e-ISSN: 2687-6698 Research Article

Green synthesis and structural characterization of ZnO nanoparticles and

ZnO@TiO2 nanocomposites by Cinnamomum verum bark extract

Gökçenur Selva Keleşoğlu1 , Mesut Özdinçer2 , Aslıhan Dalmaz3 , Kübra Zenkin1 , Sefa
Durmuş3*
1 Düzce University, Graduate Education Institute, Department of Chemistry, 81620, Düzce, Türkiye
2 Düzce University, Graduate Education Institute, Faculty of Technology, Department of Composite - Materials, 81620, Düzce, Türkiye
3 Düzce University, Faculty of Art and Science, Department of Chemistry, 81620, Düzce, Türkiye

Abstract

In this work, a facile and efficient approach for the green synthesis of ZnO@TiO 2 bimetallic oxide nanoparticles by exploiting the potential of
Cinnamomum verum bark extract as a biogenic reducing agent is presented. The synthesized nanoparticles were subjected to an extensive
characterization process involving various spectroscopic techniques. These techniques include X-ray diffraction analysis, Fourier transform
infrared spectroscopy, Scanning electron microscopy and Energy dispersive X-ray spectroscopy. Based on the obtained results, it highlights the
potential of green synthesized ZnO@TiO2 nanocomposites as a promising material for many applications.

Keywords: Cinnamomum verum, ZnO@TiO2 nanocomposites, ZnO NPs, green synthesis

1. Introduction

In recent years, the application of biosynthesis to the characterization of these nanoparticles particularly
production of nanoparticles (NPs) has attracted metal oxide nanoparticles, in the last decades. The high
attention as a more environmentally sustainable, safer surface to volume ratio of these nanoparticles is a major
and cost-effective alternative to traditional chemical and factor contributing to their distinctive properties [5–7].
physical methods [1]. Plant extracts in particular hold Among metal oxide nanoparticles zinc oxide (ZnO),
great promise for 'green' production due to their titanium dioxide (TiO2) show particularly promising
widespread availability, affordability, ease of use and physical and chemical properties [8,19]. Their unique
scalability [2,3]. These extracts contain a potent properties make them very important in a wide range of
combination of antioxidants, including polyphenols, applications [10,11] and research endeavors. Various
reducing sugars, nitrogenous bases and amino acids, methods, including chemical [1], sonochemical [12,13],
which have the ability to reduce metal ions in a metal salt electrochemical, photochemical and microemulsion
solution. The reduction of metal ions initiates the techniques, are used to produce them. However, many
formation of nucleation centers which attract additional of these methods involve complex reaction conditions
metal ions and incorporate neighboring nucleation sites, and the use of toxic chemicals, leading to environmental
ultimately leading to the formation of nanoparticles. pollution problems. As a result, researchers have sought
These particles are associated with organic substances to develop environmentally friendly methods for the
from plant extracts which help to increase the stability of synthesis of nanoparticles
the particles. It has also been reported that these Cinnamomum verum (C. verum), commonly known as
nanoparticles have no toxicity compared to those cinnamon, is a very abundant, economical and easily
produced by traditional chemical methods [4]. Due to available plant. It is known to be rich in phytochemicals
their unique properties compared to their bulk materials, such as alkaloids, polyphenolic compounds, terpenoids
there has been considerable interest in the synthesis and and flavonoids, which act as stabilizing and capping
Citation: G.S. Keleşoğlu, M. Özdinçer, A. Dalmaz, K. Zenkin, S. A u t h o r o f c o r r e s p o n d e n c e : [email protected]
Durmuş, Green Synthesis and Structural Characterization of ZnO Received: November 25, 2023 Tel: +90 (380) 541 24 04
Nanoparticles and ZnO@TiO2 Nanocomposites by Cinnamomum verum Accepted: December 06, 2023 Fax: +90 (380) 541 24 03
Bark Extract Turk J Anal Chem, 5(2), 2023, 118–123.
https://doi.org/10.51435/turkjac.1395817
Keleşoğlu et al. Turk J Anal Chem, 5(2), 2023, 118–123

