Effect of acidity on the energy level of curcumin dye extracted from Curcuma longa L.

Yuda Virgantara Agustia, Suyitno, Zainal Arifin, and Bayu Sutanto

Citation: AIP Conference Proceedings 1717, 040005 (2016); doi: 10.1063/1.4943448

View online: http://dx.doi.org/10.1063/1.4943448
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 Effect of Acidity on the Energy Level of Curcumin Dye
Extracted from Curcuma Longa L.
1,a) 1,b) 1,2,c)
Yuda Virgantara Agustia , Suyitno , Zainal Arifin Bayu Sutanto 1,d)
1
Department of Mechanical Engineering, Sebelas Maret University, Jl. Ir. Sutami 36 A, Surakarta, Indonesia
2
Department of Mechanical Engineering, Brawijaya University, Malang, Indonesia
a)
Corresponding author: yuda.mechanical.engineer@student.uns.ac.id
b)
suyitno@uns.ac.id
c)
zainal_a@uns.ac.id
d)
bayu.sutanto@student.uns.ac.id

Abstract. The purpose of this research is to investigate the effect of acidity on the energy level of curcumin dye. The
natural dye, curcumin, was synthesized from Curcuma longa L. using a simple extraction technique. The purification of
curcumin dye was conducted in a column of chromatography and its characteristics were studied. Next, the purified
curcumin dye was added by benzoic acids until various acidities of 3.0, 3.5, 4.0, 4.5, and 5.0. The absorbance spectra and
the functionality groups found in the dyes were detected by ultraviolet-visible spectroscopy and Fourier-transform
infrared spectroscopy, respectively. M eanwhile, the energy level of the dyes, E HOMO and ELUMO was measured by cyclic
voltammetry. The best energy level of curcumin dye was achieved at pH 3.5 where Ered = -0.37V, ELUMO= -4.28 eV, Eox
= 1.15V, EHOMO = -5.83 eV, and Eband gap = 1.55 eV. Therefore, the purified curcumin dye added by benzoic acid was
promising for sensitizing the dye-sensitized solar cells.

INTRODUCTION

Colors can be divided into two, namely dye and pigment. Dye has internal forces with colored substrate but
pigment does not have. The colors used in solar cells is dye because they should have internal force with
semiconductor [1]. Dye-sensitized solar cells (DSSCs) invented by Prof. Michael Gratzel in 1991 are very promising
and have attracted much attention as a replacement for traditional inorganic photovoltaic devices because of the low
cost and easy to fabricate. DSSCs consist of three main parts; i.e. semiconductor, dye adsorbed on to the surface of
semiconductor, and catalist deposited in between the two conduction glasses [2].
In DSSCs, the dye plays important roles to absorb the visible light and to inject the electrons. The common
sensitizer used in DSSCs is ruthenium-based synthetic compounds such as N719, N3, and black dye. To date, the
highest efficiency of DSSCs with TiO2 and ruthenium-based dyes has reached 10-11% [2]. However, the ruthenium-
based dyes have several drawbacks; i.e. environmentally unfriendly, complex manufacturing process, and relatively
expensive price. In contrast, the natural dyes are availability abundant in nature, renewable, simple manufacturing
process, and relatively low price [3].
Curcumin is one of natural dyes, which are abundant and traditionally used for drug in Indonesia as shown in Fig
1. Curcumin has the absorbance of visible light at a wavelength range from 425 to 500 nm that can increase the light
absorption of DSSC. It has a very good stability against heat. Moreover, it consists of functionality groups anchoring
with TiO semiconductor [4]. Curcumin is a component of the yellow-dye extracted from Turmeric plant. Curcumin
has two phenolic hydroxyl groups and two carbonyl groups in the middle, which can form keto -enol tautomerism.
Meanwhile, in the -enol form, curcumin can be easily degraded to the other two forms, namely cis - and trans-based
curcumin [5]. Unfortunately, the natural dyes have a short lifetime [6, 7] and an inappropriate energy level with
other components in DSSCs. Interestingly, the energy level of natural dyes represented by the highest occupied
molecular orbital (HOMO) and the lowest unoccupied molecular orb ital (LUMO) [8] may be tuned by adding the

Sustainable Energy and Advanced Materials

AIP Conf. Proc. 1717, 040005-1040005-5; doi: 10.1063/1.4943448
2016 AIP Publishing LLC 978-0-7354-1365-8/$30.00

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 benzoic acid [6]. Therefore, the aim of this study is to investigate the effect of acidity by adding the benzoic acid on
the energy levels of purified curcumin dye corresponding to the use of DSSCs.

