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Self-assembly of CdCO3-dye hybrid nanotubes based on Trypan Blue dye
Colloids and Surfaces A: Physicochem. Eng. Aspects 374 (2011) 129–133
Contents lists available at ScienceDirect
Colloids and Surfaces A: Physicochemical and Engineering Aspects journal homepage: www.elsevier.com/locate/colsurfa
Self-assembly of CdCO3 -dye hybrid nanotubes based on Trypan Blue dye Limin Song a , Chao Chen a , Shujuan Zhang b,∗ a College of Environment and Chemical Engineering & State Key Laboratory of Hollow-Fiber Membrane Materials and Membrane Processes, Tianjin Polytechnic University, Tianjin 300160, PR China b College of Science, Tianjin University of Science & Technology, Tianjin, 300457, PR China
a r t i c l e
i n f o
Article history: Received 9 September 2010 Received in revised form 5 November 2010 Accepted 10 November 2010 Available online 18 November 2010 Keywords: CdCO3 Trypan Blue dye Hybrid nanotubes
a b s t r a c t CdCO3 -dye hybrid nanotubes were successfully synthesized through a simple reflux process using Trypan Blue (TB) dye as template. The dye was crucial to the formation of CdCO3 hybrid nanotubes. The samples were characterized using thermogravimetric analysis, X-ray diffraction (XRD), transmission electron microscopy (TEM), and fourier transform infrared spectroscopy. The effect of different aspects on the crystal morphology of the CdCO3 –TB hybrid materials was primarily investigated. A rational mechanism was proposed for the selective formation of CdCO3 –TB hybrid nanotubes. © 2010 Elsevier B.V. All rights reserved.
1. Introduction Hybrids combining inorganic and organic materials have attracted much attention due to a specific size, shape, orientation, organization, complex form, and hierarchy. They show their important properties and potential applications in many fields, such as electricity, mechanics, corrosion-resistance, catalysis, and so on [1,2]. One-dimensional (1D) nanostructures include nanotubes, nanofibers/nanowires, and nanorods, etc. They have great potential for increasing the understanding of the fundamental physics concerning the roles of dimensionality and size characteristics [3–5]. However, although numerous types of 1D nanostructures have been developed [6–12], nanotubes consisting of CdCO3 -dye are not yet to be reported. CdCO3 is an important additive in plastics, stabilizers, and catalysts. It is also an attractive intermediate for synthesizing terylene [13]. This paper reports that Trypan Blue (TB) dye molecules can be used for the self-assembly of CdCO3 –TB hybrid nanotubes through a facile reflux process under ambient conditions. Different experiments reveal the details of their formation mechanism.
While stirring vigorously for 10 min, 0.005 g TB (0.17 g/L) was added, followed by 10 mL NH3 ·H2 O (25 wt.%) while stirring for another 20 min. The resulting solution was transferred into a 50 mL glass flask and heated at 120 ◦ C for a 48 h reflux. When the flask cooled to room temperature, the blue, solid product was washed with distilled water, followed by ethanol, and finally dried at 60 ◦ C for 3 h. The molecular structure of TB is in Fig. 1. 2.2. Characterization of CdCO3 /TB nanotubes X-ray diffraction (XRD) patterns of samples were taken on a Rigaku D/max 2500 powder diffractometer with CuK␣ radiation of wavelength of 1.5406 A˚ and were analyzed from 3◦ to 80◦ (2) equipped with a graphite monochromator. The morphology and size of as-prepared products were observed by transmission electron microscopy (TEM), which was carried out on the Hitachi H7650 transmission electron microscope. The groups on the samples were studied by infrared absorption spectroscopy (FTIR; Bruker Tensor37). Thermo gravimetric (TG) analysis curves were obtained with a PerkinElmer 7 simultaneous thermal analyzer with a heating rate of 15 ◦ C in a flowing nitrogen atmosphere.
2. Experimental 2.1. Synthesis of CdCO3 –TB nanotubes A clear solution of 0.001 mol Cd(CH3 COO)2 ·2H2 O (0.03 mol/L) dissolved in a mixture of 5 mL H2 O and 15 mL ethanol was formed.
