Lead oxide-modified TiO2 photocatalyst: tuning light absorption and charge carrier separation by lead oxidation state

Modification of TiO2 with metal oxide nanoclusters such as FeOx, NiOx has been shown to be a promising approach to the design of new photocatalysts with visible light absorption and improved electron–hole separation. To study further the factors that determine the photocatalytic properties of structures of this type, we present in this paper a first principles density functional theory (DFT) investigation of TiO2 rutile(110) and anatase(001) modified with PbO and PbO2 nanoclusters, with Pb2+ and Pb4+ oxidation states. This allows us to unravel the effect of the Pb oxidation state on the photocatalytic properties of PbOx-modified TiO2. The nanoclusters adsorb strongly at all TiO2 surfaces, creating new Pb–O and Ti–O interfacial bonds. Modification with PbO and PbO2 nanoclusters introduces new states in the original band gap of rutile and anatase. However the oxidation state of Pb has a dramatic impact on the nature of the modifications of the band edges of TiO2 and on the electron–hole separation mechanism. PbO nanocluster modification leads to an upwards shift of the valence band which reduces the band gap and upon photoexcitation results in hole localisation on the PbO nanocluster and electron localisation on the surface. By contrast, for PbO2 nanocluster modification the hole will be localised on the TiO2 surface and the electron on the nanocluster, thus giving rise to two different band gap reduction and electron–hole separation mechanisms. We find no crystal structure sensitivity, with both rutile and anatase surfaces showing similar properties upon modification with PbOx. In summary the photocatalytic properties of heterostructures of TiO2 with oxide nanoclusters can be tuned by oxidation state of the modifying metal oxide, with the possibility of a reduced band gap causing visible light activation and a reduction in charge carrier recombination.

Yielding Behaviour of Electron Beam Lithography and Focused Ion Beam Made Nanocrystalline Micro/Nanopillars

Electron beam lithography (EBL) and focused ion beam (FIB) methods were developed in house to fabricate nanocrystalline nickel micro/nanopillars so to compare the effect of fabrication on plastic yielding. EBL was used to fabricate 3 μm and 5 μm thick poly-methyl methacrylate patterned substrates in which nickel pillars were grown by electroplating with height to diameter aspect ratios from 2:1 to 5:1. FIB milling was used to reduce larger grown pillars to sizes similar to EBL grown pillars. X-ray diffraction, electron back-scatter diffraction, scanning electron microscopy, and FIB imaging were used to characterize the nickel pillars. The measured grain size of the pillars was 91±23 nm, with strong <110> and weaker <111> and <110> crystallographic texture in the growth. Load-controlled compression tests were conducted using a MicroMaterials nano-indenter equipped with a 10 μm flat punch at constant rates from 0.0015 to 0.03 mN/s on EBL grown pillars, and 0.0015 and 0.015 mN/s on FIB-milled pillars. The measured Young’s modulus ranged from 55 to 350 GPa for all pillars, agreeing with values in the literature. EBL grown pillars exhibited stochastic strain-bursts at slow loading rates, attributed to local micro yield events, followed by work hardening. Sharp yield points were also observed and attributed to the gold seed layer de-bonding between the nickel pillar and substrate due to the shear stress associated with end effects that arise from the substrate constraint. The onset of yield ranged from 108 to 1800 MPa, which is greater than bulk nickel, but within values given in the literature. FIB-milled pillars demonstrated stochastic yield behaviour at all loading rates tested, yielding between 320 and 625 MPa. Deformation was apparent at FIB-milled pillar tops, where the smallest cross-sectional area was measured, but still exhibited superior yield strength to bulk nickel. The gallium damage at the outer surface of the pillars likely aids in dislocation nucleation and plasticity, leading to lower yield strengths than for the EBL pillars. Thermal drift, substrate effects, and noise due to vibrations within the indenter system contributed to variance and inconsistency in the data.

