View Article Online / Journal Homepage / Table of Contents for this issue
COMMUNICATION www.rsc.org/chemcomm | ChemComm
Characterization of silver ions adsorbed on gold nanorods:
surface analysis by using surface-assisted laser desorption/ionization
time-of-flight mass spectrometryw
Yasuro Niidome,*a Yuki Nakamura,a Kanako Honda,b Yasuyuki Akiyama,a Koji Nishioka,a
Hideya Kawasakic and Naotoshi Nakashimaa
Published on 13 February 2009. Downloaded by University of Victoria on 26/10/2014 14:29:22.
Received (in Cambridge, UK) 28th November 2008, Accepted 22nd January 2009
First published as an Advance Article on the web 13th February 2009
DOI: 10.1039/b821402f
Surface-assisted laser desorption/ionization time-of-flight mass
spectrometry (SALDI-MS) indicated AgBr2 , which adsorbed
on gold nanorod surfaces, was a key material to control the
anisotropic growth of gold nanorods.
Gold nanorods (GNRs) are typical anisotropic gold nanoparticles
which can be synthesized in micellar solutions of hexadecyl-
trimethylammonium bromide (CTA+Br : CTAB).1–4 The
colloidal GNRs show two distinct SP bands in the visible
and near infrared (near-IR) regions that are assignable to
the transverse and longitudinal modes of SP oscillations,
respectively.5,6 Thus, GNRs are expected to be functional
materials that are responsive to near-IR light.
The formation mechanisms of GNRs have been extensively
studied. It was shown that CTAB is a key material to regulate
the shape of the GNRs.7–9 CTAB formed densely packed
bilayers on GNR surfaces and contributed to the anisotropic
growth of gold nanocrystals. If hexadecyltrimethylammonium
chloride (CTAC) was used as a stabilizing agent, the same
procedures to synthesize the GNRs gave spherical gold nano-
particles.10 Thus, the amphiphilic CTA+ ion was not the
dominant factor in realizing the anisotropic crystal growth,
but rather the bromide ion plays an important role to realize
the nanorod formation.
Silver ions, which are added to reaction solutions, are
another critical material to control the yields and shapes of
GNRs.1,11–15 It was reported that a small amount of silver
adsorbed on the GNRs contributed to the anisotropic crystal
growth of gold.12,14,15 Different chemical forms of silver on the
GNR surfaces have been proposed by some research groups.
The possibility of depositing metal silver by the underpotential
deposition was discussed by two research groups.12,14 On the
other hand, complex formation between CTAB and silver
bromide (CTABSB) was proposed as an indispensable species
for anisotropic crystal growth.16,17 The previous research was
contradictory. Thus, at the present stage of this research field,
a
Department of Applied Chemistry, Graduate School of Engineering,
Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395,
Japan. E-mail: ynidotcm@mail.cstm.kyushu-u.ac.jp;
Fax: 81 92 802 2843; Tel: 81 92 802 2841
b
Department of Biological and Environmental Chemistry, Kinki
University-Kyushu, 11-6 Kayanomori, Iizuka, 820-8555, Japan
c
Department of Applied Chemistry, Faculty of Engineering, Kansai
University, 3-3-35 Yamate-cho, Suita, 564-8680 Osaka, Japan
w Electronic supplementary information (ESI) available: An absorption
spectrum and a TEM image of GNRs, preparation procedures, replace-
ment of amphiphiles, bromide in mass spectra. See DOI: 10.1039/b821402f
1754 | Chem. Commun., 2009, 1754–1756
it is necessary to develop a new technique to discuss the
chemical form of silver on GNRs.
