Abstract
Mesoporous Ti–Co oxides were synthesized via a replication route, using a 3-D wormlike mesoporous silica as template and tetra-tert-butyl orthotitanate (TBOT) and Co(NO3)2 as source materials. The prepared materials were characterized by X-ray diffraction (XRD), N2-physisorption, TEM, EDS, and UV/Vis-DRS and found to possess a spherical morphology and a 3-D wormhole-like mesoporous structure, with the average pore size between 4.5 and 16.0 nm. The pore walls consisted mainly of a cobalt-incorporated anatase phase. The Co3+ ions were generated in the replicated mesoporous Co–Ti oxides, via the transfer of electrons from Co2+ to Ti4+ ions. The formation of cobalt-incorporated anatase phase and Co3+ ions were both favored by larger Co/Ti atomic ratios and by relatively low calcination temperatures. The specific surface area decreased and the mesopore sizes increased, with increasing Co/Ti atomic ratio or calcination temperature. The average crystal size of the anatase phase decreased with increasing Co/Ti atomic ratio but increased with increasing calcination temperature. The photocatalytic activity of the replicated mesoporous Co–Ti oxides in the degradation of methyl orange dye was investigated. It was observed that the photocatalytic activity increased with increasing Co/Ti atomic ratio and exhibited a maximum with increasing calcination temperature. With the exception of those prepared at too high calcination temperatures, the replicated mesoporous Co–Ti oxides were much more active than the pure titania. It is concluded that, in addition to a higher diffusion, the cobalt-containing anatase, as the active phase, and the Co3+ ions, as the active sites, are responsible for the high photocatalytic activity of the replicated mesoporous Co–Ti oxide.
Similar content being viewed by others
References
Chuah GK, Hu X, Zhan P, Jaenicke S (2002) J Mol Catal A: Chem 181:25–31
Sage V, Clark JH, Macquarrie DJ (2003) J Mol Catal A: Chem 198:349–358
Kalogeras IM, Vassilikou-Dova A, Neagu ER (2001) Mater Res Innov 4:322–333
Matthias G, Wark M, Wörle D, Schulz-Ekloff G (2000) Angew Chem 112:167–170
Pan A, Zheng H, Yang Z, Liu F, Ding Z, Qian Y (2003) Mater Res Bull 38:789–796
Coradin T, Larionova J, Smith AA, Rogez G, Cléac R, Guéin C, Blondin G, Winpenny REP, Sanchez C, Mallah T (2002) Adv Mater 14:896–898
Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS (1992) Nature 359:710–712
Beck JS, Vartuli JC, Roth WJ, Leonowicz ME, Kresge CT, Schmitt KD, Chu CTW, Olson DH, Sheppard EW et al (1992) J Am Chem Soc 114:10834–10843
Ciesla U, Schueth F (1999) Microporous Mesoporous Mater 27:131–149
Corma A, Kumar D (1998) In Mesoporous molecular sieves 1998, vol 117. Elsevier Science Publ B V, Amsterdam, pp 201–222
Taguchi A, Schuth F (2005) Microporous Mesoporous Mater 77:1–45
Zhao D, Feng J, Huo Q, Melosh N, Fredrickson GH, Chmelka BF, Stucky GD (1998) Science 279:548–552
Huo Q, Margolese DI, Clesla U, Feng P, Gler TE, Sieger P, Leon R, Petroff PM, Schuth F, Stucky GD (1994) Nature 368:317–321
Tanev PT, Pinnavaia TJ (1995) Science 267:865–867
Bagshaw SA, Prouzet E, Pinnavaia TJ (1995) Science 269:1242
Tanev PT, Chibwe M, Pinnavaia TJ (1994) Nature 368:321–323
Antonelli DM, Ying JY (1995) Angew Chem (International Edition in English) 34:2014–2017
Antonelli DM, Nakahira A, Ying JY (1996) Inorg Chem 35:3126
