Synthesis of nanoparticles by reverse micelle

By :
Sudheer reddy
A1218309015
Ankit poddar
A1218309016
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Synthesis of metallic nanoparticles in reverse micelles in the
presence of quercetin
Abstract
A new reducing agent for the synthesis of metallic nanoparticles in reverse micelles is suggested. Stable silver and
copper nanoparticles were obtained in the presence of air oxygen in water/AOT/n-alkane system by the reduction of
silver and copper salts with quercetin (Qr), natural plant pigment from the group of avonoids. Particle formation in
the presence of Qr in micellar solution was detected by the characteristic changes of optical absorption spectra after the
addition of AgNO
3
or Cu(NO
3
)
2
as water solutions. Changes of absorption spectra with time and Qr concentration are
also presented. Analysis of the absorption spectra of silver nanoparticles by means of the Mie theory allows us to sug-
gest that (1) the particles obtained are small in size (r=11.5 nm), (2) changes of absorption spectra with time or with
Qr concentration are caused by the increase of particle concentration and (3) at 3 mM metal salt concentration in the
micellar solution part of silver ions is not involved in the process of particle formation. .
Keywords: Metallic nanoparticles; Reverse micelles; Quercetin
1. Introduction
Metal particles of nanometer dimensions have
been extensively investigated in the recent years
because both of their present successful applica-
tions and of the perspectives of their use in vari-
ous elds of science, technology and medicine. It
is now well recognized that metal nanoparticles
may serve as efcient catalysts in chemical and
photographic processes (e.g. [13]). Metal clusters
and nanoparticles immobilized in polymer lms
give metallopolymer materials that prove to be
useful for technical purposes due to their specic
physico-chemical properties [4]. Also, some small
metal particles demonstrate a distinct biological
activity and may be applied in ecology and
medicine, for example, a signicant antimicrobial
activity of silver nanoparticles allowed the im-
provement of the water purication in some water
ltering apparatus [5].
Much attention is paid therefore to the modi-
cation of the known procedures and to the devel-
opment of new ways of particle preparation.
Methods used for the particle synthesis are de-
scribed in details in several excellent reviews [2
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4,6,7]. In the most general classication [4], nu-
merous ways of particle preparation may be di-
vided into two main groups, one including
physical, the other-chemical approaches. In the
rst group, metallic nanoparticles are either as-
sembled from atoms in the process of metal va-
porization and subsequent condensation on
various supports, or obtained through the treat-
ment of the bigger particles in colloidal disper-
sions by means of colloidal mills, ultrasound etc.
In the second group the main way is the reduction
of metal ions in solution in conditions favoring
the subsequent formation of small metal clusters
or aggregates.
With respect to the nature of reducing agent,
chemical methods may be subdivided into classi-
cal chemical, using the well-known chemical re-
ducing substances (hydrazine, sodium
borohydride, hydrogen etc.) [2,6,1117] or some
special reducing medium [10] and radiation-chem-
ical where the reduction process is initiated by
solvated electrons generated by the ionizing radia-
tion [79,18]. With respect to the character of
aggregation favoring or particle stabilizing condi-
tions, chemical methods may be divided into
those working in aqueous solutions with chemical
stabilizers (usually natural or synthetic polymers)
[711,1417] and those working in reverse micel-
lar systems where the aggregation process takes
place in the aqueous core of reverse micelles and
growing particles are surrounded by the surfac-
tant molecules [6,12,13,18].
The main disadvantages of chemical synthesis
in aqueous phase are the broad size distribution
of metal particles and their relatively low stability
that requires the use of organic stabilizers and
thus complicates the structure and studies of the
properties of the whole system. The particle sta-
bility is signicantly enhanced for the chemical
synthesis in reverse micelles [6]. Further progress
in this direction was made recently when the
radiation-chemical technique was applied in a re-
verse micellar system [18]. Here it was possible to
obtain silver nanoparticles living for months and
even years, a result which makes possible the
more systematic studies of their catalytic, adsorp-
tion and biological properties and opens some
new practical applications.
