Materials Research Bulletin 43 (2008) 90–96

www.elsevier.com/locate/matresbu

Synthesis of silver nanoparticles in a polyvinylpyrrolidone (PVP)

paste, and their optical properties in a film and in ethylene glycol
A. Slistan-Grijalva a,*, R. Herrera-Urbina b, J.F. Rivas-Silva c, M. Ávalos-Borja d,
F.F. Castillón-Barraza d, A. Posada-Amarillas e
a
Departamento de Investigación en Polı́meros y Materiales, Universidad de Sonora, Hermosillo, Sonora, Mexico
b
Departamento de Ingenierı́a Quı́mica y Metalurgia, Universidad de Sonora, Hermosillo, Sonora, Mexico
c
Coordinación de Óptica, INAOE, Tonatzintla, Puebla, Mexico
d
Centro de Ciencias de la Materia Condensada, UNAM, Ensenada, B.C., Mexico
e
Departamento de Investigación en Fı́sica, Universidad de Sonora, Hermosillo, Sonora, Mexico
Received 17 February 2006; received in revised form 10 November 2006; accepted 6 February 2007
Available online 11 February 2007

Abstract
Silver nanoparticles were synthesized in a paste of polyvinylpyrrolidone formed after mixing PVP with acetone and a small
volume of aqueous silver nitrate under magnetic stirring. A film made with the material was characterized by UV–vis spectroscopy.
The obtained spectrum shows a single peak at 438 nm, arising from the surface plasmon absorption of silver colloids. This result
clearly indicates that silver nanoparticles are embedded in PVP. When the pre-treated PVP–Ag colloid is dissolved in ethylene
glycol, the UV–vis spectrum of the resulting dispersion shows an absorption peak at 433 nm, whose maximum absorption blue
shifts to 416 nm after 18 days of agitation. The silver nanoparticles have an average particle size of 4.12 nm. Because the IR band
assigned to the carbonyl group of the PVP shifts to longer wavelengths, the interaction of this polymer with silver nanoparticles
seems to take place through the carbonyl oxygen.
# 2007 Elsevier Ltd. All rights reserved.

Keywords: A. Composite; B. Chemical synthesis; C. Infrared spectroscopy; D. Optical properties

1. Introduction

Silver nanoparticles in solution, supported onto a substrate and incorporated into organic or inorganic matrixes
show remarkable physical and chemical properties that are size and shape dependent. In the case of optical properties,
for example, particle size and shape determine the characteristics of their surface plasmon absorption band (SPAB)
[1,2], which has been observed for silver particles in solution and in solids [3]. Other factors that also affect the SPAB
of silver nanoparticles are the refractive index of the surrounding medium and adsorption phenomena at the solid–
solution interface [2,4]. Embedded in polymer films, silver nanoparticles show strong absorption at 438 nm in
polyvinyl alcohol (PVA) [5] and at 410 nm in PVP [6]. Silver nanoparticles also exhibit remarkable size effects in
biological and medicine-related properties. Recently, it has been found that the HIV-1 virus exclusively binds to silver

* Corresponding author. Current address: Centro de Estudios Superiores del Estado de Sonora, Sonora, Mexico. Tel.: +52 66222103506;
fax: +52 6622108406.
E-mail address: angel@polimeros.uson.mx (A. Slistan-Grijalva).

0025-5408/$ – see front matter # 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2007.02.013
 A. Slistan-Grijalva et al. / Materials Research Bulletin 43 (2008) 90–96 91

