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Materials Letters 62 (2008) 1403 1405 www.elsevier.com/locate/matlet

Synthesis of CoFe2O4 nanotube arrays through an improved solgel template approach

Yan Xu, Jie Wei, Jinli Yao, Junli Fu, Desheng Xue
Key Laboratory for Magnetism and Magnetic Materials of MOE, Lanzhou University, Lanzhou 730000, PR China Received 29 November 2006; accepted 23 August 2007 Available online 29 August 2007

Abstract Self-organized and ordered CoFe2O4 nanotube arrays were prepared in porous anodic aluminum oxide template using an improved solgel approach. The attraction between the negatively charged sol particles and the positively charged pore wall of AAO is the causation of tube formation process. The morphology was studied by transmission electron and high-resolution field emission scanning electron microscope. A polycrystalline phase of the nanotube was found by X-ray and select area electron diffraction. Magnetic measurements showed that the magnetic orientation was weak in the arrays of nanotube, and the reason has been discussed. 2007 Published by Elsevier B.V.
Keywords: Nanotube; CoFe2O4; Solgel; Array; Surfactant

1. Introduction Recently, one-dimensional or quasi-one-dimensional nanostructural materials have attracted much interest due to their enriched properties and potential applications in optics and electronics, [1,2]. Plenty of effort has been expended on the synthesis of nanoscale materials. Up to now, some inorganic nanotubes such as sulfides, nitrides and oxides have been fabricated [38]. Among the different preparation procedures, the most widespread is the template method [9,10]. Compared with other templates [11], anodic aluminum oxide (AAO) template is ideal for preparing ordered nanotube arrays by using solgel method because of its uniform and nearly parallel porous structures with positive charge [22]. Nanostructure Co-ferrite materials have shown promising properties for hard-magnetic applications because of their high coercivity [12,13]. Though there are numerous publications about particles [14,15] and films [16,17] of Co-ferrite, few CoFe2O4 nanotube array studies have been reported. Keller et al [18] have synthesized CoFe2O4 nanowires inside carbon
Corresponding author. E-mail addresses: xuyan04@lzu.cn (Y. Xu), weij2005@st.lzu.edu.cn (J. Wei), aaaajl02@st.lzu.edu.cn (J. Yao), fujl03@st.lzu.edu.cn (J. Fu), xueds@lzu.edu.cn (D. Xue). 0167-577X/$ - see front matter 2007 Published by Elsevier B.V. doi:10.1016/j.matlet.2007.08.066

nanotubes under mild reaction conditions using the confinement effect provided by the carbon tubular template. Ji et al [19] have combined the concept of solgel synthesis and template preparation of nanowires to fabricate CoFe2O4 nanowire arrays. In a traditional solgel template process, the only driving force is capillary action. If a higher-concentration sol is used, filling the pores will be difficult. In the present work, CoFe2O4 nanotube arrays have been synthesized through an improved solgel

Fig. 1. SEM image of CoFe2O4 nanotube arrays.

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Fig. 2. X-ray diffraction pattern of the CoFe2O4 nanotube arrays annealed at 600 C.

template method, which can overcome these limitations to a certain extent. 2. Experiment The AAO templates were prepared through two anodizing steps as reported previously [20]. It was found that the nanopores in the template are uniform and ordered with a 50 nm mean diameter. The precursor solution was prepared as follows: Fe(NO3)3 and Co(NO3)2 with a molar ratio of 2:1 were dissolved in distilled water to form 0.09 M aqueous solution of nitrate. An amount of citric acid equal to NO3 was dissolved in the mixture solution as a surfactant. The pH value of the solution was adjusted to near 7 using ammonia, and then urea was added into the solution, the molar ratio of metal and urea was 1:10. All chemicals were of analytical grade and were used without further purification. The precursor of CoFe2O4 was immersed into the AAO template with the solution for 10 h at 80 C. Subsequently, the AAO templates were taken out and placed into saturated HgCl2 solution to separate templates from the Al substrate. After rinsing with distilled water, the precursor of CoFe2O4 in template was heat treated in a tube furnace, and

