Electrochemistry Communications 8 (2006) 10211026 www.elsevier.

com/locate/elecom

High catalytic potential of Ag/Pd nanoparticles from self-regulated reduction method on electroless Ni deposition
Chien-Liang Lee *, Yu-Ching Huang, Li-Chen Kuo
Materials and Chemical Research Laboratories, Industrial Technology Research Institutes, Rm. 733, Bldg. 52, 195 Sec. 4, Chung Hsing Road, 310 Chutung, Hsinchu, Taiwan, Republic of China Received 29 March 2006; received in revised form 7 April 2006; accepted 18 April 2006 Available online 19 May 2006

Abstract
2 Bimetallic Ag/Pd nanoparticles with various the concentration ratios of the additional silver ions to palladium ions C Ag =CPd have been prepared by the self-regulated reduction in the reuxing of sodium n-dodecyl sulfate aqueous solution without additional reducers. 2 The particular size of prepared bimetallic nanoparticles from 6.0 to 2.6 nm is dependent on C Ag =CPd . Additionally, surface plasmon resonance spectra conrm that the prepared bimetallic nanoparticles are Pd shell-riched structures. As supported by the in situ analysis of quartz crystal microgravimetry, the prepared bimetallic nanoparticles can be successfully used as new activators and have the excellent activity for electroless nickel bath. 2006 Elsevier B.V. All rights reserved.

Keywords: Nanoparticle; Palladium; Electroless copper deposition; Kinetics; Electroless nickel deposition; Bimetallic; Activator; Silver

1. Introduction Metal nanostructure materials are known to exist unique characterization on the optical property of surface plasma resonance (SPR) spectrum [1,2], magnetic uids [3], and catalytic reaction [4,5] and electroanalysis [6]. Coreshell bimetallic nanoparticles, an interesting study subject, is found to have excellent activities compared with that of the pure metal nanoparticles on the catalysis, for instance Au/Pd [7] and Pd/Pt [8] nanoparticles. Electroless nickel depositions (END) is an important surface treatment technology for industries because of its good corrosion protection, hardness and wear resistance [9,10]. Although the performance of an electroless process is inuenced by many factors such as composition of the deposition solution [10,11] and choice of ligands [12], the activation step is the key factor for controlling the rate and mechanism of electroless deposition [13].

Corresponding author. Tel.: +886 3 5913919; fax: +886 3 5820001. E-mail address: cl_lee@url.com.tw (C.-L. Lee).

In the early report, we have developed one novel method for synthesis of hydrophilic and hydrophobic Pd nanoparticles via self-regulated reduction by the reux of sodium dodecyl sulfate (SDS) solution without additional reduction agents [14]. Pd nanoparticles protected with SDS were found to exist high activities for catalyzing electroless neutral Ni deposition (END) [15]. However, these nanoparticles were also measured to have longer induction period which is the time necessary to occur steady-state deposition. Accordingly, the ecient activator for END is still needed to be studied. In this paper, we synthesize Ag/Pd nanoparticles by self-regulated reduction in the reuxed SDS aqueous solution. The particular sizes of bimetallic nanoparticles are controlled by the concentration ratio of 2 the additional silver ions to palladium ions C Ag =CPd . As information given by SPR spectrum, the local structures and feature of these new Ag/Pd nanoparticles are determined to be Pd shell-rich. Subsequently, as for the potential applications, the Ag/Pd nanoparticles prepared from 2 the various C Ag =CPd values are tried as possible activator for END. As the analysis support of quartz crystal microgravimetry (QCM) and mixed potential theory (MPT), the

1388-2481/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.elecom.2006.04.013