particles whose size is in the range of 1–10 nm [7], and that silver nanoparticles embedded in PVP show bactericide
properties in complicated cases of infected burns and purulent wounds [8]. Silver nanoparticles have also been shown
to exhibit excellent antibacterial activity against E. coli [9]. In addition, films and powders of PVP containing silver
nanoparticles have potential applications in the field of optical information [10,11]. In the field of catalysis, 15 nm
silver nanoparticles supported onto alumina show catalytic activity as converters of simulated exhaust automobile
gases [12].
In any process to synthesize metal nanoparticles, it is crucial to fully understand the mechanisms leading to the
formation of the nanoparticles. An ideal synthesis should produce monodisperse particles with uniform shape.
Synthesis of silver nanoparticles by solution chemistry methods allows good control of particle size distribution,
average particle size and particle shape. All of these particle characteristics affect significantly their physical and
chemical properties. Using solution chemistry, particle size and shape, and size distribution are controlled by
judiciously choosing the reaction temperature, order of addition of reagents, and the ratio of protective agent/metal
compound. One of the non-aqueous solvents that have been widely used for the thermal-assisted synthesis of tailor-
made silver nanoparticles is ethylene glycol [13–15]. For the synthesis of silver particles, this solvent has proven to be
a good alternative to aqueous and many non-aqueous solvents because the addition of reducing agents is unnecessary
since ethylene glycol also serves as reducing agent of Ag(I) species even at a room temperature of 26 8C, thus yielding
colloidal silver dispersions [13,16]. For preventing particle aggregation and controlling the average particle size and
even particle shape, a polar polymer, namely polyvinylpyrrolidone (PVP) has been widely used in the synthesis of
silver nanoparticles from ethylene glycol–silver nitrate solutions [6,13–16]. Depending on the experimental
conditions, thermo-chemical reduction of Ag(I) species in PVP–ethylene glycol solutions results in silver
nanoparticles with different shapes: decahedrons [13], cubes [14], mixtures of cubes and tetrahedrons [17] and wire-
shaped [15,18]. Adsorption of this polymer onto silver nanoparticles leads to steric stabilization of the system and may
modify their crystal habit [15,18], thus also imparting new properties to silver colloids. There is evidence that under
certain conditions PVP also reduces Ag(I) species, which in turn nucleate and form silver nanoparticles. For example,
when an aqueous silver nitrate–PVP solution is heated at 100 8C under darkness and reacted for 1 h [13], or when
silver perchlorate and PVP are mixed in water at high concentrations and at room temperature [19].
This paper reports the synthesis of silver nanoparticles by chemical reduction of a very small volume (0.05 mL) of
aqueous silver nitrate mixed with acetone into which solid PVP is added at 25 8C. Since PVP is insoluble in acetone,
the original slightly yellow powder turns into a paste, whose color changes to dark brown after 35 min of magnetic
agitation, indicating the formation of silver nanoparticles in the polymer matrix. To the best of our knowledge this is
the first report on the synthesis of silver nanoparticles using a paste of PVP as reducing agent for Ag(I) species. A small
amount of the PVP paste containing the silver nanoparticles was used to make a film, which was characterized by UV–
vis spectroscopy. The remaining PVP paste was allowed to dry in air. A sample of the obtained powder was mixed with
KBr, and a pellet was formed and characterized by IR spectroscopy. The rest of the powder was dissolved in ethylene
glycol under magnetic stirring. One drop of this dispersion was observed under transmission electron microscopy, and
the average size and size distribution of the silver particles were evaluated from image analyses of the corresponding
micrographs. PVP-protected silver nanoparticles dispersed in ethylene glycol were characterized by UV–vis
spectroscopy, which is amply recognized to be a powerful experimental tool for investigating the effect of particle
characteristics and surrounding medium on the optical absorption of silver nanoparticles.

2. Experimental

All chemicals used in this investigation were reagent-grade materials and they were used without purification.
Silver nitrate (99%) was purchased from Aldrich, ethylene glycol (99.8%) was purchased from Productos Monterrey,
México; polyvinylpyrrolidone (PVP-K 15, MW 10,000) was purchased from Spectrum, and acetone (99.5%) was
purchased from J.T. Baker. De-ionized water was used to prepare aqueous solutions. All experiments were conducted
at 25  1 8C.
Neither PVP nor silver nitrate is soluble in acetone. Therefore, 50 mg AgNO3 (29.4 mmol) were first dissolved in
0.05 mL de-ionized water. Then, 30 mL acetone was added and the resulting solution was mixed under magnetic
agitation during 20 min. To this solution, 1.5 g PVP powder was added and the agitation was continued for another
35 min. After 30 min agitation, the PVP was observed to agglomerate and to stick onto the bottom and the walls of the
beaker. At the end of the mixing period the remaining acetone was decanted. The solid PVP, initially white, turned into
92 A. Slistan-Grijalva et al. / Materials Research Bulletin 43 (2008) 90–96

