You are on page 1of 4

Solid State Sciences 11 (2009) 20562059

Contents lists available at ScienceDirect

Solid State Sciences


journal homepage: www.elsevier.com/locate/ssscie

Morphology manipulation of a-Fe2O3 in the mixed solvent system


Ranbo Yu a, *, Zhenmin Li b, Dan Wang b, Xiaoyong Lai b, Chaojian Xing b, Xianran Xing a
a b

Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, China State Key Laboratory of Multi-phase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, PR China

a r t i c l e i n f o
Article history: Received 23 June 2009 Received in revised form 1 September 2009 Accepted 4 September 2009 Available online 11 September 2009 Keywords: Hematite Solvent effect Morphology Nanostructure

a b s t r a c t
By using simple mixed solvents, the morphologies of hematite (a-Fe2O3) particles could be manipulated, and the spherical, mulberry-like, nanospherical and top-like products could be controllably obtained. The as-obtained products were characterized by X-ray diffraction, scanning electron microscopy, and vibrating sample magnetometer. The results indicated that the morphology manipulation could be achieved by systematically adjusting the polarity of the mixed solvent via the ratio control. And the magnetic properties of the products were critically affected by their grain size and assembly morphologies. 2009 Elsevier Masson SAS. All rights reserved.

1. Introduction Inorganic nanomaterials of uniform size and shape are of special interest from both theoretical and practical perspectives [13]. To systematically manipulate the shapes of inorganic compounds would greatly benet various elds, including optics, electronics, magnetic, catalysis, and medicine [47]. However, the existing methods for size and shape control generally employ capping agents, such as surfactants, ligands, polymers, or dendrimers, to conne the growth in the nanometre regime [811]. Hematite (a-Fe2O3) is a n-type semiconductor with optical bandgap (Eg) of 2.1 eV and possesses extensive applications in magnetic devices, pigments, catalysts, gas sensors, photoanodes for photo-oxidation of water and photocatalytic oxidation [1220]. Its shape and size effect on corresponding properties has attracted much attention. A number of earlier reports have dealt with the formation of different nano and microstructures of a-Fe2O3. Usually the a-Fe2O3 nanorods were prepared by calcining or annealing the rod-like a-FeOOH or b-FeOOH precursors obtained via hydrothermal treatment of ferric solution or Fe(OH)3 [2131], or prepared via directly hydrothermal treatment of the FeCl3 in the presence of surfactant [32,33]. Vertically aligned nanobelt and nanowire arrays of a-Fe2O3 were synthesized by direct thermal oxidation of iron substrates under the ow of O2 [34]. To realize facial shape and size control of a-Fe2O3, a number of template-free

syntheses have been attempted, and some unique morphologies of

a-Fe2O3 have been obtained, such as single-crystalline nanotubes


[35], air-like nanostructures [36], cantaloupe-like and urchin-like

a-Fe2O3 [37,38]. For the morphology control in solutions, solvent


effect is no doubt an important factor. However, so far systematical investigation of the morphology manipulation from the view point of solvent is still few. In this paper, by adjusting the type and ratio of the organic solvents, uniform a-Fe2O3 nano and microstructures with morphologies including sphere, mulberry, nanosphere and top could be selectively synthesized. Moreover, with the morphology control, the corresponding magnetic performance of these products could be adjusted.

2. Experimental section 2.1. Synthesis All chemicals were analytical grade and used as received. All aqueous solutions were prepared with deionized water. Water, n-octylamine, ethylamine, and ethanol were used as solvents, either separately or as a mixture taken in a particular ratio (Table 1). In a typical procedure for synthesis of a-Fe2O3 nanocubes, 8 mmol of FeCl3$6H2O were dissolved in 8 ml of H2O under stirring, followed by adding 6 ml of octylamine. And then the mixture was stirring for 20 min to get the homogeneous solution, which was transferred into a 20 mL Teon-lined stainless-steel autoclave and heated at 180  C for 20 h. After the autoclave had cooled down to

