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In this work, photocatalytic materials constituted by Cr-doped TiO2 (Cr-TiO2) decorated with noble metals show high effectiveness in the mineralization of Acid Orange 7 (AO7) and in the disinfection of real river water. The materials were firstly obtained by sol-gel method to get Cr-TiO2 that was subsequently modified by photochemical deposition of Ag or Pd nanoparticles (Ag/Cr-TiO2, Pd/Cr-TiO2). Chemical-physical characterization results evidenced that the noble metals were homogeneously distributed on the Cr-TiO2 surface. By using Pd(0.25%)/Cr-TiO2, the AO7 discoloration efficiency was about 91.4% after only 60 min of visible irradiation, which can be due to the lowest band gap of this material. Moreover, nitrates, chlorides, total hardness, and coliform bacteria content significantly decreased after the treatment of real river water samples (that is contaminated by industrial and domestic effluents) under UV and visible light irradiation in the presence of TiCrOx decorated with noble metals. One hundred percent of elimination rate for E. coli, total coliforms, and other enterobacteriaceae (without regrowth) was achieved by using Ag/Cr-TiO2 as photocatalyst.

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Aims: The aim of this work was to investigate the impact of light modulation parameters on the degradation of terephtalic acid, an organic model pollutant, within a heterogeneous photocatalytic system under visible light. For this purpose, a fixed bed photocatalytic reactor, irradiated by white-light LEDs matrix controlled by a system for light dimming, was used. The bed consisted of a nitrogen-doped titania photocatalyst deposited on polystyrene pellets. Background: Wastewater containing TPA can be treated into conventional aerobic biological units. However, the mineralization of TPA is slow and inefficient and its presence influences negatively the biodegradation efficiency because this pollutant inhibits microbial growth. Nowadays innovative technologies named advanced oxidation processes (AOPs), such as heterogeneous photocatalysis with UV and visible light, ozonation, Fenton oxidation have gained popularity for effective organic destruction of TPA from wastewater. The heterogeneous photocatalytic oxidation process of the TPA under visible light is the most advantageous process in terms of both fixed and operating costs. Objective: In this work the successful application of light modulation techniques to degradation of TPA using a photocatalytic system with supported visible active photocatalysts (N-doped TiO2) immobilized on polystyrene pellets was reported. In particular, sinusoidal lighting has been used analyzing the influence of the period of oscillation and the amplitude of the light modulation on the reaction kinetics, in such a way as to minimize the times and energy costs for the process. Methods: To evaluate the influence of light modulation on the efficiency of the TPA removal, a discontinuous system composed by a Recirculating Photocatalytic Fixed Bed Reactor (RPFBR) irradiated by a matrix of white light LEDs was used. The flat geometry of photoreactor guarantees the efficient excitation of photocatalyst. An amount of 250 mL of aqueous solution with initial TPA concentration of 12.5 ppm was applied in the photocatalytic tests lasting 180 min of irradiation fixed or sinusoidal modulated. Results: The results show that the variation of the oscillation period of the sinusoidal modulation has a relevant influence on the photodegradation of TPA and a maximum value of the apparent kinetic constant, 0.0045 min-1 is found when the period of oscillation is 0.24 s. The sinusoidal modulation with optimal amplitude is that with current between 50-200 mA, that shows the highest value of the apparent kinetic constant, equal to 0.0046 min-1. The optimal sinusoidal modulation, as a consequence is with current between 50-200 mA and period of 0.24 s. From the data collected from the tests, it is possible to evaluate the energy cost necessary to obtain the reduction of 90% of the terephthalic acid in 1 m3 of polluted water for each modulation (E E/O ), and compare these values with other tests for TPA degradation reported in the literature. The internal comparison and with the three systems of literature showed the optima sinusoidal modulation of LEDs matrix permits a strong reduction the electrical energy consumption. Conclusion: Photocatalytic tests have demonstrated the improvement of the process energy efficiency using the light modulation technique . A further confirmation of the advantage of light modulation was obtained by comparing the energy costs required for the abatement of 90% of the terephthalic acid in 1m 3 of the photocatalytic system. Finally, a mathematical model for photocatalytic degradation of terephthalic acid within the recirculating fixed bed photocatalytic reactor, irradiated by white-light LEDs was developed.

The impact of light modulation on the decolorization of Acid Orange 7 (AO7) in aqueous solution was examined in this paper. A fixed bed batch photocatalytic reactor with a flat plate geometry, irradiated by 240 white-light LEDs, was used. A successful transfer of visible active photocatalyst (N-TiO2) in powder form on a polystyrene (PS) transparent plate was realized. The structured photocatalyst was characterized through SEM–EDX, Raman and UV-DRS analyses, evidencing the formation of a coating of N-TiO2 in the anatase phase, with a band-gap energy of 2.5 eV, and almost uniform distribution on the PS surface. Different LED dimming techniques, with fixed and variable duty-cycle values, were tested, and four types of light modulation were compared: fixed duty cycle (constant irradiation), sinusoidal variable duty cycle (sinusoidal variable irradiation), triangular variable duty cycle (triangular variable irradiation), and square wave variable duty cycle (square wave variable irradiation). The resulting responsiveness/efficiency of the LED versus the current intensity was evaluated, and the stability of the photocatalyst activity and the influence of optimized irradiation waveforms were examined in the decolorization of 400 mL of 10 ppm AO7 solution. The sinusoidal modulation, with current between 50 and 100 mA and 10 s as the period, shows the highest value of the apparent pseudo-first-order kinetic constant, resulting equal to 0.0044 min−1, at parity of total transmitted photons. An energy saving with the application of sinusoidal irradiation is highlighted with respect to the literature. Graphical Abstract

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