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

* 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-


ple metal vapor synthesis [4], exploding wire method [5,6], vac-
Nanomaterials have unique properties that distinguish them uum vapor deposition [7], sonochemical reduction [8], thermal
from the corresponding bulk materials. The shape and size reduction [9], chemical reduction [10–13], biosynthesis [14,15],
of metal nanoparticles influence their optical, catalytic and laser irradiation [16], and microemulsion techniques [17,18].
conductive properties [1]. Of all the above mentioned methods, chemical reduction is the
Copper nanoparticles (Cu-NPs) have special properties, most popular for the synthesis of Cu-NPs. The chemical reduc-
which have made them important for various applications; tion method has some advantages; it is simple, inexpensive and
for example, super strong materials, antibacterial, sensors presents an easy control of geometrical nanoparticle characteris-
and catalysts. Furthermore, they can also interact and react tics, like size and shape. However, the disadvantage of this
with other nanoparticles due to the high surface area-volume method isthat it canaffect the environment, due to the use anddis-
ratio. Recently, it has been reported that Cu-NPs possess supe- posal of toxic solvents and hazardous chemical reducing agents.
rior antibacterial activity than Ag-NPs, for E. coli and B. sub- Some examples of these toxic chemical reductants are sodium
tilis [2,3]. 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 The structural characterization using XRD of Cu-NPs was
a dark yellow; after 5 min the formation of a brown precipitate studied using a Philips X0 pertMPD. The morphology and size
began. The reaction conditions were maintained for 5 h and of the as-synthesized Cu-NPs were characterized by transmis-
then cooled to room temperature. After that, the solution with sion electron microscopy (TEM, JEM-2100F, JEOL), at an
the brown precipitate was centrifuged for 10 min at 4000 rpm. accelerating voltage of 200 kV and fitted with a CCD camera.
The precipitate was washed two times with distilled water
(5 mL) and once with ethanol anhydrous (5 mL), to remove 3. Results and discussion
any unreacted reagent. Finally, the brown powder was dried
at room temperature to obtain the Cu-NPs. Cu-NPs are very The methodology for synthesizing Cu-NPs, using NCDs as
sensible to oxidation and tend to form copper oxide nanopar- stabilizing agent in water, is very simple. However, no reports
ticles. However, the formation of the Cu-NPs was achieved have been found in the literature concerning the study of the
due to the reducing and stabilizing properties of ascorbic acid effect of the NCD size, as a stabilizing agent, on the colloidal
and NCDs, respectively. The formations of Cu-NPs were cor- synthesis of Cu-NPs at room temperature by a green chemistry
roborated by ATR-FTIR, SEM-EDX, XRD and TEM method. In Scheme 1 the proposed mechanism of nanoparticle
analyses. formation is shown, which considers that the characteristics of
the stabilizing agent used influence, the size and shape of the
2.3. Characterization of Cu-NPs nanoparticles.
Copper (II) sulfate dissolved in water, dissociates into Cu2+
The interaction between NCD and synthesized Cu-NPs was and SO2 4 . Cu
2+
is reduced to Cu0 by reduction action of
studied using a PerkinElmer Spectrum 400 FT-IR/FT-NIR ascorbic acid, forming metallic copper nuclei, which initiate
Spectrometer with Universal ATR Sampling Accessory. The the growth stage. Growing nanoparticles are stabilized by sev-
presence of elemental copper was determined using a VEGA eral molecules of cyclodextrins distributed around them (Cu-
3 Tescan scanning microscope equipped with EDX capability. 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 J. Suárez-Cerda et al.

