Surface Modified Titania Visible Light Photocatalyst Powders


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Titanium dioxide has received great attention both in fundamental and applied photocatalysis due to its low cost, non-toxicity, and stability against photocorrosion [ - ]. Unfortunately it can utilize only the very small UV part (about 3%) of solar light arriving at the earth surface. However, also the visible part (λ > 400 nm) may induce photocatalysis if titania is modified by transition or main group elements. Accordingly, many publications appeared in the last 20 years dealing with the problem of sensitizing titania for visible light photooxidation reactions. This may be achieved by doping, which means substitution of lattice ions, and by surface modification. In many cases authors not clearly differentiate between these two possibilities and so called doped titania quite often is a surface modified material. The latter is easily prepared by heating titania or its precursor compounds like titanium hydroxide in the presence of a modifier at temperatures in the range of 100 – 500 °C. In the following we summarize our work in this field using inorganic and organic sensitizers.



Solid State Phenomena (Volume 162)

Edited by:

Maria K. Nowotny and Janusz Nowotny






D. Mitoraj and H. Kisch, "Surface Modified Titania Visible Light Photocatalyst Powders", Solid State Phenomena, Vol. 162, pp. 49-75, 2010

Online since:

June 2010




[1] A. Fujishima, T.N. Rao, D.A. Tryk,; J. Photochem. Photobiol., C, Vol. 1 (2000), p.1.

[2] D.A. Tryk, A. Fujishima, K. Honda,; Electrochim. Acta, Vol. 45 (2000), p.2363.

[3] M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemann,; Chem. Rev., Vol. 95 (1995), p.69.

[4] O. Carp, C.L. Huisman, A. Reller,; Prog. Solid State Chem., Vol. 32 (2004), p.33.

[5] A.L. Linsebigler, G. Lu, J.T. Yates, Jr.; Chem. Rev., Vol. 95 (1995), p.735.

[6] T.L. Thompson, J.T. Yates, Jr.: Top. Catal., Vol. 35 (2005), p.197.

[7] H. Yamashita, Y. Ichihashi, M. Takeuchi, S. Kishiguchi, M. Anpo: J. Synch. Rad. Vol. 6 (1999), p.451.

[8] H. Yamashita, M. Harada, J, Misaka, M. Takeuchi, Y. Ichihashi, F. Goto, M. Ishida, T. Sasaki, M. Anpo; J. Synch. Rad., Vol. 8 (2001), p.569.

[9] H. Yamashita, M. Harada, J. Misaka, M. Takeuchi, K. Ikeue, M. Anpo; J. Photochem. Photobiol., A , Vol. 148 (2002), p.257.

[10] S. Klosek, D. Raftery,; J. Phys. Chem. B, Vol. 105 (2001), p.2815.

[11] H. Kisch, L. Zang, C. Lange, W.F. Maier, C. Antonius, D. Meissner,; Angew. Chem., Int. Ed., Vol. 37 (1998), p.3034.

[12] L. Zang, C. Lange, I. Abraham, S. Storck, W.F. Maier, H. Kisch,; J. Phys. Chem. B, Vol. 102 (1998), p.10765.

[13] L. Zang, W. Macyk, C. Lange, W.F. Maier, C. Antonius, D. Meissner, H. Kisch,; Chem. Eur. J., Vol. 6 (2000), p.379.

[14] W. Macyk, H. Kisch,; Chem. Eur. J. Vol. 7 (2001), p.1862.

[15] G. Burgeth, H. Kisch,; Coord. Chem. Rev. Vol. 230 (2002), p.41.

[16] W. Macyk, G. Burgeth, H. Kisch,; Photochem. Photobiol. Sci. Vol. 2 (2003), p.322.

[17] H. Kisch, G. Burgeth, W. Macyk,; Adv. Inorg. Chem. Vol. 56 (2004), p.241.

[18] G. Burgeth, A. Fernandez, H. Kisch,; unpublished results.

[19] H.P. Boehm, M.Z. Herrmann,; Anorg. Allg. Chem., Vol. 352 (1967), p.156.

[20] M. Herrmann, H.P. Boehm,; Z. Anorg. Allg. Chem.; Vol. 368 (1969), p.73.

[21] R. Flaig-Baumann, M. Herrmann, H. P. Boehm,; Z. Anorg. Allg. Chem., Vol. 372 (1970), p.296.

