Solar Photocatalytic Activity of Ba-Doped ZnO Nanoparticles: The Role of Surface Hydrophilicity.

Bare zinc oxide (ZnO) and Ba-doped ZnO (BZO) samples were prepared by using a simple precipitation method. The effects of Barium doping on the structural, morphological, and optoelectronic properties, as well as on the physico-chemical features of the surface were investigated and correlated with the observed photocatalytic activity under natural solar irradiation. The incorporation of Ba2+ ions into the ZnO structure increased the surface area by ca. 14 times and enhanced the hydrophilicity with respect to the bare sample, as demonstrated by infrared spectroscopy and contact angle measurements. The surface hydrophilicity was correlated with the enhanced defectivity of the doped sample, as indicated by X-ray diffraction, Raman, and fluorescence spectroscopies. The resulting higher affinity with water was, for the first time, invoked as an important factor justifying the superior photocatalytic performance of BZO compared to the undoped one, in addition to the slightly higher separation of the photoproduced pairs, an effect that has already been reported in literature. In particular, observed kinetic constants values of 8∙10-3 and 11.3∙10-3 min-1 were determined for the ZnO and BZO samples, respectively, by assuming first order kinetics. Importantly, Ba doping suppressed photocorrosion and increased the stability of the BZO sample under irradiation, making it a promising photocatalyst for the abatement of toxic species.

Ladder-like Poly(methacryloxypropyl) silsesquioxane-Al2O3-polybutadiene Flexible Nanocomposites with High Thermal Conductivity.

Ladder-like poly(methacryloxypropyl)-silsesquioxanes (LPMASQ) are photocurable Si-based gels characterized by a double-stranded structure that ensures superior thermal stability and mechanical properties than common organic polymers. In this work, these attractive features were exploited to produce, in combination with alumina nanoparticles (NPs), both unmodified and functionalized with methacryloxypropyl-trimethoxysilane (MPTMS), LPMASQ/Al2O3 composites displaying remarkable thermal conductivity. Additionally, we combined LPMASQ with polybutadiene (PB) to produce hybrid nanocomposites with the addition of functionalized Al2O3 NPs. The materials underwent thermal stability, structural, and morphological evaluations via thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), Fourier transform infrared spectroscopy (FTIR), and solid-state nuclear magnetic resonance (NMR). Both blending PB with LPMASQ and surface functionalization of nanoparticles proved to be effective strategies for incorporating a higher ceramic filler amount in the matrices, resulting in significant increases in thermal conductivity. Specifically, a 113.6% increase in comparison to the bare matrix was achieved at relatively low filler content (11.2 vol%) in the presence of 40 wt% LPMASQ. Results highlight the potential of ladder-like silsesquioxanes in the field of thermally conductive polymers and their applications in heat dissipation for flexible electronic devices.

Combined effect of atmospheric gas plasma and UVA light: A sustainable and green alternative for chemical decontamination and microbial inactivation of fish processing water.

The simultaneous use of UVA light irradiation coupled with low energy cold plasma generated by a dielectric barrier discharge prototype, results in significant enhancement of efficiency of the integrated process with respect to the sole plasma treatment. This effect has been demonstrated both on microbial inactivation of a food-borne pathogen, i.e. Listeria monocytogenes, and on the degradation of a compound of biological origin such as phenylalanine. In the latter case, the analysis of its reaction intermediates and the spectroscopic identification and quantification of peroxynitrites, allowed to propose mechanistic hypotheses on the nature of the observed synergistic effects. Moreover, it has been demonstrated that the process does not affect the quality of trout fillets, indicating its suitability as a chlorine-free, green, and sustainable tool for the decontamination of fish processing water.

Characterization of anthropogenic organic matter and its interaction with direct yellow 27 in wastewater: Experimental results and perspectives of resource recovery.

The concept of natural organic matter of anthropogenic origin is introduced and its characteristics and interaction with chemical pollutants are investigated by adopting several distinct analytic methodologies. Scanning electron microscopy indicates that the used sample of anthropogenic organic matter (AOM) has an amphiphilic nature, which allows its supramolecular organization in water. Fourier transform infrared spectroscopy, in turn, gives a clear indication about the presence of polysaccharide markers, lipidic and amidic fractions, and suggests the absence of free organic acid. AOM sample and AOM mixed with dye sample were examined by the three-dimensional excitation-emission matrix fluorescence spectra and the nuclear magnetic resonance mono-dimensional spectra. The results highlighted the interactions occurring between the AOM and the reactive dye, selected as a representative chemical pollutant. Electron Spin Resonance confirms that the used AOM is able to completely include the dye in its structure. Overall, the obtained results indicate that the fate, transport, and toxicity of pollutants in the environment can be drastically influenced by the presence of AOM.

