Abstract
A hydrophobic complex of Cu2+[bis-salicylic aldehyde-o-phenylenediamine], Cu-SPA, was prepared and used as a heterogeneous photocatalyst to degrade organic pollutants in water under visible irradiation (λ ⩾ 420 nm) at neutral pH. The structure of complex was characterized by using nuclear magnetic resonance (NMR), elemental analysis, IR and UV-vis spectrometries. Degradation of Rhodamine B (RhB), Sulforhodamine B (SRB) and Benzoic acid (BA) in water were used as model reactions to evaluate the photocatalytic activities of Cu-SPA. The results indicated that RhB and SRB were easily adsorbed on the hydrophobic surface of Cu-SPA from aqueous solution (the maximum adsorption amount: Q max = 11.09 and 8.05 μmol/g, respectively). Under visible irradiation, RhB and SRB were decolorized completely after 210 and 240 min, respectively, and BA was removed completely after 5 h. The efficiency of H2O2 was > 95%, in contrast to that of the reaction without catalyst or light (< 20%). In water soluble medium, the hydrophobic Cu-SPA can be used more than 6 cycles. ESR results and the behavior of cyclic voltammetry showed that, in the reaction process, Cu2+-SPA was reduced to intermediate state Cu+-SPA firstly, which was extremely unstable and reacted rapidly with H2O2, leading to high reactive oxygen species (·OH radical ) to degrade the substrate.
Article PDF
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.Avoid common mistakes on your manuscript.
References
Kubacka A, Fernández-García M, Colón G. Advanced nanoarchitectures for solar photocatalytic applications. Chem Rev, 2012, 112: 1555–1614
O’shea KE, Dionysiou DD. Advanced oxidation processes for water treatment. J Phys Chem Lett, 2012, 3: 2112–2113
Quici N, Litter MI. Photochemical advanced oxidation processes for water and wastewater treatment. Recent Pat Eng, 2010, 4: 217–241
Mira P, Jelena R, Damia B. Advanced oxidation processes (AOPs) applied for wastewater and drinking water treatment. Elimination of pharmaceuticals. Holistic Ap Environ, 2011, 2: 63–74
Malato S, Fernández-Ibáñez P, Maldonado MI, Blanco J, Gernjak W. Decontamination and disinfection of water by solar photocatalysis: Recent overview and trends. Catal Today, 2009, 147: 1–59
Lamsal R, Walsh ME, Gagnon GA. Comparison of advanced oxidation processes for the removal of natural organic matter. Water Res, 2011, 45: 3263–3269
Elias RJ, Waterhouse AL. Controlling the fenton reaction in wine. J Agric Food Chem, 2010, 58: 1699–1707
Ahmed B, Limem E, Abdel-Wahab A, Nasr B. Photo-fenton treatment of actual agro-industrial wastewaters. Ind Eng Chem Res, 2011, 50: 6673–6680
Chen LW, Ma J, Li XC, Zhang J, Fang JY, Guan YH, Xie PC. Strong enhancement on Fenton oxidation by addition of hydroxylamine to accelerate the ferric and ferrous iron cycles. Environ Sci Technol, 2011, 45: 3925–3930
Zazo JA, Pliego G, Blasco S, Casas JA, Rodriguez L. Intensification of the fenton process by increasing the temperature. Ind Eng Chem Res, 2011, 50: 866–870
Navalon S, Alvaro M, Garcia H. Heterogeneous Fenton catalysts based on clays, silicas and zeolites. Appl Catal B: Environ, 2010, 99: 1–26
Gonzalez-Olmos R, Martin MJ, Georgi A, Kopinke FD, Oller I, Malato S. Fe-zeolites as heterogeneous catalysts in solar Fenton-like reactions at neutral pH. Appl Catal B: Environ, 2012, 125: 51–58
Burton SG. Oxidizing enzymes as biocatalysts. Trends Biotechnol, 2003, 21: 543–549
Torres E, Bustos-Jaimes I, Le Borgne SL. Potential use of oxidative enzymes for the detoxification of organic pollutants. Appl Catal B: Environ, 2003, 46: 1–15
Riva S. Laccases: Blue enzymes for green chemistry. Trends Biotechnol, 2006, 24: 219–226
Karigar CS, Rao SS. Role of microbial enzymes in the bioremediation of pollutants: A review. Enzyme Res, 2011, 2011: 1–11
Li J, Ma WH, Huang YP, Tao X, Zhao JC, Xu YM. Oxidative degradation of organic pollutants utilizing molecular oxygen and visible light over a supported catalyst of Fe(bpy)3 2+ in water. Appl Catal B: Environ, 2004, 48: 17–24
Rosenthal J, Tuckett TD, Hodgkiss JM, Nocera DG. Photocatalytic oxidation of hydrocarbons by a bis-iron(iii)-μ-oxo pacman porphyrin using O2 and visible light. J Am Chem Soc, 2006, 128: 6546–6547
