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Chemical Physics Letters 454 (2008) 7579 www.elsevier.com/locate/cplett

NiO nanotubes assembled in pores of porous anodic alumina and their optical absorption properties
Chunsheng Shi *, Guoqiang Wang, Naiqin Zhao, Xiwen Du, Jiajun Li
School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China Received 17 August 2007; in nal form 28 January 2008 Available online 31 January 2008

Abstract Nickel oxide (NiO) nanotubes, embedded in a porous anodic aluminum oxide (AAO) template, have been produced by a wet chemistry templating method using a nickelammine complex as a precursor. The dimensions of the nanotubes are about 60 lm in length, with an outer diameter of about 200 nm and a wall thickness of 60 nm. They possess a polycrystalline structure and the NiO nanotube arrays exhibit an optical absorption band gap of 3.90 eV, similar to that of bulk NiO. 2008 Elsevier B.V. All rights reserved.

1. Introduction Nickel(II) oxide (NiO) with an NaCl-type structure is antiferromagnet (TN = 523 K) and a wide bandgap (Eg = 4.0 eV) p-type semiconductor [1]. Among its wide range of technological applications is its use in the manufacture of lithium ion batteries cathodes [2,3], catalysis [4], gas sensors [5], solar cells [6], solid oxide fuel cell anodes [7], electrochemical supercapacitors [8], and electrochromic lms [9]. Due to their quantum size eects, high surface area and low sintering temperature, nanoscale NiO materials have attracted much attention in the aforementioned elds and considerable eort has been expended in recent years in order to improve their performance. A variety of methods have been applied for synthesizing NiO nano particles [1012], nanorods or nanowires [1316], nanoribbons [17], and nanotubes. Compared to other nanostructures, nanotubes possess low mass density, high porosity and increased surface areas [18] which are especially important in applications involving interactions between gases or liquids and the materials surface [19]. For the fabrication of NiO nanotubes, only a

Corresponding author. Fax: +86 22 27891371. E-mail address: csshi@tju.edu.cn (C. Shi).

few methods have been reported so far. Liu et al. synthesized NiO nanotubes through a dodecylsulfate-mediated templating mechanism with homogeneous precipitation using urea [18]. The nanotubes obtained had diameters of 20160 nm and wall thicknesses of 850 nm with lengths up to several micrometers. Needham et al. produced NiO nanotubes via a two step chemical reaction in which nickel hydroxide nanotubes were rst formed within the walls of a porous anodic aluminum oxide (AAO) template followed by a heat treatment at 300 C in air [20]. Malandrino et al. fabricated ordered homogeneous arrays of NiO nanotubes by a metal-organic chemical vapor deposition (MOCVD) template route using an adduct of the nickel bis(thenoyltriuoroacetone) complex with tetramethylendiamine (Ni(tta)2tmeda) as a source [19]. The potential applications of NiO nanotubes provide good reasons for exploring additional novel synthetic routes for making these materials. In this Letter, NiO nanotubes embedded in a porous AAO template were synthesized by employing a complex transformation method using a nickelammonia complex as a precursor followed by heat treatment in air. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques were used to characterize the microstructure of the NiO nanotubes. The optical absorption spectra of the ordered NiO nanotube arrays were investigated as well.

0009-2614/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.cplett.2008.01.069

