F-doped ZnO nano- and meso-crystals with enhanced photocatalytic activity in diclofenac degradation.

Diclofenac (DCF), a non-steroidal anti-inflammatory drug, is considered one of the most widespread emerging contaminants. Its incidence in water can favor the growth of drug-resistant bacteria and harm aquatic organisms endangering both the human health and the ecosystem. Advanced oxidation processes (AOPs) based on the action of reactive oxygen species are very effective technologies for the removal of this contaminant from water. In this context, ZnO is one of the most studied semiconductors for photocatalytic water treatment. In this work, the photocatalytic activity of fluorine-doped ZnO nano- and meso-crystals synthesized by a hydrothermal approach is reported, exploring the role of a low F atomic concentration (0.25, 0.5 and 1 at. %) on the degradation of DCF in comparison with bare ZnO. All doped samples show high rates of DCF degradation and mineralization, which were realized primarily thanks to their high efficiency in the generation of hydroxyl radicals (OH). The property-structure-function relationships of the materials are investigated by complementary techniques, such as SEM, XRD, EPR, UV-vis DRS and PL, with the aim to evaluate the role of fluorine in determining their morphological, electronic and optical properties.

Photocatalytic hydrogen evolution by co-catalyst-free TiO2/C bulk heterostructures synthesized under mild conditions.

Hydrogen production by photocatalytic water splitting is one of the most promising sustainable routes to store solar energy in the form of chemical bonds. To obtain significant H2 evolution rates (HERs) a variety of defective TiO2 catalysts were synthesized by means of procedures generally requiring highly energy-consuming treatments, e.g. hydrogenation. Even if a complete understanding of the relationship between defects, electronic structure and catalytic active sites is far from being achieved, the band gap narrowing and Ti3+-self-doping have been considered essential to date. In most reports a metal co-catalyst (commonly Pt) and a sacrificial electron donor (such as methanol) are used to improve HERs. Here we report the synthesis of TiO2/C bulk heterostructures, obtained from a hybrid TiO2-based gel by simple heat treatments at 400 °C under different atmospheres. The electronic structure and properties of the grey or black gel-derived powders are deeply inspected by a combination of classical and less conventional techniques, in order to identify the origin of their photoresponsivity. The defective sites of these heterostructures, namely oxygen vacancies, graphitic carbon and unpaired electrons localized on the C matrix, result in a remarkable visible light activity in spite of the lack of band gap narrowing or Ti3+-self doping. The materials provide HER values ranging from about 0.15 to 0.40 mmol h-1 gcat -1, under both UV- and visible-light irradiation, employing glycerol as sacrificial agent and without any co-catalyst.

Techno-economic and environmental sustainability of biomass waste conversion based on thermocatalytic reforming.

The development and design of innovative biomass waste to energy conversion processes is a key issue to pursue the implementation of circular economy and to endorse a sustainable management of agricultural land. Assessing the environmental and economic sustainability of such processes is of paramount importance to prevent the trade-off of their impacts. The present study focused on a novel biomass waste to energy conversion process based on thermocatalytic reforming (TCR). Two different agricultural waste substrates (olive wood pruning and digestate) were selected as reference cases for conversion to energy and valuable material fractions. Mass and energy balances allowed the calculation of environmental and economic indexes considering alternative scenarios for the final use of the energy and of the products obtained from the TCR conversion (i.e. syngas, bio-oil and bio-char). A sensitivity analysis was carried out to assess the robustness of results. The overall performances of the TCR process resulted strongly related to the characteristics of the biomass waste and to the possible use of the product fractions obtained in the TCR process. The use of bio-char for soil amendment, allowed by the high quality of bio-char obtained from the TCR, was a key point to improve the expected environmental and economic sustainability of the conversion process.

Limitations and Prospects for Wastewater Treatment by UV and Visible-Light-Active Heterogeneous Photocatalysis: A Critical Review.

