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Co2+ doped TiO2 nanocrystals were synthetized by a hydrothermal treatment procedure applied to precursor dispersion of titania nanotubes and Co2+ ions. Mixture of polygonal and prolate spheroid-like nanocrystals was obtained. The results of X-ray diffraction (XRD) analysis showed that resulted nanocrystals retain anatase crystal phase for both dopant concentrations (1.69 and 2.5 at%), but the crystal lattice parameters were affected. Reflection spectra revealed altered optical properties compared to bare TiO2. Room temperature ferromagnetic ordering with saturation magnetic moment in the range of 0.001-0.002 μB/Co was observed for both measured films made of Co2+ doped TiO2 nanocrystals.


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Shaped Co2+ doped TiO2 nanocrystals synthesized from nanotubular precursor: Structure and ferromagnetic behavior

Show Author's information M. VRANJEŠaJ. KULJANIN JAKOVLJEVIĆaZ. KONSTANTINOVIĆbA. POMARcM. STOILJKOVIĆaM. MITRIĆaT. RADETIĆdZ. ŠAPONJIĆa( )
Vinča Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11001 Belgrade, Serbia
Center for Solid State Physics and New Materials, Institute of Physics Belgrade, University of Belgrade, Pregrevica 118, 11080 Belgrade, Serbia
Institut de Ciència de Materials de Barcelona, CSIC, Campus UAB, 08193 Bellaterra, Spain
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade, Serbia

Abstract

Co2+ doped TiO2 nanocrystals were synthetized by a hydrothermal treatment procedure applied to precursor dispersion of titania nanotubes and Co2+ ions. Mixture of polygonal and prolate spheroid-like nanocrystals was obtained. The results of X-ray diffraction (XRD) analysis showed that resulted nanocrystals retain anatase crystal phase for both dopant concentrations (1.69 and 2.5 at%), but the crystal lattice parameters were affected. Reflection spectra revealed altered optical properties compared to bare TiO2. Room temperature ferromagnetic ordering with saturation magnetic moment in the range of 0.001-0.002 μB/Co was observed for both measured films made of Co2+ doped TiO2 nanocrystals.

Keywords:

