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Materials Today: Proceedings 19 (2019) 1541–1546 www.materialstoday.com/proceedings

ICCSE 2018

From Waste Mango Kernel into High Surface Area Activated

Carbon
Jeyashelly Andas*, Norsoleha Wazil
Faculty of Applied Sciences, Universiti Teknologi MARA, 02600 Perlis, Malaysia

Abstract

Series of low cost activated carbon (AC) were successfully synthesized from chemical activation of mango kernel (MK) via three
chemical activators; ZnCl2, H3PO4 and KOH at 1:1 impregnation ratio of MK: Activator, activation temperature of 500 °C and
impregnation time of 30 min. The resultant ACs were characterized using Fourier Transform Infrared Spectroscopy (FTIR),
CHNS/O analyzer, Na2S2O3 volumetric method and Scanning Electron Microscope (SEM). FTIR analysis of MK verified the
presence of many functional groups resembling the lignocellulosic material and the absence of certain functional groups in the
synthesized ACs indicated the removal of volatile compounds during the activation process. CHNS/O analysis confirmed the
increase in Carbon % for all the prepared ACs. For example: 57.15 %, 53.63 %, 72.19 % for ZnCl2-AC, H3PO4-AC and KOH-
AC respectively, compared to the raw MK which registered only 43.18 %. Iodine Number (IN) was found to increase in a trend
as; ZnCl2-AC (1453.97 mgg-1) > H3PO4-AC (1299.30 mgg-1) > KOH-AC (1209.08 mgg-1). However, the yield percentage was
maximum for H3PO4-AC (47.3 %) followed by ZnCl2-AC (45.7 %) and KOH-AC (8.4 %). In addition, no pores were observed
for raw MK through the SEM analysis. However, SEM studies showed well-formation of porous structure for the synthesized
ACs which suggested the role of activating agents during carbonization. This study proves the successful conversion of waste
biomass into high quality ACs and to conclude, ZnCl2 was chosen as the most suitable activator to synthesize AC from MK due
to its enhanced textural characteristics and moderate yield percentage compared to other activators.

© 2019 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of the scientific committee of the International Conference on Chemical Sciences and
Engineering: Advance and New Materials, ICCSE 2018.

Keywords: Activated carbon; Activation; Mango kernel; Iodine Number; Porous

* Corresponding author. Tel.: +6049882569; fax: +6049882026

E-mail address: drshan@gmail.com

2214-7853 © 2019 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of the scientific committee of the International Conference on Chemical Sciences and
Engineering: Advance and New Materials, ICCSE 2018.
1542 J. Andas and N. Wazil / Materials Today: Proceedings 19 (2019) 1541–1546

1. Introduction

In recent years, activated carbon (AC) has received global recognition as one of the most important types of
industrial carbon materials owing to its extensive applications in medical, adsorbent, wastewater purification,
semiconductor and water filter [1]. To meet the growing demand of AC, carbonaceous materials such as coal, lignite
and peat have been widely employed as the raw materials. Nevertheless, they are expensive and AC synthesized from
these precursors showed a negative impact to the environment and food security. Therefore, exploring green precursors
for the fabrication of AC is urgently required. To note, various agricultural wastes, such as acorn shell [2], peach stone
shell [3], Langsat empty fruit bunch [4] and jackfruit peel waste [5] have emerged as the alternative precursors.
However, so far, no known studies were reported on the use of mango kernel (MK) in the production of AC.
Mango, a well-known tropical fruit has a pleasant taste, aroma and high nutritional value. Statistically, world
production of mango for the year 2005 is estimated to reach 480,000 metric tonne and India was reported as the
largest producer followed by China, Kenya and Thailand [6]. Based on its chemical composition, it is regarded as
the king of fruits. Each part of a mango tree, such as its leaves, flowers, fruit, pulp, and kernel contains essential
nutrients that is beneficial.
To synthesize AC, chemical activation is frequently opted as the best technique due to it offers high surface area
with enhanced porosity at a lower temperature and shorter activation period [7]. Generally, ZnCl2, H3PO4 and KOH
are the most common activators used as they yield AC of high surface area and good porosity [8]. For example, a
previous investigation by Elmouwahidi et al., [9] showed a high surface area of ~1626 m2g-1 for olive mill based AC
prepared using KOH activation. On the other hand, according to Duan et al. [10], H3PO4 appears to be inexpensive
activating agent which produces AC at temperature < 500 ºC. On contrary, ZnCl2 is reported to stabilize the volatile
matter and increases the percentage of carbon yield [11].
Thus, this work aims to produce a series of AC with high quality using ZnCl2, H3PO4 and KOH as the chemical
activating agents and the prepared samples were successfully characterized by several physico-chemical techniques.

2. Experimental Method

2.1. Reagents

Potassium hydroxide (KOH, HmBG), Zinc Chloride (ZnCl2, HmBG) and Phosphoric Acid (H3PO4, HmBG)
were used as the chemical activators. Other chemicals used were iodine pearl (I2, HmBG, 99%), sodium
thiosulphate-5-hydrate (Na2S203.5H2O, HmBG, 99%), sodium carbonate anhydrous (Na2CO3, HmBG, 99%),
potassium iodate (KIO3, HmBG, 99.8%), potassium iodide (KI, HmBG, 99.87), starch (C6H10O5, HmBG) and
hydrochloric acid (HCl, Fisher, 37%).

