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The extraction and absorption study of natural dye from Areca catechu for dye
sensitized solar cell application

Conference Paper in AIP Conference Proceedings · May 2017


DOI: 10.1063/1.4982191

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The extraction and absorption study of natural dye from Areca catechu for dye
sensitized solar cell application
Asmaa Soheil Najm, Abu Bakar Mohamad, and Norasikin A. Ludin

Citation: AIP Conference Proceedings 1838, 020019 (2017); doi: 10.1063/1.4982191


View online: http://dx.doi.org/10.1063/1.4982191
View Table of Contents: http://aip.scitation.org/toc/apc/1838/1
Published by the American Institute of Physics
The Extraction and Absorption Study of Natural Dye from
Areca catechu for Dye Sensitized Solar Cell Application
Asmaa Soheil Najm1, a), Abu Bakar Mohamad2, b) and Norasikin A. Ludin3, c)
1
Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment,
Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia
2
Fuel Cell Institute, Universiti Kebangsaan Malaysia, UKM Bangi, 43600 Selangor, Malaysia
3
Solar Energy Research Institute (SERI), Universiti Kebangsaan Malaysia,
43600 UKM Bangi, Selangor, Malaysia
c)
Corresponding author: sheekeen@ukm.edu.my
a)
asmaa.soheil@yahoo.com
b)
drab@vlsi.eng.ukm.my

Abstract. Natural dye from local plant has a potential to replace the synthetic dye due to the lower environmental impact
and simple processing method. This study focus on the properties of natural dye (Betalain) from Areca catechu, extracted
using different solvents, namely hexane, ethanol, acetonitrile, and methanol. Different extracting solvent were used to
observe the absorption spectra by using UV-Vis absorption spectroscopy. Fourier transforms infrared (FTIR) were used
to characterize the dye’s active components at (4000 – 650) cm-1. From the FTIR result, the CO=OH which corresponds
to the carboxylic group in betalain dye is observed. Hexane was appeared to be the best solvents according to the highest
absorbance obtained from betalain. The optimum pH and temperature for extraction were also identified at pH 4.5 and
65 oC. At these conditions, the absorbance was the highest.

INTRODUCTION

In 1991, Grätzel and O`Regan discovered the use of dye sensitized solar cell (DSSC) as a promising candidate
for PV technology [1]. In DSSC, numerous synthetic and organic dyes have been utilized as sensitizers, the dye as a
sensitizer plays a key role in absorbing sunlight and transforming solar energy into electric energy [2]. The
absorption spectrum of the dye and the anchorage of the dye to the surface of TiO2 are important parameters
determining the efficiency of the cell [3].
Generally, transition metal coordination compounds (ruthenium polypyridyl complexes) are used as the effective
sensitizers, due to their intense charge-transfer absorption in the whole visible range. However, ruthenium
polypyridyl complexes contain a heavy metal, which is undesirable from point of view of the environmental aspects
[1]. Moreover, the process to synthesize the complexes is complicated and costly [4]. Alternatively, natural dyes can
be used for the same purpose with an acceptable efficiency [5]. The advantages of natural dyes include their
availability and low cost [6].
Thus, this study aims to identify a new natural dye from the Malaysian local species and investigate the
possibility of its potential as natural sensitizer with simple method extraction. Areca catechu fruit is also known to
have betalain pigment and has an active carboxyl group. This paper highlights optimum extraction method to
produce the natural dye based on the various solvents, pH and temperature. The fruit extract was characterized by
UV-Vis spectrophotometer to observe on the absorption spectra [7]. FTIR spectral analysis was used to determine
the functional group in the nature dye [8]. The best absorbance with the optimum properties such as the type of
solvent, pH and temperature was also identified.

The 1st UKM-ISESCO-COMSATS International Workshop on Nanotechnology for Young Scientists (IWYS2016)
AIP Conf. Proc. 1838, 020019-1–020019-7; doi: 10.1063/1.4982191
Published by AIP Publishing. 978-0-7354-1508-9/$30.00

020019-1
MATERIALS AND METHODS

Sample preparation
Betalain dye was extracted and purified from Pinang Fruit [9], as shown in Fig. 1. This dye was selected based
on the need to have a dye that was affordable and that doesn’t have any toxicity when handled [10]. Also, most
inorganic dyes used as sensitizers are costly and current work being done on organic dyes shows their potential to
create efficient organic photovoltaic [11].