pound. XRD analyses of brown powders prepared using


(a) (b) 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
111 XRD analysis results. d-spacing (the interplanar spacing
between the atoms) was calculated using the Bragg law (Eq.
200 (1)), while the Debye–Scherrer was used to determine the aver-
age crystallite size. (Eq. (2))
220
2d sin h ¼ nk ð1Þ
0.21 nm where k = 0.15418 nm for Cu Ka, d is the interplanar spacing
between atoms, and n is an integer (in this particular case
(111) 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
2

diffraction angle, and D is the mean crystallite size. The lattice


parameter (a, nm) was calculated by (Eq. (3))
Figure 6 Crystal analysis of Cu-NPs (a) crystal lattice fringes,
(b) SAED pattern. 1 ðh2 þ k2 þ l2 Þ
2
¼ ð3Þ
d a2
due to the difference in water solubility of NCDs, eventually
precipitated. Finally, the NCDs present in the precipitate are The result of XRD analysis confirms that the structure of
removed during washings with water, resulting in pure powder the synthesized Cu-NPs is face centered cubic (FCC) with
Cu-NPs. the space group of Fm3m and a = 0.3620 nm [36,37].
Development of Cu-NPs synthesis reaction can be seen in
Fig. 1. A color change of the solution from blue to brownish 3.4. TEM studies
yellow was observed, with the formation of a brown powder;
showing the formation of Cu-NPs. The analyses of the TEM images are useful tools for measuring
the size and shape of the synthesized nanoparticles. Fig. 5
3.1. FTIR-ATR characterization shows typical TEM images of Cu-NPs, their appearance is
spherical in shape without any shell around them, and also
Typical FT-IR absorption spectra of b-NCD and Cu-NPs are have a broad size distribution.
presented in Fig. 2a–d, respectively. Characteristic absorption The Cu-NPs size for a-NCD is between 2 and 27 nm, with a
bands at 3297, 2926, 1646, 1416, 1152 and 1020 cm1 (Fig. 2a) mode on 4 nm (7.34%); whereas b-NCD sizes are obtained
are observed in the FT-IR spectra for the b-NCD. The band at between 2 and 23 nm, with a 6.5 nm (10%) mode. On another
3297 cm1 is attributed to the O–H stretching vibration, due to hand, Cu-NPs prepared with c-NCD show sizes between 5 and
the primary and secondary alcohols present in the NCD. The 33 nm, with a mode of 18 nm (8.86%).
bands at 1152 and 1020 cm1, can be assigned to the C–O and The NCDs prevent the growth of Cu-NPs into large aggre-
CH2-O bending or stretching vibrations respectively, due to gates and, at the same time, it can be seen that the NCDs affect
the ether groups and alcohol groups present also in the the sizes of Cu-NPs. Therefore, the size of the Cu-NPs is
NCD. So the Cu-NPs spectra do not present those bands, directly proportional to the size of the NCDs.
because the nanoparticles are in a pure form, without capping After analyzing the TEM histograms, we find that b-NCD
with the NCD. This can also be seen in the TEM images of the is the best stabilizing agent, since the synthesized particles with
Cu-NPs, in which a shell around the Cu-NPs is not presented. it, has a narrow size distribution. This is because the b-NCD
has a rather rigid structure, due to the intramolecular hydro-
3.2. SEM-EDX studies 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
The presence of Cu-NPs was confirmed by SEM–EDX analy-
compared to other NCDs [38,39]. Therefore, the b-NCD rigid
ses. The NCD-Cu-NPs obtained, seem to exhibit a cubic and
structure and its low water solubility causes those Cu-NPs
hexagonal agglomerate morphology. The EDX analysis shows
reach a determined size and precipitate easily, to finally regu-
a signal corresponding to a significant presence of copper
late the growth of nanoparticles.
Fig. 3, without oxygen; indicating that metallic Cu-NPs were
These results are in agreement with those previously
obtained.
reported, related to the comparative study of the effect of NCDs
as stabilizing agents, in the green synthesis of Ag-NPs. [40]
3.3. XRD studies
Nanoparticles synthesized by this method are small and
have a narrow size distribution than in previous reports [41–43].
X-ray diffraction (XRD) is one of the most important and easy TEM images in Fig 6a show the discernible (1 1 1) planes for
tools to determine the crystallite characteristics for any com- FCC crystalline structure of Cu-NPs (with b-NCD); which are
Green synthesis of copper nanoparticles 347

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