J Nanopart Res (2010) 12:18071811 DOI 10.

1007/s11051-009-9738-3

RESEARCH PAPER

Preparation and comparison between different thiol-protected Au nanoparticles

Itamar Gofberg Daniel Mandler

Received: 2 April 2009 / Accepted: 6 August 2009 / Published online: 2 September 2009 Springer Science+Business Media B.V. 2009

Abstract We report on the synthesis of monolayerprotected gold cluster (MPCs) in aquatic phase under different conditions. Three thiols, i.e., 2-mercaptoethanesulfonic acid (MPS), 3-mercaptopropionic acid (MPA), and cystamine (CYS) have been used as the protecting monolayer. Furthermore, we studied the effect of varying the ratio between the concentrations of the protecting layer, the gold ions, and the reducing agent in the preparation solution. Comparison was based on measuring the average diameter, stability, and size distribution of the MPCs. Best results were obtained for MPS-based MPCs and that the optimum molar concentration ratio between the protecting layer, the gold ions, and the reducing agent was 1:1:2. Keywords Monolayer-protected gold cluster (MPCs) Gold Nanoparticles Thiol 3-Mercaptopropionic acid 2-Mercaptoethanesulfonic acid Cystamine

Introduction The preparation of monolayer-protected gold clusters (MPCs) is usually carried out in either aqueous or
I. Gofberg D. Mandler (&) Institute of Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Isreal e-mail: mandler@vms.huji.ac.il

organic solutions depending on the nature, i.e., hydrophobicityhydrophilicity, of the protecting ligand. Most often the synthesis of MPCs follows the BrustShiffrin method (Brust et al. 1994) where gold chloride is transferred into toluene using tetraoctylammonium bromide and reduced by NaBH4. This procedure results in MPCs that vary between 1 10 nm and that are stabilized mostly by hydrophobic thiols. On the other hand, the older procedure reported by Turkevich et al. (1953) involves the reduction of gold chloride ions by citrate that serves also as the protecting ligand. Furthermore, the citrate can easily be substituted by other ligands, e.g., hydrophilic thiols which bind more strongly to the metal (Rouhana et al. 2007). Other methods of preparing and size-controlling of MPCs include: sonochemistry, thermolysis, photochemistry, and electrochemistry (Nakamoto et al. 2002; Sau et al. 2001; Chen et al. 2001; Aqil et al. 2008). In spite of the fact that many MPCs have been studied comprising a variety of different thiols, there have been almost no efforts to compare between different systems in terms of stability and size of the MPCs. Furthermore, the effect of the ratio between the ligand, metal ion and reducing agent on the resulting MPCs has not been explored. This communication compares between three types of MPCs stabilized by 3-mercaptopropionic acid (MPA), 2-mercaptoethanesulfonic acid (MPS), and cystamine (CYS). We nd that the nature of the stabilizing ligand and the ratio between the thiol, AuCl4-, and

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NaBH4 have a signicant effect on the size and stability of the MPCs.

Experimental MPS and CYS-stabilized MPCs About 0.1 mmol of HAuCl4 and the desirable amount of MPS or CYS were dissolved in 36 mL of water/ acetic acid (nal pH 3) and stirred for 10 min at room temperature. About 0.2 mmol of NaBH4 in 10 mL of water was added over a period of 2 min, which caused the solution to turn slowly deep purple. The solution was stirred for additional 2 h. The cleaning process (for MPS) began by precipitating the particles by adding acetonitrile (ACN) twice the sample volume. After precipitation and decantation of the ACN, the sample was rinsed twice with 5 mL of ethanol. After decantation of the ethanol, the sample was resuspended in an aqueous solution (in the proper pH). The stability of the CYS-stabilized MPCs was insufcient to allow precipitation and re-suspension. MPA-stabilized MPCs About 0.1 mmol of HAuCl4 and the desirable amount of MPA were dissolved in 36 mL of water (pH 3) and stirred for 10 min at room temperature. Then, the sample was titrated with NaOH to pH 6. About 0.2 mmol of NaBH4 in 10 mL of water was added over a period of 2 min, which caused the solution to slowly turn deep purple. The solution was stirred for additional 2 h. The cleaning procedure of the MPA sample was identical to that of the MPS-stabilized MPCs. Measurements Size and zeta-potential were measured by nanosizer (Nano-ZS, Malvern, Worcestershire, UK). Size was also measured by high resolution transmission electron microscopy (HR-TEM, Tecnai F20 G2, Tokyo, Japan).

