Materials Chemistry and Physics 249 (2020) 123128

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Development of effective and sustainable adsorbent biomaterial from an

agricultural waste material: Cu(II) removal
Nilofar Asim a, *, Mohamad Hassan Amin b, Nurul Asma Samsudin c, Marzieh Badiei d,
Halim Razali a, Md Akhtaruzzaman a, Nowshad Amin c, Kamaruzzaman Sopian a
a
Solar Energy Research Institute, Universiti Kebangsaan Malaysia, 43600, Bangi, Selangor, Malaysia
b
School of Science, RMIT University, Melbourne, VIC, 3001, Australia
c
Institute of Sustainable Energy, Universiti Tenaga Nasional, 43000, Kajang, Selangor, Malaysia
d
Independent Researcher, Razavi 16, 91777-35843, Mashhad, Iran

H I G H L I G H T S G R A P H I C A L A B S T R A C T

� Detailed characterization of alkali

treated coconut coir (CC) samples was
performed.
� Optimized sample showed 27% and
30% improved water and moisture
absorbency.
� Treated CC with various water absor­
bency could utilize for different
applications.
� Treated CC shows almost five times
higher Cu (II) removal performance.

A R T I C L E I N F O A B S T R A C T

Keywords: Motivated by the significant scope which exists to generate value-added products from agricultural waste ma­
Coconut coir terials, in this work a comprehensive study was performed on the microstructure of alkali-treated coconut coir in
Alkali treatment order to evaluate its potential as an environmentally friendly absorbent. By investigating the influence of the
Biomaterial
alkali concentration, temperature and treatment time through a systematic Design of Experiments (DOE)
Heavy metal removal
approach, it was found that alkali-treated coconut coir possessed greatly improved water and moisture ab­
Agricultural waste treatment
sorption properties (27% and 30% increases, respectively, compared to those of untreated coconut coir). The
efficiency of heavy metal removal of treated coconut coir samples has been studied by investigating Cu (II)
removal performance of selected samples with higher water and moisture absorbency. The effect of contact time
and concentration of Cu (II) on the Cu (II) removal efficiency of samples have been investigated. The results show
almost five times higher Cu (II) removal performance for the treated sample compared to raw coconut coir under
optimized conditions. These findings highlight that the alkali treatment of biomaterials such as coconut coir can
be used to tailor their water-absorbency properties as well as their adsorption properties, providing facile and
effective adsorbent materials from readily available agricultural waste materials.

* Corresponding author.
E-mail addresses: nilofarasim@ukm.edu.my, asimnilofar@gmail.com (N. Asim).

https://doi.org/10.1016/j.matchemphys.2020.123128
Received 30 September 2019; Received in revised form 19 April 2020; Accepted 25 April 2020
Available online 30 April 2020
0254-0584/© 2020 Elsevier B.V. All rights reserved.
N. Asim et al. Materials Chemistry and Physics 249 (2020) 123128