In this work, we used surface-assisted laser desorption/
ionization time-of-flight mass spectrometry (SALDI-MS), a
variation of matrix-assisted laser desorption/ionization time-
of-flight mass spectrometry (MALDI-MS), to discuss the
chemical form of the silver on GNR surfaces. In the
SALDI-MS method, photoabsorption of metal nanoparticles
induces the desorption/ionization of organic molecules
adsorbed on the nanoparticle surface.18–21
Here, we synthesized GNRs using a photochemical
method.11,22,23 An absorption spectrum and a TEM image
of the GNRs is shown in ESI.w Spherical gold nanoparticles as
a control sample were also synthesized in a CTAC solution.
Details of the synthesis of gold nanoparticles are described in
the ESI.w The CTAB in a GNR solution and CTAC in a
spherical-particle solution were replaced with the other sur-
factant to give GNRs in a CTAC solution and spherical
particles in a CTAB solution. Experimental details of the
replacements are also described in the ESI.w Before the
SALDI-MS measurements, the colloidal solutions were
centrifuged, and the precipitated nanoparticles were dispersed
in water. This centrifugation procedure was repeated twice to
remove the free CTAB/CTAC molecules from the nano-
particle surfaces. A drop of the centrifuged GNR solution
was cast on a stainless steel target. The mass spectrographs
were obtained using a MALDI-MS instrument (Autoflex,
Bruker). MS measurements were performed in a linear mode.
Negative ions were detected in a range of 0 to 3 kDa. MS
signals were accumulated 200 times.
Fig. 1(a) shows a mass spectrum of anionic species obtained
from GNRs prepared in a CTAB solution (twice centrifuged).
AgBr2 (m/z = 265.6) and AuBr2 (m/z = 355.9) were the
major species. Bromide is also found at m/z = 77.3. When
the GNRs were washed repeatedly with water and centrifuged,
the bromide peak gradually disappeared, while the peaks of
AgBr2 and AuBr2 remained (see ESIw). Thus, the silver and
gold ions forming complexes with bromide ion were assignable
to adsorbates on the GNR surfaces. Fig. 1(b) presents a mass
spectrum of the GNRs in a CTAC solution containing silver
ions. In Fig. 1(b), AgCl2 (m/z = 177.5), AgBrCl (m/z =
221.5), AgBr2 (m/z = 265.6) and AuBr2 (m/z = 355.9) were
detected. It was shown that the AgBr2 and AuBr2 ions were
the adsorbates that were retained on the GNR surfaces even
after contact with the CTAC solution. The replacement of
bromide ions with chloride ions proceeded slowly under our
This journal is
c The Royal Society of Chemistry 2009

Published on 13 February 2009. Downloaded by University of Victoria on 26/10/2014 14:29:22.
Fig. 1 Mass spectra of GNRs in CTAB (a) and CTAC (b) solutions.
experimental conditions. In addition, it should be noted that
the replacement of AgBr2 with AgCl2 also proceeded
slowly. It was found that AgBr2 adsorbed on gold surfaces
much more strongly than AgCl2 .
Fig. 2(a) shows a mass spectrum of spherical gold nano-
particles prepared in a CTAC solution; AgCl2 (m/z = 177.5)
and AuCl2 (m/z = 265.8) were observed. After the treatment
with CTAB solutions (Fig. 2(b)), the mass spectrum of the
nanoparticles showed peaks of AgBr2 (m/z = 265.6) and
AuBr2 (m/z = 355.8). This indicates that the chloride
ions complexing with the metal ions were readily replaced
with the bromide ions of CTAB. On the other hand, as shown
in Fig. 1, the bromide ions were hardly replaced with
chlorides, because the bromide ions had a larger affinity for
metal ions (or metals) than the chloride ions. Thus, SALDI-MS
was found to be an effective method to reveal the surface species
on GNRs.
These results clarified the presence of AgBr2 and AuBr2
ions on the GNR surfaces. The presence of AgBr2 on the
GNR surfaces is also supported by the following discussion.
First, the stability constants of the silver ions24 indicated that
Fig. 2 Mass spectra of the spherical gold nanoparticles in CTAC (a)
and CTAB (b) solutions.
