Skip to main content

Nitrogen-doped titanium oxide microrods decorated with titanium oxide nanosheets for visible light photocatalysis

  • Jum Suk Jang, Eun Sun Kim (a1), Hyun Gyu Kim (a2), Sang Min Ji, Youngkwon Kim and Jae Sung Lee (a1)...

Nitrogen-doped titania with a unique two-level hierarchical structure and visible light photocatalytic activity is reported. Thus, nitrogen-doped titanium oxide microrods decorated with N-doped titanium oxide nanosheets were synthesized by a hydrothermal reaction in NH4OH and postcalcination. During the calcination, the in situ incorporation of nitrogen atoms of ammonium ion into titania lattice was accompanied by the structural evolution from titanate to anatase titania. The morphological and structural evolution was monitored by scanning electron microscopy (SEM), x-ray diffraction (XRD), thermogravimetric analysis/differential thermal analysis (TGA/DTA), Raman, Fourier transform infrared (FTIR), x-ray absorption near edge structure (XANES), x-ray photoelectron spectroscopy (XPS), and adsorption isotherms. The N-doping brought visible light absorption, and the material exhibited high photocatalytic activity in the decomposition of Orange II under visible light irradiation (λ ≥ 400 nm), especially when it was loaded with 1 wt% Pt as a cocatalyst.