Electron and Energy Transfer Mechanisms: The Double Nature of TiO2 Heterogeneous Photocatalysis.

Photocatalytic chemical transformations in the presence of irradiated TiO2 are generally considered in terms of interfacial electron transfer. However, more elusive energy-transfer-driven reactions have been also hypothesized to occur, mainly on the basis of the indirect evidence of detected reaction products whose existence could not be justified simply by electron transfer. Unlike in homogeneous and colloidal systems, where energy transfer mechanisms have been investigated deeply for several organic syntheses, understanding of similar processes in heterogeneous systems is at only a nascent level. However, this gap of knowledge can be filled by considering the important achievements of synthetic heterogeneous photocatalysis, which bring the field closer to industrial exploitation. The present manuscript summarizes the main findings of previous literature reports and, also on the basis of some novel experimental evidences, tentatively proposes that the energy transfer in TiO2 photocatalysis could possess a Förster-like nature.

Features and application of coupled cold plasma and photocatalysis processes for decontamination of water.

Dielectric barrier discharge plasma and photocatalysis have been proposed as tools for decontamination of process water, especially in food industry. The present investigation aims to redefine and identify the features of coupling the two technologies in terms of degradation efficiency of a model compound. Results show that, when the process is carried out in plasma activated water in the presence of irradiated TiO2, the efficiency of the integrated process is lower than the sum of the two processes acting separately. It is proposed that afterglow species, e.g. hydrogen peroxide and/or peroxynitrites could be activated by UVA light irradiation producing hydroxyl radicals in the liquid phase. Even if TiO2 limits this additional effect by acting as UVA screen barrier material, its decontamination efficiency under certain conditions results higher than that obtained with plasma systems. These results open the route to chlorine-free decontamination processes and redefine the application framework of this integrated approach.

Highlights on Recent Developments of Heterogeneous and Homogeneous Photocatalysis.

Photocatalysis emerged in the last decades as a versatile technology, whose applications range from environmental remediation to hydrogen production, energy harvesting, and organic synthesis, with exciting examples also in medicine, electronics, and advanced functional materials [...].

Pickering Emulsions of Fluorinated TiO2: A New Route for Intensification of Photocatalytic Degradation of Nitrobenzene.

Fluorination of the TiO2 surface has been often reported as a tool to increase the photocatalytic efficiency due to the beneficial effects in terms of production of oxidizing radicals. Moreover, it is shown that the unique amphiphilic properties of the fluorinated TiO2 (TiO2-F) surface allow one to use this material as a stabilizer for the formulation of Pickering emulsions of poorly soluble pollutants such as nitrobenzene (NB) in water. The emulsions have been characterized in terms of size of the droplets, type of emulsion, possibility of phase inversion, contact angle measurements, and optical microscopy. The emulsified system presents micrometer-sized droplets of pollutant surrounded by the TiO2-F photocatalyst. Consequently, the system can be considered to be composed of microreactors for the degradation of the pollutant, which maximize the contact area between the photocatalyst and substrate. The enhanced photocatalytic activity of TiO2-F was confirmed in the present paper as the apparent rate constants of NB photodegradation were 16 × 10-3 and 12 × 10-3 min-1 for fluorinated and bare TiO2, respectively. At NB concentrations largely exceeding its solubility, the rate constant was 0.04 × 10-3 min-1 in the presence of both TiO2 and TiO2-F. However, unlike TiO2, TiO2-F stabilized NB/water emulsions and, under these conditions, the efficiency of NB photocatalytic degradation in the emulsified system was ca. 18 times higher than in the nonemulsified one. This result is relevant also in terms of practical applications because it opens the route to one-pot treatments of biphasic polluted streams without the need of preliminary physical separation treatments.

Enhanced Solar Light Photocatalytic Activity of Ag Doped TiO2-Ag3PO4 Composites.

Composites comprised of Ag3PO4 and bare TiO2 (TiO2@Ag3PO4) or silver doped TiO2 (Ag@TiO2-Ag3PO4) have been synthesized by coupling sol-gel and precipitation methods. For the sake of comparison, also the bare components have been similarly prepared. All the samples have been characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), Fourier transformed infrared spectroscopy (FTIR), photoelectrochemical measurements, and specific surface area (SSA) analysis. The optoelectronic and structural features of the samples have been related to their photocatalytic activity for the degradation of 4-nitrophenol under solar and UV light irradiation. Coupling Ag3PO4 with silver doped TiO2 mitigates photocorrosion of the Ag3PO4 counterpart, and remarkably improves the photocatalytic activity under solar light irradiation with respect to the components, to the TiO2-Ag3PO4 sample, and to the benchmark TiO2 Evonik P25. These features open the route to future applications of this material in the field of environmental remediation.

