Silver nanoparticles were spontaneously formed on pristine and oxidized single-wall nanotubes. Nanoparticles were observed on carbon nanotubes with AFM, and the presence of Ag nanoparticles were confirmed by ESR experiments. Raman spectroscopy of the Ag-treated carbon nanotubes had a 4–10X enhancement of intensity compared to untreated carbon nanotubes. Ag nanoparticles formed at defect sites on the CNT surface, where free electrons located at the defect sites reduced Ag+ to Ag. A mechanism for the propagation of the nanoparticles is through a continual negative charge generation on the nanoparticle by electron transfer from doublet oxygen (O2?). 1. Introduction Since the discovery of carbon nanotubes was first published in 1991, their unique chemical and physical properties have since attracted interest in a wide spectrum of fields, including materials science, engineering, physical sciences, and medical/health sciences [1–5]. In its simplest form, single-walled carbon nanotubes (SWCNTs) are composed of a single graphene layer rolled into a cylindrical shape, having dimensions of 0.4–1?nm diameter and lengths on the order of 103?nm. Multi walled carbon nanotubes (MWCNTs), on the other hand, are composed of an array of concentric cylinders with diameters up to 50?nm. In addition, the orientation of the graphitic rings along the tubular surface result in the CNTs exhibiting metallic or semiconducting properties [6]. Similar to CNTs, metal nanoparticles have also generated interest, especially in regards to sensors, catalysis, and fuel cell research. Integrating nanoparticles with CNTs is an attractive feature that has potential application in catalysis, sensors, and fuel cells due to the enhanced dispersion and performance [7–9]. There are many strategies for incorporating metal nanoparticles onto CNT surfaces. One of the most straight forward methods is vapor deposition of a metal layer onto the CNT surface [10]. However, this method requires the deposition of the CNTs onto a substrate, followed by depositing a metal film under vacuum. Electrodepositing Ag through electrolysis reduction [11, 12], or through a η2-coordination, where a Sn2+-activated surface reduces Ag+ onto the CNT surface [13]. Irradiating CNTs with γ-rays in the presence of Ag+ as well as some type of hydrophilic polymer has also produced Ag-decorated CNTs, presumably through the attachment of the polymer onto the CNT surface [14–16]. Here, we report the spontaneous formation of Ag nanoparticles onto freshly sonicated SWCNT surfaces. Raman spectroscopy measurements revealed signal
References
[1]
M. S. Dresselhaus, G. Dresselhaus, J. C. Charlier, and E. Hernández, “Electronic, thermal and mechanical properties of carbon nanotubes,” Philosophical Transactions of the Royal Society of London A, vol. 362, no. 1823, pp. 2065–2098, 2004.
[2]
B. S. Harrison and A. Atala, “Carbon nanotube applications for tissue engineering,” Biomaterials, vol. 28, no. 2, pp. 344–353, 2007.
[3]
W. Hoenlein, F. Kreupl, G. S. Duesberg et al., “Carbon nanotube applications in microelectronics,” IEEE Transactions on Components and Packaging Technologies, vol. 27, no. 4, pp. 629–634, 2004.
[4]
L. Santiago-Rodríguez, G. Sánchez-Pomales, and C. R. Cabrera, “DNA-functionalized carbon nanotubes: Synthesis, self-assembly, and applications,” Israel Journal of Chemistry, vol. 50, no. 3, pp. 277–290, 2010.
[5]
H. C. Wu, X. Chang, L. Liu, F. Zhao, and Y. Zhao, “Chemistry of carbon nanotubes in biomedical applications,” Journal of Materials Chemistry, vol. 20, no. 6, pp. 1036–1052, 2010.
[6]
M. S. Dresselhaus, G. Dresselhaus, R. Saito, and A. Jorio, “Raman spectroscopy of carbon nanotubes,” Physics Reports, vol. 409, no. 2, pp. 47–99, 2005.
[7]
P. Serp, M. Corrias, and P. Kalck, “Carbon nanotubes and nanofibers in catalysis,” Applied Catalysis A, vol. 253, no. 2, pp. 337–358, 2003.
[8]
B. Louis, et al., “Advances in the use of carbon nanomaterials in catalysis,” Ordered Porous Solids, pp. 621–649, 2009.
[9]
J. Nakamura, “Novel support materials for fuel cell catalysts,” Springer Series in Materials Science, pp. 185–197, American Chemical Society (ACS), 2011.
[10]
R. Kumar, H. Zhou, and S. B. Cronin, “Surface-enhanced Raman spectroscopy and correlated scanning electron microscopy of individual carbon nanotubes,” Applied Physics Letters, vol. 91, no. 22, Article ID 223105, pp. 1–3, 2007.
[11]
Y. C. Chen, R. J. Young, J. V. Macpherson, and N. R. Wilson, “Single-walled carbon nanotube networks decorated with silver nanoparticles: A novel graded SERS substrate,” Journal of Physical Chemistry C, vol. 111, no. 44, pp. 16167–16173, 2007.
[12]
Y. Qian, S. Huang, F. Gao, Q. Cai, L. Zhang, and W. Hu, “Superlong-oriented single-walled carbon nanotube arrays on substrate with low percentage of metallic structure,” Journal of Physical Chemistry C, vol. 113, no. 17, pp. 6983–6988, 2009.
