The beneficial role of nano-sized Fe3O4 entrapped in ultra-stable Y zeolite for the complete mineralization of phenol by heterogeneous photo-Fenton under solar light.

Highly efficient, separable, and stable magnetic iron-based-photocatalysts produced from ultra-stable Y (USY) zeolite were applied, for the first time, to the photo-Fenton removal of phenol under solar light. USY Zeolite with a Si/Al molar ratio of 385 was impregnated under vacuum with an aqueous solution of Fe2+ ions and thermally treated (500-750 °C) in a reducing atmosphere. Three catalysts, Fe-USY500°C-2h, Fe-USY600°C-2h and Fe-USY750°C-2h, containing different amounts of reduced iron species entrapped in the zeolitic matrix, were obtained. The catalysts were thoroughly characterized by absorption spectrometry, X-ray powder diffraction with synchrotron source, followed by Rietveld analysis, X-ray photoelectron spectroscopy, N2 adsorption/desorption at -196 °C, high-resolution transmission electron microscopy and magnetic measurements at room temperature. The catalytic activity was evaluated in a recirculating batch photoreactor irradiated by solar light with online analysis of evolved CO2. Photo-Fenton results showed that the catalyst obtained by thermal treatment at 500 °C for 2 h under a reducing atmosphere (FeUSY-500°C-2h) was able to completely mineralize phenol in 120 min of irradiation time at pH = 4 owing to the presence of a higher content of entrapped nano-sized magnetite particles. The latter promotes the generation of hydroxyl radicals in a more efficient way than the Fe-USY catalysts prepared at 600 and 750 °C because of the higher Fe3O4 content in ultra-stable Y zeolite treated at 500 °C. The FeUSY-500°C-2h catalyst was recovered from the treated water through magnetic separation and reused five times without any significant worsening of phenol mineralization performances. The characterization of the FeUSY-500°C-2h after the photo-Fenton process demonstrated that it was perfectly stable during the reaction. The optimized catalyst was also effective in the mineralization of phenol in tap water. Finally, a possible photo-Fenton mechanism for phenol mineralization was assessed based on experimental tests carried out in the presence of scavenger molecules, demonstrating that hydroxyl radicals play a major role.

Ag/Cr-TiO2 and Pd/Cr-TiO2 for Organic Dyes Elimination and Treatment of Polluted River Water in Presence of Visible Light.

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.

Visible light-driven degradation of Acid Orange 7 by light modulation techniques.

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.