Continuous flow gas phase photoreforming of methanol at elevated reaction temperatures sensitised by Pt/TiO2

Gas phase photoreforming of methanol using a Pt/TiO2 photocatalyst has been performed under flow conditions at elevated temperatures. Comparing the activity of the reforming process as a function of temperature under dark and irradiated conditions shows a significant enhancement in the rate of H2 production using the photo-assisted conditions at temperatures between 100-140 °C. At higher temperatures, the effect of irradiation is small with the process dominated by the thermal process. Deactivation of the catalyst was observed under irradiation but the catalyst was easily regenerated using an oxygen treatment at 120 °C. Diffuse Reflectance Infra-red Fourier Transform Spectroscopy (DRIFTS) showed that the activity of the catalyst could be correlated with the presence of the photogenerated trapped electrons. In addition, lower amounts of CO adsorbed on Pt, compared to those observed in the dark reaction, were found for the UV-irradiated systems. It is proposed that CO and adsorbed intermediates, such as formate, can act as inhibitors in the photoreforming process and this is further supported by the observation that, before and after the regeneration process in O2, the CO and surface adsorbed organic intermediate products are removed and the activity is recovered.

Mechanochemical synthesis of TiO2/NiFe2O4 magnetic catalysts for operation under RF field

Composite NiFe2O4–TiO2 magnetic catalysts were prepared by mechanochemical synthesis from a mixture of titania supported nickel ferrite nanoparticles and P25 titania (Evonic). The former provides fast and efficient heating under radiofrequency field, while the latter serves as an active catalyst or catalyst support. The highest heating rate was observed over a catalyst prepared for a milling time of 30 min. The catalytic activity was measured over the sulfated composite catalysts in the condensation of aniline and 3-phenylbutyric acid in a stirred tank reactor and in a continuous RF heated flow reactor in the 140–170 °C range. The product yield of 47% was obtained over the sulfated P25 titania catalyst in the flow reactor.

Surface modifications of nanocrystalline diamond films and their functionalization with phthalocyanines

Boron-doped diamond is a promising electrode material for a number of applications providing efficient carrier transport, a high stability of the electrolytic performance with time, a possibility for dye-sensitizing with photosensitive molecules, etc. It can be functionalized with electron donor molecules, like phthalocyanines or porphyrins, for the development of light energy conversion systems. For effective attachment of such molecules, the diamond surface has to be modified by plasma- or photo-chemical processes in order to achieve a desired surface termination. In the present work, the surface modifications of undoped and boron-doped nanocrystalline diamond (NCD) films and their functionalization with various phthalocyanines (Pcs) were investigated. The NCD films have been prepared by hot filament chemical vapor deposition (HFCVD) on silicon substrates and were thereafter subjected to modifications with O2 or NH3 plasmas or UV/O3 treatments for exchange of the H-termination of the as-grown surface. The effectiveness of the modifications and their stability with time during storage under different ambients were studied by contact angle measurements and X-ray photoelectron spectroscopy (XPS). Furthermore, the surface roughness after the modifications was investigated with atomic force microscopy (AFM) and compared to that of as-grown samples in order to establish the appearance of etching of the surface during the treatment. The as-grown and the modified NCD surfaces were exposed to phthalocyanines with different metal centers (Ti, Cu, Mn) or with different side chains. The results of the Pc grafting were investigated by XPS and Raman spectroscopy. XPS revealed the presence of nitrogen stemming from the Pc molecules and traces of the respective metal atoms with ratios close to those in the applied Pc. In a next step Raman spectra of Ti-Pc, Cu-Pc and Mn-Pc were obtained with two different excitation wavelengths (488 and 785 nm) from droplet samples on Si after evaporation of the solvent in order to establish their Raman fingerprints. The major differences in the spectra were assigned to the effect of the size of the metal ion on the structure of the phthalocyanine ring. The spectra obtained were used as references for the Raman spectra of NCD surfaces grafted with Pc. Finally, selected boron doped NCD samples were used after their surface modification and functionalization with Pc for the preparation of electrodes which were tested in a photoelectrochemical cell with a Pt counter electrode and an Ag/AgCl reference electrode. The light sources and electrolytes were varied to establish their influence on the performance of the dye-sensitized diamond electrodes. Cyclic voltammetry measurements revealed broad electrochemical potential window and high stability of the electrodes after several cycles. The open circuit potential (OCP) measurements performed in dark and after illumination showed fast responses of the electrodes to the illumination resulting in photocurrent generation.