FIGURE 1. Turmeric plant and the chemical structure of curcumin

METHODS

Materials

The materials used were Turmeric, ethanol 96%, silica gel 70-230 mesh ASTM, chloroform, and benzoic acid.

Synthesis of Curcumin Dye

Turmeric plants were dried until the moisture content was about 14%. Next, they were pulverized and screened
at 200 meshes. The turmeric powder was extracted by the method of maceration with ethanol. The ratio between
turmeric powder and ethanol is 1:7 g/ml. The process of maceration was conducted for 7 hours at a temperature of
65C. The solid residues and the liquid were separated using a rotary vacuum evaporator.
Next, the liquid extract was purified using a column of chromatography filled with silica gel as shown in Fig 2.
To separate the relatively pure curcumin and the other compounds, a mixture of chloroform and ethanol at a ratio of
95:5 was dripped into the chromatography column [5].
Furthermore, synthesizing the crude curcumin was performed by mixing the pure curcumin with ethanol until the
required concentration of 3 g/100 mL. Next, the benzoic acid was added to the mixture to obtain the appropriate
acidity, i.e. 5.0, 4.5, 4.0, 3.5, and 3.0.

Characterization

FIGURE 2. Scheme of chromatography column

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 The UVVisible spectroscopy (UV-1800, Rayleigh) was used to examine the light absorbance properties of the
dyes. The Fourier transform infrared spectroscopy (FTIR, Shimadzu) was implemented to conrm the presence of
the functional groups in the dyes. Meanwhile, the cyclic voltammetry (CV, Metrohm AG) was used to determine the
potential of reduction (Ered ) and oxidation (Eox) and the peak current of cathode (Ipc) and anodic (Ipa ) of the dyes. In
addition, the acidity of the dyes was measured by the pH meter (AD-110 Adwa).

RESULTS AND DISCUSSION

UV-Visible Spectra of Dyes

Figuew 3 shows the absorbance spectra of dyes. The absorbance peaks at a wavelength of 480 nm show the
existence of functionality group of curcumin. The addition of acidity from 3.0 to 5.0 has no significant effect on the
absorption spectra. There is no shift in the absorption spectra of curcumin dyes revealing that the optical properties
of curcumin dyes are almost the same.

3,5
3,0 Curcumin (as purified)
Curcumin pH 3.0
2,5
Curcumin pH 3.5
Absorbance

2,0 Curcumin pH 4.0

1,5 Curcumin pH 4.5
Curcumin pH 5.0
1,0
0,5
0,0
380 480 580 680 780
Wavelength (nm)
FIGURE 3. UV-visible absorption spectra of curcumin dyes

120
C-O
O-H

aromatic C-C and O-H

C=O
aromatic C-H

C-H
110
100
% Transmittance

90
80
Curcumin (as purified)
70
Curcumin pH 5.0
60 Curcumin pH 4.5
Curcumin pH 4.0
50 Curcumin pH 3.5
Curcumin pH 3.0
40
4000 3750 3500 3250 3000 2750 2500 2250 2000 1750 1500 1250 1000 750 500
Wavenumber (cm-1)
FIGURE 4. FT-IR spectra of curcumin dye

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 FT-IR Measurements

Figure 4 shows the FT-IR spectra of dyes. All dyes were identified as curcumin because they displayed sharp
peaks at wavenumbers of 1000-1250 cm-1 , 1250-1500 cm-1 , 1600-1750 cm-1 , and 3100-3600 cm-1 corresponding to
the presence of the C-O, C-C and O-H aromatic, C=O, and O-H groups, respectively. The existence of O-H groups
found in the curcumin dye and in the acidified curcumin -dye with benzoic acid might be easily bound to the surface
of TiO semiconductor. The bonding helps in excitation and transfer of electrons from the curcumin dye to the
conduction band of TiO in DSSCs. Therefore, a good contact (anchor) between the curcumin dyes and the TiO
semiconductors in DSSCs may be occurred to provide a fast and an efcient injection of electrons.

