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Synthesis of Gold Nanorods and Nanowires by A Microwave-Polyol Method
Synthesis of Gold Nanorods and Nanowires by A Microwave-Polyol Method
Synthesis of Gold Nanorods and Nanowires by A Microwave-Polyol Method
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Abstract
HAuCl4 was reduced by ethylene glycol, in the presence of polyvinylpyrrolidone (PVP) under microwave (MW) heating in a continuous
wave (CW) mode for 2 min. Dominant products were polygonal nanoplates and close-to-spherical nanoparticles of gold. In addition, small
amounts of single crystalline gold nanorods and nanowires (0.5 – 3% of total number of products) with diameters of 20 – 100 nm and lengths
of 0.6 – 5 Am were produced. The diameter and length of gold nanorods and nanowires could be controlled by changing the HAuCl44H2O/
PVP ratio. The formation mechanism of anisotropic gold nanostructures was discussed.
D 2004 Elsevier B.V. All rights reserved.
1. Introduction mina membranes [8], and HTAC (25 –30 wt.%) [9] were
used as templates. The disadvantage of the template-
A variety of metallic nanostructures, including particles, directed synthesis is that the templates must be removed
prisms, plates, rods, and wires, have generated significant in order to recover the individual nanowires. To avoid the
scientific and technological interest because of their step of template removal, a new convenient process must
unique optical properties as well as their novel chemical be developed.
and catalytic properties. Among them, gold nanostructures Microwave (MW) dielectric heating is a new promising
with well-defined dimensions represent a particular class technique for preparation of size-controlled metallic nano-
of interesting nanomaterials to synthesize and study be- structures due to its rapid heating and penetration. Gold
cause of their wide practical application. Compared with nanoparticles have recently been synthesized under MW
extensive experimental studies on the synthesis of gold heating (480 –1100 W) by Tu and Liu [10], Jiang et al. [11],
nanoparticles and nanorods with well-defined dimensions Pastoriza-Santos and Liz-Marzán [12], and Liu et al. [13].
[1 –6], little work has been made for the synthesis of gold When HAuCl43H2O or HAuCl4 was reduced in methanol
nanowires. Here, we define nanorods and nanowires as [10], ethanol [11], N,N-dimethylformamide [12], or water
materials with aspect ratios of 220 and >20, respectively. and sodium citrate [13] for 0.515 min, spherical nano-
The most widely used method for generating metallic particles with diameters below 85 nm were synthesized.
nanowires is template-directed synthesis that involves Malikova et al. [14] synthesized triangular and hexagonal
either chemical or electrochemical depositions [7 –9]. For nanoplates of gold by reduction of HAuCl43H2O in N,N-
the formation of needle and rod/wire shapes of gold, dimethylformamide with salicylic acid, while Gao et al. [15]
polycarbonate track-etched membranes [7], pores of alu- prepared them in aqueous solutions with the surfactant
cetyltrimethylammonium bromide under conventional oil-
bath heating. These triangular and hexagonal nanoplates
* Corresponding author. Institute for Materials Chemistry and Engi-
neering, Kyushu University, Kasuga, Fukuoka 816-8580, Japan. Fax: +81-
have also been synthesized more selectively by the photo-
92-583-7815. reduction of NaAuCl4 and HAuCl4 in the presence of PVP
E-mail address: tsuji@cm.kyushu-u.ac.jp (M. Tsuji). or polyvinylalcohol [16,17].
0167-577X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2004.02.020
M. Tsuji et al. / Materials Letters 58 (2004) 2326–2330 2327
More recently, we have prepared polygonal gold nano- graphs, PVP was separated from gold nanostructures by
plates by reduction of HAuCl44H2O in ethylene glycol in centrifugation. In this case, the reaction mixtures was diluted
the presence of PVP under MW heating in a CW or pulse with water and centrifuged at 13,000 rpm for 60 min.
mode [18 –20]. A mixture of triangular, square, hexagonal, Obscure TEM photographs were obtained without this
and close-to-spherical gold nanoplates was synthesized. procedure due to a heavy coverage of PVP.
One reason for the lack of formation of polygonal nano-
plates in the previous MW – polyol methods [10 – 13] may
be lower reaction temperatures in methanol (b.p. 65 jC), 3. Results and discussion
ethanol (78 jC), water (100 jC), and N,N-dimethylfolma-
mide (156 jC) than that in ethylene glycol (198 jC) used At first, gold nanostructures were synthesized without
in our study. adding PVP in order to examine the effects of PVP. Thus,
Sun et al. [21] have succeeded in the synthesis of only large spherical gold particles with diameters of 100–
uniform silver nanowires by reducing AgNO3 with ethyl- 300 nm were produced in solution, as shown in TEM
ene glycol in the presence of seeds and PVP under oil- photograph (Fig. 1). These large spherical gold particles
bath heating. They found that both morphology and must be formed by aggregation of small particles due to
aspect ratios of these silver nanostructures could be varied the lack of surfactant PVP. Fig. 2(a) – (d) shows TEM
from nanoparticles and nanorods to long nanowires by photographs of products obtained at four different
adjusting the reaction conditions, including the ratio of HAuCl44H2O/PVP molar ratios at a constant PVP con-
PVP to silver nitrates. By analogy with their study for centration of 1.03 mmol dm 3 . At the lowest
silver, similar anisotropic nanostructures may be created in HAuCl44H2O/PVP ratio of 1.2103, a small triangular,
the case of gold. In the present study, we have attempted square, rhombic, hexagonal, and close-to-spherical particles
to synthesize gold nanorods and nanowires by a MW – with diameters of about 20– 40 nm are produced [Fig.
