Influence of oxygen vacancies, surface composition, and crystallite size on the photoelectrochemical oxidation activity of C,N-codoped TiO2 for cefadroxil abatement along with O3.

This study aims the development of photoelectrodes to be incorporated in a photoelectrocatalytic ozonation (PECO) process for tertiary treatment of urban wastewaters, targeting the removal of contaminants of emerging concern (CEC). PECO tests were performed using urban wastewater after secondary treatment fortified with Cefadroxil (CFX, C16H17N3O5S), as target model CEC. Three Nitrogen and Carbon doped TiO2 (CN-TiO2) electrodes were synthesized by anodizing at 50, 70, and 90 V, and calcined. These materials were characterized by X-Ray diffraction and Rietveld refinement, Scanning Electron Microscopy, Diffuse Reflectance Spectroscopy, X-ray photoelectron spectroscopy, chronoamperometry, and electrochemical impedance spectroscopy, to correlate defects with photoactivity. All photoanodes considerably reduced their main bandgaps by the incorporation of C and N species, to enable absorption capacities in the UV region using a Xe lamp. The lowest oxygen vacancy content and largest crystallite size were found for CN-TiO2-70, favoring the reduction of bulk defects that could act as recombination of charge carriers. Therefore, oxygen vacancies affect more the TiO2 photoactivity compared to the crystallite size or the light absorption capacity, confirming that a lower content of vacancies in the material bulk and surface doping significantly influence the activity as detected by Rietveld refinement, DRS, and XPS. The electrochemical techniques confirm that the highest photocurrent was obtained for CN-TiO2-70, whence this photoanode was chosen to carry out the CFX degradation. A point defect model simulating Nyquist plot reveals that the photoactivity depends on the speed to diffuse oxygen vacancies through the TiO2 coating. All abatement processes were followed by high-performance liquid chromatography, and Total Organic Carbon (TOC). At neutral and alkaline conditions, CFX is eliminated to levels below the analytical detection limit after 90 min of treatment (TOC removals of 87 and 91%, respectively), indicating that the coupling between the CN-TiO2-70 photocatalyst and ozone is effective in eliminating the contaminant due to parallel routes forming •OH species. Lower CFX degradation observed at acidic pH (TOC removal of 70%) is assigned to the difficulty of oxidizing protonated CFX species.

Ethylenediamine-assisted solvothermal synthesis of ZnS/ZnO photocatalytic heterojunction for high-efficiency hydrogen production.

Organic-inorganic hybrid materials have emerged as a class of novel materials over the last two decades, as they combine functional organic components and inorganic building blocks into unique materials through various chemical or physical interactions. In the present work, the importance of the use of ethylenediamine in sulfided materials applied to photocatalytic processes in the H2 production is demonstrated. The ZnS/ZnO heterojunction was prepared by the solvothermal synthesis in the presence and absence of ethylenediamine. The photocatalytic behavior showed that the addition of ethylenediamine increases the photocatalytic efficiency up to eight times compared to the photocatalyst without the organic agent. The materials were characterized by X-ray diffraction, scanning electron microscopy, infrared and UV-visible spectroscopies of solids, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, and photoelectrochemical characterization. The ethylenediamine plays a double role: to stabilize the cubic phase of zinc sulfide and to act as a promoter molecule of charge transfer on the surface of ZnS/ZnO/en heterojunction, slowing down the rate of recombination of the electron-hole pair, which is reflected in a decrease in the resistance to transfer of charge carriers, improving the H2 production rate until 1564 µmol h-1 g-1.

The visible-light-driven photocatalytic reduction of Cr6+ using BiVO4: assessing the effect of Au deposition and the reaction parameters.

In this work, fern-leaf-like BiVO4 was used to photocatalytically reduce Cr6+ in water. Nanosized BiVO4 displayed bandgap energy and specific surface area of 2.49 eV and 5.65 m2 g-1, respectively. Metallic Au nanoparticles were deposited on the BiVO4 to increase the photocatalytic performance. To optimize the reaction conditions, the sacrificial agents methanol, ethanol, formic acid, dimethyl sulfoxide, and KI were tested, while different catalyst dosages and Au loadings were assessed. The best sacrificial agent was formic acid, which was used at an optimal concentration of 0.01 mol L-1. The complete removal of Cr6+ was attained after 90 min of visible light irradiation using a catalyst dosage of 1.5 g L-1. Depositing metallic Au nanoparticles barely improved the photocatalytic performance, thus unmodified BiVO4 was used to remove Cr6+ in tap water. The matrix effect slowed the photocatalytic process, and the complete removal of Cr6+ was achieved in 120 min. Cr3+ and Cr6+ species were precipitated on the catalyst surface at the end of the photocatalytic process; still, BiVO4 displayed high stability after three reaction cycles.

Changes in biooxidation mechanism and transient biofilm characteristics by As(V) during arsenopyrite colonization with Acidithiobacillus thiooxidans.

Chemical and surface analyses are carried out using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM-EDS), atomic force microscopy (AFM), confocal laser scanning microscopy (CLSM), glow discharge spectroscopy (GDS) and extracellular surface protein quantification to thoroughly investigate the effect of supplementary As(V) during biooxidation of arsenopyrite by Acidithiobacillus thiooxidans. It is revealed that arsenic can enhance bacterial reactions during bioleaching, which can strongly influence its mobility. Biofilms occur as compact-flattened microcolonies, being progressively covered by a significant amount of secondary compounds (S n2- , S0, pyrite-like). Biooxidation mechanism is modified in the presence of supplementary As(V), as indicated by spectroscopic and microscopic studies. GDS confirms significant variations between abiotic control and biooxidized arsenopyrite in terms of surface reactivity and amount of secondary compounds with and without As(V) (i.e. 6 µm depth). CLSM and protein analyses indicate a rapid modification in biofilm from hydrophilic to hydrophobic character (i.e. 1-12 h), in spite of the decrease in extracellular surface proteins in the presence of supplementary As(V) (i.e. stressed biofilms).