1. Introduction (DOE) software was successfully used to evaluate the

Despite the large number of investigations and feasibility studies on
the utilization of different agricultural wastes as sources of energy and
materials, this research area needs more attention. Conducting different
characterizations of raw and treated waste materials could lead to
suitable applications for different waste materials. This tailoring could
optimize both the cost and technical performance of agricultural solid
waste as a resource [1]. Considering the high cost and environmental
impact of most of the commonly used desiccant materials and re­
searchers’ new focus on employing agricultural wastes as desiccant
materials [2–4], the authors conducted a detailed study of some plen­
tifully available local agricultural wastes [5]. The advantages of utilizing
agricultural solid wastes to reduce pollution while deriving economic
benefits [6] must be highlighted to encourage their application. Agri­
cultural waste is cellulose-based fibre. Modifications of a material’s
physical and chemical surface properties are well known to contribute to
the increase of its absorption ability. Chemical treatments are among the
most-used methods for surface treating agricultural fibres. The most
common chemical treatment methods are acid and alkali treatments [7].
Both can improve the absorption properties of treated samples by
increasing hydrogen bonding and porosity as well as by lignin removal
(i.e., introducing hydrophobicity) [5].
After previous work demonstrated that rice husk could be success­
fully utilised as a green desiccant material [5], the feasibility of forming
desiccants through the modification of another common agricultural
waste, coconut coir, was investigated. Coconut coir (CC) is a natural
fibre that is obtained from coconut husk, a waste biomass, which is a
readily available and cheap material produced in the coconut fibre in­
dustry. Its fibres are bound together by lignin, cellulose and hemicel­
lulose natural polymers [8] and are traditionally utilised in hanging
baskets because of its good water absorption and retention. Most recent
studies of coconut coir have been focused on its application in polymer
composites [9], as a binder [10–12], and in pollution removal such as
heavy metal removal [13–15]. In this study, Design of Experimental
structure-absorbency relationships in alkali treated coconut coir for the
first time. DOE software was employed to consider treatment factors and
to evaluate the water and moisture absorption of coconut coir treated
samples while considering their thermal stability to find the optimal
conditions for their application. After revealing promising results for dye
removal performance for treated coconut coir samples [16], in the next
attempt, the selected treated coconut coir samples with higher water and
moisture absorbency have been studied for their adsorption capacity in
heavy metal removal application using Cu solution as the case study.
2. Experimental
2.1. Sample preparation
Coconut coir was donated by Magic Soils Australia and used as
received after cutting it into small pieces (1 cm). As determined from a
literature review of alkali treatment, a concentration range of 1.6–4.3 M,
time of 5–60 min and temperature between 25 and 60 � C were consid­
ered to introduce to Design of Experimental software (DOE) version 7
(Stat-Ease cooperation, USA), response surface mode and central com­
posite design software, and the suggested treatment conditions were
employed for coconut coir treatment (Table 1). In this work, treated
coconut coir samples are denoted as X-Y-Z, where ‘X’ refers to the molar
concentration of NaOH, ‘Y’ refers to the treatment temperature (� C), and
‘Z’ refers to the treatment time (min).
2.2. Characterization techniques
Powder X-ray diffraction (XRD) patterns of samples were measured
using a Rigaku diffractometer with Cu Kα radiation (0.1540 nm) as the
source. The data were obtained in the 2θ range of 10–40� with a step size
of 0.02� and step time of 2.4 s. Morphological studies were conducted
using a Philips XL30 scanning electron microscope (SEM). X-ray
photoelectron spectroscopy (XPS) studies were conducted on a Thermo

Table 1
Water and moisture absorption of coconut coir (CC) subjected to different NaOH treatment conditions selected using DOE software.
Sample number Concentration of NaOH (M) Temperature ( C) Time (Mins) Water absorption% Moisture absorption%
�

1 0.68 42 33 163 9
2 1.6 RT 5 155 10.5
3 1.6 RT 26 184 7.5
4 1.6 RT 33 154 6.4
5 1.6 RT 60 184 11
6 1.6 29 12 173 7.2
7 1.6 35 10 160 9.5
8 1.6 39 9 154 7.3
9 1.6 42 33 176 7.2
10 1.6 60 60 186 11
11 1.6 60 5 152 8
12 1.6 72 33 154 6
13 2.2 RT 5 158 6.2
14 2.2 RT 10 174 7.3
15 2.5 41 29 172 11
16 2.5 42 33 155 7.2
17 3 RT 5 136 10
18 3 RT 33 151 6.7
19 3 42 33 169 10.3
20 3 72 33 198 10.4
21 3 42 79 179 9
22 4.3 RT 5 147 9.3
23 4.3 RT 26 132 7.8
24 4.3 RT 45 146 8
25 4.3 RT 60 175 10.5
26 4.3 60 5 160 8.8
27 4.3 60 60 164 10.2
28 5.2 42 33 155 9.6
Raw coconut coir – – – 144 8.4
Silica gel – – – 30 23

*RT: Room temperature.