* Corresponding author. Tel./fax: 86 10 62332525. E-mail address: ranboyu@metall.ustb.edu.cn (R. Yu). 1293-2558/$ see front matter 2009 Elsevier Masson SAS. All rights reserved. doi:10.1016/j.solidstatesciences.2009.09.009

R. Yu et al. / Solid State Sciences 11 (2009) 20562059 Table 1 Synthesis conditions and morphologies of a-Fe2O3 samples. Sample Solvent(s) A1 A2 A3 A4 A5 A6 A7 A8 Water Water:n-octylamine Water:n-octylamine Water:n-octylamine:ethanol Water:1,2-propanediamine: ethanol Water:ethylamine Water:ethylamine Water:ethylamine Volume ratio 13:1 8:6 7:3.5:3.5 7:3.5:3.5 12:2 7:7 2:12 Product morphology Sphere-like nanostructures Ellipsoidal nanostructures Nanoparticles Sphere-like nanostructures Mulberry-like nanostructures Sphere-like nanostructures Top-like nanoparticles Top-like nanoparticles

2057

room temperature naturally, the precipitate was separated by ltration, washed with deionized water and absolute ethanol, and dried in air at 60  C. 2.2. Characterization The powder X-ray diffraction (XRD) patterns were recorded on the XPert PRO MPD diffractometer (Cu Ka (l 1.5405 ) radiation, operated with 30 mA and 40 kV). Scanning electron microscopy (SEM) images were obtained with a JSM-6700 operating at 5.0 kV. The magnetic properties of a-Fe2O3 samples were measured using a vibrating sample magnetometer (LakeShore 7410). 3. Results and discussion The composition and phase purity of the as-prepared products were examined by XRD (Fig. 1). From the XRD patterns of samples obtained under different reaction conditions, it can be seen that the XRD patterns of all samples are in conformity with that of rhombohedral a-Fe2O3 (a 5.0356 and c 13.7489 ) [JCPDS 33-0664]. The morphologies of the as-synthesized products were examined by FE-SEM. For water/n-octylamine system, when there was no addition of n-octylamine the micro-scale sphere-like particles

Fig. 1. XRD patterns the as-prepared a-Fe2O3 samples A2, A3, A4 and A5.

assembled by numerous nanoparticles were obtained (Fig. 2a). Along with the amount increase of n-octylamine, it is observed that the assemblies of a-Fe2O3 nanoparticles tend to be looser. Fig. 2b and c showed the FE-SEM images of samples prepared in mixed solvents of water and n-octylamine. When the water/n-octylamine volume ratio was 13:1, micro-scale hollow ellipsoidal spheres were obtained (Fig. 2c), which were composed of nanoparticles with average size of 50 nm (Fig. 2d). Further decrease the water/noctylamine volume ratio to 8:6, the products appeared to be uniform a-Fe2O3 nanospheres with diameter of about 50 nm. It is conceivable that n-octylamine is benet for the dispersion of a-Fe2O3 nanoparticles in water, and by adjusting the ratio and reciprocity of water and n-octylamine the morphology variation of the a-Fe2O3 assemblies might be realized. To adjust the reciprocity of water and n-octylamine, ethanol was added to the water/n-octylamine system, uniform sphere-like nanostructures of a-Fe2O3 with diameter of 2.3 mm were synthesized (Fig. 2e). When the n-octylamine was changed into 1,2-propanediamine, the uniform mulberry-like nanostructures with

Fig. 2. FE-SEM images of a-Fe2O3 samples: (a) sphere-like particles of sample A1; (b) low magnication and (c) high magnication images of ellipsoidal particles of a-Fe2O3 samples A2; (d) nanospheres of sample A3; (e) sphere-like nanostructures synthesized in a solvent of water, n-octylamine and ethanol (sample A4) and (f) mulberry-like nanostructures synthesized in a solvent of water, 1,2-propanediamine and ethanol (sample A5).