polyol method in a one pot. In addition to isotropic 2(a)]. It should be noted that a nanowire with a diameter of
polygonal nanoplates and close-to-spherical nanoparticles, 10 nm and a length of 600 nm is produced. At an
small amounts of anisotropic gold nanorods and nano- HAuCl44H2O/PVP ratio of 4.7103 [Fig. 2(b)], larger
wires could be synthesized under CW MW heating for triangular, square, rhombic, hexagonal, and close-to-spher-
only 2 min. It was found that the diameter and length of ical particles with diameters of 20 –100 nm were produced.
gold nanorods and nanowires can be controlled by chang- In addition, a few nanorods and nanowires with a diameter
ing the HAuCl44H2O/PVP ratio. To the best of our of f20 nm and lengths of 0.3 –1.4 Am were obtained. At
knowledge, this is the first synthesis of gold nanorods an HAuCl44H2O/PVP ratio of 9.3103 [Fig. 2(c)],
and nanowires by a MW – polyol method within a few besides larger triangular and hexagonal nanoplates and
minutes. The great advantage of this technique is that spherical particles, larger nanorods and nanowires with
templates are unnecessary as well as a short crystallization diameters of 40 –80 nm and lengths of 0.4 –2.0 Am are
time. observed. At the highest HAuCl44H2O/PVP ratio of
1.9102 [Fig. 2(d)], in addition to small and large nano-
plates and spherical nanoparticles, a long nanowire with a
2. Experimental
Fig. 2. TEM photographs of gold nanostructures obtained by MW heating after 2 min. HAuCl44H2O/PVP molar ratios were (a) 1.2103, (b) 4.7103, (c)
9.3103, and (d) 1.9102 at a PVP concentration of 1.03 mmol dm3, and (e) 9.3103 at a PVP concentration of 2.06 mmol dm3. (f) Electron diffraction
pattern of the longest nanowire shown in panel (e).
diameter of 70 nm and a length of 3 Am is observed. These mechanism of metallic ions in ethylene glycol proposed by
results indicated that the size of particles and plates and the Fievet et al. [22]:
diameter and length of nanorods and nanowires generally
increased with increasing the HAuCl44H2O/PVP ratio. CH2 OH CH2 OH ! CH3 CHO þ H2 O; ð1aÞ
The relative number ratio of nanorods and nanowires to
the total number of products increased from about 0.5% to
6CH3 CHO þ 2AuðIIIÞ ! 2Au þ 6Hþ þ 3CH3 COCOCH3 :
2% with increasing the HAuCl44H2O/PVP molar ratio
from 1.2103 to 9.3103, then decreased to 1% at ð1bÞ
the highest HAuCl44H2O/PVP ratio of 1.9102. As As a result of the above reduction process, nucleation and
shown later, the reduction of HAuCl4 was not completed growth processes of gold yield a mixture of polygonal
and a small amount of reagent remained in the solution at plates and close-to-spherical nanoparticles. These nano-
the highest HAuCl44H2O/PVP ratio of 1.9102. When plates and nanoparticles were well dispersed because of
more PVP was added, the reduction was completed. Fig. the presence of a polymeric surfactant PVP that could
2(e) shows the TEM photograph obtained at an chemically adsorb onto the surfaces of gold solid probably
HAuCl44H2O/PVP ratio of 9.3103 under a higher through an interaction between an N – C=O group and Au.
PVP concentration of 2.06 mmol dm3. Besides large The surface energies of large particles are lower than those
triangular and hexagonal nanoplates and spherical particles, of smaller ones. It is therefore expected that some small
a few long nanowires with diameters of 60 –100 nm and nanoparticles are grown to larger ones via an Ostwald-
lengths of 2– 5 Am are produced. The relative number ratio ripening process [23]. With the assistance of PVP, some of
of nanorods and nanowires to the total number of products the large nanoparticles were grown into anisotropic rod-
was about 3%, which was larger than 1% under the shaped and wire structures. PVP acts as a kinetically
condition of Fig. 2(d). controller of the growth rates of different crystalline faces
The formation of anisotropic gold nanostructures proba- through adsorption and desorption. The PVP adsorbed on
bly starts by the following reactions according to reduction specific crystalline surfaces could significantly decrease
M. Tsuji et al. / Materials Letters 58 (2004) 2326–2330 2329