[22] M. Herrmann, U. Kaluza, H.P. Boehm,; Z. Anorg. Allg. Chem. Vol. 372 (1970), p.296.

[23] J.A.R. van Veen,; Z. Phys. Chem. eue Folge, Vol. 162 (1989), p.215.

[24] A final stuctural assignment based on EXAFS measurements is in progress.

[25] For the case of simplicity the modified TH powders are abbreviated as x%H2PtCl6 wherein x% describes the mass% of platinum employed in the preparation.

[26] G. Kortum,; Reflectance Spectroscopy; Springer: New York, (1969).

[27] R.M. Edreva-Kardjieva,; Bulg. Chem. Commun., Vol. 25 (1992), p.166.

[28] B.M. Weckhuysen, R.A. Schoonheydt,; Catal. Today, Vol. 49 (1999), p.441.

[29] L.E. Cox, D.G. Peters,; Inorg. Chem. Vol. 9 (1970), p. (1927).

[30] L.E. Cox, D.G. Peters, E.L. Wehry,; J. Inorg. ucl. Chem. Vol. 34 (1972), p.297.

[31] J. Tauc, R. Grigorovici, A. Vanuc, Phys. Stat. Sol. Vol. 15 (1966), p.627.

[32] M.D. Ward, J.R. White, A.J. Bard,; J. Am. Chem. Soc. Vol. 105 (1983), p.27.

[33] J.R. White, A.J. Bard; J. Phys. Chem. Vol. 89 (1985), p. (1947).

[34] A.M. Roy, G.C. De, N. Sasmal, S.S. Bhattacharyya,; Int. J. Hydrogen Energy, Vol. 20 (1995), p.627.

[35] J.M. Bolts, M.S. Wrighton,; J. Phys. Chem., Vol. 80 (1976), p.2641.

[36] L. Kavan, M. Graetzel, S.E. Gilbert, C. Klemenz, H.J. Scheel,; J. Am. Chem. Soc., Vol. 118 (1996), p.6716.

[37] All photodegradations discussed in this review were performed on a 2. 5 ´ 10-4 M 4-CP solution. If not otherwise mentioned a cut-off filter of (l ³ 455 nm) was emplyed.

[38] Rates are comparable only if this optimum catalyst concentration is selected and if the amount of light absorbed is the same for each experiment. Thus, comparisons are justified only of results within one figure but not between different figures, except mentioned otherwise.

[39] T.A. Tetzlaff, W.S. Jenks,; Org. Lett., Vol. 1 (1999), p.463.

[40] C.M. Davidson, R.F. Jameson, Trans. Faraday Soc., Vol. 61 (1965), p.2462.

[41] A. Mills, R.H. Davies, D. Worsley, Chem. Soc. Rev., Vol. 22 (1993), p.417.

[42] A.L. Linsebigler, G. Lu, J.T. Yates Jr.,; Chem. Rev., Vol. 95 (1995), p.735.

[43] S.D. Malone, J.F. Endicott,; J. Phys. Chem., Vol. 76 (1972), p.2223.

[44] CRC Handbook of Chemistry and Physics, 76 ed.; CRC Press: Boca Raton, New York, London, Tokyo, (1995).

[45] R. Usón, J. Forniés, M. Tomás, B. Menjón, K. Sünkel, R. Bau,; J. Chem. Soc., Chem. Commun. (1984), p.751.

[46] R.C. Wright, G.S. Laurence,; J. Chem. Soc. Chem. Commun, (1972), p.132.

[47] D. Rehorek, C.M. Dubose, E.G. Janzen,; Inorg. Chim. Acta, Vol. 83 (1984), p. L7.

[48] W.L. Waltz, J. Lilie, A. Goursot, H. Chermette,; Inorg. Chem., Vol. 28 (1989), p.2247.

[49] R.B. Draper, M.A. Fox,; Langmuir, Vol. 6 (1990), p.1396.

[50] Z. -M. Dai, G. Burgeth, F. Parrino, H. Kisch, J. Organomet. Chem. FIELD Full Journal Title: Journal of Organometallic Chemistry, Vol. 694 (2009), p.1049.

[51] T.R. Cundari, E.W. Moody; THEOCHEM, Vol. 425 (1998), p.43.

[52] I.P. Alimarin, V.I. Shlenshaya O.A. Efremenko,; Russian Journal of Inorganic Chemistry, Vol. 15 (1970), p.530.

