Bioresource Technology Reports 11 (2020) 100520

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Bioresource Technology Reports

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Investigation the isotherm and kinetics of adsorption mechanism of T

herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) on corn cob biochar
⁎
Quach An Binha, , Hong-Hai Nguyenb
a
Faculty of Applied Sciences–Health, Dong Nai Technology University, Dong Nai 810000, Viet Nam
b
NTT Hi-Tech Institute, Nguyen Tat Thanh University, Ho Chi Minh City 700000, Viet Nam

A R T I C LE I N FO A B S T R A C T

Keywords: The aim of this work was to study the isotherm and kinetics of adsorption mechanism of the herbicide 2,4-D on
Biochar corn cob biochar in aqueous solution. Corn cob biochar was synthesized at 600 °C for 4 h, then, it was washed by
Adsorption HF acid modification. The characteristics of the biochar were considered including the point of zero charge,
2,4-D surface morphology, surface area, and functional groups. The specific surface area of biochar was
Isotherm
298.01 m2.g−1. Solution pH at 2.0 had the greatest removal efficiency for 2,4-D. The experimental adsorption
Kinetics
Mechanism
data fitted with the Pseudo-second-order and Langmuir isotherm models. The chemical adsorption and pore-
filling are the main interactions of 2,4-D and corn cob biochar. However, H-bonding is the most important
interaction of chemical adsorption. Corn cob biochar is a very useful material for 2,4-D removal and pesticide
pollutants, they can be further applied in the wastewater treatment plants as well as the water supply units.

1. Introduction
Nowadays, pesticides are organic compounds used widely to im-
prove agricultural yield (Machado and Martins, 2018). As a con-
sequence of their high persistence, pesticides bio-accumulate in food
and can endanger animal and human health (Vera et al., 2018), the
existence of pesticides in the environment is a risk to aquatic organisms
and healthy human (Kuśmierek et al., 2016).
2,4-D (2,4-dichlorophenoxyacetic acid) is an active ingredient of
pesticide and is classified as an herbicide belonged to the groups of
phenoxy or phenoxyacetic acid (EPA, 2005). As an herbicide, 2,4-D is
commonly applied in farming as an agent for the control of weeds
(Trivedi et al., 2016). Its action is selective and it is low-priced (Trivedi
et al., 2016). 2,4-D are hepatotoxic and nephrotoxic to animals, when
2,4-D is used to high concentrations (Qurratu and Reehan, 2016). The
poison of 2,4-D infiltrates to humans and animals through several paths
including contaminated air, drinking water, soil, and food; and are
found in human semen and urine samples (Qurratu and Reehan, 2016).
Therefore, their removal and degradation in water are extremely im-
portant. The structures and physico-chemical properties of 2,4-D are
manifested in Table S1 (Supplementary Materials).
Presently, physical (adsorption), chemical (O3/UV, hydrolysis,
Fenton, and photocatalyst), biological treatment (composting, bio-
augmentation and phytoremediation) (Hattab and Ghaly, 2012), and
enzymatic approaches are implicated to reduce pesticides from soil and
water (Parte et al., 2017). Among these methods, adsorption is an ef-
ficient method for pesticide removal from the aqueous environment
(Tsai and Chen, 2013), due to its common design and low costs (Saleh
et al., 2016).
Biochar is one of the most effective absorbents and could be ob-
tained through the pyrolysis process of biomass under oxygen-limited
conditions (Saleh et al., 2016), which is readily available and at low
cost (Saleh et al., 2016). Corn cob contains a rich amount of cellulose
(40.95 ± 0.38%) and hemicellulose (38.94 ± 1.72%), and an insig-
nificant amount of lignin (16.54 ± 0.38%) (Echeverria et al., 2018). A
small amount of corn cob is consumed as a power source for cooking at
the countryside in Vietnam (Viet et al., 2015). After the harvest, corn
cob is still considered as an environmental issue because the technology
that created the energy conversion from corn cob is absent at Vietnam
(Viet et al., 2015). The high percentage of the biomass compositions
including cellulose, hemicellulose, and lignin, which are the main
components to determine the biochar characteristics and convert to
biochar carbon matrix (Yavari et al., 2015). Hence, if they are synthe-
sized into adsorbents, they can be useful materials. Washing is an im-
portant role for biochar to remove the minerals that persist on the
biochar after the pyrolysis process (Uchimiya et al., 2012). One of the
most advantageous properties of biochar are the extreme affinity and
ability for adsorbing herbicides and insecticides (Yavari et al., 2015).