In this paper we report the new version of
chemical synthesis of metallic nanoparticles in
reverse micelles; our method enables us to obtain
highly stable particles presumably rather homoge-
neous in size. This version differs from the known
ways of particle synthesis in reverse micelles in
that here we use the reducing agent of the new
type, namely, quercetin (Qr), one of the natural
plant pigments (the group of avonoids). The idea
issued from the results of our studies on the
mechanism of quercetin interaction with radia-
tion-generated silver nanoparticles in a reverse
micellar system [19]. We found that apart from its
strong interaction with preformed nanoparticles,
quercetin reduces silver ions from aqueous salt
solutions, presumably through the formation of
an intermediate complex where electron density is
shifted towards the silver ion. The capability of
several avonoids, including quercetin, to chelate
various metal ions is well documented [20]. Fur-
ther studies showed that the reduction reaction in
reverse micelles results in the formation of silver
particles with optical absorption spectra strongly
resembling those of typical silver nanoparticles
synthesized in aqueous solution or in reverse mi-
celles. It was found also that similar procedures
allows one to obtain copper and bimetallic silver-
copper nanoparticles; we believe, that ion reduc-
tion by avonoids in reverse micelles may be used
for the synthesis of nanoparticles of other metals,
providing that their ions form chelate complexes
with the chosen avonoid.
Here we present the results, which illustrate the
synthesis of silver and copper nanoparticles in the
presence of quercetin. The process of particle
formation and the inuence of quercetin concen-
tration was followed by measuring optical absorp-
tion of the systems studied in the UV and visible
range. The absorption spectra of silver particles
were analyzed by means of the Mie theory.
2. Materials and methods
2.1. Reagents
We used analytical grade silver and copper
nitrates, sodium bis(2-ethylhexyl)sulphosuccinate
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(Aerosol-OT, AOT) from Sigma, n-octane or n-
heptane (analytical grade purity), isopropanol (Pr-
2, chromatographically pure) and deionized water
from Millipore-Q system. Quercetin (3,5,7,3%,4%-
pentahydroxyavon, C
15
HgO
7
O
2
H
2
O) was sup-
plied by Merck. Phosphate buffer (pH 7) was
prepared from sodium salts of phosphoric acid
according to the standard procedure.
2.2. Preparation of metal salts in micellar
solutions
Micellar solutions of AgNO
3
and Cu(NO
3
)
2
were prepared by injection of water salt solution
into the 0.15 M AOT solution in octane or hep-
tane to the salt concentration 38 mM. The hy-
dration extent w=[H
2
O]/[AOT] varied in the
range 110.
2.3. Preparation of nanoparticles
At the rst stage a micellar solution of Qr was
prepared by adding the solid pigment to 0.15 M
AOT solution in either octane or heptane. In
these conditions Qr partly stayed as the sediment,
partly was solubilized due to the formation of
Qr-AOT micelles. The process of Qr solubilization
was followed by measuring optical absorption
spectra of the upper, optically transparent layer of
liquid in contact with the sediment. The Qr con-
centration in micellar solution was determined
from the comparison of absorption intensity at
the maximum of the long-wave band (u
2
max
=370
nm, see Fig. 1) with that measured for the true
micellar solutions (where the pigment was fully
solubilized) in the range 3055 mM of Qr. Here
optical density at 370 nm (D
O
370
) is proportional to
the Qr concentration (C
O
Qr
). Hence, the true Qr
concentration in micellar solutions used for parti-
cle preparation (C
Qr
) could be found as C
Qr
=
C
O
Qr

D
370
/D
O
370
.
After the achievement of the stationary value of
Qr concentration in micellar solution, the desired
volume of this solution was transferred to another
ask and then a water solution of AgNO
3
or
Cu(NO
3
)
2
was added in a quantity necessary to
obtain the desired salt concentration and hydra-
tion extent. In experiments described in this pa-
per, the salt concentration was 3 mM and w=3.7;
then radius of the water core of the inverted
micelles (r
h
m
) is expected to be 13 nm [2123].
The whole system was shaken for 35 min. For-
mation of metal particles was observed rst in the
process of shaking by the appearance of intensive
coloration red-brown for silver and bright
yellow or yellow-brown for copper particles. Fur-
ther transformations in the system were followed
by means of the measurements of optical ab-
sorbance.