2.2. Preparation of Raw Material

Mango obtained from market in Perlis was cut and the kernel was separated. The kernel was washed with
copious amount of distilled water to remove contaminants. Then, it was dried under the sun for 2 days to remove
moisture and facilitate powdering. Next, the sample was oven dried at 80 °C for 12 h and subsequently was grinded
and sieved to the size of 212 µm and stored for further use.

2.3. Preparation of Activated Carbon (AC)

In brief, 10 g of the dried MK was impregnated (stirred at 210 rpm) in the 50 wt. % acid solutions containing 1:1
of MK: Chemical Activating Agent (w/w) at 25 °C for 2 h. Then, the mixture was heated in a furnace with the
following temperature profile: Room temperature to 500 °C at a heating rate of 3 °C min-1 for 30 min. The
synthesized ACs were designated as ZnCl2-AC, KOH-AC and H3PO4-AC. After the completion of carbonization
process, the char was crushed using a mortar and rinsed with 3 M HCl and successively washed with hot water until
it reaches pH 7. Later, the samples were oven dried at 80 °C for 12 h, sieved to a size of 150 µm and stored in a
sealed container for further characterization. The synthesized ACs was tested for Iodine Number (IN) and
percentage yield measurements according to Eq. (1) and (2) respectively.
 J. Andas and N. Wazil / Materials Today: Proceedings 19 (2019) 1541–1546 1543

IN =  A − ( DF )( B )( S )  / M (1)
Where,
A = Normality of I2
B = Normality of Na2S2O3
DF = Dilution
S = Volume of Na2S2O3
M = Mass of AC (g)

Yield % = (Wi / Wf ) × 100% (2)

Where,
Wi = Mass of product
Wf = Mass of precursor used

2.4. Characterization of Raw MK and ACs

The functional groups of the ACs and raw material were studied by Fourier Transform Infrared Spectrometer
(FTIR, Perkin Elmer) in the range of 400-4000 cm-1 using KBr pellet. CHNS/O Analyzer (Thermo Scientific flash
2000) based on ASTM 3172 was used to determine the composition of the ACs and raw material. A Scanning
Electron Microscope (SEM, JEOL JSM 6460LA) was employed to observe the morphology of the prepared ACs
and raw MK.

3. Results and Discussion

3.1. Surface Chemistry by FTIR Analysis

Fig. 1 displays the FTIR spectra of ZnCl2-AC, H3PO4-AC, KOH-AC and raw MK.

KOH-AC 867
3337
1583 1367
Transmittance (%)

ZnCl2-AC
3105 2166
1568 1198

H3PO4-AC 3585
3039 1567 1191 993
Raw
3277 2853 1612 1331
2918
1008
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm )
Fig. 1. FTIR spectra of the raw and synthesized ACs.

In general, all the samples showed almost similar IR patterns and functional groups. For example, broad bands
located around 3200-3500 cm-1 is attributed to the presence of hydroxyl group O-H [12]. The shoulder peak at
2918 cm-1, 2853 cm-1 and 1331 cm-1 for raw MK is attributed to the aliphatic -C-H bending [13]. The band at
1544 J. Andas and N. Wazil / Materials Today: Proceedings 19 (2019) 1541–1546

1612 cm-1 is assigned to C=C stretching vibration which indicates the presence of aromatic ring in lignin [14]. The
sharp peaks observed at 1008 cm-1 represents -C-O stretching in acids, alcohols, phenols, ether and ester [14].
However, disappearance of several peaks and reduction in the intensity of the peaks in the prepared ACs
compared to raw was observed and this clearly indicates the loss of volatile compounds during the activation
process. After carbonization, peak corresponding to -C-H stretching vibrations at ~ 2918 cm-1 were absent for all the
prepared ACs [15]. All the ACs showed a strong absorption peak at 1567-1583 cm-1 attributed to ring vibrations in
aromatic skeleton [16]. Meanwhile, the peak at 1191-1198 cm-1 observed in the IR spectra of H3PO4-AC and
ZnCl2-AC indicated -C-O stretching in alcohol, phenol, ether or ester compounds [17]. Surprisingly, similar to the
IR spectra of raw, KOH-AC also showed a shoulder band at 1367 cm-1, assigned to functional groups consisting of
oxygen such as C=O or-C-O stretching [17]. Similar IR pattern was reported by Kilic et al. [18] for AC prepared
from Euphorbia rigida via ZnCl2 and H3PO4 activation.
In comparison to ZnCl2-AC and KOH-AC, H3PO4-AC showed a peak at 993 cm-1 and 1191 cm-1 which could be
due to phosphorus containing groups and the stretching of P=O bond in phosphate ester, -O-C bond in P-O-C
linkage, or P=OOH bond [19]. As a conclusion, it was confirmed that the disappearance of several peaks in the
prepared ACs was resulted from carbonization and activation process.

