AuAg Nanoparticles Grafted on TiO2@N-Doped Porous Carbon: Improved Depletion of Ciprofloxacin under Visible Light through Plasmonic Photocatalysis.

TiO2 nanoparticles (NPs) were modified to obtain photocatalysts with different composition sophistication and displaying improved visible light activity. All of them were evaluated in the photodegradation of ciprofloxacin. The band gap of TiO2 NPs was successfully tailored by the formation of an N-doped porous carbon (NPC)-TiO2 nanohybrid through the pyrolysis of melamine at 600 °C, leading to a slight red-shift of the absorption band edge for nanohybrid NPC-TiO2 1. In addition, the in-situ formation and grafting of plasmonic AuAg NPs at the surface of NPC sheets and in close contact with TiO2 NPs leads to AuAg-NPC-TiO2 nanohybrids 2−3. These nanohybrids showed superior photocatalytic performance for the degradation of ciprofloxacin under visible light irradiation, compared to pristine P25 TiO2 NPs or to AuAg-PVP-TiO2 nanohybrid 4 in which polyvinylpyrrolidone stabilized AuAg NPs were directly grafted to TiO2 NPs. The materials were characterized by transmission electron microscope (TEM), High Angle Annular Dark Field­Scanning Transmission Electron Microscopy­Energy Dispersive X-ray Spectroscopy HAADF-STEM-EDS, X-ray photoelectron spectroscopy and solid UV-vis spectroscopy. Moreover, the active species involved in the photodegradation of ciprofloxacin using AuAg-NCS-TiO2 nanohybrids were evaluated by trapping experiments to propose a mechanism for the degradation.

An organometallic approach for the preparation of Au-TiO2 and Au-g-C3N4 nanohybrids: improving the depletion of paracetamol under visible light.

The photocatalytic degradation of paracetamol (a common analgesic also known as acetaminophen) in ultrapure water with different photocatalytic systems was performed under ultraviolet or visible irradiation. The photocatalysts employed were: commercial Degussa-P25 TiO2 and Au-TiO2 under UVA irradiation (365 nm) and g-C3N4 and Au-g-C3N4 under visible light irradiation (low-power (4 × 10 W) white light LEDs), improving the effectiveness of degradation rates when the gold nanoparticles (Au NPs) were combined with the semiconductors. The nanostructured photocatalysts were synthesised and characterised by transmission electron microscope (TEM), UV-vis diffuse reflectance spectroscopy and, in the case of g-C3N4 photocatalysts by X-ray photoelectron spectroscopy (XPS). The influence of the pH in the depletion of paracetamol with g-C3N4 and visible light was evaluated. In addition, the stability and lifetime of the photocatalyst g-C3N4 in the degradation of paracetamol were studied.

Combination of Au-Ag Plasmonic Nanoparticles of Varied Compositions with Carbon Nitride for Enhanced Photocatalytic Degradation of Ibuprofen under Visible Light.

Au-Ag/g-C3N4 nanohybrids 2-3 were synthesized by the one-pot self-reduction of the organometallic precursor [Au2Ag2(C6F5)4(OEt2)2]n in the presence of graphitic carbon nitride (g-C3N4), leading to two populations of alloyed Au-Ag nanoparticles (NPs) of different size and composition on the surface of g-C3N4, i.e., Ag-enriched Au-Ag NPs of smaller size and Au-enriched Au-Ag NPs of larger size. The combination of these two types of plasmonic NPs with g-C3N4 semiconductor displays enhanced photocatalytic properties towards the degradation of ibuprofen under visible light by the increased charge carrier separation provided by the inclusion of the plasmonic NPs on g-C3N4.

Sonophotocatalytic degradation of sodium diclofenac using low power ultrasound and micro sized TiO2.

The nonsteroidal anti-inflammatory drug sodium diclofenac (DC) is an emerging water pollutant which resists conventional wastewater treatments. Here the sonophotocatalytic degradation of DC was carried out using micrometric TiO2 (both pristine and Ag-decorated), UV-A irradiation and 20 kHz pulsed ultrasound. Sonophotocatalytic tests were compared with photolysis, sonolysis, sonophotolysis, sonocatalysis and photocatalysis data performed in the same conditions. A synergy index of over 2 was determined for tests with pristine TiO2, while values close to 1.3 were observed for Ag-TiO2. Reaction intermediates were studied by HPLC-MS, showing degradation mechanisms activated by hydroxyl radicals. Similar pathways were identified for photocatalytic and sonophotocatalytic tests, although the latter led to more oxidized compounds. Different reactor configurations (static and dynamic set ups) were studied. Sequential and simultaneous application of UV light and ultrasound led to similar performance. The role of water matrix was investigated using ultrapure and drinking water, showing marked detrimental effects of electrolytes on the DC degradation. Overall, the combined treatment proved more efficient than photocatalysis alone especially in demanding working conditions, like in drinking water matrices.

