Journal of Saudi Chemical Society (2017) 21, 341–348

King Saud University

Journal of Saudi Chemical Society

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

A green synthesis of copper nanoparticles using

native cyclodextrins as stabilizing agents
Javier Suárez-Cerda a, Heriberto Espinoza-Gómez b, Gabriel Alonso-Núñez c,
Ignacio A. Rivero a, Yadira Gochi-Ponce a, Lucı́a Z. Flores-López a,*

a
Centro de Graduados e Investigación en Quı´mica, Instituto Tecnológico de Tijuana, Blvd. Alberto Limón Padilla S/N,
Mesa de Otay, C.P. 22500 Tijuana, B.C., Mexico
b
Universidad Autónoma de Baja California, Facultad de Ciencias Quimicas e Ingenieria, Calzada Universidad 14418
Parque Industrial Internacional, C.P. 22390 Tijuana, B.C., Mexico
c
Centro de Nanociencia y Nanotecnologı´a de la Universidad Nacional Autónoma de Me´xico, km. 107 Carretera
Tijuana-Ensenada, Ensenada C.P. 22860, B.C., Mexico

Received 5 August 2016; revised 14 October 2016; accepted 27 October 2016

Available online 9 November 2016

CHEMICAL COM-
POUNDS STUDIED IN
THIS ARTICLE
Copper (II) Sulfate Pentahy-
drate (CuSO4.5H2O, Pub-
Chem CID: 24463);
a-NCD (C36H60O30, Pub-
Chem CID: 444913);
b-NCD (C42H70O35, Pub-
Chem CID: 444041);
c-NCD (C48H80O40, Pub-
Chem CID: 86575);
Ascorbic Acid (C6H8O6,
PubChem CID: 54670067)
KEYWORDS
Copper-nanoparticles;
Green chemistry method;
Cyclodextrins as stabilizing
agents
Abstract In this work, a comparative study of the effect of the NCD size as a stabilizing agent, on
the synthesis of copper nanoparticles (Cu-NPs) by an easy green method was reported. The
nanoparticles were synthesized through the chemical reduction of aqueous solutions of copper
(II) sulfate with ascorbic acid, using different native cyclodextrins (NCDs) (a-, b-, or c-NCD) as
stabilizing agents. Cu-NPs were characterized by scanning electron microscopy–energy dispersive
spectroscopy (SEM–EDX), powder X-ray diffraction (XRD) and transmission electron microscopy
(TEM). The pattern showed in the typical selected area electron diffraction (SAED) and lattice
fringes, evidence that the crystalline structure of Cu-NPs is face-centered cubic (FCC) with a
(1 1 1), (2 0 0) and (2 2 0) lattice planes of Cu. The analysis of the TEM images show that the size
of the Cu-NPs depends on the type of native cyclodextrin (NCD), also it was observed that the
nanoparticles are spherical and with a size between
2 and 33 nm. The smaller Cu-NPs were
obtained with a-NCD (mode 4 nm), while the nanoparticles obtained with b-NCD show the narrow
size distribution (mode 6.5 nm). The average particle size and particle size distribution of Cu-NPs
depend upon the type of CDs.
Ó 2016 King Saud University. Production and hosting by Elsevier B.V. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

* Corresponding author.
E-mail addresses: hespinoza@uabc.edu.mx (H. Espinoza-Gómez), lzflores@hotmail.com (L.Z. Flores-López).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

http://dx.doi.org/10.1016/j.jscs.2016.10.005
1319-6103 Ó 2016 King Saud University. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
342 J. Suárez-Cerda et al.

1. Introduction Cu-NPs can be synthesized by various methods, for exam-

Nanomaterials have unique properties that distinguish them
from the corresponding bulk materials. The shape and size
of metal nanoparticles influence their optical, catalytic and
conductive properties [1].
Copper nanoparticles (Cu-NPs) have special properties,
which have made them important for various applications;
for example, super strong materials, antibacterial, sensors
and catalysts. Furthermore, they can also interact and react
with other nanoparticles due to the high surface area-volume
ratio. Recently, it has been reported that Cu-NPs possess supe-
rior antibacterial activity than Ag-NPs, for E. coli and B. sub-
tilis [2,3].
ple metal vapor synthesis [4], exploding wire method [5,6], vac-
uum vapor deposition [7], sonochemical reduction [8], thermal
reduction [9], chemical reduction [10–13], biosynthesis [14,15],
laser irradiation [16], and microemulsion techniques [17,18].
Of all the above mentioned methods, chemical reduction is the
most popular for the synthesis of Cu-NPs. The chemical reduc-
tion method has some advantages; it is simple, inexpensive and
presents an easy control of geometrical nanoparticle characteris-
tics, like size and shape. However, the disadvantage of this
method isthat it canaffect the environment, due to the use anddis-
posal of toxic solvents and hazardous chemical reducing agents.
Some examples of these toxic chemical reductants are sodium
borohydride [19,20], hydrazinium hydroxide [21], sodium
hypophosphite [22], amines [23], diethylenetriamine [24], or poly-

Scheme 1 General reaction for the synthesis and stabilization of Cu-NPs with NCDs.