2
N. Asim et al. Materials Chemistry and Physics 249 (2020) 123128

K-5 Alpha XPS instrument using Al Kα (E ¼ 1486.6 eV) radiation at a

pressure lower than 10 9 torr to avoid noise in the spectra. Fourier
transform infrared (FTIR) spectroscopic analysis was performed using an
FTIR (PerkinElmer, Frontier) spectrophotometer equipped with a Pike
Technologies GladiATR probe in the range of 400–4000 cm 1. Ther­
mogravimetric analysis (TGA) was conducted on a PerkinElmer TGA-7
instrument at a temperature range of 30 � C–800 � C under air flow.
The evaporation rate for raw and selected treated coconut coir that had
been soaked in water for 24 h was studied at 85 � C using a moisture
analyser (AND, MAX-50). Atomic absorption spectroscopy (AAS,
Thermo Scientific, iCE 3000 series) has been used to measure Cu con­
centration during heavy metal removal test.

2.3. Water and moisture absorption tests

Fig. 1. Percentage of water versus time at 85 � C.
The efficiency of raw and alkali-treated coconut coir for water and
moisture adsorption was studied. The performance evaluation of the
revealed its higher water retention property. The evaporation perfor­
prepared samples was conducted by their water absorption properties
mance of the samples could be used to determine specific suitable ap­
measurement using the ASTM D570–98 method [5,17].
plications for each material despite their water and moisture absorbency
In the next step, the samples with higher water absorption rates were
similarities. For applications in which a longer water retention time at
introduced for moisture absorption measurement using ASTM D5229 [5,
high temperature is needed (such as maintaining moisture for growing
18] while the saturated salt-water system was prepared using ASTM E
plants), Sample 5 would be a better choice, while for fast-regeneration
104-02 (NaCl solution at 28 � 2 � C; humidity ~ 50–75%) [5,19].
applications, Sample 10 would be preferred. The results indicated that
the treatment temperature had a strong influence on the sample
2.4. Removal of Cu
properties.
The heavy metal adsorption performance of treated coconut coirs
3.2. XRD characterization
have been investigated by their capacity of Cu (II) removal. A 5 ppm Cu
stock solution was prepared by dissolving 0.0190 g copper nitrate (Cu
The XRD patterns of raw and treated samples are presented in Fig. 2.
(NO3)2 (R&M Chemicals) in 1 L of distilled water. The stock solution
Coconut coir, which contains cellulose, hemicellulose, and lignin, had
thus prepared was used for various other concentrations; to be used for
the crystalline structure of cellulose. It was found that most of the
experimental runs.
samples had three major peaks at 2θ of ~16� , 22� , and 35� , indicating
the presence of cellulose-I [20,21]. Their crystalline structure is attrib­
3. Results and discussion
uted to hydrogen bond and Van der Waals forces between adjacent
molecules [22,23]. The peaks correspond to the (110), (200), and (004)
Selected samples were characterized by XRD, SEM, FTIR, TGA and
planes, respectively [24,25]. However, under harsh treatment condi­
XPS, as are presented in the following Sections.
tions (produced by using two of these conditions: high temperature, high
NaOH concentration, or extended time), the crystallinity in the XRD