FIGURE 1. Pinang Fruit

The fresh fruit was obtained from Pinang Malaysia. The kind of Pinang fruit used in this research is from big
orange species. The fresh fruit was washed repeatedly with water to remove dust and take off their crusts, and was
allowed to dry first at room temperature in a shade and then in an oven - dried at 40°C for 24 hours, until the crust
became crisp. After being dried, the crusts were crushed in a grinder (Mulry function disintegrator SY - 04) [12] to
make them into powder (Fig. 2).

FIGURE 2. Powder of betalain Dye

Solvent Test
2 g of the powder was then put into 30 mL of four different solvents, Fig. 3 namely (methanol, ethanol,
acetonitrile, and hexane), and after that the extracted solution was put in a shaker (Ambient Shaker Incubators, SKU:
SI-100), for 24 hours [13]. The extract solution was then filtered using filter paper (NICE, 12.5 cm, 102 Qualitative)
[14]. The absorption spectra of the dye extracts were measured using UV-Vis spectrophotometer. The structures of
the isolated dyes were confirmed using Fourier transmission infrared (FTIR).

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FIGURE 3. Betalain dye in various solvent

PH Test
The extracted solution of betalain dye was divided into four flasks different pH [15]. First sample of dye extract,
pH of 7.5 was recorded. The second, the extracted dye had a pH of 2 and the pH of the third was adjusted to 4.5 by
adding known drops of 37 % HCl (0.1 M) to solution, and the last one after adding several drops of NaOH (0.1 M)
had a pH value 12. All solutions mentioned were kept in ambient temperature without exposing to direct sunlight,
for 24 hr. After that extracted solutions were ready for testing.

Temperature Test
2 g of dried sample was weighed and transferred into 50 mL conical flask of solvent (that consider the best
solvent for extraction natural dye). The effect of temperature on the betalain dye was examined at temperatures of
35, 45, 55, 65 and 75Co. Extraction was performed using stirrer Heater (Model hot plate magnetic stirrer 34532).The
static time for the extraction to be completed was 20 minutes at atmospheric pressure [16]. All extracts were filtered
to be ready for UV-Visible spectroscopic analysis.

Characterization
The natural dye was measured using UV – VIS spectrophotometer (Perkin-Elmer, Lambda 35) [17], the
wavelength used was from 300 nm to 600 nm. The Fourier Transform Infrared Spectroscopy (FTIR) was recorded
using the Nicolet 6700, with Omnic 7.2 software, with mid-infrared light (4000 – 650) cm-1 is energetic enough to
excite molecular vibrations to higher energy states.

RESULTS AND DISCUSSION

Effect of Solvent in Extraction


The absorption spectra of extracts dye from Areca catechu using different solvents were compared as shown in
Fig. 4. Betalain Dye extract indicates that wide absorption range from 300 nm to 600 nm. The absorbance of the
dye shows a broad range of wavelength frequency between 362 nm to 525 nm, which is located within visible range,
and with four main peaks located at 444, 445,446 and 447 nm.

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FIGURE 4. UV-Vis absorption spectra of different solvents for betalain dye

The solvents used to extracted betalain dye were similar to the previous study, by Al-Alwani, M.A., [12].
Extraction betalain using hexane showed the highest absorption peak at 445 nm, while C. fruticosa dyes extracted
from methanol exhibited strong absorption of the visible light. In contrast methanol was showed the lowest
absorbent peak for Areca catechu dye with 444 nm, while acetonitrile in C. fruticosa dye indicated as the lowest
absorbent solvent. The ability of extraction dyes for each solvent is depended on the chemical structure of dye and
the polarity.
The Fourier Transform Infra-Red spectra of betalain dye in different solvents are shown in Fig. 5. Each figure
explained how the solvent can express the characterization of functional group for natural dye.

