ISSN 1063 7850, Technical Physics Letters, 2011, Vol. 37, No. 3, pp. 253255. Pleiades Publishing, Ltd.

., 2011. Original Russian Text Yu.I. Golovin, D.Yu. Golovin, A.V. Shuklinov, R.A. Stolyarov, V.M. Vasyukov, 2011, published in Pisma v Zhurnal Tekhnichesko Fiziki, 2011, Vol. 37, No. 6, pp. 2126.

Electrodeposition of Nickel Nanoparticles onto Multiwalled Carbon Nanotubes

Yu. I. Golovin*, D. Yu. Golovin, A. V. Shuklinov, R. A. Stolyarov, and V. M. Vasyukov
Nanotechnology and Nanomaterials Research and Education Center, Tambov State University, Tambov, 392000 Russia *e mail: golovin@tsu.tmb.ru
Received October 13, 2010

AbstractThe process of nickel nanoparticle nucleation and growth during galvanochemical deposition on the surface of multiwalled carbon nanotubes has been studied. The dependences of the morphology, size, and spacing of nickel nanoparticles on the deposition time at a current density of 5 and 0.5 A/dm2 are determined. DOI: 10.1134/S1063785011030217

As is well known, the chemical, biological, bacteri cidal, catalytic, and other activities on metal nanopar ticles depend not only on their elemental composi tion, but on the shape, dimensions, and structure as well. Submicro and nanodimensional metal particles are employed in various fields of science and technol ogy. In particular, nickel particles are widely used as catalysts for the selective synthesis of various sub stances, including the growth of carbon nanotubes (CNTs), hydrogenation of citral, catalytic cracking of methane, etc. [14]. These particles are also used in order to increase the hydrogen storage capacity of fuel cells [5, 6] and in the fabrication of supercapacitors [7], biosensors [8], etc. Nickel is known to possess rather high catalytic activity at a relatively low cost as compared to other (especially, noble metal) catalysts. In this context, a topical task consists in obtaining Ni nanoparticles with identical structure, narrow size distribution, and homogeneous distribution in the vol ume of a medium. There were attempts at solving this task by various methods, including the stabilization of growing nanoparticles by various surface passivators, disintegration of agglomerated particles [1, 9], and dispersion of nanoparticles over a substrate [68, 10]. The first approach complicates the composition of reactants and contaminates the synthesized nanopar ticles by stabilizers; the second method does not pro vide particles with dimensions below ~1020 nm and does not exclude secondary agglomeration; and the third pathway is limited by possibilities of the matrix. An outstanding combination of the properties of CNTshigh specific surface, mechanical strength, chemical inertness, and thermal stabilitymake them an ideal medium for the arrangement, storage, and use of Ni nanoparticles. On the other hand, nickel can expand the functional possibilities of CNTs by imparting to them desired magnetic, biomedical, and catalytic properties. In particular, Ni nanoparticles

can be good catalysts for the synthesis of new CNTs with diameters dependent on the particle size. The present investigation was aimed at establishing the laws that govern the nucleation and growth of Ni nanoparticles on the surface of CNTs under condi tions of electrochemical deposition. Nanoparticles were obtained using the gal vanochemical deposition of nickel from the Watts electrolyte (70 vol % NiSO4, 20 vol % NiCl2, 10 vol % HBO3). The average current density pert unit substrate surface area was 5 or 0.5 A/dm2. The experiments were performed with multiwalled carbon nanotubes (MCNTs) commercially available under the trade mark of Taunit (Tambov Innovation Technology Cen ter for Machine Building). The MCNTs were 5 10 m long and had diameters within D ~ 1030 nm. The electrolyte acidity (pH 4.26 0.02) was checked by a Selecta 2005 pH meter. The microstructure, morphology, and dimensions of Ni nanoparticles and MCNTs were studied by electron microscopy in the scanning (SEM) and transmission (TEM) modes in a Neon 40 instrument (Carl Zeiss, Germany). The polished surface of a copper cathode was degreased in an 80% aqueous NaOH solution. Then MCNTs were applied onto the cathode surface from an aqueous suspension (0.1 g/l) prepared in a 50 ml tube by ultrasonic dispersion at 22 kHz for 10 min at a power of 780 W. Water was evaporated, and MCNTs retained on the cathode surface were used for the galvanochemical deposition of nickel. The dimensions of deposited Ni particles were determined by processing their SEM images using a Structure 5.0 program package (Videotest, Russia). As can be seen from the SEM image presented in Fig. 1a, nickel initially deposits on MCNTs in the form of almost equiaxial particles rather than homoge neously covers the surface. It was shown [8, 10] that

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MCNT

()

200 nm

Ni

(b)

400 nm

(c)

10 nm

Fig. 1. SEM images (left) and schematic cross sectional diagrams (right) of MCNTs with Ni deposited for (a) 5 s and (b) 15 s at j = 5 A/dm2; (c) TEM micrograph of a Ni nanoparticle on the MCNT surface (5 s, 5 A/dm2).

