Ruthenium bipyridyl complex-sensitized dechlorination of CCl4 in aqueous micellar solutions under visible light

Youngmin Cho; Yiseul Park; Wonyong Choi

Journal of Industrial and Engineering Chemistry, Vol.14, No.3, 315-321, May, 2008

DOI10.1016/j.jiec.2008.01.003 Export Citation

Ruthenium bipyridyl complex-sensitized dechlorination of CCl4 in aqueous micellar solutions under visible light

Youngmin Cho, Yiseul Park¹, and Wonyong Choi^{1, †}

Environment and Fire Research Team, Korea Railroad Research Institute, Uiwang 437-757, Korea
¹School of Environmental Science and Engineering, Pohang University of Science and Technology, Hyoja-dong, Pohang 790-784, Korea

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The sensitized dechlorination of CCl4 in water was successfully demonstrated in the presence of nonionic surfactants (Brij-35) and ruthenium bipyridyl complexes [Ru-II(bpy)(3)] under visible light illumination (lambda > 420 nm). The ruthenium complex plays the role of a visible light sensitizer for this reductive conversion process, which is excited by absorbing visible light and subsequently transfers an electron to CCl4. The photoinduced electron transfers from the excited sensitizer to CCl4 take place only in the presence of the surfactant, which concentrates both reactants within a micelle. The ruthenium sensitizer should be oxidized after transferring an electron to CCl4, but immediately regenerated by abstracting an electron from surrounding surfactant molecules. As a result, the ruthenium sensitizer acts as a photocatalyst with producing chlorides far above the stoichiometric concentration of the added sensitizer. The dechlorination rate was significantly reduced in the presence of dissolved oxygen, because the excited sensitizer is quenched by O-2. With increasing each concentration of the surfactant, sensitizer, or CCl4, the corresponding CCl4 dechlorination rate progressively increased, to reach a saturation at the concentration of 4.0 g/L (surfactant), 5 mu M (sensitizer), or 30 mM (CCl4), respectively. The visible light activity was strongly dependent on the kind of surfactants as well. (C) 2008 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

Keywords:surfactant;Brij;ruthenium complex;CCl4;photolysis;dechlorination

[References]

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Kalyanasundaram K, Gratzel M, Nazeeruddin MK, J. Phys. Chem., 96, 5865 (1992)
Guha S, Jaffe PR, Peters CA, Environ. Sci. Technol., 32, 930 (1998)
Mayer AS, Zhong L, Pope GA, Environ. Sci. Technol., 33, 2965 (1999)
Prak DJL, Abriola LM, Walter J, Weber J, Bocskay KA, Environ. Sci. Technol., 34, 476 (2000)
Cowell MA, Kibbey TCG, Zimmerman JB, Hayes KF, Environ. Sci. Technol., 34, 1583 (2000)
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Zacheis GA, Gray KA, Kamat PV, Environ. Sci. Technol., 34, 3401 (2000)
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Chu W, Jafvert CT, Environ. Sci. Technol., 28, 2415 (1994)
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Sigman ME, Schuler PF, Ghosh MM, Dabestani RT, Environ. Sci. Technol., 32, 3980 (1998)
Chu W, Jafvert CT, Diehl CA, Marley K, Larson RA, Environ. Sci. Technol., 32, 1989 (1998)
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Cho Y, Choi W, Lee CH, Hyeon T, Lee HI, Environ. Sci. Technol., 35, 966 (2001)
Bae E, Choi W, Environ. Sci. Technol., 37, 147 (2003)
Abraham MH, Chem. Soc. Rev., 65, 73 (1993)
Quina FH, Alonso EO, Farah JPS, J. Phys. Chem., 99, 11708 (1995)
Edwards DA, Luthy RG, Liu Z, Environ. Sci. Technol., 25, 127 (1991)
Kalyanasundaram K, Photochemistry in Microheterogeneous Systems, Academic Press Inc. (1987)

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[7] Schmelling DC, Poster DL, Chaychian M, Neta P, Silverman J, Al-Sheikhly M, Environ. Sci. Technol., 32, 270 (1998)

[8] Zacheis GA, Gray KA, Kamat PV, Environ. Sci. Technol., 34, 3401 (2000)

[9] Freeman PK, Lee YS, J. Org. Chem., 57, 2846 (1992)

[10] Chu W, Jafvert CT, Environ. Sci. Technol., 28, 2415 (1994)

[11] Shi Z, Sigman ME, Ghosh MM, Dabestani R, Environ. Sci. Technol., 31, 3581 (1997)

[12] Sigman ME, Schuler PF, Ghosh MM, Dabestani RT, Environ. Sci. Technol., 32, 3980 (1998)

[13] Chu W, Jafvert CT, Diehl CA, Marley K, Larson RA, Environ. Sci. Technol., 32, 1989 (1998)

[14] Chu W, Environ. Sci. Technol., 33, 421 (1999)

[15] Epling GA, Florio EM, Bourque AJ, Qian XH, Stuart JD, Environ. Sci. Technol., 22, 952 (1988)

[16] Hawari J, Demeter A, Samson R, Environ. Sci. Technol., 26, 2022 (1992)

[17] Isosaari P, Tuhkanen T, Vartiainen T, Environ. Sci. Technol., 35, 1259 (2001)

[18] Larson RA, Jafvert CT, Bosca F, Marley KA, Miller PL, Environ. Sci. Technol., 34, 505 (2000)

[19] Bunce NJ, Kumar Y, Ravanal L, Safe S, J. Chem. Soc., Perkin Trans., 2, 880 (1978)

[20] Navon G, Sutin N, Inorg. Chem., 13, 2159 (1974)

[21] Kalyanasundaram K, Photochemistry of Polypyridine and Porphyrin Complexs, Academic Press Inc. (1992)

[22] Oh WC, Jung AR, Ko WB, J. Ind. Eng. Chem., 13(7), 1208 (2007)

[23] Nazeeruddin MK, Kay A, Rodicio I, Humphry-Baker R, Muller E, Liska P, Vlachopoulos N, Gratzel M, J. Am. Chem. Soc., 115, 6382 (1993)

[24] Jeong YB, Lee DY, Song JS, Kim SS, Sung YE, Kim DW, J. Ind. Eng. Chem., 10(4), 499 (2004)

[25] Cho Y, Choi W, Lee CH, Hyeon T, Lee HI, Environ. Sci. Technol., 35, 966 (2001)

[26] Bae E, Choi W, Environ. Sci. Technol., 37, 147 (2003)

[27] Abraham MH, Chem. Soc. Rev., 65, 73 (1993)

[28] Quina FH, Alonso EO, Farah JPS, J. Phys. Chem., 99, 11708 (1995)

[29] Edwards DA, Luthy RG, Liu Z, Environ. Sci. Technol., 25, 127 (1991)

[30] Kalyanasundaram K, Photochemistry in Microheterogeneous Systems, Academic Press Inc. (1987)