Table of Contents Author Guidelines Submit a Manuscript
Journal of Chemistry
Volume 2013, Article ID 831694, 5 pages
http://dx.doi.org/10.1155/2013/831694
Research Article

Synthesis of Colloidal Ruthenium Nanocatalyst by Chemical Reduction Method

Department of Chemical Engineering, Sardar Vallabhbhai National Institute of Technology, Gujarat, Surat-395007, India

Received 27 February 2012; Revised 12 May 2012; Accepted 25 May 2012

Academic Editor: Danielle Ballivet-Tkatchenko

Copyright © 2013 R. G. Patharkar et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

Colloidal ruthenium nanoparticles were prepared by chemical reduction of ruthenium trichloride (RuCl3) using sodium borohydrate (NaBH4) as reducing agent and sodium dodecyl sulfate (SDS) as a stabilizer. Size and size distribution of synthesized colloidal Ru nanoparticles were studied by varying different parameters such as molar ratio (MR) of SDS/RuCl3, NaBH4/RuCl3, effects of different stabilizers, and reducing agents. Prepared nanoparticles were characterized by transmission electron microscope (TEM) and dynamic light scattering (DLS). Stability of colloidal nanoparticles was detected by Turbiscan. Stable Ru nanoparticles were dispersed on γ-Al2O3 to prepare Ru/γ-Al2O3 catalyst. This catalyst was characterized by X-ray Diffraction (XRD) and transmission electron microscope (TEM).

1. Introduction

Metal nanoparticles have of great fundamental and practical interest due to their unique physical properties, chemical reactivity, and potential applications in electronics, catalysis, and biochemistry [1, 2]. Nanoparticles of many metals, such as gold, platinum, palladium, cobalt, silver [3], and rhodium [4], have been synthesized by different experimental techniques. However, the synthesis of ruthenium (Ru) nanoclusters is scarcely reported, despite the important technological role of ruthenium [5] as a catalyst and redox processes [6]. It also serves as electrocatalyst in the electrooxidation of methanol and CO, the core reaction that occurs in direct methanol fuel cells [7]. The catalytic activities of the Ru nanoparticles have been tested for partial oxidation of methane shows high activity and high CO selectivity [8].

Among the various techniques to obtain nanosized metal particles, the wet chemical method is probably the most popular due to its simplicity, low cost, and ability to produce large quantity. Chemical reduction of metal salts using various reducing agents in the presence of protecting agent is preferred due to the advantage of controllable size and shape of the particles [8]. Chemical reduction method have been carried out in the presence of a stabilizer such as linear polymers, ligands, surfactants, or heterogeneous supports, which prevents the nanoparticles from aggregating, allowing at the same time their isolation [9]. In order to synthesize uniformly distributed nanocatalyst, stability of the colloidal nanoparticles and the homogeneous dispersion over the support play the most important role.

In view of above literature, attempts had been made to synthesize uniformly distributed stable ruthenium by chemical reduction method using SDS as stabilizing agent. Different parameters which affect particle size and size distribution such as molar ratio (MR) of SDS/RuCl3, NaBH4/RuCl3, effects of different stabilizers, and reducing agents were studied systematically. Turbiscan had been used to monitor stabilized Ru nanoparticles and dispersions in the kinetic studies of their stability. Stable colloidal ruthenium nanoparticles were dispersed on γ-Al2O3 by mechanical stirring and characterized using XRD and TEM.

2. Experimental

2.1. Materials

Ruthenium trichloride (RuCl3·nH2O), sodium borohydrate (NaBH4, 95%), hydrazine hydrate (80%), sodium dodecyl sulphate (SDS), and cetyltrimethylammonium bromide (CTAB) were purchased from Finar Chemicals, India. Poly(N-vinyl-2-pyrrolidone) (PVP, average molecular weight 40,000) and Aerosol OT (AOT) were purchased from Heny Fine Chemicals, India. Gamma alumina powder of 98% purity was purchased from National Chemicals, India. Distilled water of pH 5.9 ± 0.2, conductivity 1.0 μS/cm (Millipore, Elix, India) was used throughout the experiments for preparing the aqueous solutions.