∗ Corresponding author. Tel.: +86 22 60600658; fax: +86 22 60600658. E-mail address: [email protected] (S. Zhang). 0927-7757/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.colsurfa.2010.11.023
3. Results and discussion 3.1. XRD characterization of CdCO3 –TB Fig. 2 illustrates the X-ray diffraction profiles of the CdCO3 –TB hybrid nanotubes and TB. Comparing the XRD pattern of TB in Fig. 2a and that of CdCO3 TB in Fig. 2b, the absence of TB peaks in the pattern of CdCO3 –TB hybrid nanotubes may indicate that TB molecules have been dispersed into the structure of CdCO3 . Fur-
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L. Song et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 374 (2011) 129–133
Fig. 1. Molecular structure of Trypan Blue.
vibrational modes in TB molecules, respectively, indicating that the TE molecules have been hybridized into CdCO3 nanotubes. 3.3. DTG characterization of CdCO3 –TB To investigate whether the TB molecules exist in the as-prepared CdCO3 nanotubes, DTG of the CdCO3 –TB nanotubes was carried out. Fig. 4a shows the DTG curve of the CdCO3 –TB nanotubes. In the DTG curve, a distinct endothermic peak was observed at 294 ◦ C, which is associated with the decomposition of TB. The DTG curve indicated a 29.7% weight loss occurring from 232 to 390 ◦ C, which may be an indication that the TB molecules have been dispersed into the CdCO3 nanotubes. In order to investigate the TB molecules whether to exist in the as-prepared CdCO3 nanotubes, the composition of the CdCO3 nanotubes was determined by EDX (Fig. 4b). The atom ratio of N and S, about 0.64 and 3.46 at.%, was estimated from the EDX semi-quantitative acquisition. It proved the presence of S and N atoms in the CdCO3 nanotubes, thus indicating that the hybrid Fig. 2. X-ray diffraction patterns of TB and CdCO3 /TB nanotubes.
ther EDX also proves the result. As shown in Fig. 1b, all the peaks are attributed to the rhombohedral CdCO3 phase (space group R3c [No. 167]) with the lattice constants a = b= 4.915 A˚ and c = 16.267 A˚ (JCPDS card no. 02–0725). No other impurities were detected in the hybrid nanotube samples. 3.2. FTIR characterization of CdCO3 –TB The formation of CdCO3 –TB nanotubes was further confirmed by FTIR studies. The peaks (Fig. 3) around 1400 and 850 cm−1 are the characteristic vibration bands of CO3 2− [14]. The sample also showed absorption in the regions 3435, 1795, 1628, and 750 cm−l . The peaks may be assigned to the O H, C C , SO3 , and N H
Fig. 3. Infrared (IR) spectrum of the CdCO3 /TB nanotubes.
Fig. 4. (a) DTG and (b) EDX curve of CdCO3 /TB nanotubes.
L. Song et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 374 (2011) 129–133
131
Fig. 5. EM images of the as-synthesized products with different concentration of TB. (a) 0.17 g/L, (b) 0.08 g/L, (c) 0.04 g/L, and (d) 0.17 g/L using H2 O as solvent.
is successful. In the EDX peaks, the Al atom peak was attributed to the aluminum specimen support. In addition, the 30% loss of mass occurring from 390 to 710 ◦ C was in good agreement with the 25.6% final mass loss calculated for CdO. The following is the corresponding reaction:
using H2 O as solvent under the mentioned conditions. Nanorod bundles, 300 nm long and 50 nm wide, were observed in the products.
