Journal of ELECTRONIC MATERIALS, Vol. 46, No.

2, 2017
DOI: 10.1007/s11664-016-4942-2
 2016 The Minerals, Metals & Materials Society

Green Synthesis of Ag-Cu Nanoalloys Using Opuntia

ficus-indica

O. ROCHA-ROCHA,1 M. CORTEZ-VALADEZ,2,5,6
A. R. HERNÁNDEZ-MARTÍNEZ,3 R. GÁMEZ-CORRALES,4
RAMÓN A.B. ALVAREZ,1 R. BRITTO-HURTADO,1 Y. DELGADO-BELEÑO,1
C.E. MARTINEZ-NUÑEZ,1 A. PÉREZ-RODRÍGUEZ,1 H. ARIZPE-CHÁVEZ,1
and M. FLORES-ACOSTA1

1.—Departamento de Investigación en Fı́sica, Universidad de Sonora, Apdo. Postal 5-88,

83190 Hermosillo, Sonora, Mexico. 2.—CONACYT - Departamento de Investigación en Fı́sica,
Universidad de Sonora, Apdo. Postal 5-88, 83190 Hermosillo, Sonora, Mexico. 3.—Centro de
Fı́sica Aplicada y Tecnologı́a Avanzada (CFATA), Universidad Nacional Autónoma de México,
Campus Juriquilla, Blvd. Juriquilla 3000, Juriquilla, Querétaro, Mexico. 4.—Departamento de
Fı́sica, Universidad de Sonora, Apdo. Postal # 130, 83000 Hermosillo, Sonora, Mexico. 5.—e-mail:
manuelcortez@live.com. 6.—e-mail: jose.cortez@unison.mx

Bimetallic Ag/Cu nanoparticles have been obtained by green synthesis using

Opuntia ficus-indica plant extract. Two synthesis methods were applied to
obtain nanoparticles with core–shell and Janus morphologies by reversing the
order of precursors. Transmission electronic microscopy revealed size of 10 nm
and 20 nm for the core–shell and Janus nanoparticles, respectively. Other
small particles with size of up to 2 nm were also observed. Absorption bands
attributed to surface plasmon resonance were detected at 440 nm and 500 nm
for the core–shell and Janus nanoparticles, respectively. Density functional
theory predicted a breathing mode type (BMT) located at low wavenumber due
to small, low-energy clusters of (AgCu)n with n = 2 to 9, showing a certain
correlation with the experimental one (at 220 cm 1). The dependence of the
BMT on the number of atoms constituting the cluster is also studied.

Key words: AgCu nanoparticles, radial breathing modes, Raman in small

metal nanoparticles, DFT approximations, Opuntia ficus-indica,
green synthesis

INTRODUCTION clusters of Ag/Cu, specifically Ag32Cu6, could sub-

stitute for Pt in alkaline fuel cells. This cluster was
Recently, the optical properties of metal nanopar-
designed theoretically (at density functional theory
ticles and nanoalloys have provoked great interest
level) by Zhang et al.16 They also obtained an
because of their potential applications as catalysts,
experimental approximation beyond 500 atoms
sensors in optoelectronic devices, etc.1–10 Recent
(Ag444Cu147) by using the pulsed laser deposition
studies have reported nanoalloys with nonlinear
(PLD) technique. The synthesis method proposed
optical properties, in addition to applications based
herein could be a viable alternative to obtain small
on increased Raman dispersion due to surface-
clusters of Ag/Cu such as Ag32Cu6.
enhanced Raman scattering (SERS).11–13 On the
Identification of appropriate synthesis methods
other hand, Ag/Cu nanoalloys, like various other
for nanoparticles remains as the main obstacle to
nanoparticles, have important applications due to
massive and industrialized production of nanoma-
their bactericidal effects.14,15 Additionally, small
terials, due to the high costs of materials and
equipment used in such synthesis. Green synthesis
has emerged as a novel approach over recent years,
(Received February 19, 2016; accepted September 6, 2016;
published online October 3, 2016) representing an effective, simple, and low-cost