the arrays of CoFe2O4 nanotube inside the AAO templates were obtained at 600 C for 10 h in air. In order to avoid the precipitation of Fe(OH)3 and Co(OH)2 in our experiments, an improved solgel approach was used. We dissolved citric acid in the mixture solution to keep the solution from precipitating. Here citric acid was used as a surfactant. When the solution was heated, the pH value of the solution increased because of urea undergoing hydrolysis above 60 C, the OH combined with Fe3+ and Co2+ formed negatively charged Fe [(OH)x](H2O)y and Co[(OH)x](H2O)y sol, which is similar to one resultant of hydrolyzation [21]. Meanwhile, the pore walls of the AAO were positively charged [22]. As coexistence of the charge interaction and the capillary action, it is reasonable that the nanotubes firstly formed near wall areas of the pores and then extended to the center area gradually. During the sintering process, the sol within the AAO's nanochannels would be changed into CoFe2O4 by the condensation reactions. Field Emission Scanning Electron Microscope (FE-SEM) was performed by using a Hitachi S-4800 microscope operated at 10 kV. Structural and morphology data were collected by X-ray diffraction (XRD) using an X Pertpro Philips diffractometer with Cu K radiation and transmission electron microscopy (TEM, Hitachi H-600), respectively. The magnetic properties were measured by a vibrating sample magnetometer (VSM, Lakeshore 7300).
3. Results and discussion Fig. 1 shows the FE-SEM image of CoFe2O4 nanotube arrays grown within an AAO template. It is found that the nanotubes are roughly parallel to each other orderly and uniformly. The mean outer diameter of these nanotubes is about 50 nm, corresponding to the diameter of channels in the AAO template. The thickness of the tube wall is about 15 nm. Fig. 2 shows the XRD pattern of the sample within AAO templates annealed at 600 C. Although the background diffraction peaks of Al2O3 are present, the diffraction peaks of CoFe2O4 can be observed. The main peaks correspond to a cubic, spinel-type lattice (Fd3m) with lattice parameter a = 8.20(1) . The lattice parameter a is smaller to

Fig. 3. (a) TEM image and (b) SAED pattern of CoFe2O4 nanotubes.

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Fig. 4. Magnetic hysteresis loops for the cobalt ferrite nanotubes measured at room temperature with the applied field (a) parallel (b) perpendicular to the axis of the nanotubes.

that of the bulk (a = 8.400 ) because of crystallite size reduction plus lattice disorder. The crystallite size is 9.4 nm calculated by Scherrer equation. The fine crystallites form the tube wall of samples. Fig. 3 shows the TEM image and the select area electron diffraction (SAED) pattern of CoFe2O4 nanotubes. The outer diameter is from 40 nm to 60 nm and the mean diameter is basically equal to that of the pores in the AAO template. Fig. 3(a) shows typical nanotubes observed by the TEM, which have a diameter consistent with that of the SEM. The image shows that the nanotube is composed of grains. Fig. 3(b) shows the SAED pattern of sample in Fig. 3 (a). The SAED pattern indicates that the CoFe2O4 nanotube is polycrystalline phase. The pattern for the sample is well resolved at (220), (311), (400), (422), (511) and (440) reflections as in XRD patterns. Fig. 4 shows the hysteresis loops measured at the maximum field of 12 kOe at room temperature with the external applied field parallel or perpendicular to the nanotube. It is found that the coercivity is about 162 and 136 Oe in parallel and perpendicular to the channel axis, respectively. Both hysteresis loops are similar in shape and saturation field, which means that the sample has almost no preferential magnetic orientation. The magnetic anisotropy of the magnetic nanotube arrays is mainly influenced by the magnetocrystalline anisotropy of each particle, the shape anisotropy of the nanotube, and the dipole interaction between the nanotubes. For cobalt ferrite, the magnetocrystalline anisotropy energy is very large [19]. Therefore, magnetocrystalline anisotropy of CoFe2O4 nanotube arrays makes the main contribution to the total anisotropy, and the samples obtained in our experiments are polycrystalline with the magnetic domain irregularly distributed, resulting in the absence of anisotropy. So the coercivity of CoFe2O4 nanotube arrays corresponds with that of the nanoparticles [23].

Acknowledgements This work was supported by the NSFC (Graint No. 50671046 and 10374038) and SRFDP (Graint No. 20030730002) of PR China. Reference
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4. Conclusion In summary, we have successfully prepared cobalt ferrite nanotube arrays of about 50 nm in diameter by an improved sol gel template method. The attraction between the negatively charged sol particles and the positively charged pore wall of AAO, as well as the capillary action control tube formation process of the sol. The cobalt ferrite nanotube arrays are polycrystalline structure which result in almost no preferential magnetic orientation in the tube. Magnetocrystalline anisotropy is the mainly effective anisotropy which results in the coercivity about 136 and 162 Oe in the vertical and parallel direction of nanotube axis. It can be expected that the method presented in this letter is also appropriate for the preparation of other ferrite nanotubes.