Sequential biological and photocatalysis based treatments for shipboard slop purification: A pilot plant investigation

This study investigated the treatment of a shipboard slop containing commercial gasoline in a pilot plant scale consisting of a membrane biological reactor (MBR) and photocatalytic reactor (PCR) acting in series. The MBR contributed for approximately 70% to the overall slop purification. More precisely, the biological process was able to remove approximately 40%, on average, of the organic pollution in the slop. Nevertheless, the membrane was capable to retain a large amount of organic molecules within the system, amounting for a further 30% of the influent total organic content removal. However, this affected the membrane fouling, thus resulting in the increase of the pore blocking mechanism that accounted for approximately 20% to the total resistance to filtration (2.85∙10 13 m −1 ), even if a significant restoration of the original membrane permeability was obtained after chemical cleanings. On the other hand, the biological treatment produced a clear solution for the photocatalytic system, thereby optimizing the light penetration and generation of highly oxidizing active oxygen species that enabled the degradation of bio-recalcitrant compounds. Indeed, low total organic carbon (TOC) values (<10 mg L −1 ) were achieved in the output of the photocatalytic reactor by means of only 60 Einstein (E) of cumulative impinging energy after the addition of K 2 S 2 O 8 . Overall, coupling the two processes enabled very high TOC removal (ca. 95%)

Review on Recent Advances in the Removal of Organic Drugs by Advanced Oxidation Processes

In recent years, due to the high consumption of drugs both for human needs and for their growing use, especially as regards antibiotics, in the diet of livestock, water pollution has reached very high levels and attracted widespread attention. Drugs have a stable chemical structure and are recalcitrant to many treatments, especially biological ones. Among the methods that have shown high efficiency are advanced oxidation processes (AOPs) which are, among other things, inexpensive and eco-friendly. AOPs are based on the production of reactive oxygen species (ROS) able to degrade organic pollutants in wastewater. The main problem related to the degradation of drugs is their partial oxidation to compounds that are often more harmful than their precursors. In this review, which is not intended to be exhaustive, we provide an overview of recent advances in the removal of organic drugs via advanced oxidation processes (AOPs). The salient points of each process, highlighting advantages and disadvantages, have been summarized. In particular, the use of AOPs such as UV, ozone, Fenton-based AOPs and heterogeneous photocatalysis in the removal of some of the most common drugs (tetracycline, ibuprofen, oxytetracycline, lincomycin) has been reported

N-TiO2 Photocatalysts highly active under visible irradiation for NOX abatement and 2-propanol oxidation

N-doped TiO2 powders were prepared by two different sol–gel methods. Samples were characterised by X-ray diffraction (XRD), BET specific surface area measurements (SSA), scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) and Electron Paramagnetic Resonance (EPR). XPS measurements revealed a signal at 400 eV assignable to nitrogen in the form of Ti N O. EPR signals are attributed to molecular NO trapped with cavities/defects possibly interacting with oxygen vacancies. The photocatalytic activity under UV and visible light was determined following the abatement of NOx and the photodegradation of 2-propanol in gas–solid systems. N-doped TiO2 showed a higher activity compared with the pristine commercial and home prepared samples under visible light irradiation. A good photoactivity in the abatement of both NOx and 2-propanol is also observed for mechanical dispersions of N-TiO2 in CaCO3 serving as a model in view of perspective application in photocatalytically active construction and architectural materials

Selective photocatalytic and photoelectrocatalytic synthesis of valuable compounds in aqueous medium

In the past decades, photocatalytic and photoelectrocatalytic methods have been widely employed for the degradation of harmful compounds present both is gaseous and aqueous effluents. In the last years scientists have paid great attention to the synthesis of valuable compounds and hydrogen production. Organic syntheses are generally carried out in organic solvents, under high temperature/pressure, with toxic oxidants such as permanganate. On the other hand, photocatalysis and photoelectrocatalysis using water as solvent, air or water as oxidant, and sunlight as energy source, can be an efficient alternative to the traditional, non-environmentally friendly methods. This review summarizes the photocatalytic and photoelectrocatalytic transformations of organic molecules to commercially valuable products in water, sometimes evaluating also the contemporary H2 production. The reaction conditions, mechanisms and kinetics are presented and discussed. Future perspectives are also given

Enhancing H2 production rate in PGM-free photoelectrochemical cells by glycerol photo-oxidation

The photo-oxidation of glycerol was carried out by using TiO2 NTs photoanodes and Ni foam as the cathode for the Hydrogen Evolution Reaction. The photoanodes were prepared by anodizing Ti foils and titanium felt and then annealed under air exposure. They were tested in acidic aqueous solution without and with the addition of glycerol. When glycerol was present, the hydrogen production rate increased and allowed the simultaneous production of high value added partial oxidation compounds, i.e. 1,3-dihydroxyacetone (DHA), and glyceraldehyde (GA). The highest H2 evolution and partial oxidation compounds production rates were obtained by using home prepared TiO2 nanotubes (TiO2 NTs) synthesized on Ti fiber felt as the photoanode with an irradiated area of 90 cm2. These photoanodes were found to be highly stable both from a mechanical and a chemical point of view, so they can be reused after a simple cleaning step

Selective aqueous oxidation of aromatic alcohols under solar light in the presence of TiO2 modified with different metal species