1022

C.-L. Lee et al. / Electrochemistry Communications 8 (2006) 10211026

deposition kinetics and rate catalyzed by Ag/Pd nanoparticles are studied. Fair comparison regarding the activity can be thus made among these bimetallic nanomaterials. 2. Experimental 2.1. Preparation of nanoparticles The facile synthesis of Ag/Pd (1:1) nanoparticles by selfregulated reduction in sodium dodecyl sulfate (SDS) aqueous solution is illustrated in the following descriptions. Initially, 0.054 g of palladium acetate (Pd(OAc)2) and 0.0409 g of silver nitrate (AgNO3) were gradually dissolved in 50 ml of a neutral aqueous 0.1 M SDS solution. The solution was then heated slowly in an oil bath and reuxed at 130 C. After 6 h, the solution turned dark brown and Ag/Pd nanoparticles were thus obtained. Based on the same method, Ag/Pd (10:1) and Ag/Pd (1:10) nanoparticles were prepared. For preparation of Ag/Pd (10:1) nanoparticles, 0.409 g AgNO3 and 0.054 g Pd(OAc)2 was added in the reuxing solution. If 0.0409 g AgNO3 and 0.54 g Pd (OAc)2 is as reactive source, Ag/Pd (1:10) nanoparticles were formed. In order to compare with the characterization and activities of prepared bimetallic nanoparticles, pure Pd and Ag nanoparticles were prepared by this synthesis method. For the formation of Ag and Pd nanoparticles, 0.049 g AgNO3 was added into the SDS solution of reuxed and 0.054 g Pd(OAc)2 is for synthesis of Pd nanoparticles. 2.2. Property measurement of nanoparticles The characteristic spectra of surface plasma resonance (SPR) for preparing Ag/Pd nanoparticles were monitored by UVVis spectrum (Carry 100, Varian). The size and shape of nanoparticles was measured with a High-Resolution Transmission Electron Microscope (HR-TEM; JEOL JEM-2000EX) and High-Resolution Field Emission Scanning Electron Microscope (FE-SEM; Hitachi S-4700I). 2.3. Electrochemical measurement
2 The synthesized Ag/Pd nanoparticles of C Ag =CPd of 1:10, 1:1 and 10:1 were then tried as activator for END.

The bath compositions of the END for electrochemical quartz crystal microbalance (QCM, SEIKO QCA922) and linear sweep voltammetery (LSV) measurement are listed in Table 1, respectively. All electrochemical experiments were carried out in the baths controlled at 80 C and rst bubbled with N2 gas for 15 min prior to the measurement. For the QCM experiment, the working electrode in END measurement was prepared by applying 3 ll nanoparticles solution uniformly on a 0.159 cm2 Au surface of the QCM substrate. The QCM substrate (SEIKO EG& G QA20-A9M-Au) was sputtered with gold on top of titanium lm from both sides and was connected 100 A to a home-build oscillator. The reference electrode (Hg/ Hg2Cl2) was separated from the main solution compartment by a Luggin capillary, which was lled with saturated KCl solution. For LSV and mixed-potential theory analysis, the resulting nanoparticle solution of 3 ll was uniformly dropped onto 0.07 cm2 glassy carbon electrode (GCE) and heated at 70 C to evaporate H2O for 5 min. In order to prevent the catalyst from falling o the electrode, the glass carbon electrode was rinsed by 3 ll 5 wt% Naon solution and heated at 70 C for 10 min. LSV measurement was carried out by using a potentiostat (Autolab PGATAT30) incorporating a rotation disk electrode (RDE). A three-electrode cell, consisting of a GCE working electrode, a Pt counter electrode and a Hg/Hg2Cl2 reference electrode, was used for the measurement. The LSV experiment was performed in anodic or cathodic reaction (see Table 1) at a scan rate of 5 mV/s and a rotation speed of working electrode of 3600 rpm. 3. Results and discussion When synthesizing Ag/Pd nanoparticles, the time is needed for the solution to turn dark brown, which signals the completion of reaction. Figs. 1AC present FE-SEM images of Ag/Pd nanoparticles prepared from three dier2 ent C Ag =CPd values which are 10:1, 1:1 and 1:10, respectively. It can be seen that Ag/Pd nanoparticles are uniformly distributed on the QCM substrate and the parti2 cles size is function of the C Ag =CPd added. The particles size decreases sequentially from Fig. 1A to C. Actually