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2. Experimental details The porous AAO templates used in the present study were AnodiscTM 47 (Whatman Ltd.) membrane disks with a macroscopic diameter of 47 mm and a thickness of 60 lm. The pores are specied as 200 nm in diameter, reciprocally parallel, and penetrating the membranes. All of the chemicals used were of analytical grade and used as received. A precursor solution of nickelammine complex 2 NiNH3 x was prepared by dripping 10 ml of 2 wt.% ammonia into 10 ml of 0.1 M NiCl26H2O aqueous solution under constant stirring. Then, a 1 M NH4Cl aqueous solution was added dropwise to the solution until a blue transparent nickelammine complex solution was obtained. To prepare NiO nanotubes, a porous AAO template was immersed in the precursor solution for about 30 min, ensuring that the pores of the template were completely lled with the complex solution by the capillary force. Subsequently, the system was placed in a water-bath, and kept at 40 C for 1030 min. The templates were then carefully cleaned several times with distilled water and subsequently dried in an oven, in air, at 60 C for 2 h. Finally, the templates assembled with the precursor were calcined at 500 C for 5 h in a tube furnace in air, during which the precursor decomposed and crystallized to form NiO arrays embedded in the AAO templates. The NiO nanotubes were characterized using FESEM (JEOL JSM-6700F) and TEM (Philips Tecnai G2 F20). Several drops of suspension, obtained by dissolving the AAO templates with a 1 M NaOH solution under sonication, were deposited onto copper grids for TEM observation. The crystalline structure of the NiO nanotubes was investigated using XRD (RIGAKU D/Max 2500) after both surfaces of the templates was polished with alumina powders. The UVVis (200800 nm) absorption spectra of the nanotubes were measured with a SHIMADZU UV-3600 spectrophotometer at room temperature. 3. Results and discussion Fig. 1 shows the XRD pattern of the NiO nanotubes in the AAO template after the template, embedded with precursors, was calcined at 500 C for 5 h. For comparison, the standard spectrum of NiO with an fcc structure is also depicted in the gure. It can be seen that the peaks denoted as (1 ,1 ,1), (2 0 0), (2 2 0) and (3 1 1) correspond well with the standard crystallographic data of NiO with an fcc structure (JCPDS-ICDD card 65-2901). The broad peaks indicate that the NiO may be comprised of nanocrystals. From the width of the (2 0 0) peak, the diameter of the nanocrystals was estimated to be about 12.5 nm according to the Scherrer formula. Typical SEM images of the cross section of an AAO template embedded with NiO are shown in Fig. 2, which demonstrates that most of the AAO pores were lled with tubular shaped material (Fig. 2a). We note that the tubular

Fig. 1. X-ray diraction pattern of NiO nanotube arrays embedded in the alumina template.

Fig. 2. Cross-section SEM images of NiO nanotube arrays embedded in the alumina template: (a) a low magnication image, and (b) a high magnication image (the arrows point to holes in the nanotubes).

structure of the llers is evident from the holes at the broken ends of the llers, as indicated by the arrows in Fig. 2b.

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The diameters of the nanotubes, which were determined by the size of the pores of the AAO template, were estimated to be about 200 nm. Some NiO tubes were pulled from the AAO pores, indicating poor interfacial bonding between the wall of AAO pores and the NiO tubes. It is noted that the NiO nanotubes were brittle and susceptible to fracture during the preparation of SEM samples. Nevertheless, high lling loads of NiO tubes were obtained by using the method described in this Letter. Fig. 3 shows the representative TEM images of NiO nanotubes. As shown in Fig. 3a, the NiO nanotubes exhibit dierent appearances, such as branched, multi forked, capped and uncapped, which exactly duplicated the appearances of the AAO pores. Due to the morphological disparity of the AAO pores, the diameters of the nano NiO tubes are not uniform. But the wall thickness of the tubes is almost the same since the wall growth mainly depends on the time for deposition of Ni(OH)2. Some ller grew into bers instead of tubes, especially those in narrower pores. The lengths of the NiO tubes shown in the TEM images

are shorter than the thickness of the AAO template (about 60 lm) because they were fractured by sonication during the preparation of TEM samples. A NiO nanotube with hierarchical forked structure is presented in Fig. 3b, again showing that branches existed in the AAO template. We note that the inner and outer walls of the NiO nanotube are coarse and the tiny fork near one end of the NiO nanotube does not have the feature of hollow tubes. Fig. 3c is a high magnication image of two parallel NiO nanotubes with an inner diameter of about 120 nm and a wall thickness of about 60 nm. It shows clearly that the wall of the nanotube is comprised of a large number of nanocrystals. Fig. 3d shows that the wall of the NiO nanotube is composed of nanocrystals with diameters ranging from 5 to 20 nm, in agreement with the average diameter of 12.5 nm estimated by the Scherrer formula from the XRD pattern. The growth mechanism of NiO nanotubes in the AAO pores could be proposed as follows. The main chemical reactions involved in the synthetic process can be simply expressed as

Fig. 3. TEM images of NiO nanowires showing: (a) general appearances of NiO nanotubes, (b) forked structure of a NiO nanotube, (c) two parallel nanotubes under high magnication, and (d) an HRTEM image of the nanotube showing polycrystalline structures.