agents during the synthesis process [14]. Moreover, the obtained as a result of the studies was determined by
bark of C. verum contains a notable concentration of energy dispersive X-ray analysis (EDX), and their
carboxylic and phenolic functional groups, such as morphology and size were determined by scanning
bisabolol, cinnamic acid, heptanoic acid, hexadecenoic electron microscopy (SEM) (FEI Quanta FEG 250).
acid, linalool, and phytol [15]. However, it is of great The functional groups present in the structure of the
importance to identify accurately the specific nanoparticles were recorded using a Perkin Elmer
phytochemicals responsible for the formation of Spectra Two UATR Fourier transform infrared
nanoparticles with controlled properties. This spectroscopy (FT-IR) spectrophotometer. X-ray
understanding can significantly contribute to the diffraction (XRD) patterns of ZnO NPs and ZnO@TiO2
utilization of cinnamon in various applications, nanocomposites were obtained using a Smart Lab
instrument with Cu-Kα radiation (1.5406 Å).
especially in the field of nanotechnology [16,17].
As a result, it has become essential to investigate
2.3. Preparation of Cinnamomum verum bark extract
synthesis routes for ZnO NPs and TiO2 nanocomposites
Cinnamomum verum was first obtained from local
and to explore their properties and applications through
markets and ground into powder. The powdered
extensive research. In this context, our study aims to
cinnamon was washed several times with deionized
investigate the synthesis of ZnO@TiO2 nanocomposites
water to remove impurities. Following this step, to
using C. verum bark extract, which is a sustainable and
prepare extract, 2.5 g C. verum bark was heated in 100 mL
environmentally friendly approach
deionized water for one hour in a magnetic stirrer. After
this time, the extract (Fig. 2) was allowed to cool at room
2. Materials and methods temperature and filtered with Whatman filter paper. It
was stored in the refrigerator at 4 °Cto be used for the
2.1. Reagents and chemicals synthesis of ZnO NPs and ZnO@TiO2 nanocomposites.
Cinnamomum verum, used as a stabilizing and reducing
agent in the study (Fig. 1), was obtained from local
markets in Düzce province. In addition, all of the
chemical materials used in the study are of analytical
purity. Sodium hydroxide, zinc nitrate hexahydrate and
titanium(IV)isopropoxide chemicals used in the
synthesis stage of metal oxide nanoparticles were
obtained from Merck company.

Figure 2. Schematic representation of the preparation steps of C. verum

bark extract

2.4. Green synthesis of ZnO NPSs

In order to synthesize ZnO NPs, 25 mL C. verum bark
extract was heated to 60 °Cand 2.08 g Zn(NO3)2.6H2O
was dissolved in 25 mL deionized water and added. The
resulting solution was stirred with a magnetic stirrer at
60 °C for one hour color change were observed.
Following this step, 0.1 M NaOH was added to adjust the
pH of the solution to 8. The mixture was centrifuged at
Figure 1. Image of Cinnamomum verum bark
5000 rpm for 7 min. and then washed several times with
deionized water. The resulting product was then dried
2.2. Apparatus in an oven at 60 °C for 24 hours. After the drying step
Heidolph brand magnetic stirrer was used to ensure was completed, it was subjected to calcination at 450 °C
homogeneous mixing of the solutions throughout the for 2.5 hours. The white-colored ZnO NPs formed as a
experimental studies. An Isolab brand pH meter was result of calcination was stored in a desiccator at room
used to ensure that the nanoparticles precipitated temperature (Fig. 3).
appropriately. Elektromag M5040P brand oven was
used to dry the synthesized products. Radwag brand
electronic balance was used throughout the
experimental studies. Separation of the products was
carried out using a VWR brand centrifuge. Filtration of
C. verum extract and nanoparticles obtained through the
extract was carried out using an Isolab brand vacuum
pump. The elemental composition of the nanoparticles Figure 3. Schematic representation of the preparation steps of ZnO NPs

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2.5. Green synthesis of ZnO@TiO2 nanocomposites were analyzed, no vibrations belonging to organic
Cinnamomum verum bark extract was heated to 60 °C, compounds in the structure of cinnamon extract were
then a solution of 2.97 g Zn (NO3)2.6H2O in 10 mL observed.
deionized water was added slowly. To this solution 0.1
M NaOH was added until pH = 8, then 3 mL of
titanium(IV) isopropoxide was added slowly and
stirring was continued at 60 °C for one hour on a

Transmittance (%)
magnetic stirrer. The resulting mixture was centrifuged
at 5000 rpm for 7 min. and the product was washed C. verum
several times with deionized water to remove
impurities. It was then placed in an oven to dry at 60 °C
for 24 hours. The dried product was then subjected to ZnO NPs

calcination in a muffle furnace at 450 °C for 2.5 hours

(Fig. 4) and the off-white-colored product was stored in
a desiccator for analysis. ZnO@TiO2

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )
Figure 5. FT-IR spectra of dry C. verum extract, ZnO NPs and
ZnO@TiO2 nanocomposites

3.2. XRD analysis

In the XRD pattern of ZnO NPs and ZnO@TiO 2

nanocomposites are shown in Fig. 6. Different peaks
Figure 4. Schematic representation of the preparation steps of were observed in the XRD pattern of ZnO NPs at
ZnO@TiO2 nanocomposites 2θ=31.82°, 34.45°, 36.29°, 47.60°, 56.63°, 62.91°, 66.46°,
67.98°, 69.06°, 72.63° and 77.06°. These peaks were
interrelated to (100), (002), (101), (102), (110), (103), (200),
3. Results and discussion
(112), (201), (004) and (202) hkl planes. All these
diffraction peaks are consisted to wurtzite (hexagonal)
3.1. FT-IR spectra
structure compatible with JCPDS Card No. 036-1451 [23]
FT-IR spectroscopy analysis was carried out to
and space group: P63mc [24]. Moreover, the cell
determine the presence of functional biomolecular parameters of the ZnO NPs a= b= 3.24 Å, and c= 5.20 Å.
groups in C. verum extract and synthesized ZnO NPs and The absence of distinct peaks in the XRD pattern
ZnO@TiO2 nanocomposites. When the FT-IR spectrum indicates that the nanoparticles do not contain
of C. verum shown in Fig. 5 is examined, the bands at impurities. In the XRD pattern of ZnO@TiO2
3271 and 2928 cm-1 are due to O-H stretching vibrations nanocomposites, in addition to the peak belonging to
in the structure of polyphenols and asymmetric C-H ZnO NPs, 25.41° and the associated (101) hkl planes of
stretching vibrations of -CH3 groups in the structure of the anatase phase (space group: I4₁/amd) of TiO2 with
biomolecules. The presence of the O-H group in the JCPDS card no. 21-1272 are shown [25].
structure of water is indicated by the peak at 1586 cm-1 in
the FT-IR spectrum. Also observed at 1408 cm-1 and 1386 * TiO2
(101)