Table 1 Composition of electroless nickel bath for QCM and LSV analysis Composition of electroless nickel bath QCM analysis Nickel chloride (NiCl2) Sodium critrate (HOC(COONa) (CH2COONa)2 2H2O) Sodium hypophosphie (NaH2PO2 H2O) Triethanolamine (C6H15NO3) PH (adjustment with HCl) 0.1 mol/dm3 0.15 mol/dm3 0.093 mol/dm3 0.15 mol/dm3 8 LSV Anodic bath Sodium hypophosphie (NaH2PO2 H2O) Sodium critrate (HOC(COONa) (CH2COONa)2 2H2O) Triethanolamine (C6H15NO3) 0.093 mol/dm3 0.15 mol/dm3 0.15 mol/dm3 LSV Cathodic bath Nickel chloride (NiCl2) Sodium critrate (HOC(COONa) (CH2COONa)2 2H2O) Triethanolamine (C6H15NO3) 0.1 mol/dm3 0.15 mol/dm3 0.15 mol/dm3

C.-L. Lee et al. / Electrochemistry Communications 8 (2006) 10211026

1023

2 Fig. 1. The SEM and HR-TEM images of the Ag/Pd nanoparticles prepared from three C Ag =CPd ratios, Pd and Ag nanoparticles synthesized by selfregulated reduction of SDS method. (A) Ag/Pd (10:1); (B) Ag/Pd (1:1); (C) Ag/Pd (1:10); (D) Ag; (E) Pd.

the diameter of nanoparticles measured by SEM or STM (scanning tunneling microscopy) may include the protection agent surrounding the particle [16]. In addition, the particles contained in solution dropped on the substrate are easily found to aggregate when they are dried naturally. So, the actual particles diameter and morphology have been measured by HR-TEM, as shown in the insets of Fig. 1AC. As a contrast to HR-TEMs results in the inset pictures of Fig. 1D and E for pure Ag and Pd nanoparticles prepared by the same method, note that the calculated mean diameter of the prepared Ag/Pd nanocolloids 2 decreases theoretically with a decreasing C Ag =CPd , i.e.

Ag/Pd (10:1) (6.0 nm) > Ag/Pd (1:1) (5.7 nm) > Ag:Pd (1:10) (2.56 nm), as summarized and shown in Fig. 2. It is interesting to be seen that the average diameters and standard deviations of the prepared Ag/Pd nanoparticles 2 are function of C Ag =CPd . Both the values acutely decrease with a decrease on the concentration ratio. The prepared bimetallic particle has a narrowest size distribution if the 2 C Ag =CPd is 1:10. This means that the particles size can be 2 controlled via C Ag =CPd by this synthesis method. The information for ne structure on the prepared bimetallic nanoparticles is provided by surface plasmon resonance (SPR) spectra. For synthesized bimetallic

1024
20

C.-L. Lee et al. / Electrochemistry Communications 8 (2006) 10211026

Statistical Calculation in diameter (nm)

18 16 14 12 10 8 6 4 2 0

mean diameter stand deviation

Ag

Ag:Pd=10:1

Ag:Pd=1:1

Ag:Pd=1:10

Pd

Fig. 2. The statistical calculation in diameter of the prepared Ag/Pd (10:1), Ag/Pd (1:1), Ag/Pd (1:10), Ag and Pd nanoparticles.

nanoparticles, the UVVis spectrum is a simple and eective tool to determine that the microstructure is a core-shell or mixed alloy structure. In general, if the outer layer is pure metal and substantial, the characteristic SPR band

presenting the outer metal is more pronounced [17]. Fig. 3 shows a comparability of the SPR spectra for the 2 prepared Ag/Pd nanoparticles of C Ag =CPd of the three types, Ag and Pd nanoparticles. Theoretically, according to Mie theory [17], the intensity of SPR band for Ag nanoparticles can be detected and observed obviously at 428 nm in the UVVis spectrum, as shown in Fig. 3. For the Pd nanoparticles solution of black brown, the major SPR band was measured in the UV region. In the experimental observation on Ag/Pd nanoparticles, the SPR bands are almost detected to be located at 203 nm, even in the case of Ag/Pd (10:1) nanoparticles of high Ag concentration. The bimetallic nanoparticles spectra are consisting with Pd nanoparticles. As a contrast to the SPR spectrum of physical mixture solution which contains concentration ratio of 1:1 of the Pd and Ag nanoparticles, the apparent SPR bands for Ags characterization is still observed. It is plausible that the Pd atoms dominates and enriches the prepared Ag/Pd nanoparticles surface. As for the catalytic potential on electroless nickel deposition, the activity of prepared Ag/Pd nanoparticles are remarkable, which have short induction period and addi-

