Materials Science and Engineering B 142 (2007) 115

Review

Synthesis of silver nanoparticlesEffects of concerned

parameters in water/oil microemulsion
Wanzhong Zhang a,b, , Xueliang Qiao a, , Jianguo Chen a
a
State Key Laboratory of Material Processing and Die & Mould Technology,
Huazhong University of Science and Technology, Wuhan 430074, PR China
b School of Pharmaceutical Sciences, Southern Medical University, Guangzhou 510515, PR China

Received 22 October 2006; received in revised form 7 June 2007; accepted 23 June 2007

Abstract
Noble metallic nanomaterials are of particular interest today because of their applications in many areas. The selected topic is one of the most active
regions in the metallic nanomaterials. First, common synthetic methods of silver nanomaterials, e.g., chemical reduction, photochemical method,
ultrasonic-assisted reduction, electrochemical method, template, irradiating reduction and biochemical method, are introduced. The advantages
and drawbacks of these methods are also reviewed. Secondly, we mainly discuss the formation of silver nanoparticles in microemulsion. Besides an
introduction to the concept, type and formation of microemulsion, we focus especially on the influencing factors of silver nanoparticle formation.
Effects of the type of continuous phase, molar ratio of water to surfactant (W), precursor concentration and reductant type and concentration on
the particle formation are summarized and evaluated. Furthermore, current and possible developing trends of the synthetic technology of silver
nanoparticles are also prospected.
2007 Elsevier B.V. All rights reserved.

Keywords: Synthesis; Silver nanoparticles; Water-in-oil microemulsion; Influencing factor

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. A brief overview on the preparation of silver nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Microemulsion formation and silver nanoparticles preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
4. Effects of the parameters on the formation of silver nanoparticles in microemulsion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

Abbreviations: AAO, anodic aluminium oxide; AOT, sodium bis(2-ethylhexyl)sulfosuccinate; BSPP, bis(p-sulphonatophenyl)phenylphosphine dihydrate dipotas-
sium; CTAB, cetyltrimethylammonium bromide; DMAC, dimethylacetamide; DPS, dibutyl--naphthalin sulfonate; DTR, diffusion transfer reversal system; Daxad
19, sodium salt of a high-molecular weight naphthalene sulfonate formaldehyde condensate; EDTA, ethylenediaminetetraacetic acid disodium salt; EG, ethylene gly-
col; fs, femtosecond; Genamin T020, a nonionic surfactant; HLB, hydrophiliclypophilic balance; IPA, 2-propanol; MeOH, methanol; MPEG, methoxypolyethylene
glycol; N2 H4 H2 O, hydrazine hydrate; NaBH4 , sodium borohydride; N,N-DMF, N,N-dimethylformamide; ns, nanosecond; NTA, nitrilotriacetate; P123, triblock
copolymer (PEO20 PPO70 PEO20 ); PDCE, polydichloroethylene; PEG, poly(ethylene glycol); PFPE-NH4 , ammonium perfluoropolyether; (Styrene-DVB), (styrene-
divinylbenzene); PSS, poly(styrene sulfonate); PVA, polyvinyl alcohol; PVP, poly(vinylpyrrolidone); SCF, supercritical fluid; SDBS, sodium dodecyl benzene
sulfonate; SDS, lauryl sodium sulfate; TTF, tetrathiafulvalene; -CD, -cyclodextrin; Vc, ascorbic acid
Corresponding author. Tel.: +86 2787541540; fax: +86 2787541540.

E-mail addresses: xueliangq@163.com (X. Qiao), zhangwz998@yahoo.com.cn (W. Zhang).

