Green Chemistry Letters and Reviews

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Green synthesis of zinc oxide nanoparticles: a

comparison

Shabnam Fakhari, Mina Jamzad & Hassan Kabiri Fard

To cite this article: Shabnam Fakhari, Mina Jamzad & Hassan Kabiri Fard (2019) Green synthesis
of zinc oxide nanoparticles: a comparison, Green Chemistry Letters and Reviews, 12:1, 19-24, DOI:
10.1080/17518253.2018.1547925

To link to this article: https://doi.org/10.1080/17518253.2018.1547925

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GREEN CHEMISTRY LETTERS AND REVIEWS
2019, VOL. 12, NO. 1, 19–24
https://doi.org/10.1080/17518253.2018.1547925

Green synthesis of zinc oxide nanoparticles: a comparison

Shabnam Fakharia, Mina Jamzada and Hassan Kabiri Fard b

a
Department of Chemistry, Shahr-e-Qods Branch, Islamic Azad University, Tehran, Iran; bDepartment of Chemistry, North Tehran Branch, Islamic
Azad University, Tehran, Iran

ABSTRACT ARTICLE HISTORY

Green synthesis of nanoparticles by biological systems especially plant extracts has become an Received 27 July 2018
emerging field in nanotechnology. In this study, zinc oxide nanoparticles were synthesized using Accepted 10 November 2018
Laurus nobilis L. leaves aqueous extract and two different zinc salts (zinc acetate and zinc nitrate)
KEYWORDS
as precursors. The synthesized nanoparticles were characterized by Ultraviolet–Visible Zinc oxide nanoparticles;
spectroscopy (UV–Vis), Fourier Transform Infrared Spectroscopy (FT-IR), X-Ray Diffraction analysis Lauruas nobilis L. extract;
(XRD), Energy-Dispersive X-ray analysis (EDX) and Scanning Electron Microscopy (SEM). UV–Vis green synthesis
spectra showed typical absorption peaks in around 350 nm due to their large excitation binding
energy at room temperature. Chemical bond formations of zinc oxide were confirmed by FT-IR
analyses. XRD results revealed the formation of hexagonal wurtzite structure, and SEM analyses
showed spherical shape with the average size (21.49, 25.26) nm for the synthesized
nanoparticles by zinc acetate and zinc nitrate respectively. EDX analyses confirmed high purity
for the synthesized nanoparticles.

Introduction
preparations suffer from high energy demand and also
Nanotechnology is an emerging technology that can involve toxic and hazardous chemicals, which may lead
bring revolution to different scientific fields. Nanomater- to biological risks. In contrast, biological methods are
ials have wide range applications due to their size and becoming the most preferred methods as they are
morphology, and have been an important subject in often single step, clean, safe and cost effective (10).
the fields of basic and applied sciences. In the recent According to Raveendran et al., biosynthetic routes
years, there has been a great focus on nano-sized semi- provide nanoparticles of better defined sizes and mor-
conductors because of their novel properties which have phology as compared to other physicochemical
applications in optoelectronic. Among various nanoparti- methods (11). Biological systems include natural com-
cles, zinc oxide nanoparticles (ZNPs) are versatile semi- pounds which play essential and versatile role in the syn-
conductors that display significant optical transparency thesis of nanoparticles and act as capping agents to
and luminescent properties in UV–Visible (UV–Vis) stabilize them. The literature survey shows that using
regions (1). These nanoparticles have become important plants offers important advantages over other biological
in recent years, due to their excellent chemical and systems. The plants are easily available and safe to
thermal stability (2). Various approaches for the prep- handle and the nanoparticles synthesized by plants
aration of ZNPs have been developed, such as sol–gel, extracts are more stable (12).
hydrothermal, spray pyrolysis, microwave-assisted tech- Green synthesis of ZNPs has been carried out by
niques, chemical vapor deposition, ultrasonic condition different plant extracts such as Cassia fistula, Trifolium
and precipitation methods (3–9). These types of pratenese, Ocimum basilicum and so on (13–24).