2
Ag:Pd (10:1)

1 0
2 1 0 2 1 0 2 1 0 2 1 0

Ag:Pd (1:1)

Ag:Pd (1:10)

Absorbance

Ag

Pd

2 1 0 200

Physical mixture

300

400

500 600 Wavelength (nm)

700

800

Fig. 3. The surface plasmon spectra of the Ag/Pd (10:1) nanoparticles, Ag/Pd (1:1) nanoparticles and Ag/Pd (1:10) nanoparticles and the contrast spectra of Ag, Pd nanoparticles and their physical mixture.

C.-L. Lee et al. / Electrochemistry Communications 8 (2006) 10211026

1025

-60000

Frequence change(Hz)

-50000

-40000

Ag/Pd (10:1) Ag/Pd (1:1) Ag/Pd (1:10) Ag Pd

-30000

-20000

-10000

0 0 30 60 90 120 150 180 210

Deposition time (sec)

1.8

Electroless depsotion rate(g /cm S)

2

1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 Ag Ag:Pd=10:1 Ag:Pd=1:1 Ag:Pd=1:10 Pd

Fig. 4. The in situ QCM analysis of deposition kinetics of electroless nickel deposition catalyzed with the Ag/Pd nanoparticles prepared from three 2 C Ag =CPd ratios by self-regulated reduction of SDS method, and the contrast deposition kinetics catalyzed with Pd and Ag nanoparticles prepared by the self-regulated reduction of SDS method. (A) Deposition kinetics. (B) Mean deposition rate.

2 tionally increase with a decreasing C Ag =CPd of Ag/Pd (1:10) > Ag/Pd (1:1) > Ag/Pd (10:1). Fig. 4A shows the results of QCM upon in situ measuring the catalytic activity of corresponding bimetallic nanoparticles which are sprayed on the electrodes and thus seen in the SEM images of Fig. 1AC in the END bath. The short induction periods, dened as the time necessary for occurring steady-state deposition, for Ag/Pd (1:10), Ag/Pd (1:1) and Ag/Pd (10:1) were observed. The deposition rates are recalculated from the electrode frequency changes according to the Sauerbreys equation [18]. The average value of deposition rate on Ag/Pd (10:1) nanoparticles is about 1.36 lg/cm2 s, about 1.48 lg/cm2 s on Ag/ Pd (1:1) nanoparticles and about 1.62 lg/cm2 s on Ag/ Pd (1:10) nanoparticles, as shown in Fig. 4B. Note that the deposition rate catalyzed by the prepared alloy nano-

particles is higher than Pd and Ag nanoparticles prepared by the same method. This indicates that the prepared Pd/ Ag nanoparticles of Pd shell-rich resulted by SPR spectrum exists excellent activity on END bath. Theoretically, for electroless metal deposition, the catalytic particles play roles as carriers in the path of transfer of electrons from reducing agent to metal ions in the bath. The solid catalysts are thus the import factor for the kinetics. The mixed potential theory, which is described by the Tafel equation, is often used as an analysis method for the deposition rate of electroless metal deposition [19,20]. Fig. 5 presents the electrochemical currentpotential curves of the Tafel equation of END catalyzed by the prepared nanoparticles, which analyzed by using potentiostat. According to the mixed potential theory, the coordinates of the intersection point of anodic and cathodic curve are

1026
-1500

C.-L. Lee et al. / Electrochemistry Communications 8 (2006) 10211026

4. Conclusion
Ag/Pd (10:1) Ag/Pd (1:1)

-1000

Ag/Pd (1:10)