2.4. Spectrophotometry
Optical absorption spectra of the samples stud-
ied were recorded on spectrophotometers
Specord M-40 or Beckman-DU 7 at room tem-
perature in the range 200900 nm (50 00011 000
cm
1
) in quartz cuvettes with an optical path of 1
mm. In measurements of micellar solutions the
reference solutions were 0.15 M AOT/octane
(heptane) or H
2
O/0.15 M AOT/octane (heptane)
at w=3.7.
Fig. 1. Absorption spectra of Qr solutions. (A) True micellar
solution of Qr in 0.15 M AOT/octane, C
Qr
=55 mM (dashed
line); Qr solution in 0.1 5 M AOT/octane in equilibrium with
solid pigment (solid line, see text for details). Insert: structure
of quercetin molecule. (B) Molecular solutions of Qr in Pr-2
(dashed line) and 50 mM phosphate buffer, pH 7 (dotted line);
true micellar solution of Qr in 0.15 M AOT/octane. C
Qr
=55
mM (solid line).
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Fig. 2. Absorption spectra of AgNO
3
(A) and Cu(NO
3
)
2
(B) in
0.3 M water solutions (1, solid lines) and 3 mM micellar
solutions in AOT/octane at w=3.7 (2, dashed lines).
presence of hydroxyl group at the C
3
-position in
the pyrrole ring. The coincidence of the maxima
positions in different solvents indicates the similar
polarity of the environment of Qr molecules. In
other words, there seems to be no signicant
change in polarity when a Qr molecule is trans-
ferred from the alcohol (or water) solution to the
ternary system Qr/AOT/a. Then it is possible to
assume, that in the ternary system a Qr molecule
is bound with crystalline water molecules.
Further examination of Fig. 1(B) shows that,
for a given Qr concentration, the spectra in differ-
ent solvents demonstrate (1) different absorption
in the visible range and (2) the decrease in the
magnitude of absorption in the UV range from
Pr-2 to micellar solution. The latter point testies
probably to the inuence of the higher degree of
organization in the micellar system on the optical
properties of the pigment molecules; the fall of
absorbance may be due to the structure con-
straints which suffer part of the Qr molecules
inside the reverse micelles, thus being unable to
realize the characteristic electron transfer avail-
able to a free molecule in solution.
The absorption spectra of AgNO
3
and
Cu(NO
3
)
2
water solutions and of their water solu-
tions solubilized in reverse micelles are shown in
Fig. 2. The absorption bands in water solutions
(solid lines) are known to originate from the dd
electron transfer in the central metal atom of the
corresponding aqua-complexes; the values of u
max
,
303 nm for silver (A) and 808810 nm for copper
(B), agree well with the relevant data given in the
literature [26]. Solubilization of the salt solutions
in reverse micelles at the millimolar concentra-
tions (the highest of those used in the particle
synthesis) gives the AgNO
3
(H
2
O)/AOT/alkane
(A) or Cu(NO
3
)
2
(H
2
O)/AOT/alkane (B) systems
(dashed lines), which practically do not absorb
light in the wide range of interest: for u\250 nm
and u\280 nm, respectively.
3.2. Absorption spectra of
AgNO
3
/Qr/AOT/alkane system
The injection of a small portion of water salt
solution (13 vol% H
2
O) into the colorless micel-
lar solution of Qr, for the excess of salt over Qr
3. Results
3.1. Absorption spectra of reagents
Fig. 1(A) shows the typical absorption spec-
trum of quercetin in micellar solution (thick line);
it is one of the working solutions used further for
the particle preparation. As mentioned in the
previous section, the Qr concentration in solu-
tions used for the particle synthesis was found
from the comparison of D
370
values for the given
solution with those measured for the true, more
dilute micellar solutions of the pigment. Here we
show the spectrum for one of such true solutions,
with C
O
Qr
=55 mM (dashed line); it may be easily
found that Qr concentration in the working solu-
tion shown in Fig. 1(A) was 142 mM.
The two main bands registered in micellar solu-
tion with u
1
max
=256 nm and u
2
max
=370 nm and a
small maximum at 295300 nm are the same as
those found on the Qr spectra in Pr-2 and water
solutions (Fig. 1(B)), in accordance with the data
reported in the literature [24,25]. The two main
bands are supposed to result from the y
y*electron transfer in the rings A and B, respec-
tively (see insert in Fig. 1(A)); the maximum at
295300 nm is presumably connected with the
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concentration leads both to the appearance of
intensive red-brown coloration and to the drastic
change of absorption spectrum of the pigment.