CONTACT Mina Jamzad minajamzadiau@gmail.com; m.jamzad@qodsiau.ac.ir

© 2019 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
20 S. FAKHARI ET AL.

Laurus nobilis L. has also been used in the synthesis L. nobilis leaves aqueous extract. The mixture was stirred
of nanoparticles (25,26). In our previous work, we syn- for 2 h using a magnet stirrer at room temperature.
thesized silver nanoparticles by aqueous extract of Then 0.02 M NaOH was added drop by drop to reach
L. nobilis and the antioxidant activity of the extract and pH 12. The mixture was stirred for 1 extra hour until a
silver nanoparticles were evaluated. In the other solid product with a light yellow color was obtained.
reports, different pharmaceutical properties were evalu- The precipitate was purified by several re-dispersions in
ated for the plant extract (27–30). deionized water and then centrifuged. The final product
Here we report the syntheses of ZNPs by using was a white color powder material which was dried over-
L. nobilis L. leaves aqueous extract and two different night in an oven at 60°C. In green synthesis of ZNPs by
zinc salts (acetate and nitrate) as precursors. The struc- zinc nitrate, 25 mL of 0.05 M Zn(NO3)2.6H2O solution
tural properties of the synthesized ZNPs have been was mixed with 4 mL of L. nobilis leaves aqueous extract
confirmed by using UV–Vis, FT-IR (Fourier Transform and then the reaction was continued as we explained
Infrared Spectroscopy), XRD (X-Ray Diffraction), SEM above in the previous method.
(Scanning Electron Microscopy) and EDX (Energy-Disper-
sive X-ray analysis) technics.
Characterization of zinc oxide nanoparticles
The synthesized nanoparticles were characterized by
Materials and methods
different techniques. For the UV–Vis analysis, 1 mL of
Chemical and instrumental the suspension was collected from the purified sample
at the end of the reaction and was sonicated at
All the chemicals and solvents were purchased from
4000 rpm for 15 min. The UV–Vis spectra was recorded
Merck company (Germany). UV–Visible (UV.1800, Shi-
over the 200–800 nm range. FT-IR analysis of the dried
madzu, Japan); FT-IR (100 Spectrum, Perkin Elmer,
ZNPs was carried out by the KBr pellet method and the
Germany); XRD (EQUINX 3000; Intel, France); FESEM
presence of the various vibrational modes in the syn-
(ZIGMAVP-500, Zeiss, Germany; EDS, Oxford instruments,
thesized nanoparticles was investigated. The phase
UK); Ultra sonic (S15H, Germany); Heater-Stirrer (MR Hei-
structure and material identification of ZNPs were
End, Germany); Oven (Memmert 100-800, Germany);
studied by X-ray diffractometer. The SEM technique
Rotary evaporator (4003 Heidolph, Germany); Centrifuge
was employed to visualize the size and morphology of
(EBA 20 Hettich, Germany).
the particles. Energy-dispersive x-ray spectrometer
(EDX) was employed to analyze the elemental compo-
Preparation of the extract sition of the synthesized particles.

Fresh leaves of L. nobilis L. (Family Lauraceae) commonly

known as Bay were collected from the sea side area of Results and discussion
Roudsar (a city located in the north of Iran) in June
UV–Visible spectroscopy
2015. The leaves were washed and left to dry. Then the
dried leaves were powdered by a mortar and 20 g of UV–Visible absorption spectrum of synthesized nanopar-
powdered leaves was mixed with 200 mL deionized ticles is shown in Figure 1. The distinct peak centered
water and heated at 80°C using a heater-stirrer for around 350 nm is specific for ZNPs which is due to
10 min. Then the mixture was filtered and centrifuged their large excitation binding energy at room tempera-
to remove the plant residue and impurities and was ture (18). It is well known from absorption spectroscopy
stored for further uses. that the band gap increases on decreasing particle size.
There is also an opposite ratio between band gap and
the wavelength of absorption. As we know, the absorp-
Synthesis and purification of zinc oxide tion for bulk ZnO occurs around 385 nm. The high blue
nanoparticles shift absorption for the synthesized ZNPs in comparison
ZNPs were synthesized by the co-precipitation method with the bulk ZnO can be due to a high decrease in par-
reported previously by Singh et al. with some modifi- ticle size.
cations (31). In order to find the optimal method of
synthesizing the nanoparticles, we needed to do several
FT-IR analysis
trial and error testing. For synthesis of ZNPs by zinc
acetate and the plant extract, 25 mL of 0.02 M Zn FT-IR studies of L. nobilis leaves aqueous extract and the
(OAc)2.2H2O solution was mixed with 1 mL of the synthesized ZNPs are given in Figure 2. Infrared studies
 GREEN CHEMISTRY LETTERS AND REVIEWS 21

