Diamond & Related Materials 127 (2022) 109199

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Diamond & Related Materials

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Upgrading low rank coal into mesoporous activated carbon via microwave
process for methylene blue dye adsorption: Box Behnken Design and
mechanism study
Ali H. Jawad *, S.N. Surip
Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia

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

Keywords: This research aims to upgrade Malaysian low rank coal namely Merit Kapit (MK) into mesoporous activated
Activated carbon carbon (MKAC) via fast and convenient microwave-assisted H3PO4 activation. The best activation conditions for
Low rank coal MKAC were observed at 1:2 (MK to H3PO4) impregnation ratio, radiation power 600 W, and radiation time 20
Box Behnken Design
min. These optimum activation conditions are responsible for producing a mesoporous structure of MKAC with
Microwave activation
Methylene Blue
an increase of ca. 848.7 folds (specific surface area (BET) of MKAC = 848.7 m2/g) as compared with natural MK
without thermal modification (specific surface area (BET) of MKAC = 1.00 m2/g). The adsorptive performance of
MKAC towards the removal of methylene blue dye (MB) was statistically optimized by using Box Behnken Design
(BBD). The BBD results indicate the best removal (86.6 %) of 50 mg/L MB can be achieved at the following
optimum adsorption conditions; MKAC dose = 0.06 g, solution pH = 7, and process time = 50 min. The
adsorption process of MB by MKAC was well described by Freundlich isotherm model and second-order kinetic,
with a maximum adsorption capacity of 186.4 mg/g at 25 ◦ C ± 2. Thus, several types of interactions such as
electrostatic interaction, H-bonding, and pi-pi interaction are responsible for capturing MB onto MKAC surface.

1. Introduction treatment [9]. The high performance of AC relies on several prepara­

The presence of dyes in water usually comes from printing, food,
leather, carpet, textile, and paper industries and not only makes the
water unusable but also causing severe health problems for human be­
ings [1]. Every year 5000 tons of dye containing substances come to the
usable aqueous environment and pollute it [2]. Methylene Blue (MB) is a
toxic carcinogenic cationic dye highly soluble in water and its xenobiotic
characteristic with aromatic stability makes it very difficult to degrade
in water and very dangerous as it reduces the water quality [3]. Thus,
several treatment methods such as advanced Fenton oxidation [4],
electrolysis [5], adsorption [6], photocatalysis [7], and electrochemical
process [8] have been applied for the removal of MB from contaminated
water. Among these treatment methods, adsorption process presented
itself as the prime treatment method due to several advantages such as
efficiency, simplicity, and selectivity [1,6].
Activated carbon (AC) is a promising multifunctional material with
desirable surface area enriched with various functional groups (car­
boxylic, hydroxide, carbonyl, and aromatic rings) and unique pore
structure, and widely applied as an efficient adsorbent in water
tional and operational factors such as precursor source, activation
method, activation agent, surface property, functionality of the surface
and design of pore structure [10]. Thus, various types of starting ma­
terials can be utilized to produce the AC such as fossil based carbona­
ceous substance (coal) [9], biopolymer [11], biomass leaves [12], tyre
char [13], fruit hulls [14], and biomass shell [15].
In fact, coals are abundant, relatively carbon-rich and low cost which
can be divided into two main groups; low rank coals and high rank coals
[9,10]. Hence, low rank coals contain high water content, high oxygen
content, high ash and heteroatom content and not desirable material for
energy production due to their low calorific values. However, low rank
coals can be upgraded into useful materials with potential applications
in different areas by reducing the mineral matter content and increasing
the porosity and carbon content. In this regard, coal can be converted
into AC by a physical process where CO2 gas passes through it at high
temperatures (700–900 ◦ C) [16], and by a chemical process where the
initial material gets impregnated with an activating agent like KOH,
H3PO4, NaOH, and ZnCl2 [17,18]. Among various thermal activation
processes, microwave activation process offers many desirable

* Corresponding author.
E-mail addresses: ali288@uitm.edu.my, ahjm72@gmail.com (A.H. Jawad).