[53] K. Szacilowski, W. Macyk, G. Stochel,; J. Am. Chem. Soc., Vol. 128 (2006), p.4550.

[54] S. Sakthivel, H. Kisch,; Angew. Chem., Int. Ed., Vol. 42 (2003), p.4908.

[55] S. Sakthivel, H. Kisch; ChemPhysChem, Vol. 4 (2003), p.487.

[56] The sensitivity of HPLC instrument is about 1. 0 mmol dm-3.

[57] W. Choi, A. Termin, M.R. Hoffmann,; J. Phys. Chem., Vol. 98 (1994), p.13669.

[58] Assuming that light absorption originates rather from transitions between rhodium and conduction band energy levels than within localized rhodium energy states.

[59] For the mechanism of the further reactions steps see, e. g; Cunningham, J.; Al-Sayyed, G. J. Chem. Soc., Faraday Trans. 1990, 86, 3935; Theurich, J.; Lindner, M.; Bahnemann, D. W. Langmuir 1996, 12, 6368.

[60] E.R. Carraway, A.J. Hoffman, M.R. Hoffmann,; Environ. Sci. Technol. Vol. 28 (1994), p.786.

[61] E.R. Carraway, A.J. Hoffman, M.R. Hoffmann,; Environ. Sci. Technol., Vol. 28 (1994), p.776.

[62] C. Kormann, D.W. Bahnemann, M.R. Hoffmann,; Environ. Sci. Technol., Vol. 22 (1988), p.798.

[63] H. Kominami, K. Sumida, K. Yamamoto, N. Kondo, K. Hashimoto, Y. Kera,; Res. Chem. Intermed,; Vol. 34 (2008), p.587.

[64] T. Ohno, T. Mitsui, M. Matsumura,; Chem. Lett., Vol. 32 (2003), p.364.

[65] S. Sakthivel, M. Janczarek, H. Kisch,; J. Phys. Chem. B, Vol. 108 (2004), p.19384.

[66] Throughout this paper we use the term modifying" instead of "doping, since in most cases it is unknown if the non-metal really substitutes a lattice atom in the titania structure.

[67] For the recent reviews see; Di Valentin, C.; Finazzi, E.; Pacchioni, G.; Selloni, A.; Livraghi, S.; Paganini, M. C.; Giamello, E. Chem. Phys. 2007, 339, 44.

DOI: 10.1016/j.chemphys.2007.07.020

[68] X. Qiu, C. Burda,; Chem. Phys,. Vol. 339 (2007), p.1.

[69] S. Sato,; Chem. Phys. Lett., Vol. 123 (1986), p.126.

[70] R. Beranek, B. Neumann, S. Sakthivel, M. Janczarek, T. Dittrich, H. Tributsch, H. Kisch,; Chem. Phys., Vol. 339 (2007), p.11.

[71] Y. Yamamoto, S. Moribe, T. Ikoma, K. Akiyama, Q. Zhang, F. Saito, S. Tero-Kubota,; Mol. Phys., Vol. 104 (2006), p.1733.

[72] Y. Cong, J. Zhang, F. Chen, M. Anpo,; J. Phys. Chem. C, Vol. 111 (2007), p.6976.

[73] H. Kisch, S. Sakthivel, M. Janczarek, D. Mitoraj,; J. Phys. Chem. C, Vol. 111 (2007), p.11445.

[74] R. Bacsa, J. Kiwi, T. Ohno, P. Albers, V. Nadtochenko,; J. Phys. Chem. B, Vol. 109 (2005), p.5994.

[75] R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga,; Science (Washington, DC, U. S. ), Vol. 293 (2001), p.269.

[76] N. Serpone,; J. Phys. Chem. B 2006, 110, 24287; Kuznetsov, V. N.; Serpone, N. J. Phys. Chem. B 2006, 110, 25203.

[77] A.V. Emeline, N. V. Sheremetyeva, N.V. Khomchenko, V.K. Ryabchuk, N. Serpone,; J. Phys. Chem. C, Vol. 111 (2007), p.11456.

[78] V.N. Kuznetsov, N. Serpone,; J. Phys. Chem. C, Vol. 111 (2007), p.15277.

[79] D. Li, H. Haneda, S. Hishita, N. Ohashi,; Mater. Sci. Eng., B, Vol. B117 (2005), p.67.

[80] S. Yin, Q. Zhang, F. Saito, T. Sato,; Chem. Lett., Vol. 32 (2003), p.358.

