Optimization of copper oxide nanotube synthesis Amanda Scalza Department of Chemical Engineering, University of New Haven

ABSTRACT CuO nanotubes were synthesized via hydrothermal route using CTAB as a soft template. Synthesized samples were characterized by SEM, TEM and XRD. Optimal conditions for isolated nanotube formation were found to be as follows: 4M NaOH, 60mM CTAB, 8mM CuCl2, 2 hour reaction time at 60C.

EXPERIMENTAL Copper(II) oxide nanomaterials were synthesized in solution using a soft-template created by CTAB. To begin, 90mL of NaOH solution at varying concentrations between 1.5 and 4.5M was preheated to about 60C. CuCl2 was dissolved in 10mL of high purity deionized water (DDI) and added to the NaOH solution, immediately followed by CTAB. The

INTRODUCTION The study of nanomaterials is a topic of great interest because of the unique properties these materials have in comparison to the same material in bulk form. The structure of the material and crystals plays an important role in these unique properties. These materials show promise in applications in catalysts, sensors and electronics1. Copper-based nanomaterials are of particular interest in the field of electronics because copper is already known to be a good conductor, commonly used in electronics and wiring. In previous studies, CuO was synthesized with a variety of techniques, including metal-organic chemical vapor deposition1, reduction of metalorganic complexes and through a template-free solution synthesis3. Cao et al4 used a hydrothermal synthesis route with an ionic surfactant, cetyltrimethylammonium bromide (CTAB), as a soft template for nanotubes. The research by Cao et al was the basis for this study, which simplified, refined, and optimized the creation of CuO nanotubes.
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mixture was stirred at very high speed (~1150rpm) for 7 minutes, than the speed was reduced (~200rpm). This ensured the CTAB was fully dissolved into the solution. The solution continued to be heated and stirred at this lower speed for 2 hours. After the reaction was completed, the solution was filtered, washed with DDI water, and the filter contents saved in a vial with a small amount of DDI. For best results under imaging, the contents were sonicated for approximately 1 minute before preparing for imaging.

RESULTS In order to obtain the most ideal product of long, isolated, bundles of nanotubes, the following recipe was found to give the best results: 4.0M NaOH, 60mM CTAB, 8mM Cu2+, with a 2 hour reaction time immediately followed by filtration, and washing with DDI water. Figure 1 is a TEM image of CuO product at these conditions, showing bundles of tubes of lengths around 1 micron. No autoclaving was necessary to create the nanotubes, and autoclaving was found to cause the formation of nanorods instead

of the desired nanontubes. For best results under microscopy, the filter contents were placed into 23mL of DDI water and sonicated for approximately 1 minute. This separated the nanobundles to make them easier to see under TEM and SEM. This level of sonication was not sufficient to break up the bundles into single nanotubes.

To make the best product, the CTAB concentration needed to be at the point where CTAB micelles take the form of cylinders instead of spheres, and before they transform from cylinders into long, lamellar sheets. For a hydroxyl concentration of 4M, this was found to be at 60mM CTAB. At concentrations of 75mM and 90mM, the CuO formed large, separate sheets of material (figure 2) and at 45mM, the CuO product morphology suggested a mix of all three types of micelles were formed. At a concentration of 60mM CTAB, the CuO morphology suggests that the highest proportion of cylindrical micelles with the smallest amount of other types of micelles were formed (figure1).

Figure 1: TEM image of CuO sample, showing many bundles of unconnected nanotubes. Synthesis conditions as follows: 4M NaOH, 60mM CTAB, 8mM Cu2+, 2 hour reaction time.

DISCUSSION Using the selected synthesis method, CTAB functioned as a soft template onto which the Copper hydroxyls deposited4. The form of the CTAB micelle and the concentration of the micelles played an important role in the type of product that was formed. The critical micelle concentration transition (CMC2) of CTAB is the point where a micelle transforms from spherical to cylindrical. This point is greatly affected by presence of ionic solutes, such as NaOH, which lowers the CMC2 point. Temperature can also affect this CMC2, however, in a more complex and indirect manner5, 6. All tests for this study were carried out at a reaction temperature of 60C, and the affect of the temperature on the CMC2 was therefore not a factor during optimization. In the paper by Cao et al., the basis for this study, the authors claimed that nanotubes were using a recipe of 3M NaOH, 8mM CuCl2, 60mM CTAB, at 50C reaction temperature for 30 minutes, followed by autoclaving for 12 hours at 120C 4. In this investigation, when reproducing this original formula described by Cao, none of the desired nanotube material was found. By eliminating the use of the autoclave, the first signs of nanotubes were apparent.
Figure 2: (Left) TEM image of CuO sample, showing mass of sponge-like material. Synthesis conditions as follows: 4M NaOH, 75mM CTAB, 8mM Cu2+, 2 hour reaction time.

This recipe was then used for optimization. Increasing the temperature improved the quality of the product, and this positive effect was best around the temperature zone of 60-62C. The CTAB and copper concentrations used by Cao et al. were found to indeed be the optimal concentrations, but this was not so for the concentration of NaOH. At 3M NaOH, there was a reasonably large amount of product (figure 3), but the quality of the product was poor as compared to using 4M NaOH (figure 1). With the higher hydroxyl concentration, there was less overall product but most of the product was nanotubes, the desired product.

The amount of copper chloride added also greatly affected both the quality and quantity of the product. As the copper concentration increased, so did the quantity of product. The best quality product, however, did not follow this trend. The ideal concentration of copper was found to be at 8mM Cu2+. At 2mM Cu2+, there was no evidence of CuO formation and at higher concentration the CuO product was made mostly of sheets of material (figure 4). Refer to figure 1 for the image of long, isolated nanobundles seen at the copper concentration of 8mM.

Figure 4. SEM images of CuO samples. Interconnected sheets of material at 12mM Cu2+, with synthesis conditions of 4M NaOH, 60mM CTAB, 2 hour reaction time.

CONCLUSION The desired product of long isolated nanotubes can be synthesized very simply using the soft template of cylindrical micelles of CTAB. Though the optimal Figure 3: SEM images of CuO samples depicting: mass of interconnected sheets and wires at 3.0M NaOH (top) and sheet of material with fringe wires at 3.5M NaOH (bottom). Synthesis conditions as follows: 8mM Cu2+, 60mM CTAB, 2 hour reaction time. ACKNOWLEDGMENTS Contributions by W. D. Harding, University of New Haven, as well as Mark Schwab, Fang Fang, recipe deviated greatly from the primary paper, it is much simpler and gives a much higher yield of the desired nanotubes.

Eswaramoorthi Iyyamperumal, Gayatri Keskar and Magdalenda Majewska from Yale University. Amanda Scalza is a junior at the University of New Haven majoring in Chemical Engineering and Chemistry. Her planned graduation date is May 2012.

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