Photocatalytic degradation of methyl-red by immobilised nanoparticles of TiO2 and ZnO

none6noIn this work, we report on the degradation of methyl-red (2-(4-Dimethylamino-phenylazo)-benzoic acid - C.I. 13020) under UV irradiation in the presence of nanosized ZnO and TiO2. Oxide nanocrystals with controlled size were synthesised by using non-hydrolytic approaches and tested for the photocatalysed degradation. The performances of the immobilised nanoparticles were compared with their commercial counterparts after immobilization onto a solid support. The influence of some experimental conditions, namely pH and dye concentration, were investigated by monitoring the dye decoloration spectrophotometrically. Several intermediate by-products were identified by HPLC-MS, showing that two different mechanisms were operative during the photocatalytic oxidationsee at: http://www.iwaponline.com/wst/04904/wst049040183.htmopenR. COMPARELLI; P. D. COZZOLI; M. L. CURRI; A. AGOSTIANO; G. MASCOLO; G. LOVECCHIOR., Comparelli; Cozzoli, Pantaleo Davide; M. L., Curri; A., Agostiano; G., Mascolo; G., Lovecchi

UV and solar-based photocatalytic degradation of organic pollutants by nano-sized TiO2 grown on carbon nanotubes

Anew photocatalyst based on nano-sized TiO2 supported on single wall carbon nanotubes (SWCNTs) with tailored photocatalytic properties upon irradiation by both UV and solar simulated light was successfully employed for the degradation of a mixture of 22 organic pollutants in both ultrapure water and real secondary wastewater effluent. First-order degradation rates showed that under UV irradiation nanosized TiO2 supported on SWCNTs is much more effective than conventional Degussa P25 for degradation of iopamidol, iopromide, diatrizoic acid, diclofenac, triclosan and sulfamethoxazole in ultrapure water. For the remaining organics the degradation rates were comparable being in most of the cases Degussa P25 slightly more effective than nano-sized TiO2 supported on SWCNTs. Reactions performed in real secondary wastewater effluent showed a general reduction of degradation rates. Specifically, such a reduction was in the range 9-87% and 9-96% for the Degussa P25 and the nano-sized TiO2 supported on SWCNTs, respectively. Overall, the nano-sized TiO2 supported on SWCNTs under UV irradiation displayed comparable degradation rates with respect to convention Degussa P25. Under simulated solar irradiation the new prepared photocatalyst showed lower efficiency than Degussa P25 in ultrapure water. Such a gap was greatly reduced when the reactions were carried out in real secondary wastewater effluent. The nano-sized TiO2 supported on SWCNTs demonstrated to have the addition benefit to be easily removed from the aqueous solution by a mild centrifugation or a filtration step and, consequently, can be reused for a further photocatalytic treatment batch. Therefore, the obtained results showed that new photocatalyst based on nano-sized TiO2 supported on SWCNTs has proved to be a promising candidate to be used in a photocatalytic based-AOP and to be integrated with a biological step for the effective removal of emerging organic pollutants

Enhanced performances of RGO-AuNPs hybrids towards electroanalytical applications

In recent years, lot of attention has been devoted to understanding the properties of hybrid nanocomposites, \u201cbrave new materials\u201d made of two or more organic and inorganic components. These systems show enhanced or novel physico-chemical properties with respect to the single components, resulting not only from the sum of the precursors\u2019 ones, but also from interactions occurring at their interface, the so-called \u201cheterojunction\u201d. However, a remaining challenge is to understand in depth the phenomena here originating. In the present work, to start fulfilling this gap, a deep electrochemical study of hybrids made of Reduced Graphene Oxide (RGO) and Au nanoparticles (NPs) is performed, analysing carefully the role played by each single component of the material on the electrochemical properties. In more details, RGO platforms are surface functionalized with 1-aminopyrene or 1-pyrene carboxylic acid that act as heteronucleation and growing sites of the amine- or thiol-coated Au NPs of different dimensions (from 3 to 20 nm). At first, Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) measurements are carried out in order to characterize the different hybrids. Then, the materials are applied as electroanalytical sensors for both organic and inorganic molecules (dopamine and As, respectively) with very promising results, comparable or even better than analogous systems reported in literature. Moreover, preliminary tests on H2O2 detection open the venue to the application of these materials in biosensor applications. The properties of the hybrid nanocomposite, enhanced with respect to those of the single components, are ascribed to charge transfer occurring at the heterojunction from the Au NPs to the RGO, assisted and channelled by the pyrene linker

