A critical review on N-modified TiO2 limits to treat chemical and biological contaminants in water. Evidence that enhanced visible light absorption does not lead to higher degradation rates under whole solar light.

Intensive research has been focused on the synthesis of N-modified TiO2 materials having visible light absorption in order to get higher solar photocatalytic degradation rates of pollutants in water. However, an exhaustive revision of the topic underlines several controversial issues related to N-modified TiO2 materials; these issues concern (a) the methodology used for preparation, (b) the assessment of the structural characteristics, (c) the mechanistic action modes and (d) the raisons argued to explain the limited performances of the prepared materials for organic and biological targets photodegradation in water. Taking advantage of last year's progress in analytical chemistry and in material characterization methods, the authors show, for example, that some works in the literature controversially attribute the term nitrogen doping without enough analytical evidence. Additionally, some papers describe N-modified TiO2 photocatalysts as being able to generate holes with enough oxidative potential to form hydroxyl radicals under visible light. This last assertion often derives from a no pertinent use of illumination sources, light filters, or targets or a limited understanding of the thermodynamic aspects of the studied systems. None of N-containing materials prepared by herein presented methods leads, under solar light, to a significant enhancement in pollutants degradation and microorganism's inactivation kinetics.

Resistance and induction of viable but non culturable states (VBNC) during inactivation of E. coli and Klebsiella pneumoniae by addition of H2O2 to natural well water under simulated solar irradiation.

Inactivation of E. coli and Klebsiella pneumoniae by addition of H2O2 10 mg L-1 into natural well water samples containing natural total iron concentrations (around 0.3 mg L-1) under simulated solar light was followed by bacterial culturability (plate count) and viability (DVC-FISH). Results showed that culturability of both bacteria was totally reduced while viability was only completely depleted for E. coli in well water samples depending of total iron concentration. Post-irradiation effects in presence of residual H2O2 showed that viability of both bacteria kept dropping being totally reduced for E. coli cells while K. pneumoniae decreased only 1-log. SEM micrographs showed that E. coli and K. pneumoniae cells underwent morphological changes and size reduction according to VBNC states. Different dark and photo-induced processes where physical-chemical features of groundwater samples play an important role could be responsible of bacteria abatement.

Effect of Metal Content on Ethanol Decomposition over Ni-Co Catalysts Supported on La-Ce Oxides.

The search for catalysts with features that can improve coke resistance and decrease byproduct formation is a current goal in H2 production from renewable sources. In this work, the effect of the presence of Ni nanoparticles over Co/La-Ce oxides on the ethanol decomposition reaction was studied. Catalysts were synthetized using as precursor a La0.8Ce0.2NixCo1-xO3 perovskite-type material to ensure a low segregation of phases and a high dispersion of metals. After reduction at 873 K, the perovskite structure was destroyed, and metal Co-Ni particles were supported over a lanthanum-cerium oxide. The materials were characterized by different techniques before and after reaction. Solids exhibited metal particle sizes between 5 and 15 nm demonstrating the advantages of the preparation method to obtain Ni-Co alloys. Although the results of adsorption of ethanol followed by diffuse reflectance infrared fourier transformed spectroscopy (DRIFTS) showed acetate species strongly adsorbed on the catalyst's surface, the material (Ni0.7Co0.3/La0.8Ce0.2) with the lowest particle size was the most stable system leading to the lowest amount of carbon deposits during ethanol decomposition. This catalyst showed the better performance, with a higher ethanol conversion (98.4%) and hydrogen selectivity (75%). All catalysts exhibited carbonaceous deposits, which were an ordered and disordered carbon phase mixture.

Photo-Fenton process at natural conditions of pH, iron, ions, and humic acids for degradation of diuron and amoxicillin.