0921-5107/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2007.06.014
2 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115
Nomenclature
dp number average particle size
Ep separation between oxidation and reduction peaks
kex second-order exchange rate coefficient
Np number of nanoparticles as seen on TEM micro-
graph
W n(H2 O)/n(emulsifier)
Greek letters
max wavelength of maximum absorbance
d standard deviation
1. Introduction
Due to their small size, nanomaterials exhibit novel prop-
erties which largely differ from the bulk materials. The new
emergent properties include quantum size effect, nonlinear opti-
cal properties, and so on. As a result, the nanomaterials have
extensive applications in civil and industrial areas. For exam-
ple, they can be used as microelectronic materials, bacteriostatic
materials [1], catalytic materials or magnetic recording materials
[2]. They even have potential applications in DNA detection [3]
and photodetection [4]. In the past few years, nanoparticle pro-
duction by a size-controlled or shaped-controlled procedure has
become a new and interesting research focus. Silver nanoparti-
cles, a noble metallic nanomaterial, can be used as antibacterial
materials [5], antistatic materials, cryogenic superconducting
materials [6], biosensor materials [7], etc. Composite fibers can
be prepared for the attainment of permanent antibacterial activ-
ity by addition silver nanopowder in common synthetic textiles
[8]. The antibacterial activity of the composite fibers is excel-
lent when the fibers are used as the sheath. In the electronic
industry, there are growing demands for decreasing the thick-
ness of conductive films and the width of printed circuits. It is
thus required that the diameter of silver nanoparticles in the con-
ductive paste is small as far as possible [9]. At the same time,
the materials expended are also minimized. As catalytic mate-
rials, the catalytic activity of silver nanoparticles is dependent
on their size [10], structure, shape [11], size distribution and
chemicalphysical environment. Generally, the shape, size and
size distribution of silver particles can be controlled by adjust-
ing the reaction conditions such as reducing agent, stabilizer
and so on [12,13] or employing different synthetic methods.
Therefore, it is necessary to review the preparation methods
and elucidate the influences of reaction conditions on the nucle-
ation and morphology of silver nanoparticles. During the last
few years, many methods have been employed to prepare silver
nanoparticles. In these methods, reverse microemulsion method
has received considerable attentions. The method can be used
to prepare both spherical and anisotropic silver nanoparticles.
In this review, besides an overview on the general methods
for the preparation of silver nanoparticles, the main content
aims to describe the formation of microemulsion, the prepa-
ration of silver nanoparticles with various morphologies and the
effects of the concerned parameters on the particle formation in
microemulsion.
2. A brief overview on the preparation of silver
nanoparticles
A lot of methods have been employed to synthesize silver
nanoparticles, including chemical reduction (chemical reduc-
tion of silver ions in aqueous solutions [1421] or non-aqueous
solutions [2224]), template method [2530], electrochemical
or ultrasonic-assisted reduction [10,3137], photoinduced or
photocatalytic reduction [3845], microwave-assisted synthe-
sis [12,4650], irradiation reduction [5154], microemulsion
method [5561], biochemical reduction [6268], and so on.
Foremost among them is chemical reduction for production of
large quantities of nanoparticles in relatively short periods of
time. Moreover, nanoparticles with different shapes can be easily
prepared by controlling the reaction conditions. However, upon
extraction in powder form, the resulting particles tend to grow
or aggregate to form large particles. However, the coalescence
of the nanoparticles may lose their characteristic properties.
Thus, the most important key in this method is to avoid the
agglomeration of silver nanoparticles during the synthesis and
preservation procedure. Usually special organic compounds,
such as surfactants, polymers and stabilizing ligands, are used
to passivate the particles to prevent them from aggregation. The
organic compounds can inhibit the coalescence and allow iso-
lated nanoparticles produced. Polymeric materials are usually
used as protective agents to prevent the agglomeration via their
interaction with small particles. The choice of a particular pro-
tective agent is perhaps one of the most important factors in
the preparation of nanoparticles. Due to the growth process of
nanocrystallites controlled by the stabilizers, it is possible to
manipulate the shape and size of silver nanoparticles by choos-
ing different stabilizers. Thus, the protective agent employed
may be different with different shapes of silver nanoparticles
required in the targeted application.
Of course, chemical reduction also has obvious disadvan-
tages. For instance, most of the reactants used in the reaction
system are toxic chemical agents which have potential risks
for environment and health. As above mentioned, the protective
agent on the surface of nanoparticles may have influence on the
characteristics of nanoparticles. Thus, some natural compounds
such as sodium citrate and reducing sugars are usually used as
reducing agents, although the reduction activity is generally low
and the reducing reaction takes place under higher temperature
and needs a long time. These reducing agents are mild, inex-
pensive, and nontoxic. Some of them simultaneously play dual
roles of a protective agent and a reducing agent. For instance, sil-
ver particles prepared by citrate reduction are nearly spherical,
and the crystallites have relatively large diameters (50100 nm)
and wide range distributions in size and shape. Citrate serves as
not only the dual roles of a reductant and stabilizer but also the
role of a template [16]. In addition, some physical techniques
such as microwave, irradiation, and photo inducement and so
on, are also applied to prepare silver nanoparticles. For exam-
ple, the microwave-assisted synthesis is increasingly applied in
 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115
the preparation of silver nanomaterials due to its unique reaction
effects such as rapid volumetric heating and the consequent dra-
matic increase in reaction rate. However, silver particles or clus-
ters with a narrow size distribution are often difficult to achieve.
To overcome the limitation of chemical reduction and prevent
particle aggregation, reverse microemulsion (reverse micelle)
method is introduced to obtain the uniform and size controllable
nanoparticles. This method has obvious advantages to synthe-
size nanoparticles with specific diameter and morphology. The
nucleation and growth are restricted within the water cores of
inverse micelles. The droplet dimension can be modulated by
various parameters, in particular W (water-to-surfactant molar
ratio) [69]. Preparation of silver nanoparticles by microemulsion
method has many influencing factors and the synthesis system
also has some characteristics different from other system. We
will discuss them in detail at the next sections.
Biological reduction is recently developed as a promising
method because of its special advantages such as sufficient
material sources, mild reaction conditions, good dispersion of
nanoparticles as well as few chemical additives and poisonous
byproducts. The method for preparation of silver nanoparticles
has two mechanisms, namely enzymatic reduction mechanism
and non-enzymatic reduction mechanism. It has been known for
a long time that a variety of nanoparticles are synthesized by bio-
logical processes. For example, using a thermophilic bacterial
strain, magnetite nanoparticles (Fe3 O4 ) have been synthesized
outside of bacterial cells by reducing a magnetite precursor con-
taining Fe ions [70]. When challenged with toxic metals such as
cadmium, certain yeasts can also react with the metal to form
nontoxic CdS nanocrystallites as a mechanism of detoxification
[71]. The nucleation capabilities found in biomolecules have
been utilized to prepare silver nanoparticles [65,66]. Owing to
the environment friendly nature of biosynthetic process, there
is a great interest in studying the synthesis of silver nanopar-
ticle by biological route. Up to now, biological templates such
as DNA or proteins have been applied to synthesize anisotropic
silver nanoparticles by the self-assembly of silver nanoparticles
[62,72]. However, the reaction time required for complete reduc-
tion of silver ions is very long and the reduction rate is thus rather
slow. For example, the synthesis of silver nanoparticles using
fungi [66,67] or bacteria [7375], the time for completion of the
reaction ranges from 24 to 120 h, which is an obvious disad-
vantage of the biosynthetic procedures compared with chemical
methods for nanoparticle synthesis. In recent study, the defi-
ciency has been improved significantly, e.g., the reduction of
silver ions by the extract of Geranium leaf occurs fairly rapidly,
more than 90% of which is completely reduced within 9 h [64].
Table 1 gives a summary of various preparation methods
employed by various researchers. The summary includes the
main parameters and particle feature, such as the reductant or
solvent used; the protective agent or template used and the
particle morphology obtained, etc. The literatures involved in
Table 1 were published from 2002 to 2005, though it is incom-
plete. From Table 1 it is seen that various structures of silver
nanomaterials can be synthesized by these methods. Besides
spherical silver nanoparticles, anisotropic silver nanoparticles
including nanorods, nanowires, nanodisks, nanocubes, and den-
3
dritic nanostructures can be also prepared. As the requirements
of use in different domains for diameters and morphologies
of silver nanoparticles may be different, it is often difficult to
say which one is better in the synthetic techniques. For com-
mon preparation of silver particles, chemical reduction is used
frequently for its convenience and rapidity. To preparation of uni-
form and size controllable silver nanoparticles, microemulsion
method has obvious advantages.
3. Microemulsion formation and silver nanoparticles
preparation
Microemulsion consists of a ternary mixture of water, sur-
factant and oil or a quaternary mixture of water, surfactant,
co-surfactant and oil. Depending on the proportion of various
components and hydrophiliclypophilic balance (HLB) value of
the surfactant used, the microdroplets in the microemulsion can
be in the form of oil-swollen micelles dispersed in aqueous phase
as O/W microemulsion or water-swollen micelles dispersed in
oil phase as W/O microemulsion. Usually, many surfactants can
be used to form microemulsion, including cationic surfactants
such as cetyltrimethylammonium bromide (CTAB), anionic sur-
factants such as bis(2-ethylhexyl)sulfosuccinate (AOT), sodium
dodecyl benzene sulfonate (SDBS) and lauryl sodium sulfate
(SDS), and nonionic surfactants such as Triton X-100, etc. Cor-
respondingly, the microemulsion can be divided into three types,
namely, cationic microemulsion, nonionic microemulsion and
anionic microemulsion. The choice of surfactants should base on
the demands of the experiment and reaction conditions. Differ-
ent surfactant, that is, different microemulsion system employed
in the fabrication process, silver nanoparticles with different
diameters or morphologies will be obtained.
W/O microemulsion is generally transparent, isotropic liquid
media with nanosized water droplets dispersed in the continu-
ous oil phase and stabilized by surfactant molecules at water/oil
interface. The microdroplet size can be modified by varying
concerned parameters, e.g., W. The water droplets covered by
surfactant molecules, which act as microreactors for processing
reactions, offer a unique microenvironment for the formation
of nanoparticles. When the particle size approaches that of the
water pool, the surfactant molecules will be adsorbed on the par-
ticle surface to inhibit the particles from sticking. In other words,
the diameter and morphology of nanoparticles obtained in such
a medium can be controlled by the microreactors based on the
microemulsion droplets, which are very important to fabricate
smaller particles in controlled synthesis. As a result, the resultant
particles have good monodisperse and high stabilization.
The preparation procedure of silver nanoparticles in
microemulsion commonly consists in mixing of two microemul-
sions carrying silver salt and reducing agent, respectively. After
mixing of two microemulsions, the interchange between reac-
tants takes place during the collisions of water droplets. The
exchange process of solubilizates and subsequent reaction can
be thought of as consisting of the following five main steps [76]:
(1) Brownian diffusion of reverse micelles leading to collisions;
(2) surfactant layer opening through effective collisions and a
coalescence of the micelles happening; (3) diffusion of solu-
4 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115

Table 1
Preparation of silver nanoparticles using different methodsa
Methods Reductant or solvent Protective agent or Particle morphology Influencing factors or References
template features