2058

R. Yu et al. / Solid State Sciences 11 (2009) 20562059

Fig. 3. Images of a-Fe2O3 samples obtained in the mixed solvent of water and ethylamine: (a) A6; (b) A7; (c) A8.

a diameter of 400 nm and a length of 1.2 mm could be synthesized, which was composed of numerous nanoparticles of 100 nm (Fig. 2f). For the water/ethylamine system, similar results were observed. Fig. 3 shows the image of products obtained in the solvent composed of water and ethylamine. In this system, the water/ethylamine ratio was also found to be important factors to inuence the morphology variation of the products. When the water/ethylamine ratio was 12/2, the product was composed of micro-scale sphere-like particles (Fig. 3). As shown in Fig. 3b and c, when the water/ethylamine ratio decreased to 7/7 and 2/12, top-like nanoparticles about 100 nm were obtained. The coercivity and other magnetic properties such as ferromagnetism carry a direct relationship with the crystallite shapes and sizes [39]. In this work, the shape- and size-dependent coercive nature of a-Fe2O3 samples at room temperature was studied. The results indicated that the size as well as the shape of the particles

could modify the magnetic properties of a-Fe2O3. The hysteresis loops for samples A2, A3, A4, and A5 are measured and shown in Fig. 4. It can be seen that saturation is not reached up to the maximum in applied magnetic eld. Except for the nanospherical sample A3 (average size 60 nm), the other three samples are all nanostructures assembled by a-Fe2O3 nanoparticles of 6080 nm. It is observed that the coercivity of A3 is obviously lower than those of the other three samples, which might implied that the assembly of a-Fe2O3 into uniform nanostructures may enhance the magnetic coercivity. According to the increase in the coercivity the three nanostructures can be put in the order of A5 < A2 < A4. The increase in coercivity may have occurred because of higher shape and magnetocrystalline anisotropy [40]. With higher shape anisotropy, where magnetic spins are preferentially aligned along the long axis and their reversal to the opposite direction required higher energies than that for the spheres or slightly elongated particles.

Fig. 4. The room temperature shape-dependent hysteresis measurement of a-Fe2O3 samples A2, A3, A4 and A5.

R. Yu et al. / Solid State Sciences 11 (2009) 20562059

2059

4. Conclusion In summary, we have synthesized a-Fe2O3 in its various nano and microstructural formations and studied its shape- and sizedependent magnetic properties. The morphology evolution of aFe2O3 is dependent on the nature of the solvent. The coercivity and remanence were found to be dependent on the shape and size of the samples. Acknowledgements The authors are thankful for the nancial support from the National Natural Science Foundation of China (No. 20871015 and 20401015), Program for New Century Excellent Talents in University (NCET), Beijing Natural Science Foundation (No. 2092019 and 2082022), and GF Fundamental Research Foundation (A1320070102). References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] M.A. El-Sayed, Acc. Chem. Res. 34 (2001) 257. A.P. Alivisatos, Science 271 (1996) 933. X.H. Zhong, Y.Y. Feng, W.G. Knoll, M.Y. Han, J. Am.Chem. Soc. 125 (2003) 13559. F.E. Favier, C.M. Walter, P. Zach, T. Benter, R.M. Penner, Science 293 (2001) 2227. S. Mann, G.A. Ozin, Nature 382 (1996) 313. H. Yang, N. Coombs, G.A. Ozin, Nature 386 (1997) 692. F. Caruso, R.A. Caruso, H. Mohnwald, Science 282 (1998) 1111. G. Frens, Nature 241 (1973) 20. D.G. Duff, A. Baiker, P.P. Edwards, Langmuir 9 (1993) 2301. M.T. Reetz, W. Helbig, J. Am. Chem. Soc. 116 (1994) 7401. D.V. Leff, P.C. Ohara, J.R. Heath, W.M.J. Gelbart, Phys.Chem. 99 (1995) 7036. K. Siroky, J. Jiresova, L. Hudec, Thin Solid Films 245 (1994) 211. J.H. Kennedy, K.W. Frese, J. Electrochem. Soc. 125 (1978) 709.