802
Green Synthesis of Ag-Cu Nanoalloys Using Opuntia ficus-indica
method for production and stabilization of nanoma-
terials. Obtaining nanoparticles by green synthesis
is based on reduction of metal ions using vitamins,
proteins, or various other organic molecules con-
tained in plants, fruits, fungi, etc.
Use of Opuntia ficus-indica (Ofi) plant in such
green synthesis methods enables a cost reduction
because it only requires room conditions and min-
imal care for cultivation. In recent work, we syn-
thesized several metallic nanoparticles using plant
extracts.17–19 However, synthesis of bimetallic
nanoparticles using extract from this plant is novel.
Therefore, we present herein a simple and ecological
synthesis method to obtain bimetallic nanoparticles
using Ofi plant extract for possible application for
bactericides and optimization of fuel cell production.
The optical properties were corroborated based on
absorption bands in the ultraviolet–visible (UV–Vis)
spectra assigned to Ag/Cu nanoalloys. Additionally,
vibrational properties were detected in the Raman
spectra after nanoparticle synthesis.
EXPERIMENTAL PROCEDURES
Preparation of Ag-Cu Bimetallic
Nanoparticles
Ofi wild plant (cactus) was used for green syn-
thesis of nanoparticles. Two young (2 weeks to
3 weeks) leaves were selected. Leaves were peeled
and sliced into small (50 g) pieces, which were
added to 100 mL deionized water. This mixture was
stirred for 1 h at 55C. The mixture was then
immediately filtered, obtaining a thick liquid. The
precursors used to obtain Ag+ and Cu2+ ions for
nanoparticle formation were AgNO3 and Cu(NO3)2,
respectively. Two 0.1 M solutions were prepared
separately from these precursors in 25 mL deion-
ized water each, and both solutions were stirred for
1 h at 55C.
Ag/Cu Core–Shell Nanoparticles
Ofi extract (2 mL) was added to AgNO3 solution
under stirring for 10 h at 55C. Then, 25 mL Cu(NO3)2
solution were added to the previous mixture, and
within 2 min, 2 mL Ofi extract were added. The
resulting mixture was stirred for 1 h at 55C. During
this time, the solution adopted a slight green shade.
Ag/Cu-Linked Monometallic Nanoparticles
Ofi extract (2 mL) was added to Cu(NO3)2 solution
under stirring for 40 min at 55C. Then, 25 mL AgNO3
solution were added to the previous mixture, and
within 2 min, 2 mL of Ofi extract were added. The
resulting mixture was stirred for 1 h at 55C. During
this time, the solution adopted a slight blue shade.
Sample Characterization
A drop of each colloidal sample was deposited on a
nickel microgrid covered with carbon for sample
803
preparation for transmission electronic microscopy
(TEM). The sample was later dried at room tem-
perature for 4 h. After preparation of samples, they
were analyzed by transmission electron microscopy
with a JEOL JEM-2010F at accelerating voltage of
200 keV. Before Raman spectroscopy measure-
ments, small drops were dried in a sample holder
for 1 h. Samples were characterized using an
HORIBA Jobin Yvon XploRA Olympus BX41TF
Raman microscopy with class 3B argon laser
(20 mW to 25 mW, 532 nm). The optical absorption
by the colloidal samples was characterized and
analyzed using a PerkinElmer Lambda 19 ultravi-
olet–visible–near infrared (UV–Vis–NIR) spectrom-
eter, which has resolution of 0.05 nm to 5.00 nm
(UV and Vis) and 0.2 nm to 20 nm (NIR).
Theory and Calculations
To provide a theoretical hypothesis for the early
stages of nanoalloy formation for comparison with
experimental evidence, we analyzed small mini-
mum-energy clusters formed by Cu and Ag atoms
[Agn and Cun and (AgCu)n with n = 2 to 10] at the
level of the local spin density approximation (LSDA)
in combination with the Los Alamos National
Laboratory 2 double-Z (LANL2DZ) basis set. Struc-
tural studies confirmed coalescence between the Ag
and Cu clusters after reaching the minimal struc-
tural energy (local minimum). The vibrational spec-
trum for each structure was predicted,
corresponding to a vibrational mode with higher
relative intensity of ‘‘breathing’’ type in each case.
The dependence of the location of the breathing
mode type (BMT) on the number and type of atoms
forming each cluster was analyzed. All calculations
were carried out using Gaussian 09 software.20
RESULTS AND DISCUSSION
Two colloidal solutions of nanoparticles were
obtained, differing in the reversed order of the steps
in the synthesis process. Figure 1a shows that the
first solution contained bimetallic nanoparticles of
core–shell type, having a slight green tone. This was
generated when using the Ag+ ion precursor solu-
tion first in the synthesis process. Figure 1b shows a
colloidal solution with a slight blue tone containing
linked monometallic nanoparticles. This resulted
when using the Cu2+ ion precursor solution first in
the synthesis process.
The samples were analyzed by transmission
electronic microscopy, revealing nanoparticles with
size of 10 nm to 20 nm for both synthesis processes.
Figure 1a shows bimetallic nanoparticles of core–
shell type with ellipsoidal shape, having the core
displaced from the center. Two tones (black and
gray) are observed; we suppose that the black shade
corresponds to the silver core, because silver has
better contrast in TEM images, while the gray tone
from copper nanoparticles, or high concentration of
copper. This is consistent with the synthesis process
804 Rocha-Rocha, Cortez-Valadez, Hernández-Martı́nez, Gámez-Corrales, Alvarez,
Britto-Hurtado, Delgado-Beleño, Martinez-Nuñez, Pérez-Rodrı́guez, Arizpe-Chávez, and Flores-Acosta

Fig. 1. Bimetallic nanoparticles: (a) Ag–Cu core–shell type and (b) linked monometallic.