Aqua-solution chemical NH2 OH HCl No Polydispersed Sodium hydroxide, mixing [14]

reduction nanospheroids order and rate
Sodium citrate Citrate Nanowires or spheroid Hydroxide ion [15,16]
concentration
Tollens reagents No Nanospheroids Resultant particles stable in [17]
water
Raney nickel No Ag skeleton structure Raney Ni and Ag seeds [18]
NaBH4 Dodecanethiol Nanospheroids 27 nm Ep influenced by the size [19]
of particles
Polyol PVP Nanowires 150 m The crystal facets [20]
selectively covered
Ethylene glycol PVP Nanocubes PVP and n(PVP):n(AgNO3 ) [21]
Non-aqueous chemical DMAC PEG Nanospheroids AgNO3 and PEG [22]
reduction concentration
DMF PVP Nanoprisms and Particles stable in ethanol [23]
spheroids and water
Acetonitrile TTF Dendritic particles n(AgNO3 ):n(TTF) and PVP [24]
Template method Genamin T020 Multilamellar vesicles Nanospheroids 39.6 nm Surfactant vesicles as a [25]
reductant, stabilizer and
template
Vc Rod-like micelles Triangular nanoplates Silver seeds, concentration [26]
of CTAB
Keggin ion, UV Ag+ -Keggin colloids Nanoparticle network Keggin ions as template and [27]
irradiation reductant
Free radicals AAO Nanowires Architecture of precursor, [28]
ultrasound
NaBH4 and hydroquinone Protein microtubule Nanoparticle and Bioorganic templates [29]
nanowire
H2 Poly(styrene-DVB) Nanospheroids Supercrit. route, clean [30]
preparation
Electrochem. reduction Cyclic voltammetry Polyphenylpyrrole Nanospheroids 320 nm Generation of conducting [31]
polymers and
electrodeposition of silver
Zeolite film modified Zeolites Nanospheroids 118 nm Supercages and the dense [32]
electrodes of zeolite film
Rotating platinum PVP Nanospheroids 1020 nm PVP concentration and [33,34]
cathode electrode rotating speed,
SDBS
Ultrasonic-assisted reduction Sonoelectrodeposition PVP Nanosphere, wire and EDTA, ultrasonic field, [35]
dendrite silver nitrate concentration
Sonoelectrochemistry NTA Nanosphere 82700 nm Pulse ultrasonic wave, [36]
reduction processing time
Sonication, NaBH4 PDCE and DPS Nanospheroids Precursor, stabilizers, DTR [10,37]
system
Photoinduced or Visible light, ascorbic PVP Nanospheroids and Wavelength and intensity of [38]
photocatalytic reduction acid plate-like powders light, irradiation time,
weight ratio of PVP to Vc
PSS, polychromatic PSS Nanospheroids 8 nm Microscale capsules [39]
irradiation template, light intensity or
AgNO3 concentration
Ambient light, P123 P123 Nanospheroids [Ag(NH3 )2 ]+ [40]
concentration, ethanol
Visible light, NaBH4 PVP and sodium citrate Nanospheroids and Molecular weight of PVP, [41]
prisms irradiation time
Dual-beam illumination, Citrate and BSPP Triangular nanoprisms Illumination wavelengths [42]
citrate 30120 nm
UV irradiation, MPEG MPEG Nanospheroids Irradiation time, polymer [43]
concentration
Colloidal Ag2 S, light PVA or gelatin Nanospheroids Concentration of the [44]
catalyst, temperature,
concentration of Ag+
 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115 5

Table 1 (Continued )
Methods Reductant or solvent Protective agent or Particle morphology Influencing factors or References
template features

NaBH4 , UV irradiation
Microwave-assisted synthesis EG, DMF, IPA, MeOH
Sodium citrate
Citrate, formaldehyde
Ethylene glycol
Formaldehyde
Polyacrylamide
Irradiation reduction IPA, -irradiation Mesoporous silica
IPA, -irradiation PVP
IPA, EB irradn.
fs and ns laser ablation
Microemulsion method Vc
KBH4
N2 H4
NaBH4
Quercetin or -radiolysis AOT
Biochemical methods Peptide
Living alfalfa plants
Geranium leaf extension
Yeast strain
Fungus
Neem leaf extension
a In electrochemical reduction, ultrasonic-assisted and irradiation reduction, reductant or solvent column is used for labelling the electrode materials or synthetic
TiO2 nanorods Nanospheroids 1560 nm Irradiation time, inorganic [45]
stabilizers, nonpolar
solution
PVP or -CD Nanospheroids 210 nm n(stabilizer):n(AgNO3 ), [12]
reducing activity
Citrate Nanorods or spheroids Temperature, citrate [46]
concentration
PVP Distorted sphere and Concentration of [47]
prism trisodium citrate,
additives
PVP Nanospheroids Molecular weight of PVP [48]
and pH
Sodium citrate Nanospheroids States of silver cations [49]
Polyacrylamide Nanospheroids 66 nm Concentration of PAM [50]
and silver ion, pH
Nanospheroids 14 nm Irradiation dose, pore size [51]
and morphology of silica
Nanospheroids Organics containing thiol [52]
group
PVA Nanospheroids 30 nm Temperature, electron [53]
beam irradiation
No Nanospheroids 41/27 nm Medium and pulse time of [54]
laser ablation
CTAB + SDS molecules Silver nanowires and Mixed surfactant [55,56]
dendrites concentration, the
reducer, concentration of
Vc , electrolyte (NaCl)
Ellipsoidal micelles Needle-shaped and Ultrasonication time [57]
wire-shaped particles
Dodecanethiol, AOT Silver hexagonal The amount of reducing [58,59]
micelles nanoparticles agent, ultrasonication
PFPE-NH4 Nanospheroids 3.5 nm Reducing agent, W, SCF [60]
CO2
Nanospheroids Synthetic ways, ageing [61]
11000 nm time
Peptide Hexagonal, spherical and Nature of peptide [62]
triangular
Alfalfa tissue Nanospheres, wire Nucleation inside the [63]
alfalfa tissue
Proteins or enzyme Nanospheres, quasi-wire Rate of reduction rapid, [64]
silver concentration high
Proteins Nanospheres 25 nm Extracellular synthesis [65]
Proteins or enzyme Nanospheres 515 nm Silver hydrosol stable, [66,67]
reaction time
Flavanones, terpenoids Polydisperse spheres Rate of reduction rapid, [68]
535 nm silver concentration high

methods, etc.

bilizate molecules resulting in exchange of materials between
micelles; (4) reaction between solubilizates resulting in forma-
tion of silver nuclei; (5) the aggregates splitting to return as
reverse micelles. The above steps take place time and again until
the nuclei grow to attain the size of water-pool. One can be seen
that the nucleation reaction and particle growth take place within
the micelles and the size and morphology of as-synthesized
nanoparticles depend on the size and shape of the microdroplets.
In addition, the surfactant molecules are attached on the sur-
face of particles to stabilize and protect them against further
growth.
Many surfactants are available for formation of the
microemulsion in the preparation of silver nanoparticles. In
these surfactants, AOT is one of the most efficient surfactants in
the formation of water-in-oil microemulsion [78,79]. The AOT
microemulsion system is only made up of three kinds of com-
ponents, i.e., AOT, water, alkane. Thus, the size and shape of
the final nanoparticles are also controlled easily [69]. Due to
its enormous advantages, AOT microemulsion has extensively
been applied to prepare silver nanoparticles with multifar-
ious morphologies. For instance, Petit et al. [80] prepared
silver colloidal particles in AOT-water-isooctane microemul-
6 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115

Fig. 1. (a) TEM micrograph and (b) size distribution of silver particles prepared in AOT microemulsion [77].

sions by using a functionalized surfactant, silver sulfosuccinate
(Ag(AOT)), as the source of silver ions. Compared to the parti-
cles produced with cationic or nonionic microemulsions, the
resultant particles have a smaller average size and narrower
size distribution. We have also studied the preparation of sil-
ver nanoparticles in AOT microemulsion system in detail. By
the choice of organic solvents and control of reaction condi-
tions, the resulting particles have both a small mean diameters
(25 nm) and a narrow size distribution [81]. Furthermore,
the silver colloidal solution has high stabilization and thus
can be preserved for a long time without precipitation. Fig. 1
shows the typical TEM micrograph and size distribution of sil-
ver nanoparticles synthesized in AOT microemulsion in our
work.
The morphology of reverse micelles is different with the
surfactant concentration. At different concentrations, the sur-
factant molecules can form various molecule aggregations, e.g.,
micelle, liquid crystal and vesicle which are used as perfect
templates to prepare nanostructure materials. May and Ben-
Shaul [69] found that the change of micelle structures had
an energetic barrier. That is, at a low surfactant concentration
only spherical micelles appear in solution. When the surfactant
concentration in the solution reaches a well-defined satura-
tion value, i.e., second critical micelle concentration (second
CMC), the energetic barrier will be overcome and the micelle
structure will change from a spherical micelle to other spe-
cial structure, and then the micelle will be steady again at a
new concentration range. For example, if the concentration of
surfactant attains to 4050%, the spherical micelle turns into
rod-shaped or column-shaped micelle. Furthermore, the micelle
is also able to self-assemble into layer or liquid crystal struc-
ture. The special micelles can be usually used as effective
structure-directing agents to prepare nanoparticles with desired
morphologies [21,83]. Thus, the micelle formed by the surfac-
tant with a proper concentration can offer an appropriate growth
condition for nanoparticles. Some typical micelle structures are
shown in Fig. 2.
In a mixed cationicanionic surfactant solution, such as
CTAB-SDS solution, the strong interaction between headgroups
(SO4 and R4 N+ ) mediated by tailtail interactions leads
to a strong synergism [84]. The synergism favors the forma-
tion of a worm-like micelle which directs the growth of the

Fig. 2. Sketches of the typical structures of different micelles [82].