This journal is
c The Royal Society of Chemistry 2009
View Article Online
AgBr2 is the dominant species in a solution containing
80 mM of bromide ions (see ESIw). Second, ascorbic acid does
not reduce silver ions to metal silver at low pH (the under-
potential deposition of GNR surfaces may be possible).12,14,15
Third, no positive gold and silver clusters were observed
by the SALDI-MS measurements; this indicated that the
fragmentation/vaporization of the metals, which might give
AuBrn (n 1) or AgBrn (n 1) complexes in the presence of
bromide, was negligible in our MS measurements.
Our experimental results indicated the adsorption of the
AgBr2 and the AuBr2 ions on the GNR surfaces. CTA+
molecules were the counter cations of the anionic adsorbates.
The CTA+ monolayers on the GNR surfaces were probably
static, because the AgBr2 strongly adsorbed on gold surfaces.
The AgBr2 would contribute to form stable CTA+ bilayers
of CTA+. The combination of AgBr2 and CTA+ bilayers,
which corresponded to the CTABSB complex,16,17 is an
important factor to regulate the anisotropic crystal growth
of GNRs. On the other hand, the combination of AgCl2 and
CTA+ bilayers results in the formation of spherical gold
nanoparticles. This strongly suggested that the CTA+ bilayers
on AgCl2 ions formed different structures, which would be
dynamic and loosely packed structures.
Effects of anions on metal nanoparticle formation has been
discussed in previous papers.25–27 It was shown that the anions
on metal surfaces were critical to control the shape and size of
the nanoparticles. In the case of GNR formation, adsorption
of AgBr2 is an important key to control the anisotropic
crystal growth of gold. AgCl2 , AuBr2 , and AuCl2 are
inappropriate adsorbates for realizing the anisotropic crystal
growth. In photochemical synthesis of GNRs, silver ions are
indispensable.11,23 This is consistent to the discussion about
AgBr2 ; however, a seeding method can give GNRs in the
absence of silver ions.28 It is reasonable to suppose that
anisotropic crystal growth of the seeding methods in the
absence of silver ions proceeded differently from that of the
photochemical method. This is the reason why the seeding
without silver ions and the photochemical methods gave
different crystal structures.12 The amphiphilic cation was
another important factor to control the shape of GNRs;7
however, it was shown the identical amphiphilic cation
(CTA+) formed two kinds of GNRs, penta-twinned and single
crystal, depending on anionic species in the reaction solutions.
Thus, the anisotropic crystal growth was dominantly affected
by the anions on GNR surfaces. In other words, we should
concentrate upon what kind of molecular assemblies stabilize
the surfaces of metal nanoparticles; if ionic species were
adsorbed on the surfaces, properties of ion pairs (cation and
anion) should be evaluated.16 In the case of photochemical
synthesis of GNR, CTA+ and AgBr2 would be the critical
species to control the anisotropic growth.
SALDI-MS was found to be a useful technique to analyze
adsorbates on GNRs. This technique revealed the presence
of AgBr2 on the GNR surfaces and the contribution of
the anisotropic crystal growth of GNRs in the photo-
chemical synthesis. Further characterization of AgBr2 and
AgCl2 on specific gold facets will illustrate a general mecha-
nism of how they control the anisotropic crystal growth
of gold.
Chem. Commun., 2009, 1754–1756 | 1755

This work was partially supported by a Grant-in-Aid for
Scientific Research (No. 15350085), on Priority Area ‘‘Strong
Photon-Molecule Coupling Fields (No. 470)’’.
Notes and references
1 Y.-Y. Yu, S.-S. Chang, C.-L. Lee and C. R. C. Wang, J. Phys.
Chem. B, 1997, 101, 6661–6664.