The typical change observed with silver nitrate is
shown in Fig. 3. As seen from the gure, the Qr
bands are completely eliminated; instead one can
observe the appearance of a new absorption band,
u
max
=400410 nm, characteristic for the surface
plasmon band of small silver nanoaggregates, as
found for the silver hydrosols and nanoparticles
synthesized in aqueous solution or reverse mi-
celles, either by chemical or by radiation-chemical
technique [810,12,1517].
The time-course of particle formation is
reected in the evolution of absorption spectra
with time after the addition of silver nitrate (Fig.
3). It is seen that the particle band grows with
time. Formation of the silver band is practically
accomplished during the rst h; in the subsequent
2 days (and later on) the spectrum suffers only
very small changes, so that there is not more than
a 5% change in u
max
.
The intermediate stages of particle formation
may be observed as changes of the absorption
spectra of AgNO
3
/Qr/AOT/alkane system upon
Fig. 4. Changes in the Qr/AOT/octane system upon the step-
wise addition of AgNO
3
in small quantities: 1, Qr/AOT/oc-
tane, C
Qr
=37 mM; AgNO
3
was added to the concentrations
(mM): 230, 5110. Insert: C
AgNO
3
(mM): 360, 481, 5110,
6170.
the small stepwise changes of salt concentration
(Fig. 4). It is seen that the increase of salt concen-
tration provokes the fall of the u
2
max
band of Qr
and, in parallel, the appearance of absorption in
the visible range, with gradual formation of the
new band in the visible region, its u
max
(420430
nm) being close or equal to that known for silver
nanoparticles. It is seen also, that, for the small
content of metal salt, there is a signicant increase
of absorption at 295 nm with formation of the
new intensive band which seems to be present in
the spectra of fully formed nanoparticles as the
shortwave shoulder (Figs. 3 and 5). As suggested
in our recent study of Qr interaction with radia-
tion-induced silver nanoparticles [19], the 295 nm
band may result from the formation of either
smaller silver particles or some more complicated
structures where Qr is bound with growing silver
particles, both processes being preceded by the
formation of intermediate complex the QrAg.
For a given salt concentration, the greater the
Qr concentration in micellar solution, the greater
the nal intensity (D
max
410
) of the particles band. As
examples, we present the data for 3 mM silver
nitrate in 42 mM, 115 mM and 142 mM Qr solu-
tions (Fig. 5). All bands have the half-width about
Fig. 3. Formation of Ag nanoparticles in reverse micelles.
Absorption spectra of Qr/AOT/octane system 5 min (1), 25
min (2), 1 h (3) and 2 days (4) after the addition of AgNO
3
.
C
Qr
=124 mM, C
Ag
=3 mM, w=3.7. Dashed line, spectrum
of the initial Qr/AOT/octane system.
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180 nm; it is seen also that the difference in D
max
410
is not directly proportional to the difference in Qr
concentrations. This may indicate to a rather
complicated character of Ag-Qr interaction.
3.3. Absorption spectra of
Cu(NO
3
)
2
/Qr/AOT/alkane system
Similarly to what was observed with silver,
addition of copper salts in water solutions to the
micellar solutions of Qr resulted in the appear-
ance of intensive coloration, bright yellow for
smaller and light brown for larger copper concen-
trations. The change of color happened immedi-
ately after the addition of salt solution, while for
silver this change became visible after about a min
after the salt addition. Fig. 6 shows the typical
absorption spectra of Qr micellar solutions after
the addition of Cu(NO
3
)
2
to the 3 mM concentra-
tion in reverse micellar system. It is seen that
there takes place a drastic fall of the u
2
max
and of
Qr, with the appearance of the new band with
u
max
=425440 nm which we refer to the copper
nanoparticles. This band is somewhat less stable
than that registered for silver particles; it may fall
with time, the loss of absorbance depending on
the copper and Qr concentrations. We found,
however, that highly stable copper particles (with
Fig. 6. Formation of Cu nanoparticles in reverse micelles.
