Green synthesis of ZnO nanoparticles via

complex formation by using Curcuma longa

extract
Cite as: AIP Conference Proceedings 1710, 030027 (2016); https://doi.org/10.1063/1.4941493
Published Online: 09 February 2016

Is Fatimah, Septian P. Yudha, and Nur Afisa Lintang Mutiara

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AIP Conference Proceedings 1710, 030027 (2016); https://doi.org/10.1063/1.4941493 1710, 030027

© 2016 AIP Publishing LLC.

 Green Synthesis of ZnO Nanoparticles via Complex
Formation by using Curcuma Longa Extract

Is Fatimaha), Septian P. Yudha, Nur Afisa Lintang Mutiara

Chemistry Department, Islamic University of Indonesia

Kampus Terpadu UII, Jl. Kaliurang Km 14, Sleman, Yogyakarta
a)
Corresponding author: isfatimah@uii.ac.id
Abstract. Synthesis of ZnO nanoparticles(NPs) were conducted via Zn(II) complex formation by using Curcuma
longa extract as template. Curcuma longa extract has the ability to form zinc ions complex with curcumin as ligating
agent. Study on synthesis was conducted by monitoring thermal degradation of the material. Successful formation of
zinc oxide nanoparticles was confirmed by employing x-ray diffraction, surface area analysis and transmission
electron microscopy(TEM) studies. From the XRD analysis it is denoted that ZnO in hexagonal wurtzite phase was
formed and particle size was varied as varied temperature. The data are also confirmed by TEM analysis which
shows the particle size at the range 20-80nm. The NPs exhibited excelent photocatalytic activity for methylene blue
degradation and also significant antibacterial activity for Eschericia coli. The activity in methylene blue degradation
was also confirmed from fast chemical oxygen demand (COD) reduction.
Keywords: ZnO, nanoparticle, Curcuma longa, photocatalysis

INTRODUCTION

Nanoparticles synthesis is one of emerging and widely developed technology in nantechnology. Synthesis
of nanoparticles have recently attracted considerable attention towards scientific concern because of their novel
properties and potential technological applications; one of these is in the field of catalysis, solar cell, cosmetic
and health and also optoelectronics devices. For catalysis especially photocatalysis, ZnO is choosen beside of
TiO2 due to its wide band gap energy (3.37eV)[1]. Many papers reported novel routes to prepare ZnO
nanoparticles with the goal of high activity in photocatalysis mechanism. Such nanostructure of ZnO have been
reported such as nanorods, nanowires, nanocombs, nanoflowers, nanobridges, etc. which are related to their
characteristic application. However, low cost process in ZnO synthesis is an important thing for more economist
materials. Nanoparticles formation via zinc complexes formation from natural complexing agent are selected
route for this. Several plants extracts such as Camelia sinensis, Abrus precatorius, Aeromonas hydrophila have
been reported in the biosynthesis of ZnO[2]–[5]. The formation of ZnO nanoparticles having high performance
as photocatalyst is also the main objective in this work. Considering the succed of ZnO nanoparticle synthesis
via Zn-Curcumin complex formation, this research studied the similar synthesis by using Curcuma longa
extract. This study attempts to take advantage of the more economist value of Curcuma longa extract compare
to curcumin as single compound so the development of the preparation procedure for industry will be more
compatible. The basic idea of the nanoparticle formation was came from the chemical interaction between
curcumin structure with zinc metal ions creating the chelating structure. During the calcination, the huge
complex structure will leads into the cleavage of Zn-curcumine to form more individual nano ZnO. [6]. Refer to
some studies revealed that temperature of calcination affect to the transformation of ZnO, the effect of
calcination temperature on the chrystal formation and also photocatalytic activity were investigated in this
study[1][7]. Photodegradation of methylene blue (MB) was choosen as reaction model.

