Industrial synthesis and characterization of nanophotocatalysts materials: titania

Despite the recent synthesis and identification of a diverse set of new nanophotocatalysts that has exploded recently, titanium dioxide (TiO2) remains among the most promising photocatalysts because it is inexpensive, non-corrosive, environmentally friendly, and stable under a wide range of conditions. TiO2 has shown excellent promise for solar cell applications and for remediation of chemical pollutants and toxins. Over the past few decades, there has been a tremendous development of nanophotocatalysts for a variety of industrial applications (i.e. for water purification and reuse, disinfection of water matrices, air purification, deodorization, sterilization of soils). This paper details traditional and new industrial routes for the preparation of nanophotocatalysts and the characterization techniques used to understand the physical chemical properties of them, like surface area, ζ potential, crystal size, and phase crystallographic, morphology, and optical transparency. Finally we present some applications of the industrial nanophotocatalysts.

Síntese hidrotérmica assistida por micro-ondas de tiO2, e aplicação em nanocompósito

In recent decades have seen a sharp growth in the study area of nanoscience and nanotechnology and is included in this area, the study of nanocomposites with self-cleaning properties. Since titanium dioxide (TiO2) has high photocatalytic activity and also antimicrobial, self-cleaning surfaces in your application has been explored. In this study a comparison was made between two synthesis routes to obtain TiO2 nanoparticles by hydrothermal method assisted by microwave. And after analysis of XRD and SEM was considered the best material for use in nanocomposites. It was deposited nanocomposite film of poly (dimethyl siloxane) (PDMS) with 0.5, 1, 1.5 and 2% by weight of nanoparticles of titanium dioxide (TiO2) by the spraying method. The nanocomposite was diluted with hexane and the suspension was deposited onto glass substrate, followed by curing in an oven with forced air circulation. The photocatalytic activity of the nanocomposite impregnated with methylene blue was evaluated by UV- vis spectroscopy from the intensity variation of absorption main peak at 660nm with time of exposure to the UV chamber. Changes in the contact angle and microhardness were analyzed before and after UV aging test. The effect of ultraviolet radiation on the chemical structure of the PDMS matrix was evaluated by spectrophotometry Fourier transform infrared (FTIR).The results indicated that the addition of TiO2 nanoparticles in the coating PDMS gave high photocatalytic activity in the decomposition of methylene blue, an important characteristic for the development of self-cleaning coatings

Photocatalytic production of chemicals and hydrogen from biomass

In this work, with the aim to tackle several approaches towards sustainable chemistry, two reactions were studied: aerobic photo-oxidation of biomass derived 5-hydroxymethyl-2-furfural (HMF), and anaerobic photo-reforming of glycerol known as a by-product in biodiesel industry, towards production of chemicals and hydrogen. Solar-assisted reactions were performed by means of heterogeneous photocatalysis, in mild conditions such as atmospheric pressure, room temperature and water as a benign solvent. Titanium dioxide (lab-synthesized and commercial) was used as a photo-active catalyst, which surface was modified by introducing different metal (e.g. Au, Au-Cu, Pt) and metal oxide (e.g. NiO) nanoparticles. The prepared materials were characterized by XRD, DRS, BET, TEM, SEM, RAMAN and other techniques. The influence of the support, the size and type of the deposited metal and metal oxide nanoparticles on the photo-catalytic transformation of HMF and glycerol was evaluated. In the case of HMF, the influence of the base addition and the oxygen content on the reaction selectivity was also studied. The effect of the crystalline phase composition and morphology of TiO2 in the glycerol photo-reforming reaction was assessed as well. The surface of the synthesized TiO2 nano-powders was investigated by means of Surface Organometallic Chemistry (SOMC) approach. In particular, the surface was characterized by chemical titration and DRIFT techniques. Furthermore, the SOMC concept allowed preparing of well-dispersed Pt nanoparticles on the TiO2 surface. The photo-catalytic activity of this sample in the glycerol photo-reforming process was tested and compared to that of other Pt-containing catalysts prepared by conventional technics. In view of avoiding the agglomeration and sedimentation of suspended titania powders in water media, thick films of synthesized and commercial TiO2 were deposited on a conductive substrate using screen-printing technique. The prepared electrodes were characterized by profilometry, SEM, XRD, optical, electrochemical and photo-electrochemical methods.

