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Vol. 8 No. 1 (2016)

Room-Temperature Magnetism of Ceria Nanocubes by Inductively Transferring Electrons to Ce Atoms from Nearby Oxygen Vacancy

https://doi.org/10.1007/s40820-015-0056-2
Yue Kang
Department of Applied Physics, Chongqing University, Chongqing 400044, People’s Republic of China
Qiang Leng
Department of Applied Physics, Chongqing University, Chongqing 400044, People’s Republic of China
Donglin Guo
Department of Applied Physics, Chongqing University, Chongqing 400044, People’s Republic of China
Dezhi Yang
Department of Applied Physics, Chongqing University, Chongqing 400044, People’s Republic of China
Yanping Pu
School of Public Affairs, Chongqing University, Chongqing 400044, People’s Republic of China
Chenguo Hu
Department of Applied Physics, Chongqing University, Chongqing 400044, People’s Republic of China

Corresponding Author: Chenguo Hu

hucg@cqu.edu.cn

Nano-Micro Letters, Vol. 8 No. 1 (2016), Article Number: 13-19

Abstract

Ceria (CeO2) nanocubes were synthesized by a hydrothermal method and weak ferromagnetism was observed in room temperature. After ultraviolet irradiation, the saturation magnetization was significantly enhanced from ~3.18 × 10−3 to ~1.89 × 10−2 emu g−1. This is due to the increase of oxygen vacancies in CeO2 structure which was confirmed by X-ray photoelectron spectra. The first-principle calculation with Vienna ab-initio simulation package was used to illustrate the enhanced ferromagnetism mechanism after calculating the density of states (DOSs) and partial density of states (PDOSs) of CeO2 without and with different oxygen vacancies. It was found that the increase of oxygen vacancies will enlarge the PDOSs of Ce 4f orbital and DOSs. Two electrons in one oxygen vacancy are respectively excited to 4f orbital of two Ce atoms neighboring the vacancy, making these electron spin directions on 4f orbitals of these two Ce atoms parallel. This superexchange interaction leads to the formation of ferromagnetism in CeO2 at room temperature. Our work indicates that ultraviolet irradiation is an effective method to enhance the magnetism of CeO2 nanocube, and the first-principle calculation can understand well the enhanced magnetism.

