₂ on SiC was corroborated by scanning electron microscopy analysis; the thickness of the thin layer of TiO₂ deposited on SiC increases as the proportion of TiO₂ increases. The energy band gap values obtained for these compounds were around 3.0 eV. SiC–TiO₂ photocatalysts prepared by mechanical milling exhibited better activity under UV-light irradiation for the degradation of methylene blue and rhodamine B than commercial TiO₂ powder (titania P25).     

Electrophoretic deposition of mesoporous TiO2 nanoparticles consisting of primary anatase nanocrystallites on a plastic substrate for flexible dye-sensitized solar cells

A film of mesoporous TiO(2) nanoparticles (MTNs) consisting of anatase nanocrystallites was electrophoretically deposited and compressed on a plastic substrate for the corresponding DSSC that gave an excellent conversion efficiency (η) of 5.25% under illumination of 100 mW cm(-2).     

A high-performing nanostructured TiO2 filter for volatile organic compounds using atomic layer deposition

Novel nanostructured gas filtering systems with TiO(2) thin films using atomic layer deposition (ALD) were developed for volatile organic compounds. A superior toluene adsorption efficiency was found for the nanostructured TiO(2) thin films.     

Determining the orientation and molecular packing of organic dyes on a TiO2 surface using X-ray reflectometry

The determination of the orientation and molecular density for several porphyrin dyes adsorbed on planar TiO(2) surfaces using X-ray reflectometry (XRR) is reported. Adsorption of nanoscale water layers occurred rapidly upon exposure of freshly prepared TiO(2) surfaces to ambient conditions; however, this was successfully eliminated, resulting in clearly discernible adsorbed dye layers for sensitized surfaces. Adsorbed dye orientations, determined from computations constrained by the measured dye layer thickness, were calculated to have a binding tilt angle of 35°-40°. Combining the XXR data with the orientation models indicates that the porphyrins form densely packed surfaces with an intermolecular spacing of 3-4 ?, consistent with π-π stacking interactions. Changes in the molecular size of probe dyes were reflected in corresponding changes in the measured dye layer thickness, confirming the ability of this technique to resolve small variations in dye layer thickness and consequently adsorption orientation. Application of these results to understanding the behavior of dye-sensitized devices is discussed.     

Energy alignment and surface dipoles of rylene dyes adsorbed to TiO2 nanoparticles

The energy loss in dye-sensitized solar cells calculated from the energy difference between the lowest electronic transition of the dye and the obtained open-circuit voltage is often 1 eV or even more. To minimize this loss, it is important to accurately determine the energy alignment at the TiO(2)/dye/redox-mediator interface. In this study, we compared the results from electrochemistry and photoelectron spectroscopy for determining the energy alignment of three rylene dyes, two of which absorb relatively far in the red. The trends observed with the methods were different, as in the former, the energy alignment is measured relative to an external reference and includes contributions from solvent reorganization energies, while in the latter, it is measured relative to the energetics of the TiO(2) and is lacking such contributions. The influence of the dyes' dipole moments on the energetics of the TiO(2) was also measured and explained some of the differences in trends. Finally, we compared the injection efficiencies of the two red-absorbing dyes and found that the differences in injection efficiencies can be better explained using the energy alignment determined from photoelectron spectroscopy. This shows that the method for measuring the energetics of a DSC should be chosen according to what process one intends to study.     

Electrophoretic deposition of phthalocyanine in organic solutions containing trifluoroacetic acid

The absorption spectra of copper phthalocyanine (CuPc) 1,2-dichloroethane (DCE) solutions containing trifluoroacetic acid (TFAA) shows that the number of protons coordinating to the CuPc molecule was 1 and 2 for the first and second proton adducts, respectively, which indicates the formations of CuPcH(+) and CuPcH(2)(2+). This CuPc molecule may act as a catalyst to dissociate TFAA into trifluoroacetate anion (A(-)) and H(+) and form the proton adducts. The electrical conductivity dependence of the solution on CuPc concentration also supports this mechanism. A dense film of CuPc was deposited on an indium tin oxide cathode plate by electrophoresis of the solution. Similar dense films of a wide variety of phthalocyanines (MPc; M = Cu, H(2), Fe, Ni, Zn, Pb, VO) were also deposited using this method. Similar films of CuPc were also formed using dichloromethane (DCM) and 1,1,1-trichloroethane (TCE) in place of DCE. Depositions are ascribed to the migration of positively charged monomers (i.e., protonated MPc). Scanning electron microscopy revealed that these films are composed of fibrous crystallites, size of which was found to increase with the electrophoresis time, the strength of the applied electrical field and the concentration of CuPc in the bath. The influence of the dielectric constant of the organic solvent on the film growth is discussed.     