Development and optimization of fibre-shaped dye-sensitized solar cells employing an innovative fully organic sensitizer

The quality of human life depends to a large degree on the availability of energy. In recent years, photovoltaic technology has been growing extraordinarily as a suitable source of energy, as a consequence of the increasing concern over the impact of fossil fuels on climate change. Developing affordable and highly efficiently photovoltaic technologies is the ultimate goal in this direction. Dye-sensitized solar cells (DSSCs) offer an efficient and easily implementing technology for future energy supply. Compared to conventional silicon solar cells, they provide comparable power conversion efficiency at low material and manufacturing costs. In addition, DSSCs are able to harvest low-intensity light in diffuse illumination conditions and then represent one of the most promising alternatives to the traditional photovoltaic technology, even more when trying to move towards flexible and transparent portable devices. Among these, considering the increasing demand of modern electronics for small, portable and wearable integrated optoelectronic devices, Fibre Dye-Sensitized Solar Cells (FDSSCs) have gained increasing interest as suitable energy provision systems for the development of the next-generation of smart products, namely “electronic textiles” or “e-textiles”. In this thesis, several key parameters towards the optimization of FDSSCs based on inexpensive and abundant TiO2 as photoanode and a new innovative fully organic sensitizer were studied. In particular, the effect of various FDSSCs components on the device properties pertaining to the cell architecture in terms of photoanode oxide layer thickness, electrolytic system, cell length and electrodes substrates were examined. The photovoltaic performances of the as obtained FDSSCs were fully characterized. Finally, the metal part of the devices (wire substrate) was substituted with substrates suitable for the textile industry as a fundamental step towards commercial exploitation.

Design and evaluation of aerosol and liquid separation systems

Conventional chromatographic columns are packed with porous beads by the universally employed slurry-packing method. The lack of precise control of the particle size distribution, shape and position inside the column have dramatic effects on the separation efficiency. In the first part the thesis an ordered, three-dimensional, pillar-array structure was designed by a CAD software. Several columns, characterized by different fluid distributors and bed length, were produced by a stereolithographic 3D printer and compared in terms of pressure drop and height equivalent to a theroretical plate (HETP). To prevent the release of unwanted substances and to provide a surface for immobilizing a ligand, pillars were coated with one or more of the following materials: titanium dioxide, nanofibrillated cellulose (NFC) and polystyrene. The external NFC layer was functionalized with Cibacron Blue and the dynamic binding capacity of the column was measured by performing three chromatographic cycles, using bovine serum albumin (BSA) as target molecule. The second part of the thesis deals with Covid-19 pandemic related research activities. In early 2020, due to the pandemic outbreak, surgical face masks became an essential non-pharmaceutical intervention to limit the spread. To address the consequent shortage and to support the reconversion of the Italian industry, in late March 2020 a multidisciplinary group of the University of Bologna created the first Italian laboratory able to perform all the tests required for the evaluation and certification of surgical masks. More than 1200 tests were performed on about 350 prototypes, according to the standard EN 14683:2019. The results were analyzed to define the best material properties and masks composition for the production of masks with excellent efficiency. To optimize the usage of surgical masks and to reduce their environmental burden, the variation of their performance over time of usage were investigated as to determine the maximum lifetime.