Effect of ferric ions at concentrations typically found in natural waters (0.05 to 1.06 mg L-1) and low H2O2 concentrations (between 0.5 and 17.9 mg L-1) on simulated sunlight-induced (300 W m-2) photo-Fenton degradation at initial neutral pH (7.0) of amoxicillin and diuron in Milli-Q water was studied using an rotatable central composite experimental design 22 with a central and two axial points. H2O2 concentration was the parameter playing the key role on the degradation of both pollutants. Despite that initial pH was 7.0 in Milli-Q water, this latter decreased rapidly in the first minutes, reaching values of 3.5 and 5.0 for diuron and amoxicillin respectively after 15 min of simulated sunlight irradiation. In contrast, in presence of bicarbonate/carbonate (HCO3-/CO3=), fluoride (F-), and humic acids (HAs) at concentrations found often in surface and well waters with ferric ion and H2O2 concentrations of 0.3 and 9.7 and 15.2 mg L-1 respectively, both pollutants exhibited a strong degradation keeping the circumneutral pH. Amoxicillin and diuron degradation byproducts found by HPLC/MS were compatible with HO• and/or CO3-• radical attack. Several photo-induced processes such as photo-Fenton (by dissolved ferric-HA complexes), heterogeneous photocatalysis (by colloidal iron), UV-B H2O2 photolysis, irradiated-dissolved organic matter, and their reactions with pollutants would be the main oxidative route responsible of degradations. These findings demonstrated that it could be possible using iron concentrations often found in natural waters to oxidize via photo-Fenton processes among other events, organic pollutants at natural pH conditions.

Inactivation of carbapenem-resistant Klebsiella pneumoniae by photo-Fenton: Residual effect, gene evolution and modifications with citric acid and persulfate.

The photo-Fenton process application to eliminate carbapenem-resistant Klebsiella pneumoniae, an antibiotic-resistant priority pathogen, was evaluated. Initially, reagents concentration effect was tested and under suitable conditions (5 mg L-1 of Fe2+ and 50 mg L-1 of H2O2) complete bacteria inactivation by action of hydroxyl radical and UVA plus hydrogen peroxide was achieved at 120 min. The process presented a strong residual disinfecting effect when light was turned off at only 20 min. Besides, the cultivability of treated K. pneumoniae in a selective medium containing carbapenem antibiotics was considered. bla-KPC, gene responsible for the resistance, evolution was also assessed. The bacteria response to carbapenem antibiotics was higher as the treatment time increased. In turn, bla-KPC gene remained when K. pneumoniae was completely inactivated (120 min); nevertheless, treatment times longer than 120 min diminished bla-KPC presence. Finally, the photo-Fenton process and its modifications (citric acid addition or persulfate anion instead hydrogen peroxide) were applied to a real hospital wastewater in Colombia. In such complex matrix, the conventional photo-Fenton system reached a moderate disinfection (∼3.5 log-units at 300 min). Meanwhile, in presence of citric acid total inactivation was completed at the same time. Interestingly, the H2O2 substitution by persulfate strongly accelerated the microorganism elimination, achieving the 6-log-units reduction after only 60 min of process action. Thus, the effective elimination of K. pneumoniae from water by the modified photo-Fenton evidenced the potential applicability of this process to limit the proliferation of antibiotic resistant bacteria.

Low-frequency ultrasound induces oxygen vacancies formation and visible light absorption in TiO2 P-25 nanoparticles.

Low-frequency ultrasound (LFUS) irradiation induces morphological, optical and surface changes in the commercial nano-TiO(2)-based photocatalyst, Evonik-Degussa P-25. Low-temperature electron spin resonance (ESR) measurements performed on this material provided the first experimental evidence for the formation of oxygen vacancies (V(o)), which were also found responsible for the visible-light absorption. The V(o) surface defects might result from high-speed inter-particle collisions and shock waves generated by LFUS sonication impacting the TiO(2) particles. This is in contrast to a number of well-established technologies, where the formation of oxygen vacancies on the TiO(2) surface often requires harsh technological conditions and complicated procedures, such as annealing at high temperatures, radio-frequency-induced plasma or ion sputtering. Thus, this study reports for the first time the preparation of visible-light responsive TiO(2)-based photocatalysts by using a simple LFUS-based approach to induce oxygen vacancies at the nano-TiO(2) surface. These findings might open new avenues for synthesis of novel nano-TiO(2)-based photocatalysts capable of destroying water or airborne pollutants and microorganisms under visible light illumination.