2 J. Pérez-Juste, I. Pastoriza-Santos, L. M. Liz-Marzán and
P. Mulvaney, Coord. Chem. Rev., 2005, 249, 1870–1901.
3 C. J. Murphy, T. K. Sau, A. M. Gole, C. J. Orendorff and J. Gao,
Published on 13 February 2009. Downloaded by University of Victoria on 26/10/2014 14:29:22.
J. Phys. Chem. B, 2005, 109, 13857–13870.
4 C. J. Murphy, A. M. Gole, S. E. Hunyadi, J. W. Stone, P. N. Sisco,
A. Alkilany, B. E. Kinard and P. Hankins, Chem. Commun., 2008,
544–557.
5 P. K. Jain, K. S. Lee, I. H. El-Sayed and M. A. El-Sayed, J. Phys.
Chem. B, 2006, 110, 7238–7248.
6 A. Brioude, X. C. Jiang and M. P. Pileni, J. Phys. Chem. B, 2005,
109, 13138–13142.
7 J. Gao, C. M. Bender and C. J. Murphy, Langmuir, 2003, 19,
9065–9070.
8 B. Nikoobakht and M. A. El-Sayed, Langmuir, 2001, 17,
6368–6374.
9 J. Pérez-Juste, L. M. Liz-Marzán, S. Carnie, D. Y. C. Chan and
P. Mulvaney, Adv. Funct. Mater., 2004, 14, 571–579.
10 K.-T. Yong, Y. Sahoo, M. T. Swihart, P. M. Schneeberger and
P. N. Prasad, Top. Catal., 2008, 47, 49–60.
11 F. Kim, J. H. Song and P. Yang, J. Am. Chem. Soc., 2002, 124,
14316–14317.
1756 | Chem. Commun., 2009, 1754–1756
View Article Online
12 C. J. Orendorff and C. J. Murphy, J. Phys. Chem. B, 2006, 110,
3990–3994.
13 T. K. Sau and C. J. Murphy, Langmuir, 2004, 20, 6414–6420.
14 M. Liu and P. Guyot-Sionnest, J. Phys. Chem. B, 2005, 109,
22192–22200.
15 D. Seo, C. I. Yoo, C. Park, S. M. Park, S. Ryu and H. Song,
Angew. Chem., Int. Ed., 2008, 47, 763–767.
16 F. Hubert, F. Testard and O. Spalla, Langmuir, 2008, 24,
9219–9222.
17 X.-H. Liu, X.-H. Luo, S.-X. Lu, J.-C. Zhang and W.-L. Cao,
J. Colloid Interface Sci., 2007, 307, 94–100.
18 J. Wei, J. M. Buriak and G. Siuzdak, Nature, 1999, 399,
243–246.
19 Y.-F. Huang and H.-T. Chang, Anal. Chem., 2006, 78,
1485–1493.
20 Y.-F. Huang and H.-T. Chang, Anal. Chem., 2007, 79, 4852–4859.
21 H. Kawasaki, T. Sugitani, T. Watanabe, T. Yonezawa,
H. Moriwaki and R. Arakawa, Anal. Chem., 2008, 80, 7524–7533.
22 K. Nishioka, Y. Niidome and S. Yamada, Langmuir, 2007, 23,
10353–10356.
23 Y. Niidome, K. Nishioka, H. Kawasaki and S. Yamada, Chem.
Commun., 2003, 2376–2377.
24 S. Ahrland, Pure Appl. Chem., 1990, 62, 2077–2082.
25 H. Kawasaki, K. Nishimura and R. Arakawa, J.Phys. Chem. C,
2007, 111, 2683–2690.
26 M. P. Pileni, Nat. Mater., 2003, 2, 145–150.
27 A. Filankembo and M. P. Pileni, J. Phys. Chem. B, 2000, 25,
5865–5868.
28 N. R. Jana, L. Gearheart and C. J. Murphy, J. Phys. Chem. B,
2001, 105, 4065–4067.
This journal is
c The Royal Society of Chemistry 2009