https://doi.org/10.1016/j.diamond.2022.109199
Received 17 May 2022; Received in revised form 21 June 2022; Accepted 22 June 2022
Available online 24 June 2022
0925-9635/© 2022 Elsevier B.V. All rights reserved.
A.H. Jawad and S.N. Surip Diamond & Related Materials 127 (2022) 109199

properties over other traditional heating methods such as quick acti­ Table 1
vation time, less consumption of energy, the microwave energy dissi­ Actual and coded variables with their levels for MB removal.
pates in the form of heat, and high yield of AC [19]. Factors name Factors code Level of factors
In Malaysia, 1712 million tons of different types of coal are produced
− 1 0
in various locations of 7324 km2 and these coals have various organic
+1

and inorganic phases [20,21]. Therefore, it can be a good precursor for Adsorbent dose (g) A 0.02 0.04 0.06
pH B 4 7 10
activated carbon preparation and used for potential application in Time (min) C 10 30 50
wastewater treatment. Previously, several successful trails had been
made for upgrading low rank coal by thermal treatment with sulfuric
acid (H2SO4) [9], and by microwave-assisted alkaline (KOH) activation ∑
n ∑
n ∑
n
[10]. Thus, the main focus of this research work is to upgrade Malaysian Y = βo + βiXi + βiiXi2 + βijXiXj + ε (1)
low rank coal namely Merit Kapit (MK) into mesoporous AC (MKAC) i=1 i=1 1≤i≤j

with high surface area by microwave-assisted H3PO4 activation to be a

potential adsorbent for MB from aqueous environment. Moreover,
response surface methodology (RSM) is a mathematical technique that is
mainly used for statistical analysis of output response by input variables
[22]. Therefore, RSM has been applied for optimizing the adsorption key
parameters for heavy metals removal [23], organic solvents removal
[24,25] and toxic dyes removal [7] as an output response and solutions
parameter (dose, pH, time, etc) are the input variables. In this applica­
tion, Box Behnken Design (BBD) is a tool that requires smaller experi­
mental runs with maximum output efficiency and gives complete
information about the optimization studies.
2. Material and method
2.1. Materials
The Malaysian Kapit (MK) coal was obtained from the Batu Arang
coal field of Peninsular, Sarawak state, Malaysia. This MK coal was
washed with warmed distilled water up to five times to remove the
adherents completely. Then, MK was oven-dried at 100 ◦ C for 1 day.
Finally, the MK was grounded into fine particles of mess size 0.5–0.85
mm. All the chemicals, reagents and Methylene Blue (MB) dye (molec­
ular weight is 319.86 g/mol) used in this study were analytical grade
and provided by R&M Chemicals, Malaysia.
2.2. Microwave activation process
The microwave activation process of MK coal was carried in SAM­
SUNG Solo 20 L Microwave Oven. The whole process was done in a
quartz chamber sealed on both sides and N2 gas continuously flows
through it. In this activation process, 1 g of MK powder was treated with
1–3 mL of (85 %) H3PO4 acid solution (impregnation ration (IR) of MK to
H3PO4 ratio of 1:1, 1:2, and 1:3) for 24 h at 110 ◦ C. Then the microwave
activation process was carried out at different microwave radiation
power of 400 W, 600 W and 800 W and the microwave radiation time
was also varied in 5 min, 10 min, 15 min, and 20 min to obtain the
optimum activation conditions. The produce activated from MK is
labelled as (MKAC) and rinsed several times with distilled water till
neutral pH and then kept in the oven for 24 h at 100 ◦ C.
2.3. Experimental design
Response surface methodology (RSM) is a design tool that gives a
collection of mathematical and statistical techniques to improve and
develop the optimization of processes [26]. It not only lowers the
experimental runs but also gives exact and accurate optimum condi­
tions. Here, Box-Behnken Design (BBD), a tool of RSM was used for MB
removal optimization by MKAC. Here, adsorbent dose (A: 0.02–0.06 g/
L), pH (B: 4–10) and time (C: 10–50 min) were the independent input
parameter; their actual and coded values in different levels (− 1, 0 and +
1) are tabulated in Table 1. The MB removal (%) was set as the output
response corresponding to input parameter and expressed by a second-
order polynomial equation as shown in Eq. (1).
Here, βo, βi, βii and βij represent the coefficients of regression; Xi and
Xj are the coded independent variables; Y is the response of MB removal
and ε is a model error [27]. Design expert 13.0 software (Stat-Ease,
Minneapolis, USA) was applied for a complete analysis of regression
model, process variables and statistical model equation calculation.
2.4. Batch adsorption experiments
Batch solution experiments for MB removal by MKAC were con­
ducted according to the BBD design. In this experiment, 100 mL of initial
50 mg/L of MB solutions were transferred to a 250 mL conical flask and
the required amount of MKAC (0.02–0.06 g) was added to it. Then, the
solutions were rapidly mixed in a rotary shaker for the required time
(10–50 min) at 150 rpm at room temperature (25 ± 2 ◦ C). For pH
adjustment, 0.1 M NaOH and HCl solutions were used to reach the
desired pH. After that, MB-loaded MKAC was separated from MB solu­
tion by using 0.45 μm syringe filter, and MB concentration was analyzed
by UV–visible spectrophotometer at wavelength 664 nm. The uptake
capacity (qe) of MKAC and MB removal percentage is calculated using
the following equations;
( )
C0 − Cf
qe = ×v (2)
w
( )
Co − Cf
R (%) = × 100 (3)
Co
qe is the uptake capacity of MKAC (mg/g); R is the removal rate (%); Co
and Cf are the initial and final MB concentration; v is the volume of MB
solution (L) and w is the weight of MKAC adsorbent (g).
2.5. Sample characterization
Iodine Number (IN) is the mg of iodine present in 1 g of carbon and
calculated by standard process [28]. It is directly associated with the
surface area, as the higher the surface area, the higher the IN and the
more active binding sites there will be. SEM (JSM-6460LA, JEOL, Japan)
instrument was used for MK, MKAC and MB loaded MKAC surface
morphology analysis and elemental composition calculation. To get a
better resolution, these materials were sonicated for 20 min and dropped
in glass plates which were coated in gold by a Polaron SC 515, then put
in SEM instrument for analysis. X-ray diffractometer (XRD, X'Pert PRO)
instrument with Cu-Kα X-rays operated at 40KV was utilized to study the
crystalline or amorphous structure of the MK and MKAC. Fourier
transforms infrared (Perkin-Elmer, Spectrum RX I) spectrophotometer
was applied at room temperature in 4000–400 cm− 1 range for surface
functional group detection on MK and MKAC surface before and after
MB adsorption. Here, the MK and MKAC powder were very superbly
ground and assorted with KBr in the weight ratio of 1:60, then com­
pressed into a pellet using a hydraulic press. CHNO Analyzer (Flash
2000, Thermo-scientific, Netherlands) was used for elemental compo­
sition detection in MK and MKAC. The pH meter (Metrohm, 827 pH lab)
was used for the zero point of charge (pHpzc) calculation for the MKAC,
according to the previously reported method [29].