Study of intermediate by-products and mechanism of the photocatalytic degradation of ciprofloxacin in water using graphitized carbon nitride nanosheets.

The photocatalytic degradation of the antibiotic ciprofloxacin in water was carried out with nanosheets of graphitic carbon nitride (g-C3N4) as catalyst and visible light irradiation using low-power (4 × 10 W) white light LEDs. The aim of this study was to identify the intermediate by-products formed during the degradation and to propose a pathway for CIP degradation. To achieve this goal, photocatalytically degraded CIP solutions were analysed by liquid chromatography coupled to high-resolution mass spectrometry using a QTOF instrument. The accurate mass and the MS/MS data of the detected ions allowed us to determine the elementary composition of eight by-products and to propose the chemical structures for seven of them. Three of these by-products have been reported for the first time and the elementary composition of a fourth one that had been wrongly reported in the literature was accurately established. CIP degradation followed a pseudo-first order kinetics with a pseudo-first order kinetic constant of 0.035 min-1. In addition, a study of the influence of several scavengers showed that only the presence of triethanolamine dramatically reduced the pseudo-first order kinetic constant (0.00072 min-1), pointing out that the reactive species were the holes produced in the catalyst. Finally, the main pathway of CIP degradation seems to be the attack to the piperazine group by ·OH radicals, following heterocycle breakup and the subsequent loss of two of its carbon atoms as CO2 molecules, and then defluorination, oxidation and cleavage of the cycles of this intermediate.

Photocatalytic degradation of ibuprofen in water using TiO2/UV and g-C3N4/visible light: Study of intermediate degradation products by liquid chromatography coupled to high-resolution mass spectrometry.

The photocatalytic degradation of ibuprofen with TiO2 nanoparticles (NPs) and UV light and with graphitic carbon nitride (g-C3N4) 2D nanosheets and visible light are proposed and compared as advanced oxidation treatments for the removal of ibuprofen in water. By-products formed with both photocatalytic systems have been tentatively identified based on the results of ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry, using a quadrupole-time of flight mass spectrometer in positive and negative ionization modes, which allowed to obtain the elementary composition of their precursors and fragment ions. The removal of ibuprofen and the by-product formation were studied at three pH values. Ibuprofen depletion followed pseudo fist-order kinetics with rate constants of 0.04, 1.0 and 0.0006 min-1 at pH 2.50, 5.05 and 12.04 for TiO2/UV and 0.03, 0.007 and 0.0005 min-1 at pH 2.51, 5.05 and 11.33 for g-C3N4/vis, respectively. Around eighteen by-products have been detected with slight differences between the two photocatalytic systems studied. The evolution of the main common by-products (tentatively identified as 1-(4-ethylphenyl)-2-methylpropan-1-one, 1-(4-isobutylphenyl)ethan-1-ol, 1-(4-ethylphenyl)-2-methylpropan-1-ol and 1(-4-acetylphenyl)-2-methylpropan-1-one) were monitored and the results were consistent with reaction pathways based on hydroxyl radical attacks following/followed by decarboxylation. Moreover, some by-products have been reported for the first time in the photocatalytic oxidation of ibuprofen.

Determination of cinnamaldehyde, carvacrol and thymol in feedstuff additives by pressurized liquid extraction followed by gas chromatography-mass spectrometry.

Specific blends of essential oils (BEOs) are promising substitutes for antibiotics to promote livestock performance and to reduce the incidence of intestinal disorders. Microencapsulation of BEOs has shown to improve their stability, bioavailability and to control their release rate once they are added to the feedstuff. The development and validation of a method for determining essential oil components such as carvacrol, thymol and cinnamaldehyde in a microencapsulated material used as feed additive is presented. Analytes were extracted from feed additives and feedstuff by pressurized liquid extraction (PLE) with methanol at 50°C for 5min. Methanol provided good recovery values and cleaner extracts than other polar organic solvents tested. However, for certain kind of composite additives ethyl acetate showed to be a better option because trans-cinnamaldehyde undergoes chemical reaction in methanol. Then PLE extracts were analysed by gas chromatography coupled to ion trap mass spectrometry in selected ion storage (SIS) mode. The analyte stability and the absence of analyte losses during the PLE process was checked by a recovery study. Also, the matrix effect was studied to assess accuracy. Recovery values were between 85 and 115% in most cases. Intra- and inter-day relative standard deviation values were less than 4 and 14%, respectively. Finally, the developed method was applied to the analysis of a microencapsulated feed additive, several composite feed additive samples containing microencapsulated BEOs and a spiked feedstuff, for quality control and in stability studies.