A new class of porphyrin(Pp)/Fe co-loaded TiO2 composites opportunely prepared by impregnation of [5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (H2Pp) or Cu(II)[5,10,15,20-tetra(4-tert-butylphenyl)] porphyrin (CuPp) onto Fe-loaded TiO2 particles showed high activities by carrying out the degradation of 4-nitrophenol (4-NP) as probe reaction in aqueous suspension under heterogeneous photo-Fenton-like reactions by using UV-visible light. The combination of porphyrin-Fe-TiO2 in the presence of H2O2 showed to be more efficient than the simple bare TiO2 or Fe-TiO2. 1. Introduction Nowadays, due to the increasing presence of refractory molecules in the wastewater streams, it is important to develop new technologies to degrade such recalcitrant pollutant molecules into smaller innocuous ones. For this reason efficient oxidation processes operating under environmentally friendly conditions are needed [1]. As well known, Fenton chemistry encompasses reactions of hydrogen peroxide in the presence of iron to generate highly reactive species such as the hydroxyl radical and possibly others. In the last few years, Fenton-like reactions, in combination with other advanced oxidation processes, are assuming fundamental and practical perspectives in water treatment processes [2, 3]. The combination of various technologies, in fact, is often effective to achieve a complete mineralization of the pollutant(s) present in the starting effluents because many stable products of environmental concern can be persistent after the treatment by Fenton reaction. Recently, the utilization of TiO2 as catalyst for the photooxidation of organic pollutants in water is becoming a relevant topic in view of a possible application in economically advantageous and environmentally friendly processes not only performed with the aim to abate pollutants but also for synthetic purposes [4–8]. Various advanced oxidation technologies have been used in the presence of TiO2, H2O2, and irradiation to enhance the efficiency of the overall photodegradation process [9–12]. Also, in the last years, dye-sensitized TiO2-based materials have been employed for improving the efficiency of energy light conversion towards photocatalytic processes [13–19]. In this work the design of novel composites metal free or Cu-porphyrin/Fe co-loaded TiO2 as well as their application as catalytic systems for photoassisted heterogeneous Fenton-like reactions has been reported. In particular, we demonstrated that the presence of porphyrins and Fe species co-loaded onto the TiO2 surface along with H2O2 in the reacting medium
References
[1]
P. R. Gogate and A. B. Pandit, “A review of imperative technologies for wastewater treatment I: oxidation technologies at ambient conditions,” Advances in Environmental Research, vol. 8, no. 3-4, pp. 501–551, 2004.
[2]
J. J. Pignatello, E. Oliveros, and A. MacKay, “Advanced oxidation processes for organic contaminant destruction based on the fenton reaction and related chemistry,” Critical Reviews in Environmental Science and Technology, vol. 36, no. 1, pp. 1–84, 2006.
[3]
J. Kiwi, C. Pulgarin, and P. Peringer, “Effect of Fenton and photo-Fenton reactions on the degradation and biodegradability of 2 and 4-nitrophenols in water treatment,” Applied Catalysis B, vol. 3, no. 4, pp. 335–350, 1994.
[4]
M. Schiavello, Ed., Photocatalysis and Environment: Trends and Applications, Kluwer Academic, Dodrecht, The Netherlands, 1988.
[5]
V. Augugliaro, L. Palmisano, A. Sclafani, C. Minero, and E. Pelizzetti, “Photocatalytic degradation of phenol in aqueous titanium dioxide dispersions,” Environmental Toxicology and Chemistry, vol. 16, no. 2, pp. 89–109, 1988.
[6]
D. F. Ollis, E. Pelizzetti, and N. Serpone, “Photocatalyzed destruction of water contaminants,” Environmental Science & Technology, vol. 25, no. 9, pp. 1522–1529, 1991.
[7]
J. A. H. Meliàn, J. M. Dona Rodrìguez, A. V. Suàrez et al., “The photocatalytic disinfection of urban waste waters,” Chemosphere, vol. 41, pp. 323–327, 2000.
[8]
G. Palmisano, V. Augugliaro, M. Pagliaro, and L. Palmisano, “Photocatalysis: a promising route for 21st century organic chemistry,” Chemical Communications, no. 33, pp. 3425–3437, 2007.
[9]
S. J. Kim, S. C. Kim, S. G. Seo et al., “Photocatalyzed destruction of organic dyes using microwave/UV/O3/H2O2/TiO2 oxidation system,” Catalysis Today, vol. 164, no. 1, pp. 384–390, 2011.
[10]
A. Dixit, A. J. Tirpude, A. K. Mungray, and M. Chakraborty, “Degradation of 2, 4 DCP by sequential biological-advanced oxidation process using UASB and UV/TiO2/H2O2,” Desalination, vol. 272, no. 1–3, pp. 265–269, 2011.