3.1. Water and moisture absorption
pattern decreased or became amorphous. According to the literature
[26,27], this behaviour could be attributed to the extensive attack of the
The treatment conditions suggested by DOE, along with more sam­
lignocellulosic structure by a base or acid, which affects the breadth of
ples used for comparison (taken from DOE suggestions for next steps)
linear cellulose and lignin through cleavage of their linkages, leading to
and their water and moisture absorption properties, are presented in
smaller molecules. Another cause could be from washing of the solubi­
Table 1. The listed results are the average of a minimum of 3 samples for
lized lignin with a harsh alkaline treatment, which led to the release of
each treatment condition.
hemicellulose and caused cellulose structural swelling that decreased
Comparing samples subjected to the low treatment conditions cho­
the cellulose crystallinity [28]. Lignin and hemicelluloses are more
sen by DOE as the optimum conditions (Sample 5 or CC 1.6M-RT-60)
amorphous than cellulose, but amorphous zones offer more free volume,
with raw coconut coir showed an improvement of 27% and 30% of
which can store more water [29], in agreement with the observed
the water and moisture absorbency properties, respectively. Despite the
evaporation rate results.
higher water absorbency of treated CC compared to silica gel, its per­
formance was lower than that of the treated rice husk in a previous study
3.3. Scanning electron microscopy
[5]. Since some of the treated samples showed very similar water or
moisture absorbency capabilities, an evaporation (regeneration) test
In order to examine the surfaces of the materials, selected samples
was conducted on these materials to study their water loss performance.
were sputter-coated with gold to a thickness of ~10 nm prior to analysis
Fig. 1 shows the evaporation rates for raw and selected treated co­
by electron microscopy. SEM images of raw CC and differently treated
conut coir that had been soaked in water for 24 h. Tests were conducted
CC are shown in Fig. 3.
at 85 � C using a moisture analyser (AND, MAX-50). Removing the layer
Scanning electron microscopy of the surface of the fibres showed that
of extractives along with alkali treatment increased the available OH
a layer of extractives was removed after the alkaline treatment. Addi­
groups on the surface of the fibre and thereby increased the hydrogen
tionally, depending on the treatment conditions, alkali-treated samples
bonding between the fibre and water. It can be seen that Sample 5
possessed porous structural features compared to raw CC, and some of
(1.6M-RT-60) required the longest time to lose its adsorbed water
the pores were ruptured, some were opened and broken apart, and some
among all of the samples. This means that the hydrogen bonding be­
had a highly serrated surface. These results indicate that the tempera­
tween water and the treated fibre surface in Sample 5 was stronger than
ture has a significant influence on the treatment results.
that of other samples. Although the time required for Sample 10 (1.6M-
60-60) was similar to that of raw coconut coir, Sample 5 retained more
water in the fibre after completion of the evaporation procedure, which