Visible light assisted photocatalytic degradation of organic dyes on TiO2–CNT nanocomposites

Journal of Sol-Gel Science and Technology - Carbon nanotubes (CNTs) uniformly decorated with nano-anatase TiO2 particles corresponding to different TiO2–CNT weight ratios (up to 90 %...     

Electrophoretic mobility measurements of fluorescent dyes using on-chip capillary electrophoresis

We present an experimental study of the effect of pH, ionic strength, and concentrations of the electroosmotic flow (EOF)-suppressing polymer polyvinylpyrrolidone (PVP) on the electrophoretic mobilities of commonly used fluorescent dyes (fluorescein, Rhodamine 6G, and Alexa Fluor 488). We performed on-chip capillary zone electrophoresis experiments to directly quantify the effective electrophoretic mobility. We use Rhodamine B as a fluorescent neutral marker (to quantify EOF) and CCD detection. We also report relevant acid dissociation constants and analyte diffusivities based on our absolute estimate (as per Nernst-Einstein diffusion). We perform well-controlled experiments in a pH range of 3-11 and ionic strengths ranging from 30 to 90 mM. We account for the influence of ionic strength on the electrophoretic transport of sample analytes through the Onsager and Fuoss theory extended for finite radii ions to obtain the absolute mobility of the fluorophores. Lastly, we briefly explore the effect of PVP on adsorption-desorption dynamics of all three analytes, with particular attention to cationic R6G.     

Electrophoretic analysis of food dyes using a miniaturized microfluidic system

A simple and sensitive on-chip preconcentration, separation, and electrochemical detection (ED) method for the electrophoretic analysis of food dyes was developed. The microchip comprised of three parallel channels: the first two are for the field-amplified sample stacking (FASS) and subsequent field-amplified sample injection (FASI) steps, while the third one is for the micellar EKC with ED (MEKC-ED) step. The food dyes were initially extracted from real samples by employing a method that was simpler, easier, and faster compared with a standard method. The extraction of the samples was characterized by UV-Vis and electrochemical experiments. The chronoamperometric detection was performed with a glassy carbon electrode coupled horizontally with the microchip at the separation channel exit. Experimental parameters affecting the analytical performance of the method were assessed and optimized. The sensitivity of the method was improved by approximately 10,800-fold when compared with a conventional MEKC-ED analysis. Reproducible response was observed during multiple injections of samples with an RSD of <7.2% (n=5). The calibration plots were linear (r2=0.998) within the range of 1.0 nM-1.0 microM for all food dyes. LODs were estimated between 1.0 and 5.0 nM, based on S/N=3, for food dyes. The applicability of the method for the analysis of food dyes in real sample was demonstrated.     

Mapping the frontier electronic structures of triphenylamine based organic dyes at TiO2 interfaces

The frontier electronic structures of a series of organic dye molecules containing a triphenylamine moiety, a thiophene moiety and a cyanoacrylic acid moiety have been investigated by photoelectron spectroscopy (PES), X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES) and resonant photoelectron spectroscopy (RPES). The experimental results were compared to electronic structure calculations on the molecules, which are used to confirm and enrich the assignment of the spectra. The approach allows us to experimentally measure and interpret the basic valence energy level structure in the dye, including the highest occupied energy level and how it depends on the interaction between the different units. Based on N 1s X-ray absorption and emission spectra we also obtain insight into the structure of the excited states, the molecular orbital composition and dynamics. Together the results provide an experimentally determined energy level map useful in the design of these types of materials. Included are also results indicating femtosecond charge redistribution at the dye/TiO(2) interface.     