2
A.H. Jawad and S.N. Surip
3. Results and discussions
3.1. Single-factor experiments to prepare MKAC
The effect of the microwave activation process parameters on the
iodine number (porosity) of MKAC parameters was determined. Fig. 1
presents the individual effects i.e. impregnation ratio, power level, and
radiation time on the iodine number (IN) of MKAC. The effect of the
impregnation ratio on the IN was evaluated at fixed radiation time (10
min) and power level (600 W) as shown in Fig. 1a. It can be observed
that increasing the activation agent (H3PO4) ration from 1:1 to 1:2 is
reopenable for improving the IN from 727.4 mg/g to 879.9 mg/g. In this
case, by increasing the ratio of H3PO4/MK, the activation process will
play a fundamental role in porosity development of MK, and providing
noticeable increment in the IN. Beyond this optimum point, the addi­
tional amount of H3PO4 (1:3) will lead to vigorous gasification process
[30], which damages the porous structure of the carbon and leading to
remarkable decreases in the IN of MKAC. Hence, impregnation ratio of
1:2 was chosen as the best ratio for the production of MKAC. Moreover,
the effect of power level (W) on the IN of the MKAC was investigated at
fixed mixing ration (1:2) and radiation time (10 min) as shown in
Fig. 1b. As can be seen, the IN increased from 780 mg/g to 860 mg/g by
increasing the power level from 400 W to 600 W. After that the IN slowly
reduced to 736 mg/g with the maximum power up to 800 W respec­
tively. At lower power, the surface area of MKAC was low due to the
lower content of released gases from the surface and at higher power the
pore structure was destroyed which also reduced the surface area
respectively [31]. Hence, optimum power 600 W was chosen for the best
production of MKAC. After that, Fig. 1c shows the effect of radiation
time on IN of MKAC at fixed impregnation ratio (1:2) and radiation
power (600 W). It can be observed that with time the IN increased
Fig. 1. Effect of (a) chemical impregnation ratio (preparation conditions: microwave power = 500 W; radiation time = 10 min), (b) microwave power level
(preparation conditions: chemical impregnation ratio = 1:2; radiation time = 10 min) and (c) radiation time (preparation conditions: chemical impregnation ratio =
1:2; microwave power = 600 W) on the iodine number value (IN) (mg/g).
3
Diamond & Related Materials 127 (2022) 109199
significantly from 627 mg/g to 860 mg/g by increasing the radiation
time from 5 min to 20 min. This observation clearly revealed that pro­
longing radiation time promotes an acceleration of activation energy,
that leads to increment in reaction rates, thus improvement in the IN
(porosity) of MKAC will be achieved [30,32]. Hence, 20 min was taken
as the best irradiation time for MKAC preparation.
3.2. Characterization of samples
The XRD analysis was carried out to investigate the crystallographic
structure of the material. Fig. 2a and 2b show XRD peaks of MK and
MKAC respectively. The patterns of MK indicated that a broad peak near
25◦ was for amorphous carbonaceous structure and the existence of a
sharp peak at 26.5◦ was due to crystalline hexagonal graphite phases of
carbon on MK surface respectively [33]. After microwave activation
process, XRD pattern of MKAC was altered and two new peaks were seen
at 24◦ and 42.5◦ for 002 and 101 planes respectively. The shifting in
carbon peak was mainly due to the lattice expansion of the graphene
layer and the slight ash content present on the MKAC surface [34].
The elemental composition of MK and MKAC was determined by
CHNS analysis and Table 2 gives the detailed CHNS data of MK and
MKAC. The elemental composition shows that MK has C = 55.27 %; H =
4.13 %, N = 0.58 %, and O = 40.02 %. After microwave activation
process, an increment in carbon content of MKAC was detected, and
MKAC has C = 61.11 %; H = 3.48 %, N = 0.10 %, and O = 35.31 %
respectively. This observation indicates that microwave chemical acti­
vation with H3PO4 is responsible for increasing the carbon content of
MKAC and effectively releases volatile species from the MK surface.
The FTIR spectral analysis of the MK, MKAC, and MKAC after MB
adsorption are presented in Fig. 3. The FTIR spectrum of MK (Fig. 3a)
shows that the –OH stretching vibration was seen at 3600 cm− 1 which
A.H. Jawad and S.N. Surip Diamond & Related Materials 127 (2022) 109199