MATERIALS AND METHOD

For the synthesis of ZnO nanoparticles all chemical reagents used in the experiment were of analytical
grade [with 99% purity] without further purification. Zinc acetate dihydrate [Zn(CH3COO)2·2H2O] (Aldrich),

6th Nanoscience and Nanotechnology Symposium (NNS2015)

AIP Conf. Proc. 1710, 030027-1–030027-7; doi: 10.1063/1.4941493
© 2016 AIP Publishing LLC 978-0-7354-1357-3/$30.00

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Acetic acid and isopropanol(Merck-Millipore) were involved in the reaction as precursor material. Curcuma
longa extract used for synthesis was obtained from local market.
The complex of zinc-curcumin [Zn(OH)(curc)] was prepared by adopting previously reported method[6],
[8]. An ethanolic mixture solution of zinc acetate and curcumin in a 1:2 mol ratio
was refluxed for 1 h. For the calculation, the content of curcumin in Curcuma longa extract is about 80% wt.
The resulting solution product was filtered and washed several times by de-ionized water, dried in oven for 24 h
at 80oC. The solid sample obtained from these steps were then calcined at varied temperature 400, 500, 600 and
700oC. Samples obtained from varied temperature were then assigned as ZnO-400, ZnO-500, ZnO-600 and
ZnO-700 respectively. In order to ensure the thermal transformation during calcination differential thermal
analysis-thermal gravimetric analysis (DTA-TGA) Perkin Elmer was utilized. X-ray diffraction (XRD)
analysis was also performed for chrystal size analysis using Philips 6000 instrument. The JEOL JEM 1400
Transmission Electron Microscopy (TEM) was also used for nanoparticle profile of obtained sample.
Photocatalytic activity of the ZnO nanocomposites was measured by photodegradation of methylene blue
(MB) as a model dye. Photocatalytic test was engaged in photocatalytic reactor with schematic diagram
presented in Figure 1. For each photocatalytic test, the initial concentration and volume of MB are 10−5 M and 1
L with the presence of H2O2 10-6M. The content of photocatalyst in 500mL MB solution was 0.2g. The
degradation rate was measured by wavelength scan profile from UV–Vis spectrophotometer analysis. In order
to proof the degradation, high performance liquid chromatography (HPLC) analysis to treated solution and
chemical oxygen demand (COD) analysis was also determined. Photocatalytic test was also examined in E.coli
disinfection. An E.coli culture solution (500mL) was added with 0.1g of ZnO nanoparticles followed by stirring
under UV illumination. Amount of E.coli in the treated solution was analyzed by Most Probable Number (MPN)
method with the counting process using Scan 500 instrument. As control, untreated solution and treated solution
without UV illumination was used.

FIGURE 1. Photoreactor Set up

DISCUSSION

The profile of the complex of zinc-curcumin [Zn(OH)(curc)] thermal transformation by DTA-TGA

identification resulted the thermogram in Figure 2. From thermal analysis during the range of room temperature
to 600oC it is revealed some thermal degradation of the complex during heating. The complex looses about 11%
of its weight until the temperature of 200oC attributed to decomposition of H2O as moisture, and then around
50% weight loss of its total at around 300oC. The weight loss was gradually increased at the range of 300-
600oC. An exothermic peak of DTA profile at 300-350oC correspond to the transformation of Zn-complex to
wurtzite. Furthermore a characteristic thermal transformation occurred at 450oC in which double transformation
was identified. This is probably due to thermal transformation of ZnO from wurtzite phase to cubic phase. This
phase change is also identified by significant change in mass loss.

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 FIGURE 2. DTA-TGA Profile of [Zn(OH)(curc)] thermal transformation

FIGURE 3. XRD pattern of (a) ZnO-700 (b) ZnO-600 (c) ZnO-500 (d) ZnO-400.

In order to ensure the phase change during thermal treatment XRD analysis is conducted. Difractogram in
Figure 3 showed the different pattern in each temperature calcination variation. Calcination at 400oC showed
the diffraction peaks located at 31.84◦, 34.52◦, 36.33◦, 47.63◦, 56.71◦, 62.96◦, 68.13◦, and 69.18◦ have been
keenly indexed as hexagonal wurtzite phase of ZnO. The difference come from the pattern of samples calcined
at other temperature (500,600 and 700oC) in that some reflections indicated ZnC structure are obtained at around
29o that is associated with the reflection at (101)*. The presence of carbon in the turmeric extract is possibly the
reason for the formation of ZnS structure[9].
Effect of temperature on the crystal size was measured by following Scherer formula:
0.89. 𝜆
𝑑=
𝛽. 𝑐𝑜𝑠𝜃

030027-3
with 0.89 is Scherer constant, λ is wavelength, β is the full width at half maximum (FWHM) and θ is reflection
angle. The calculated data is presented in Table 1.