Figure 1 Color development of the synthesis reaction of Cu-NPs formation.

Green synthesis of copper nanoparticles 343

Figure 2 ATR-FTIR spectra of (a) b-NCD, and Cu-NPs synthesized with (b) a-NCD, (c) b-NCD, and (d) c-NCD.

ols (e.g., ethylene glycol) [25,26]; which they can be ‘‘caught” on ous solution was poured in a round bottom flask, and heated
the surface of Cu-NPs increasing nanoparticle toxicity [27]. at 80 °C. Later, the mixture of aqueous solutions of ascorbic
Therefore, green chemistry synthesis of Cu-NPs is an alter- acid and NCD was added drop wise to the metallic solution
native method for its preparation, due to some advantages: it is with magnetic vigorous agitation (700 rpm). The color of the
eco-friendly, environmentally benign and non-toxic solvents
are used [28–30].
Native cyclodextrins (NCDs) have a large number of pri-
mary and secondary hydroxyl groups, which can be used as
coordination sites for metal chelation, forming covalent bonds
at basic pH. Due to those groups, NCDs are water-soluble mole-
cules. These cyclic oligosaccharides possess a non-toxic nature,
so they have applications in the pharmaceutical, food, and cos-
metic industry, as well as in analytical separations [31–35].
The aim of this study is to determine the effect of the NCDs
size used as stabilizing agent, in the characteristics of Cu-NPs
synthesized (shape and size) by a green chemistry method, in
order to determine which one is the best stabilizing agent. This
work is part of a responsible green approach for the develop-
ment of nanotechnology.

2. Methodology

2.1. Materials and methods

CuSO.45H2O and a(C36H60O30, 972.84 g/mol) P 98%, b

(C42H70O35, 1,134.98 g/mol) P 97% and c (C48H80O40,
1297.12 g/mol) P 98% -NCDs were supplied by Sigma–
Aldrich. The other reagents used in this work are laboratory
grade. The solutions were prepared with distilled water. All
glassware was thoroughly washed and rinsed with distilled
water, then dried in an oven before use and thus avoid poten-
tial contamination.

2.2. Preparation of Cu nanoparticles (Cu-NPs)

Initially, separate aqueous solutions of CuSO45H2O

(0.3975 g/25 mL H2O), ascorbic acid (1.09 g/25 mL H2O) and Figure 3 SEM-EDX analysis of synthesized Cu-NPs. (a) a-
native cyclodextrin (NCD) (0.25 g/25 mL H2O) were prepared; NCD-Cu-NPs, (b) b-NCD-Cu-NPs, (c) c-NCD-Cu-NPs
whereas each NCD was handled separately. The copper aque- agglomerates.
344 J. Suárez-Cerda et al.

3500
3500 (a) (b) 3500 (c)
111
3000 3000 3000
111 111
2500 2500 2500

2000 2000 2000

1500 200 1500 1500

200 200
220 1000 1000
1000
220
220
500 500 500

0 0 0
30 40 50 60 70 80 30 40 50 60 70 80 30 40 50 60 70 80
2 theta 2 theta 2 theta

Figure 4 XRD of Cu-NPs synthesized with (a) a-NCD, (b) b-NCD, (c) c-NCD.

Table 1 XRD analyses of the obtained Cu-NPs.

CD type Peak 2h FWHM (degrees) hkl (planes) d-spacing (nm) D (nm) a (nm)
a-NCD P1 43.09 0.2363 111 0.2099 35.77 0.3636
P2 50.23 0.2849 200 0.1816 30.28 0.3632
P3 73.93 0.3894 220 0.1282 25.27 0.3626
b-NCD P1 43.32 0.1919 111 0.2089 44.09 0.3619
P2 50.44 0.2484 200 0.1809 34.98 0.3618
P3 74.12 0.2229 220 0.1279 44.2 0.3618
c-NCD P1 43.28 0.2024 111 0.2090 41.78 0.3620
P2 50.42 0.2782 200 0.1810 31.24 0.3620
P3 74.06 0.3385 220 0.1280 29.09 0.3620