Vanillin: The Case for Greener Production Driven by Sustainability Megatrend.

Approaching the end of the second decade of the 21st century, almost the whole demand of vanillin is met by the synthetic product obtained either via a petrochemical process starting from phenol and glyoxylic acid or from energy intensive alkaline oxidative depolymerization of lignin. Only a minor fraction is comprised of natural vanillin obtained from ferulic acid fermentation, and even less of highly valued Vanilla planifolia extracts. Are there alternative green production methods? And, if yes, are they suitable to find practical application?

Three-Dimensional Calibration for Routine Analyses of Bromide and Nitrate Ions as Indicators of Groundwater Quality in Coastal Territories.

Nitrate and bromide ions are generally considered indicators of anthropogenic pollution and seawater intrusion, respectively, in the groundwater of coastal territories. The analysis of these species is generally carried out with routine chromatographic analyses which generally afford partially merged or poorly resolved peaks. In the present paper a simple method for the correct evaluation of their concentration in water is reported. This method does not imply utilization of other instruments or technologies, only the mathematical elaboration of the data obtained from routine analysis of standard solutions containing the two species. Standard binary solutions of nitrate and bromide ions at different concentrations, ranging between 0.1 and 2 mM, were analyzed by means of ion chromatography. Splitting two partially merged chromatographic peaks and considering each resulting area as originating from a single species produces "measured" concentration values which differ from the nominal ones. Such a procedure generates errors (one per species) which can be written as a function of the above mentioned "measured" concentrations and which can be graphically represented by means of a surface in a three-dimensional (3D) space. In this way, "measured" concentrations of bromide and nitrate ions can be corrected by calculating the errors generated under the experimental conditions at which the chromatographic separation is performed. Notably, this is analogous with the two-dimensional (2D) calibration normally carried out for analytical purposes. Indeed, both methods allow estimation of the unknown concentration of species in solution by correlating the instrumental response with the concentration of standard solutions.

Photocatalytic Degradation Enhancement in Pickering Emulsions Stabilized by Solid Particles of Bare TiO2.

Pickering emulsions provide a new way to enhance the efficiency of photocatalytic degradation of water-insoluble pollutants. Indeed, the semiconductor solid particles dually act as the photocatalyst and stabilizer of the emulsion droplets whose size dramatically affects the photocatalytic reaction. The present work aims at the validation of this concept by using bare TiO2 without any surface modification. Nanostructured TiO2 has been prepared by a simple sol-gel process and characterized by X-ray diffraction, specific surface area analysis, scanning electron microscopy, and diffuse reflectance spectroscopy. The emulsions were prepared by using 1-methylnaphthalene (1-MN) as a model organic contaminant scarcely soluble in water and bare TiO2 as the photocatalyst/stabilizer. The emulsions have been characterized by electrical conductivity, optical microscopy, and light-scattering analyses. The photocatalytic degradation of 1-MN was 50 times faster in stable Pickering emulsions with respect to the case of biphasic liquid systems containing TiO2. This finding allows us to propose Pickering emulsions stabilized by TiO2 nanoparticles as an effective and novel way to intensify the photocatalytic degradation of water-insoluble organic pollutants.

Influence of Surface-Related Phenomena on Mechanism, Selectivity, and Conversion of TiO2 -Induced Photocatalytic Reactions.

Heterogeneous photocatalysis is the result of an inextricable connection of several factors differently contributing to the overall process. Photon absorption is the "sine qua non" condition for the reaction to occur. In fact, photons can be considered as immaterial reactants, and all of the phenomena related to the interaction of light-matter play a prominent role. However, other factors contribute in a concerted way to address the reaction, so that the relative contribution of each of them is often difficult to evaluate. In this framework, the present paper highlights some aspects of the interaction of TiO2 surface-adsorbate species that could be underestimated and their influence on the conversion, selectivity, and mechanisms of photocatalytic reactions. To this aim, some paradigmatic examples on the adsorption of water and organics on TiO2 are reported.

Photocatalytic ozonation under visible light for the remediation of water effluents and its integration with an electro-membrane bioreactor.