hydrothermal synthesis, X-ray diffraction (XRD), transmission electron microscopy (TEM), doped TiO2, magnetic properties
Received: 02 January 2017 Revised: 24 April 2017 Accepted: 31 May 2017 Published: 29 September 2017 Issue date: September 2017
References(63)
[1]
R Janisch, P Gopal, NA Spaldin. Transition metal-doped TiO2 and ZnO—Present status of the field. J Phys: Condens Matter 2005, 17: R657-R689.
[2]
HH Nguyen, W Prellier, J Sakai, et al. Substrate effects on the room-temperature ferromagnetism in Co-doped TiO2 thin films grown by pulsed laser deposition. J Appl Phys 2004, 95: 7378-7380.
[3]
J-Y Kim, J-H Park, B-G Park, et al. Ferromagnetism induced by clustered Co in Co-doped anatase TiO2 thin films. Phys Rev Lett 2003, 90: 017401.
[4]
RJ Kennedy, PA Stampe, E Hu, et al. Hopping transport in TiO2:Co: A signature of multiphase behavior. Appl Phys Lett 2004, 84: 2832-2834.
[5]
NH Hong, J Sakai, W Prellier. Distribution of dopant in Fe:TiO2 and Ni:TiO2 thin films. J Magn Magn Mater 2004, 281: 347-352.
[6]
P Sharma, A Gupta, KV Rao, et al. Ferromagnetism above room temperature in bulk and transparent thin films of Mn-doped ZnO. Nat Mater 2003, 2: 673-677.
[7]
S-W Lim, M-C Jeong, M-H Ham, et al. Hole-mediated ferromagnetic properties in Zn1-xMnxO thin films. Jpn J Appl Phys 2004, 43: L280-L283.
[8]
SKS Patel, NS Gajbhiye. Room temperature magnetic properties of Cu-doped titanate, TiO2(B) and anatase nanorods synthesized by hydrothermal method. Mater Chem Phys 2012, 132: 175-179.
[9]
M Venkatesan, CB Fitzgerald, JG Lunney, et al. Anisotropic ferromagnetism in substituted zinc oxide. Phys Rev Lett 2004, 93: 177206.
[10]
L Yan, CK Ong, XS Rao. Magnetic order in Co-doped and (Mn,Co) codoped ZnO thin films by pulsed laser deposition. J App Phys 2004, 96: 508-511.
[11]
A Gupta, H Cao, K Parekh, et al. Room temperature ferromagnetism in transition metal (V, Cr, Ti) doped In2O3. J Appl Phys 2007, 101: 09N513.
[12]
XL Wang, ZX Dai, Z Zeng. Search for ferromagnetism in SnO2 doped with transition metals (V, Mn, Fe, and Co). J Phys: Condens Matter 2008, 20: 045214.
[13]
SB Ogale. Dilute doping, defects, and ferromagnetism in metal oxide systems. Adv Mater 2010, 22: 3125-3155.
[14]
JMD Coey, M Venkatesan, CB Fitzgerald. Donor impurity band exchange in dilute ferromagnetic oxides. Nat Mater 2005, 4: 173-179.
[15]
LA Errico, M Rentería, M Weissman. Theoretical study of magnetism in transition-metal-doped TiO2 and TiO2−δ. Phys Rev B 2005, 72: 184425.
[16]
B Choudhury, A Choudhury. Oxygen vacancy and dopant concentration dependent magnetic properties of Mn doped TiO2 nanoparticle. Curr Appl Phys 2013, 13: 1025-1031.
[17]
M Weissmann, LA Errico. The role of vacancies, impurities and crystal structure in the magnetic properties of TiO2. Physica B 2007, 398: 179-183.
[18]
SC Erwin, L Zu, MI Haftel, et al. Doping semiconductor nanocrystals. Nature 2005, 436: 91-94.
[19]
JD Bryan, DR Gamelin. Doped semiconductor nanocrystals: Synthesis, characterization, physical properties, and applications. Prog Inorg Chem 2005, 54: 47-126.
[20]
M Vranješ, J Kuljanin-Jakovljević, T Radetić, et al. Structure and luminescence properties of Eu3+ doped TiO2 nanocrystals and prolate nanospheroids synthesized by the hydrothermal processing. Ceram Int 2012, 38: 5629-5636.
[21]
M Vranješ, J Kuljanin-Jakovljević, SP Ahrenkiel, et al. Sm3+ doped TiO2 nanoparticles synthesized from nanotubular precursors—Luminescent and structural properties. J Lumin 2013, 143: 453-458.
[22]
M Vranješ, Z Konstatinović, A Pomar, et al. Room-temperature ferromagnetism in Ni2+ doped TiO2 nanocrystals synthesized from nanotubular precursors. J Alloys Compd 2014, 589: 42-47.
[23]