 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115
Fig. 3. TEM image of the obtained silver dendrites [55].
one-dimensional nanostructure [85]. Using the mixed surfac-
tant system, Xie and co-workers [55,56] had synthesized silver
nanowires with a high aspect ratio of ca. 6070 (Fig. 3) and
dendrites with a long central backbone and symmetrically ram-
ified secondary branches (Fig. 4). The research results indicate
that an increase of the surfactant concentration is favorable for
the formation of silver dendrites. The surfactant concentration
has an important influence on the coadsorption of the binary
surfactants and affects the surfactant coverage and the charge
state on the surface of nanoparticles in solution. As a result,
the oriented hitting and sticking process have been drastically
influenced.
In addition, both the reducing agent (ascorbic acid) and
electrolyte (NaCl) play important roles in controlling the mor-
phology of silver nanoparticles. For instance, the reduction of
Fig. 4. TEM image of the obtained silver nanowires [56].
7
AgNO3 is accelerated at a high concentration of ascorbic acid.
As a result, a nonequilibrium system is easily built, which is
beneficial in the formation of dendrites [86]. In contrast, the rate
of nucleation will be decrease at a low concentration of ascor-
bic acid. With the aid of surfactant molecules, the silver clusters
preferentially grow along the one-dimensional direction to form
one-dimensional silver nanowires. A high concentration of NaCl
promotes the aggregation of nanocrystals into threadlike one-
dimensional structures, which are beneficial for the formation
of flexible, wormlike microstructures [87]. That is to say, the
presence of electrolyte is favorable for the formation of silver
nanowires.
Ultrasonic was also reported to influence the morphology
of reverse micelles in the microemulsion. With the aid of
low-intensity ultrasonication, Zhang and coworkers [57] had
synthesized needle-shaped and wire-shaped silver nanoparticles
in AOT-water-isooctane microemulsion. By small angle X-ray
scattering (SAXS), they had obtained the information on the
microstructural change of the reverse micelles in the ultrasonic
bath. The introduction of ultrasonication into the solution results
in the reassembly of AOT molecules. As a result, the micelle
shape changes from a spherical to an ellipsoidal structure. The
special micelle structure can act as a template to orient the parti-
cle growth or aggregation to form a special morphology of silver
nanoparticles.
Size-tunable silver nanodisks were also obtained by mix-
ing two reverse micellar solutions [58]. The first solution is
composed of Ag(AOT), Na(AOT), isooctane and water, and
the second solution is composed of Na(AOT), isooctane and
hydrazine aqueous solution. The mixed solution was diluted with
Na(AOT) solution and then subjected to ultrasound. According
to the amount of hydrazine hydrate added, the color of silver
colloidal solution changed from red to green and gray, indicat-
ing that the average size of the hexagons and spheres increasing
with hydrazine content. Actually, the so-produced particles are a
mixture of spheres and hexagons. Furthermore, the hexagons are
mainly single crystals, but the spherical particles are polycrys-
talline. A typical morphology of a hexagon of silver nanodisk is
shown in Fig. 5.
For the formation of spherical silver nanoparticles, a model
can be given to illustrate the template role of reverse micelles
in the microemulsion (Fig. 6). At the beginning of reaction, the
attractive van der Waals force and the repulsive osmotic and elas-
tic force between reverse micelles lead to collisions of micelles
and result in exchange of the reactants (AgNO3 and N2 H4 H2 O)
solubilized in two different reverse micelles respectively. As a
result, the initial monomeric silver nuclei begin to form and
grow. Owing to the fast exchange between the water cores, the
initial silver nuclei grow quickly and then remain unchanged
when the particle size reaches a certain size which corresponds
to the thermodynamically best stabilized species in the presence
of microemulsion. Due to the possible aggregation, the final size
of silver particles is generally larger than that of the water cores.
In fact, the adsorption of AOT molecules on the formed nanopar-
ticles and the interactions among surfactant molecules, particles
and solvent molecules are responsible for the steric stabilization
of the silver nanoparticles in the colloidal solution. However,
8 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115
Fig. 5. Dark-field TEM image of a hexagon of silver nanodisk [58].
the surfactant molecules layers could be opened at high colli-
sion frequency sometimes. As a result, the aggregation between
the particles takes place, and then some bigger nanoparticles
are formed. Thus, the particle size distribution also becomes
wider.
Fig. 6. Model of the micelles served as the template for fabricating spherical
silver nanoparticles [88].
4. Effects of the parameters on the formation of silver
nanoparticles in microemulsion
Formation of nanoparticles in the reverse microemulsion is
a strong function of the intermicellar exchange and the con-
cerned parameters discussed later. The intermicellar exchange
rate, which is denoted by the intermicellar exchange rate coef-
ficient (kex ), is affected by many factors such as the type of
continuous phase, the precursor content dissolved within the
microdroplets, and the water content, referred to as molar ratio
of water to surfactant (W), etc. As a common dynamics rule
of the effect of intermicellar exchange rate on the particle size,
when the exchange reaction between the micelles takes place at
a high kex , silver nuclei formed in the solution would be higher
than that of the critical nucleation. As a result, smaller particles
are formed due to limited silver atoms left for growth. That is
to say, high exchange rate between the micelles is favorable to
yield large numbers of nanoparticles with relatively small diam-
eter. On the contrary, slow exchange of materials between the
micelles leads to formation of a few numbers of silver nuclei.
Thus an amount of silver atoms reduced by reducing agent in
the later exchange process would be available for the growth of
the nucleated particles. It is found that the final particle size is
larger and the number of the formed particles is also lower.
It is well known that the bulk solvent served as continuous
phase in microemulsion plays an important role in the intermi-
cellar potential. As one of the important factors, the effect of
continuous phase on the intermicellar exchange rate has been
mentioned previously [76,78,80,89]. As a matter of fact, the
solvents used as continuous phase in microemulsion are mainly
some alkanes such as heptane, octane, decane and cyclohex-
ane, etc. Bagwe and Khilar [76,89] have reported the effects of
intermicellar exchange rate on the formation of silver and sil-
ver chloride nanoparticles in AOT reverse microemulsion. The
results are shown in Fig. 7 and Table 2. Fig. 7 shows that the plas-
mon resonance peak shifts toward longer wavelengths (red shift)
as the solvent changes from decane to heptane to cyclohexane.
Usually, the position of the absorption peak depends on the parti-
cle size, shape and the adsorption of nucleophile or electrophile
Fig. 7. Absorption spectra of silver nanoparticles showing the effect of contin-
uous phase [76].
 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115 9