[14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] [40]

J. Moser, M. Gratzel, Nature 353 (1991) 737. B.C. Faust, M.R. Hoffmann, D.W. Bahnemann, J. Phys. Chem. 93 (1989) 6371. M. Fukazawa, H. Matuzaki, K. Hara, Sensor. Actuator. B 13 (1993) 521. E. Comini, V. Guidi, C. Frigeri, I. Ricco, G. Sberveglieri, Sensor. Actuator. B 77 (2001) 16. T. Ohmori, H. Takahashi, H. Mametsuka, E. Suzuki, Phys. Chem. Chem. Phys. 2 (2000) 3519. S.N. Frank, A.J. Bard, J. Phys. Chem. 81 (1977) 1484. J.W. Gues, Appl. Catal 25 (1986) 313. C.Z. Wu, P. Yin, X. Zhu, C.Z. OuYang, Y. Xie, J. Phys. Chem. B 110 (2006) 17806. S.Y. Zeng, K.B. Tang, T.W. Li, J. Colloid Interface Sci. 312 (2007) 513. B. Tang, G.L. Wang, L.H. Zhuo, J.C. Ge, L. Cui, J. Inorg. Chem. 45 (2006) 5196. L. Vayssieres, N. Beermann, S.E. Lindquist, A. Hagfeldt, Chem. Mater 13 (2001) 233. P.C. Wu, W.S. Wang, Y.T. Huang, H.S. Sheu, Y.W. Lo, T.L. Tsai, D.B. Shieh, C.S. Yeh, J. Chem. Eur. 13 (2007) 3878. X. Wang, X.Y. Chen, L.S. Gao, H.G. Zheng, M.R. Ji, C.M. Tang, T. Shen, Z.D. Zhang, J. Mater. Chem. 14 (2004) 905. B. Baruwati, R.K. Madhusudan, S.V. Manorama, J. Am. Ceram. Soc. 89 (2006) 2602. S.Y. Lian, E. Wang, Z.H. Kang, Y.P. Bai, L. Gao, M. Jiang, C.W. Hu, L. Xu, Solid State Commun. 129 (2004) 485. B.D. Mao, Z.H. Kang, E.B. Wang, C.G. Tian, Z.M. Zhang, C.L. Wang, S.H. Li, Chem. Lett. 36 (2007) 70. Z.Y. Zhong, J.D. Ho, J. Teo, S.C. Shen, A. Gedanken, Chem. Mater 19 (2007) 4776. Z.Y. Zhong, M. Lin, V. Ng, G.X. Boon Ng, Y.L. Foo, A. Gedanken, Chem. Mater 18 (2006) 6031. Z. Pu1, M.H. Cao, J. Yang, K.L. Huang, C.W. Hu, Nanotechnology 17 (2006) 799. L. Liu, H.Z. Kou, W.L. Mo, H.J. Liu, Y.Q. Wang, J. Phys. Chem. B 110 (2006) 15218. X.G. Wen, S.H. Wang, Y. Ding, Z.L. Wang, S.H. Yang, J. Phys. Chem. B 109 (2005) 215. C.J. Jia, L.D. Sun, Z.G. Yan, L.P. You, F. Luo, X.D. Han, Y.C. Pang, Z. Zhang, C.H. Yan, Angew. Chem. Int. Ed. 44 (2005) 4328. S.Z. Li, H. Zhang, J.B. Wu, X.Y. Ma, D. Yang, Cryst. Growth Des. 6 (2006) 351. L.P. Zhu, H.M. Xiao, S.Y. Fu, Cryst. Growth Des. 7 (2007) 177. L.P. Zhu, H.M. Xiao, X.M. Liu, S.Y. Fu, J. Mater.Chem. 16 (2006) 1794. M. Sorescu, R.A. Brand, D.M. Tarabasanu, L. Diamandescu, J. Appl. Phys. 85 (1999) 5546. B. Tang, G. Wang, L. Zhuo, J. Ge, L. Cui, Inorg. Chem. 45 (2006) 5196.

You might also like