TABLE 1. Oxidation energy, reduction energy, HOM O, and LUM O measured by cyclic voltammetry.
Dyes Eox (V) Ered (V) EHOMOa (eV) ELUMOb (eV) EEnergy Gap c (eV)
Crude curcumin 1.15 0.30 -5.80 -4.95 0.85
Curcumin pH 5 1.06 -0.05 -5.71 -4.60 1.11
Curcumin pH 4.5 1.03 -0.10 -5.68 -4.55 1.13
Curcumin pH 4 1.12 -0.12 -5.77 -4.53 1.24
Curcumin pH 3.5 1.18 -0.37 -5.83 -4.28 1.55
Curcumin pH 3 1.28 -0.28 -5.93 -4.37 1.56

[ ]
[ ]
[ ]

Cyclic Voltammetry Measurement

-4,0 -4,28 -4,37

-4,5 -4,6 -4,55 -4,53
-4,5 -4,95
-5,0 LUMO (eV) HOMO (eV)
-5,8 -5,71 -5,68 -5,77
-5,5 -5,83 -5,93
E (eV)

-6,0
Curcumin (as purified)
TiO

Curcumin pH 3.0
Curcumin pH 4.0

Curcumin pH 3.5
Curcumin pH 5.0

Curcumin pH 4.5

-6,5
-7,0
-7,5
-7,5
-8,0
FIGURE 5. Energy levels of curcumin dye at various acidities

Figure 5 illustrates the energy levels of each dye. The highest occupied and the lowest unoccupied molecular
orbital, HOMO and LUMO, represent the ability to donate and to accept electrons, respectively. Therefore, the
higher the LUMO, the easier the dyes gains electrons from the HOMO state. The h ighest LUMO was produced in
the curcumin dye at pH of 3.5. The LUMO of the curcumin dye at pH of 3.5 was more positive than the Fermi level
of TiO. The different between the LUMO of sensitizers and that of TiO was suggested more than 0.2 eV to achieve
an efficient electron injection from the excited dye to the TiO semiconductor [9]. Moreover, acidifying curcumin

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 dyes until pH of 4.5 increased the HOMO level and consistent with the previous s tudy [10]. Therefore, acidification
of dye extract has shown improvement in the photocurrent conversion efficiency of DSSCs [10].
Meanwhile, the HOMO-LUMO energy gap reflects the chemical activity and the ultimate charge transfer
interface within the molecules [11]. Addition benzoic acid enhanced the HOMO-LUMO energy gap. However, the
curcumin dye at pH of 3.0 showed a decline in the energy gap because the solution has already saturated and formed
the white crystals.

CONCLUSIONS

Curcumin dyes were successfully synthesized and purified from Turmeric plants. The addition of benzoic acid in
purified curcumin dyes affected on the HOMO-LUMO energy gaps. The addition of acidity from 3.0 to 5.0 has no
significant effect on the absorption spectra of curcumin dyes. Meanwhile, the C-O, C-C, O-H aromatic, and C=O
groups were detected in curcumin dyes examined by Fourier transform infrared spectroscopy. Therefore, a good
contact (anchor) between the dyes and the semiconductors in DSSCs may be occurred to provide a fast and an
efcient injection of electrons. In addition, the best curcumin dye to be used in DSSCs synthesized by adding the
benzoic acid until pH of 3.5 where Ered = - 0.37 V, ELUMO = - 4.28 eV, Eox = 1.18 V, EHOMO = - 5.83 eV, and Eenergy gap
= 1.55 eV. The acidifying of purified curcumin dyes is very promising for sensitizing the DSSCs.

ACKNOWLEDGEMENT

The authors thank the Rector of Sebelas Maret University, LPDP (Indonesia Endowment Fund for Education)
No.PRJ-755/LPDP/2014 and PNBP UNS (Non-Tax Revenues of Sebelas Maret University)
No.624/UN27.11/PL/2015 for supporting the funding for doing the research.

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