Abstract
The effect of protonation on the surface acidic properties of titanate nanowires (TiONWs) was investigated. Nanowires were synthesized by the alkali hydrothermal method which resulted in one dimensional nanostructures of large external surface area and well-defined lamellar interlayer structure. The Na+/H+ ratio in the structure can be tuned by ion-exchange. Our aim was to characterize the morphology of the as-synthesized nanostructures by HRTEM and SEM measurements and assess their surface acidity using in situ infrared spectroscopic measurements and temperature programmed desorption. It was found that the numbers of Lewis and Brönsted acidic sites in the Na-form and the H-form of the TiONWs is different. The ratio and the nature of acidic sites can be tuned by the ion exchange process. The wire-like morphology and the tunable acidity are features of titanate nanowires that may render them a promising material in various heterogeneous catalytic applications.
Similar content being viewed by others
References
Bezrodna, T., Puchkovska, G., Shimanovska, V., Chashechnikova, I., Khalyavka, T., Baran, J.: Pyridine–TiO2 surface interaction as a probe for surface active centers analysis. Appl. Surf. Sci. 214, 222–231 (2003)
Busca, G.: Spectroscopic characterization of the acid properties of metal oxide catalysts. Catal. Today 41, 191–206 (1998)
Byrne, M.T., McCarthy, J.E., Bent, M., Blake, R., Gunko, Y.K., Horvath, E., Konya, Z., Kukovecz, A., Kiricsi, I., Coleman, J.N.: Chemical functionalisation of titania nanotubes and their utilisation for the fabrication of reinforced polystyrene composites. J. Mater. Chem. 17, 2351–2358 (2007)
Cook, D.: Vibrational spectra of pyridinium salts. Can. J. Chem. 39, 2009–2024 (1961)
Darányi, M., Csesznok, T., Kukovecz, A., Konya, Z., Kiricsi, I., Ajayan, P.M., Vajtai, R.: Layer-by-layer assembly of TiO2 nanowire/carbon nanotube films and characterization of their photocatalytic activity. Nanotechnology 22, 195701 (2011)
Ertl, G., Knötzinger, H., Weitkamp, J.: Handbook of Heterogenous Catalysis. VCH Verlagsgesellschaf mbH, Weinheim (1997)
Gonzalez Pena, L.F., Sad, M.E., Padro, C.L., Apesteguia, C.R.: Study of the alkylation of phenol with methanol on Zn(H)-exchanged NaY zeolites. Catal. Lett. 141, 939–947 (2011)
Halász, J., Kónya, Z., Fudala, A., Béres, A., Kiricsi, I.: Indium and gallium containing ZSM-5 zeolites: acidity and catalytic activity in propane transformation. Catal. Today 31, 293–304 (1996)
Hodos, M., Horvath, E., Haspel, H., Kukovecz, A., Konya, Z., Kiricsi, I.: Photo sensitization of ion-exchangeable titanate nanotubes by CdS nanoparticles. Chem. Phys. Lett. 399, 512–515 (2004)
Hodos, M., Kónya, Z., Kiricsi, I.: Catalysis by pre-prepared platinum nanoparticles supported on trititanate nanotubes. React. Kinet. Catal. Lett. 84, 341–350 (2005)
Horváth, E., Kukovecz, A., Konya, Z., Kiricsi, I.: Hydrothermal conversion of self-assembled titanate nanotubes into nanowires in a revolving autoclave. Chem. Mater. 19, 927–931 (2007)
Kasuga, T., Hiramatsu, M., Hoson, A., Sekino, T., Nihara, K.: Formation of titanium oxide nanotubes. Langmuir 14, 3160–3163 (1998)
Kitano, M., Nakajima, K., Kondo, J.N., Hayashi, S., Hara, M.: Protonated titanate nanotubes as solid acid catalyst. J. Am. Chem. Soc. 132, 6622–6623 (2010)
Kónya, Z., Hannus, I., Kiricsi, I.: Infrared spectroscopic study of adsorption and reactions of methyl chloride on acidic, neutral and basic zeolites. Appl. Catal. B Environ. 8, 391–404 (1996)
Kukovecz, A., Hodos, M., Horvath, E., Radnoczi, G., Konya, Z., Kiricsi, I.: Oriented crystal growth model explains the formation of titania nanotubes. J. Phys. Chem. B 109, 17781–17783 (2005)
Kukovecz, A., Potari, G., Oszko, A., Konya, Z., Erdohelyi, A., Kiss, J.: Probing the interaction of Au, Rh and bimetallic Au–Rh clusters with the TiO2 nanowire and nanotube support. Surf. Sci. 605, 1048–1055 (2011)
Li, J.R., Tang, Z.L., Zhang, Z.T.: Layered hydrogen titanate nanowires with novel lithium intercalation properties. Chem. Mater. 17, 5848–5855 (2005)