Figure 1. UV–Visible spectrum of the synthesized ZNPs by (A) zinc acetate and L. nobilis extract and (B) zinc nitrate and L. nobilis extract
as precursors.

were carried out in order to ascertain the purity and and 76.83 degrees. These peaks are indexed as (100),
nature of the nanoparticles and also the presence of phy- (002), (101), (102), (110), (103), (112), and (202) diffraction
tochemicals in the extract. The phytochemicals such as lattice planes respectively which confirm the hexagonal
alcohols, phenols, amines, carboxylic acids and so on wurtzite structure for the synthesized nanoparticles.
can interact with the zinc surface and aid in the stabiliz- This pattern is in accordance with the standard peaks dis-
ation of ZNPs. The peaks that were observed at 1634 and played by the International Centre for Diffraction Data.
(600, 450) cm−1 correspond to Zn–O stretching and The average size of ZNPs was calculated from the
deformation vibration, respectively. Metal oxides gener- highest intense peak (101) using the Debye–Scherer
ally give absorption peaks in the regions between 600 equation (1), where ω is the X-ray wavelength coming
and 400 cm−1. The Zn–O frequencies observed for the from Cu-Kα (1.540560 Å), β is the full width at half
synthesized ZNPs are in accordance with literature maxima of the diffraction peak in radians, θ is the
values (32,33). The broad peak observed at about Braggs̕ angle in degrees, and K is the shape factor and
3300 cm−1 indicates the OH stretching vibrations. its value is equal to 0.9.


D = Kv
(1)
b cos u
X-ray diffraction analysis
XRD pattern of synthesized ZNPs clearly indicates XRD analyses revealed the average size of (21.49,
crystalline structure for the synthesized nanoparticles 25.26 nm) for nanoparticles using zinc acetate and zinc
(Figure 3). The sharp diffraction peaks were observed at nitrate as precursors respectively. Details of XRD analyses
2θ values 31.46, 34.29, 36.33, 47.51, 56.50, 62.84, 67.79 are given in Table 1.
The particle size of the synthesized ZNPs was in close
Table 1. Details of XRD analyses for the synthesized ZNPs. agreement with the previous findings (34,35).
Samplea d-spacing (Å ) FWHMb Estimated crystallite size (nm)
A 2.47093 0.349 25.26
B 2.46305 0.295 29.48 Scanning electron microscopy
a
Synthesized ZNPs by L. nobilis leaves aqueous extract and A: zinc acetate;
B: zinc nitrate. The shape, structure and size of the synthesized ZNPs
b
Full width at half maximum. were determined by the SEM analyses (Figure 4). The
22 S. FAKHARI ET AL.