CdCO3 → CdO + CO2
Our proposed mechanism for producing the CdCO3 nanoparticles is as follows:
3.4. Morphological characterization of CdCO3 –TB The morphologies of the as-synthesized products were examined through TEM. Fig. 5a shows the typical TEM image of the sample prepared with 0.17 g/L of TB. The products are primarily composed of nanotubes with lengths up to 100–200 nm and diameters of 10–20 nm. Interestingly, the use of the same experimental conditions with a reduced TB concentration of 0.08 g/L produces porous nanorods (Fig. 5b). The aspect ratio of the nanorods with 200 nm length and 20 nm diameter is 10. When the sample was prepared with 0.04 g/L TB concentration, only irregular nanoparticles were obtained (Fig. 5c). The products were mainly nanoparticles with diameters of 20 nm. The experiment revealed that the morphology of the as-synthesized CdCO3 strongly depends on the solvent, in which the concentration of Cd(CH3 COO)2 ·2H2 O and TB was kept constant at 0.03 mol/L and 0.17 g/L, respectively. Fig. 5d shows the TEM image of the as-synthesized products
3.5. The growth mechanism of the CdCO3 –TB nanotubes
(1) Cd(CH3 COO)2 → Cd2+ + 2CH3 COO− (2) NH3 ·H2 O → NH4 + + OH− (3) CO2 (in air) + OH− → HCO3 − → H+ + CO3 2− (4) Cd2+ + CO3 2− → CdCO3 (5) CdCO3 + TB → CdCO3 –TB nanotubes Experimental results confirm that the concentration of TB and the solvent have a significant effect on the morphologies and sizes of the final products. The morphologies of CdCO3 –TB depending on the growth time are shown in Fig. 6 to illustrate the growth mechanism of the CdCO3 –TB nanotubes. The concentration of Cd(CH3 COO)2 ·2H2 O and TB was kept constant at 0.03 mol/L and 0.17 g/L using a mixture of 5 mL H2 O and 15 mL ethanol as solvent.
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L. Song et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 374 (2011) 129–133
Fig. 6. TEM images of the as-synthesized products with different growth time. (a) 6 h, (b) 12 h, (c) 24 h, (d) 36 h, and (e) 48 h. The concentration of Cd(CH3 COO)2 ·2H2 O and TB was kept constant at 0.03 mol/L and 0.17 g/L using a mixture of 5 mL H2 O and 15 mL ethanol as solvent.
As shown in Fig. 6a and b, when the reaction time was kept at 6 or 12 h, irregular nanoparticles were produced. Increasing the reaction time to 24 h transforms the petals of the nanoparticles into porous nanorods (Fig. 6c). As shown in Fig. 6d, when the reaction time was prolonged to 36 h, the little pores gradually changed to
bigger eyelets, whereas the porous nanorods also gradually transformed into hollow nanorods (Fig. 6e). The following is a proposed growth mechanism: combining Cd(CH3 COO)2 and TB results in fast nucleation and small particles. The CdCO3 crystal nucleus was adsorbed on long-chained
L. Song et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 374 (2011) 129–133
TB molecules. Subsequently, chains of particles form through the dissolution of small sphere-like particles which assemble into nanorods. The nanorods dissolve from the tips toward the interior under the action of hydrogen ions; this results in the formation of CdCO3 nanotubes. 4. Conclusion A simple reflux route of modifying parameters was used to synthesize CdCO3 –TB nanotubes successfully. TB can be used as a template to prepare CdCO3 nanostructures. By introducing TB as a heterogeneous template of the mineralization system, the structures can be further modified into nanorods and nanotubes. Acknowledgment This work was supported by Tianjin Planning Project of Science and Technology (10JCZDJC22500). References [1] H.P. Cong, S.H. Yu, Hybrid ZnO dye hollow spheres with new optical properties from a self-assembly process based on evans blue dye and cetyltrimetlammonium bromide, Adv. Funct. Mater. 17 (2007) 1814–1820. [2] H.P. Cong, S.H. Yu, Synthesis of microscale raft-shaped Zinc (II) phenylalanine complexes and zinc(II)/phenylalanine/dye hybrid bundles with new optical properties, Adv. Funct. Mater. 18 (2008) 195–202.