Mechanochemical solvent-free synthesis of Sn-β Zeolite and Ag2O/TiO2 catalysts

Preparations of heterogeneous catalysts are usually complex processes that involve several procedures as precipitation, crystallization and hydrothermal treatments. This processes are really dependent by the operative conditions such as temperature, pH, concentration etc. Hence the resulting product is extremely affected by any possible variations in these parameters making this synthesis really fragile. With the aim to improve these operations has been decided to exploit a new possible strong environment-respectful process by mechanochemical treatment, which permits to carry out solvent free-solvent synthesis exploiting the Mixer Mill MM400 (Retsch) in order to have reproducible results. Two different systems have been studied in this kind of synthesis: a tin β -zeolite tested in a H-trasnfer reaction of cyclohexanone and a silver on titania catalyst used in the fluorination of 2,2 dimethyl glucaric acid. Each catalyst has been characterized by different techniques in order to understand the transformations involved in the mechanochemical treatment.

Effet du greffage de TiO2 à la surface de fibres de lin sur les propriétés mécaniques d'un composite PLA/fibre de lin longues unidirectionnelles

Les matériaux composites sont utilisés dans beaucoup de domaines pour leurs propriétés mécaniques spécifiques, leur mise en forme facile et leur bas coût. Cependant, lorsque les composites pétro-sourcées sont en fin de vie, le traitement des déchets a un fort impact environnemental. C’est pour cette raison que les industriels se tournent vers des matériaux bio-sourcés. Ils souhaitent ainsi abaisser le coût des matières premières mais aussi se donner une image plus « verte » grâce à l’utilisation de matériaux renouvelables et/ou compostables. Le projet présenté s’inscrit dans dans cette optique où il est question d’élaborer de nouveaux composites à renfort et matrices bio-sourcés et tout particulièrement des composites fibre de lin/acide polylactique (PLA). Ces derniers sont généralement appelés bio-composites. L’originalité de cette étude réside dans le traitement des fibres de lin afin de les compatibilité avec la matrice PLA. Le traitement consiste au greffage de dioxyde de titane sur la surface de fibres de lin fonctionnalisée par oxydation au TEMPO. Ces fibres longues sont ensuite utilisées comme renfort sous forme de tissu unidirectionnel dans la matrice PLA. Le comportement mécanique en traction, flexion et la résistance à l’impact de ces biocomposites sont étudiés afin d’analyser l’influence du traitement des fibres sur leur performances.

Implications of TiO2 surface functionalization on polycrystalline mixed halide perovskite films and photovoltaic devices

We exploit TiO2 surface functionalization as a tool to induce the crystallization process of CH3NH3PbI3xClx perovskite thin films resulting in a reduction of the degree of orientation of the (110) crystallographic planes. Notably, the variation of the film crystalline orientational order does not affect the photovoltaic performances of the perovskite-based devices, whose efficiency remains mostly unchanged. Our findings suggest that other factors are more significant in determining the device efficiency, such as the non-homogenous coverage of the TiO2 surface causing charge recombination at the organic/TiO2 interface, defect distribution on the perovskite bulk and at the interfaces, and transport in the organic or TiO2 layer. This observation represents a step towards the comprehension of the perovskite film peculiarities influencing the photovoltaic efficiency for high performance devices.

Greffage d’un film mince de nano-TiO2 sur les fibres naturelles cellulosiques pour le renforcement de biocomposites polymériques

Abstract : Natural materials have received a full attention in many applications because they are degradable and derived directly from earth. In addition to these benefits, natural materials can be obtained from renewable resources such as plants (i.e. cellulosic fibers like flax, hemp, jute, and etc). Being cheap and light in weight, the cellulosic natural fiber is a good candidate for reinforcing bio-based polymer composites. However, the hydrophilic nature -resulted from the presence of hydroxyl groups in the structure of these fibers- restricts the application of these fibers in the polymeric matrices. This is because of weak interfacial adhesion, and difficulties in mixing due to poor wettability of the fibers within the matrices. Many attempts have been done to modify surface properties of natural fibers including physical, chemical, and physico-chemical treatments but on the one hand, these treatments are unable to cure the intrinsic defects of the surface of the fibers and on the other hand they cannot improve moisture, and alkali resistance of the fibers. However, the creation of a thin film on the fibers would achieve the mentioned objectives. This study aims firstly to functionalize the flax fibers by using selective oxidation of hydroxyl groups existed in cellulose structure to pave the way for better adhesion of subsequent amphiphilic TiO[subscript 2] thin films created by Sol-Gel technique. This method is capable of creating a very thin layer of metallic oxide on a substrate. In the next step, the effect of oxidation on the interfacial adhesion between the TiO[subscript 2] film and the fiber and thus on the physical and mechanical properties of the fiber was characterized. Eventually, the TiO[subscript 2] grafted fibers with and without oxidation were used to reinforce poly lactic acid (PLA). Tensile, impact, and short beam shear tests were performed to characterize the mechanical properties while Thermogravimetric analysis (TGA), Differential Scanning Calorimetry (DSC), Dynamic mechanical analysis (DMA), and moisture absorption were used to show the physical properties of the composites. Results showed a significant increase in physical and mechanical properties of flax fibers when the fibers were oxidized prior to TiO[subscript 2] grafting. Moreover, the TiO[subscript 2] grafted oxidized fiber caused significant changes when they were used as reinforcements in PLA. A higher interfacial strength and less amount of water absorption were obtained in comparison with the reference samples.