Photocatalytic activities of tin(IV) oxide surface-modified titanium(IV) dioxide show a strong sensitivity to the TiO 2 crystal form

Surface modification of rutile TiO2 with extremely small SnO2 clusters gives rise to a great increase in its UV light activity for degradation of model organic water pollutants, while the effect is much smaller for anatase TiO2. This crystal form sensitivity is rationalized in terms of the difference in the electronic modification of TiO2 through the interfacial Sn−O−Ti bonds. The increase in the density of states near the conduction band minimum of rutile by hybridization with the SnO2 cluster levels intensifies the light absorption, but this is not seen with modified anatase. The electronic transition from the valence band to the conduction band causes the bulk-to-surface interfacial electron transfer to enhance charge separation. Further, electrons relaxed to the conduction minimum are smoothly transferred to O2 due to the action of the SnO2 species as an electron transfer promoter.

Effect of Titanium Tetrafluoride and Amine Fluoride Treatment Combined with Carbon Dioxide Laser Irradiation on Enamel and Dentin Erosion

Objective: This in vitro study aimed to analyze the influence of carbon dioxide (CO(2)) laser irradiation on the efficacy of titanium tetrafluoride (TiF(4)) and amine fluoride (AmF) in protecting enamel and dentin against erosion. Methods: Bovine enamel and dentin samples were pretreated with carbon dioxide (CO(2)) laser irradiation only (group I), TiF(4) only (1% F, group II), CO(2) laser irradiation before (group III) or through (group IV) TiF(4) application, AmF only (1% F, group V), or CO(2) laser irradiation before (group VI) or through (group VII) AmF application. Controls remained untreated. Ten samples of each group were then subjected to an erosive demineralization and remineralization cycling for 5 days. Enamel and dentin loss were measured profilometrically after pretreatment, 4 cycles (1 day), and 20 cycles (5 days) and statistically analyzed using analysis of variance and Scheffe's post hoc tests. Scanning electron microscopy (SEM) analysis was performed in pretreated but not cycled samples (two samples each group). Results: After 20 cycles, there was significantly less enamel loss in groups V and IV and significantly less dentin loss in group V only. All other groups were not significantly different from the controls. Lased surfaces (group I) appeared unchanged in the SEM images, although SEM images of enamel but not of dentin showed that CO(2) laser irradiation affected the formation of fluoride precipitates. Conclusion: AmF decreased enamel and dentin erosion, but CO(2) laser irradiation did not improve its efficacy. TiF(4) showed only a limited capacity to prevent erosion, but CO(2) laser irradiation significantly enhanced its ability to reduce enamel erosion.

In vitro precision of fit of computer-aided design and computer-aided manufacturing titanium and zirconium dioxide bars

OBJECTIVES Optical scanners combined with computer-aided design and computer-aided manufacturing (CAD/CAM) technology provide high accuracy in the fabrication of titanium (TIT) and zirconium dioxide (ZrO) bars. The aim of this study was to compare the precision of fit of CAD/CAM TIT bars produced with a photogrammetric and a laser scanner. METHODS Twenty rigid CAD/CAM bars were fabricated on one single edentulous master cast with 6 implants in the positions of the second premolars, canines and central incisors. A photogrammetric scanner (P) provided digitized data for TIT-P (n=5) while a laser scanner (L) was used for TIT-L (n=5). The control groups consisted of soldered gold bars (gold, n=5) and ZrO-P with similar bar design. Median vertical distance between implant and bar platforms from non-tightened implants (one-screw test) was calculated from mesial, buccal and distal scanning electron microscope measurements. RESULTS Vertical microgaps were not significantly different between TIT-P (median 16μm; 95% CI 10-27μm) and TIT-L (25μm; 13-32μm). Gold (49μm; 12-69μm) had higher values than TIT-P (p=0.001) and TIT-L (p=0.008), while ZrO-P (35μm; 17-55μm) exhibited higher values than TIT-P (p=0.023). Misfit values increased in all groups from implant position 23 (3 units) to 15 (10 units), while in gold and TIT-P values decreased from implant 11 toward the most distal implant 15. SIGNIFICANCE CAD/CAM titanium bars showed high precision of fit using photogrammetric and laser scanners. In comparison, the misfit of ZrO bars (CAM/CAM, photogrammetric scanner) and soldered gold bars was statistically higher but values were clinically acceptable.