Absorption spectra of Qr/AOT/heptane system 1 h (solid line)
and 3 days (dashed line) after the addition of Cu(NO
3
)
2
.
C
Qr
=224 mM, C
Cu(NO3)
2
3 mM. w=3.7. Dashed line, initial
spectrum of the Qr/AOT/heptane system.
absorption band stable for weeks and months)
may be obtained for the selected combinations of
copper and Qr concentrations, and hydration ex-
tents in the range 15.
Similarly to what was observed with silver par-
ticles, for a given concentration of copper in
micellar solution the intensity of absorption band
increases with the increase of Qr concentration
without changes of the maximum position (Fig.
7). The rise of absorption at u
max
is accompanied
with the appearance of the short-wave shoulder,
probably due to the contribution of the oxidized
form of quercetin.
4. Discussion
4.1. Surface plasmon spectra of sil6er particles
For the analysis of the absorption spectra of
silver particles we used the expression given by the
Mie model for small spherical metal particles,
with sizes less than wavelength of the incident
light (for 2rB20 nm); then their light absorption
is described by the dipolar term of the Mie series
[7,12]:
Fig. 5. The effect of Qr concentration on absorption spectra of
silver nanoparticles in Qr/AOT/heptane system. C
Ag
=3 mM,
w=3.7, C
Qr
(mM): 42 (1), 115 (2) and 142 (3).
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OD=
18yVNlm
3/2
O
2.303u
m
2
(m
1
+2m
O
)
2
+m
2
2
(1)
where V is the particle volume, N is the number of
the particles per unit volume (calculated from the
metal concentration), l is optical path length, m
O
is
permittivity of the medium (here n-heptane or
n-octane), m
1
and m
2
are, respectively, the real and
imaginary part of the metal dielectric constant, u
is wavelength in vacuum. The maximum in ab-
sorption spectra occurs at surface plasmon reso-
nance, when m
1
=2m
O
. Both m
1
and m
2
depend on
u.
For such small metal particles their size is less
than the mean free path of electron (52 nm for
silver [12]), consequently the size effects on dielec-
tric constants should be taken into account. Fol-
lowing the way established in the relevant studies
of metallic [9,12] and bimetallic [7] particles, we
used for this purpose the method suggested by
Kreibig [27], with m
2
expressed as:
m
2
(r) =m
2
(bulk) +
2
p
w
F
/
3
r (2)
where r is particle radius,
p
=2yc/u (plasmon
frequency for the bulk metal), V
F
the Fermi veloc-
ity. For silver we take
p
=1.3510
16
s
1
, and
w
F
=1.410
6
m s
1
[7,9,12]. The most precise
optical constants available (the bulk m
2
and m
1
Fig. 8. Absorption spectra of silver particles calculated from
the Mie theory (Eq. (1)) for C
AgNO
3
=3 mM, and particle
radius, r=1 nm (1), 1.5 nm (2), 2.5 nm (3) and 5 nm (4).
values for silver clusters) were taken from the
paper by Quinen [28].
Our main purpose in the analysis of the experi-
mental data was to elucidate the reason of the
spectral changes with time (Fig. 3) and with Qr
concentration (Fig. 5). More precisely, we aimed
to nd out, whether the increase in absorbance
was caused by the change of particle sizes or by
the change of particle concentration at a given
size. For this purpose, surface plasmon spectra
were calculated for silver particles of various sizes
at the constant silver concentration (Fig. 8) and
for various silver concentrations at the constant
particle size (Fig. 9).
As seen from Fig. 8, for all the theoretical
spectra u
max
is placed at 400410 nm; the increase
of particle diameter in the range 210 nm leads to
the considerable increase of absorbance at the
maximum wavelength with the simultaneous de-
crease of the half-width of the plasmon band,
Du
1/2
. For the constant particle size (r=1 nm),
the increase of silver (hence, particle) concentra-
tion leads to the overall increase of absorbance
(Fig. 9); both the maximum position and the band
half-width remain unchanged and equal to 410
and :140 nm, respectively. Similar behavior of
the calculated spectra is observed for the radii in
the range 1.55 nm.