X-Ray Absorption Spectroscopy and Computer Modelling Study of Nanocrystalline Binary Alkaline Earth Fluorides

Nanocrystalline samples of Ba1-xCaxF2 prepared by high-energy milling show an unusually high F-ion conductivity, which exhibit a maximum in the magnitude and a minimum in the activation energy at x = 0.5. Here, we report an X-ray absorption spectroscopy (XAS) at the Ca and Sr K edges and the Ba L-3 edge and a molecular dynamics (MD) simulation study of the pure and mixed fluorides. The XAS measurements on the pure binary fluorides, CaF2, SrF2 and BaF2 show that high-energy ball-milling produces very little amorphous material, in contrast to the results for ball milled oxides. XAS measurements of Ba1-xCaxF2 reveal that for 0 < x < 1 there is considerable disorder in the local environments of the cations which is highest for x = 0.5. Hence the maximum in the conductivity corresponds to the composition with the maximum level of local disorder. The MD calculations also show a highly disordered structure consistent with the XAS results and similarly showing maximum disorder at x = 0.5.

Associação de sistema biológico do tipo lodo ativado com reatores air lift e fotocatálise heterogênea com TiO2 para a remediação de efluente oriundo da produção industrial de TNT

Trinitrotoluene in the purification step (TNT) produced in industries, are carried out two washes at the end of the process. The first wash is done with vaporized water, which originates from the first effluent called yellow water, then the second washing with the use of sodium sulfite is performed (Na2SO3), generating a second effluent red water. This study aimed to study the individual effects, as well as the association of heterogeneous photocatalysis using TiO2 and biological treatment in air lift reactor using activated sludge (bacterial biomass) for the remediation of wastewater contaminated with nitroaromatic compounds in order to reduce toxicity and adjust the legal parameters according to regulatory agencies for disposal in waterways. The photocatalytic treatment was conducted by factorial design obtaining the best reaction conditions (pH 6.5 and concentration of TiO2 0.1 gL-1), with best results obtained at 360 minutes of reaction, reducing the absorbance 97.00%, 94.20% of the chemical oxygen demand (COD), 67.70% of total phenols, as well as a total reduction of observed peaks and assigned to nitroaromatic compounds by high-performance liquid chromatography. In the biological treatment, there was a 53.40% reduction in absorbance at 275 nm 10.00% 36.00% COD and total phenols in a short time (3 days), while for extended periods (48 days) there was an antagonistic influence on the results so that was the elevation of these parameters (COD and total phenols) instead of reducing. Chromatographic analysis confirmed the effectiveness of the biological degradation by reducing the peaks corresponding to compounds DNT and TNT. The Association of photocatalytic and biological treatments decreased results in the order of 91.10% absorbance, 70.26% of total phenols and 88.87% of COD. While the combination of biological and photocatalytic treatments generated relatively lower efficiencies, with 77.30% of absorbance reduction, 62.10% reduction of total phenols and a decrease of 87.00% of COD. In general, when comparing the chemical and biological processes in isolation, the photocatalytic treatment showed the best results. However, comparing the results of isolation and established associations, the association biological x photocatalysis showed more promising results in the treatment of red water effluent.