Table 2 Another one should be the water content, which is denoted by

Effect of solvent on the absorption spectra of silver nanoparticles synthesized
in reverse micelles of AOT [76]
System kex (M1 s1 ) max (nm) dp (nm) d Np
AOT/decane 108 406 6.0 6.41
AOT/heptane 107 414 22.0 9.97
AOT/cyclohexane 106 422 5.4 4.70
to the particle surface. It is well-known that adsorption of the
nucleophile to the particle surface increases the Fermi level of
the silver particle owing to its donation of electron density to the
particles [90]. The red shift of the absorption peak, which is
associated with the withdrawal of electron density from the par-
ticle surface, means an increase in the particle size. The kex value
of decane, heptane, and cyclohexane is approximately 108 , 107 ,
and 106 M1 s1 , respectively. Table 2 shows that the particle
size increases as the solvent changes from decane to heptane but
decreases for cyclohexane. The number-average particle sizes
are 6.0, 22.0, and 5.4 nm corresponding to the absorption spectra
of 406, 414, and 422 nm for decane, heptane, and cyclohexane,
respectively.
Bagwe and Khilar thought that the micellar dynamics is
affected by the chain length of the solvent molecules. With the
chain length increasing, the alkane molecules become increas-
ingly coiled and their penetration in the surfactant layer becomes
difficult. Thus, the interaction between surfactant and sol-
vent molecules decreases with an increase in chain length of
the alkane molecules. As a result, the micellar exchange rate
increases with the chain length. On the contrary, short chain
alkane and cyclohexane molecules can easily penetrate the sur-
factant layer to generate additional interfacial rigidity. Thus, the
micellar exchange rate would decrease, which further affects the
formation of silver atoms. As a result, the nucleation and growth
process continue in parallel, and the obtained particle size has
a large mean diameter and a broad size distribution. However,
using cyclohexane as continuous phase, the corresponding sur-
factant layer is too rigid to attain a common exchange rate.
In other words, the reaction for the particle formation may be
incomplete in a short duration. Therefore, both the observed total
number of the particles and the particle size are significantly
decreased. Meantime, the excessive silver ions are absorbed on
the particle surface to form a silver ionic layer, resulting in an
increase of absorption bandwidth and a change of absorption
maximum toward higher wavelength.
the molar ratio of water to surfactant (W). In microemulsions,
the volume of water is proportional to the cubic radius of the
water core, and the amount of surfactant which is present as a
188 film around the water cores is proportional to the surface area
of the microdroplets. Thus the molar ratio of water to surfactant
72 (W) has a linear relationship with the radii of the water cores
(Rw). It has been observed in AOT microemulsion system that
the water-pool radius increases with the water content. For exam-
ple, by dynamic light scattering technique, it has been confirmed
that the water core radius, Rw, is coincident with the equation
Rw (nm) = 0.18W + 1.5 in a wide range of alkanes [91]. How-
ever, Pileni et al. [92] found that the linear relationship between
Rw and W was Rw (A) = 1.5 W in the AOTwaterisooctane
microemulsion system, which is different from that of the above
example. Thus the linear relationship may be different in vari-
ous systems. Generally, low water content is favorable to form
smaller reverse micelles which yield tiny silver nanoparticles
with a narrow size distribution. On the contrary, high water con-
tent is favorable to form bigger microemulsion droplets which
are easy to fabricate larger particles [80]. Actually, at low water
content, the water solubilized in the polar core is bound by
the surfactant molecules, which increases the boundary strength
and decreases the intermicellar exchange rate. As a result, a
decrease in water content induces formation of monodisperse
silver nanoparticles with small particle size. However, the bound
water would turn into bulk water with an increase in water
content, which is benefit for the water pools to exchange their
contents by collisions and makes the chemical reaction or co-
precipitation between compounds solubilized in two different
reverse micelles complete more quickly. Since the nature of bulk
water is drastically different from that of bound water, reactants
would be rapidly transferred from one water core to another,
and thus the resultant particle size is relatively big and the size
distribution becomes relatively wide.
Fig. 8 and Table 3 provide an overview of the effect of var-
ious water contents on the wavelength of absorption maximum
and the average diameter of silver nanoparticles. It is clear from
Fig. 8b that the absorption spectrum is broader with a low optical
density at low water content, and then the plasmon peak becomes
narrower and higher with the increase of water content. Mean-
while, the absorption maximum of the particles is also slightly
blue-shifted. Authors explained that the blue shift of the absorp-
tion peak with the water content could be correlated to the size
of the nanoparticles. In fact, the particle size does influence the

Table 3
Characteristic of silver particles obtained in Ag(AOT)Na(AOT)waterisooctane microemulsion [80]

W Reducing agent [Red] (M) max (nm) 1/2 (nm)

Diameter (A)
(A)

2 NaBH4 2.5 104 421 170

5 NaBH4 2.5 104 419 138 27 10
7.5 NaBH4 1.0 105 430 200
7.5 NaBH4 1.0 104 414 108 45 15
7.5 NaBH4 2.5 104 406 82 55 21
15 NaBH4 1.0 104 409 90 60 20
15 NaBH4 2.5 104 400 75 70 30
10 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115

Fig. 8. (a) Simulated UVvis spectra of spherical silver nanoparticles. (b) UVvis spectra of silver nanoparticles obtained at various water contents. (c)(h) TEM
micrograph and size distribution of silver nanoparticles obtained at various water contents [80]. The marks represent 20.8 nm.

position of the surface plasmon band, that is to say, an increase
in particle size is associated with a red shift of the wavelength of
absorption maximum. In addition, the half-width of the plasmon
band has a linear correlation with the reciprocal of the particle
diameter. The point of view has been confirmed by experimental
results and thus the particle diameter can be predicted from Mie
theory. For small nanoparticles, the absorption maximum and
bandwidth of the plasmon peak also depend on the surrounding
medium. When nanoparticles strongly interact with the matri-
ces, a blue shift and a large broadening of the plasmon would
 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115
Fig. 9. TEM micrograph and size distribution of silver nanoparticles obtained at W = 5 in the different microemulsion systems: (a and b) AOTwaterdodecane; (c
and d) SDSwaterisoamylalcoholcyclohexane).
be observed. On the contrary, a red shift and a small broadening
would take place with low interactions between the particles and
matrices. The characteristic spectra of spherical silver nanopar-
ticles are well understood in general, but the correlation between
blue shift or red shift of the plasmon absorption and the size of
the formed particles is still the subject of debate. Further work
in this direction is still needed.
From the calculated spectra shown in Fig. 8a, it is clear that
the characteristic absorption of silver nanoparticles is centered
at approximately 410 nm. The plasmon absorption band of small
particles is very broad, that is to say, the peak width at half-height
is large. For the large particles, the absorption band is narrower
with an increase in the absorption intensity. If comparing Fig. 8a
with b, it is obviously that the particle size increases with the
water content (W). On the contrary, there would be a decrease
in the particle size if the water content decreases. The deduction
is confirmed by the electron microscopy pictures (Fig. 8c, e
and g). It is also noticed that there is a decrease in the size
distribution at low water content compared to that of the particles
obtained at higher W values (Fig. 8d, f and h). Hence, lower
water content induces formation of smaller reverse micelles and
the decrease in the micellar size induces formation of smaller
and more monodisperse particles. The phenomena mentioned
above should be attributed to both the controllable effect of the
water content to the micellar sizes and the protecting effect of
surfactant molecules for the nanoparticles.
11
Due to the structures and charged properties of differ-
ent surfactants, the microdroplet sizes in various surfactant
microemulsion systems are different, and the linear relationship
between W and Rw also has a little change. The nanoparticles
with different diameters or morphologies would be prepared
when different surfactants are used in the fabrication process.
The images shown in Fig. 9 are our unpublished research results
in AOT and SDS microemulsions and show that the particle size
and size distribution are obviously different. The nanoparticles
synthesized in AOT microemulsion system have smaller mean
diameter and narrower size distribution.
In addition, precursor concentration is also a key factor in the
formation of silver nanoparticles in the microemulsion. Both the
nucleation rate and the growth rate of the particles will increase
with AgNO3 concentration. The particle size will decrease until
an optimum amount and thereafter increase as AgNO3 concen-
tration increases. These opinions have been confirmed by some
experimental results. As shown in Fig. 10, the absorption peak
at approximately 420 nm corresponds well with that of silver
nanoparticles [80,93], and the absorption intensity of silver par-
ticles plasmon resonance increases with AgNO3 concentration
which reflects that there are more and more silver nanoparticles
formed in the solution. The maximum absorption wavelength
depends on the initial silver ion concentration. For example, in
Fig. 10a, the plasmon peak shifts toward shorter wavelengths
(blue shift) from 425 to 415 nm, meaning a decrease of the par-
12 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115

