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Materials Today: Proceedings 5 (2018) 16472–16477 www.materialstoday.com/proceedings

SCICON 2016

Green synthesis of zinc oxide nanoparticles using extract of

Averrhoa bilimbi(L) and their photoelectrode applications
Rajita Ramanarayanan, Bhabhina N.M, Dharsana M.V, Nivedita C.V , Sindhu.S*
Department of Nanoscience & Technology, University of Calicut, Thenhipalam, Kerala- 673635, India.

Abstract

Stable zinc oxide nanoparticles were synthesized by co-precipitation method using the fruit extract of
Averrhoa bilimbi(L). Zinc acetate dihydrate was used as precursor. The extract of Averrhoa bilimbi (L) was used as
reducing as well as capping agent. The fruit of extract has been reported as reducing agent in gold and silver
nanoparticle synthesis. Zinc oxide nanoparticles synthesis using this extract is being reported for the first time in this
study to the best of our knowledge. Green synthesis method involved in this study is simple, cost effective,
environment friendly and less time consuming compared to other green methods reported. The formation of zinc
oxide nanoparticles was confirmed by UV-Visible spectroscopy, X-ray Diffraction techniques. Electron microscopy
has been used to study the shape and size of the synthesized zinc oxide nanoparticles. The photoelectrode activity of
these ZnO nanoparticles was tested in photoelectrochemical cells and analysed in this report.
© 2017 Elsevier Ltd. All rights reserved.
Selection and/or Peer-review under responsibility of International Conference on Advanced Materials (SCICON ‘16).

Keywords: Keywords: nanoparticles;green synthesis;zinc oxide

1. Introduction

Amongst the large number of semiconducting materials Zinc Oxide (ZnO) has been extensively studied
because of its unique physico-chemical properties and potential applications in diverse areas. ZnO is a direct
bandgap semiconductor which shows near UV emission, transparent conductivity, piezoelectric properties etc .In
addition ZnO is safe and biocombatible with rich variety of structures making it one of the most promising nano
metal oxide material for future research and applications [1].

* Corresponding author. +91-494-240-7373; fax: +91-494-240-0269.

E-mail address: sindhus@uoc.ac.in

2214-7853 © 2017 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of International Conference on Advanced Materials (SCICON ‘16).
 Ramanarayanan et al. / Materials Today: Proceedings 5 (2018) 16472–16477 16473

The development of green chemistry methods for synthesis of nanomaterials have become major focus of
researchers due to their environment friendly techniques [2]. Nanomaterials using plants are suitable candidates for
large scale bio-synthesis because of their stability and faster rate of synthesis compared to other biological
methods.The nanomaterials of different shapes and sizes could be synthesized by plants leading to a variety of
applications in science and industry.
Biosynthesis of ZnO nanoparticles by plants such as Azadirachta indica(L)[3],Aloe barbadenis miller
leaf[4],Solanum nigrum [5], Seaweeds [6] have been reported. In this work a cost effective, less time consuming
simple method has been utilised to synthesize ZnO nanoparticles using extract of Averrhoa bilimbi(L).
Averrhoa bilimbi (L) is a tropical small tree commonly known as Bilimbi, Cucumber Tree belonging to
Oxalidacea. The ripe bilimbi fruits have thin skin, yellowish green colour, soft texture and juicy nature. The ripe
fruits are rich in phytochemical constituents [7] which could be responsible for the reducing power of the extract.
In this work we report the synthesis of ZnO nanoparticles using the ripe fruits of bilimbi which due to its
environment friendly nature is suitable for large scale production in the near future.

2. Materials and methods

2.1. Materials

Zinc acetate dihydrate and NaOH used in this study were obtained from Merck and Sigma-Aldrich chemicals
respectively. The ripe fruits of bilimbi were collected, washed with distilled water and air-dried for some time. The
fruits were then cut into small pieces and boiled and stirred with distilled water for 15 minutes. The extract was
filtered using Whatman filter paper and stored at 4oC for analysis.