3
N. Asim et al.
Fig. 2. The XRD pattern of raw and selected alkali-treated coconut coir with (a), (b) and (c) treated with the same temperature and time, (d) and (e) treated with the
same concentration and time, and (f) treated with the same concentration and temperature, respectively.
3.4. FTIR characterization
FTIR spectroscopy was performed to identify the functional groups
present in raw coconut coir and treated samples. Fig. 4 presents the FTIR
spectra of selected samples (see Section 3.1). The peak area within the
region 3200–3500 cm 1 is due to OH stretching vibrations, while the
peak located at 2920 cm 1 is due to a hydrocarbon (C–H) stretching
vibration. The peaks observed at approximately 1420 cm 1 and 1158
cm 1 are the typical absorption peaks of cellulose [30]. The peak at
approximately 1032 cm 1 is due to the C–O/C–C stretching vibration
[31]. The carbonyl bond peak from the carboxylic group which appears
at ~1732 cm 1 from hemicelluloses and pectin [30,32], is seen in the
raw coconut coir but disappeared in the alkali-treated samples. This
result could be attributed to the removal of hemicellulose from the fi­
bre’s surface due to NaOH treatment. As seen in Fig. 4, the peak at
~1245 cm 1 was assigned to the C–O stretching vibration of acetyl
groups of lignin and was very clear in raw coconut coir, but became
weaker in the treated samples because of partial lignin removal by alkali
treatment [30,33]. These results are in agreement with other research
results [30] and revealed that the alkaline solution removed hemicel­
lulose, pectin, and some of the lignin from coconut coir during the
chemical treatment.
4
Materials Chemistry and Physics 249 (2020) 123128
3.5. TGA characterization
The influence of the treatment conditions on the thermal stability of
coconut coir was studied. The TGA comparison of samples treated at the
same temperature and time but at different NaOH concentrations
(Fig. 5) revealed that increasing the molarity resulted in a higher ther­
mal stability for the treated samples, which could be attributed to the
greater removal of lignin, hemicellulose and α-cellulose from the CC
under these conditions.
It can be seen that alkali-treated CC had less weight loss than the raw
specimen. According to the literature [34], this increment of thermal
stability is attributed to the partial removal of lignin, hemicellulose, and
α-cellulose from the fibre during alkali treatment. From these results, it
can be determined that the decomposition process mainly occurred on
cellulose, resulting in an overall increase in the degradation temperature
of the treated fibres. The degradation profiles of raw CC and treated
samples showed similar decomposition patterns to that of bamboo fibre
[30]. The first weight loss occurred below 100 � C and was due to
moisture evaporation from the fibre structure. The second step occurred
in the range of 200–370 � C for raw CC and 200–400 � C in the treated
samples. This weight loss is due to the decomposition of hemicellulose
and cellulose. The upward shift of the degradation temperature in
treated samples could be attributed to the fact that cellulose decompo­
sition temperature which is around 250–350 � C is higher than hemi­
cellulose which decomposes around 180–280 � C [30,34]. Therefore, the
N. Asim et al.
Fig. 3. SEM images of (a) raw CC and (b) samples CC 1.6M-RT-60, (c) CC 1.6M-
60-60, (d) CC 4.3M-RT-60, (e) CC 3M-RT-33, (f) CC 1.6M-RT-26, (g) CC 1.6M-
42-33, and (h) CC 1.6M-72-33, respectively.
higher thermal stability is caused by more cellulose decomposition,
which increases the overall degradation temperature of the treated fi­
bres. The last step attributed to the decomposition of lignin and occurred
Fig. 4. FTIR spectra of raw CC and selected treated samples.
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Materials Chemistry and Physics 249 (2020) 123128
in the range 356–450 � C. Because of higher thermal stability of lignin
compared to others, it has a lower decomposition. The different thermal
stability of untreated and treated fibres is another proof that the hemi­
cellulose and lignin constituents were dissolved and removed from the
fibre by the alkali treatment [30]. At temperatures higher than 520 � C,
the fibres were completely decomposing and no change of mass
appeared with further increase of temperature.
The same pattern was found for increasing the treatment time while
the concentration and temperature were kept the same (Fig. 6). For
temperature changes, two different patterns were found. For lower
treatment times, an increase of temperature resulted in a higher stability
for treated samples, while for higher treatment times, the increase of
temperature led to lower thermal stability for treated samples. Lignin
has the highest thermal stability among other affected constituents
