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The fast, single‐step and easily scalable production by plasma electrolytic oxidation (PEO) of large area TiO2 electrodes with excellent photoactivity in water splitting under simulated solar light is systematically investigated here. In particular, the effects that the cell voltage (100–180 V) and the processing time (0.5–15 min) have on the electrode properties are studied. The PEO‐produced oxide layers are porous, the predominant crystalline structure shifting from anatase, to an anatase‐rutile mixture, and finally to rutile by rising the cell voltage. The electrodes show a double‐layered structure, with a more compact layer at the interface with the titanium substrate and a thick porous layer on the external surface. The photocurrent density versus wavelength reflects the phase composition, with a maximum incident photon‐to‐current efficiency of 90% at 320 nm. The highest H2 production rate is attained with the mixed anatase‐rutile electrode prepared by 300 s‐long PEO at 150 V. [ABSTRACT FROM AUTHOR]

Plasma Electrolytic Oxidation (PEO) was applied to extruded ZM21 Mg alloys to improve their corrosion resistance in a chloride-containing environment. PEO was carried out in DC mode and voltage control in a fluoride-free electrolyte. Potentiodynamic polarization tests in 3.5 wt.% NaCl aqueous solution and neutral salt spray (NSS) tests were carried out. Microstructural and profilometric characterization, as well as NSS tests were performed in different conditions: (i) bare ZM21, (ii) PEO-treated ZM21, (iii) powder-coated ZM21 (without PEO interlayer), and (iv) PEO-treated ZM21 with powder coating top layer (carboxyl-functionalized polyester resin). The PEO + powder coating double layer was identified as the best-performing corrosion protection. [ABSTRACT FROM AUTHOR]

Photoelectrocatalysis (PEC), photolysis (PL), and photocatalysis (PC) were applied to increase the biodegradability of wastewaters effluents sampled from a plant collecting both municipal wastewaters and aqueous waste. In PEC, the catalyst was a porous TiO2 photoanode obtained by plasma electrolytic oxidation and electrically polarized during operation. In PC a dispersion of TiO2 powders was used. The same irradiation shielding, and similar catalyst surface areas were set for PC and PEC, allowing a straightforward evaluation of the catalytic effect of the electrical polarization of TiO2 during operation. Results showed that the chemical oxygen demand (COD) and color removal rates follow the order: PEC > PL and PEC > PC. The specific biodegradability rate (SBR) increased following the same order, the PEC process allowing SBR values more than twice higher than PL and PC. The operating costs were calculated based on the electrical energy per order of COD, color, and SBR values, demonstrating that at the laboratory scale the energy demand of PEC is significantly lower than the other two tested processes. [ABSTRACT FROM AUTHOR]

In this study, we report an investigation of the photoelectrochemical activity of TiO2 films formed by DC plasma electrolytic oxidation (PEO) at a variable potential in a sulfuric acid electrolyte at 0 and 25 °C. The surface morphology was mainly determined by the oxide-forming potential. X-Ray Diffraction and Raman analyses showed that the relative amount of the anatase and rutile phases varied from 100% anatase at low potential (110–130 V) to 100% rutile at high potential (180–200 V), while mixed-phase oxide films formed at intermediate potential. Correspondingly, the band gap of the TiO2 films decreased from about 3.20 eV (pure anatase) to 2.94 eV (pure rutile) and was red-shifted about 0.1 eV by reducing the electrolyte temperature from 25 °C to 0 °C. Glow-Discharge Optical Emission Spectroscopy (GD-OES) and X-ray Photoelectron Spectroscopy (XPS) analyses evidenced S-containing species located preferentially close to the TiO2/Ti interface. The photoelectrochemical activity was assessed by measuring the incident photon-to-current efficiency (IPCE) under Ultraviolet C (UV-C) irradiation, which showed a non-gaussian normal trend as a function of the PEO cell potential, with maximum values exceeding 80%. Photoelectrocatalytic activity was assessed by decolorization of model solutions containing methylene blue. Photoanodes having higher IPCE values showed faster decolorization kinetics. [ABSTRACT FROM AUTHOR]