2.2. Synthesis of Zinc oxide nanoparticles

0.1M of 50ml precursor solution was taken and the extract was added drop by drop using a pipette till a cloudy
precipate formation was achieved under constant stirring at 80oC.The pH was maintained at 5 during the reaction.
The reaction mixture was allowed to cool and washed with water and ethanol using ultra centrifuge technique. The
precipitate was first dried in oven at 60oC and calcined in furnace at a temperature of 400oC for 30 minutes. The
white powder obtained was stored in storage vials for further characterizations.

Fig.1. Graphical representation of synthesis of ZnO nanoparticles

2.3. Measurements

The UV-vis absorption measurements were recorded using spectrophotometer (T90, PG Instruments) in the range
of 200-900 nm. Fourier transform infrared spectra (FTIR) of the extract and the zinc oxide particles were measured
using Perkin Elmer spectrometer in the range 4000-450 cm-1.Photoluminescence(PL) measurement was carried out
16474 Ramanarayanan et al./ Materials Today: Proceedings 5 (2018) 16472–16477

using Perkin Elmer fluorescence spectrometer (LS 55) in the range 350 -650 nm. Nanoparticle size analysis using
Dynamic Light scattering(DLS ) measurements was done using particle size analyzer (Nano-S90,Malvern
instruments).X-ray diffraction data was recorded by using Cu-Kα radiation(1.5406Aᵒ) and morphology observed
through field emission electron microscope(FE-SEM).The photo-electrochemical properties were measured using
computer controlled electrochemical interface(SP 150,Biologic) under visible light illumination.

3. Results and Discussion

3.1. UV-Vis absorption spectrum

Fig.2 shows the UV-Vis absorption spectra of ZnO nanopartiles with the characteristic peak at 372 nm. From the
absorption peak the band gap energy was found using the formula E= hc/λ in Joules ; 1.24*10-6/λ (nm) in eV
Where h is the plancks constant,c is the velocity of light and λ is the wavelength of the absorption peak.
The band gap calculated using the above equation is 3.3 eV.

Fig.2 ZnO nanoparticles (a) UV-Vis absorption spectrum (b) Photoluminescence (PL) spectrum

3.2. Photoluminescence (PL) spectrum

The PL spectrum showing emission of ZnO nanoparticles is shown in Fig.2 (b).The emission spectra shows a
sharp band in UV region and slightly broad peaks in the visible region. The visible emission could be due to defect
emission arising from surface related defects (dangling bonds, hydroxyl groups), extrinsic impurities, intrinsic
defects like oxygen vacancy, zinc vacancy etc. Though visible emission is undesirable for near UV-emitting devices,
defect emission shows great promise in futuristic applications like sensing, catalysis and biological applications [8].
Further the visible emission hints that the particle is in nanoregime as bulk ZnO has a sharp UV emission and
relative intensity of visible emission decreases with increase in particle size.

3.3. X-ray diffraction analysis(XRD)

The XRD pattern of biosynthesized ZnO nanoparticles are shown in Fig.3.The diffraction pattern of the sample
are in agreement with the standard X-ray diffraction peaks (JCPDS-89-0510) confirming that the synthesized
material is ZnO of hexagonal wurtzite phase. The XRD peaks at 31.46, 34, 36, 47, 56.3, 62.5, 67.6 theta values
correspond to (100), (002), (101), (102), (110), (103), (112) reflections respectively.
 Ramanarayanan et al. / Materials Today: Proceedings 5 (2018) 16472–16477 16475