a light brown and then dark brown paste at the end of this treatment with the aqueous solution of silver nitrate and
acetone, indicating the formation of silver nanoparticles embedded in the polymer matrix. A small amount of this
material was deposited onto a microscope glass slide and pressed with another slide to produce a sufficiently thin and
transparent film for UV–vis characterization. The final solid recovered was allowed to dry in air for 48 h and then
characterized by IR spectroscopy using the KBr pellet technique.
Colloidal dispersions of PVP-protected silver in ethylene glycol were prepared by dissolving the dry, pre-treated
PVP–Ag colloid powder in 50 mL ethylene glycol under magnetic agitation and keeping the stirring for up to 18 days.
UV–vis spectra of the film made with the PVP paste formed after mixing this polymer with acetone–aqueous silver
nitrate, and of the colloidal dispersions of PVP-protected silver in ethylene glycol were obtained with a Perkin-Elmer
Lambda 2 spectrophotometer, at a rate of 60 nm/min and a spectral resolution of 2 nm. In the case of silver dispersions,
0.1 mL colloidal silver was added to 10 mL ethylene glycol in a quartz cell with a pathlength of 1 cm. The blank was
the corresponding ethylene glycol–PVP solution. IR spectra were obtained with a Perkin-Elmer spectrophotometer,
model 1600, using the KBr pellet technique, which involves mixing thoroughly the material to be tested with KBr
before forming a pellet at high pressure.
Silver nanoparticles were also characterized by transmission electron microscopy using a JEOL microscope, model
2010. A drop of the ethylene glycol–PVP-protected silver nanoparticles dispersion was deposited onto a carbon-
coated copper grid. After the solvent was evaporated, the grid was observed under the microscope in bright field mode.
The average particle size and the size distribution were determined from image analyses of the microphotographs
taken.

3. Results and discussion

Polyvinylpyrrolidone is a white (or slightly yellow) hygroscopic powder that can be made into clear films. This
polar polymer is a protective colloid, and it has been amply used as stabilizer of colloidal silver, a hydrophobic
material, dispersed in various solvents. Under certain conditions, this macromolecule can also act as reducing agent of
Ag(I) species in solution, thus producing metallic silver in the form of nanoparticles [13].
Fig. 1 presents the experimental UV–vis spectrum of a PVP film made from a sample of 1.5 g of PVP added to an
aqueous silver nitrate–acetone solution, at a solid ratio of PVP:AgNO3 equal to 30, and stirred under magnetic
agitation during 35 min at 25  1 8C. This spectrum shows a single peak, well defined but broad and asymmetric,
whose maximum absorbency occurs at 438 nm, and that arises from the surface plasmon absorption of silver colloids.
The position of this peak occurs in the same region where nearly spherical silver colloids produced in gelatin have been
reported to show maximum absorption, namely 434 nm [20], thus indicating clearly the presence of silver particles in

Fig. 1. UV–vis absorption spectrum of a polyvinylpyrrolidone (PVP) film prepared after mixing 1.5 g of PVP in powder form with an aqueous silver
nitrate–acetone solution (0.05 mL de-ionized water, 50 mg AgNO3 and 30 mL acetone) for 35 min at 25  1 8C, and discarding the remaining
solution.
 A. Slistan-Grijalva et al. / Materials Research Bulletin 43 (2008) 90–96 93

the PVP film. Films of polyvinyl alcohol (PVA) containing silver nanoparticles also show strong absorption at 438 nm
[5], whereas thin films prepared from an alcohol solution of PVP–silver nitrate by spin coating show an asymmetric
absorption band whose maximum occurs at 425 nm [10], and PVP films with silver nanoparticles synthesized by
ultrasound in ethylene glycol show maximum absorption at 410 nm [6].
The position of the surface plasmon absorption peak of spherical silver particles, separated by long distances,
depends on the refractive index of the surrounding medium, particle size and adsorbed substances on their surfaces. If
one considers that the ‘‘true’’ position of the surface plasmon band of spherical silver particles (particle
diameter  10 nm) in water has been predicted (from its values in salt matrices) to be 382  1 nm [2], the red shift
observed for the absorption peak of silver particles in solid PVP must be due to the larger refractive index (n = 1.53) of
this polymeric matrix. This experimental result agrees with theoretical predictions, which indicate that the position of
the SPAB of silver particles embedded in solid PVP shifts to longer wavelengths [4].
Indirectly, the UV–vis spectrum presented in Fig. 1 clearly indicates that a paste of PVP reduces aqueous Ag(I)
species from silver nitrate to Ag(0) atoms, which then nucleate and form silver nanoparticles at room temperature. The
ability of PVP as a reducing agent of aqueous Ag(I) species has been previously reported by Silvert et al. [13], who
synthesized silver nanoparticles from an aqueous silver nitrate–PVP solution heated at 100 8C under darkness to avoid
reduction of aqueous Ag(I) species by light.
The theoretical SPAB of spherical silver nanoparticles with particle radii from 1 nm to 26 nm embedded in PVP
were calculated using the Mie Theory [3]. Fig. 2 presents the theoretical SPAB peak position of silver nanoparticles as
a function of particle radii under these conditions, and shows that for particles with a radius shorter than about 7 nm the
SPAB peak position is almost constant at about 426 nm. As the particle radius increases above 6 nm, the peak position
of the SPAB shifts steadily to longer wavelengths. From this graph, the particle radius that corresponds to a theoretical
SPAB with a peak position at 438 nm (same peak position of the experimental UV–vis spectrum of the PVP–silver
nanoparticles film) is 16 nm. As will be shown later, according to TEM characterization, silver particles initially
embedded in PVP and then dispersed in ethylene glycol are substantially smaller (average particle
diameter = 4.12 nm). The reason for this discrepancy may be associated to silver ions adsorption on silver
nanoparticles [16], because this interaction shifts the position of the SPAB to longer wavelengths [2,21].
The IR spectra of PVP, AgNO3 and PVP treated with aqueous AgNO3 and acetone are presented in Fig. 3. The main
feature of the spectrum of untreated PVP, whose monomer contains an amide carbonyl, is a strong band at 1666 cm1.
According to the literature [22], the shape of the amide carbonyl stretch absorption is one of the broadest of the
carbonyl family and is positioned between 1695 cm1 and 1615 cm1. Other bands on this spectrum are centered at
1462 cm1 and 1424 cm1 which result from vibration of the tertiary nitrogen, and at 2360 cm1, 2954 cm1 and
3448 cm1, assigned to environmental CO2, CH and OH, respectively. The IR spectrum of PVP treated with aqueous
silver nitrate and acetone also shows the strong band due to the amide carbonyl stretch vibration, but shifted to
1662 cm1. A shift of the carbonyl absorption band to lower frequencies has also been reported for PVP treated with