Fig. 7. The effect of Qr concentration on absorption spectra of
copper nanoparticles. C
Cu(NO3)
2
=3 mM. w=3.7. C
Qr
(mM):
60 (1), 123 (2) and 212 (3).
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4.2. Analysis of experimental data obtained for
sil6er particles
Comparison of Figs. 8 and 9 with Figs. 3 and 5
allows us to make the following observations.
First, we can see that in the range 300500 nm,
the absorption spectrum measured at the early
stage of particle formation (the 5 min curve)
strongly resembles those calculated at C
AgNO
3
=3
mM for the small particle radii (Fig. 8, r=1 or
1.5 nm): in both cases u
max
is 400410 nm and the
bands are rather broad, with Du
1/2
about 180 nm
for experimental spectrum and about 140 nm for
the theoretical ones. Second, it is clear that, for
the growing particle size, the theory predicts the
considerable narrowing of the absorption band,
while in our measurements the overall increase of
absorbance with time is observed, with the half-
width practically unchanged. At the same time,
for the increase of silver concentration at a con-
stant particle size the theory predicts the overall
increase of absorbance, with Du
1/2
being constant
(Fig. 9). Hence we conclude that (1) our silver
particles are most likely of very small size and (2)
the evolution of absorption spectra with time or
spectral changes with increasing Qr concentration
are connected not with the increase of particle
size, but rather with the increase of the number of
Fig. 10. Fitting of the theoretical curves to the experimental
data for silver particles. , spectrum measured for the parti-
cles obtained in Qr/AOT/heptane, C
Qr
=163 mM, C
AgNO
3
=
3mM. Theoretical spectra were calculated for r=1.5 nm and
C
AgNO
3
(mM), indicated in gures on the curve.
particles per unit volume, i.e. with particle con-
centration.
Now we can try to nd out, what part of silver
ions introduced into the Qr micellar solution
turned into particles. This may be done by tting
theoretical spectra calculated for a small radius
and various silver concentrations to the experi-
mental absorption spectra at their stationary
stage, when they reached the maximal optical
densities at a given Qr concentration.
The example given in Fig. 10 shows the results
obtained for the stationary absorption spectrum
of particles formed in the 163 mM Qr solution; for
the convenience of comparison, the experimental
spectrum is given in points. It is clear that the
theoretical curve for r=1.5 nm and C
AgNO
3
=3
mM lies much higher than the experimental one;
it means that not all silver ions present in the
system participate in the particle formation. The
curves calculated for C
AgNO
3
=1.75 mM and 1.85
mM t the experiment in the short-wave range; at
u\420 nm the measured absorbance is higher
than that predicted by the theory. To the rst
approximation, this result may be interpreted as
showing that only about 60% of ions participate
in particle formation. The increase of absorbance
Fig. 9. Absorption spectra of silver particles calculated from
the Mie theory for r=1 nm and C
AgNO
3
=1 mM (1), 2 mM
(2) and 3 mM (3).
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at the long-wave side is similar to that observed
by Petit et al. [12] for silver nanoparticles ob-
tained in reverse micelles by the reduction of Ag
+
ions with NaBH
4
from AgNO
3
water solution.
This increase may be connected with the interac-
tion of particle surface with the surrounding
medium (e.g. with the headgroups of surfactant)
[9,12]. Alternatively, it may result from the inter-
action of particles, which is disregarded in the
Mie theory; as shown recently by Karpov et al.
[29], for silver hydrosols the appearance of a
long-wave wing in absorption spectrum may be
caused by the formation of the aggregates of
silver particles (so-called fractal clusters); the
aggregation process may be accelerated by the
laser irradiation.
4.3. Absorption spectra of copper particles
Comparison with absorption spectra of copper
nanoparticles known from literature [6,1316]
shows that in our case the copper absorption
band is (1) much more pronounced and (2) shifted
signicantly to shorter wavelengths. Indeed, here
we have u
max
=425440 nm, while for copper
nanoparticles stabilized in water solutions by
gelatin [15,16] and polyvinylpyrrolidone [14] u
max
was found to be 620630 and 580582 nm, re-
spectively. Reduction by hydrazine from
Cu(AOT)
2
surfactant in reverse micelles gives cop-
per nanoparticles with u
max
=566 nm [13]; the
authors found also that for w\3, a strong ab-
sorption at 800 nm is registered, caused by the
copper oxide formation.