(cellulose, lignin, and hemicellulose) and decomposes at higher tem­
peratures [5,35]. For the first phenomenon, the reason could be the
lower amount of lignin removal compared to hemicelluloses and α-cel­
lulose, which resulted in a higher stability of the treated sample.
For the higher treatment times, the increment of temperature may
have led to higher lignin removal compared to hemicellulose and
α-cellulose, which led to lower thermal stability in the sample treated
under these conditions (see Fig. 7).
3.6. XPS characterization
X-ray photoelectron spectra were collected to investigate the
changes in the surface chemical structure of the treated samples. Fig. 8
show the C1s and O1s XPS spectrum of the selected samples (see Section
3.1).
The C1s spectra of raw coconut coir deconvoluted into 5 peaks at
approximately 284.6, 285.9, 287.5, 289.2 and 290.7 eV, which were
attributed to the C1, C2, C3, C4 and phenyl/benzene groups of lignin
[36], respectively. Based on the results of previous research on ligno­
cellulosic materials [37], the amount of C1 signal in the XPS spectra
reflects the non-carbohydrate bonds in the materials and only exists in
lignin. Signals from C2, C3 and C4 are mainly found in carbohydrates.
The different ratios of C1, C2, C3, and C4 in the treated coconut coir
samples (Fig. 8) could be attributed to the alkali treatment conditions
and the different degrees of degradation caused by various lignocellu­
losic components.
Deconvolution of the O1s spectra (Fig. 8 (e)) of raw coconut coir
produced five main peaks at approximately 531.9, 533.4, 534.9, 536.6
and 538.6 eV, which were assigned to C– – O, C–O, the chemisorbed/
N. Asim et al.
Fig. 5. TGA results for samples that had been treated under the same time and temperature conditions but with different alkali concentrations.
intercalated adsorbed oxygen in water molecules [38], potential sodium
Auger line overlap with O1s [39] and phenyl/benzene groups of lignin
[36], respectively. Additional deconvolution of the O1s spectrum of the
CC 4.3M-RT-60 sample yielded a signal that corresponded to quinone,
which was attributed to the oxidative degradation of lignin that can
form quinone under certain conditions [40]. According to the literature,
O1 with its low binding energy is from lignin and O2 with its high
binding energy is mainly from carbohydrates in lignocellulosic materials
[41–43].
Table 2 shows the relative surface composition in atomic % for raw
CC and some treated samples. The results showed that C and O are the
predominant species in all tested samples, but the presence of nitrogen
and silicon on the surface of some samples was detected based on the
characteristic emission peaks of these elements (Table 2). The N1s line
with a binding energy value of approximately 400 eV corresponds to the
–NH2 group of the amino acids/proteins found in a small amount on the
surface of some lignocellulosic materials, while Si is an impurity. The
oxygen-to-carbon (O/C) ratios of the materials were calculated from the
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Materials Chemistry and Physics 249 (2020) 123128
low-resolution XPS spectra. The O/C ratios can be used to estimate the
surface coverage by lignin [44]. According to the literature [37], a lower
O/C ratio indicates a higher content of lignin on the surface, while a
higher O/C ratio is characteristic of a higher content of carbohydrates on
the surface.
As seen in Table 2, alkali treatment of raw coconut coir led to higher
O/C ratios for the treated samples due to the oxidation and hydrolysis
reactions, which causes the surface of the treated samples to contain
more carbohydrate compared to raw coconut coir. That is, the alkali
treatment solubilized [28] or degraded the lignin on the surface of raw
coconut coir and produced a more carbohydrate-rich structure on the
surface. A higher carbohydrate content on the surface means more hy­
drophilic groups on the surface [37], which led to better hydrogen
bonding and higher water and moisture absorbency. These results are in
agreement with the water absorption results in Section 3.1.
N. Asim et al.
Fig. 6. TGA results for samples which had been treated under the same alkali concentration and temperature conditions but different times.
3.7. The Cu (II) removal performance
Previous studies on lignocellulosic fibers heavy metals removal po­
tential [45,46] and alkali treated coconut coir [13,15] encouraged us to
investigate the removal of Cu (II) by some optimized coconut coirs.
Adsorption studies were carried out using raw coconut coir (CC raw) and
treated coconut coir namely; CC NaOH 1.6M-RT-60, CC NaOH
1.6M-60-60, and CC NaOH 4.3M-RT-60, under different conditions as
listed in Table 3 to optimize the removal efficiency and absorption ca­
pacity of Cu. Batch adsorption experiments were carried and performed