[81] R.R. Bacsa, J. Kiwi; J. Appl. Catal., B, Vol. 16 (1998), p.19.

[82] H. -L. Qin, G. -B. Gu, S. Liu, J. -J. Li,; Huanan Ligong Daxue Xuebao, Ziran Kexueban, Vol. 34 (2006), p.78.

[83] E.A. Reyes-Garcia, E. A., Y. Sun, K. Reyes-Gil, D.J. Raftery,; Phys. Chem. C, Vol. 111 (2007), p.2738.

[84] M. Alvaro, E. Carbonell, V. Fornes, H. Garcia,; Chem. Phys. Chem., Vol. 7 (2006), p.200.

[85] Y. Nosaka, M. Matsushita, J. Nishino, A.Y. Nosaka,; Science and Technology of Advanced Materials, Vol. 6 (2005), p.143.

[86] S. Yin, K. Ihara, Y. Aita, M. Komatsu, T. Sato,; J. Photochem. Photobiol., A, Vol. 179 (2006), p.105.

[87] K. Kobayakawa, Y. Murakami, Y. Sato,; J. Photochem. Photobiol., A, Vol. 170 (2005), p.177.

[88] J. Yuan, M. Chen, J. Shi, W. Shangguan,; Int. J. Hydrogen Energy, Vol. 31 (2006), p.1326.

[89] D. Chen, Z. Jiang, J. Geng, Q. Wang, D. Yang,; Ind. Eng. Chem. Res., Vol. 46 (2007), p.2741.

[90] R. Beranek, H. Kisch,; J. Photochem. Photobiol. Sci., Vol. 7 (2008) p.40.

[91] Formic acid was selected as a model organic acid pollutant since it does not form colored CT complexes with titania, preventing visible light absorption by the semiconductor, and is oxidized without forming long-lived, light-absorbing intermediates.

[92] A. Schmidt,; Chem. Ing. Tech., Vol. 38 (1966), p.1140.

[93] A.G. Koryakin, V.A. Gal'perin, A.N. Sarbaev, A.I. Finkel'shtein,; Zh. Org. Khim., Vol. 7 (1971), p.972.

[94] Melem and melon are stable in air up to ca. 550 °C; Costa, L.; Camino, G. J. Therm. Anal. 1988, 34, 423; Thomas, Y.; Taravel, B.; Fromage, F.; Delorme, P. Materials Chemistry 1980, 5, 117.

[95] B. Juergens, E. Irran, J. Senker, P. Kroll, H. Mueller, W. Schnick,; J. Am. Chem. Soc., Vol. 125 (2003), p.10288.

[96] T. Komatsu,; Macromol. Chem. Phys., Vol. 202 (2001), p.19.

[97] N.E.A. El-Gamel, L. Seyfarth, J. Wagler, H. Ehrenberg, M. Schwarz, J. Senker, E. Kroke,; Chem. -Eur. J., Vol. 13 (2007), p.1158.

DOI: 10.1002/chem.200600435

[98] S. Yin, K. Ihara, M. Komatsu, Q. Zhang, F. Saito, T. Kyotani, T. Sato,; Solid State Commun., Vol. 137 (2006), p.132.

[99] A.P. Dementjev, A. De Graaf, M.C.M. Van de Sanden, K.I. Maslakov, A.V. Naumkin, A.A. Serov,; Diamond Relat. Mater., Vol. 9 (2000), p. (1904).

[100] Q. Guo, Y. Xie, X. Wang, S. Zhang, T. Hou, S. Lu,; Chem. Commun. (Cambridge, U. K. ), (2004), p.26.

[101] K.J. Boyd, B. Marton, S.S. Todorov, A.H. Al-Bayati, J. Kulik, R.A. Zuhr, J.W. Rabalais,; J. Vac. Sci. Technol., A, Vol. 13 (1995), p.2110.

[102] A. F. Carley, M. Chinn, C.R. Parkinson,; Surf. Sci., Vol. 517 (2002), p. L563.

[103] J.M. Pan, B.L. Maschhoff, U. Diebold, T.E. Madey,; J. Vac. Sci. Technol., A, Vol. 10 (1992), p.2470.

[104] U. Diebold, J. Lehmann, T. Mahmoud, M. Kuhn, G. Leonardelli, M. Hebenstreit, M. Schmid, P. Varga,; Surf. Sci., Vol. 411 (1998), p.137.