Fig. 2. Theoretical peak position of the surface plasmon absorption band (SPAB) of spherical silver nanoparticles embedded in solid PVP (refractive
index = 1.33), calculated using the Mie Theory, as a function of the particle radius.
94 A. Slistan-Grijalva et al. / Materials Research Bulletin 43 (2008) 90–96

Fig. 3. FTIR spectra of KBr pellets mixed with: (a) solid PVP; (b) solid PVP mixed with solid AgNO3; (c) solid AgNO3; (d) solid PVP pre-treated
with an aqueous silver nitrate–acetone solution (0.05 mL de-ionized water, 50 mg AgNO3 and 30 mL acetone).

ethanol saturated with silver nitrate [23]. This band displacement indicates coordination of the amide carbonyl oxygen
with silver species. The band at 1384 cm1 indicates the presence of silver nitrate in the PVP + Ag colloid composite.
The PVP + Ag  PVP spectrum was obtained subtracting the spectrum of PVP to that of PVP + Ag. In this spectrum,
the displacement of the carbonyl stretch vibration is better appreciated because a weak band appears at 1640 cm1.
Fig. 4 presents a transmission electron micrograph that shows the nanoparticles obtained after dry PVP pre-treated
with aqueous silver nitrate and acetone is dissolved in ethylene glycol, and the dispersion is agitated for 24 h. These
nanoparticles of silver have an average particle size of 4.12 nm and a standard deviation of 2.76 nm. Fig. 3 also
includes the histogram that shows their size distribution. Using the same PVP:AgNO3 weight ratio, volume of ethylene
glycol, and experimental conditions, but without pre-treatment of the PVP, the silver nanoparticles produced have an
average particle size of 9.3 nm [16]. As opposed to the synthesis of silver nanoparticles from aqueous or ethylene
glycol–PVP–silver nitrate solutions, it seems that nucleation of silver atoms is enhanced onto solid PVP because there
is no competition with the solvent.

Fig. 4. Transmission electron micrograph of silver nanoparticles synthesized from 1.5 g dry PVP pre-treated with an aqueous silver nitrate–acetone
solution (0.05 mL de-ionized water, 50 mg AgNO3 and 30 mL acetone), dissolved in 50 mL ethylene glycol under magnetic stirring at 25  1 8C,
after 24 h of reaction. Inset: the corresponding histogram of the silver particles size distribution.
 A. Slistan-Grijalva et al. / Materials Research Bulletin 43 (2008) 90–96 95

Fig. 5. UV–vis absorption spectra of PVP-protected silver nanoparticles in ethylene glycol, synthesized from 1.5 g dry PVP pre-treated with an
aqueous silver nitrate–acetone solution (0.05 mL de-ionized water, 50 mg AgNO3 and 30 mL acetone), dissolved in 50 mL ethylene glycol under
magnetic stirring at 25  1 8C, after 24 h and 18 days of reaction.