Fig. 10. (a) UVvis spectra of silver nanoparticles obtained at different AgNO3 concentration [77]. (be) TEM micrograph and size distribution of silver nanoparticles
obtained at 0.1 and 0.2 M AgNO3 [88].

ticle size [12,94], when AgNO3 concentration changes from 0.1
to 0.2 M. However, the maximum absorption gives rise to a red
shift from 415 to 440 nm, meaning that the particle size increases
and large silver aggregates have been formed, when AgNO3
concentration increases from 0.2 to 0.4 M. These conclusions
are coincident with the results shown by the TEM micrograph.
Fig. 10b and d indicate that there are only a few but large silver
nanoparticles generated in 0.1 M AgNO3 microemulsion; how-
ever there are many but small nanoparticles formed in 0.2 M
AgNO3 microemulsions. That is to say, if AgNO3 concentration
increases, the mean diameter of silver nanoparticles decreases
when [AgNO3 ] 0.2 M and increases when [AgNO3 ] > 0.2 M.
At a higher concentration, the silver nanoparticles begin to
aggregate and form into large particles [95].
This phenomenon is believed to come from two possi-
ble reasons: (1) the formation rate of nuclei increases more
significantly than the growth rate of silver nanocrystals with
increasing AgNO3 concentration. As a result, large numbers of
tiny nanoparticles with high special surface area are formed in
a short time. Due to the adsorption of AOT molecules on the
particle surface, aggregation between the particles is inhibited,
which is favorable to form fine nanoparticles. Using a surfactant
containing sulfonic group, Daxad 19, as stabilizing agent, Sondi
et al. [96] also found the similar phenomenon in the prepara-
tion of silver nanoparticles. Authors have explained their results,
assuming that the interaction between the Ag+ ions and the sul-
fonic group of the Daxad 19 forms an Ag-emulsifier complex,
which may act as a more effective protective agent to prevent the
 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115
particles from aggregation. The decrease of the initial concentra-
tion of Ag+ will result in a lower concentration of complex which
weakens the protection to the resultant particles. (2) A large num-
ber of silver nanoparticles are formed at a higher concentration
of AgNO3 . As a result, the collision frequency increases signif-
icantly, which neutralizes the AOT molecules protective effect
and results in aggregation of the particles.
As a main reducing agent, sodium borohydride (NaBH4 )
is commonly employed to reduce silver ions. The resulting
nanoparticles have a smaller particle size and a narrower par-
ticle size distribution. Meanwhile, the reaction period becomes
shorter than that in the case of other reducing agents. However,
the solubility of NaBH4 in AOT reverse micelles is very poor
[80], that is to say, the reduction of silver ions is not complete
even if excessive NaBH4 is added. On the contrary, it is possible
to totally reduce silver ions solubilized in the water pools due
to the higher solubility of N2 H4 H2 O in AOT microemulsions.
At a low concentration of N2 H4 H2 O, a large amount of sil-
ver nanoclusters and a few amount of nanoparticles are formed.
In other words, the reduction of silver ions is not complete. At
a high concentration of N2 H4 H2 O, the tiny particles begin to
aggregate into larger particles. As a result, the total amount of
nanoparticles is decreased. Thus the mean diameter of silver
nanoparticles increases with N2 H4 H2 O concentration.
In conclusion, the reverse micelles are essential to inhibit the
possible aggregation and thus stabilize the resultant nanoparti-
cles. The nature of water solubilized in reverse micelles seems
to play an important role in the control of the particle diameter.
The average size of final silver nanoparticles is dependent on
the micellar size, the solvent type and the reducing agent con-
centration. The particles formed in AOT microemulsion have
relatively strong electrostatic interactions with the negatively
charged head polar group of AOT molecules, which comes into
being a protective effect against aggregation. As a result, as-
produced nanosilver colloid can be preserved for a very long
time without precipitation. However, it is expensive due to the
large amounts of surfactant and organic solvent added to the
system, and it is also difficult to separate and remove them
from the products. So far the synthesis of the nanoparticles with
microemulsion method described previously can obtain the sta-
ble silver dispersions only at relatively low concentrations and
is not suitable for large-scale manufacturing.
There is another question in the method is the toxicity of
the microemulsion components [97] and the reducing agents.
Owing to the environmental protection, one begins to consider
green synthesis of the nanoparticles in recent years. In order
to minimize the toxicity of organic solvents, supercritical CO2
(CO2scrit ) has been used as continuous phase for the synthesis
of silver nanoparticles [98]. However, a cosurfactant, perfluo-
ropolyether phosphate (PFPEP), must be added into AOT system
to make the microemulsion soluble in CO2scrit . Compared with
the traditional reducing agent, NaBH4 , NaBH3 CN dissolved in
CO2scrit is effective to reduce Ag+ in the water core of the micro-
droplets. The average size of resultant nanosilver is only 4 nm
in diameter. By the choice of long carbon chain and low toxic
alkane solvent and the control of reductant amount, we have
synthesized silver colloid with a high colloidal stability and a
13
narrow size distribution. Duo to its low toxicity, the silver colloid
has possibilities to be used directly in the practical application
in many fields, e.g., antibacterial domains, etc.
Biochemical reductants such as quercetin, one of the natural
plant pigments, are reported for the synthesis of silver nanoparti-
cles in reverse micelles to obtain highly stable and monodisperse
particles [61,99]. Research results show that silver nanoparti-
cles are prepared by the formation of an intermediate complex
in AOT microemulsion in the presence of oxygen. Due to its
strong interaction with the formed nanoparticles, quercetin can
also act as a protective agent to inhibit the particle aggrega-
tion. Other methods such as irradiation reduction (reduction by
solvated electrons) [61] for the synthesis of silver nanoparti-
cles in reverse micelles have been proposed. For example, silver
nanoparticles are prepared in the microemulsion under gamma
radiation, and the obtained nanoparticles are stable in air for
several months. Even though conventional surfactants are com-
monly used in the microemulsion, non-conventional surfactants,
i.e., reactive surfactants, are found to be more efficient and appli-
cable. Since reactive surfactant molecules can be bound to the
particle surface, a critical amount of the surfactant needed for the
stabilization of silver nanoparticles would be obviously reduced.
5. Conclusions
There have been many methods employed to synthesize silver
nanoparticles. Using different methods, the obtained nanoparti-
cles show significant difference in both particle diameter and
morphology. Thus, the choice of synthetic methods in the
synthetic process depends on the materials applications require-
ment. For example, small particles are desirable in catalysis
where the main emphasis is on surface-to-volume ratio, whereas
larger particles are often necessary for optical applications. Sil-
ver nanoparticles with size below 10 nm have been prepared by
traditional chemical methods, however the tiny particles tend
to grow and aggregate into large particles. The major prob-
lems for non-traditional physical methods are its high cost; the
obtained silver nanoparticles also have a wide particle size distri-
bution. In microemulsion, the nucleation and growth of particles
are restricted within the water core of inverse micelles. Thus,
microemulsion method is often used to synthesize nanoparticles
with specific size and morphology. The advantage of the method
is the ability to control the particle size and morphology easily
by adjusting the concerned parameters, e.g., the concentration
and type of surfactant, the type of continuous phase, the con-
centration of precursors and molar ratio of water to surfactant.
Biochemical reduction is a promising method for sufficient raw
materials, mild reaction conditions and few poisonous byprod-
ucts. By the choice of solvent, reducing agent and protecting
agent, completely green synthesis can be put in practice in the
preparation of silver and other metal nanoparticles, though the
reaction efficiency is needed to be further improved.
Although significant advances have been made in preparation
of silver nanoparticles, we are also faced some problems. One
challenge is to prepare silver colloidal nanoparticles with high
stability and good exchangeability of solvents. It is an important
process to transfer silver nanoparticles to different chemico-
14 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115