Nanocrystalline TiO2 based films onto fibers for photocatalytic degradation of organic dye in aqueous solution

Nanocrystalline titania (TiO2) synthesized via sol–gel, by using an alkoxide precursor were deposited onto commercially available silica and alumina fibers, namely E-Glass and Nextel 650, respectively. Different processing conditions and material preparation parameters, such as amount of TiO2, film composition and annealing temperature were tested in order to obtain nanocrystalline TiO2 with different morphological and structural characteristics. The materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and the Brunauer, Emmett, and Teller (BET) surface area measurements. The photocatalytic activity of the obtained coated fibers was investigated by monitoring the degradation of a model molecule, an azo dye (Methyl Red), under UV irradiation in aqueous solution. The detected photocatalytic performance of the sol–gel derived nanocrystalline TiO2 was explained on the basis of mechanism associated to the photocatalytic decomposition of organic molecules using semiconductor oxides and accounted for the structural and morphological characteristics of the TiO2 based coating. The materials with the most suited characteristics for photocatalysis were used to scale up the deposition onto a larger sample of fiber and then tested in a photocatalytic reactor. A commercially available TiO2 standard material (TiO2 P25 Degussa) was used as reference, in order to ultimately assess the viability of the coating process for real application

Luminescent Oil-Soluble Carbon Dots toward White Light Emission: A Spectroscopic Study

Carbon dots (C-dots) are emerging as new emitting nanomaterials for optoelectronics, bioimaging, and biosensing thanks to their high quantum yield (QY), biocompatibility, low toxicity, and cost-effective sources. Although the origin of their photoluminescence (PL) mechanism (i.e., their strong blue-green emission and excitation dependent fluorescence) is still controversial, it has been demonstrated to depend on the synthetic protocols and experimental conditions, able to modify the surface properties. Here oil-dispersible C-dots, synthesized by carbonization of citric acid in the presence of hexadecylamine in high boiling organic solvent, are thoroughly investigated by systematically controlling the synthetic reaction parameters. Similarly to what was found for water-soluble C-dots, citric acid in the presence of amine-containing passivating agents improves the PL emission of C-dots via the formation of molecular fluorescent derivatives alongside the carbonization process. We demonstrate that at growth temperature of 200 °C such C-dots exhibit an interesting and intense white emission, when excited in the blue region, thus resulting in a biocompatible colloidal white emitting single nano-objects. The incorporation of the nanoparticles in a poly(methyl methacrylate) (PMMA) host matrix, to obtain free-standing nanocomposite films, is demonstrated not to affect the color point, which still falls in the white color region of the 1931 CIE diagram. Remarkably, the emission properties are retained even after several months of films exposure to air and sunlight, thus confirming the color stability of the nanoparticles against aging

High surface area mesoporous silica nanoparticles with tunable size in the sub-micrometer regime: Insights on the size and porosity control mechanisms

Mesoporous silica nanostructures (MSNs) attract high interest due to their unique and tunable physical chemical features, including high specific surface area and large pore volume, that hold a great potential in a variety of fields, i.e., adsorption, catalysis, and biomedicine. An essential feature for biomedical application of MSNs is limiting MSN size in the sub-micrometer regime to control uptake and cell viability. However, careful size tuning in such a regime remains still chal-lenging. We aim to tackling this issue by developing two synthetic procedures for MSN size mod-ulation, performed in homogenous aqueous/ethanol solution or two-phase aqueous/ethyl acetate system. Both approaches make use of tetraethyl orthosilicate as precursor, in the presence of cetyltri-methylammonium bromide, as structure-directing agent, and NaOH, as base-catalyst. NaOH catalyzed syntheses usually require high temperature (>80 °C) and large reaction medium volume to trigger MSN formation and limit aggregation. Here, a successful modulation of MSNs size from 40 up to 150 nm is demonstrated to be achieved by purposely balancing synthesis conditions, being able, in addition, to keep reaction temperature not higher than 50 °C (30 °C and 50 °C, respectively) and reaction mixture volume low. Through a comprehensive and in-depth systematic morphologi-cal and structural investigation, the mechanism and kinetics that sustain the control of MSNs size in such low dimensional regime are defined, highlighting that modulation of size and pores of the structures are mainly mediated by base concentration, reaction time and temperature and ageing, for the homogenous phase approach, and by temperature for the two-phase synthesis. Finally, an in vitro study is performed on bEnd.3 cells to investigate on the cytotoxicity of the MNSs