-500

In conclusion, Ag/Pd nanoparticles of Pd-shell-riched were successively prepared via simultaneous reduction of the corresponding ions by self-regulated of surfactant method. The diameter of prepared bimetallic nanoparticles can be controlled from 6.0 to 2.6 nm by concentration ratio of Ag to Pd ions added. The SPR characterization spectra conrm that the prepared bimetallic nanoparticles are palladium-shell-riched structures. As supported by the analysis of QCM and LSV, the prepared bimetallic nanoparticles can be successfully used as new activators and have the excellent activity for electroless nickel deposition. References
[1] W.L. Barnes, A. Dereux, T.W. Ebbesen, Nature 424 (2003) 824. [2] R. Elghanian, J.J. Storho, R.C. Mucic, R.L. Letsinger, C.A. Mirkin, Science 277 (1997) 1078. [3] M.P. Pileni, Adv. Funct. Mater. 11 (2001) 323. [4] H. Bo nnemann, R.M. Richards, Eur. J. Inorg. Chem. (2001) 2455. [5] G.G. Wildgoose, C.E. Banks, R.G. Compton, Small 2 (2006) 182. [6] C.M. Welch, R.G. Compton, Anal. Bioanal. Chem. 384 (2006) 601. [7] Y. Mizukoshi, T. Fujimoto, Y. Nagata, R. Oshima, Y. Maeda, J. Phys. Chem. B 104 (2000) 6028. [8] N. Toshima, Y. Shirashi, A. Shitsuki, D. Ikenaga, Y. Wang, Eur. Phys. J. D 16 (2001) 209. [9] J. Colaruotolo, D. Tramontana, in: G.O. Mallory, J.B. Hajdu (Eds.), Electroless Plating: Fundamentals and Applications, American Electroplaters and Surface Finishers Society, Orlando, 1990 (Chapter 8). [10] R.L. Zeller, Corrosion 50 (1994) 457. [11] M. Bayes, I. Sinitskaya, K. Schell, R. House, Trans. Inst. Met. Finish. 69 (1991) 140. [12] G.F. Cui, N. Li, D.Y. Li, M. Li, J. Electrochem. Soc 152 (2005) C669. [13] J.F. Hamilton, R.C. Baetzold, Science 205 (1979) 1213. [14] C.L. Lee, C.C. Wan, Y.Y. Wang, Adv. Funct. Mater. 11 (2001) 344. [15] C.J. Lee, Y.C. Huang, C.C. Wan, Y.Y. Wang, Y.J. Ju, L.C. Kuo, J.C. Oung, J. Electrochem. Soc. 152 (2005) C520. [16] T. Reetz, W. Hwlbig, S.A. Qualser, U. Stimming, N. Breuer, R. Vogel, Science 267 (1995) 367. [17] P. Mulvaney, Langmuir 12 (1996) 788. [18] A.J. Bard, L.R. Faulkner, Electrochemical Methods: Fundamentals and Applications, second ed., Wiley, New York, 2001, p. 725. [19] G.O. Mallory, in: G.O. Mallory, J.B. Hajdu (Eds.), Electroless Plating: Fundamentals and Applications, American Electroplaters and Surface Finishers Society, Orlando, 1990 (Chapter 1). [20] Y. Sverdlov, V. Bogush, H. Einati, Y. Shacham-Diamand, J. Electrochem. Soc 152 (2005) C631.

E (mV)
500 1000 -9 -8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3

log I (mA / cm2)

Fig. 5. Cathodic and anodic polarization curves of electroless nickel deposition catalyzed by Ag/Pd (10:1), Ag/Pd (1:1) and Ag/Pd (1:10) nanoparticles prepared by self-regulated reduction in the absence of either NaH2PO2 or Ni2+.

the deposition current (I), at which the deposition reaction steady-stately occurs. First, it can be seen that the peak current of Ag/Pd (1:10) > Ag/Pd (1:1) > Ag/Pd (10:1) in the anodic IE curve are measured and observed. This indicates that Ag/Pd (1:10) nanoparticles has the maximum power toward the catalytic oxidation of reducing agent. The END deposition rate (Rmp) by mixed potential theory can be expressed by Faradays law [19] Rmp 1:09 idep So, the Rmp on Ag/Pd (1:10), Ag/Pd (1:1), Ag/Pd (10:1), Pd and Ag nanoparticles are about 0.98, 0.77 and 0.39 lg/cm2 s, respectively, showing the order of Ag/Pd (1:10) > Ag/Pd (1:1) > Ag/Pd (10:1), which is consisting with the result trend analyzed by QCM data. It strongly indicates again that the high activity exists in these prepared bimetallic nanocatalysts.