[11]
J. Zou and J. Gao, “H2O2-sensitized TiO2/SiO2 composites with high photocatalytic activity under visible irradiation,” Journal of Hazardous Materials, vol. 185, no. 2-3, pp. 710–716, 2011.
[12]
J. Carbajo, C. Adán, A. Rey, A. Martínez-Arias, and A. Bahamonde, “Optimization of H2O2 use during the photocatalytic degradation of ethidium bromide with TiO2 and iron-doped TiO2 catalysts,” Applied Catalysis B, vol. 102, no. 1-2, pp. 85–93, 2011.
[13]
G. Marcì, E. García-López, G. Mele, L. Palmisano, G. Dyrda, and R. S?ota, “Comparison of the photocatalytic degradation of 2-propanol in gas-solid and liquid-solid systems by using TiO2-LnPc2 hybrid powders,” Catalysis Today, vol. 143, no. 3-4, pp. 203–210, 2009.
[14]
G. Mele, R. Del Sole, G. Vasapollo et al., “TiO2-based photocatalysts impregnated with metallo-porphyrins employed for degradation of 4-nitrophenol in aqueous solutions: role of metal and macrocycle,” Research on Chemical Intermediates, vol. 33, no. 3–5, pp. 433–448, 2007.
[15]
C. Wang, G. M. Yang, J. Li et al., “Novel meso-substituted porphyrins: synthesis, characterization and photocatalytic activity of their TiO2-based composites,” Dyes and Pigments, vol. 80, no. 3, pp. 321–328, 2009.
[16]
G. Mele, E. Garcìa-Lòpez, L. Palmisano, G. Dyrda, and R. S?ota, “Photocatalytic degradation of 4-nitrophenol in aqueous suspension by using polycrystalline TiO2 impregnated with lanthanide double-decker phthalocyanine complexes,” The Journal of Physical Chemistry C, vol. 111, no. 17, pp. 6581–6588, 2007.
[17]
R. S?ota, G. Dyrda, K. Szczegot, G. Mele, and I. Pio, “Photocatalytic activity of nano and microcrystalline TiO2 hybrid systems involving phthalocyanine or porphyrin sensitizers,” Photochemical & Photobiological Sciences, vol. 10, no. 3, pp. 361–366, 2011.
[18]
M. Y. Duan, J. Li, G. Mele et al., “Photocatalytic activity of novel tin porphyrin/TiO2 based composites,” The Journal of Physical Chemistry C, vol. 114, no. 17, pp. 7857–7862, 2010.
[19]
C. Wang, J. Li, G. Mele et al., “Efficient degradation of 4-nitrophenol by using functionalized porphyrin-TiO2 photocatalysts under visible irradiation,” Applied Catalysis B, vol. 76, no. 3-4, pp. 218–226, 2007.
[20]
G. Mele, R. Del Sole, G. Vasapollo, E. García-López, L. Palmisano, and M. Schiavello, “Photocatalytic degradation of 4-nitrophenol in aqueous suspension by using polycrystalline TiO2 impregnated with functionalized Cu(II) -porphyrin or Cu(II)-phthalocyanine,” Journal of Catalysis, vol. 217, no. 2, pp. 334–342, 2003.
[21]
B. Zhao, G. Mele, I. Pio, J. Li, L. Palmisano, and G. Vasapollo, “Degradation of 4-nitrophenol (4-NP) using Fe-TiO2 as a heterogeneous photo-Fenton catalyst,” Journal of Hazardous Materials, vol. 176, no. 1–3, pp. 569–574, 2010.
[22]
S. Sakthivel, M. Janczarek, and H. Kisch, “Visible light activity and photoelectrochemical properties of nitrogen-doped TiO2,” The Journal of Physical Chemistry B, vol. 108, no. 50, pp. 19384–19387, 2004.
[23]
G. Granados-Oliveros, E. A. Páez-Mozo, F. M. Ortega, C. Ferronato, and J. M. Chovelon, “Degradation of atrazine using metalloporphyrins supported on TiO2 under visible light irradiation,” Applied Catalysis B, vol. 89, no. 3-4, pp. 448–454, 2009.
[24]
Z. Mesgaria, M. Gharagozlou, A. Khosravi, and K. Gharanjig, “Spectrophotometric studies of visible light induced photocatalytic degradation of methyl orange using phthalocyanine-modified Fe-doped TiO2 nanocrystals,” Spectrochimica Acta A, vol. 92, pp. 148–153, 2012.
[25]
I. Zebger, L. Poulsen, Z. Gao, L. K. Andersen, and P. R. Ogilby, “Singlet oxygen images of heterogeneous samples: examining the effect of singlet oxygen diffusion across the interfacial boundary in phase-separated liquids and polymers,” Langmuir, vol. 19, no. 21, pp. 8927–8933, 2003.