Heterogeneous photocatalysis (HPC) has been widely investigated in recent decades for the removal of a number of contaminants from aqueous matrices, but its application in real wastewater treatment at full scale is still scarce. Indeed, process and technological limitations have made HPC uncompetitive with respect to consolidated processes/technologies so far. In this manuscript, these issues are critically discussed and reviewed with the aim of providing the reader with a realistic picture of the prospective application of HPC in wastewater treatment. Accordingly, consolidated and new photocatalysts (among which the visible active ones are attracting increasing interest among the scientific community), along with preparation methods, are reviewed to understand whether, with increased process efficiency, these methods can be realistically and competitively developed at industrial scale. Precipitation is considered as an attractive method for photocatalyst preparation at the industrial scale; sol-gel and ultrasound may be feasible only if no expensive metal precursor is used, while hydrothermal and solution combustion synthesis are expected to be difficult (expensive) to scale up. The application of HPC in urban and industrial wastewater treatment and possible energy recovery by hydrogen production are discussed in terms of current limitations and future prospects. Despite the fact that HPC has been studied for the removal of pollutants in aqueous matrices for two decades, its use in wastewater treatment is still at a "technological research" stage. In order to accelerate the adoption of HPC at full scale, it is advisable to focus on investigations under real conditions and on developing/improving pilot-scale reactors to better investigate scale-up conditions and the potential to successfully address specific challenges in wastewater treatment through HPC. In realistic terms, the prospective use of HPC is more likely as a tertiary treatment of wastewater, particularly if more stringent regulations come into force, than as pretreatment for industrial wastewater to improve biodegradability.

Facile method to immobilize ZnO particles on glass spheres for the photocatalytic treatment of tannery wastewater.

In order to apply the photocatalytic processes on a real scale for the treatment of industrial wastewaters, the use of slurry reactors employing suspended photocatalysts is not suitable due to the need for an uncomfortable and expensive separation phase of photocatalyst. To overcome this disadvantage, the photocatalyst particles must be immobilized on a transparent support: our work proposes, for this reason, a simple and cost effective method for the deposition of ZnO photocatalyst on glass spheres in order to formulate a structured photocatalyst effective in the treatment of aqueous solutions containing various organic dyes, commonly used in the tannery industries and in the treatment of a real wastewater at high COD content (11 g/L) coming from the refining unit of the tanning process. In particular, ZnO was immobilized on glass spheres (ZnO/GS) with a simple dip coating method, starting from zinc acetate aqueous solution, without using complexing agent and strong basic compounds. The optimization of ZnO amount on glass spheres was evaluated employing Acid Blue 7 dye, as model pollutant. In particular, it was found that best performances in terms of discoloration and mineralization of the target dye were obtained using the photocatalyst with a ZnO loading equal to 0.19 wt% (ZnO_ac1), prepared through only one dip-coating step. Moreover, the ZnO_ac1 photocatalyst can be easily separated from the reaction mixture, maintaining excellent photocatalytic activity and durability even after several reuse cycles. Finally, ZnO_ac1 showed a high photocatalytic activity in the treatment of the real wastewater, obtaining a COD removal equal to 70% after 180 min of UV light irradiation.

Inactivation of an urban wastewater indigenous Escherichia coli strain by cerium doped zinc oxide photocatalysis.

Heterogeneous photocatalysis (HPC) is a subset of Advanced Oxidation Processes (AOPs) with potential future applications in water disinfection. Herein, a zinc oxide photocatalyst was doped with cerium at various atomic ratios ranging from 0 to 0.1 Ce : Zn. Keeping in mind that the application of HPC is often limited by its cost of use, a simple and easy to upscale method, that is the hydroxide induced hydrolysis of zinc nitrate in the presence of Ce3+ followed by calcination at 300 °C, was used to synthesise the catalysts. The catalysts have been characterized by different techniques such as X-ray diffraction (XRD), UV-vis diffuse reflectance (UV-vis DRS) and Raman spectroscopy. XRD results showed that Ce3+ ions were successfully incorporated into the ZnO lattice. UV-vis DRS spectra evidenced that Ce-ZnO samples present band-gap values of about 2.97 eV, lower than those of undoped ZnO (3.21 eV). These various photocatalysts, at 0.1 g L-1 in saline 0.85%, were used to inactivate Escherichia coli previously isolated from an urban wastewater treatment plant. Higher atomic ratios of Ce in the ZnO lattice, as confirmed by XRD and Raman spectroscopy, showed significant improvements to the inactivation rate; the resulting recommended optimum cerium loading of 0.04 : 1 Ce : Zn gave multiple orders of magnitude higher rate of inactivation after 60 min of treatment when compared to un-doped ZnO. This optimum loading of cerium was faster than the de facto literature standard TiO2-P25 tested under identical conditions.