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[3] A.P. Alivisatos, Semiconductor clusters, nanocrystals, and quantum dots, Science 271 (1996) 33–937. [4] Y Cui, C.M. Lieber, Functional nanoscale electronic devices assembled using silicon nanowire building blocks, Science 291 (2001) 851–853. [5] J. Hu, M. Ouyang, P. Yang, C.M. Lieber, Growth and electrical properties of nanotube/nanowire heterojunctions, Nature 399 (1999) 48–51. [6] H.M. Yang, G.Z. Qiu, X.C. Zhang, A.D. Tang, W.G. Yang, Preparation of CdO nanoparticles by mechanochemical reaction, J. Nanopart. Res. 6 (2004) 539–542. [7] A. Askarinejad, A. Morsali, Synthesis of cadmium(II) hydroxide, cadmium(II) carbonate and cadmium(II)oxide nanoparticles; investigation of intermediate products, Chem. Eng. J. 150 (2009) 569–571. [8] Z.Y Jia, Y.W. Tang, L.J. Luo, B.H. Li, Shape-controlled synthesis of singlecrystalline CdCO3 and corresponding porous CdO nanostructures, Cryst. Growth and Design 8 (2008) 2116–2120. [9] S. Ashoka, P. Chithaiah, G.T. Chandrappa, Studies on the synthesis of CdCO3 nanowires and porous CdO powder, Mater. Lett. 64 (2010) 173–176. [10] S.H. Yui, H.M. Colfen, K. Tauer, M. Antonietti, Tectonic arrangement of BaCO3 nanocrystals into helices induced by a racemic block copolymer, Nat. Mater. 4 (2005) 51–55. [11] S.H. Yui, H.M. Colfen, A.W. Xu, W.F. Dong, Complex spherical BaCO3 superstructures self-assembled by a facile mineralization process under control of simple polyelectrolytes, Cryst. Growth and Design 4 (2004) 33–37. [12] S.H. Yui, H.M. Colfen, K. Tauer, M. Antonietti, Polymer-controlled morphosynthesis and mineralization of metal carbonate superstructures, J. Phys. Chem. B 107 (2003) 7396–7405. [13] E. Dalas, P. Klepetsanis, P.G. Koutsoukos, The overgrowth of calcium carbonate on poly (vinyl chloride-co-vinyl acetate-co-maleic acid), Langmuir 15 (1999) 8322–8327. [14] S.K.H. Khalil, M.A. Azooz, Application of vibrational spectroscopy in identification of the composition of the urinary stones, J. Appl. Sci. Res. 3 (2007) 387–391.
Contents lists available at ScienceDirect
Colloids and Surfaces A: Physicochemical and Engineering Aspects journal homepage: www.elsevier.com/locate/colsurfa
Self-assembly of CdCO3 -dye hybrid nanotubes based on Trypan Blue dye Limin Song a , Chao Chen a , Shujuan Zhang b,∗ a College of Environment and Chemical Engineering & State Key Laboratory of Hollow-Fiber Membrane Materials and Membrane Processes, Tianjin Polytechnic University, Tianjin 300160, PR China b College of Science, Tianjin University of Science & Technology, Tianjin, 300457, PR China
a r t i c l e
i n f o
Article history: Received 9 September 2010 Received in revised form 5 November 2010 Accepted 10 November 2010 Available online 18 November 2010 Keywords: CdCO3 Trypan Blue dye Hybrid nanotubes
a b s t r a c t CdCO3 -dye hybrid nanotubes were successfully synthesized through a simple reflux process using Trypan Blue (TB) dye as template. The dye was crucial to the formation of CdCO3 hybrid nanotubes. The samples were characterized using thermogravimetric analysis, X-ray diffraction (XRD), transmission electron microscopy (TEM), and fourier transform infrared spectroscopy. The effect of different aspects on the crystal morphology of the CdCO3 –TB hybrid materials was primarily investigated. A rational mechanism was proposed for the selective formation of CdCO3 –TB hybrid nanotubes. © 2010 Elsevier B.V. All rights reserved.