The two UV–vis spectra presented in Fig. 5 correspond to samples of PVP-protected silver nanoparticles obtained
after 24 h and 18 days of magnetic stirring in ethylene glycol, and diluted with fresh ethylene glycol. In the first case,
the spectrum shows an absorption peak centered at 433 nm, with a bandwidth of 124 nm at half-maximum height. The
position of this peak, which depends strongly on the refractive index of the surrounding medium and the adsorption of
chemical species at the silver particle–solution interface, occurs in the same region where PVP-protected silver
colloids show strong absorption in aqueous and non-aqueous solutions: at 410 nm in water [24] and 406 nm [4], at
416 nm [4] and 410 nm in ethylene glycol [16,25], at 425 nm in ethanol [23]. After 18 days of agitation, the
characteristics of the silver nanoparticles SPAB change considerably: the maximum absorbance increases
significantly, the position of the peak blue shifts to 416 nm, and the width at half-height decreases to 74 nm. In this
system the increase in maximum absorbance after 18 days of reaction may be explained by an increase in particle
density and by reduction of silver ions at the interface with time. The blue shift of the absorption peak to 416 nm can
only be explained considering the reduction of silver ions adsorbed on the surface [16]. Detachment of PVP from silver
nanoparticles after 18 days does not seem to take place because the system remains disperse.
Kreibig and Fragstein [26] established that the values of the product kmaxd, where kmax is the extinction constant of
the maximum absorbency (in nm1) and d is the width at half-height of the maximum absorbency, can be used to
calculate the size of spherical silver nanoparticles that grow from aggregation of atoms after nucleation has ceased, and
proposed the following equation:
 
ðkmax dÞnþ1 1=3
Rnþ1 ¼ Rn
ðkmax dÞn

When experimental values of the product kmaxd and this equation are used to calculate the average particle size of silver
nanoparticles after 24 h and 18 days of reaction, the obtained results indicate an increase in particle size from 4.1 nm to
4.8 nm, after a period of 17 days. In addition, TEM images (not presented here) of silver nanoparticles after 18 days of
reaction also confirm the slight increase in the average particle size. Therefore, the increase in maximum absorbency
cannot be attributed to a significant growth of the particles. Instead, this maximum absorbency after 18 days of reaction
can be explained taking into consideration both the formation of new particles and a slow particle growth that may
involve the reduction of silver species adsorbed onto the nanoparticles surfaces.
Taking into consideration the characteristics of the experimental SPAB of silver nanoparticles dispersed in ethylene
glycol reported here, theoretical calculations indicate that the total number of spherical silver particles produced per
gram of PVP after 24 h of reaction is equal to 2.1  1016. As has been already reported [24], high-resolution
96 A. Slistan-Grijalva et al. / Materials Research Bulletin 43 (2008) 90–96

transmission electron micrographs of single silver nanoparticles synthesized from ethylene glycol–silver nitrate–PVP
solutions clearly show that these nanoparticles are multi-twinned and have a pentagonal bi-pyramid shape.

4. Conclusions

Mixing polyvinylpyrrolidone with acetone containing a very small volume of aqueous silver nitrate at 25  1 8C
results in the formation of a PVP paste that contains silver nanoparticles. A film of this material exhibits significance
absorbance in the visible region, and the corresponding spectrum shows a broad and well-defined band that peaks at
438 nm. This peak arises from the surface plasmon absorption of silver nanoparticles, thus confirming that PVP
reduces Ag(I) species from aqueous silver nitrate to Ag(0) atoms, which then nucleate and produce silver
nanoparticles.
When the dried PVP–silver nanoparticles composite is dissolved in ethylene glycol, TEM micrographs reveal that
the silver nanoparticles obtained after 24 h of reaction have an average particle size of 4.1 nm and a standard deviation
of 2.8 nm. This average particle size is significantly smaller than that of silver nanoparticles synthesized from a PVP–
ethylene glycol solution to which silver nitrate is added, at the same PVP–AgNO3 weight ratio, namely 30, and volume
of the solvent. Solvated PVP may exhibit fewer sites for the reduction of solvated Ag(I) species, thus leaving ethylene
glycol to play its role of reducing agent. Under these circumstances, nucleation is slow and the nuclei grow to bigger
particle sizes.

Acknowledgements

This work was supported by CONACYT through project no. ER-0074. Access to the facilities and the use of the
transmission electron microscope of the Centro de Ciencias de la Materia Condensada of the Universidad Nacional
Autónoma de México in Ensenada, is greatly appreciated. Special thanks are due to F. Ruiz and G. Vilchis for their
technical assistance during TEM characterization. A. Slistan Grijalva thanks CESUES for partial support.

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