Corresponding author
a)Address all correspondence to this author. e-mail:
Hide All
1.Chen, C.C., Herhold, A.B., Johnson, C.S., Alivisatos, A.P.Size dependence of structural metastability in semiconductor nanocrystals. Science 276, 398 (1997)
2.Mann, S., Ozin, G.A.Synthesis of inorganic materials with complex form. Nature 382, 313 (1996)
3.Tokudome, H., Miyauchi, M.Electrochromism of titanate-based nanotubes. Angew. Chem. Int. Ed. 44, 1974 (2005)
4.Alivisatos, A.P.Perspectives on the physical chemistry of semiconductor nanocrystals. J. Phys. Chem. 100, 13226 (1996)
5.Riss, A., Berger, T., Grothe, H., Bernardi, J., Diwald, O., Knözinger, E.Chemical control of photoexcited states in titanate nanostructures. Nano Lett. 7, 313 (2007)
6.Kasuga, T., Hiramatsu, M., Hoson, A., Sekino, T., Niihara, K.Formation of titanium oxide nanotube. Langmuir 14, 3160 (1998)
7.Sun, X., Chen, X., Li, Y.Large-scale synthesis of sodium and potassium titanate nanobelts. Inorg. Chem. 41, 4996 (2002)
8.Chen, Q., Zhou, W., Du, G., Peng, L-M.Trititanate nanotubes made via a single alkali treatment. Adv. Mater. 14, 1208 (2002)
9.Horváth, E., Kukovecz, A., Kónya, Z., Kiricsi, I.Hydrothermal conversion of self-assembled titanate nanotubes into nanowires in a revolving autoclave. Chem. Mater. 19, 927 (2007)
10.Ma, R., Fukuda, K., Sasaki, T., Osada, M., Bando, Y.Structural features of titanate nanotubes/nanobelts revealed by Raman, x-ray absorption fine structure and electron diffraction characterizations. J. Phys. Chem. B 109, 6210 (2005)
11.Du, G.H., Chen, Q., Che, R.C., Yuan, Z.Y., Peng, L-M.Preparation and structure analysis of titanium oxide nanotubes. Appl. Phys. Lett. 79, 3702 (2001)
12.Kim, J.C., Choi, J., Lee, Y.B., Hong, J.H., Lee, J.I., Yang, J.W., Lee, W.I., Hur, N.H.Enhanced photocatalytic activity in composites of TiO2 nanotubes and CdS nanoparticles. Chem. Commun. (Camb.) 5024 (2006)
13.Torrente-Murciano, L., Lapkin, A.A., Bavykin, D.V., Walsh, F.C., Wilson, K.Highly selective Pd/titanate nanotube catalysts for the double-bond migration reaction. J. Catal. 245, 272 (2007)
14.Lim, S.H., Luo, J., Zhong, Z., Ji, W., Lin, J.Room-temperature hydrogen uptake by TiO2 nanotubes. Inorg. Chem. 44, 4124 (2005)
15.Wei, M., Qi, Z-m., Ichihara, M., Honma, I., Zhou, H.Ultralong single-crystal TiO2–B nanowires: Synthesis and electrochemical measurements. Chem. Phys. Lett. 424, 316 (2006)
16.Lan, Y., Gao, X.P., Zhu, H.Y., Zheng, Z.F., Yan, T.Y., Wu, F., Ringer, S.P., Song, D.Y.Titanate nanotubes and nanorods prepared from rutile powder. Adv. Funct. Mater. 15, 1310 (2005)
17.Qamar, M., Yoon, C.R., Oh, H.J., Kim, D.H., Jho, J.H., Lee, K.S., Lee, W.J., Lee, H.G., Kim, S.J.Effect of post treatments on the structure and thermal stability of titanate nanotubes. Nanotechnology 17, 5922 (2006)
18.Morgado, E. Jr., Abreu, M.A.S., Moure, G.T., Marinkovic, B.A., Jardim, P.M., Araujo, A.S.Characterization of nanostructured titanates obtained by alkali treatment of TiO2-anatases with distinct crystal sizes. Chem. Mater. 19, 665 (2007)
19.Zhu, H.Y., Lan, Y., Gao, X.P., Ringer, S.P., Zheng, Z.F., Song, D.Y., Zhao, J.C.Phase transition between nanostructures of titanate and titanium dioxides via simple wet-chemical reactions. J. Am. Chem. Soc. 127, 6730 (2005)
20.Poudel, B., Wang, W.Z., Dames, C., Huang, J.Y., Kunwar, S., Wang, D.Z., Banerjee, D., Chen, G., Ren, Z.F.Formation of crystallized titania nanotubes and their transformation into nanowires. Nanotechnology 16, 1935 (2005)
21.Zhang, S., Peng, L-M., Chen, Q., Du, G.H., Dawson, G., Zhou, W.Z.Formation mechanism of H2Ti3O7 nanotubes. Phys. Rev. Lett. 91, 256103 (2003)
22.Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K., Taga, Y.Visible-light photocatalysis in nitrogen-doped titanium oxides. Science 293, 269 (2001)
23.Lee, J.S.Photocatalytic water splitting under visible light with particulate semiconductor catalysts. Catal. Surv. Asia 9, 217 (2006)
24.Rhee, C.H., Lee, J.S., Chung, S.H.Synthesis of nitrogen-doped titanium oxide nanostructures via a surfactant-free hydrothermal route. J. Mater. Res. 20, 3011 (2005)
25.Rhee, C.H., Bae, S.W., Lee, J.S.Template-free hydrothermal synthesis of high surface area nitrogen-doped titania photocatalyst active under visible light. Chem. Lett. 34, 660 (2005)
26.Jang, J.S., Kim, H.G., Ji, S.M., Bae, S.W., Jung, J.H., Shon, B.H., Lee, J.S.Formation of crystalline TiO2−xNx and its photocatalytic activity. J. Solid State Chem. 179, 1067 (2006)
27.Kruk, M., Jaroniec, M.Application of large pore MCM-41 molecular sieves to improve pore size analysis using nitrogen adsorption measurements. Langmuir 13, 6267 (1997)
28.Ankudinov, A.L., Bouldin, C.E., Rehr, J.J., Sims, J., Hung, H.Parallel calculation of electron multiple scattering using Lanczos algorithms. Phys. Rev. B 65, 104107 (2002)
29.Newville, M.IFEFFIT: Interactive XAFS analysis and FEFF fitting. J. Synchrotron Radiat. 8, 322 (2001)
30.Choi, S.H., Lee, J.S.XAFS characterization of Pt–Mo bimetallic catalysts for CO hydrogenation. J. Catal. 167, 364 (1997)
31.Park, E.D., Choi, S.H., Lee, J.S.Active states of Pd and Cu in carbon-supported wacker-type catalysts for low-temperature CO oxidation. J. Phys. Chem. B 104, 5586 (2000)
32.Sayer, D.E., Bunker, B.A.X-ray Absorption: Principles, Applications, Techniques of EXAFS, SEXAFS and XANES edited by D.C. Koningsberger and R. Prins (Wiley, New York 1988)211
33.Kim, W.B., Choi, S.H., Lee, J.S.Quantitative analysis of Ti–O–Si and Ti–O–Ti bonds in Ti–Si binary oxides by the linear combination of XANES. J. Phys. Chem. B 104, 8670 (2000)
34.Lee, J.S., Kim, W.B., Choi, S.H.Linear combination of XANES for quantitative analysis of Ti–Si binary oxides. J. Synchrotron Radiat. 8, 163 (2001)
35.Fukuda, K., Nakai, I., Oishi, C., Nomura, M., Harada, M., Yasuo, Y., Sasaki, T.Nanoarchitecture of semiconductor titania nanosheets revealed by polarization-dependent total reflection fluorescence x-ray absorption fine structure. J. Phys. Chem. B 108, 13088 (2004)
36.Choi, H.C., Ahn, H-J., Jung, Y.M., Lee, M.K., Shin, H.J., Kim, S.B., Sung, Y-E.Characterization of the structures of size-selected TiO2 nanoparticles using x-ray absorption spectroscopy. Appl. Spectrosc. 58, 598 (2004)
37.Sing, K.S.W., Evertt, D.H., Haul, R.A.W., Moscou, L., Pierotti, R.A., Rouquerol, J., Siemieniewska, T.Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984). Pure Appl. Chem. 57, 603 (1985)
38.Saha, N.C., Tomkins, H.G.Titanium nitride oxidation chemistry: An x-ray photoelectron spectroscopy study. J. Appl. Phys. 72, 3072 (1992)
39.Gole, J.L., Stout, J.D., Burda, C., Lou, Y., Chen, X.Highly efficient formation of visible light tunable TiO2−xNx photocatalysts and their transformation at the nanoscale. J. Phys. Chem. B 108, 1230 (2004)
40.György, E., Pérez del Pino, A.A., Serra, P., Morenza, J.L.Surface nitridation of titanium by pulsed Nd:YAG laser irradiation. Appl. Surf. Sci. 186, 130 (2002)
Recommend this journal

Email your librarian or administrator to recommend adding this journal to your organisation's collection.

Journal of Materials Research
  • ISSN: 0884-2914
  • EISSN: 2044-5326
  • URL: /core/journals/journal-of-materials-research
Please enter your name
Please enter a valid email address
Who would you like to send this to? *



Full text views

Total number of HTML views: 0
Total number of PDF views: 6 *
Loading metrics...

Abstract views

Total abstract views: 122 *
Loading metrics...

* Views captured on Cambridge Core between September 2016 - 21st March 2018. This data will be updated every 24 hours.