3.2. Elemental Analysis

The composition of carbon, hydrogen, nitrogen, oxygen and sulphur element in raw MK and AC samples are
compared in Table 1.

Table 1. Ultimate analysis of raw material, H3PO4-AC, ZnCl2-AC and KOH-AC.

Element (% wt) C H N S O
Raw 43.18 5.58 1.95 1.82 47.47
H3PO4--AC 53.63 3.12 2.06 0.96 40.23
ZnCl2-AC 57.15 4.18 3.11 1.39 34.17
KOH-AC 72.19 2.34 2.73 0.53 22.21

On contrary to the raw MK, the carbon content in all the ACs were higher whereas hydrogen and oxygen showed
reduction. This is due to the release of volatiles during carbonization process that results in the elimination of the
non-carbon species and enrichment of carbon [20]. A similar trend was reported by Pelaez-Cid et al.[21]. Moreover,
these results confirmed the disappearance of organic functional groups after carbonization process. During
activation process, volatile compounds which mainly consists of H, O, and N experienced decomposition and
volatilized from deposit of raw MK and produces AC that is rich in carbon [15]. In addition, all the ACs exhibited a
lower sulphur content compared to the raw. Among H3PO4-AC, ZnCl2-AC, KOH-AC and raw MK, KOH-AC
showed the highest C and lowest O, H and S.

3.3. Percentage yield and Iodine Number (IN)

The bar graph in Fig. 2 compares the trend in yield percentage and IN of the synthesized ACs. Referring Fig. 2,
ZnCl2-AC possessed the largest IN of 1453.97 mgg-1 followed by H3PO4-AC (1299.30 mgg-1) and the least IN was
registered by KOH-AC (1209.08 mgg-1). Utilization of ZnCl2 as the chemical activating agent increases the
degradation of raw material and thereby, resulted in enhanced dehydration effect through carbonization [11].
However, it was worth to report that all the prepared ACs from MK were of high surface area compared to those
reported elsewhere [20, 21]. This undoubtedly proves that MK is a suitable precursor for the production of highly
carbonaceous and good quality of AC. The yield percentage was found to increase in a trend as given: H3PO4-AC
(47.3 %) > ZnCl2-AC (45.7 %) > KOH-AC (8.4 %). Higher surface area and textural properties of AC promises a
good performance in catalysis or absorption. Thus, to conclude, activation by ZnCl2 was found to be efficient due to
the production of high surface area AC and comparable yield percentage.
 J. Andas and N. Wazil / Materials Today: Proceedings 19 (2019) 1541–1546 1545

60 1500

50
1400

Yield percentages (%)

Iodine number (mgg )

-1
40
1300

30

1200
20

1100
10

0 1000
ZnCl2-AC H3PO4-AC KOH-AC
Activated carbon
Fig. 2. Yield percentage and Iodine Number registered for the ACs.

3.4. SEM observation

The porous structure and external surface of MK and ACs were examined by SEM and the images are shown in
Fig. 3.

a b

c d

Fig. 3. SEM micrographs of (a) raw mango kernel; (b) H3PO4-AC; (c) ZnCl2-AC and (d) KOH-AC at x2400.
1546 J. Andas and N. Wazil / Materials Today: Proceedings 19 (2019) 1541–1546

Referring Fig. 3(a), some occasional cracks with no pore formation was observed on the surface of the precursor.
On contrary, all the ACs samples showed good porosity, however, H3PO4-AC and ZnCl2-AC exhibited different
sizes of pores. Yet, ZnCl2-AC (Fig. 3(c)) showed slightly reduced number of holes compared to that observed for
H3PO4-AC (Fig. 3(b)).
As can be noticed in Fig. 3(d), upon impregnation with KOH, well-developed and small pores with enhanced
porosity were clearly observed on the surface of the AC. Diffusion of KOH molecules into the pores might have
enhanced the KOH–carbon reactions, which thereby increases the pores in the AC [22]. Different activating agents
produces various sizes of pores and selection of appropriate activator promises a good and well porosity. Thus, to
conclude, high porosity was greatly enhanced in the presence of KOH.

4. Conclusion

Good quality of ACs was produced from cheap waste mango kernel via chemical activation using ZnCl2, H3PO4
and KOH as the dehydrating agents for only 30 min of activation time and 500 ºC of impregnation temperature. The
prepared ACs were subjected for Iodine Number and yield percentage which ranged from 1209.08 - 1453.97 mgg-1
and 8.4 - 47.3 % respectively. Despite KOH produced great porosity as observed through SEM studies, however,
under the studied experimental condition, ZnCl2 was chosen as the best activating agent due to the production of
high surface area AC with good yield percentage. Few functional groups were absent in the IR spectra of ACs
compared to the raw material which confirms the removal of volatile matter during the activation process.
Undeniably, this research introduces a facile route to prepare AC with good properties and low sulphur content as
evidenced through CHNSO analysis.

Acknowledgements

J. Andas gratefully acknowledged Universiti Teknologi MARA for providing the CHNSO analysis and chemicals
required for this research.

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