A set of metals modified TiO2 photocatalysts were prepared starting from titanium tetraisopropoxyde and different metal precursors to study the influence of the addition of the various foreign agents on the physico-chemical and photocatalytic properties of the catalysts. The powders were characterized by X-ray diffraction, Raman spectroscopy, specific surface area measurements, scanning electron microscopy, energy dispersive X-ray spectroscopy, UV–Vis diffuse reflectance spectroscopy, photoluminescence, temperature programmed desorption after CO2 adsorption. The photocatalytic activity was evaluated using as probe reactions the partial oxidation of three aromatic alcohols: benzyl alcohol (BA), 4-methoxy benzyl alcohol (4-MBA), and 4-hydroxy benzyl alcohol (4-HBA) under simulated solar light irradiation. Different oxidation and selectivity values were obtained for the three substrates depending not only on the type of metals but also on the nature and position of the substituent in the phenyl ring of benzyl alcohol. As a general behaviour, the doped samples allowed the achievement of a greater selectivity especially for 4-MBA even if sometimes with minor conversions. The presence of W or Nb was beneficial for both conversion and selectivity for all the substrates with respect to bare TiO2. Graphical abstract: [Figure not available: see fulltext.

Photocatalytic and photoelectrocatalytic H2 evolution combined with valuable furfural production

In this work the photocatalytic (PC) and photoelectrocatalytic (PEC) reforming of furfuryl alcohol (FA) under environmental friendly conditions was investigated. Both H2 evolution and partial oxidation to furfuraldehyde were followed. For the first time TiO2 based photocatalysts were studied and the photocatalytic activity of home prepared photocatalysts was compared with that of commercial ones under both UVA and simulated solar irradiation. PEC tests were performed by using home prepared TiO2 nanotubes (TiO2 NTs) as photoanode and Pt free Ni foam as cathode to improve the Hydrogen Evolution Reaction (HER). Both the partial FA oxidation reaction rate and H2 evolution rate were normalized for the lamp specific power to account for the different photon flux and the rates were higher for PEC process. PEC is a promising strategy for the valorization of biomasses with simultaneous H2 production in spite of the cost of the bias

Overview on oxidation mechanisms of organic compounds by TiO2 in heterogeneous photocatalysis

This review provides the reader with a general overview on heterogeneous photocatalytic oxidation mechanisms in the presence of TiO2, with a special address to conversion of aliphatic and aromatic organic species. The aim was to clarify the steps of the photo-oxidation of the various classes of compounds and to relate them with the properties of the catalysts and the experimental conditions used. Reactions carried out to perform complete degradation and photocatalytic partial oxidations have been deeply discussed. Recent isotopic studies highlighted new reaction pathways concerning partial oxidation of alcohols to aldehyde and oxidation of benzene while EPR investigations confirmed that not only the photogenerated hole but also the OH radicals are involved in the oxidation of the substrates

Facile preparation of CuBi2O4/TiO2 hetero-systems employed for simulated solar-light selective oxidation of 4-methoxybenzyl alcohol model compound

The selective photocatalytic oxidation of organic substances is today considered one of the green techniques to synthesize important starting materials in different technological applications. This work reports an efficient, simple and cheap strategy for the synthesis of a new photocatalytic CuBi2O4-TiO2 (CBO/TiO2) heterosystem at room temperature. The prepared powders were characterized by X-ray diffraction (XRD), UV–Vis diffuse reflectance spectra (DRS), field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements. The photocatalytic activity was evaluated by performing a probe reaction, namely the partial oxidation of 4-methoxybenzyl alcohol (4-MBA) to 4-methoxybenzaldehyde (4-MBAld) in aqueous solution under irradiation of simulated sunlight. The CBO/TiO2 coupled systems showed a higher photoactivity than the single photocatalysts reaching a selectivity of 45% towards 4‑methoxy-benzaldehyde with an alcohol conversion of 77% after 4 h of irradiation. Furthermore, although a high alcohol conversion was achieved, the selectivity towards 4-MBAld was significant, unlike what has been reported in the literature for many heterogeneous photocatalytic reactions whose selectivity generally decreases significantly with the increasing conversion of the starting alcohol molecule. The improved photocatalytic activity could be attributed to the partial coverage of the TiO2 surface by CBO which reduces the subsequent oxidation of the formed aldehyde

Photocatalytic CO2 Reduction in Gas-Solid Regime in the Presence of Bare, SiO2 Supported or Cu-Loaded TiO2 Samples

Both commercial and home prepared (HP) TiO2 samples have been tested for the photocatalytic reduction of CO2. (HP) TiO2 powders were prepared by using TiCl4 or Ti(OC4H9)4 as the precursors to obtain HP1 and HP2 samples, respectively. Also HP Cu-loaded and SiO2 supported TiO2 powders were prepared. The HP samples were more active than the commercial ones for the photoreduction of CO2 with and without water vapour. HP1 produced mainly formaldehyde, HP2 principally methane. Acetaldehyde was found to be the primary product obtained when HP1 was supported on SiO2. The addition of Cu increased the photocatalytic reactivity either of bulk and SiO2-supported HP1. In particular, 1 wt % of Cu improved the formaldehyde yield obtained with the bare HP1 by one order of magnitude. Differently, the presence of Cu or SiO2 in the HP2 samples markedly reduced the production of methane