Some theoretical estimations [30] give for the
plasmon excitation band in copper colloids the
absorption maximum between 570 and 590 nm.
However, we are unaware of any attempts to
compare the experimental spectra of nanoparticles
with those calculated from the Mie theory, most
likely because, to our knowledge, for copper no
reliable data have been obtained so far for the
wavelength dependence of optical constants (in-
cluding size effects) necessary for the accurate
calculation of absorption spectra for such small
particles in liquid phase.
At present we can throw some light on the
cause of such a striking difference in u
max
values,
comparing the absorption spectra of the copper
particles formed by the reduction from different
copper salts. Fig. 11 shows the spectra measured
for the particles obtained at one and the same
concentration of Qr in micellar solution by addi-
tion of Cu(NO
3
)
2
(1) and Cu(NH
3
)
4
Cl
2
(2) water
solutions to the metal salt concentration 3 mM, at
w=3.7. In the case of copper nitrate we have
u
max
=435 nm, while for the copper ammonium
chloride u
max
=545 nm, so we observe the marked
red shift of the particle absorption band, with the
fall of its intensity. The spectrum obtained for the
copper ammonium chloride strongly resembles
those reported in literature [1315] (example from
[13] is given as insert in Fig. 11), with respect to
both the position and intensity of the absorption
band.
The two salts we used for the particle formation
differ in the state of copper ion introduced into
the Qr/AOT/heptane system. As known from the
literature on chemistry of complex compounds of
transition metals (e.g. [26,31]), taken as copper
nitrate, in water solution copper ion exists as
tetrahedral or octahedral aqua-complex
[Cu(H
2
O)
4
]
2+
or [Cu(H
2
O)
6
]
2+
, while taken as
copper ammonium salts it forms a much more
stable complex [Cu(NH
3
)
4
]
2+
or [Cu(NH
3
)
6
]
2+
.
Fig. 11. Comparison of absorption spectra measured for cop-
per nanoparticles formed in the Qr/AOT/heptane system after
the addition of Cu(NO
3
)
2
(1) and Cu(NH
3
)
4
Cl
2
(2). C
Qr
=173
mM, C
Cu
=3 mM, w=3.7. Insert: absorption spectrum of
copper nanoparticles from ref. [13], w=4, optical path 1 cm.
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Obviously the reduction of copper ion to atom
and the subsequent formation of particles in these
two cases goes with different rates and results,
most likely, in different surface structure of the
particles which, in its turn, may manifest itself in
the different properties of surface plasmon. This
may be the reason, for example, for the closeness
of u
max
values obtained in reverse micelles for
copper ammonium chloride and for specially syn-
thesized copper salt of AOT [13], 545 and 566 nm,
respectively. The latter salt is a very stable com-
pound and hence there must be similar restrictions
in the reduction and particle formation processes.
5. Conclusions
In the present paper it has been shown that
synthesis of silver and copper nanoparticles may
be realized in AOT reverse micelles in the presence
of the natural reducing agent, the plant pigment
quercetin. This method is very quick and simple
since it does not require any special technological
procedures and allows highly stable nanoparticles
in the presence of air oxygen to be obtained. For
silver particles, analysis of absorption spectra by
means of the Mie theory shows that (1) particles
are very small (r=11.5 nm) and (2) their size is
unlikely to change with time or with concentration
of the reducing substance.
References
[1] B.C. Gates, L. Guezi, H. Knosinger (Eds.), Metal Clus-
ters in Catalysis, Elsevier, Amsterdam, 1986.
[2] B.H. Robinson, A.N. Khan-Lodhi, T. Towey, Micropar-
ticle synthesis and characterization in reverse micelle, in:
M. Pileni (Ed.), Structure and Reactivity in Reverse Mi-
celles, Elsevier, Amsterdam, 1989, pp. 199219.
[3] M.I. Truchin, J. Int. Rec. Mater. 14 (3764) (1986) 3764
83118.
[4] A.D. Pomogailo. Polymer-immobilized nanoscale and
cluster metal particles. In: Uspekhi Chimii (Russian
Chemical Reviews), V.66 (1988) pp.750791.
