Effect of charge trapping species of cupric ions on the photocatalytic oxidation of resorcinol |
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| Affiliation: | 1. ARC Centre for Functional Nanomaterials, School of Chemical Engineering and Industrial Chemistry, The University of New South Wales (UNSW), Sydney, NSW 2052, Australia;2. Institute of Environmental Science and Engineering (IESE), Innovation Centre (NTU), Block 2, Unit 237, 18 Nanyang Drive, 637723 Singapore;3. Analytical and Environmental Chemistry Section, NSW Department of Environment and Conservation, P.O. Box 29, Lidcombe, NSW 1825, Australia;1. Department of Life Sciences, Gachon University, Seongnamdaero 1342, Seongnam-si, Gyeonggi-do 461-701, South Korea;2. Department of Biotechnology, The Catholic University of Korea, Bucheon 420-743, South Korea;1. Consejería de Educación, Junta de Andalucía, 41092 Sevilla, Spain;2. Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Científicas, Universidad de Sevilla, Avda Américo Vespucio 49, 41092 Sevilla, Spain;3. Laboratorio de rayos-X CITIUS, Avda, Reina Mercedes 4b, 41012 Sevilla, Spain;4. Unité de Catalyse et de Chimie du Solide, UCCS, CNRS, UMR 8181, Université Lille Nord de France, 59655 Villeneuve d’Ascq, France;5. Escuela de Ciencias Químicas, Universidad Pedagógica y Tecnológica de Colombia, UPTC, Avda, Central del Norte, Vía Paipa, Tunja, Boyacá, Colombia;1. The State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China;2. Department of Chemistry, Western Michigan University, Kalamazoo, MI 49008, United States;1. School of Pharmacy, Key Laboratory of Molecular Pharmacology and Drug Evaluation (Yantai University), Ministry of Education, Collaborative Innovation Center of Advanced Drug Delivery System and Biotech Drugs in Universities of Shandong, Yantai University, Yantai 264005, PR China;2. School of Life Sciences, Yantai University, Yantai 264005, PR China;3. Hebei Gogin Pharmaceutical Co., LTD., Xingtai 054000, PR China |
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| Abstract: | The photocatalytic oxidation of resorcinol, a potent endocrine disrupting chemical, in oxygenated aqueous suspensions of pure and cupric ions modified Degussa P25 titanium dioxide has been investigated at pH 3.0 ± 0.5. The initial rate of photocatalytic oxidation of resorcinol increased until an optimum dissolved cupric ions concentration was reached at 1.04 mM. At the optimum concentration of cupric ions, the initial rate of photocatalytic mineralisation and degradation of resorcinol was improved by 400%. The observed beneficial effect of cupric ions on the initial rate of resorcinol oxidation could be attributed to the formation of complex and its participation in the photoredox cyclic reaction.Two of the initial oxidation intermediates detected were 1,2,3-trihydroxybenzene and 1,2,4-trihydroxybenzene. These intermediates were formed via hydroxylation of the aromatic ring of resorcinol. Evidences have revealed that 1,2,4-trihydroxybenzene interacted strongly with cupric ions forming copper(II)-trihydroxybenzoate complexes that possessed good adsorption onto TiO2 surface. These dual-effects help to draw the metal ions closer to the photocatalyst surface and subsequently trigger the electron trapping mechanism by cupric ions. As a result, this improved the charge carriers’ separation. Furthermore, in the presence of oxygen, reoxidation of photoreduced cupric ions occurred and this eliminated the possibility of copper photodeposition, while inducing a photoredox cyclic reaction to regenerate copper species that may potentially act as co-catalyst for the oxidation of 1,2,4-trihydroxybenzene. In contrast, no obvious complex formation was seen between 1,2,3-trihydroxybenzene and cupric ions. This pointed to an intriguing finding which indicates that the positioning of functional group on benzene ring influences the role of cupric ions. |
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