(a) 500 l, nm 400 300 200 100 10 2.0 1.5 1.0 0.5 0 10 20 30 40 50 q, a. u. 60 (b) 1 2 20 30 40 50 q, a. u. 60 1 3

2 4 250 150 100 50 70 80 d, nm 200

70

80

Fig. 2. Plots of (a) the spacing l (1, 2) and diameter d (3, 4) of Ni nanoparticles grown at j = 5 A/dm2 (1, 3) and 0.5 A/dm2 (2, 4) and (b) the ratio of Ni and MCNT sur face areas for j = 5 A/dm2 (1) and 0.5 A/dm2 (2) versus charge q transferred during the electrochemical deposition of nickel.

energetically favorable centers for the nucleation and growth of Ni clusters are provided by special sites on the MCNT surface such as various surface defects and nanotube ends. The growing metal particles encir cle the MCNT, thus forming a set of beads stringed on the tube (Fig. 1b). As the nanoparticle diameter d increases, the particles merge together and completely cover the MCNT surface. According to TEM data (Fig. 1c), the metal beads possess a polycrystalline structure. Thus, using the galvanochemical deposition method, it is possible to obtain a structure comprising Ni nanoparticles with a narrow size distribution arranged in the framework of CNTs. A volume array of MCNTs ensures a uniform spatial distribution and storage of Ni nanoparticles, while remaining highly permeable for a flow of liquid or gas (not presenting large hydrodynamic resistance in contrast to com pacted powders). An analysis of the dependence of the average dis tance l between Ni particles on the transferred charge q showed that the initial spacing of nuclei at the onset of deposition was l0 ~ 200 nm (Fig. 2a). In the course of Ni electrodeposition, the l value increases, while the number of particles on each MCNT decreases (Fig. 2a). This fact indicates that smaller particles are dissolved and nickel is redistributed to coarser particles, around which screened zones with reduced probability of nucleation are formed [11]. Thus, it can be suggested that the main role in the for
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mation of spherical nanoparticles is played by the dif fusion processes and the redistribution of electric cur rent lines about MCNTs with growing Ni beads. Presently, the cost of MCNTs is still rather high. In order to assess the expediency of using them as carriers for metal catalyst particles, it is necessary to determine the optimum ratio of surface areas. Figure 2b shows a plot of the ratio of the total surface area of the cata lyst to that of MCNTs versus charge transferred during electrochemical deposition. As can be seen, the sur face area of Ni catalyst nanoparticles can exceed the area of nanotubes by a factor of 2 and even more, which implies that the choice of MCNTs as a matrix for the spatial arrangement of Ni nanoparticles is quite expedient. A system of these particles strongly fixed on this framework can expand the spectrum of MCNT applications to include filters, bioactive composites, nanowires, quantum dots, etc. Acknowledgments. The authors are grateful to A.G. Tkachev and Yu.V. Litovk for kindly providing nanotubes and the Watts electrolyte. This study was supported in part by the Ministry of Science and Education of the Russian Federation within the framework of Federal Targeted Programs Scientific and Pedagogical Staff for Innovative Russia (20092013) and Development of Scien tific Potential of Universities (20092010) (project no. 2.1.1/2643).

REFERENCES
1. B. Bushan, Handbool of Nanotechnology (Springer Ver lag Berlin, 2010). 2. Yu. I. Golovin, Introduction to Nanotechnology (Mashi nostroenie, Moscow, 1985) [in Russian]. 3. Y. Tang, D. Yang, F. Qin, J. Hu, Ch. Wang, and H. Xu, Solid State Chem. 182, 2279 (2009). 4. I. Gonzalez, J. C. De Jesus, C. U. de Navarro, and M. Garcia, Catal. Today 149, 352 (2010). 5. C. Y. Chen, K. Y. Lin, W. T. Tsai, J. K. Chang, and C. M. Tseng, Int. J. Hydrogen Energy 35, 5490 (2010). 6. K. Y. Lin, W. T. Tsai, and J. K. Chang, Int. J. Hydro gen Energy 35, 7555 (2010). 7. Y. Liu, W. Jiang, L. Xu, X. Yang, and F. Li, Materials Lett. 63, 2526 (2009). 8. C. Bittencourt, A. Felten, J. Ghijsen, J. J. Pireaux, W. Drube, R Erni, and V. G. Tendeloo, Chem. Phys. Lett. 436, 368 (2007). 9. Yu. A. Zakharov and R. P. Kolmykov, Polzunov. Vestn., No. 3, 137 (2008). 10. A. Susumu, E. Morinobu, and K. Norio, Carbon 42, 641 (2004). 11. Yu.Ya. Lukomskii and D.Yu. Gamburg, Physicochemi cal Principles of Electrochemistry (Intellekt, Dolgoprud nyi, 2008) [in Russian].

Translated by P. Pozdeev

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2011