2.2. Preparation of Ruthenium Nanoparticles

Ruthenium nanoparticles were synthesized by the reduction of ruthenium trichloride in presence of reducing agents and stabilizing agents using water as solvent. RuCl3 solution (0.2 mM) was prepared by dissolving the known amount of RuCl3 in 50 mL distilled water under continuous stirring. Separately, known amount of SDS and NaBH4 was dissolved into 50 mL distilled water. Molar ratios of NaBH4/RuCl3 and SDS/RuCl3 were maintained at 30 and 20, respectively. Colloidal ruthenium nanoparticles were produced by gradual addition of prepared RuCl3 solution into the mixture of NaBH4 and SDS slowly under continuous stirring for 1 h [10].

2.3. Ru/γ-Al2O3 Catalyst Preparation

To prepare Ru/γ-Al2O3 catalyst, synthesized colloidal nanoparticles were collected by centrifugation and redispersed into the methanol by sonication (B. Braun Biotech International, Labsonic). 5 gm of γ-alumina was added in to the solution and the mixture was mechanically stirred at 6500 rpm using Ultraturax (IKA WERKE, GmBH & Co. KG) for 24 h at room temperature to form a homogeneous suspension. The mixture was washed with acetone and water to remove the organic material and dried at 100°C for 6 h. The Ru supported on γ-alumina was found in a powder with a dark brown color. The catalyst was calcinated at 300°C for 6 h in an oven. The catalyst was stored in moisture-free atmosphere.

2.4. Characterization

The sizes of nanoparticles were measured using DLS (Malvern Zetasizer, Nano ZS-90, UK). Morphology of the nanoparticles was observed by TEM analysis (Philips Tecnai—20, Holland) operating at 200 kV provides 0.27 nm point resolution. Nanoparticles stability was analyzed using Turbiscan Classic MA 2000 at light rays of 880 nm wavelength (Formulaction, France). Phase composition of Ru/γ-Al2O3 catalyst was observed by X-ray diffraction (Philips, X Pert-MPD, Holland).

3. Results and Discussion

3.1. Effect of SDSRuCl3 Molar Ratio

Generally, anionic surfactant, SDS, was used as stabilizer to prevent the growth and aggregation of nanoparticles. SDS/RuCl3 molar ratio was changed from 1–40 keeping RuCl3 concentration at 0.2 mM and 30 molar ratio (MR) of NaBH4/RuCl3 (Figure 1). The size of the particles decreased with increasing MR of SDS/RuCl3 up to 20. Hydrodynamic diameter of the colloidal Ru nanoparticles, which was formed due to aggregation of nanocrystals inside micelles was found to be 90 nm at MR = 1 and 20 nm at MR = 20. Above 20 MR, size of the particles increased with increasing the MR of SDSRuCl3. Actually larger size of the ruthenium nanoparticles was produced at lower concentration of SDS because of higher rate of agglomeration due to insufficient amount of stabilizing agent in the system [11]. The increase of SDS/RuCl3 MR, increased the concentration of SDS. High concentration of surfactant increased viscosity, the increase in viscosity led to reduce rate of surfactant migration or reduced rate of diffusion speed of micelles and decreased the electrostatic repulsion, there by promoting the particle agglomeration [12, 13].

831694.fig.001
Figure 1: Study of effect of SDS/RuCl3 MR on particle size using particle-size analyser.
3.2. Effect of NaBH4RuCl3 Molar Ratio

Sodium borohydrate was used as reducing agent for the synthesis of Ru nanoparticles. The effect of NaBH4 concentration was studied by varying MR of NaBH4/RuCl3 (10–30), keeping other parameters constant RuCl3 = 0.2 mM and 20 MR of SDS/RuCl3 (Figure 2).

831694.fig.002
Figure 2: Study of effect of NaBH4/RuCl3 MR on particle size using particle-size analyser.

At lower value of MR of NaBH4/RuCl3 (MR = 10), larger size of nanoparticles was observed by DLS due to the insufficient reduction of RuCl3. However, with increasing the MR of NaBH4/RuCl3 from 15 to 30, narrow peaks were obtained, suggesting that Ru nanoparticles were produced with smaller size. Liu et al. [14] also found that lower concentration of NaBH4 produced boron hydroxide through hydrolysis of NaBH4. This boron hydroxide was absorbed to the Ru nanoparticles, reducing the electron density of surface and causing aggregation of Ru nanoparticles which resulted larger nanoparticles size. On the other hand, higher concentration of NaBH4 increased the concentration of boron hydroxide which formed thick BH4 layer preventing the boron hydroxide from absorbing into the surface of Ru nanoparticles, resulting in well-dispersed smaller nanoparticles.