Electrophoretic deposition of nickel, iron and aluminum nanoparticles on carbon fibers

The electrophoretic deposition (EPD) of nickel (Ni), iron (Fe) and aluminum (Al) nanoparticles fabricated by an active hydrogen plasma evaporation method on the surface of carbon fibers was investigated, which will allow the obtained composites to be applied as practical catalysts or electrodes. SEM observations show that the Ni nanoparticles can build up a thick EPD coating with some cracks on the surface of carbon fibers, and the analyses of X-ray diffraction (XRD) and BET specific surface area indicate that fine particles from the as-received Ni powders were finally deposited after the EPD process without crystal growth. The surface oxidation of Fe and Al nanoparticles takes serious effect on the EPD process and the morphology of the as-prepared coatings.     

Alternating current electrophoretic deposition (EPD) of TiO2 nanoparticles in aqueous suspensions

TiO(2)-nanostructured coatings from aqueous suspensions have been successfully prepared by the application of alternating current (AC) instead of direct current (DC) during electrophoretic deposition (EPD). No organic additives in suspension were required for successful EPD. The quality of the AC-EPD TiO(2) coatings in terms of homogeneity and extent of microcracking, upon drying, observed by SEM, was superior to that of DC-EPD coatings made from the same type of suspensions. The main difference between AC- and DC-EPD was the suppression of bubble formation. The absence of water electrolysis at the electrodes can be explained by the particular distribution of the electric field during AC mode, which prevents the nucleation of bubbles. The preparation of TiO(2) coatings from aqueous suspension and without the aid of organic stabilizers opens the possibility for co-deposition of sensitive materials such as biomolecules and even cells for biomedical applications, given the high biocompatibility of TiO(2). The deposition of TiO(2) coatings from aqueous suspensions is also attractive from environmental and economical points of view.     

One-pot deposition of palladium on hybrid TiO2 nanoparticles and catalytic applications in hydrogenation

One-pot deposition of Pd onto TiO(2) has been achieved through directly contacting palladium(II) salt with nanosized functionalized TiO(2) support initially obtained by sol-gel process using titanium isopropoxide and citric acid. Citrate groups act as functional moieties able to directly reduce the Pd salt avoiding any further reducing treatment. Various palladium salts (Na(2)PdCl(4) and Pd(NH(3))(4)Cl(2)·H(2)O) and titanium to citrate (Ti/CA) ratios (20, 50, and 100) were used in order to study the effect of the nature of the precursor and of the citrate content on the final Pd particle size and catalytic properties of the as-obtained Pd/TiO(2) systems. Characterization was performed using N(2) adsorption-desorption isotherms, ICP-AES, FTIR, XRD, XPS, and TEM. The as-obtained hybrid Pd/TiO(2) catalysts were tested in the selective hydrogenation (HYD) of an α,β-unsaturated aldehyde, i.e. cinnamaldehyde. Citrate-free Pd/TiO(2)-based catalysts present lower selectivity into saturated alcohol. However, citrate-functionalized Pd/TiO(2) catalyst seems to control the selectivity, the particle size and dispersion of Pd NPs leading to high intrinsic activity.     

Acquired pH-responsive and reversible enrichment of organic dyes by peroxide modified ultrathin TiO2 nanosheets

The acquired pH-responsive and reversible enrichment of organic dyes from aqueous solutions by peroxide modified ultrathin nanosheets of anatase and TiO(2)(B) is illustrated in comparison with P25 and TiO(2)(B) nanowires.     

Detection of organic gases using TiO2 nanotube-based gas sensors

We fabricated porous gas sensing films composed of TiO₂ nanotubes prepared by a hydrothermal treatment for the detection of organic gases, such as alcohol and toluene. The morphology of the sensing films was controlled with a ball-milling treatment and calcination at high temperature to improve the sensitivity of the films. The sensor using nanotubes with the ball-milling treatment exhibited the improved sensor responses to toluene at 500oC. The results obtained indicated the importance of the microstructure control of sensing layers in terms of particle packing density, pore size distribution, and particle size and shape for detecting large sized organic gas molecules.     