Keywords

UV irradiation Oxygen vacancies Saturation magnetism Spin direction Superexchange interaction
Kang, Yue, Qiang Leng, Donglin Guo, Dezhi Yang, Yanping Pu, and Chenguo Hu. 2015. “Room-Temperature Magnetism of Ceria Nanocubes by Inductively Transferring Electrons to Ce Atoms from Nearby Oxygen Vacancy”. Nano-Micro Letters 8 (1):13-19. https://doi.org/10.1007/s40820-015-0056-2.
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References
  1. X.L. Wang, S.Z. Yi, E.W. Liang, Y.Y. Wu, Z.X. Fang, Study on preparation of polishing powder for LCD. Adv. Mater. Res. 785–786, 480–483 (2013). doi:10.4028/www.scientific.net/AMR.785-786.480
  2. Y. Chen, Z.N. Li, N.M. Miao, Polymethylmethacrylate (PMMA)/CeO2 hybrid particles for enhanced chemical mechanical polishing performance. Tribol. Int. 82, 211–217 (2015). doi:10.1016/j.triboint.2014.10.013
  3. M. Ozawa, Role of cerium-zirconium mixed oxides as catalysts for car pollution: a short review. J. Alloy. Compd. 275, 886–890 (1998). doi:10.1016/S0925-8388(98)00477-0
  4. S.Y. Christou, S. Garacia-Rodriguez, J.L.G. Fierro, A.M. Efstathiou, Deactivation of Pd/Ce0.5Zr0.5O2 model three-way catalyst by P, Ca and Zn deposition. Appl. Catal. B: Environ. 111, 233–245 (2012). doi:10.1016/j.apcatb.2011.10.004
  5. Z.X. Yang, X.H. Yu, Z.S. Lu, S.F. Li, K. Hermansson, Oxygen vacancy pairs on CeO2 (110): a DFT+U study. Phys. Lett. A 373(31), 2786–2792 (2009). doi:10.1016/j.physleta.2009.05.055
  6. K.C. Anjaneya, G.P. Nayaka, J. Manjanna, G. Govindaraj, K.N. Ganesha, Preparation and characterization of Ce1-xGdxO2-delta (x = 0.1–0.3) as solid electrolyte for intermediate temperature SOFC. J. Alloy. Compd. 578, 53–59 (2013). doi:10.1016/j.jallcom.2013.05.010
  7. E. Bekyarova, P. Fornasiero, J. Kaspar, M. Graziani, CO oxidation on Pd/CeO2-ZrO2 catalysts. Catal. Today 45(1–4), 179–183 (1998). doi:10.1016/S0920-5861(98)00212-0
  8. H. Yahiro, Y. Baba, K. Eguchi, H. Arai, High-temperature fuel-cell with ceria-yttria solid electrolyte. J. Electrochem. Soc. 135(8), 2077–2080 (1988). doi:10.1149/1.2096212
  9. M.F. Al-Kuhaili, S.M.A. Durrani, I.A. Bakhtiari, Carbon monoxide gas-sensing of CeO2-ZnO thin films. Appl. Surf. Sci. 255(5), 3033–3039 (2008). doi:10.1016/j.apsusc.2008.08.058
  10. B. Choudhury, A. Choudhury, Ce3+ and oxygen vacancy mediated tuning of structural and optical properties of CeO2 nanoparticles. Mater. Chem. Phys. 131(3), 666–671 (2012). doi:10.1016/j.matchemphys.2011.10.032
  11. Y. Taga, Recent progress in coating technology for surface modification of automotive glass. J. Non-Cryst. Solids 218, 335–341 (1997). doi:10.1016/S0022-3093(97)00281-0
  12. S. Zec, S. Boskovic, B. Kaluderovic, Z. Bogdanov, N. Popovic, Chemical reduction of nanocrystalline CeO2. Ceram. Int. 35(1), 195–198 (2009). doi:10.1016/j.ceramint.2007.10.031
  13. L. Zhang, H. Jiang, M. Selke, X.M. Wang, Selective cytotoxicity effect of cerium oxide nanoparticles under UV irradiation. J. Biomed. Nanotechnol. 10(2), 278–286 (2014). doi:10.1166/jbn.2014.1790
  14. R. Si, M. Flytzani-Stephanopoulos, Shape and crystal-plane effects of nanoscale ceria on the activity of Au-CeO2 catalysts for the water-gas shift reaction. Angew. Chem. Int. Edit. 47(15), 2884–2887 (2008). doi:10.1002/anie.200705828
  15. N. Izu, S. Nishizaki, T. Itoh, M. Nishibori, W. Shin, I. Matsubara, Gas response, response time and selectivity of a resistive CO sensor based on two connected CeO2 thick films with various particles sizes. Sens. Actuators B 136(2), 364–370 (2009). doi:10.1016/j.snb.2008.12.018
  16. M. Nolan, Hybrid density functional theory description of oxygen vacancies in the CeO2 (110) and (100). Chem. Phys. Lett. 499(1–3), 126–130 (2010). doi:10.1016/j.cplett.2010.09.016
  17. X.P. Han, J.C. Lee, H.I. Yoo, Oxygen-vacancy-induced ferromagnetism in CeO2 from first principles. Phys. Rev. B 79(10), 100403 (2009). doi:10.1103/PhysRevB.79.100403
  18. S. Phokha, S. Pinitsoontorn, S. Maensiri, Structure and magnetic properties of monodisperse Fe3+-doped CeO2 nanospheres. Nano-Micro Lett. 5(4), 223–233 (2013). doi:10.5101/nml.v5i4.p223-233
  19. M.S. Si, D.Q. Gao, D.Z. Yang, Y. Peng, Z.Y. Zhang, D.S. Xue, Y.S. Liu, X.H. Deng, G.P. Zhang, Intrinsic ferromagnetism in hexagonal boron nitride nanosheets. J. Chem. Phys. 140, 204701 (2014). doi:10.1063/1.4879055