Precision of fit of implant-supported screw-retained 10-unit computer-aided-designed and computer-aided-manufactured frameworks made from zirconium dioxide and titanium: an in vitro study

OBJECTIVE To analyze the precision of fit of implant-supported screw-retained computer-aided-designed and computer-aided-manufactured (CAD/CAM) zirconium dioxide (ZrO) frameworks. MATERIALS AND METHODS Computer-aided-designed and computer-aided-manufactured ZrO frameworks (NobelProcera) for a screw-retained 10-unit implant-supported reconstruction on six implants (FDI positions 15, 13, 11, 21, 23, 25) were fabricated using a laser (ZrO-L, N = 6) and a mechanical scanner (ZrO-M, N = 5) for digitizing the implant platform and the cuspid-supporting framework resin pattern. Laser-scanned CAD/CAM titanium (TIT-L, N = 6) and cast CoCrW-alloy frameworks (Cast, N = 5) fabricated on the same model and designed similar to the ZrO frameworks were the control. The one-screw test (implant 25 screw-retained) was applied to assess the vertical microgap between implant and framework platform with a scanning electron microscope. The mean microgap was calculated from approximal and buccal values. Statistical comparison was performed with non-parametric tests. RESULTS No statistically significant pairwise difference was observed between the relative effects of vertical microgap between ZrO-L (median 14 μm; 95% CI 10-26 μm), ZrO-M (18 μm; 12-27 μm) and TIT-L (15 μm; 6-18 μm), whereas the values of Cast (236 μm; 181-301 μm) were significantly higher (P < 0.001) than the three CAD/CAM groups. A monotonous trend of increasing values from implant 23 to 15 was observed in all groups (ZrO-L, ZrO-M and Cast P < 0.001, TIT-L P = 0.044). CONCLUSIONS Optical and tactile scanners with CAD/CAM technology allow for the fabrication of highly accurate long-span screw-retained ZrO implant-reconstructions. Titanium frameworks showed the most consistent precision. Fit of the cast alloy frameworks was clinically inacceptable.

Magnetic properties of Co-doped TiO(2) anatase nanopowders

This letter reports on the magnetic properties of Ti(1-x)Co(x)O(2) anatase phase nanopowders with different Co contents. It is shown that oxygen vacancies play an important role in promoting long-range ferromagnetic order in the material studied in addition to the transition-metal doping. Furthermore, the results allow ruling out the premise of a strict connection between Co clustering and the ferromagnetism observed in the Co:TiO(2) anatase system.

Ionic-covalent transition in titanium oxides

The nature of the chemical bond in three titanium oxides of different crystal structure and different formal oxidation state has been studied by means of the ab initio cluster-model approach. The covalent and ionic contributions to the bond have been measured from different theoretical techniques. All the analysis is consistent with an increasing of covalence in the TiO, Ti2O3, and TiO2 series as expected from chemical intuition. Moreover, the use of the ab initio cluster-model approach combined with different theoretical techniques has permitted us to quantify the degree of ionic character, showing that while TiO can approximately be described as an ionic compound, TiO2 is better viewed as a rather covalent oxide.