FIGURE 5. FTIR Spectra of betalain dye extracted from different solvent

Betalain dye extracted from hexane displays sharp peaks at 2959.4, 2921.9, cm-1, that correspond to the presence
of carboxylic acids groups [18]. In addition, typical bands corresponding to C–H and O–H, groups are observed
within the respective regions: 1466.7, cm-1, 721.13 cm-1. In contrast, acetonitrile features a broad band within the
2253.9 cm-1 region that corresponds to the presence of C≡C groups. C=H stretches were also noted at 1441.01 cm-1.
The absorption peaks at 1034.93 cm-1 is assigned for C – O stretches. However acetonitrile show weak features,
thereby suggesting the lower amounts of O–H and C=O groups in the betalain dye.

020019-4
Ethanol and methanol were similar to the spectra reported by Kim, H., et al [19]. The absorption peaks at
2970.84 and 2942.73 cm-1 in ethanol and methanol is assigned to (–CH) bending modes. (C=C) stretching vibration
at 1655.76 cm-1 appear in ethanol and can be correlated with the stretching of aromatic in betalain dye. The presence
of the (C-O) group at 1041.18 cm-1 as in ethanol and 1019.31 cm-1 as in methanol, noted as a strong peak, which
observe the partial appearance of the betaxanthin pigment included in the structure of betalain dye which is the core
composition for natural dye in DSSC [20].

Effect of pH on Extraction
Figure 6 shows the UV–Vis optical absorption spectra of the betalain dye extracts at four different pH. The four
dyes extracts show absorption peaks centered between 384 nm to 532 nm in the UV-range, with maximum two
peaks at 443 nm and 470 nm for pH 2, 4.5, 7.5 and 12. The dye extracts at pH 2, 4.5 and 7.5 have about the same
absorption intensity in short wavelength range, with dye extract at a pH of 12 having the lowest intensity in this
range. Betalain are generally unstable; however, they are stable in slightly acidic environments (pH of 4–7) [22].
Therefore; the highest absorption intensity is observed in pH 4.5. It can be seen the drop rate of pH became
gradually slower while gradually approaching to more acidic environment [21].

FIGURE 6. UV-Vis absorption spectra of different pH for betalain dye

Effect of Temperature
The maximum absorbance of dye extracted at different temperature was measured by UV-Visible
spectrophotometer in a wavelength range of 300-600 nm as shown in Fig. 7. Betalain dye shows at temperature
65 °C the absorption peak is the highest compared to other temperature. It can be observe an increase in temperature
from 35°C to 65 °C increased the absorbance value due to the color intensity of the extract increased with increasing
extraction temperature. [23] When temperature increasing up to 75°C, the redness effect slightly decreasing, due to
at a higher temperature, water was able to extract a larger amount of less polar compound. Previous studies reported
that temperature considerably influenced the extraction and stability of natural pigments in the presence and absence
of light [24].

020019-5
FIGURE 7. UV-Vis absorption spectra of different Temperature for betalain dye

CONCLUSION
This study used plant species, which grow in Malaysia, for the extraction of betalain dye from it is crust. The
results show that betalain dye was soluble in different solvents (i.e., methanol, hexane, ethanol, and acetonitrile).
Ultraviolet-visible Spectrophotometry (UV-Vis) and Fourier transform infrared spectroscopy (FTIR) using to study
the characteristics of the extraction in different solvents, pH, and temperature. The results identified that hexane was
the best solvents to use for dye extraction. It was found also extracted solution showed high absorbent at pH 4.5 and
65 oC. Moreover, the high abundance of O–H and C=O functionalities in the betalain dye indicating the partial
appearance of carboxylic Acids. At these conditions the dye has a potential to be the sensitizer for DSSC.

ACKNOWLEDGEMENT
The authors are grateful for the Department of Chemical and Process Engineering, Faculty of Engineering and
Built Environment (FKAB) and Solar Energy Research Institute (SERI), Universiti Kebangsaan Malaysia. This
paper was presented at The 1ST UKM-ISESCO-COMSATS International Workshop on Nanotechnology for Young
Scientists (IWYS2016).

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