by contacting 0.05 g of modified coconut coir with 100 mL of an aqueous
Cu solution. Experiments were carried out for 180 min at ambient
temperature in 250 mL conical flask, which place in shaking water bath
with a constant agitation 120 rpm. The treated Cu solution was collected
and the final concentration of the Cu present in the solution was
determined using AAS. The removal efficiency (%) of Cu and the ab­
sorption capacity of the modified coconut coir were determined using
the following equation:
Removal Effeciency (%) ¼ Ci – Cf / Ci � 100
Adsorption Capacity ¼ (Co–Cf � V)/m
where Ci and Cf are the initial and final concentration of Cu (II) (mg L 1),
respectively. V is the volume (mL) and m is the mass of treated coconut
coir (g).
Materials Chemistry and Physics 249 (2020) 123128
3.7.1. Influence of Cu(II) initial concentration
The influence of Cu (II) initial concentration was investigated in the
range of 1–5 mg L 1 using a fixed dosage of treated coconut coir (0.05 g).
The experiment was carried out for 30 min with constant shaking in a
water bath at 120 rpm. Finally, the final concentration of the treated Cu
solutions was measured and the removal efficiency and absorption ca­
pacity were calculated.
Fig. 9(a) and (b) display the adsorption capacity and removal effi­
ciency of CC raw, CC NaOH 1.6M-RT-60, CC NaOH 1.6M-60-60, and CC
NaOH 4.3M-RT-60 as a function of different Cu initial concentrations.
CC raw sample shows a small absorption capacity of 0.5–1.15 mg g 1
with an increase of initial Cu concentration from 1 to 5 mg L 1. An
improvement in adsorption capacity was observed from 0.60 to 6.25 mg
g 1 for CC NaOH 4.3M-RT-60, 0.78–5.95 mg g 1 for CC NaOH 1.6M-RT-
60, 0.80–3.71 mg g 1 for CC NaOH 1.6M-60-60 using the same Cu initial
concentration. These results clearly show that alkaline-treated coconut
coir enhances the absorption capacity of Cu up to 5 times higher than CC
raw. The amount of Cu absorbed at higher initial concentration was due
to the increase in Cu concentration gradient and driving force between
(1)
bulk solution and modified coconut coir surface [43,44].
(2) Fig. 9 (b) shows that the removal efficiency of CC raw and CC NaOH
1.6M-60-60 decreased from 41.56 to 13.43% and 67.43 to 40.98%
respectively for initial Cu concentration from 1 to 5 mg L 1. The decline
in Cu removal in these samples was due to the binding site saturation
[43,45]. The removal efficiency for CC NaOH 1.6M-RT-60 shows
7
N. Asim et al.
Fig. 7. TGA results for samples which were treated under the same time and concentration conditions but different temperatures.
insignificant values as the removal maintain at 65.90 to 65.72%, how­
ever, a notable enhancement in removal efficiency was observed for CC
NaOH 4.3M-RT-60 as the percentage increase from 50.99 to 73.30%.
This was due to the availability of binding sites and high surface area
possessed by the samples.
3.7.2. Influence of contact time
The influence of contact time on the removal of Cu solution was
studied by using 100 mL of Cu solution at the fixed initial concentration
of 5 mg L 1 and 0.05 g of treated coconut coir at ambient temperature
with constant shaking in the water bath at 120 rpm. The final concen­
tration of treated Cu solutions was analyzed at contact time ranging
from 10 to 180 min and the removal efficiency was calculated for each
contact time. Fig. 10(a) and (b) shows the absorption capacity and
removal efficiency of CC raw, CC NaOH 1.6M-RT-60, CC NaOH 1.6M-
60-60, and CC NaOH 4.3M-RT-60 as a function of different contact
time at ambient temperature. The results exhibit increments in absorp­
tion capacity and removal efficiency of Cu for the CC raw and all treated
8
Materials Chemistry and Physics 249 (2020) 123128
coconut coir as longer contact time applied to the samples. This was
because longer contact time was required for Cu to fully diffuse and
adsorbed by the samples. Shorter contact time leads to insufficient
contact between Cu and the coconut coir which leads to lower absorp­
tion capacity and removal efficiency. Though the CC raw and all treated
coconut coir samples show a good absorption ability on Cu, each sample
possesses different adsorption capacities. CC NaOH 4.3M-RT-60 gave
the highest absorption capacity of 3.07–7.86 mg g 1 and removal ca­
pacity of 43.42–92.19% for contact time from 10 to 180 min. Therefore,
the removal of Cu was dependent on the contact time of the experiment.
Longer contact time leads to higher removal of Cu. The results show that
by optimizing the Cu (II) removal conditions, simply tailored alkali
treated coconut coir with 5 times more removal performance compared
to raw coconut coir could utilize as cheap and effective heavy metal
adsorbent for wastewater treatment specially in remote and rural areas.
N. Asim et al. Materials Chemistry and Physics 249 (2020) 123128