Electrochemical Characterization and Electroanalytical Aplications of RGO_AuNPs Hybrids

A novel synthetic route for the synthesis of gold nanoparticles (AuNPs) modified graphene electrodes has been developed: Reduced Graphene Oxide (RGO) sheets are functionalized with pyrene linkers acting as growing sites for gold nanoparticles (AuNPs) of different dimensions (approximatively 5, 10 and 20 nm). The Au surface is functionalized with oleylamine or 3,4-dimethylbenzenethiol as capping agents. The hybrid material is deposited onto Carbon Screen Printed Electrodes (C-SPEs) for a deep physico-chemical and electrochemical characterization, using Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) measurements. The role played by every single hybrid counterpart has been investigated, showing a synergistic effect, which is responsible of the enhancement of the system properties. The charge transfer from gold nanoparticles to graphene, assisted and stimulated by the pyrene linker, seems to be the key point to understand the peculiarities of this innovative material. The as prepared RGO-AuNPs hybrids have been used in the electroanalytical detection of both inorganic and organic species (arsenic, H2O2, dopamine), showing promising results in terms of sensitivities and detection limits. In particular, regarding the detection of the neurotransmitter dopamine by means of Differential Pulse Voltammetry in Phosphate Buffer Solution, a LOD of (3.3 \ub1 0.2) ppb has been reached, comparable with other electroanalytical results in the literature and in accordance with the benchmark for this molecule [1]. For arsenic detection, the hybrid devices show increased performances in comparison with bare gold or gold NPs, also allowing speciation between arsenic (III) and (V), appropriately adjusting the experimental conditions. In the case of H2O2, the hybrid devices display high electrocatalytic activity and fast electron-transfer kinetics, representing an ideal platform for developing oxidoreductase-based electrochemical biosensors as well as for detecting H2O2 in real samples. [1] J.A. Ribeiro, P.M.V. Fernandes, C.M. Pereira, F. Silva, Talanta 160 (2016) 653-679

Three-Dimensional Self-Assembly of Networked Branched TiO2 Nanocrystal Scaffolds for Efficient Room-Temperature Processed Depleted Bulk Heterojunction Solar Cells

In this work, we report on 4% power conversion efficiency (PCE) depleted bulk heterojunction (DBH) solar cells based on a high-quality electrode with a three-dimensional nanoscale architecture purposely designed so as to maximize light absorption and charge collection. The newly conceived architecture comprises a mesoporous electron-collecting film made of networked anisotropic metal-oxide nanostructures, which accommodates visible-to-infrared light harvesting quantum dots within the recessed regions of its volume. The three-dimensional electrodes were self-assembled by spin-coating a solution of colloidal branched anatase TiO2 NCs (BNC), followed by photocatalytic removal of the native organic capping from their surface by a mild UV-light treatment and filling with small PbS NCs via infiltration. The PCE = 4% of our TiO2 BNC/PbS QD DBH solar cell features an enhancement of 84% over the performance obtained for a planar device fabricated under the same conditions. Overall, the DBH device fabrication procedure is entirely carried out under mild processing conditions at room temperature, thus holding promise for low-cost and large-scale manufacturing

Low temperature synthesis of photocatalytic mesoporous tio2 nanomaterials

We report the synthesis of mesoporous TiO2 nanostructures based on the decomposition of TiOSO4 in aqueous alkaline solution at room temperature, followed by mild thermal treatment (110◦C) in an oven and suitable to yield up to 40 g of product per batch. The duration of the thermal treatment was found to be crucial to control crystalline phase composition, specific surface area, surface chemistry and, accordingly, the photocatalytic properties of the obtained TiO2 nanocrystals. The thorough investigation of the prepared samples allowed us to explain the relationship between the structure of the obtained nanoparticles and their photocatalytic behavior, that was tested in a model reaction. In addition, the advantage of the mild treatment against a harsher calcination at 450◦C was illustrated. The proposed approach represents a facile and sustainable route to promptly access an effective photocatalyst, thus holding a significant promise for the development of solutions suitable to real technological application in environmental depollution