3.3. Effect of Different Types of Stabilizing Agents on Particles Size

In order to know the effect of different types of stabilizing agent like PVP, SDS, CTAB, and AOT on the size of Ru nanoparticles, at constant (RuCl3) = 0.2 mM, 20 MR of SurfactantRuCl3 and 30 MR of NaBH4RuCl3. It was observed that the smallest particle size (Figure 3) was obtained for PVP (20 nm) and SDS (25 nm) and the particle size was significantly smaller than AOT and CTAB. Actually PVP would act as stabilizing as well as a reducing agent, which resulted in the lowest particle size of ruthenium. For cationic surfactant (CTAB), Ru nanoparticles were attracted by the positive charge of the surfactant, hence agglomerated near the outside of micelle which resulted larger nanoparticles [15, 16].

831694.fig.003
Figure 3: Study of effect of different type of stabilizing agents on particle size using particle-size analyser.

TEM image and DLS histogram of SDS stabilized colloidal Ru nanoparticles were shown in Figure 4. TEM showed that average particle size was 3–25 nm, lower than that of the particle size (20–70 nm) obtained by DLS. Actually in TEM only nanoparticles without surfactant layers were visible, this resulted lower in particle size.

fig4
Figure 4: (a) TEM image and number distribution and (b) DLS distribution of Ru nanoparticles using SDS using particle-size analyser.
3.4. Stability of Ruthenium Nanoparticles

The nanoparticles were stabilized due to attractive and repulsive electrostatic forces created by stabilizing agents present in the system. Nanoparticles stability was analyzed using transmission and back scattering (BS) profiles, scanning the colloidal sample by light rays of 880 nm wavelength using Turbiscan. It was observed that BS profiles at different times for SDS and PVP at 20 MR (Figure 5) were superimposing which indicated that the structure and average size of the Ru nanoparticles were not changing up to 24 h.

fig5
Figure 5: Study of stability of Ru nanoparticles at different stabilizing agents, (a) SDS and (b) PVP, using Turbiscan.
3.5. Characterization of Ru∕γ-Al2O3 Catalyst

XRD diagram (Figure 6) showed that the diffraction peak at , which was exactly consistent with the value (2.07 Å) of ruthenium metal [16]. The size of the Ru cluster was calculated by the Debye Scherrer formula [17] which was found to be 15 nm, nearly close to the average diameter observed by TEM analysis of Ru/γ-Al2O3 catalyst as shown in Figure 7.

831694.fig.006
Figure 6: XRD of Ru/γ-Al2O3 supported catalyst.
831694.fig.007
Figure 7: TEM image of Ru/γ-Al2O3-supported catalyst.

4. Conclusion

SDS-stabilized ruthenium nanoparticles were synthesized by proper selection of stabilizer, reducing agent and optimizing SDS/RuCl3 MR at 20, NaBH4/RuCl3 MR at 30. Stabilized ruthenium nanoparticles were dispersed on γ-alumina by mechanical stirring to obtain uniformly distributed supported catalyst. The size of the nanoparticles obtained from XRD was consistent with TEM data.