[105] E.A. Konstantinova, A.I. Kokorin, S. Sakthivel, H. Kisch, K. Lips,; Chimia, Vol. 61 (2007), p.810.

[106] J. Orth-Gerber, H. Kisch,; Titanium dioxide photocatalyst containing carbon and method for its production; (Kronos International Inc., Germany). US Pat. Appl. Publ. US 2005226761, (2005), 19 pp.

[107] S. Yin, M. Komatsu, Q. Zhang, F. Saito, T. Sato,; J. Mater. Sci., Vol. 42 (2007), p.2399.

[108] C. Xu, R. Killmeyer, M. Gray, S.U.M. Khan,; Appl. Catal., B, Vol. 64 (2006), p.312.

[109] W. Ren, Z. Ai, F. Jia, L. Zhang, X. Fan, Z. Zou,; Appl. Catal., B, Vol. 69 (2007), p.138.

[110] L. Lin, W. Lin, Y.X. Zhu, B.Y. Zhao, Y.C. Xie, Y. He, Y.F. Zhu,; J. Mol. Catal. A: Chem., Vol. 236 (2005), p.46.

[111] S.Y. Treschev, P. -W. Chou, Y. -H. Tseng, J. -B. Wang, E.V. Perevedentseva, C. -L. Cheng,; Appl. Catal., B, Vol. 79 (2008), p.8.

[112] Y. Li, D. -S. Hwang, N.H. Lee, S. -J. Kim,; Chem. Phys. Lett., Vol. 404 (2005), p.25.

[113] C. Lettmann, K. Hildenbrand, H. Kisch, W. Macyk, W.F. Maier,; Appl. Catal., B, Vol. 32 (2001), p.215.

[114] G. Yu, Z. Chen, Z. Zhang, P. Zhang, Z. Jiang,; Catal. Today, Vol. 90 (2004), p.305.

[115] Y. -H. Tseng, C. -S. Kuo, C. -H. Huang, Y. -Y. Li, P. -W. Chou, C. -L. Cheng, M. -S. Wong,; anotechnology, Vol. 17 (2006), p.2490.

[116] H. Irie, Y. Watanabe, K. Hashimoto,; Chem. Lett., Vol. 32 (2003), p.772.

[117] Y. Cheng, H. Sun, W. Jin, N. Xu,; Chem. Eng. J. (Amsterdam, eth. ), Vol. 128 (2007), p.127.

[118] P. Zabek, J. Eberl, H. Kisch,; Photochem. Photobiol. Sci., Vol. 8 (2009), p.264.

[119] H. Liu, A. Imanishi, Y. Nakato,; J. Phys. Chem. C, Vol. 111 (2007), p.8603.

[120] K. Nagaveni, G. Sivalingam, M.S. Hegde, G. Madras,; Appl. Catal., B, Vol. 48 (2004), p.83.

[121] C. -S. Kuo, Y. -H. Tseng, C. -H. Huang, Y. -Y. Li,; J. Mol. Catal. A: Chem., Vol. 270 (2007), p.93.

[122] H. Irie, S. Washizuka, K. Hashimoto,; Thin Solid Films, Vol. 510 (2006), p.21.

[123] Y. Choi, T. Umebayashi, M. Yoshikawa,; J. Mater. Sci., Vol. 39 (2004), p.1837.

[124] J. Riga, J.J. Pireaux, R. Caudano, J.J. Verbist,; Phys. Scr., Vol. 16 (1977), p.346.

[125] R. Larsson, B. Folkesson,; Chemica Scripta, Vol. 9 (1976), p.148.

[126] J. Schnadt, J.N. O'Shea, L. Patthey, J. Schiessling, J. Krempasky, M. Shi, N. Martensson, P.A. Bruhwiler,; Surf. Sci., Vol. 544 (2003), p.74.

[127] X. Yang, C. Cao, K. Hohn, L. Erickson, R. Maghirang, D. Hamal, K.J. Klabunde, ; J. Catal., Vol. 252 (2007), p.296.

[128] X. Zhang, M. Zhou, L. Lei,; Carbon, Vol. 44 (2005), p.325.

[129] C. Di Valentin, G. Pacchioni, A. Selloni,; Chem. Mater., Vol. 17 (2005), p.6656.

[130] R. Rahal, S. Daniele, L.G. Hubert-Pfalzgraf, V. Guyot-Ferreol, J. -F. Tranchant,; Eur. J. Inorg. Chem., (2008), p.980.

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