ZnO@TiO2

cm-1 are peaks belonging to aliphatic C-H stretching and

(100)

CH3 symmetric bending vibrations. The C-O stretch

(002)

(110)

(103)

vibration of hydroxy flavonoids in the biostructure of C.

(112)
Intensity (a.u.)

(102)
(*101)

(201)
(200)

(004)

(202)

verum is seen at 1260 cm-1, while the band at 1043 cm-1 is

related to the C-O stretch of primary alcohols. The peak
ZnO NPs
corresponding to the C=C vibrations in the structure of
the benzene ring was observed at 614 cm-1 [18-20]. In the
FT-IR spectrum of ZnO NPs, only the peak at 402 cm-1
belonging to Zn-O bond was observed. Moreover, in the
FT-IR spectrum of ZnO@TiO2 nanocomposites,
vibrations at 402 cm-1 are attributed to Zn-O bond [21,22] 20 25 30 35 40 45 50 55 60 65 70 75 80
and vibrations at 388 cm-1 to Ti-O bond. When the FT-IR 2q (degree)
spectra of ZnO NPs and ZnO@TiO2 nanocomposites Figure 6. XRD pattern of ZnO NPs and ZnO@TiO2 nanocomposites

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Table 1. The structural parameters of ZnO and TiO2 NPs.

Sample JCPDS Card no: Crystal Structure Space Group Lattice Parameters (Å) Cell Volume (Å3) Unit Cell

a= b= 3.24
ZnO 036-1451 Hexagonal P63mc 54.58
c= 5.20

a= b= 3.80
TiO2 21-1272 Anatase I4₁/amd 138.76
c= 9.61

The cell parameters of the TiO2 NPs a= b= 3.80 Å, and ZnO NPs exhibit hexagonal and near-spherical shapes,
c= 9.61 Å as shown in Table 1. In addition, the weight with some irregularities indicating non-homogeneity
fraction of ZnO@TiO2 nanocomposites was determined [27,28]. The particle size of ZnO NPs falls within the
using the Whole Powder Pattern Fitting (WPPF) method, range of 30 - 50 nm, and there is a noticeable tendency
which approximates the components and fraction of the for slight agglomeration (Fig. 7(a)).
sample based on the measured XRD pattern and the Recent studies have shown that there is an optimum
materials [26]. According to WPPF weight fraction amount of TiO2 that is effective in inhibiting growth and
analysis, ZnO@TiO2 nanocomposites consists of 89% phase transformation of ZnO NPs, leading to production
ZnO and 11% TiO2 NPs. of smaller ZnO NPs [29]. This method resulted in
obtaining ZnO@TiO2 nanocomposites with an average
size of 20 nm, as shown in Fig. 7 (b, c). The surface
3.3. SEM-EDX analysis
morphology of the ZnO@TiO2 nanocomposites shows
The SEM images in Fig. 7(a-c) depict the surface
the presence of both spherical and hexagonal shapes. In
morphology of green-synthesized ZnO NPs and
addition, TiO2 NPs are widely dispersed on the surface
ZnO@TiO2 nanocomposites using C. verum extract. The
of the ZnO@TiO2 nanocomposites.

Figure 7. SEM images of the synthesized (a) ZnO NPs (b, c) ZnO@TiO2 nanocomposites

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Energy dispersive X-ray spectroscopy, a mode of nanocomposites have more extensive application in
operation of SEM, is used to determine the elemental biotechnology, optical device, medical, sensors, coatings,
composition of nanomaterials and provides information catalysis and drug delivery. This green synthesis is a
on the percentage of each element in the materials (Fig. highly efficient approach, using fewer chemicals and
8). The presence of oxygen, titanium and zinc elements controlling costs. This has led to additional research to
were observed in the EDX spectra of ZnO NPs and investigate the further implementation of
ZnO@TiO2 nanocomposites. The stoichiometric ratios environmentally friendly nanoparticles.
seen in the spectra are compatible with the proposed
structure and it is seen from these ratios that the amount Acknowledgement
of TiO2 doped corresponds to 10.8% [30].
This work is supported by Düzce University Scientific
Project (Project no: 2022.05.03.1365).

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