⁎
Corresponding author.
E-mail address: quachanbinh@dntu.edu.vn (Q.A. Binh).

https://doi.org/10.1016/j.biteb.2020.100520
Received 30 May 2020; Received in revised form 10 July 2020; Accepted 11 July 2020
Available online 03 August 2020
2589-014X/ © 2020 Elsevier Ltd. All rights reserved.
Q.A. Binh and H.-H. Nguyen
Moreover, the useful porous structure, the functional groups, high
surface area, ash contents, and mineral component are potential char-
acteristics of biochar (Yavari et al., 2015).
The functional groups upon biochar surface are the main role par-
ticipating in the adsorption process (Inyang and Dickenson, 2015).
Many interactions can be formed between the organic compounds and
biochar such as electrostatic interaction, H-bonding, and π-π EDA in-
teraction (electron-donor-acceptor) (Inyang and Dickenson, 2015).
Besides, the uptake of organic compounds has a high correlation with
the pore size and surface properties of the biochar (Tan et al., 2015).
The micropore sizes (< 2 nm) and small mesopore sizes (2–20 nm)
were suggested to be the primary factor for pore-filling adsorption
(Inyang and Dickenson, 2015).
Currently, in the adsorption method, many adsorbents are being
used to treat 2,4-D from the water such as carbonaceous materials
(Kuśmierek et al., 2016), magnetic Fe3O4-graphene nanocomposite
(FGN) (W. Liu et al., 2016), and cotton plant char (Trivedi et al., 2016).
To our knowledge, some studies concerning the 2,4-D removal by
biochar have been implemented, utilizing the materials synthesized
from corn cob, bamboo, wood chips (Kearns et al., 2014), and cotton
plant (Trivedi et al., 2016). However, research on the insight into the
adsorption interaction of 2,4-D and biochar is rarely investigated.
Therefore, this study aimed to study the isotherm, kinetics, influence of
pH to adsorption ability for 2,4-D onto biochar. Notably, the adsorption
mechanism between the corn cob biochar and 2,4-D pollutant were
investigated.
2. Material and methods
2.1. Chemicals and materials
The corn cob biomass was cut into cubiform of approximately
1 cm3. Then the biomass was put into the oven at 105 °C for 6 h. The
2,4-D (80% w/v) was provided by Tigicam company, Vietnam. HCl
(37.00%), HF (48.00%), and NaOH (99.00%) were provided by Merck
company, Germany. Deionized (DI) water was used in the experiment
(resistivity: 18 MΩ.cm).
2.2. Preparation of adsorbents
The biomass was enclosed in a ceramic pot, the lid was put on the
ceramic pot properly to prevent the external oxygen influx during the
pyrolysis process (Zhang et al., 2013). Then, the biomass was burned in
the furnace (Nabertherm, Germany). The temperature for the pyrolysis
condition was slowly increased by 3 °C per minute (Krzesin'ska and
Zachariasz, 2007). The pyrolysis process was operated in the limitation
of oxygen at 600 °C for 4 h. The pristine corn cob biochar (CCB) was
crushed by using a pestle and mortar, then, it was passed through a 0.8-
mm sieve. To remove excess minerals, the biochar was washed with
0.1 M HF (27 g.L−1, based on the biochar mass) (Uchimiya et al.,
2012). After the washing step, the solution was kept to stabilize for
10 h, and then the liquid was removed. Lastly, the biochar was dried in
the oven at 80 °C overnight (Uchimiya et al., 2012).
2.3. Characterization of the biochar
The scanning electron microscope (SEM) was carried out on corn
cob biochar to determine the surface morphology (Carl Zeiss
Microscopy GmbH, England - LEO 1455 VP model). The samples were
loaded on the tape coating with gold and the tape was stuck on an
aluminum stub before loading the samples, the surface morphology
analysis was implemented with an accelerating voltage of 20 kV. BET
(Brunauer–Emmett–Teller) method (TriStar II 3020, USA) was utilized
to investigate the specific surface area and total pore volume (TPV) of
CCB. The biochar samples were outgassed in the oven at 80 °C for 24 h,
the specific surface area and total pore volume were measured using N2
2
Bioresource Technology Reports 11 (2020) 100520
adsorption at 77.3 K. The functional groups were identified following
the FT-IR (Fourier transform infrared spectroscopy) method (Nicolet
6700 FTIR spectrometer, USA). A wavelength range of 400–4000 cm−1
was proceeded to determine the functional groups of biochar. The point
of zero charge (pHpzc) of biochar was measured by following the
method of N. Liu et al. (2016).
2.4. Adsorption experiment
The adsorption experiment was implemented using the batch
method. A fixed amount of biochar was added to the Erlenmeyer flasks
containing a volume of 2,4-D with ratio 1.5 g.L−1. Erlenmeyer flasks
were agitated by a shaker at 25 °C at 120 rpm in dark conditions until
equilibrium time. The 2,4-D solutions were taken during the experiment