[5] A.A. Revina, E.M. Egorova. Radiation-chemical technol-
ogy for the synthesis of stable metallic and bimetallic
clusters, In: Papers of the International Conference on
Advanced Technologies of the Twenty First Century
(ICAT 98), Moscow, 59 October 1998, pp. 411413.
[6] M.P. Pileni, Langmuir 13 (1997) 32663276.
[7] M. Treuger, C. de Cointet, H. Remita, J. Khatouri, M.
Mostafavi, J. Amblard, J. Belloni, J. Phys. Chem. B 102
(1998) 43104321.
[8] T. Linnert, P. Mulvaney, A. Henglein, H. Weller, J. Am.
Chem. Soc. 112 (1990) 46574664.
[9] M. Gutierrez, A. Henglein, J. Phys. Chem. 97 (1993)
1136811372.
[10] Z.-Y. Huang, G. Nills, B. Hajok, J. Phys. Chem. 97
(1993) 1154211550.
[11] D.V. Leff, P.C. OHara, J.R. Heath, W.M. Gelbrat, J.
Phys. Chem. 99 (1995) 70367041.
[12] C. Petit, P. Lizon, M.-P. Pileni, J. Phys. Chem. 97 (1993)
1297412983.
[13] I. Lisiecki, M.-P. Pileni, J. Phys. Chem. 99 (1995) 5077
5082.
[14] H.H. Huang, F.Q. Yan, Y.M. Kek, C.H. Chew, G.Q. Xu,
W. Ji, P.S. Oh, S.H. Tang, Langmuir 13 (1997) 172175.
[15] A.V. Toporko, V.V. Zwetkov, V.D. Yagodovsky, J. Phys.
Chem. (Russia) 69 (1995) 867870.
[16] A.V. Toporko, V.V. Zweikov, V.D. Yagodovsky, J. Phys.
Chem. (Russia) 70 (1996) 17941798.
[17] A.V. Butenko, P.A. Chubakov, Y.E. Danilova, et al., Z.
Phys. D Atoms, Mol. Clust. 17 (1990) 283290.
[18] A.G. Dokuchaev, T.G. Myasoedova, A.A. Revina,
Chem. High Energies (Russia) 31 (1997) 353356.
[19] A.A. Revina, E.M. Egorova, A.D. Karataeva, The inter-
action of the natural pigment quercetin with silver
nanoparticles in reverse micelles, J. Phys. Chem. (Russia)
10 (1999) 18971904.
[20] T. Sakaguchi, A. Nakajima, J. Chem. Tech. Biotechnol.
48 (1987) 133141.
[21] R.A. Day, B.H. Robinson, J. Chem. Soc. Faraday Trans.
I 75 (1979) 132139.
[22] M. Zulauf, H.-F. Eicke, J. Phys. Chem. 83 (1979) 480
486.
[23] A. Jada, J. Lang, S.-J. Candau, R. Zana, Colloids Surf.
38 (1989) 251261.
[24] I.I. Rodionov, E.Y. Morosova, On the formation of
bioactive complex albumin-quercetin. In: Biologically Ac-
tive Substances in the Life of Plants and Animals, Minsk,
1973, pp.4044.
[25] T.G. Lucik, Studies on the intermediate products of pulse
radiolysis of avonoids, Ph.D. thesis, Kishinev, 1989.
[26] B.D. Berezin, O.A. Golubchikov, Coordination Chem-
istry of Solvatocomplexes of Transition Metal Salts,
Nauka, Moscow, 1992.
[27] J. Sinzig, U. Radtke, N. Quinen, U. Kreibig, Z. Phys. D
26 (1993) 242250.
[28] M. Quinen, Z. Phys. B 101 (1996) 211217.
[29] S.V. Karpov, A.K. Popov, V.V. Slatko, G.B. Shevnina,
Colloid J. (Russia) 57 (1995) 199206.
[30] E.R. Savinova, A.L. Chuvilin, V.N. Parmon, J. Mol.
Catal. 48 (1988) 217.
[31] N.A. Kostromina, V.N. Kumok, H.A. Scorik, Chemistry
of Complex Compounds, High School, Moscow, 1990.
.
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