shift and reduction in bands at 3600 cm− 1 and 1050 cm− 1 which in­
(a) dicates the involvement of the –OH, –COOH, C–O–C groups in
capturing MB dye molecules on the surface of MKAC.
The morphological surface and elemental composition of MK, MKAC,
and MKAC-MB systems were examined by SEM-EDX analysis as pre­
sented in Fig. 4. In this regard, Fig. 4a shows SEM image of MK which
appears as a heterogenous, irregular and wavy surface with irregular
Intensity (a.u)

cavities. Thus, the corresponding EDX profile (Fig. 4b) indicates the
main elemental content of MK is carbon and oxygen, and this observa­
(b) tion is in line with recorded results in Table 2. After microwave chemical
activation, the micrographical image of MKAC is presented in Fig. 4c.
The surface of MKAC seems more porous and heterogeneous compared
to the MK (Fig. 4a) in addition to the different cracks and pores with
different sizes that can be seen in the MKAC image. Moreover, the EDX
analysis of MKAC (Fig. 4d) shows more carbon content compared to the
EDX spectrum of MK (Fig. 4d) which reveals that microwave chemical
activation with H3PO4 is responsible for increasing the carbon content of
MKAC and effectively releases volatile species from the MK surface.
10 20 30 40 50 60 70 80 90 After adsorption of MB dye (Fig. 4e), the surface of MKAC was turned to
2θ (Degree) be more compact, less porous, and less heterogenous compared to Fig. 4c
due to the loading of MB dye molecules onto MKAC surface. This
Fig. 2. XRD patterns of (a) MK and (b) MKAC. assumption was confirmed by EDX analysis (Fig. 4f) by detection of
sulfur from MB molecular structure in the EXD spectra, in addition to
noticeable increment in the carbon content. This observation confirmed
Table 2
Elemental analysis of MK and MKAC.
the attachment of MB dye molecules on the MKAC surface.
The specific surface area of MK and MKAC were determined and the
Sample C (%) H (%) N (%) O (%) by difference
obtained results are presented in Table 3 and plotted in Fig. 5. The
MK 55.27 4.13 0.58 40.02 hysteresis loop of the MK is type I isotherm (Fig. 5a) according to IUPAC
MKAC 61.11 3.48 0.10 35.31 classification, and it is a nonporous material due to its extremely low
surface area (1.00 m2/g). After microwave chemical activation with
H3PO4, the specific surface area of MKAC is significantly increased to
(a) reach 848.7 m2/g and the hysteresis loop of the MKAC is a type IV
isotherm based on the IUPAC classification [12]. An increase (ca. 848.7-
fold) in specific surface area and pore volume (2.22 nm) is observed. The
measurement of pore volume of MKAC indicates that it is mesoporous in
structure. Thus, it can be concluded that MKAC with mesoporous nature,
Transmittance (%)