physical environments in practical applications. Another one [24] X.Q. Wang, H. Itoh, K. Naka, Y. Chujo, Langmuir 19 (2003) 6242.
is to fabricate size-controlled or shape-controlled and chemi- [25] C. Faure, A. Derre, W. Neri, J. Phys. Chem. B 107 (2003) 4738.
[26] S.H. Chen, D.L. Carroll, Nano Letters 2 (2002) 1003.
cally clean silver nanoparticles with narrow size distribution,
[27] S. Mandal, D. Rautaray, M. Sastry, J. Mater. Chem. 13 (2003) 3002.
which are easily incorporated into a variety of substances to form [28] G. Malandrino, S.T. Finocchiaro, I.L. Fragala, J. Mater. Chem. 14 (2004)
nanocomposites or assembled into higher-order nanostructures. 2726.
In addition, it is an important goal for advanced projects to pre- [29] S. Behrens, J. Wu, W. Habicht, E. Unger, Chem. Mater. 16 (2004) 3085.
pare three-dimensional nanomaterials with controlled geometry [30] K.S. Morley, P.C. Marr, P.B. Webb, A.R. Berry, F.J. Allison, G. Moldovan,
and structure. Besides theoretical and experimental studies on P.D. Brown, S.M. Howdle, J. Mater. Chem. 12 (2002) 1898.
[31] C. Johans, J. Clohessy, S. Fantini, K. Kontturi, V.J. Cunnane, Electrochem.
the novel synthetic technologies and the important influence fac- Commun. 4 (2002) 227.
tors, the combination of traditional and non-traditional methods [32] Y.H. Zhang, F. Chen, J.H. Zhuang, Y. Tang, D.J. Wang, Y.J. Wang, A.G.
needs much further attention. The synthesis of silver nanopar- Dong, N. Ren, Chem. Commun. (2002) 2814.
ticles by irradiation, ultrasound or biochemical reduction in [33] H.Y. Ma, B.S. Yin, S.Y. Wang, Y.L. Jiao, W. Pan, S.X. Huang, S.H. Chen,
reverse micelles represents early examples of such development. F.J. Meng, ChemPhysChem 5 (2004) 68.
[34] B.S. Yin, H.Y. Ma, S.Y. Wang, S.H. Chen, J. Phys. Chem. B 107 (2003)
8898.
Acknowledgements [35] J.Q. Cheng, S.W. Yao, Rare Met. 24 (2005) 376.
[36] Y. Socol, O. Abramson, A. Gedanken, Y. Meshorer, L. Berenstein, A.
This work was financially supported by the Ph.D. Pro- Zaban, Langmuir 18 (2002) 4736.
grams Foundation of Ministry of Education of China (No. [37] J.P. Zhang, L.Q. Sheng, P. Chen, Chin. Chem. Lett. 14 (2003) 645.
[38] Q.F. Zhou, Z. Xu, J. Mater. Sci. 39 (2004) 2487.
20050487011). The authors would like to thank Analytical and [39] D.G. Shchukin, I.L. Radtchenko, G.B. Sukhorukov, ChemPhysChem 4
Testing Center, Huazhong University of Science and Technol- (2003) 1101.
ogy, P.R. China, for the test of TEM images. Dr. Wanzhong [40] L.Z. Zhang, J.C. Yu, H.Y. Yip, Q. Li, K.W. Kwong, A.W. Xu, P.K. Wong,
Zhang also would like to sincerely acknowledge Dr. Guang- Langmuir 19 (2003) 10372.
nian Xu, Wei Wang and Dapeng Chen for discussions and their [41] A.M. Junior, H.P.M. de Oliveira, M.H. Gehlen, Photochem. Photobiol. Sci.
2 (2003) 921.
valuable advices. [42] R.C. Jin, Y.C. Cao, E.C. Hao, G.S. Metraux, G.C. Schatz, C.A. Mirkin,
Nature 425 (2003) 487.
References [43] K. Mallick, M.J. Witcomb, M.S. Scurrell, J. Mater. Sci. 39 (2004) 4459.
[44] A.I. Kryukov, N.N. Zinchuk, A.V. Korzhak, S.Y. Kuchmii, Theor. Exp.
[1] K.H. Cho, J.E. Park, T. Osaka, S.G. Park, Electrochim. Acta 51 (2005) 956. Chem. 39 (2003) 9.
[2] S.H. Sun, C.B. Murray, D. Weller, L. Folks, A. Moser, Science 287 (2000) [45] P.D. Cozzoli, R. Comparelli, E. Fanizza, M.L. Curri, A. Agostiano, D.
1989. Laub, J. Am. Chem. Soc. 126 (2004) 3868.
[3] Y.W.C. Cao, R.C. Jin, C.A. Mirkin, Science 297 (2002) 1536. [46] F.K. Liu, P.W. Huang, Y.C. Chang, F.H. Ko, T.C. Chu, J. Mater. Res. 19
[4] J.F. Wang, M.S. Gudiksen, X.F. Duan, Y. Cui, C.M. Lieber, Science 293 (2004) 469.
(2001) 1455. [47] T. Yamamoto, H.B. Yin, Y. Wada, T. Kitamura, T. Sakata, H. Mori, S.
[5] H.Q. Jiang, S. Manolache, A.C.L. Wong, F.S. Denes, J. Appl. Polym. Sci. Yanagida, Bull. Chem. Soc. Jpn. 77 (2004) 757.
93 (2004) 1411. [48] S. Komarneni, D.S. Li, B. Newalkar, H. Katsuki, A.S. Bhalla, Langmuir
[6] S. Hirano, Y. Wakasa, A. Saka, S. Yoshizawa, Y. Oya-Seimiya, Y. Hish- 18 (2002) 5959.
inuma, A. Nishimura, A. Matsumoto, H. Kumakura, Physica C 392 (2003) [49] H.B. Yin, T. Yamamoto, Y. Wada, S. Yanagida, Mater. Chem. Phys. 83
458. (2004) 66.
[7] X.L. Ren, F.Q. Tang, Acta Chim. Sinica 60 (2002) 393. [50] A.M. Qin, Z.L. Jiang, Q.Y. Liu, L. Liao, Y.M. Jiang, Chin. J. Anal. Chem.
[8] S.Y. Yeo, H.J. Lee, S.H. Jeong, J. Mater. Sci. 38 (2003) 2143. 30 (2002) 1254.
[9] H.S. Wang, X.L. Qiao, J.G. Chen, X.J. Wang, S.Y. Ding, Mater. Chem. [51] V. Hornebecq, M. Antonietti, T. Cardinal, M. Treguer-Delapierre, Chem.
Phys. 94 (2005) 449. Mater. 15 (2003) 1993.
[10] J.P. Zhang, P. Chen, C.H. Sun, X.J. Hu, Appl. Catal. A: Gen. 266 (2004) [52] S.H. Choi, S.H. Lee, Y.M. Hwang, K.P. Lee, H.D. Kang, Radiat. Phys.
49. Chem. 67 (2003) 517.
[11] R.J. Chimentao, I. Kirm, F. Medina, X. Rodriguez, Y. Cesteros, P. Salagre, [53] L.H. Xin, R.M. Zhou, E.B. Gracien, A.O. Francis, J. Radiat. Res. Radiat.
J.E. Sueiras, Chem. Commun. 4 (2004) 846. Process 22 (2004) 69.
[12] B.L. He, J.J. Tan, Y.L. Kong, H.F. Liu, J. Mol. Catal. A: Chem. 221 (2004) [54] T. Tsuji, T. Kakita, M. Tsuji, Appl. Surf. Sci. 206 (2003) 314.
121. [55] X.W. Zheng, L.Y. Zhu, X.J. Wang, A.H. Yan, Y. Xie, J. Cryst. Growth 260
[13] H.S. Wang, X.L. Qiao, J.G. Chen, S.Y. Ding, Colloids Surf. A: Physic- (2004) 255.
ochem. Eng. Aspects 256 (2005) 111. [56] X.W. Zheng, L.Y. Zhu, A.H. Yan, X.J. Wang, Y. Xie, J. Colloid Interface
[14] N. Leopold, B. Lendl, J. Phys. Chem. B 107 (2003) 5723. Sci. 268 (2003) 357.
[15] K.K. Caswell, C.M. Bender, C.J. Murphy, Nano Letters 3 (2003) 667. [57] J.L. Zhang, B.X. Han, M.H. Liu, D.X. Liu, Z.X. Dong, J. Liu, D. Li, J.
[16] Z.S. Pillai, P.V. Kamat, J. Phys. Chem. B 108 (2004) 945. Wang, B.Z. Dong, H. Zhao, L.X. Rong, J. Phys. Chem. B 107 (2003) 3679.
[17] Y.D. Yin, Z.Y. Li, Z.Y. Zhong, B. Gates, Y.N. Xia, S. Venkateswaran, J. [58] M. Maillard, S. Giorgio, M.P. Pileni, J. Phys. Chem. B 107 (2003) 2466.
Mater. Chem. 12 (2002) 522. [59] M. Maillard, S. Giorgio, M.P. Pileni, Adv. Mater. 14 (2002) 1084.
[18] Y.C. Zhu, M.R. Ji, H.G. Zheng, Y. Li, Z.P. Yang, Y.T. Qian, Mater. Lett. 58 [60] M.C. McLeod, R.S. McHenry, E.J. Beckman, C.B. Roberts, J. Phys. Chem.
(2004) 1121. B 107 (2003) 2693.
[19] N.K. Chaki, J. Sharma, A.B. Mandle, I.S. Mulla, R. Pasricha, K. Vijayamo- [61] E.M. Egorova, A.A. Revina, Colloid J. 64 (2002) 301.
hanan, Phys. Chem. Chem. Phys. 6 (2004) 1304. [62] R.R. Naik, S.J. Stringer, G. Agarwal, S.E. Jones, M.O. Stone, Nat. Mater.
[20] Y.G. Sun, B. Mayers, T. Herricks, Y.N. Xia, Nano Letters 3 (2003) 955. 1 (2002) 169.
[21] Y.G. Sun, Y.N. Xia, Science 298 (2002) 2176. [63] J.L. Gardea-Torresdey, E. Gomez, J.R. Peralta-Videa, J.G. Parsons, H.
[22] D.H. Chen, Y.W. Huang, J. Colloid Interface Sci. 255 (2002) 299. Troiani, M. Jose-Yacaman, Langmuir 19 (2003) 1357.
[23] I. Pastoriza-Santos, L.M. Liz-Marzan, Nano Letters 2 (2002) 903. [64] S.S. Shankar, A. Ahmad, M. Sastry, Biotechnol. Prog. 19 (2003) 1627.
 W. Zhang et al. / Materials Science and Engineering B 142 (2007) 115 15