The synthesis involved the reduction of AuCl4- by slowly adding NaBH4 in the presence of the ligands (Riley 2002). Initially, we studied the effect of the ratio between the reductant to AuCl4- on the size of MPCs stabilized by MPS. Table 1 summarizes the results The reduction of AuCl4- by NaBH4 is well studied. The stoichiometry ratio between the reductant agent and gold ions should be 3:8 (Eq. 1). Typically, the ratio that is used is much higher than what is needed and often exceeds 10. We found that increasing this ratio caused the formation of larger MPCs. The ratio between MPS:AuCl4- was unity in all these experiments. Under these conditions, increasing the ratio between NaBH4 and AuCl4- above 2 resulted in very large ([100 nm) MPCs. Moreover, the addition of the reductant must be slow to avoid also the formation of large MPCs even at lower ratio. 8AuCl 3BH 24OH 4 4 ! 8Au 3BO 32Cl 18H2 O 2 1

The effect of the ratio between the reductant to the metal ions on the resulting MPCs size is explained by the fast formation of a relatively large number of small gold clusters that aggregate before being stabilized by the ligand. Evidently, slow addition of NaBH4 prevents such aggregation. Table 2 shows the effect of the ligand to AuCl4ratio on the diameter of the nanoparticles which were formed by the different ligands. Two observations are

Table 1 The size of MPS-stabilized MPCs (measured by a nanosizer) as a function of the ratio between the reductant and gold chloride ions [NaBH4]/[AuCl4-] Size/nm 1 2.4 1 2 61 5 Large 10 Large

Table 2 The size of stabilized MPCs by three thiolated ligands (measured by a nanosizer) as a function of the ratio between the ligand and the gold chloride ions Ligand/AuCl40.04 MPS 8.5 4 17.8 7 61 Large Large MPA Large 1.5 0.5 15 2 Large 55 20 23 5 87 30 Large CYS

Results and discussion We have synthesized MPCs using three different thiolated ligands that differ in their functional groups.

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evident: the different thiols affect the size of the gold MPCs, and for each ligand there is a certain ratio which yields the smallest MPCs. Usually, the smallest MPCs were the most stable particles. While samples made with an optimal ratio of ligand/gold did not precipitate for months, samples made with other ratios usually precipitated within a few days or even after a few hours. The stability of these MPCs will be discussed later. Interestingly, the ratio between the ligand to AuCl4- that gives the smallest MPCs is by far much smaller than that typically reported in MPCs synthesis (Shon et al. 2001). Yet, even a 1:1 ratio between the stabilizer and gold is much higher than required assuming either a 1:1 Au:S surface ratio or an adp p layer ( 3 3 R30) similar to that formed upon adsorption of alkanethiols on a gold surface (Schreiber 2000). The minima shown in Table 2 can be explained by two phenomena. At low ligand to gold ratio, it is conceivable that the MPCs are not entirely covered by the charged ligands and, therefore, tend to coagulate and grow. On the other hand, at high ligand to AuCl4- ratio, it is very probable that either an amorphous multilayer of the organic stabilizer is formed or the dissolved charged ligands shield the MPCs repulsion causing them to coagulate and grow. The latter is expressed in a decrease of the zetapotential, vide infra. Table 3 shows the effect of AuCl4- concentration on the size of the Au MPCs that were formed. It should be noted that the [AuCl4-]/[MPS] as well as the [NaBH4]/[AuCl4-] ratios were kept constant and equal 1 and 2, respectively. In all experiments mentioned above, the [AuCl4-] was 2 mM. It is evident that increasing the concentration of the gold chloride ions increases the nal size of the MPCs. We attribute this effect to increasing the ionic strength, which reduces the MPCs repulsion forces (see for example: Henglein and Giersig 1999). Yet, it is also plausible that the higher concentration of AuCl4- leads to higher Au-cluster nucleation density in solution, leading to aggregation.
Table 3 The size of MPCs stabilized by MPS (measured by a nanosizer) as a function of gold chloride concentration [AuCl4-]/mM Size/nm 2 61 6 63 10 Large 20 Large