(b)
high surface area, and preferable mesoporosity is a demanded carbon-
based material for adsorption-based applications, especially for big
dye molecules and polyaromatic dyes such as MB.

3.3. BBD model analysis

(c)

BBD was used to optimize the adsorption input variables (adsorbent

4000 3500 3000 2500 2000 1500
Wavenumber (cm-1)
Fig. 3. FTIR spectra of (a) MK, (b) MKAC and (c) MKAC+MB.
informed that the phenol and carboxylic groups were present on the MK
surface [35]. The respective bands at 2300–2400 cm− 1 and 1638 cm− 1
were for CO2 formation and the C– – O stretching vibration of amide.
Moreover, the corresponding bands at 1550 cm− 1 and 1050 cm− 1 were
signature for C–
– C bonds in aromatic rings and C–O–C stretching vi­
bration of alcohol, acid, and phenol groups [36,37]. Thus, Fig. 3b shows
that the FTIR bands of MKAC were similar to the bands of MK with slight
red/blue shifts and reduction in band intensities. This observation can
be assigned to catalytic breaking of bond that associate with microwave
activation with H3PO4. In the same respect, the FTIR spectrum of MKAC
after MB adsorption was recorded and depicted in Fig. 3c. The bands of
MKAC after loading MB dye shows similar profile to MKAC with slight
dose coded as A, solution pH coded as B, and contact time coded as C)
and to determine the maximum output (MB removal % as a response) as
recorded in Table 4. It was observed that MB removal was found in the
range of 23.1 % to 86.6 % in several experimental conditions. Inside the
model, different models such as a cubic model, sequential model, sum of
1000 500 square, linear model, and quadratic model were tested [38]. Among
these, the polynomial quadratic model equation (Eq. (4)) was able to
explain and give the exact significant interactions between independent
input variables and predicted output responses for MB removal.
Y = +34.78 + 18.18A + 14.00B + 14.73C + 10.47AB + 9.03AC + 7.88BC
+2.35A2 + 5.50B2 + 5.10C2
(4)
Here, A (adsorbent dose), B (pH), and C (time) are the coded units
and Y is the response of MB removal. The Analysis of Variance (ANOVA)
results of the corresponding model is given in Table 5. The model given
by BBD for MB removal by MKAC was highly significant. The p-value
(<0.05) indicates the model significantly fits the data and here except
for the square of adsorbent dose term, all other terms were significant
[39]. Here, the F-value of the model was 804.92 and the p-value was
<0.0001. The effect of adsorbent dose shows a high impact on MB
removal as it had a high F-value of 2642.65, this indicates that active
adsorption sites and surface functionality and porosity are responsible

4
A.H. Jawad and S.N. Surip Diamond & Related Materials 127 (2022) 109199

Fig. 4. SEM and EDX images of MK (a, b), and MKAC (c, d) and MKAC after MB adsorption (e, f).