The use of heterogeneous chemistry for the characterization of functional groups at the gas/particle interface of soot and TiO(2) nanoparticles

Six gases (N((CH3)3), NH2OH, CF3COOH, HCl, NO2, O3) were selected to probe the surface of seven combustion aerosol (amorphous carbon, flame soot) and three types of TiO2 nanoparticles using heterogeneous, that is gas-surface reactions. The gas uptake to saturation of the probes was measured under molecular flow conditions in a Knudsen flow reactor and expressed as a density of surface functional groups on a particular aerosol, namely acidic (carboxylic) and basic (conjugated oxides such as pyrones, N-heterocycles) sites, carbonyl (R1-C(O)-R2) and oxidizable (olefinic, -OH) groups. The limit of detection was generally well below 1% of a formal monolayer of adsorbed probe gas. With few exceptions most investigated aerosol samples interacted with all probe gases which points to the coexistence of different functional groups on the same aerosol surface such as acidic and basic groups. Generally, the carbonaceous particles displayed significant differences in surface group density: Printex 60 amorphous carbon had the lowest density of surface functional groups throughout, whereas Diesel soot recovered from a Diesel particulate filter had the largest. The presence of basic oxides on carbonaceous aerosol particles was inferred from the ratio of uptakes of CF3COOH and HCl owing to the larger stability of the acetate compared to the chloride counterion in the resulting pyrylium salt. Both soots generated from a rich and a lean hexane diffusion flame had a large density of oxidizable groups similar to amorphous carbon FS 101. TiO2 15 had the lowest density of functional groups among the three studied TiO2 nanoparticles for all probe gases despite the smallest size of its primary particles. The used technique enabled the measurement of the uptake probability of the probe gases on the various supported aerosol samples. The initial uptake probability, g0, of the probe gas onto the supported nanoparticles differed significantly among the various investigated aerosol samples but was roughly correlated with the density of surface groups, as expected. [Authors]

Ionic-covalent transition in titanium oxides

The nature of the chemical bond in three titanium oxides of different crystal structure and different formal oxidation state has been studied by means of the ab initio cluster-model approach. The covalent and ionic contributions to the bond have been measured from different theoretical techniques. All the analysis is consistent with an increasing of covalence in the TiO, Ti2O3, and TiO2 series as expected from chemical intuition. Moreover, the use of the ab initio cluster-model approach combined with different theoretical techniques has permitted us to quantify the degree of ionic character, showing that while TiO can approximately be described as an ionic compound, TiO2 is better viewed as a rather covalent oxide.

Thermoluminescence, structural and magnetic properties of a Li(2)O-B(2)O(3)-Al(2)O(3) glass system doped with LiF and TiO(2)

A Li(2)O-B(2)O(3)-Al(2)O(3) glass system, un-doped and doped with LiF, and/or TiO(2) was synthesized by the fusion method and its physical properties were investigated by thermoluminescence (TL), X-ray diffraction (XRD), electron paramagnetic resonance (EPR), atomic force microscopy (AFM) and differential thermal analysis (DTA). The samples were subjected to gamma-rays from a colbalt-60 ((60)Co) source. These techniques provided evidence of LiF and LiF doped with Ti crystal formation in the glass system. A TL glow peak at about 433 K was sensitive to (60)Co gamma-rays and showed good linearity with doses and consequently could be used to quantify radiation doses. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.

Thermodynamics and Lithium Intercalation in CeO(2)-TiO(2) Thin Film

The kinetics and the thermodynamics of electrochemical intercalation of lithium into CeO(2)-TiO(2) films prepared by the sol-gel process were studied by galvanostatic intermittent titration technique (GITT) as function of the depth of lithium intercalation. The open-circuit-potential versus x in Li(x)(CeO(2)-TiO(2)) curve consists of two straight lines with different slopes, one in the range of 0.03 <= x <= 0.09 and the other of 0.09 < x <= 0.15. The standard Gibbs energy for lithium intercalation Delta G(1)(0) was 6kJ/mol for x = 0.09 in Li(x)(CeO(2)-TiO(2)) at room temperature. The chemical diffusion coefficient value, D(Li+), of lithium intercalation into thin film oxide was 2.14.10(-11) cm(2)/s at x = 0.15, and the value of the component diffusion coefficient D(Li+),(k) was about one order of magnitude lower than the coefficient of chemical diffusion.