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NH3 H2 O NH OH 4 Ni
2

1 2
2

2OH NiOH2 #

NiOH2 nNH3 H2 O NiNH3 n 2OH nH2 O Ni

2

3 4 5

mNH3 NiNH3 m
D

NiOH2 nH2 O ! NiO n 1H2 O "

When a small amount of aqueous ammonia solution was added to the NiCl2 solution, the precipitation of Ni(OH)2 occurred as indicated in Reaction (2) [21]. With further NH3H2O addition, free NH3 in the solution reacted with the Ni(OH)2 precipitate to form the NiNH3 2 complex and the precipitation dissolved prox gressively (c.f. Reaction (3)). Then, an appropriate amount of NH4Cl was added to the system to prevent NH3 from ionizing and to promote complex formation. The nickel ammonia complex solution was obtained when the precipitate dissolved and the solution became clear. By altering certain equilibrium conditions (e.g. temperature of the solution) after the AAO template was immersed in the solution, the ammonia could be removed by volatilization. 2 Accordingly, Ni2+ was released from the NiNH3 x complex (Reaction (4)). As the reaction continued, the concentration of the Ni2+ in the solution increased, leading to Ni2+ combining with OH to form Ni(OH)2 in the pores of the AAO template. After calcination, NiO nanotubes formed (Reaction (5)). In this process, the transformation of the precipitates of Ni(OH)2 to the complex and the reverse process is important. We call this a complex transformation method. This method is also feasible for synthesizing nanostructures of other metal oxides, such as ZnO, CuO, and Ag2O etc., which can be derived from metal amine complexes. The optical absorption spectra of the blank AAO template and the NiO nanotubes/AAO system are shown in Fig. 4. The blank AAO is transparent throughout the entire UVVis region. As shown in the gure, the NiO nano-

Fig. 5. (aht)2 versus ht plot for NiO nanotube arrays embedded in alumina template.

tubes/AAO system shows strong absorption in the UV range, which is attributed to the NiO band gap absorption. Generally, the correlation between absorption coecient a and optical band gap Eg, as expressed by Eq. (6), can be used to characterize the nature of interband transitions [22]. aht / ht Eg n 6

Where ht is the photon energy, and n is 1/2 for direct interband transitions or 2 for indirect interband transitions. By extrapolating the linear portion of the (aht)2 versus ht plot to a = 0, we can estimate the optical band gap from the absorption peak. Fig. 5 shows that the optical absorption in the edge region ts well with (aht)2 $ ht Eg, indicating that NiO nanotubes embedded in AAO have a direct band gap. The band gap is estimated to be 3.90 eV, which is in agreement with the normal bulk NiO (3.64.0 eV), but larger than the value of NiO nanowires embedded in AAM reported by Lin et al. [14]. 4. Conclusions Ordered NiO nanotube arrays embedded in AAO templates have been prepared employing a novel chemical transition approach which used a nickelammonia complex solution as the precursor. The NiO nanotubes were dense and continuous and had a diameter of about 200 nm. The nanotubes were stacked with NiO nanocrystals with fcc crystalline structure. The optical absorption band gap of the nanotubes arrays was 3.90 eV, within the range of the bandgap of bulk crystalline NiO. The method reported here is also valuable for preparing other metal oxide nanobers or nanotube arrays by AAO templating methods. Acknowledgements

Fig. 4. Optical absorption spectra of a blank AAO template and NiO nanotube arrays embedded in the alumina template.

This work was supported by the Foundation of Tianjin Municipal Science and Technology Commission (No.

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05YFJMJC15000), and the Scientic Research Foundation for the Returned Overseas Chinese Scholars from the State Education Ministry of China. References
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