[13]
S. K. Choi, K. Y. Chun, and S. B. Lee, “Selective decoration of silver nanoparticles on the defect sites of single-walled carbon nanotubes,” Diamond and Related Materials, vol. 18, no. 4, pp. 637–641, 2009.
[14]
J. Cveticanin, A. Krkljes, Z. Kacarevic-Popovic et al., “Functionalization of carbon nanotubes with silver clusters,” Applied Surface Science, vol. 256, no. 23, pp. 7048–7055, 2010.
[15]
K. A. Dubey, C. V. Chaudhari, R. Rao, Y. K. Bhardwaj, N. K. Goel, and S. Sabharwal, “Radiation processing and characterization of poly(vinyl alcohol) nano-composites—part 1: nano-particulate filler tuned crosslinking behavior,” Journal of Applied Polymer Science, vol. 118, no. 6, pp. 3490–3498, 2010.
[16]
S. D. Oh, B. K. So, S. H. Choi et al., “Dispersing of Ag, Pd, and Pt-Ru alloy nanoparticles on single-walled carbon nanotubes by γ-irradiation,” Materials Letters, vol. 59, no. 10, pp. 1121–1124, 2005.
[17]
M. Milnera, J. Kürti, M. Hulman, and H. Kuzmany, “Periodic resonance excitation and intertube interaction from quasicontinuous distributed helicities in single-wall carbon nanotubes,” Physical Review Letters, vol. 84, no. 6, pp. 1324–1327, 2000.
[18]
S. D. M. Brown, A. Jorio, P. Corio et al., “Origin of the Breit-Wigner-Fano lineshape of the tangential G-band feature of metallic carbon nanotubes,” Physical Review B, vol. 63, no. 15, pp. 1–8, 2001.
[19]
C. G. Salzmann, S. A. Llewellyn, G. Tobias, M. A. H. Ward, Y. Huh, and M. L. H. Green, “The role of carboxylated carbonaceous fragments in the functionalization and spectroscopy of a single-walled carbon-nanotube material,” Advanced Materials, vol. 19, no. 6, pp. 883–887, 2007.
[20]
S. B. Fagan, A. G. S. Filho, J. M. Filho, P. Corio, and M. S. Dresselhaus, “Electronic properties of Ag- and CrO3-filled single-wall carbon nanotubes,” Chemical Physics Letters, vol. 406, no. 1–3, pp. 54–59, 2005.
[21]
M. Terrones, A. Filho, and A. Rao, “Doped carbon nanotubes: synthesis, characterization and applications,” in Carbon Nanotubes, pp. 531–566, Springer, Berlin, Germany, 2008.
[22]
R. Kumar and S. B. Cronin, “Raman scattering of carbon nanotube bundles under axial strain and strain-induced debundling,” Physical Review B, vol. 75, no. 15, Article ID 155421, pp. 1–4, 2007.
[23]
G. Mitrikas, C. C. Trapalis, N. Boukos, V. Psyharis, L. Astrakas, and G. Kordas, “Size distribution and EPR of silver nanoparticles in SiO2 matrix,” Journal of Non-Crystalline Solids, vol. 224, no. 1, pp. 17–22, 1998.
[24]
G. Mitrikas, C. C. Trapalis, and G. Kordas, “Electron spin-lattice relaxation of silver nanoparticles embedded in SiO2 and TiO2 matrices,” Journal of Chemical Physics, vol. 111, no. 17, pp. 8098–8104, 1999.
[25]
M. V. Chursanova, L. P. Germash, V. O. Yukhymchuk, V. M. Dzhagan, I. A. Khodasevich, and D. Cojoc, “Optimization of porous silicon preparation technology for SERS applications,” Applied Surface Science, vol. 256, no. 11, pp. 3369–3373, 2010.
[26]
R. A. Salkar, P. Jeevanandam, S. T. Aruna, Y. Koltypin, and A. Gedanken, “The sonochemical preparation of amorphous silver nanoparticles,” Journal of Materials Chemistry, vol. 9, no. 6, pp. 1333–1335, 1999.
[27]
J. M. Maley, T. K. Sham, A. Hirose, Q. Yang, M. P. Bradley, and R. Sammynaiken, “Chemical reactions and applications of the reductive surface of porous silicon,” Journal of Nanoscience and Nanotechnology, vol. 10, no. 10, pp. 6332–6339, 2010.
[28]
I. Coulthard, R. Sammynaiken, S. J. Naftel, P. Zhang, and T. K. Sham, “Porous silicon: a template for the preparation of nanophase metals and bimetallic aggregates,” Physica Status Solidi (A) Applied Research, vol. 182, no. 1, pp. 157–162, 2000.
[29]
Y. D. Kim and G. Gantef?r, “Formation of di-oxygen species on Ag anion clusters,” Chemical Physics Letters, vol. 383, no. 1-2, pp. 80–83, 2004.
[30]
J. Yang, G. Schatte, J. Maley, and R. Sammynaiken, “Surface Charge and Doublet Oxygen in Nanotoxicology,” In preparation.