model is an accurate one [40]. Again, the signal to noise ratio was
Table 3
28.964 (>4) which is very adequate and could be applied for circum­
BET textural data of MK and MK-AC.
navigating space design (i.e. predicted response for MB removal) [41].
Textural properties MK MKAC Thus, Fig. 6a presents a normal probability plot, data that came out from
Single point surface area at p/p◦ = 0.077/(m2/g) 0.41 786.8 the model are scattered in a straight line and very few points existed
BET surface area/(m2/g) 1.00 848.7 outside the line. The same results were observed in predicted versus
Langmuir surface area/(m2/g) 1.34 1277.5
actual removal (Fig. 6b) percentage of MB respectively. Hence, this
t-Plot external surface area/(m2/g) 1.66 120.4
Average pore width/nm <0.2 2.22
relationship was significant among the experimental and output
response from the model [42].

for playing a crucial role in this adsorption process. The solution pH and
contact time also exhibit a high effect on MB removal due to their higher
F-values of 1568 and 1734.60 respectively. All the interaction terms
were also significant which enhanced the model efficiency.
The regression coefficient (R2) was 0.9913, which said that only
0.0087 % was not explained by the model due to error. The predicted
and adjacent R2 values of the model were 0.9801 and 0.9119 respec­
tively. These high R2 values were reasonably in agreement with one
another and enhanced the model significance. The lack of fit test is
insignificant due to pure error and if this term is non-significant then the
3.4. Interactions of variables
The mutual interaction of MKAC dose and solution pH on MB
removal efficiency at a constant time of 30 min is presented in Fig. 7a.
The MB removal was increased sharply with the increase in adsorbent
dose and pH. Here, a higher dose provides a larger surface area with a
higher number of binding sites which enhances the accessibility of MB
on its surface [43]. Effect of pH is a crucial factor as it is directly asso­
ciated with adsorbent surface charge and solution pH increased the MB

5
A.H. Jawad and S.N. Surip Diamond & Related Materials 127 (2022) 109199

Table 5
Analysis of variance (ANOVA) for MB removal (%) by MKAC.
Source Sum of df Mean F- p-Value Significant
squares square value

Model 7244.30 9 804.92 88.69 <0.0001 *

A-Dose 2642.65 1 2642.65 291.16 <0.0001 *
B-pH 1568.00 1 1568.00 172.76 <0.0001 *
C-Time 1734.60 1 1734.60 191.12 <0.0001 *
AB 438.90 1 438.90 48.36 0.0002 *
AC 325.80 1 325.80 35.90 0.0005 *
BC 248.06 1 248.06 27.33 0.0012 *
A2 23.20 1 23.20 2.56 0.1539 #
B2 127.25 1 127.25 14.02 0.0072 *
C2 109.41 1 109.41 12.05 0.0104 *
Residual 63.53 7 9.08
Lack of 37.70 3 12.57 1.95 0.2640 #
Fit
Pure 25.83 4 6.46
Error
Cor Total 7307.84 16
2
R = 0.9913
Adj-R2 = 0.9801.
* = Significant.
# = Not significant.

higher contact time. Lastly, the simultaneous effect of pH and time is

illustrated in Fig. 7d while dose became constant. Similar results were
obtained for solution pH and time as explained above and maximum
percentage of MB removed at higher pH and in longer contact time
respectively.

3.5. Adsorption study

Fig. 5. Isotherms of N2 adsorption–desorption of (a) MK, and (b) MKAC.