Fig. 2. TEM images of bimetallic nanoparticles: (a) Ag–Cu core–shell type and (b) linked monometallic.

where silver nanoparticles are first synthesized to
form the core in the first growth stage. As copper is
incorporated subsequently, it easily forms the shell
of the bimetallic nanoparticles, as observed in
Fig. 2a.
Performing the same synthesis process but inter-
changing the order of the precursor solutions (i.e.,
starting with Cu2+ ion solution and then the Ag+
solution), bimetallic nanoparticles of monometallic
bond type were obtained, i.e., AgNP–link–CuNP
(commonly called Janus form), as observed in
Fig. 2b. In this image, several gray clouds are
observed, corresponding to CuNPs, each in contact
with a high-contrast AgNP. Moreover, very small
particles of the order of 2 nm are observed in both
images as tiny black dots inside. These may repre-
sent an early stage of bimetallic nanoparticle
growth (nanoalloys) in the form of small clusters
of AgnCum type, constituted randomly. This could
lead to the formation of several stable structures of
smaller size, possibly like Ag32Cu6.16 Because of the
high content of ascorbic acid in Ofi plant extract, we
suppose that carboxylic groups in the extract are
(one of the factors) responsible for the reduction
process.21 However, the plant extract also contains
several types of starches, vitamins, and proteins
that could facilitate this process.22 In addition, the
extract contains glucose, which could also act as a
catalyst in the synthesis process.23
The optical properties were detected by UV–Vis
spectroscopy after synthesis of the bimetallic
nanoparticles. For the case of the Ag–Cu nanopar-
ticles of core–shell type, a band centered at 440 nm
was detected. This band corresponds to the surface
plasmon resonance of the nanoalloys of the Ag–Cu
nanoparticles of core–shell type (colloidal sam-
ples),24 in agreement with the TEM image shown
in Fig. 2a.
On the other hand, an absorption band centered
at 500 nm was observed after synthesis of the linked
monometallic nanoparticles (of Janus type25), as
shown in Fig. 3b. Other authors reported an
Green Synthesis of Ag-Cu Nanoalloys Using Opuntia ficus-indica
Fig. 3. Optical absorption of bimetallic Ag–Cu nanoparticles: (a)
core–shell type and (b) linked monometallic (Janus).
Fig. 4. Raman spectrum of bimetallic Ag–Cu nanoparticles: (a)
core–shell type, (b) linked monometallic (Janus), and spectral range
of BMT predicted for Agn, Cun, and (AgCu)n clusters.
absorption band centered at around 505 nm and
assigned this to nanoparticles of Ag/Cu alloys
obtained using the same concentrations.26
The vibrational properties of the samples were
analyzed by Raman spectroscopy. The Raman spec-
trum showed a band with high amplitude centered at
277 cm 1 and two bands with low intensity located at
158 cm 1 and 220 cm 1 after both synthesis processes
(Fig. 4). The Raman bands remained for both the
Janus- and core–shell-type nanoparticles, as shown in
Fig. 4. The Raman bands located at 158 cm 1 and
277 cm 1 were assigned to the vibrational properties
of small silver and copper nanoparticles, respec-
tively.17,18 The Raman band at about 220 cm 1 could
805
Fig. 5. Small low-energy clusters of Ag, Cu, and Ag/Cu obtained by
DFT at LSDA level.
originate from the minor presence of Ag–Cu bonds in
this material. We suppose that these bands could be
associated with several clusters of AgnCum type of
small size. These could correspond to the small
particles observed experimentally in these samples
in Fig. 2a (upper right corner) and Fig. 2b (upper
center part). Clearly, bulk metals do not exhibit
Raman bands, but when the material is dimensionally
confined to entities of a few nanometers, vibrational
properties quantifiable by Raman spectroscopy may
be exhibited.27,28
To try to understand this behavior, we used
density functional theory (DFT) as an approach for
adequate modeling of atomic interactions. This
theory uses basis functions to describe the electrons
and nuclei of atoms, as well as their interactions
through pseudopotentials. Recent results have pre-
sented great advances in understanding the vibra-
tional and structural correlations for several types
of cluster using this level of theory.27,28
In this work we therefore studied the vibrational
properties of small clusters of Ag and Cu (Ag2n and
Cu2n) as well as the interaction of Ag-Cu, i.e., (AgCu)n
clusters of nanoalloy type with n = 1 to 9. All