  20. C. Klein, R. Ramchal, A.K. Schmid, M. Farle, Controlling the kinetic order of spin-reorientation transitions in Ni/Cu(100) films by tuning the substrate step structure. Phys. Rev. B 75, 193405 (2007). doi:10.1103/PhysRevB.75.193405
  21. S. Qin, D. Liu, Z. Zuo, Y. Sang, H. Liu, UV-irradiation-enhanced ferromagnetism in BaTiO3. J. Phys. Chem. Lett. 1(1), 238–241 (2010). doi:10.1021/jz900131x
  22. L. Feng, D.T. Hoang, C.K. Tsung, W.Y. Huang, S.H.Y. Lo, J.B. Wood, H. Wang, J.Y. Tang, P.D. Yang, Catalytic properties of Pt cluster-decorated CeO2 nanostructures. Nano Res. 4(1), 61–71 (2011). doi:10.1007/s12274-010-0042-4
  23. G. Kresse, J. Furthmuller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54(16), 11169–11186 (1996). doi:10.1103/PhysRevB.54.11169
  24. D.A. Andersson, S.I. Simak, N.V. Skorodumova, I.A. Abrikosov, B. Johansson, Theoretical study of CeO2 doped with tetravalent ions. Phys. Rev. B 76(17), 174119 (2007). doi:10.1103/PhysRevB.76.174119
  25. M. Nolan, S.C. Parker, G.W. Watson, The electron structure of oxygen vacancy defects at the low index surfaces of ceria. Surf. Sci. 595(1–3), 223–232 (2005). doi:10.1016/j.susc.2005.08.015
  26. C. Loschen, J. Carrasco, K.M. Neyman, F. Illas, First-principles LDA+U and GGA+U study of cerium oxides: dependence on the effective U parameter. Phys. Rev. B 75, 035115 (2007). doi:10.1103/PhysRevB.75.035115
  27. J. Li, Z. Chen, X.X. Wang, D.M. Proderpio, A novel two-dimensional mercury antimony telluride: low temperature synthesis and characterization of RbHgSbTe3. J. Alloys Compd. 262, 28–33 (1997). doi:10.1016/S0925-8388(97)00324-1
  28. J. Xu, C.G. Hu, Y. Xi, C. Peng, B.Y. Wan, X.S. He, Synthesis, photoluminescence and magnetic properties of barium vanadate nanoflowers. Mater. Res. Bull. 46(6), 946–950 (2011). doi:10.1016/j.materresbull.2011.02.023
  29. X.A. Huang, D. Kocaefe, Y. Kocaefe, Y. Boluk, A. Pichette, A spectrocolorimetric and chemical study on color modification of heat-treated wood during artificial weathering. Appl. Surf. Sci. 258(14), 5360–5369 (2012). doi:10.1016/j.apsusc.2012.02.005
  30. D.C. Cronemeyer, Infrared absorption of reduced rutile TiO2 single crystals. Phys. Rev. 113(5), 1222–1226 (1959). doi:10.1103/PhysRev.113.1222
  31. D.L. Guo, C.G. Hu, Y. Xi, UV-irradiation-enhanced ferromagnetism of barium vanadate (Ba3V2O8) nanoflowers. J. Alloy. Compd. 550, 389–394 (2013). doi:10.1016/j.jallcom.2012.10.152
  32. X.H. Lu, X. Huang, S.L. Xie, D.Z. Zheng, Z.Q. Liu, C.L. Liang, Y.X. Tong, Facile electrochemical synthesis of single crystalline CeO2 octahedrons and their optical properties. Langmuir 26(10), 7569–7573 (2010). doi:10.1021/la904882t
  33. A. Arumugam, C. Karthikeyan, A.S.H. Hameed, K. Gopinath, S. Gowri, V. Karthika, Synthesis of cerium oxide nanoparticles using Gloriosa superba L. leaf extract and their structural, optical and antibacterial properties. Mater. Sci. Eng. C 49, 408–415 (2015). doi:10.1016/j.msec.2015.01.042
  34. L.N. Wang, F.M. Meng, Oxygen vacancy and Ce3+ ion dependent magnetism of monocrystal CeO2 nanopoles synthesized by a facile hydrothermal method. Mater. Res. Bull. 48(9), 3492–3498 (2013). doi:10.1016/j.materresbull.2013.05.036
  35. Z. Zhang, C. Hu, M. Hashim, P. Chen, Y. Xiong, C. Zhang, Synthesis and magnetic properties of FeMoO4 nanorods. Mater. Sci. Eng. B 176(9), 756–761 (2011). doi:10.1016/j.mseb.2011.02.018
  36. X.Y. Wu, J. Du, H.B. Li, M.F. Zhang, B.J. Fan, Y.C. Zhu, Y.T. Qian, Aqueous mineralization process to synthesize uniform shuttle-like BaMoO4 microcrystals at room temperature. J. Solid State Chem. 180(11), 3288–3295 (2007). doi:10.1016/j.jssc.2007.07.010
  37. G. Kresse, D. Joubert, From ultrasoft pseudopotential to the projector augmented-wave method. Phys. Rev. B 59(3), 1758–1775 (1999). doi:10.1103/PhysRevB.59.1758
  38. J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple. Phys. Rev. Lett. 77(18), 3865–3868 (1996). doi:10.1103/PhysRevLett.77.386
  39. J.B. Goodenough, Magnetism and the Chemical Bond (Interscience, New York, 1963)
  40. S. Yamanaka, K. Koizumi, Y. Kitagawa, T. Kawakami, M. Okumura, K. Yamaguchi, Chemical bonding, less screening, and Hund’s rule revisted. Int. J. Quantum Chem. 105(6), 687–700 (2005). doi:10.1002/qua.20784
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