Photocatalytic air-cleaning using TiO2 nanoparticles in porous silica substrate

For air-cleaning, TiO₂ photocatalysis represents one of the very efficient advanced oxidation processes (AOPs) that can decompose chemically and microbiologically stable volatile organic compounds (VOCs). However, the photocatalytic activity of nanocrystalline TiO₂ powders can be significantly suppressed due to TiO₂’s poor adsorption characteristics for organic compounds and its relatively low surface area. The present study sought to solve this problem by immobilising nanocrystalline TiO₂ in the porous silicate substrate. Two titania sources were used in an aqueous solution form: a suspension from a TiO₂ producer in Slovenia, Cinkarna Celje (CC-40) and a TiO₂ sol, prepared by a low-temperature synthesis developed at the University of Nova Gorica (TiO₂-UNG). Two different types of mesoporous silica were used: SBA-15 with an ordered hexagonal pore arrangement and KIL-2 with disordered inter-particle mesoporosity. The structural characteristics, adsorption properties and photocatalytic activity of catalysts deposited on aluminium plates as thin films were investigated. CC-40 exhibited higher adsorption and photocatalytic activity than TiO₂-UNG due to the greater quantity of Ti-OH groups on its surface. The addition of mesoporous silica led to higher adsorption and catalytic activity for both TiO₂ sources. SBA-15 was more efficient than KIL-2.     

Facile decoration of TiO2 nanoparticles on graphene for solar degradation of organic dye

The reduced graphene oxide is interesting material for the synthesis of TiO₂-based photocatalyst. In the present investigation, blackberry fruit, which contains high levels of anthocyanins and other phenolic compounds, was employed as a reducing agent mainly due to its high antioxidant capacity. The nano-crystalline TiO₂ was decorated on different amounts of graphene oxide with sol–gel method and then the photocatalytic activity for degradation of cationic dye was evaluated by UV spectroscopy to achieve the optimum content of graphene oxide. The decoration of anatase nanoparticles on prepared reduced graphene oxide was investigated by X-ray diffraction, scanning and transmission electron microscopy techniques. The new composite gives significantly higher activity when is compared to the compositions fabricated by graphene oxide. The compact layer provides a large TiO₂-graphene contact area and reduces the electron recombination. The decoration of TiO₂ nanoparticles, 5–10 nm, on the graphene oxide reduced by blackberry juice further improves the dye removal. The results imply that the nanoparticle decoration is the key strategy to increase the degradation capacity.     

F–B-codoping of anodized TiO2 nanotubes using chemical vapor deposition

Chemical vapor deposition (CVD) was firstly used to simultaneously codope fluorine and boron into TiO₂ nanotubes anodized Ti in C₂H₂O₄ · 2H₂O + NH₄F electrolyte. F–B-codoping was successfully carried out by annealing the anodized TiO₂ nanotubes through CVD, as evidenced from XPS analysis. SEM images showed that the higher the annealing temperature, the greater structure damage of F–B-codoped sample. XRD results confirmed that annealing temperature had an influence on the phase structure and boron and fluorine impurities could retard anatase–rutile phase transition. F–B-codoped samples displayed remarkably strong absorption in both UV and visible range. Under visible-light irradiation, F–B-codoped samples showed the higher I_ph and catalytic activity in methyl orange photoelectrodegradation than F-doped sample and B-doped sample. This showed a convincing evidence of F–B-codoping of TiO₂ had an obvious synergistic effect on the enhancement of photocurrents and photoelectrocatalytic activity.     

Modeling and optimization of simultaneous photocatalysis of three dyes on ceramic-coated TiO2 nanoparticles using chemometrics methods: phytotoxicological assessment during degradation process

In this paper, ceramic plates were used as a support of TiO₂ nanoparticles for photocatalytic decolorization of a mixture of three dyes. The three textile dyes (C.I. Basic Red 46, C.I. Basic Blue 3 and Malachite Green) were quantified simultaneously during the photocatalytic degradation process. The partial least squares modeling was successfully applied for the multivariate calibration of the spectrophotometric data. Also, the central composite design has been applied to the optimization of photocatalytic decolorization of the dye solution containing three dyes using an immobilized UV/TiO₂ process. The optimum initial concentration of three dyes, reaction time, and UV light intensity were found to be 5 mg/L, 240 min, and 47.2 W/m², respectively. The chronic phytotoxicity of mixture of dyes was evaluated using aquatic species Spirodela polyrhiza (S. polyrhiza) prior to and after photocatalysis. The phytotoxicity results revealed that the photocatalysis process could effectively reduce the phytotoxicity of the dyes from their aqueous solutions.