Tian Z-R, Tong W, Wang J-Y, Duan N-G, Krishnan VV, Suib SL (1997) Science 276:926–930
Srivastava DN, Perkas N, Gedanken A, Felner I (2002) J Phys Chem B 106:1878–1883
Yuan M, Shan Z, Tian B, Tu B, Yang P, Zhao D (2005) Microporous Mesoporous Mater 78:37–41
Shyue JJ, DeGuire MR (2005) J Am Chem Soc 127:12736–12742
Perkas N, Palchik O, Brukental I, Nowik I, Gofer Y, Koltypin Y, Gedanken A (2003) J Phys Chem B 107:8772–8778
Liu Z, Zhang J, Han B, Du J, Mu T, Wang Y, Sun Z (2005) Microporous Mesoporous Mater 81:169–174
Ruckenstein E, Chao ZS (2001) Nano Lett 1:739–742
Wu G, Wang X, Chen B, Li J, Zhao N, Wei W, Sun Y (2007) Appl Catal A: Gen 329:106–111
Kruk M, Jaroniec M, Ryoo R, Joo SH (2000) J Phys Chem B 104:7960–7968
Hashimoto K, Wasada K, Osaki M, Shono E, Adachi K, Toukai N, Kominami H, Kera Y (2001) Appl Catal B: Environ 30:429–436
Buciuman FC, Patcas F, Hahn T (1999) Chem Eng Process 38:563–569
Chen H, Sayari A, Adnot A, Larachi F (2001) Appl Catal B: Environ 32:195–204
Bessell S (1993) Appl Catal A: Gen 96:253–268
Hoffmann MR, Martin ST, Choi W, Bahnemann DW (1995) Chem Rev 95:69–96
Yang Q, Choi H, Dionysiou DD (2007) Appl Catal B: Environ 74:170–178
Gracien EB, Shen J, Sun X, Liu D, Li M, Yao S, Sun J (2007) Thin Solid Films 515:5287–5297
Kazachkov SG, Chashechnikova IT, Vorotyntsev VM, Golodets GI (1989) Petrol Chem USSR 29:123–129
Sun C, Tao L, Liang H, Huang C, Zhai H, Chao Z (2006) Mater Lett 60:2115–2118
Ryoo R, Joo SH, Jun S (1999) J Phys Chem B 103(37):7743–7746
Wang Y, Chen S, Tang X, Palchik O, Zaban A, Koltypin Y, Gedanken A (2001) J Mater Chem 11:521–526
Wang Y, Tang X, Yin L, Huang W, Hacohen YR, Gedanken A (2000) Adv Mater 12:1183–1186
Barrett EP, Joyner LG, Halenda PP (1951) J Am Chem Soc 73:373–380
Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouqerol J, Siemieniewska T (1985) Pure Appl Chem 57:603–619
Kruk M, Jaroniec M (2001) Chem Mater 13:3169–3183
Brik Y, Kacimi M, Ziyad M, Bozon-Verduraz F (2001) J Catal 202:118–128
Anpo M, Takeuchi M (2003) J Catal 216:505–516
Anpo M (2004) Bull Chem Soc Japan 77:1427–1442
Iketani K, Sun R-D, Toki M, Hirota K, Yamaguchi O (2004) Mater Sci Eng B: Solid-State Mater Adv Technol 108:187–193
Martin ST, Morrison CL, Hoffmann MR (1994) J Phys Chem 98:13695–13704
Sathish M, Viswanathan B, Viswanath RP, Gopinath CS (2005) Chem Mater 17:6349–6353
Vorontsov AV, Dubovitskaya VP (2004) J Catal 221:102–109
Wu JCS, Chen C (2004) J Photochem Photobiol A: Chem 163:509–515
Nozik AJ (1993) In: Ollis DF, Al-Ekabi H (eds) Photocatalytic purification and treatment of water and Air [M]. Elsevier, Amsterdam, p 391
Martin ST, Herrmann H, Choi WY, Hoffmann MR (1994) Faraday Trans 90:3315–3323
Lever ABP (1984) Inorganic electronic spectra. Elsevier, Amsterdam, p 480
Lin J, Yu JC, Lo D, Lam SK (1999) J Catal 183:368–372
Acknowledgment
We are grateful to the financial support from the Program for New Century Excellent Talents in University, the Ministry of Education of P. R. China; and the Program for Lotus Scholar in Hunan Province, P. R. China.
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Sun, CG., Tao, L., Fan, ML. et al. Replication Route Synthesis of Mesoporous Titanium–Cobalt Oxides and Their Photocatalytic Activity in the Degradation of Methyl Orange. Catal Lett 129, 26–38 (2009). https://doi.org/10.1007/s10562-008-9835-4
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10562-008-9835-4