Meng X, Qin C, Wang XL, Su ZM, Li B, Yang QH. Chiral salenmetal derivatives of polyoxometalates with asymmetric catalytic and photocatalytic activities. Dalton Trans, 2011, 40: 9964–9966
Drozd D, Szczubiałka K, Łapok kL, Sklba M, Patel H, Gorun SM, Nowakowska M. Visible light induced photosensitized degradation of Acid Orange 7 in the suspension of bentonite intercalated with perfluoroalkyl perfluoro phthalocyanine zinc complex. Appl Catal B: Environ, 2012, 125: 35–40
Kim W, Park J, Jo HJ, Kim HJ, Choi W. Visible light photocatalysts based on homogeneous and heterogenized tin porphyrins. J Phys Chem C, 2008, 112: 491–499
Ardo S, Achey D, Morris AJ, Abrahamsson M, Meyer GJ. Non-nernstian two-electron transfer photocatalysis at metalloporphyrin-TiO2 interfaces. J Am Chem Soc, 2011, 133: 16572–16580
Yella A, Lee HW, Tsao HN, Yi C, Chandiran AK, Nazeeruddin MK, Diau EWG, Yeh CY, Zakeeruddin SM, Gratzel M. Porphyrinsensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12 percent efficiency. Science, 2011, 334: 629–634
Chen X, Ma WH, Li J, Wang ZH, Chen CC, Ji HW, Zhao JC. Photocatalytic oxidation of organic pollutants catalyzed by an iron complex at biocompatible pH values: Using O2 as main oxidant in a Fenton-like reaction. J Phys Chem C, 2011, 115: 4089–4095
Ghosh A, Mitchell DA, Chanda A, Ryabov AD, Popescu DL, Upham EC, Collins GJ, Collins TJ. Catalase-peroxidase activity of iron(III)-TAML activators of hydrogen peroxide. J Am Chem Soc, 2008, 130: 15116–15126
Chung LW, Li X, Hirao H, Morokuma K. Comparative reactivity of ferric-superoxo and ferryl-oxo species in heme and non-heme complexes. J Am Chem Soc, 2011, 133: 20076–20079
Yamada S. Advancement in stereochemical aspects of Schiff base metal complexes. Coord Chem Rev, 1999, 190: 537–555
Ruck RT, Jacobsen EN. Asymmetric catalysis of hetero-ene reactions with tridentate schiff base chromium(III) complexes. J Am Chem Soc, 2002, 124: 2882–2883
Gupta KC, Sutar AK. Catalytic activities of Schiff base transition metal complexes. Coord Chem Rev, 2008, 252: 1420–1450
Liu L, Jiang DL, Mcdonald A, Hao YQ, Millhauser GL, Zhou FM. Copper redox cycling in the prion protein depends critically on binding mode. J Am Chem Soc, 2011, 133: 12229–12237
Mohamed RM, Mohamed MM. Copper (II) phthalocyanines immobilized on alumina and encapsulated inside zeolite-X and their applications in photocatalytic degradation of cyanide: A comparative study. Appl Catal A: Gen, 2008, 340: 16–24
Islam SM, Roy AS, Mondal P, Mubarak M, Mondal S, Hossain D, Banerjee S, Santra SC. Synthesis, catalytic oxidation and antimicrobial activity of copper(II) Schiff base complex. J Mol Catal A: Chem, 2011, 336: 106–114
Sedai B, Díaz-Urrutia C, Baker RT, Wu RL, “Pete” Silks LA, Hanson SK. Comparison of copper and vanadium homogeneous catalysts for aerobic oxidation of lignin models. ACS Catal, 2011, 1: 794–804
Ramalingam B, Lee GH, Chen C. Copper complex of aminoisoborneol Schiff base Cu2(SBAIB-d)2: An efficient catalyst for direct catalytic asymmetric nitroaldol (Henry) reaction. Adv Synth Catal, 2012, 354: 2511–2520
Zhang ZJ, Li X, Wang CG, Zhang CC, Liu P, Fang TT, Xiong Y, Xu WJ. A novel dinuclear Schiff-base copper(II) complex modified electrode for ascorbic acid catalytic oxidation and determination. Dalton Trans, 2012, 41: 1252–1258
Cao TT, Zou CQ, Li RP, Huang YP. Heterogenous degradation of toxic organic pollutants by hydrophobic iron(Ó) Schiff base complex under visible irradiation. Chem J Chinese Univ, 2011, 1: 105–112
Golcu A, Tumer M, Demirelli H, Wheatley RA. Cd(II) and Cu(II) complexes of polydentate Schiff base ligands: Synthesis, characterization, properties and biological activity. Inorg Chem Acta, 2005, 358: 1785–1797
Ma JH, Ma WH, Song WJ, Chen CC, Tang YL, Zhao JC, Huang YP, Xu YM, Zang L. Fenton degradation of organic pollutants in the presence of low-molecular-weight organic acids: Co-operative effect of quinone and visible light. Environ Sci Technol, 2006, 40: 618–624
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Song, Q., Jia, M., Ma, W. et al. Heterogeneous degradation of toxic organic pollutants by hydrophobic copper Schiff-base complex under visible irradiation. Sci. China Chem. 56, 1775–1782 (2013). https://doi.org/10.1007/s11426-013-4948-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11426-013-4948-z