Nazar Delegan

Electrochemical degradation of chlortetracycline using N-doped Ti/TiO2 photoanode under sunlight irradiations

The appearance and the persistence of pharmaceutical products in the aquatic environment urgently call for the development of an innovative and practical water treatment technology. This study deals with the development of nanostructured nitrogen-doped TiO2 photoanodes and their subsequent use for chlortetracycline (CTC) photoelectrocatalytic oxidation under visible light. The N-doped TiO2 photoanodes with different nitrogen contents were prepared by means of a radiofrequency magnetron sputtering (RF-MS) process, with the objective to tune shift their optical absorption from the UV towards the visible. The N-doped TiO2 consist of nanostructured anatase phase with average TiO2 nanocrystallite size of 29 nm. The nitrogen doping is clearly shown to produce the desired red shift of the absorption onset of the TiO2 coatings (from ~380 nm to ~550 nm). Likewise, the N-doped TiO2 are found to be highly photo-electroactive not only under the UV light but most interestingly under the visible light as well. Using the optimal N-doped photoanodes, 99.6% of CTC (100 μg/L) was successfully degraded after 180 min of treatment time with a current intensity of 0.6 A. Under these conditions, a relatively high mineralization of CTC (92.5% ± 0.26% of TOC removal and 90.3% ± 1.1% of TN removal) was achieved.

Field electron emission enhancement of graphenated MWCNTs emitters following their decoration with Au nanoparticles by a pulsed laser ablation process

A plasma-enhanced chemical vapor deposition (PECVD) process was adapted to alter the growth of multiwall carbon nanotubes (MWCNTs) so that graphene sheets grow out of their tips. Gold nanoparticle (Au-NP) decoration of graphenated MWCNTs (g-MWCNTs) was obtained by subsequent decoration by a pulsed laser deposition (PLD) process. By varying the number of laser ablation pulses (N(Lp)) in the PLD process, we were able to control the size of the gold nanoparticles and the surface coverage of the decorated g-MWCNTs. The presence of Au-NPs, preferentially located at the tip of the g-MWCNTs emitters, is shown to significantly improve the field electron emission (FEE) properties of the global g-MWCNT/Au-NP nanohybrid films. Indeed, the electric field needed to extract a current density of 0.1 μA cm(-)(2) from the g-MWCNT/Au-NP films was decreased from 2.68 V μm(-1) to a value as low as 0.96 V μm(-1). On the other hand, UV photoelectron spectroscopy (UPS) characterization revealed a decrease in the global work function of the Au-decorated g-MWCNT nanohybrids compared to that of bare g-MWCNT emitters. Surprisingly, the work function of g-MWCNT was found to decrease from 4.9 to 4.7 eV with the addition of Au-NPs-a value lower than the work function of both materials worth 5.2 and 4.9 eV for gold and g-MWCNT, respectively. Our results show that the N(Lp) dependence of the FEE characteristics of the g-MWCNT/Au-NP emitters correlates well with their work function changes. Fowler-Nordheim-theory-based calculations suggest that the significant FEE enhancement of the emitters is also caused by the Au-NPs acting as nanoscale electric field enhancers.

Removal of chlortetracycline from spiked municipal wastewater using a photoelectrocatalytic process operated under sunlight irradiations.

The degradation of chlortetracycline in synthetic solution and in municipal effluent was investigated using a photoelectrocatalytic oxidation process under visible irradiation. The N-doped TiO₂ used as photoanode with 3.4 at.% of nitrogen content was prepared by means of a radiofrequency magnetron sputtering (RF-MS) process. Under visible irradiation, higher photoelectrocatalytic removal efficiency of CTC was recorded using N-doped TiO₂ compared to the conventional electrochemical oxidation, direct photolysis and photocatalysis processes. The photoelectrocatalytic process operated at 0.6A of current intensity during 180 min of treatment time promotes the degradation of 99.1 ± 0.1% of CTC. Under these conditions, removal rates of 85.4 ± 3.6%, 87.4 ± 3.1% and 55.7 ± 2.9% of TOC, TN and NH₄(+) have been recorded. During the treatment, CTC was mainly transformed into CO₂ and H₂O. The process was also found to be effective in removing indicator of pathogens such as fecal coliform (log-inactivation was higher than 1.2 units).

In-situ co-doping of sputter-deposited TiO2:WN films for the development of photoanodes intended for visible-light electro-photocatalytic degradation of emerging pollutants

We report on the magnetron sputtering deposition of in-situ codoped TiO2:WN films intended for electro-photocatalytic (EPC) applications under solar irradiation. By varying the RF-magnetron sputtering deposition parameters, we were able to tune the in-situ incorporation of both N and W dopants in the TiO2 films over a wide concentration range (i.e., 0–9 at. % for N and 0–3 at. % for W). X-ray photoelectron spectroscopy analysis revealed that both dopants are mostly of a substitutional nature. The analysis of the UV-Vis transmission spectra of the films confirmed that the optical bandgap of both TiO2:N and TiO2:WN films can be significantly narrowed (from 3.2 eV for undoped-TiO2 down to ∼2.3 eV for the doped ones) by tuning their dopant concentrations. We were thus able to pinpoint an optimal window for both dopants (N and W) where the TiO2:WN films exhibit the narrowest bandgap. Moreover, the optimal codoping conditions greatly reduce the recombination defect state density compared to the monodoped TiO2:N films. These electronically passivated TiO2:WN films are shown to be highly effective for the EPC degradation of atrazine (pesticide pollutant) under sunlight irradiation (93% atrazine degraded after only 30 min of EPC treatment). Indeed, the optimally codoped TiO2:WN photoanodes were found to be more efficient than both the undoped-TiO2 and equally photosensitized TiO2:N photoanodes (by ∼70% and ∼25%, respectively) under AM1.5 irradiation.We report on the magnetron sputtering deposition of in-situ codoped TiO2:WN films intended for electro-photocatalytic (EPC) applications under solar irradiation. By varying the RF-magnetron sputtering deposition parameters, we were able to tune the in-situ incorporation of both N and W dopants in the TiO2 films over a wide concentration range (i.e., 0–9 at. % for N and 0–3 at. % for W). X-ray photoelectron spectroscopy analysis revealed that both dopants are mostly of a substitutional nature. The analysis of the UV-Vis transmission spectra of the films confirmed that the optical bandgap of both TiO2:N and TiO2:WN films can be significantly narrowed (from 3.2 eV for undoped-TiO2 down to ∼2.3 eV for the doped ones) by tuning their dopant concentrations. We were thus able to pinpoint an optimal window for both dopants (N and W) where the TiO2:WN films exhibit the narrowest bandgap. Moreover, the optimal codoping conditions greatly reduce the recombination defect state density compared to the monodoped TiO2:N...