The stability of the MPCs depends signicantly on the ligand and its concentration relative to AuCl4-. Figure 1 shows the aging effect (in pH 3), namely the change in the diameter of the Au MPCs as a function of time and ligand. The CYS-stabilized MPCs were omitted because of their very low stability, which resulted in coagulation and precipitation within hours or 1 or 2 days. An important observation of Fig. 1 is the slower aggregation rate of the clean MPS-stabilized MPCs. Clean refers to a sample, which was purposely precipitated, washed, and re-dispersed. Evidently, the excess of reagents as well as synthesis products, e.g., borate and chloride ions, accelerates the aggregation process by presumably shrinking the double layer. Furthermore, we found that the core size dispersion is narrower in the clean MPCs than in the original sample. Additional experiments conducted in pH 5 showed higher stability of MPS-stabilized MPCs. This was attributed to the higher charge which was due to fully ionization of the MPCs at this pH. Measuring the zeta-potential shows that the three types of MPCs are initially electrostatically stable. Namely, the zeta-potential was usually higher or lower than 40 mV, respectively. In other words, this conrms that none of the solutions were at their isoelectric point. Hence, the instability of CYS MPCs cannot be attributed to the lack of electrostatic interactions. The CYS-stabilized MPCs were still unstable when the chloride ions, which are known to cause aggregation by a bridging ion mechanism, were substituted by other ions.
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MPS diameter/nm

50 40 30 20 10 0 0 5 10 15 20 25

Time/days
Fig. 1 The change of MPCs average diameter as a function of time. Filled square MPS, lled circle MPA, and lled triangle MPS MPCs after precipitation and dispersed

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Fig. 2 TEM image of a MPA and b MPS-stabilized MPCs

The process of aggregation is partially disclosed by TEM. Figure 2a shows a TEM image of MPAstabilized MPCs prepared using optimal ligand/gold ratio (0.2:1), a few hours after preparation. It is noticeable that there are two main MPCs populations: the rst group with an average core diameter of 1.5 0.5 nm and a second group with a larger average core diameter of 7.0 2.0 nm. The same phenomenon of two size populations is detected with the MPS-stabilized MPCs as well (Fig. 2b). The average diameters of the two populations were 1.5 0.5 and 10 3.0. This is repeated in all three MPCs and conrms that aggregation begins immediately. Our ndings are in agreement with those reported by (Chen et al. 2000).

The formation of MPCs is usually monitored spectroscopially, which is not straightforward to quantify. We found that it was possible to determine the amount of MPCs by electrochemistry using linear sweep voltammetry. Figure 3 shows the linear sweep voltammetry (LSV) of three volumes of MPS-stabilized MPCs added into a 0.05 M KCl solution. The oxidation wave that is observed at 0.94 V versus Ag/ AgCl is due to Au MPCs oxidation. As the initial potential is insufcient to cause the reduction of AuCl4-, it is obvious that the oxidation wave must be due to the formation of MPCs and not to the electrochemical reduction of gold chloride ions. It is clear that the charge associated with the oxidation of MPCs increases linearly with the amount of the nanoparticles.

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Summary and conclusions

0.75 0.50 0.25 15 20 25 30 35 40 45 % MPCs (v/v)

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In conclusion, we have shown that the formation and stability of MPCs strongly depend on the ratio between the three primer components, that is the gold salt, the stabilizer, and the reducing agent. Optimizing the ratio between these components is essential for controlling the size and stability of MPCs.

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References
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E/V vs. Ag/AgCl

Fig. 3 MPS-stabilized MPCs electrochemical oxidation. ac addition of 15, 30, and 45% (v/v) of MPCs/electrolyte 0.05 M KCl solution. Scan rate equals 100 mV s-1

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