Carbamazepine (CBZ) is a pharmaceutical compound recalcitrant to conventional wastewater treatment plants and widely detected in wastewater bodies. In the present study, advanced oxidation processes for carbamazepine removal are investigated, with particular regard to the degradation pathways of carbamazepine by photoelectrocatalysis and conventional photocatalysis. Photoelectrocatalysis was carried out onto TiO2 meshes obtained by Plasma Electrolytic Oxidation, a well-known technique in the field of industrial surface treatments, in view of an easy scale-up of the process. By photoelectrocatalysis, 99% of carbamazepine was removed in 55 min while only 65% removal was achieved by photolysis. The investigation of the transformation products (TPs) was carried out by means of UPLC-QTOF/MS/MS. Several new TPs were identified and accordingly reaction pathways were proposed. Above 80 min the transformation products disappear, probably forming organic acids of low-molecular weight as final degradation products. The results demonstrated that photoelectrocatalysis onto TiO2 meshes obtained by plasma electrolytic oxidation is a useful alternative to common advanced oxidation processes as wastewater tertiary treatment aimed at removing compounds of emerging concern. [ABSTRACT FROM AUTHOR]

Several beneficial features maintain TiO 2 in the top list of viable materials for photocatalytic purposes. However, its relatively large band-gap (3.0–3.2 eV) still hampers practical applications under sunlight. This work explores Direct Current (DC) Plasma Electrolytic Oxidation (PEO) of titanium as a fast, easily-scalable and single-step tool to synthesise doped TiO 2 photoanodes with controlled morphology, crystalline structure and thickness. Zn-, Cu- and Fe-doped crystalline TiO 2 films were obtained in H 2 SO 4 aqueous solutions containing ZnSO 4 , CuSO 4 and FeSO 4 precursors, respectively. As-prepared TiO 2 films showed a porous and homogeneous sponge-like surface morphology, typical of PEO-produced oxides, and a crystalline phase structure consisting of a mixture of anatase and rutile phases. The anatase content varied in the 54–100 % range and correspondingly the band-gap energy was in the 2.85–3.07 eV range. Doped oxides prepared with a low concentration of the metal precursors showed monochromatic incident-photon-to-current-efficiency (IPCE) values exceeding those obtained with pristine TiO 2 by up to 24 %, best performing in the order Zn- > Cu- > Fe-doped TiO 2. Photocurrent under polychromatic UV-Vis irradiation showed an analogous trend and the estimated efficiency of solar-light harvesting was in the 0.3–4 % range, with Zn- ≈ Cu- > Fe-doped TiO 2. Although the superior performance of the PEO-prepared metal-doped TiO 2 could not be fully confirmed by photoelectrocatalytic oxidation tests of organics, the present investigation showed the viability of DC PEO for the synthesis of metal-doped TiO 2 photoanodes. [Display omitted] • Zn, Cu, Fe doped crystalline TiO 2 films obtained by plasma electrolytic oxidation. • Best photoeletrochemical activity at low doping levels. • IPCE and LSV values exceeding pristine TiO 2. • No straightforward correlation between photoelectrochemical and catalytic activity. [ABSTRACT FROM AUTHOR]

Ammonia, produced by human and animal activities, contributes to water and soil pollution because it is toxic for aquatic flora and fauna, and responsible for eutrophication. In this work, the photoelectrocatalytic (PEC) oxidation of ammonia is investigated employing a stainless-steel PEC reactor, consisting of a central UV Hg-vapor lamp surrounded by a metallic Ti mesh coated with a photoactive TiO 2 film, directly grown by Plasma Electrolytic Oxidation (PEO). The so prepared TiO 2 film is characterized by XRD, SEM, UV–vis DRS and IPCE. The PEC reactor operates at 4 V potential drop between the TiO 2 coated mesh (photoanode) and the body of the reactor (cathode). The effect of the operating parameters (recirculation flowrate and air bubbling) and type of electrolyte solution (KCl or K 2 SO 4) on the PEC performance are investigated in terms of ammonia conversion and selectivity to nitrite, nitrate and molecular nitrogen. Full ammonia conversion (X NH3) with a selectivity to molecular nitrogen up to 67 % are attained after 12 h in 5 mM KCl electrolyte solution. Nitrite is produced within the first 6 h irradiation and then fully converted into nitrate. By contrast, only a slight X NH3 (ca. 10 %) is observed in K 2 SO 4 electrolyte solution. These results suggest that chlorine has a crucial role in the ammonia PEC oxidation process: photo-generated holes on the photoanode surface can oxidize Cl− to Cl• (electro-induced process), which is a reactive radical able to oxidase ammonia. [Display omitted] • TiO 2 coated mesh prepared with PEO has excellent photoelectrochemical properties. • PEC exploits UV/electro-chloride process to oxidize NH 3 with high selectivity to N 2. • NH 3 removal follows a pseudo zero order kinetics under this PEC conditions. • No photocurrent decays after 160 h, proving the stability of the TiO 2 coated mesh. [ABSTRACT FROM AUTHOR]