Fig. 8. High-resolution XPS C1s spectra of (a) CC Raw, (b) CC NaOH 1.6M-RT- 60, (c) CC NaOH 1.6M-60-60, (d) CC NaOH 4.3M-RT-60 and O1s spectra of (e) CC
Raw, (f) CC NaOH 1.6M-RT-60, (g) CC NaOH 1.6M-60-60, and (h) CC NaOH 4.3M-RT-60, respectively.

9
N. Asim et al. Materials Chemistry and Physics 249 (2020) 123128

Table 2
Experimental atomic composition (%) and O/C ratios obtained by XPS analysis
for selected samples.
Sample %C %O %N %Si O/C

1.6M-RT-60 72.7 24.57 0 1.98 0.34

1.6M-60-60 69.52 24.08 1.98 4.21 0.35
4.3M-RT-60 69.49 24.36 1.18 1.46 0.35
CC Raw 70.07 20.02 5.86 – 0.29

Table 3
Effective factors on removal of Cu (II).
Removal Treated Cu initial Treated Contact
parameters coconut concentration, mg coconut coir time, min
coir L 1 dosage, g

Cu (II) CC Raw 1, 3 and 5 0.05 30

concentration, CC NaOH
mg L 1 1.6M-RT-
60
CC NaOH
1.6M-60-
60
CC NaOH
4.3M-RT-
60
Contact time, CC Raw 5 0.05 10, 30
min CC NaOH and 180
1.6M-RT-
60
CC NaOH
1.6M-60-
60
CC NaOH
4.3M-RT-
60 Fig. 9. (a) Absorption capacity and (b) removal efficiency of Cu by CC raw, CC
NaOH 1.6M-RT-60, CC NaOH 1.6M-60-60, and CC NaOH 4.3M-RT-60 as a
function of Cu initial concentration.
4. Conclusions

Alkalization of coconut coir changes the surface topography of the

fibres, and their crystallographic structure and composition depend on
the treatment conditions. Removal of surface impurities and partial
removal of hemicellulose, cellulose and lignin could increase the
amount of available OH groups on the surface of the fibre and increase
the water and moisture absorbency, adsorption properties, thermal
stability and water retention of coconut coir. Depending on the treat­
ment conditions, the percentage of cellulose, lignin and hemicellulose
removed varies, producing different properties in the treated materials.
The investigation of selected treated coconut coir samples with higher
water and moisture absorbency for Cu (II) removal revealed that treated
coconut coir samples gave a higher performance for removal of Cu (II)
compared to CC raw. Highest absorbance capacity (7.86 mg g 1) and
removal efficiency (92.19%) obtained by CC NaOH 4.3M-RT-60 which
was 5 times higher than CC raw. Considering the resulting composition
and properties of coconut coir subjected to different treatment condi­
tions, it shows much promise as an effective, environmentally sustain­
able absorbent material for a wide variety of applications. The modified
waste coconut coir could use for depollution in rural area.

Data availability

The raw/processed data required to reproduce these findings cannot

be shared at this time due to technical or time limitations but will be
made available on request.

Declaration of competing interest

Fig. 10. (a) Absorption capacity and (b) removal efficiency of Cu by CC raw,
CC NaOH 1.6M-RT-60, CC NaOH 1.6M-60-60, and CC NaOH 4.3M-RT-60 as a
The authors declare that they have no known competing financial
function of contact time.
interests or personal relationships that could have appeared to influence

10
N. Asim et al.
the work reported in this paper.
CRediT authorship contribution statement
Nilofar Asim: Conceptualization, Methodology, Software, Writing -
original draft, Investigation. Mohamad Hassan Amin: Methodology,
Writing - original draft, Investigation. Nurul Asma Samsudin: Writing -
original draft, Formal analysis. Marzieh Badiei: Writing - original draft,
Formal analysis. Halim Razali: Writing - review & editing, Visualiza­
tion. Md Akhtaruzzaman: Writing - review & editing, Visualization.
Nowshad Amin: Project administration, Funding acquisition, Visuali­
zation. Kamaruzzaman Sopian: Project administration, Funding
acquisition, Visualization.
Acknowledgements
The authors gratefully acknowledge the financial support of the
Endeavour Scholarships and Fellowships program (Australian Govern­
ment) and GUP-2018-129 from Universiti Kebangsaan Malaysia. In
addition, the authors acknowledge the facilities, and the scientific and
technical assistance, of the Australian Microscopy & Microanalysis
Research Facility at RMIT University. We would like to express our
special thanks to Prof. Suresh K. Bhargava for his valuable support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.matchemphys.2020.123128.
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