vibrational calculations yielded positive frequencies,
806 Rocha-Rocha, Cortez-Valadez, Hernández-Martı́nez, Gámez-Corrales, Alvarez,
Britto-Hurtado, Delgado-Beleño, Martinez-Nuñez, Pérez-Rodrı́guez, Arizpe-Chávez, and Flores-Acosta
Fig. 6. BMT in small clusters of Agn, Cun, and (AgCu)n as obtained
by DFT at LSDA level.
corroborating the minimal energy state. In each of the
predicted vibrational spectra, a mode with higher
relative intensity was evident for n ‡ 2. This mode
was of breathing type, in general presenting a trend
towards lower wavenumber as the cluster size was
increased. The spectral range of the BMT predicted
for the studied Agn, Cun, and (AgCu)n clusters is
presented in Fig. 4.
The clusters, after reaching the structural config-
uration with minimal local energy, are shown in
Fig. 5. For n = 1, one is therefore studying the
stretching modes of Ag2 and Cu2 dimers and the Ag–
Cu bond, located at 214.6 cm 1, 309 cm 1, and
258.8 cm 1, respectively.
The structures of the (AgCu)n clusters were obtained
after coalescence of smaller clusters, as well as by
random substitution of silver atoms in a copper cluster
and vice versa. Based on this study, the cases with the
lowest structural energy were selected (Fig. 5).
The location of the BMT as the number of atoms in
each cluster was increased is presented in Fig. 6. On
performing a linear fit (see Electronic Supplementary
Information), three nearly parallel lines appear,
intersecting with the X-axis at around 50 to 60 units
(n, atom number). This corresponds approximately to
the maximum number of atoms allowed in a cluster
for a radial breathing mode (RBM) to be present at
this approximation level. We can therefore suppose
that this type of vibration can be found in nanopar-
ticles of size less than approximately 5 nm.
This theoretical study considers clusters formed by
even numbers of atoms, having the same number of
atoms of each metal. However, the results shown in
Fig. 6 also implicitly delimit the spectral range in
Raman spectroscopy of clusters formed from different
numbers of atoms, i.e., of the form AgnCum. We
supposed that BMT(Cux) > BMT(AgnCum) and
BMT(Agx)< BMT(AgnCum), with x = n + m; For
example, the cluster Ag32Cu6 should have a BMT
located between approximately 74 cm 1 and 107 cm 1
at this level of theory, according to the linear fit
presented in the Electronic Supplementary Informa-
tion, in other words, bounded from below by 74 cm 1
for the Ag38 cluster and from above by 107 cm 1 for
the Cu38. Because of the computational cost of
analyzing these structures theoretically, atomic com-
positions up to 19 atoms were considered. This result
could be extended to provide correlations with vibra-
tional spectroscopy of new AgnCum species.
CONCLUSIONS
Synthesis of Ag/Cu core–shell and Janus-type
nanoparticles with size of 10 nm to 20 nm was
achieved by a green approach using Ofi plant extract.
Additionally small nanoparticles formed by Ag and
Cu were also obtained by this technique, represent-
ing an early stage of growth of AgnCum clusters with
size of the order of 2 nm. We suppose that these
structures constitute a diversity of clusters of
AgnCum type. The nanoparticles exhibited absorp-
tion bands attributable to surface plasmon reso-
nance, located at 450 nm and 500 nm for the core–
shell- and Janus-type nanoparticles, respectively.
Experimentally, a Raman band centered at
275 cm 1 was detected after synthesis of both types
of nanoparticles. DFT calculations at LSDA level
predicted that very small clusters of Agn, Cun, and
(AgCu)n with n = 2 to 9 present BMT located at low
wavenumbers between 151 cm 1 and 214 cm 1,
209 cm 1 and 309 cm 1, and 175.3 cm 1 and
258.9 cm 1, respectively. The Raman band detected
experimentally at 220 cm 1 could originate from
vibrational modes of breathing type in small clus-
ters of AgnCum type.
These results could be used to identify new
species of AgnCum particles, as well as for interpre-
tation of the experimental vibrational spectra of
very small nanomaterials.
ACKNOWLEDGEMENTS
The computational research in this investigation
was facilitated by UNISON/Acarus. We appreciate
the support given by the DCEN through Projects
USO315001053 and USO315000709.
ELECTRONIC SUPPLEMENTARY
MATERIAL
The online version of this article (doi:
10.1007/s11664-016-4942-2) contains supplemen-
tary material, which is available to authorized
users.
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