M Vranješ, J Kuljanin-Jakovljević, Z Konstatinović, et al. Room temperature ferromagnetism in Cu2+ doped TiO2 nanocrystals: The impact of their size, shape and dopant concentration. Mater Res Bull 2016, 76: 100-106.
[24]
J Kuljanin-Jakovljević, M Radoičić, T Radetić, et al. Presence of room temperature ferromagnetism in Co2+ doped TiO2 nanoparticles synthesized through shape transformation. J Phys Chem C 2009, 113: 21029-21033.
[25]
HG Yan, HC Zeng. Synthetic architectures of TiO2/H2Ti5O11·H2O, ZnO/H2Ti5O11·H2O, ZnO/TiO2/ H2Ti5O11·H2O, and ZnO/TiO2 nanocomposites. J Am Chem Soc 2005, 127: 270-278.
[26]
X Yang, C Karthik, X Li, et al. Oriented nanocrystal arrays of selectable polymorphs by chemical sculpture. Chem Mater 2009, 21: 3197-3201.
[27]
Kasuga T, Hiramatsu M, Hoson A, et al. Titania nanotubes prepared by chemical processing. Adv Mater 1999, 11: 1307-1311.10.1002/(SICI)1521-4095(199910)11:15<1307::AID-ADMA1307>3.0.CO;2-H
[28]
RW Cheary, A Coelho. A fundamental parameters approach to X-ray line-profile fitting. J Appl Cryst 1992, 25: 109-121.
[29]
HM Rietveld. A profile refinement method for nuclear and magnetic structures. J Appl Cryst 1969, 2: 65-71.
[30]
VK Pecharsky, PY Zavalij. Fundamentals of Powder Diffraction and Structural Characterization of Materials. New York: Springer, 2009.
[31]
ZV Šaponjić, NM Dimitrijević, OG Poluektov, et al. Charge separation and surface reconstruction:  A Mn2+ doping study. J Phys Chem B 2006, 110: 25441-25450.
[32]
NM Dimitrijević, ZV Šaponjić, BM Rabatić, et al. Effect of size and shape of nanocrystalline TiO2 on photogenerated charges. An EPR study. J Phys Chem C 2007, 111: 14597-14601.
[33]
AS Barnard, LA Curtiss. Prediction of TiO2 nanoparticle phase and shape transitions controlled by surface chemistry. Nano Lett 2005, 5: 1261-1266.
[34]
T Sugimoto, X Zhou. Synthesis of uniform anatase TiO2 nanoparticles by the gel-sol method: 2. Adsorption of OH− ions to Ti(OH)4 gel and TiO2 particles. J Colloid Interface Sci 2002, 252: 347-353.
[35]
T Sugimoto, X Zhou, A Muramatsu. Synthesis of uniform anatase TiO2 nanoparticles by gel-sol method: 1. Solution chemistry of Ti(OH)n(4-n)+ complexes. J Colloid Interface Sci 2002, 252: 339-346.
[36]
J-N Nian, H Teng. Hydrothermal synthesis of single-crystalline anatase TiO2 nanorods with nanotubes as the precursor. J Phys Chem B 2006, 110: 4193-4198.
[37]
BL Bischoff, MA Anderson. Peptization properties in the sol-gel preparation of porous anatase (TiO2). Chem Mater 1995, 7: 1772-1778.
[38]
DM De los Santos, J Navas, A Sánchez-Coronilla, et al. Highly Al-doped TiO2 nanoparticles produced by ball mill method: Structural and electronic characterization. Mater Res Bull 2015, 70: 704-711.
[39]
AV Delgado, F González-Caballero, RJ Hunter, et al. Measurement and interpretation of electrokinetic phenomena. J Colloid Interface Sci 2007, 309: 194-224.
[40]
MB Yahia, F Lemoigno, T Beuvier, et al. Updated references for the structural, electronic, and vibrational properties of TiO2(B) bulk using first-principles density functional theory calculations. J Chem Phys 2009, 130: 204501.
[41]
M Vranješ, ZV Šaponjić, LS Živković, et al. Elongated titania nanostructures as efficient photocatalysts fordegradation of selected herbicides. Appl Catal B: Environ 2014, 160-161: 589-596.
[42]
ZV Šaponjić, NM Dimitrijević, DM Tiede, et al. Shaping nanometer-scale architecture through surface chemistry. Adv Mater 2005, 17: 965-971.
[43]
C Khurana, OP Pandey, B Chudasama. Synthesis of visible light-responsive cobalt-doped TiO2 nanoparticles with tunable optical band gap. J Sol-Gel Sci Technol 2015, 75: 424-435.
[44]
Cobalt: Radii of atoms and ions. Available at .
[45]
M You, TG Kim, Y-M Sung. Synthesis of Cu-doped TiO2 nanorods with various aspect ratios and dopant concentracion. Cryst Growth Des 2010, 10: 983-987.