solution changed, from light blue to light green, and finally to
a dark yellow; after 5 min the formation of a brown precipitate
began. The reaction conditions were maintained for 5 h and
then cooled to room temperature. After that, the solution with
the brown precipitate was centrifuged for 10 min at 4000 rpm.
The precipitate was washed two times with distilled water
(5 mL) and once with ethanol anhydrous (5 mL), to remove
any unreacted reagent. Finally, the brown powder was dried
at room temperature to obtain the Cu-NPs. Cu-NPs are very
sensible to oxidation and tend to form copper oxide nanopar-
ticles. However, the formation of the Cu-NPs was achieved
due to the reducing and stabilizing properties of ascorbic acid
and NCDs, respectively. The formations of Cu-NPs were cor-
roborated by ATR-FTIR, SEM-EDX, XRD and TEM
analyses.
2.3. Characterization of Cu-NPs
The interaction between NCD and synthesized Cu-NPs was
studied using a PerkinElmer Spectrum 400 FT-IR/FT-NIR
Spectrometer with Universal ATR Sampling Accessory. The
presence of elemental copper was determined using a VEGA
3 Tescan scanning microscope equipped with EDX capability.
The structural characterization using XRD of Cu-NPs was
studied using a Philips X0 pertMPD. The morphology and size
of the as-synthesized Cu-NPs were characterized by transmis-
sion electron microscopy (TEM, JEM-2100F, JEOL), at an
accelerating voltage of 200 kV and fitted with a CCD camera.
3. Results and discussion
The methodology for synthesizing Cu-NPs, using NCDs as
stabilizing agent in water, is very simple. However, no reports
have been found in the literature concerning the study of the
effect of the NCD size, as a stabilizing agent, on the colloidal
synthesis of Cu-NPs at room temperature by a green chemistry
method. In Scheme 1 the proposed mechanism of nanoparticle
formation is shown, which considers that the characteristics of
the stabilizing agent used influence, the size and shape of the
nanoparticles.
Copper (II) sulfate dissolved in water, dissociates into Cu2+
and SO2 4 . Cu
2+
is reduced to Cu0 by reduction action of
ascorbic acid, forming metallic copper nuclei, which initiate
the growth stage. Growing nanoparticles are stabilized by sev-
eral molecules of cyclodextrins distributed around them (Cu-
NPs-NCD). These agglomerates grow to a certain size and,
Green synthesis of copper nanoparticles 345

Figure 5 Histograms and TEM images of Cu-NPs with different NCDs.