The adsorption study of MB dye by MKAC was performed by adop­
tion of the optimum adsorption conditions recorded in run 8 of Table 4
and as follows, optimum does =0.06 g and solution pH = 7. Then to
Table 4
Experimental design and response for MB removal.
investigate the effect of time (0–400 min) on the removal of MB dye by
MKAC, a series of initial MB concentrations from 20 mg/L to 250 mg/L
Run A:Dose (g) B:pH C:Time (min) MB removal (%)
were reconnoitred and the obtained data is presented in Fig. 8. The
1 0.02 4 30 23.1 adsorption capacity of the MKAC was found to be 34.4 mg/g at 20 mg/L,
2 0.06 4 30 34.2 and increased to 224.8 mg/g at 250 mg/L. With the increase in MB
3 0.02 10 30 30.1
4 0.06 10 30 83.1
concentration, the adsorption capacity of MKAC was increased as well,
5 0.02 7 10 15.9 and this observation can be attributed to the greater number of MB
6 0.06 7 10 38.5 molecules that were diffused on the MKAC pores and also intraparticle
7 0.02 7 50 27.9 diffusion of MB molecules from the surface to the micropores of MKAC,
8 0.06 7 50 86.6
respectively [45].
9 0.04 4 10 24.8
10 0.04 10 10 37.1
11 0.04 4 50 37.9
3.6. Adsorption kinetics
12 0.04 10 50 81.7
13 0.04 7 30 35.6
14 0.04 7 30 30.9 Pseudo-first-order (PFO) and Pseudo-second-order kinetics models
15 0.04 7 30 37.5 were applied for MB removal by MKAC to determine the rate and
16 0.04 7 30 36.1 interaction mechanism of adsorbate and adsorbent. Here, nonlinear ki­
17 0.04 7 30 33.8
netics equations for PFO and PSO are presented in Eqs. (5) and (6)
respectively.
removal efficiency, reaching a maximum at higher solution pH. In this ( )
qt = qe 1 − exp− k1 t (5)
regard, Fig. 7b presents the pHPZC of MKAC, and it was seen that at lower
pH, the of MKAC surface has fewer negative charges which increases
q2e k2 t
gradually by increasing the solution pH towards basic environment. qt = (6)
1 + qe k2 t
Hence maximum interaction through electrostatic attraction was going
on among negatively charged MKAC surface and positively charged MB where, qt and qe: uptake capacity of MKAC at time t and equilibrium time
molecules respectively [44]. The effect of MKAC dose and time was (mg/g); k1: rate constant for PFO and k2: rate constant for PSO respec­
examined and presented in Fig. 7c while pH remains constant at 7. The tively. The nonlinear fitting results obtained from the above models and
higher dose provided more available functional groups to adsorb MB, so their parameters are tabulated in Table 6. The kinetics parameters at
the maximum amount of MB was removed at a high adsorbent dose. different concentrations showed that the PSO model was extraordinarily
With time, the MB removal rate was drastically increased as MB dye fitted with the experimental data compared to the PFO model. The R2 of
requires more time to penetrate into the inner and outer pores of MKAC PSO was much higher (near to 1) than PFO model at all the initial
surface and the maximum amount of MB removal was observed at a concentrations. The qt cal. Value was in agreement with the qt exp. Value

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A.H. Jawad and S.N. Surip Diamond & Related Materials 127 (2022) 109199

Fig. 6. (a) Normal probability plot and (b) experimental and actual removal of MB (%).

Fig. 7. 3D response surface plot showing the interaction between dose and pH (b), dose and time (b) and pH and time (c) for MB removal by MKAC.

for PSO model respectively. Hence, MB diffusion on the MKAC surface
was followed by a chemisorption process which is the rate-determining
step [18,42].
3.7. Adsorption isotherm
Isotherms generally give the idea of a relationship, interaction, or
distribution of adsorbate molecules on solid-liquid phases [46]. Thus,
nonlinear Langmuir [47], Freundlich [48] and Temkin [49] isotherm

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A.H. Jawad and S.N. Surip Diamond & Related Materials 127 (2022) 109199

250

200

150

qe (mg/g)
100 Experimantal data
Langmuir model
Freundlich model
Temkin model
50

0 20 40 60 80 100 120

Ce (mg/L)

Fig. 8. Influence of contact time on MB adsorption by MKAC at MKAC does Fig. 9. Nonlinear adsorption isotherms for MB dye by MKAC at 25 ◦ C ± 2.
=0.06 g, solution pH =7, Temp. =25C ± 2, MB vol. =100 mL.

Table 7
Table 6 Isotherms parameters of MB adsorption on MKAC at 25 ◦ C ± 2.
PFO and PSO kinetic parameters for MB dye adsorption on MKAC.
Model Parameter Values
Concentration qe exp. PFO PSO
(mg/L) (mg/g) Langmuir qmax (mg/g) 186.4
qe cal k1 (1/ R2 qe cal k2 * R2 Ka (L/mg) 0.30
(mg/ min) (mg/ 10− 2 R2 0.90
g) g) (g/mg Freundlich KF (mg/g (L/mg)1/n) 76.7
min) n 5.01
20 34.4 33.2 0.5 0.97 34.7 2.56 0.99 R2 0.98
50 88.6 76.3 0.94 0.89 84.8 1.79 0.92 Temkin KT (L/mg) 44.4
80 118.8 108.4 0.05 0.89 118.5 0.07 0.95 bT (J/mol) 116.0
100 143.3 122.7 0.05 0.91 134.1 0.052 0.95 R2 0.94
200 180.4 142.1 0.02 0.83 178.1 0.050 0.91
250 224.8 196.9 0.05 0.82 221.4 0.020 0.90