Remoción de la hemoglobina por adsorción sobre nanopartículas magnéticas de Fe3O4/TiO2

La remoción de la hemoglobina (Hb) por adsorción de la proteína sobre nanopartículas (Nps) magnéticas de Fe3O4/TiO2 (núcleo/coraza) aplicando un campo magnético externo, fue investigada mediante espectroscopia ultravioleta en el rango del ultravioleta y visible (UV-VIS). Durante la etapa de contacto de las Nps con la Hb se varió la concentración de las Nps y la temperatura, complementariamente durante la etapa de remoción del complejo Fe3O4/TiO2-Hb se varió la intensidad del campo magnético externo. Con una concentración inicial de Nps de 8 mg ml-1, el valor de la absorbancia del sobrenadante disminuye en un 11% con respecto a la solución inicial de Hb (0,8 g l-1) y al aumentar en un 50% la concentración de Nps, el valor disminuye hasta un 17%. Al incrementar la temperatura de 25 a 35ºC disminuye la adsorción de la Hb pero no se observa indicios de desnaturalización de la misma. Durante la etapa de remoción del complejo Fe3O4/TiO2-Hb, al incrementar la fuerza magnética se logra una caída en la intensidad de la absorbancia, casi un 30%. Finalmente, se determinó la demanda bioquímica de oxígeno (DBO5) de la solución inicial de Hb y del sobrenandante, el valor para la solución inicial de Hb fue de 100 mg ml-1 y los resultados obtenidos para todas las soluciones tratadas fueron inferiores (62 mg ml-1) verificando el impacto que tuvo el uso de las Nps magnéticas de Fe3O4/TiO2 en la remoción de la Hb.

Solar Energy Conversion by Nanostructured TiO2

Research in solar energy conversion and the associated photoactive materials has attracted continuous interest. Due to its proper electronic band structure, high quantum efficiency, and photonic and chemical innerness, TiO2 has been demonstrated as a versatile oxide semiconductor capable of efficiently utilizing sunlight to produce electrical and chemical energy. Its outstanding physicochemical performances have led to an array of advanced photocatalytic and photoelectrochemical applications including environmental photocatalysis, dye/semiconductor-sensitized solar cell, and solar fuel productions.

Preparation, Characterization, and Photocatalytic Applications of MWCNTs/TiO2 Composite

The multiwall carbon nanotubes (MWCNTs)/titanium dioxide (P25) composite in different ratios was prepared using simple evaporation and drying process. The composite was characterized by Raman spectroscopy, X-ray diffraction (XRD), UV-visible diffuse reflectance spectroscopy, and scanning electron microscopy (SEM). The photocatalytic activity of this composite was investigated using degradation of the Bismarck brown R dye (BBR). An optimal MWCNTs/TiO2 ratio of 0.5% (w/w) was found to achieve the maximum rate of BBR degradation. It was observed that the composite exhibits enhanced photocatalytic activity compared with TiO2. The enhancement in photocatalytic activity performance of the MWCNTs/P25 composite is explained in terms of recombination of photogenerated electron-hole pairs. In addition, MWCNTs act as a dispersing support to control the morphology of TiO2 particles in the MWCNTs/TiO2 composite.

Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions

Titania modified nanoparticles have been prepared by the photodeposition method employing platinum particles on the commercially available titanium dioxide (Hombikat UV 100). The properties of the prepared photocatalysts were investigated by means of the Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), atomic force microscopy (AFM), and UV-visible diffuse spectrophotometry (UV-Vis). XRD was employed to determine the crystallographic phase and particle size of both bare and platinised titanium dioxide. The results indicated that the particle size was decreased with the increasing of platinum loading. AFM analysis showed that one particle consists of about 9 to 11 crystals. UV-vis absorbance analysis showed that the absorption edge shifted to longer wavelength for 0.5% Pt loading compared with bare titanium dioxide. The photocatalytic activity of pure and Pt-loaded TiO2 was investigated employing the photocatalytic oxidation and dehydrogenation of methanol. The results of the photocatalytic activity indicate that the platinized titanium dioxide samples are always more active than the corresponding bare TiO2 for both methanol oxidation and dehydrogenation processes. The loading with various platinum amounts resulted in a significant improvement of the photocatalytic activity of TiO2. This beneficial effect was attributed to an increased separation of the photogenerated electron-hole charge carriers.