TABLE 1. Particle size of Samples

Calcination temperature (oC) Particle size (nm)

400 80.5
500 32.9
600 35.2
700 37.2

From Table 1, it is clear that as the calcination temperature of[Zn(OH)(curc)] affect the particle size
explained that nano ZnO with same crystal type but different particle size can be obtained by varying the
calcination temperature. At 400 oC the formation of particles give the higher size compared to other samples. It
is probably caused by the incomplete thermal formation at lower temperature. The formation of chrystal going
better at 500oC but then after increased to 700oC there was microstrain broadening occurred producing bigger
particle size. From the intensity of (101) reflections data, it is also noted that sample calcined at 500oC give
better chrystallinity associated with the uniform or homogeneous d-spacing of the particles. The formation of
particles in nanoscale is proofen by TEM analysis of ZnO obtained with the calcination temperature of
400oC(Figure 4). The surface profile revealed the relative heterogeneous particles with the size of 20-80nm. The
profile exhibits the random distribution of particle size and the biggest size (80nm) data is coincise with
calculation from XRD. However from the profile it is noted that particles in smaller size are also contained.

FIGURE 4. TEM profile of ZnO-400

Particle sizes of ZnO nanoparticles are theoretically related to photocatalytic activity. The kinetics of
methylene blue photodegradation is presented by kinetic curve in Figure 5. In general the addition of
photocatalysts samples increase the MB degradation rate compared to no catalyzed treatment. Calculated initial
rate data of the degradations demonstrated that the sample calcined at 500oC was founded as the highest active
photocatalyst from the highest initial rate compared to other samples. It is concluded that the particle size of the
photocatalyst is lineary correlated with the photoactivity in which the photocatalyst having highest activity is the
smallest size[10].

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 FIGURE 5. Kinetic curve of MB degradation over varied photocatalyst

The proof of MB degradation instead of adsorption during the treatment is shown by COD reduction
profile of treated solution over ZnO-500 photocatalyst (Table 2). After treatment for 30 mins the treated solution
give non detected COD value as result of MB destruction. HPLC analysis and also UV-Visible spectra (Figure 6
and Figure 7) also indicate the destruction of MB compounds.

TABLE 2. COD reduction profile of treated solution over ZnO-500 photocatalyst

Time(minutes) COD (mg/L)

0 253
10 34
20 30
30 n.d
60 n.d
120 n.d

FIGURE 6. UV-Visible spectra of initial MB solution and treated solution at varied time

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 FIGURE 7. HPLC profile of (a) initial MB solution (b) treated solution for 30 mins (c) treated solution for 120 mins.

Another photocatalytic test of ZnO-500 sample was performed in E.coli disinfection. Figure 8 exhibits the
difference between initial E.coli culture solution and 30 minutes treated solution with the addition of ZnO-500
and stirring for 30 mins under UV solution. It is noted that the disinfection is successfully achieved since there
is no E.coli cultured in the treated solution. It is also noted that the disinfection occurred under the UV
illumination as expressed by the presence of E.coli with the addition of ZnO-500 without UV.

030027-6
 FIGURE 8. Profile of E.coli culture (a) initial solution (b) + ZnO-500 without UV (c) + ZnO-500 with UV

CONCLUSION

In summary, ZnO nanoparticles were successfully prepared by a biosynthesis using Curcuma longa extract.
Calcination temperature influence on particle size of the nanoparticles and it is found that the optimum
calcination temperature is 500oC. Nanoparticles expressed the photocatalytic activity in MB solution as well as
in E.coli disinfection. UV-Visible spectrophotometric and GC analysis of the treated sample (Figure 5) are also
indicate the change of the composition of solution from the treatment.

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