Abstract
Studies on the photo-catalytic redox reaction of C1–C3 alcohols such as methanol, ethanol and 2-propanol were carried out in aqueous solution containing TiO2 photocatalyst (0.1% w/v) as suspension using 350 nm light. Other hydrocarbons such as ethane and ethene in the case of ethanol, and propene in the case of 2-propanol with low yields were produced along with the major photolytic products methane and carbon dioxide. The yields of methane and CO2 were found to be dependent on the light exposure time and ambient conditions. Methane yields were higher in 2-propanol and ethanol systems than in methanol system, showing their better hole-scavenging properties. In the aerated condition, methane was produced during photolysis of all alcohols in the presence of TiO2 and the yield was comparable to those observed in the corresponding CO2-saturated systems. The overall results reveal that the surface adsorbed, as well as in-situ-generated CO2 from photo-oxidation of alcohols are equally responsible for methane formation through photo-reduction in presence of TiO2. In the O2-saturated system, the methane yield was lower as compared to that in aerated system, in contrast to the CO2 yield. In N2O-and N2-purged systems, the yield of methane was observed to be low, inferring that the methane generation has not taken place through photodecomposition/photodissociation of alcohols. Again, photolysis of alcohols without TiO2 did not generate any methane.
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G. R. Dey, A. D. Belapurkar and K. Kishore, J. Photochem. Photobiol. A: Chem. 163, 501 (2004).
G. R. Dey and K. Kishore, in S. Kaneco (Ed.), Photo/Electrochemistry & Photobiology in the Environment, Energy and Fuel, p. 357. Research Signpost, Kerala (2005).
R. Memming, Top. Curr. Chem. 143, 79 (1988).
D. W. Bahnemann, in E. Pelizzetti and M. Schiavello (Eds), Photochemical Conversion and Storage of Solar Energy, p. 251. Kluwer, Dordrecht (1991).
G. Mills and M. R. Hoffmann, Environ. Sci. Technol. 27, 1681 (1993).
M. R. Hoffmann, S. T. Martin, W. Choi and D. W. Bahnemann, Chem. Rev. 95, 69 (1995).
B. C. Faust, M. R. Hoffmann and D. W. Bahnemann, J. Phys. Chem. 93, 6371 (1989).
Y. Mao, C. Schoneich and K.-D. Asmus, J. Phys. Chem. 95, 10080 (1991).
K. Tanaka, T. Hisanaga and A. P. Rivera, in H. Al-Ekabi and D. F. Ollis (Eds), Photocatalytic Purification and Treatment of Water and Air, p. 169. Elsevier, Amsterdam (1993).
A. Fujishima, T. N. Rao and D. A. Tryk, J. Photochem. Photobiol. C: Photochem. Rev. 1, 1 (2000).
M. Anpo, Res. Chem. Intermed. 11, 67 (1989).
T. Inoue, A. Fujishima, S. Konishi and K. Honda, Nature 277, 637 (1979).
S. Kaneco, H. Kurimoto, K. Ohta, T. Mizuno and A. Saji, J. Photochem. Photobiol. A: Chem. 109, 59 (1997).
S. Kaneco, Y. Shimizu, K. Ohta and T. Mizuno, J. Photochem. Photobiol. A: Chem. 115, 223 (1998).
H. Noda, S. Ikeda, Y. Oda, K. Imai, M. Maeda and K. Ito, Bull. Chem. Soc. Jpn. 63, 2459 (1990).
R. G. Russell, N. Novac, S. Srinivasan and M. Steinberg, J. Electrochem. Soc. 124, 1329 (1977).
K. Hirano, K. Inoue and T. Yatsu, J. Photochem. Photobiol. A: Chem. 64, 255 (1992).
J. Chen, D. F. Ollis, W. H. Rulkens and H. Bruning, Water Res. 33, 1173 (1999).
O. I. Micic, Y. Zhang, K. R. Cromack, A. D. Trifunac and M. C. Thurnauer, J. Phys. Chem. 97, 13284 (1993).
M. L. Cubeiro and J. L. G. Fierro, J. Catal. 179, 150 (1998).
P. Forzatti, E. Tronconi, A. S. Elmi and G. Busca, Applied Catalysis A: General 157, 387 (1997).
S. P. Bates and M. J. Gillan, J. Phys. Chem. B 102, 2017 (1998).
C.-C. Chuang, C.-C. Chen, and J.-L. Lin, J. Phys. Chem. B 103, 2439 (1999).
C. U. Morgan, J. Phys. Chem. 76, 494 (1972).
T. Kawai and T. Sakata, Chem. Commun., 694 (1980).
M. L. Sauer and D. F. Ollis, J. Catal. 158, 570 (1996).
D. S. Muggli, J. T. McCue and J. L. Falconer, J. Catal. 173, 470 (1998).
D. S. Muggli, S. A. Larson and J. L. Falconer, J. Phys. Chem. 100, 15886 (1996).
M.-J. Kim, W. Nam and G. Y. Han, Korean J. Chem. Eng. 21, 721 (2004).
P.-O. Larsson and A. Andersson, J. Catal. 179, 72 (1998).