1. Introduction Hybrids combining inorganic and organic materials have attracted much attention due to a specific size, shape, orientation, organization, complex form, and hierarchy. They show their important properties and potential applications in many fields, such as electricity, mechanics, corrosion-resistance, catalysis, and so on [1,2]. One-dimensional (1D) nanostructures include nanotubes, nanofibers/nanowires, and nanorods, etc. They have great potential for increasing the understanding of the fundamental physics concerning the roles of dimensionality and size characteristics [3–5]. However, although numerous types of 1D nanostructures have been developed [6–12], nanotubes consisting of CdCO3 -dye are not yet to be reported. CdCO3 is an important additive in plastics, stabilizers, and catalysts. It is also an attractive intermediate for synthesizing terylene [13]. This paper reports that Trypan Blue (TB) dye molecules can be used for the self-assembly of CdCO3 –TB hybrid nanotubes through a facile reflux process under ambient conditions. Different experiments reveal the details of their formation mechanism.
While stirring vigorously for 10 min, 0.005 g TB (0.17 g/L) was added, followed by 10 mL NH3 ·H2 O (25 wt.%) while stirring for another 20 min. The resulting solution was transferred into a 50 mL glass flask and heated at 120 ◦ C for a 48 h reflux. When the flask cooled to room temperature, the blue, solid product was washed with distilled water, followed by ethanol, and finally dried at 60 ◦ C for 3 h. The molecular structure of TB is in Fig. 1. 2.2. Characterization of CdCO3 /TB nanotubes X-ray diffraction (XRD) patterns of samples were taken on a Rigaku D/max 2500 powder diffractometer with CuK␣ radiation of wavelength of 1.5406 A˚ and were analyzed from 3◦ to 80◦ (2) equipped with a graphite monochromator. The morphology and size of as-prepared products were observed by transmission electron microscopy (TEM), which was carried out on the Hitachi H7650 transmission electron microscope. The groups on the samples were studied by infrared absorption spectroscopy (FTIR; Bruker Tensor37). Thermo gravimetric (TG) analysis curves were obtained with a PerkinElmer 7 simultaneous thermal analyzer with a heating rate of 15 ◦ C in a flowing nitrogen atmosphere.
2. Experimental 2.1. Synthesis of CdCO3 –TB nanotubes A clear solution of 0.001 mol Cd(CH3 COO)2 ·2H2 O (0.03 mol/L) dissolved in a mixture of 5 mL H2 O and 15 mL ethanol was formed.
∗ Corresponding author. Tel.: +86 22 60600658; fax: +86 22 60600658. E-mail address: [email protected] (S. Zhang). 0927-7757/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.colsurfa.2010.11.023
3. Results and discussion 3.1. XRD characterization of CdCO3 –TB Fig. 2 illustrates the X-ray diffraction profiles of the CdCO3 –TB hybrid nanotubes and TB. Comparing the XRD pattern of TB in Fig. 2a and that of CdCO3 TB in Fig. 2b, the absence of TB peaks in the pattern of CdCO3 –TB hybrid nanotubes may indicate that TB molecules have been dispersed into the structure of CdCO3 . Fur-
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L. Song et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 374 (2011) 129–133
Fig. 1. Molecular structure of Trypan Blue.
vibrational modes in TB molecules, respectively, indicating that the TE molecules have been hybridized into CdCO3 nanotubes. 3.3. DTG characterization of CdCO3 –TB To investigate whether the TB molecules exist in the as-prepared CdCO3 nanotubes, DTG of the CdCO3 –TB nanotubes was carried out. Fig. 4a shows the DTG curve of the CdCO3 –TB nanotubes. In the DTG curve, a distinct endothermic peak was observed at 294 ◦ C, which is associated with the decomposition of TB. The DTG curve indicated a 29.7% weight loss occurring from 232 to 390 ◦ C, which may be an indication that the TB molecules have been dispersed into the CdCO3 nanotubes. In order to investigate the TB molecules whether to exist in the as-prepared CdCO3 nanotubes, the composition of the CdCO3 nanotubes was determined by EDX (Fig. 4b). The atom ratio of N and S, about 0.64 and 3.46 at.%, was estimated from the EDX semi-quantitative acquisition. It proved the presence of S and N atoms in the CdCO3 nanotubes, thus indicating that the hybrid Fig. 2. X-ray diffraction patterns of TB and CdCO3 /TB nanotubes.