Ma, R., Bando, Y., Sasaki, T.: Directly rolling nanosheets into nanotubes. J. Phys. Chem. B 108, 2115–2119 (2004)
Martra, G.: Lewis acid and base sites at the surface of microcrystalline TiO2 anatase: relationships between surface morphology and chemical behavior. Appl. Catal. A Gen. 200, 275–285 (2000)
Mor, G.K., Shankar, K., Paulose, M., Varghese, O.K., Grimes, C.A.: Enhanced photocleavage of water using titania nanotube arrays. Nano Lett. 5, 191–195 (2005)
Ohsaki, Y., Masaki, N., Kitamura, T., Wada, Y., Okamoto, T., Sekino, T., Niihara, K., Yanagida, S.: Dye-sensitized TiO2 nanotube solar cells: fabrication and electronic characterization. Phys. Chem. Chem. Phys. 7, 4157–4163 (2005)
Parry, E.P.: An infrared study of pyridine adsorbed on acidic solids. Characterization of surface acidity. J. Catal. 2, 371–379 (1963)
Peng, C.W., Richard-Plouet, M., Ke, T.Y., Lee, C.Y., Chiu, H.T., Marhic, C., Puzenat, E., Lemoigno, F., Brohan, L.: Chimie douce route to sodium hydroxo titanate nanowires with modulated structure and conversion to highly photoactive titanium dioxides. Chem. Mater. 20, 7228–7236 (2008)
Poudel, B., Wang, W., Dames, C., Huang, J., Kunwar, S., Wang, D., Barnerjee, D., Chen, G., Ren, Z.: Formation of crystallized titania nanotubes and their transformation into nanowires. Nanotechnology 16, 1935 (2005)
Sasaki, T., Ma, R., Nakano, S., Yamauchi, S., Watanabe, M.: Fabrication of titanium dioxide thin flakes and their porous aggregate. Chem. Mater. 9, 602–608 (1997)
Tsai, C., Teng, H.: Structural features of nanotubes synthesized from NaOH treatment on TiO2 with different post-treatments. Chem. Mater. 18, 367–373 (2006)
Toledo-Antonio, J.A., Cortes-Jacome, M.A., Navarrete, J., Angeles-Chavez, C., Lopez-Salinas, E., Rendon-Rivera, A.: Morphology induced CO, pyridine and lutidine adsorption sites on TiO2: Nanoparticles, nanotubes and nanofibers. Catal. Today 155, 247–254 (2010)
Toth, M., Kiss, J., Oszko, A., Potari, G., Laszlo, B., Erdohelyi, A.: Hydrogenation of carbon dioxide on Rh, Au and Au–Rh bimetallic clusters supported on titanate nanotubes, nanowires and TiO2. Top. Catal. 55, 747–756 (2012)
Wu, M.C., Hiltunen, J., Sapi, A., Avila, A., Larsson, W., Liao, H.C., Huuhtanen, M., Toth, G., Shchukarev, A., Laufer, N., Kukovecz, A., Konya, Z., Mikkola, J.P., Keiski, R., Su, W.F., Chen, Y.F., Jantunen, H., Ajayan, P.M., Vajtai, R., Kordas, K.: Nitrogen-doped anatase nanofibers decorated with noble metal nanoparticles for photocatalytic production of hydrogen. ACS Nano 5, 5025–5030 (2011)
Yang, D.J., Sarina, S., Zhu, H.Y., Liu, H.W., Zheng, Z.F., Xie, M.X., Smith, S.V., Komarneni, S.: Capture of radioactive cesium and iodide ions from water by using titanate nanofibers and nanotubes. Angew. Chem. Int. Ed. 50, 10594–10598 (2011)
Yang, D.J., Zheng, Z.F., Zhu, H.Y., Liu, H.W., Gao, X.P.: Titanate nanofibers as intelligent absorbents for the removal of radioactive ions from water. Adv. Mater. 20, 2777–2781 (2008)
Zhang, Y.Y., Fu, W.Y., Yang, H.B., Li, M.H., Li, Y.X., Zhao, W.Y., Sun, P., Yuan, M.X., Ma, D., Liu, B.B., Zou, G.T.: A novel humidity sensor based on Na2Ti3O7 nanowires with rapid response-recovery. Sens. Actuators B Chem. 135, 317–321 (2008)
Zhao, B., Chen, F., Liu, H., Zhang, J.: Mesoporous TiO2-B nanowires synthesized from tetrabutyl titanate. J. Phys. Chem. Solids 72, 201–206 (2011)
Zhu, G.N., Wang, Y.G., Xia, Y.Y.: Ti-based compounds as anode materials for Li-ion batteries. Energy Environ. Sci. 5, 6652–6667 (2012)
Acknowledgments
The financial support of the TÁMOP-4.2.2.A-11/1/KONV-2012-0047 and TÁMOP-4.2.2.A-11/1/KONV-2012-0060 projects and the EC FP7 INCO “NAPEP” network is acknowledged.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Madarász, D., Szenti, I., Nagy, L. et al. Fine tuning the surface acidity of titanate nanostructures. Adsorption 19, 695–700 (2013). https://doi.org/10.1007/s10450-013-9494-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10450-013-9494-7