Figure 2. FT-IR spectra of (A) L. nobilis L. aqueous extract; (B) ZnO/extract prepared by zinc nitrate, and (C) ZnO/extract prepared by zinc
acetate.

micrographs of ZNPs proved that they had nano-sized L. nobilis aqueous extract and zinc acetate, were like
range, spherical shape and uniform distribution. The bullets. We also used zinc nitrate to find whether or
SEM results illustrated that using different precursors not the salt could influence the shape and size of the
affected the size and shape of the nanoparticles. As it nanoparticles. The nanoparticles were like flower when
is seen when using zinc acetate as a precursor, the zinc zinc nitrate was the precursor. The size of the nanoparti-
oxide molecules grow slowly and form small spherical cles in our study was also smaller (21.49, 25.25 nm) than
structures and accumulate like bullets. On the other the previous report (47.27 nm). The method which we
hand, by using zinc nitrate as a precursor, the spherical used was to some extent different from the previous
ZNPs are formed and the nanoparticles grow and method, and our results look better in regard to the
accumulate to form flower-shaped bundles. This agglom- sizes and shapes of the nanoparticles.
eration is due to polarity and electrostatic attraction of
ZnO nanoparticles. Similar kinds of observations have
Energy-dispersive X-ray spectroscopy
been documented by Madan et al. (36).
In the previous study on the green synthesis of ZNPs The elemental composition analyses of the ZNPs from the
by L. nobilis leaves aqueous extract and zinc acetate as EDX plot of the SEM images are shown in Figure 5. The
precursors, the shapes of the nanoparticles were like EDX spectra revealed that the required phase of Zn
flowers (26). While, the ZNPs, which we synthesized by and O is present in the samples and confirmed high

Figure 3. XRD results for the synthesized ZNPs by (A) zinc acetate and L. nobilis extract; (B) zinc nitrate and L. nobilis extract as
precursors.
 GREEN CHEMISTRY LETTERS AND REVIEWS 23

Figure 4. SEM micrographs of ZnO nanoparticles synthesized by (A) zinc acetate and L. nobilis L. aqueous extract; zinc nitrate and
L. nobilis L. aqueous extract as precursors.

Figure 5. EDX analyses of ZnO nanoparticles synthesized by (A) zinc acetate and L. nobilis L. extract and (B) zinc nitrate and L. nobilis
L. aqueous extract as precursors.

purity for the synthesized ZNPs. Theoretically, the acetate and zinc nitrate. UV–Visible spectrum showed a
expected stoichiometric mass percent of Zn and O are distinct peak around 350 nm, which is specific for
80.3% and 19.7% respectively. The EDX analyses in our ZNPs. The XRD results confirmed the efficiency of the
study show similar results for the both synthesized nano- synthesis process, evidencing the production of single
particles, while in the previous study, the elemental com- crystalline ZNPs with hexagonal wurtzite structure. The
position of zinc and oxygen was reported 57.16% and average size of ZNPs synthesized by zinc acetate and
14.87% respectively (26). zinc nitrate was found to be (21.49, 25.26) nm, exhibiting
bullets and flower like structures, respectively which
were confirmed by XRD and SEM analyses. EDX results
Conclusion
confirmed the presence of zinc and oxygen in the syn-
In this study, ZNPs was synthesized by L. nobilis leaves thesized ZNPs. FT-IR studies clearly showed the for-
aqueous extract using two different precursors: zinc mation of ZnO and indicated that the plant extract
24 S. FAKHARI ET AL.

contains various phytochemicals, which work as capping [13] Suresh, D.; Nethravathi, P.C.; Udayabhanu, H.; Rajanaika,
and stabilizing agent for the synthesized ZNPs. From the H.; Nagabhushana, H.; Sharma, S.C. Mat. Sci. Semicon.
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[14] Dobrucks, R.; Dugazewska, J. Saudi J. Biol. Sci. 2016, 23(4),
played a vital role in surface morphology and structure 517–523.
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Kumar, M.A.; Nagabhushan, H.; Sharma, S.C. Spectrochim.
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[17] Vimala, K.; Sundarraj, S.; Paulpandi, M.; Vengatesan, S.;
Disclosure statement Kannan, S. Process Biochem. 2014, 49, 160–172.
No potential conflict of interest was reported by the authors. [18] Bhuyan, T.; Mishra, K.; Khanuja, M.; Prasad, R.; Varma, A.
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[19] Elumalai, K.; Velmurugan, S.; Ravi, S.; Kathiravan, V.;
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Shabnam Fakhari is a student of PhD course in the Shahr-e- 952, 137–140.
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