ther EDX also proves the result. As shown in Fig. 1b, all the peaks are attributed to the rhombohedral CdCO3 phase (space group R3c [No. 167]) with the lattice constants a = b= 4.915 A˚ and c = 16.267 A˚ (JCPDS card no. 02–0725). No other impurities were detected in the hybrid nanotube samples. 3.2. FTIR characterization of CdCO3 –TB The formation of CdCO3 –TB nanotubes was further confirmed by FTIR studies. The peaks (Fig. 3) around 1400 and 850 cm−1 are the characteristic vibration bands of CO3 2− [14]. The sample also showed absorption in the regions 3435, 1795, 1628, and 750 cm−l . The peaks may be assigned to the O H, C C , SO3 , and N H
Fig. 3. Infrared (IR) spectrum of the CdCO3 /TB nanotubes.
Fig. 4. (a) DTG and (b) EDX curve of CdCO3 /TB nanotubes.
L. Song et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 374 (2011) 129–133
131
Fig. 5. EM images of the as-synthesized products with different concentration of TB. (a) 0.17 g/L, (b) 0.08 g/L, (c) 0.04 g/L, and (d) 0.17 g/L using H2 O as solvent.
is successful. In the EDX peaks, the Al atom peak was attributed to the aluminum specimen support. In addition, the 30% loss of mass occurring from 390 to 710 ◦ C was in good agreement with the 25.6% final mass loss calculated for CdO. The following is the corresponding reaction:
using H2 O as solvent under the mentioned conditions. Nanorod bundles, 300 nm long and 50 nm wide, were observed in the products.
CdCO3 → CdO + CO2
Our proposed mechanism for producing the CdCO3 nanoparticles is as follows:
3.4. Morphological characterization of CdCO3 –TB The morphologies of the as-synthesized products were examined through TEM. Fig. 5a shows the typical TEM image of the sample prepared with 0.17 g/L of TB. The products are primarily composed of nanotubes with lengths up to 100–200 nm and diameters of 10–20 nm. Interestingly, the use of the same experimental conditions with a reduced TB concentration of 0.08 g/L produces porous nanorods (Fig. 5b). The aspect ratio of the nanorods with 200 nm length and 20 nm diameter is 10. When the sample was prepared with 0.04 g/L TB concentration, only irregular nanoparticles were obtained (Fig. 5c). The products were mainly nanoparticles with diameters of 20 nm. The experiment revealed that the morphology of the as-synthesized CdCO3 strongly depends on the solvent, in which the concentration of Cd(CH3 COO)2 ·2H2 O and TB was kept constant at 0.03 mol/L and 0.17 g/L, respectively. Fig. 5d shows the TEM image of the as-synthesized products
3.5. The growth mechanism of the CdCO3 –TB nanotubes
(1) Cd(CH3 COO)2 → Cd2+ + 2CH3 COO− (2) NH3 ·H2 O → NH4 + + OH− (3) CO2 (in air) + OH− → HCO3 − → H+ + CO3 2− (4) Cd2+ + CO3 2− → CdCO3 (5) CdCO3 + TB → CdCO3 –TB nanotubes Experimental results confirm that the concentration of TB and the solvent have a significant effect on the morphologies and sizes of the final products. The morphologies of CdCO3 –TB depending on the growth time are shown in Fig. 6 to illustrate the growth mechanism of the CdCO3 –TB nanotubes. The concentration of Cd(CH3 COO)2 ·2H2 O and TB was kept constant at 0.03 mol/L and 0.17 g/L using a mixture of 5 mL H2 O and 15 mL ethanol as solvent.
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L. Song et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 374 (2011) 129–133
Fig. 6. TEM images of the as-synthesized products with different growth time. (a) 6 h, (b) 12 h, (c) 24 h, (d) 36 h, and (e) 48 h. The concentration of Cd(CH3 COO)2 ·2H2 O and TB was kept constant at 0.03 mol/L and 0.17 g/L using a mixture of 5 mL H2 O and 15 mL ethanol as solvent.