[65] M. Kowshik, S. Ashtaputre, S. Kharrazi, W. Vogel, J. Urban, S.K. Kulkarni, [81] W.Z. Zhang, X.L. Qiao, J.G. Chen, Chem. Phys. 330 (2006) 495.
K.M. Paknikar, Nanotechnology 14 (2003) 95. [82] J.H. Fendler, Chem. Rev. 87 (1987) 877.
[66] A. Ahmad, P. Mukherjee, S. Senapati, D. Mandal, M.I. Khan, R. Kumar, [83] C.J. Murphy, N.R. Jana, Adv. Mater. 14 (2002) 80.
M. Sastry, Colloids Surf. B: Biointerfaces 28 (2003) 313. [84]
V. Tomasic, I. Stefani
c, N. Filipovic-Vincekovic, Colloid Polym. Sci. 277
[67] K.C. Bhainsa, S.F. DSouza, Colloids Surf. B: Biointerfaces 47 (2006) 160. (1999) 153.
[68] S.S. Shankar, A. Rai, A. Ahmad, M. Sastry, J. Colloid Interface Sci. 275 [85] B.A. Simmons, S. Li, V.T. John, G.L. McPherson, A. Bose, W. Zhou, J.
(2004) 496. He, Nano Letters 2 (2002) 263.
[69] S. May, A. Ben-Shaul, J. Phys. Chem. B 105 (2001) 630. [86] T. Fukuyo, H. Imai, J. Cryst. Growth 241 (2002) 193.
[70] L.W. Yeary, J.W. Moon, L.J. Love, J.R. Thompson, C.J. Rawn, T.J. Phelps, [87] E. Leontidis, K. Kleitou, T. Kyprianidou-Leodidou, V. Bekiari, P. Lianos,
IEEE Trans. Magn. 41 (2005) 4384. Langmuir 18 (2002) 3659.
[71] C.T. Dameron, R.N. Reese, R.K. Mehra, A.R. Kortan, P.J. Carroll, M.L. [88] W.Z. Zhang, X.L. Qiao, J.G. Chen, Colloids Surf. A: Physicochem. Eng.
Steigerwald, L.E. Brus, D.R. Winge, Nature 338 (1989) 596. Aspects 299 (2007) 22.
[72] B. Zhang, X.C. Ye, W. Dai, W.Y. Hou, F. Zuo, Y. Xie, Nanotechnology 17 [89] R.P. Bagwe, K.C. Khilar, Langmuir 13 (1997) 6432.
(2006) 385. [90] A. Henglein, J. Phys. Chem. 97 (1993) 5457.
[73] T. Klaus-Joerger, R. Joerger, E. Olsson, C.G. Granqvist, Trends Biotechnol. [91] J. Eastoe, B.H. Robinson, A. Visser, D.C. Steytler, J. Chem. Soc., Faraday
19 (2001) 15. Trans. 87 (1991) 1899.
[74] R. Joerger, T. Klaus, C.G. Granqvist, Adv. Mater. 12 (2000) 407. [92] M.P. Pileni, T. Zemb, C. Petit, Chem. Phys. Lett. 118 (1985) 414.
[75] B. Nair, T. Pradeep, Cryst. Growth Design 2 (2002) 293. [93] Z.Q. Zhang, R.C. Patel, R. Kothari, C.P. Johnson, S.E. Friberg, P.A. Aikens,
[76] R.P. Bagwe, K.C. Khilar, Langmuir 16 (2000) 905. J. Phys. Chem. B 104 (2000) 1176.
[77] W.Z. Zhang, X.L. Qiao, J.G. Chen, H.S. Wang, J. Colloid Interface Sci. [94] M.P. Zheng, M.Y. Gu, Y.P. Jin, G.L. Jin, Mater. Res. Bull. 36 (2001) 853.
302 (2006) 370. [95] L.M. Liz-Marzan, I. Lado-Tourino, Langmuir 12 (1996) 3585.
[78] C.L. Kitchens, M.C. McLeod, C.B. Roberts, J. Phys. Chem. B 107 (2003) [96] I. Sondi, D.V. Goia, E. Matijevic, J. Colloid Interface Sci. 260 (2003) 75.
11331. [97] K.P. Johnston, T. Randolph, F. Bright, S. Howdle, Science 272 (1996) 1726.
[79] G. Hota, S. Jain, K.C. Khilar, Colloids Surf. A: Physicochem. Eng. Aspects [98] H. Ohde, F. Hunt, C.M. Wai, Chem. Mater. 13 (2001) 4130.
232 (2004) 119. [99] E.M. Egorova, A.A. Revina, Colloids Surf. A: Physicochem. Eng. Aspects
[80] C. Petit, P. Lixon, M.P. Pileni, J. Phys. Chem. 97 (1993) 12974. 168 (2000) 87.