Photocatalysis and photocatalytic ozonation under visible light have been applied for the purification of a complex aqueous matrix such as the grey water of Masdar City (UAE), by using N-doped brookite-rutile catalysts. Preliminary runs on 4-nitrophenol (4-NP) solutions allowed to test the reaction system in the presence of a model pollutant and to afford the relevant kinetic parameters of the process. Subsequently, the remediation of grey water effluent has been evaluated in terms of the reduction of total organic carbon (TOC) and bacterial counts. The concentration of the most abundant inorganic ionic species in the effluent has been also monitored during reaction. Photocatalytic ozonation under visible light allowed to reduce the TOC content of the grey water by ca. 60% in the optimized experimental conditions and to reduce the total bacterial count by ca. 97%. The extent of TOC mineralization reached ca. 80% when the photocatalytic ozonation occurred downstream to a preliminary electro-membrane bioreactor (eMBR). Coupling the two processes enhanced the global efficiency. In fact, the eMBR treatment lowered the turbidity and the organic load of the effluent entering the photocatalytic ozonation treatment, which in turn enhanced the extent of purification and disinfection.

The Existence of Nitrate Radicals in Irradiated TiO2 Aqueous Suspensions in the Presence of Nitrate Ions.

Evidence of the existence of nitrate radical in irradiated aqueous TiO2 suspensions in the presence of nitrate ions are reported for the first time. The joint use of UV/Vis and EPR spectroscopy showed that nitrate radicals are formed by hole induced oxidation of nitrate ions. Photocatalytic degradation of a model alkene compound allowed to highlight the presence of an intermediate organic nitrate deriving from nitrate radical attack to the double bond of the substrate. These results not only allow deeper understanding of photocatalytic processes, but open the route to new green photocatalytic syntheses initiated by nitrate radicals and to new insights in the field of atmospheric chemistry.

Photocatalytic partial oxidation of limonene to 1,2 limonene oxide.

The silylation of crystalline TiO2 P25, commonly used for photocatalytic degradation of pollutants, results in an exceptionally selective catalyst for the aerobic limonene epoxidation to 1,2-limonene oxide under solar light irradiation. The hypothesized mechanism involves the singlet oxygen generated through energy transfer from the excited TiO2 to adsorbed O2 molecules. The reaction product is the valued precursor of bio-based poly(limonene carbonate), a thermoplastic polymer of superior thermal and optical properties whose industrial production is in need of an efficient green synthesis of limonene oxide.

Polymers of Limonene Oxide and Carbon Dioxide: Polycarbonates of the Solar Economy.

Limonene epoxide (1,2-limonene oxide) readily reacts with carbon dioxide inserted in a ring-opening copolymerization reaction and forms polycarbonates of exceptional chemical and physical properties. Both poly(limonene carbonate) and poly(limonene dicarbonate) can be synthesized using low-cost Zn or Al homogeneous catalysts. This study addresses selected relevant questions concerning the technical and economic feasibility of limonene and carbon dioxide polymers en route to the bioeconomy.

Tuning the photocatalytic activity of bismuth wolframate: towards selective oxidations for the biorefinery driven by solar-light.

The sol-gel entrapment of nanostructured Bi2WO6 enhances the activity and the selectivity of the short-gap semiconductor in the sunlight-driven photo-oxidation of trans-ferulic and trans-cinnamic acid dissolved in water with air as the primary oxidant. Valuable products such as vanillin, benzaldehyde, benzoic acid and vanillic acid are obtained. This provides the proof of concept that photocatalysis could be a promising technology in tomorrow's solar biorefineries.

Elemental Bromine Production by TiO2 Photocatalysis and/or Ozonation.

Significant production of elemental bromine (Br2 ) was observed for the first time when treating bromide containing solutions at acidic pH, with TiO2 photocatalyst, ozone, or a combination thereof. Br2 selectivities up to approximately 85 % were obtained and the corresponding bromine mass balance values satisfied. The process is general and may be applied at a laboratory scale for green bromination reactions, or industrially as a cheap, safe, and environmentally sustainable alternative to the currently applied bromine production methods.

Nanostructured anatase TiO2 densified at high pressure as advanced visible light photocatalysts.

This study reports on characterization and photoactivity of nanostructured TiO2 samples, which have been permanently densified under high pressures, up to 2.1 GPa. Commercial Mirkat 211 anatase has been used as a benchmark sample, in order to investigate the effect of unidirectional high pressure on structural, optical and photocatalytic properties of TiO2. Vibrational Raman spectroscopy shows that the treatment does not cause transitions among the different crystalline phases of titanium dioxide. UV-vis diffuse reflectance spectra reveal that increasing pressure gives rise to a shift of the absorption onset towards higher wavelength enhancing the photoactivity under visible radiation. Samples are also photo-electrochemically characterized and tested in the gas phase with partial oxidation of ethanol to acetaldehyde under visible irradiation. Compaction up to 0.8 GPa depresses both the alcohol conversion and the aldehyde yield, while samples treated under higher pressures show enhanced characteristics of conversion compared to the pristine material. Moreover, promising results in the reduction of CO2 are also obtained under UV-visible radiation.