As shown in Fig. 6a and b, when the reaction time was kept at 6 or 12 h, irregular nanoparticles were produced. Increasing the reaction time to 24 h transforms the petals of the nanoparticles into porous nanorods (Fig. 6c). As shown in Fig. 6d, when the reaction time was prolonged to 36 h, the little pores gradually changed to
bigger eyelets, whereas the porous nanorods also gradually transformed into hollow nanorods (Fig. 6e). The following is a proposed growth mechanism: combining Cd(CH3 COO)2 and TB results in fast nucleation and small particles. The CdCO3 crystal nucleus was adsorbed on long-chained
L. Song et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 374 (2011) 129–133
TB molecules. Subsequently, chains of particles form through the dissolution of small sphere-like particles which assemble into nanorods. The nanorods dissolve from the tips toward the interior under the action of hydrogen ions; this results in the formation of CdCO3 nanotubes. 4. Conclusion A simple reflux route of modifying parameters was used to synthesize CdCO3 –TB nanotubes successfully. TB can be used as a template to prepare CdCO3 nanostructures. By introducing TB as a heterogeneous template of the mineralization system, the structures can be further modified into nanorods and nanotubes. Acknowledgment This work was supported by Tianjin Planning Project of Science and Technology (10JCZDJC22500). References [1] H.P. Cong, S.H. Yu, Hybrid ZnO dye hollow spheres with new optical properties from a self-assembly process based on evans blue dye and cetyltrimetlammonium bromide, Adv. Funct. Mater. 17 (2007) 1814–1820. [2] H.P. Cong, S.H. Yu, Synthesis of microscale raft-shaped Zinc (II) phenylalanine complexes and zinc(II)/phenylalanine/dye hybrid bundles with new optical properties, Adv. Funct. Mater. 18 (2008) 195–202.
133
[3] A.P. Alivisatos, Semiconductor clusters, nanocrystals, and quantum dots, Science 271 (1996) 33–937. [4] Y Cui, C.M. Lieber, Functional nanoscale electronic devices assembled using silicon nanowire building blocks, Science 291 (2001) 851–853. [5] J. Hu, M. Ouyang, P. Yang, C.M. Lieber, Growth and electrical properties of nanotube/nanowire heterojunctions, Nature 399 (1999) 48–51. [6] H.M. Yang, G.Z. Qiu, X.C. Zhang, A.D. Tang, W.G. Yang, Preparation of CdO nanoparticles by mechanochemical reaction, J. Nanopart. Res. 6 (2004) 539–542. [7] A. Askarinejad, A. Morsali, Synthesis of cadmium(II) hydroxide, cadmium(II) carbonate and cadmium(II)oxide nanoparticles; investigation of intermediate products, Chem. Eng. J. 150 (2009) 569–571. [8] Z.Y Jia, Y.W. Tang, L.J. Luo, B.H. Li, Shape-controlled synthesis of singlecrystalline CdCO3 and corresponding porous CdO nanostructures, Cryst. Growth and Design 8 (2008) 2116–2120. [9] S. Ashoka, P. Chithaiah, G.T. Chandrappa, Studies on the synthesis of CdCO3 nanowires and porous CdO powder, Mater. Lett. 64 (2010) 173–176. [10] S.H. Yui, H.M. Colfen, K. Tauer, M. Antonietti, Tectonic arrangement of BaCO3 nanocrystals into helices induced by a racemic block copolymer, Nat. Mater. 4 (2005) 51–55. [11] S.H. Yui, H.M. Colfen, A.W. Xu, W.F. Dong, Complex spherical BaCO3 superstructures self-assembled by a facile mineralization process under control of simple polyelectrolytes, Cryst. Growth and Design 4 (2004) 33–37. [12] S.H. Yui, H.M. Colfen, K. Tauer, M. Antonietti, Polymer-controlled morphosynthesis and mineralization of metal carbonate superstructures, J. Phys. Chem. B 107 (2003) 7396–7405. [13] E. Dalas, P. Klepetsanis, P.G. Koutsoukos, The overgrowth of calcium carbonate on poly (vinyl chloride-co-vinyl acetate-co-maleic acid), Langmuir 15 (1999) 8322–8327. [14] S.K.H. Khalil, M.A. Azooz, Application of vibrational spectroscopy in identification of the composition of the urinary stones, J. Appl. Sci. Res. 3 (2007) 387–391.