Table 8
models were used to analyze the mechanism of interactions of MB dyes Adsorption capacity of MB by various types of activated carbon synthesized from
different materials with H3PO4 activation.
on MKAC surface. The respective isotherm equations of Langmuir,
Freundlich, Temkin are presented in Eqs. (7), (8), and (9), respectively. Precursor name Activator Adsorption capacity (mg/ Reference
g)
qmax Ka Ce
qe = (7) Coconut leave H3PO4 250 [4]
1 + Ka Ce Grass waste H3PO4 241.3 [51]
MKAC H3PO4 186.4 This study
qe = Kf Ce1/n (8) Elaeagnus angustifolia H3PO4 72 [52]
seeds
RT Corncob H3PO4 28.65 [53]
qe = ln(KT Ce ) (9) Pineapple waste H3PO4 9.61 [54]
bT

qe: adsorption capacity of MKAC (mg/g); Ka: Langmuir constant (L/mg);

Ce: equilibrium concentration (mg/L); Kf (mg/g) (L/mg) and n:
Freundlich constants; KT (L/mg) and bT (J/mol): Temkin constants; R:
the universal gas constant and T: temperature. The nonlinear fitting
results of MB removal are presented in Fig. 9 and the parameters are
tabulated in Table 7. From the data, the Freundlich model was esteemed
to match with the experimental data with high R2 value compared to
Langmuir and Temkin models. Hence, multilayer adsorption of MB took
place on the heterogeneous surface of MKAC [50]. The maximum uptake
capacity of the MKAC is 186.4 which is very high as compared to pre­
viously reported activated carbon activated with different reagents as
shown in Table 8.

3.8. Adsorption mechanism Fig. 10. Proposed adsorption mechanism of MB onto MKAC surface.

The adsorption mechanism of capturing MB dye molecules was in MB molecular structure by H-bond, hydrophobic and pi -pi in­
proposed and presented in Fig. 10. Thus, the FTIR results indicate that teractions [34]. In this regard, Fig. 10 represents the different types of
the oxygen containing functional groups (–OH, –COOH, C–O–C) adsorption mechanisms going on for MB removal by MKAC adsorbent.
may increase the adsorption capacity of MKAC towards cationic species

8
A.H. Jawad and S.N. Surip
Mainly, three types of interactions were carried out: (i) electrostatic
interaction of surface negative charge (at high pH 7.0) of MKAC with the
positively charged cationic MB dye. (ii) H-bonding of active groups on
the MKAC surface with the N and S atoms of MB molecules. (iii) Lastly,
the hexagonal structure of MKAC formed a pi-pi interaction with the
aromatic ring of MB [51]. Hence, above are the interactions mainly
responsible for MB removal from aqueous solutions. In the same regard,
similar observations were reported in the literature for adsorption of MB
by activated carbon-based adsorbents [34,51].
4. Conclusions
Malaysian low rank coal namely Merit Kapit (MK) was converted
into mesoporous activated carbon (MKAC) by microwave assisted
chemical activation. The microwave activation conditions such as
impregnation ratio, radiation power, and radiation time were deter­
mined. The effectiveness of the MKAC was evaluated towards removal of
a cationic dye namely methylene blue (MB) from aqueous environment.
Response surface methodology with Box-Behnken design (RSM-BBD)
was applied to optimize the adsorption operation conditions. From BBD,
it was found that 86.6 % of MB was removed at optimum operation
conditions of 0.06 g MKAC dose, pH 7, and time 50 min. Multilayer
chemisorption of MB was detected on the heterogeneous surface of
MKAC. The MB was attached to MKAC surface by pi-pi interaction,
electrostatic attraction, and H-bonding mechanism.
CRediT authorship contribution statement
Ali H. Jawad: Conceptualization, Methodology, Software, Supervi­
sion, Project administration, Data curation, Funding acquisition,
Writing – review & editing. S.N. Surip: Project administration, Funding
acquisition, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
The authors are grateful to the Ministry of Higher Education
(MOHE), Malaysia, for supporting this research project under funda­
mental research grant scheme (FRGS/1/2019/TK02/UiTM/02/15).
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