[46]
JD Lee. Concise Inorganic Chemistry. John Wiley & Sons, 2008.
[47]
B Choudhury, A Choudhury. Luminescence characteristics of cobalt doped TiO2 nanoparticles. J Lumin 2012, 132: 178-184.
[48]
S Husain, LA Alkhtaby, E Giorgetti, et al. Influence of cobalt doping on the structural, optical and luminescence properties of sol-gel derived TiO2 nanoparticles. Philos Mag A 2017, 97: 17-27.
[49]
J Tauc, R Grigorovici, A Vancu. Optical properties and electronic structure of amorphous germanium. Phys Status Solidi b 1966, 15: 627-637.
[50]
M Pal, U Pal, JMGY Jimenez, et al. Effects of crystallization and dopant concentration on the emission behavior of TiO2:Eu nanophosphors. Nanoscale Res Lett 2012, 7: 1-12.
[51]
K Das, SN Sharma, M Kumar, et al. Morphology dependent luminescence properties of Co doped TiO2 nanostructures. J Phys Chem C 2009, 113: 14783-14792.
[52]
PI Archer, SA Santangelo, DR Gamelin. Direct observation of sp-d exchange interactions in colloidal Mn2+- and Co2+-doped CdSe quantum dots. Nano Lett 2007, 7: 1037-1043.
[53]
AV Emeline, VN Kuznetsov, VK Rybchuk, et al. Visible-light-active titania photocatalysts: The case of N-doped TiO2s—Properties and some fundamental issues. International Journal of Photoenergy 2008, 2008: Article ID 258394.
[54]
Justicia I, Ordejon P, Canto G, et al. Designed self-doped titanium oxide thin films for efficient visible-light photocatalysis. Adv Mater 2002, 14: 1399-1402.10.1002/1521-4095(20021002)14:19<1399::AID-ADMA1399>3.0.CO;2-C
[55]
F Zuo, L Wang, T Wu, et al. Self-doped Ti3+ enhanced photocatalyst for hydrogen production under visible light. J Am Chem Soc 2010, 132: 11856-11857.
[56]
B Anitha, A Abdul Khadar, A Banerjee. Paramagnetic behavior of Co doped TiO2 nanocrystals controlled by self-purification mechanism. J Solid State Chem 2016, 239: 237-245.
[57]
A Punnoose, J Hays, V Shutthanandan, et al. Room-temperature ferromagnetism in chemically synthesized Sn1-xCoxO2 powders. Appl Phys Lett 2004, 85: 1559.
[58]
NA Spaldin. Magnetic Materials: Fundamentals and Applications. Cambridge University Press, 2003.
[59]
WT Geng, KS Kim. Interplay of local structure and magnetism in Co-doped TiO2 anatase. Solid State Commun 2004, 129: 741−746.
[60]
AY Yermakov, GS Zakharova, MA Uimin, et al. Surface magnetism of cobalt-doped anatase TiO2 nanopowders. J Phys Chem C 2016, 120: 28857−28866.
[61]
BM Rabatic, NM Dimitrijevic, RE Cook, et al. Spatially confined corner defects induce chemical functionality of TiO2 nanorods. Adv Mater 2006, 18: 1033−1037.
[62]
N Daude, C Gout, C Jouanin. Electronic band structure of titanium dioxide. Phys Rev B 1977, 15: 3229.
[63]
B Santara, PK Giri, K Imakita, et al. Evidence of oxygen vacancy induced room temperature ferromagnetism in solvothermally synthesized undoped TiO2 nanoribbons. Nanoscale 2013, 5: 5476−5488.
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Publication history

Received: 02 January 2017
Revised: 24 April 2017
Accepted: 31 May 2017
Published: 29 September 2017
Issue date: September 2017

Copyright

© The author(s) 2017

Acknowledgements

The financial support for this work was provided by the Ministry of Education, Science and Technological Development of Republic of Serbia (Project Nos. OI 172056 and III 45020). This work was done under umbrella of COST Action MP1106. Z. K. thanks for the support from the project III 45018 from the Ministry of Education, Science and Technological Development of Republic of Serbia. TEM characterization of titania nanotubes was provided by Prof. P. Ahrenkiel, South Dakota School of Mines & Technology, Rapid City, SD, USA.

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