346
(a) (b)
111
200
220
0.21 nm
(111)
2
Figure 6 Crystal analysis of Cu-NPs (a) crystal lattice fringes,
(b) SAED pattern.
due to the difference in water solubility of NCDs, eventually
precipitated. Finally, the NCDs present in the precipitate are
removed during washings with water, resulting in pure powder
Cu-NPs.
Development of Cu-NPs synthesis reaction can be seen in
Fig. 1. A color change of the solution from blue to brownish
yellow was observed, with the formation of a brown powder;
showing the formation of Cu-NPs.
3.1. FTIR-ATR characterization
Typical FT-IR absorption spectra of b-NCD and Cu-NPs are
presented in Fig. 2a–d, respectively. Characteristic absorption
bands at 3297, 2926, 1646, 1416, 1152 and 1020 cm1 (Fig. 2a)
are observed in the FT-IR spectra for the b-NCD. The band at
3297 cm1 is attributed to the O–H stretching vibration, due to
the primary and secondary alcohols present in the NCD. The
bands at 1152 and 1020 cm1, can be assigned to the C–O and
CH2-O bending or stretching vibrations respectively, due to
the ether groups and alcohol groups present also in the
NCD. So the Cu-NPs spectra do not present those bands,
because the nanoparticles are in a pure form, without capping
with the NCD. This can also be seen in the TEM images of the
Cu-NPs, in which a shell around the Cu-NPs is not presented.
3.2. SEM-EDX studies
The presence of Cu-NPs was confirmed by SEM–EDX analy-
ses. The NCD-Cu-NPs obtained, seem to exhibit a cubic and
hexagonal agglomerate morphology. The EDX analysis shows
a signal corresponding to a significant presence of copper
Fig. 3, without oxygen; indicating that metallic Cu-NPs were
obtained.
3.3. XRD studies
X-ray diffraction (XRD) is one of the most important and easy
tools to determine the crystallite characteristics for any com-
J. Suárez-Cerda et al.
pound. XRD analyses of brown powders prepared using
NCDs as stabilizing agent, confirmed that the final product
is metallic. Fig. 4(a–c) shows XRD patterns of the Cu-NPs
obtained, which are very similar to those reported in JCPDS
Copper: 04-0836 (43.6, 50.8, 74.4). Table 1 summarized the
XRD analysis results. d-spacing (the interplanar spacing
between the atoms) was calculated using the Bragg law (Eq.
(1)), while the Debye–Scherrer was used to determine the aver-
age crystallite size. (Eq. (2))
2d sin h ¼ nk ð1Þ
where k = 0.15418 nm for Cu Ka, d is the interplanar spacing
between atoms, and n is an integer (in this particular case
n = 1).
Kk
D¼ ð2Þ
FWHM cos h
where K is a numerical constant factor (0.89), k = 0.15418 nm
for Cu Ka, FWHM is the full width at half maximum, h is the
diffraction angle, and D is the mean crystallite size. The lattice
parameter (a, nm) was calculated by (Eq. (3))
1 ðh2 þ k2 þ l2 Þ
2
¼ ð3Þ
d a2
The result of XRD analysis confirms that the structure of
the synthesized Cu-NPs is face centered cubic (FCC) with
the space group of Fm3m and a = 0.3620 nm [36,37].
3.4. TEM studies
The analyses of the TEM images are useful tools for measuring
the size and shape of the synthesized nanoparticles. Fig. 5
shows typical TEM images of Cu-NPs, their appearance is
spherical in shape without any shell around them, and also
have a broad size distribution.
The Cu-NPs size for a-NCD is between 2 and 27 nm, with a
mode on 4 nm (7.34%); whereas b-NCD sizes are obtained
between 2 and 23 nm, with a 6.5 nm (10%) mode. On another
hand, Cu-NPs prepared with c-NCD show sizes between 5 and
33 nm, with a mode of 18 nm (8.86%).
The NCDs prevent the growth of Cu-NPs into large aggre-
gates and, at the same time, it can be seen that the NCDs affect
the sizes of Cu-NPs. Therefore, the size of the Cu-NPs is
directly proportional to the size of the NCDs.
After analyzing the TEM histograms, we find that b-NCD
is the best stabilizing agent, since the synthesized particles with
it, has a narrow size distribution. This is because the b-NCD
has a rather rigid structure, due to the intramolecular hydro-
gen bonds between C2-OH groups and C3-OH groups of adja-
cent glucose units. These hydrogen bonds stabilize the b-NCD,
and are probably the reason for its lowest water solubility
compared to other NCDs [38,39]. Therefore, the b-NCD rigid
structure and its low water solubility causes those Cu-NPs
reach a determined size and precipitate easily, to finally regu-
late the growth of nanoparticles.
These results are in agreement with those previously
reported, related to the comparative study of the effect of NCDs
as stabilizing agents, in the green synthesis of Ag-NPs. [40]
Nanoparticles synthesized by this method are small and
have a narrow size distribution than in previous reports [41–43].
TEM images in Fig 6a show the discernible (1 1 1) planes for
FCC crystalline structure of Cu-NPs (with b-NCD); which are
Green synthesis of copper nanoparticles
consistent with the SAED pattern analysis (Fig 6b), and XRD
results previously discussed (Table 1).
4. Conclusions
The effect of NCDs type on the green synthesis of Cu-NPs, are
reported on this paper; through a simple, safe, and green
chemical reduction method. The nanoparticles synthesized by
this method, proved to be stable for several months without
physical or chemical changes.
SEM-EDX and XRD analyses demonstrate the presence of
a significant copper content without oxygen, indicating that
the synthesized nanoparticles were metallic copper, without
trace of copper oxide nanoparticles.
The crystallographic structure of the synthesized Cu-NPs
was confirmed by XRD, TEM and SAED pattern, proving
to be FCC.
TEM analyses show that the Cu-NPs obtained are between
2 nm and 33 nm (a-NCD 2–23 nm; b-NCD 2–23 nm; c-NCD
5–33 nm) in size. The sizes of the nanoparticles were as follows:
Cu-NPs (a-NCD) < Cu-NPs (b-NCD) < Cu-NPs (c-NCD),
the smaller Cu-NPs were obtained with a-NCD. Therefore,
we conclude that the Cu-NPs size is directly proportional to
the size of the NCDs.
On the other hand, the b-NCD is the best stabilizing agent,
because the particles synthesized with it, have a smallest size
distribution. This is due to the rigid structure and low water
solubility of b-NCD, causing their complex precipitate easily;
thereby regulating the growth of nanoparticles.
In conclusion, the nanoparticle size and size distribution
depend on the NCD used as stabilizing agent.
Acknowledgments
We gratefully acknowledge Francisco Ruiz for his technical
assistance, also we thank Emigdio Z. Flores López for
improvement of the English grammar.
This study was funded in part by Dirección General de Edu-
cación Superior Tecnológica (DGEST, Grant 5872.16-P) and
Consejo Nacional de Ciencia y Tecnologı́a (CONACYT,
Grant 174689, CEMIE-Sol-P28 and PAPIIT IN104714).
Acknowledgment to CONACyT (259931) and DGAPA-
UNAM by sabbatical support (Gabriel Alonso Nuñez).
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