The effect of synthesis conditions on the properties of nanoporous TiO 2 coatings obtained by PEO in refrigerated electrolytes have been investigated. Linear sweep voltammetry was carried out on the TiO 2 coatings, in dark and under UV-C irradiation, in order to assess the photoelectrochemical behavior of samples. The largest photocurrents (0.18 mA/cm 2 ) were measured on TiO 2 coatings obtained by PEO in refrigerated aqueous solutions. UV–vis spectra revealed that lowering the processing temperature from 20 to −3.5 °C induced a blue-shift of the absorption band of the TiO 2 coatings from 3.05 to 3.42 eV. The main advantage of PEO in refrigerated aqueous solutions over current approaches, based on anodic oxidation and thermal treatments, is that the synthesis of photoactive TiO 2 coatings can be carried out in a relatively easy, quick and reproducible way, without annealing pre- and post-treatments. Furthermore, by controlling the solution temperature in PEO process, the photocurrent of the resulting TiO 2 coating reaches quite high values. [ABSTRACT FROM AUTHOR]

Anatase-type TiO 2 nanotube arrays (TiO 2 -NTAs) were grown on Ti foil by anodic oxidation in CH 3 COOH/NH 4 F solutions followed by thermal treatment. The surface of TiO 2 -NTAs was further decorated by palladium and silver metal clusters through a chemical-reduction method and its photocatalytic activity was tested by investigating the degradation of p-nitrophenol (PNP) in aqueous solution under visible-light irradiation and electrical polarization. The effects of preparation variables both on microstructural properties of samples and photocatalytic activity were examined by using the 3D response surface and the 2D contour plots. The experimental investigations carried out by using XRD, SEM, HRTEM, EDS, XRF, ICP-AES, XPS, DRS, and PL, demonstrated a strong relation between the phase structure and the photocatalytic activity of TiO 2 -NTAs. Titania nanotubes grown in acetic acid solution and thermally post-treated have stable anatase crystal structure, to a point that by performing annealing at 800 °C for 3 h, only the 35% of anatase transforms into rutile. Finally, it was shown that the TiO 2 -NTAs decorated with Pd(0.72 wt%) and Ag(1.26 wt%) particles show higher photocatalytic activity compared with nanotubes modified with single metal particles. It is believed that the high photoactivity of TiO 2 nanotubes decorated with Pd–Ag heterostructures is due to the prolonged lifetimes of photogenerated electron–hole pairs. The possible mechanism for the enhanced photocatalytic activity is discussed in detail. [ABSTRACT FROM AUTHOR]

• A real pharmaceutical wastewater has been treated with photo-electrocatalysis (PEC). • H 2 O 2 -assisted PEC allowed to obtain the best decolorization. • H 2 O 2 -assisted PEC best performed in increasing the biodegradability of the wastewater. • PEC combined with a single-step dosage of H 2 O 2 optimized energy costs. In recent years, photoelectrocatalysis (PEC) for the treatment of industrial wastewaters (IWWs) has been repeatedly proposed. However, despite the number of tests reported in literature, only a few of them were conducted on real IWWs. In this study, real pharmaceutical IWWs showing an intense recalcitrant color were treated by PEC and H 2 O 2 -assisted PEC (UV/TiO 2 /Bias and UV/H 2 O 2 /TiO 2 /Bias, respectively) on TiO 2 meshes having sub-micrometric features obtained by Plasma Electrolytic Oxidation. Photolysis (UV), chemical oxidation (H 2 O 2) and H 2 O 2 -assisted photolysis (UV/H 2 O 2) were tested in the same reactor for comparison. The configuration UV/H 2 O 2 /TiO 2 /bias showed the best results in term of decolorization efficiency and rate, where decolorization was 55 % (single-step H 2 O 2 dosing) and 44 % (three-step H 2 O 2 dosing), after 2 h of contact time. In the same contact time, UV and UV/TiO 2 /Bias processes did not give decolorization. A more effective COD removal was measured for the PEC processes, UV/H 2 O 2 /TiO 2 /Bias (-24 %) and UV/TiO 2 /Bias (-20 %), while COD removal by UV was almost 0 %. Correspondingly, the SOUR values showed that PEC combined with a single-step H 2 O 2 dosage was the most effective configuration, leading to the highest biodegradability of the treated IWW with respect to the other processes. The energy consumption analysis demonstrated that PEC+H 2 O 2 (single-step dosage) optimized energy costs. [ABSTRACT FROM AUTHOR]