Fig.3 XRD spectra of the synthesized ZnO nanoparticles

3.4. Fourier Transform Infrared (FTIR) Analysis

The FTIR spectra of bilimbi extract and ZnO nanoparticles have been shown in Fig.4.The absorption bands
of the extract at 3416 and 2912 cm-1 represent O-H and C-H stretching vibration of polyols. The peak located at
1646 cm-1 represents C=O streching vibration of tertiary amides [9]. The stretching vibrations at 1073 and 668 cm-1
correspond to C-N stretching and N-H wagging of amines respectively .These bands indicate the presence of various
phytochemical compounds present in bilimbi fruit. The green synthesized ZnO nanoparticles show absorption bands
at 3449, 1636, 1052,671 and 486 cm-1 respectively. The band at 486 confirms the stretching vibrations of zinc oxide
nanoparticles. The shift in FTIR spectra after formation of nanoparticles clearly indicate the role of biomolecules in
the bilimbi extract as reducing and capping agents for ZnO nanoparticle synthesis.

Fig.4 FTIR spectra of bilimbi and ZnO nanoparticles

3.5. Scanning Electron Microscope(SEM) and Dynamic Light Scattering(DLS) analysis

SEM analysis of synthesized nanoparticles is depicted in Fig.5 (a). The nanoparticles show spherical morphology
with size around 37.5 nm. The particles are well distributed showing aggregation due to large surface energy. The
distribution and hydrodynamic radius of the ZnO nanoparticles was analysed using DLS measurement shown in
Fig.5 (b).The particles show narrow size distribution which is desirable for any nanoparticle synthesis .The average
hydrodynamic radius size is around 70 nm which could be due to aggregation of individual particles.
16476 Ramanarayanan et al./ Materials Today: Proceedings 5 (2018) 16472–16477

Fig.5 ZnO nanoparticles (a) SEM image (b) DLS particles size distribution

3.6. Photoelectrochemical studies

To understand light driven photoelectrochemical properties Linear Sweep Voltammetry(LSV) and

Electrochemical Impedence Study(EIS) were conducted. The ZnO samples on F.T.O was treated as working
electrode, platinum wire as counter electrode and Ag/AgCl as reference electrode in a cell containing 0.2 M Na2SO4
as electrolyte. The Linear sweep voltammetry(LSV) was conducted in the potential range 1.4 to 0 V at a scan rate of
100 mv/sec. The increase in photocurrent density of the electrodes with increase in positive bias suggests the n type
nature of the electrode material. Also the increase in photocurrent with illumination shows the photogeneration and
conduction of carriers as shown in Fig.6 (a).The EIS measurements are conducted to study the charge transfer
process of photoanode-electrolyte surface in the frequency range of 1mHz to 1MHz as shown in Fig.6 (b).The
reduction in arc diameter in light in the EIS-Nyquist plot indicates efficient charge transfer at the electrode-
electrolyte surface under visible light illumination [10]. Thus the EIS data supports the data obtained from LSV
curves that on illumination the Zinc oxide electrode shows better current hence lesser impedence as compared to
dark conditions showing photoelectrode property.Hence the visible light harvesting efficiency of ZnO photoanode
could be exploited for use in photoelectrochemical cells in future.

` Fig.6 Photoelectrochemical study of ZnO nanoparticles (a) LSVcurves (b) Nyquist Plot
 Ramanarayanan et al. / Materials Today: Proceedings 5 (2018) 16472–16477 16477

4. Conclusion

ZnO nanoparticles were synthesized through green synthesis by using fruit extract of Averrhoa bilimbi in this
report. The size, shape and structure of the prepared nanoparticles were confirmed through SEM, DLS and XRD
measurements. The optical properties associated with the ZnO nanoparticles were obtained from UV-Vis and PL
spectroscopy. The biomolecules involved in this reduction of ZnO were confirmed through FTIR spectra. The
phtoelectrochemical properties investigated though LSV curves and EIS measurements show that the obtained ZnO
nanoparticles show good photoelectrode characteristics for solar cell applications.

Acknowledgements

The authors would like to acknowledge University Grants Commission (UGC) for teacher fellowship under FDP
scheme and Council of Scientific and Industrial Research (CSIR) India for their research fellowships.

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