J. C. Kennedy III and A. K. Datye, J. Catal. 179, 375 (1998).
T. Reztsova, C.-H. Chang, J. Koresh and H. Idriss, J. Catal. 185, 223 (1999).
A. Bernas, M. Bodard and D. Saghattchian, J. Chim. Phys. 62, 1418 (1965).
M. Harada, M. Honda, H. Yamashita and M. Anpo, Res. Chem. Intermed. 25, 757 (1999).
S. A. Larson, J. A. Widegren and J. L. Falconer, J. Catal. 157, 611 (1995).
R. I. Bickley and R. K. M. Jayanty, Faraday Discuss. Chem. Soc. 58, 194 (1974).
B. Ohtani, M. Kakimoto, H. Miyadzu, S.-I. Nishimoto and T. Kagiya, J. Phys. Chem. 92, 5773 (1988).
I. Ait-Ichou, M. Formenti, B. Pommier and S. J. Teichner, J. Catal. 91, 293 (1985).
R. I. Bickley, G. Munuera and F. S. Stone, J. Catal. 31, 398 (1973).
H. Yamashita, M. Honda, M. Harada, Y. Ichihashi, M. Anpo, T. Hirao, N. Itoh and N. Iwamoto, J. Phys. Chem. B 102, 10707 (1998).
Y. Ohko, A. Fujishima and K. Hashimoto, J. Phys. Chem. B 102, 1724 (1998).
D. Brinkley and T. Engel, J. Phys. Chem. B 102, 7596 (1998).
J. E. Rekoske and M. A. Barteau, J. Catal. 165, 57 (1997).
J. Manuel G.-A., T. Armaroli, G. Ramis, E. Finocchio and G. Busca, Appl. Catal. B: Environ. 22, 249 (1999).
H. Miyata, K. Hata, T. Nakajima and Y. Kubokawa, Bull. Chem. Soc. Jpn. 53, 2401 (1980).
J. Cunningham and S. Srijaranai, J. Photochem. Photobiol. A: Chem. 55, 219 (1990).
B. Ohatani, M. Kakimoto, S. Nishimoto and T. Kagiyo, J. Photochem. Photobiol. A: Chem. 70, 265 (1993).
J. Cunningham and B. K. Hodnett, J. Chem. Soc. Faraday Trans. 77, 2777 (1981).
J. Cunningham and P. Meriaudeau, J. Chem. Soc. Faraday Trans. 72, 1499 (1976).
N. R. Blake and G. L. Griffin, J. Phys. Chem. 92, 5697 (1988).
P. A. Mandelbaum, A. E. Regazzoni, M. A. Blesa and S. A. Bilmes, J. Phys. Chem. B 103, 5505 (1999).
O. A. Semenikhin, V. E. Kazarinov, L. Jiang, K. Hashimoto and A. Fujishima, Langmuir 15, 3731 (1999).
C.-B. Wang, Y. Cai and I. E. Wachs, Langmuir 15, 1223 (1999).
M. Miyake, H. Yoneyama and H. Timura, Chem. Lett., 635 (1976).
M. Miyake, H. Yoneyama and H. Timura, Denki Kagaku 45, 411 (1977).
J. W. T. Spinks and R. J. Woods, in An Introduction to Radiation Chemistry, 3rd edn, p. 152. Wiley, New York, NY (1990).
A. J. Elliot, Radiat. Phys. Chem. 34, 753 (1989).
G. V. Buxton, C. L. Greenstock, W. P. Helman and A. B. Ross, J. Phys. Chem. Data 17, 513 (1988).
A. Sauer, H. Cohen and D. Meyerstein, Inorg. Chem. 28, 2511 (1989).
J. K. Thomas, J. Phys. Chem. 71, 1919 (1967).
E. R. Kantrowitz, M. Z. Hoffman and J. F. Endicott, J. Phys. Chem. 75, 1914 (1971).
J. Cunningham, E. Finn and N. Samman, Faraday Discuss. Chem. Soc. 58, 160 (1974).
A. K. Vijh and B. E. Conway, Chem. Rev. 67, 623 (1967).
B. Kraeutler and A. J. Bard, J. Am. Chem. Soc. 100, 5985 (1978).
B. Kraeutler and A. J. Bard, J. Am. Chem. Soc. 99, 7729 (1977).
J. Rabani and M. S. Metheson, J. Am. Chem. Soc. 80, 3175 (1964).
Y. Tabata, in Pulse Radiolysis, p. 399. CRC Press, Boca Raton, FL (1991).
B. H. J. Bieski, D. E. Cabelli, R. L. Arudi and A. B. Ross, J. Phys. Chem. Ref. Data 14, 1041 (1985).
C. D. Jaeger and A. J. Bard, J. Phys. Chem. 83, 3146 (1979).
J. R. Harbour and M. L. Hair, J. Phys. Chem. 83, 652 (1979).
K. Tennakone, A. H. Jayatissa and S. Punchihewa, J. Photochem. Photobiol. A: Chem. 49, 369 (1989).
M. Anpo, H. Yamashita, Y. Ichihashi and S. Ehara, J. Electroanal. Chem. 396, 21 (1995).
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Dey, G.R., Pushpa, K.K. Methane generated during photocatalytic redox reaction of alcohols on TiO2 suspension in aqueous solutions. Res Chem Intermed 32, 725–736 (2006). https://doi.org/10.1163/156856706778606462
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DOI: https://doi.org/10.1163/156856706778606462