References

  1. T. Teranish and M. Miyake, “Size control of palladium nanoparticles and their crystal structures,” Chemistry of Materials, vol. 10, no. 2, pp. 594–600, 1998. View at Publisher · View at Google Scholar
  2. T. Tsukatani and H. Fujihara, “New method for facile synthesis of amphiphilic thiol-stabilized ruthenium nanoparticles and their redox-active ruthenium nanocomposite,” Langmuir, vol. 21, no. 26, pp. 12093–12095, 2005. View at Publisher · View at Google Scholar · View at Scopus
  3. F. Bonet, C. Guéry, D. Guyomard, R. Herrera Urbina, K. Tekaia-Elhsissen, and J. M. Tarascon, “Electrochemical reduction of noble metal compounds in ethylene glycol,” International Journal of Inorganic Materials, vol. 1, no. 1, pp. 47–51, 1999. View at Google Scholar · View at Scopus
  4. Y. Wang, J. Ren, K. Deng, L. Gui, and Y. Tang, “Preparation of tractable platinum, rhodium, and ruthenium nanoclusters with small particle size in organic media,” Chemistry of Materials, vol. 12, no. 6, pp. 1622–1627, 2000. View at Publisher · View at Google Scholar · View at Scopus
  5. X. Yan, H. Liu, and K. Y. Liew, “Size control of polymer-stabilized ruthenium nanoparticles by polyol reduction,” Journal of Materials Chemistry, vol. 11, no. 12, pp. 3387–3391, 2001. View at Publisher · View at Google Scholar
  6. H. Li, R. Wang, Q. Hong et al., “Ultrasound-assisted polyol method for the preparation of SBA-15-supported ruthenium nanoparticles and the study of their catalytic activity on the partial oxidation of methane,” Langmuir, vol. 20, no. 19, pp. 8352–8356, 2004. View at Publisher · View at Google Scholar · View at Scopus
  7. F. Maillard, G. Q. Lu, A. Wieckowski, and U. Stimming, “Ru-decorated Pt surfaces as model fuel cell electrocatalysts for CO electrooxidation,” Journal of Physical Chemistry B, vol. 109, no. 34, pp. 16230–16243, 2005. View at Publisher · View at Google Scholar · View at Scopus
  8. K. S. Chou, Y. C. Lu, and H. H. Lee, “Effect of alkaline ion on the mechanism and kinetics of chemical reduction of silver,” Materials Chemistry and Physics, vol. 94, no. 2-3, pp. 429–433, 2005. View at Google Scholar
  9. K. D. Kim, D. N. Han, and H. T. Kim, “Optimization of experimental conditions based on the Taguchi robust design for the formation of nano-sized silver particles by chemical reduction method,” Chemical Engineering Journal, vol. 104, no. 1–3, pp. 55–61, 2004. View at Publisher · View at Google Scholar
  10. K. C. Song, S. M. Lee, T. S. Park, and B. S. Lee, “Preparation of colloidal silver nanoparticles by chemical reduction method,” Korean Journal of Chemical Engineering, vol. 26, no. 1, pp. 153–155, 2009. View at Publisher · View at Google Scholar
  11. Y. Liguo and Z. Yanhum, “Preparation of nano-silver flake by chemical reduction method,” Rare Metal Materials and Engineering, vol. 39, no. 3, pp. 401–404, 2010. View at Publisher · View at Google Scholar
  12. R. Patakfalvi, S. Papps, and I. Dekany, “The kinetics of homogeneous nucleation of silver nanoparticles stabilized by polymers,” Journal of Nanoparticle Research, vol. 9, no. 3, pp. 353–364, 2007. View at Google Scholar
  13. R. Pataklvi, Z. Viranyi, and I. Dekany, “Kinetics of silver nanoparticle growth in aqueous polymer solutions,” Colloid & Polymer Science, vol. 283, pp. 299–305, 2004. View at Google Scholar
  14. J. Liu, J. B. Lee, D. H. Kim, and Y. Kim, “Preparation of high concentration of silver colloidal nanoparticles in layered laponite sol,” Colloids and Surfaces A, vol. 302, no. 1–3, pp. 276–279, 2007. View at Publisher · View at Google Scholar · View at Scopus
  15. S. U. Nandanwar, M. Chakraborty, S. Mukhopadhyay, and K. T. Shenoy, “Stability of ruthenium nanoparticles synthesized by solvothermal method,” Crystal Research and Technology, vol. 46, no. 4, pp. 321–420, 2006. View at Google Scholar
  16. X. Yan, H. Liu, and K. Y. Liew, “Size control of polymer-stabilized ruthenium nanoparticles by polyol reduction,” Journal of Materials Chemistry, vol. 11, no. 12, pp. 3387–3391, 2011. View at Google Scholar
  17. E. Godocikova, P. Balaz, E. Gock, W. Choi, and B. Kim, “Mechanochemical synthesis of the nanocrystalline semiconductors in an industrial mill,” Powder Technology, vol. 164, no. 3, pp. 147–152, 2006. View at Google Scholar