to examine the remaining concentration at a wavelength of 230 nm (the
spectra were scanned at a range of 200–600 nm by UV–Vis spectro-
meter (Genesys 10S, Thermo Scientific, USA), and the maximum ab-
sorbance was observed at 230 nm). Whatman Grade 42 filter paper
(retention: 2.5 μm) was utilized for taking the filtrate from the 2,4-D
solution. In each run of the adsorption experiment, the samples were
collected in duplicates, the average values were calculated and used for
the data analysis. Moreover, the pH influence was tested to estimate the
ability of 2,4-D removal. The pH within the range of 2.0 to 12.0 were
manipulated by HCl and NaOH.
2.5. Mathematical models of kinetics and isotherm studies
The kinetics and adsorption isotherm were used to examine the
experiment results, the amounts qt (mg.g−1) of 2,4-D adsorbed on
biochar at time t, and at equilibrium time qe (mg.g−1) were determined
using Eq. (1), qt = V·(Co - Ct)/W and Eq. (2), qe = V·(Co - Ce)/W.
Where Co (mg.L−1) and Ce (mg.L−1) are the values of the initial and
the equilibrium 2,4-D concentration; W (g) is the mass of biochar and V
(L) is the solution volume of 2,4-D (Tan et al., 2016; Lam et al., 2019).
To estimate the adsorption capacities of the 2,4-D on CCB, the iso-
therm models were used to calculate the adsorption experiment data.
Langmuir isotherms showed as below Eq. (3)
Qo KL Ce
qe =
1 + KL Ce (3)
where Qo (mg.g−1) is the maximum adsorption capacity; KL (L.mg−1) is
the Langmuir isotherm constant (Tan et al., 2016; Mpatani et al., 2020).
RL is computed from the Langmuir isotherm and confirmed the fa-
vorable adsorption between adsorbent and adsorbate (Essandoh et al.,
2017). The equation of RL is presented below:
1
RL =
(1 + KL Co ) (4)
Freundlich adsorption isotherm is defined the heterogeneous ad-
sorption on the surface and is presented in Eq. (5)
1
q e = Kf Cen (5)
where Kf (mg.g−1)(mg.L−1)-n is constant of the Freundlich isotherm; n
is the adsorption intensity (Tan et al., 2016; Mpatani et al., 2020).
The adsorption kinetics of 2,4-D and CCB were defined by Pseudo-
first-order (PFO) and Pseudo-second-order (PSO). The PFO model
showed mononuclear sorption (Eq. (6)), whereas the PSO model illu-
strated binuclear sorption (Eq. (7)) (Tan et al., 2016), the equations are
showed below:
ln (q e − qt) = ln q e − k1t (6)
t 1 1
= + t
qt k2q 2e qe (7)
−1 −1 −1
where: k1 (h ) of PFO model and k2 (g.mg .h ) of PSO model are
the sorption rate constants.
Q.A. Binh and H.-H. Nguyen
2.6. Statistical analysis
All experiments were performed in duplicates. The parameters of
adsorption isotherm, adsorption kinetic data, the correlation coeffi-
cients (R2) were calculated by Microsoft excel 2010. The error bars
displayed in figures were accomplished by the Origin 6.0 Professional.
3. Results and discussion
3.1. Characterization of the corn cob biochar
3.1.1. Biochar surface characterization
The surface morphology of non-modified and acid-modified biochar
are presented in Fig. S1. The results indicated that the pore size on
surface morphology of non-modified and acid-modified CCB were
ranged from 4.01–31.05 μm and 3.85–21.16 μm, respectively. The
surface morphology of non-modified CCB contained a lot of minerals.
Whereas, biochar that was modified with HF acid had less or no mi-
nerals on the surface areas. This improved the biochar surface and al-
lowed higher adsorption capacities (Zhang et al., 2016).
3.1.2. The point of zero charge, specific surface area, and the total pore
volume of corn cob biochar
The point of zero charge (pHpzc) of biochar was verified by the
batch experiment and was 1.1. The charge of the biochar surface de-
pends chiefly on this pHpzc. When the pH of the solution was adjusted
to values greater than this pHpzc, the surface of biochar will be nega-
tively charged. However, if the pH of the solution is lower than this
pHpzc, the surface of biochar will generate positively charged (N. Liu
et al., 2016). The specific surface area (SSA) of CCB is presented in
Table S2 (Supplementary Materials) and was 298.01 m2.g−1. The SSA is
the major parameter to estimate the adsorption capacity of biochar. If
high SSA exposes on the biochar surface, it brings on more interfaces to
adsorb the pollution (Tan et al., 2016). Likewise, the total pore volume
(TPV) was 0.126 cm3.g−1 and the pore volume distributions of the CCB
of narrow mesopores (2–20 nm) and micropores (< 2 nm) were 57.69%
and 20.29%, respectively. The majority of the pores volume were from
micropores to narrow mesopores. The TPV is one of the main assessed
factors for the great adsorption of biochar, and the pore size of biochar
is contributed to adsorb adsorbate significantly (Wang et al., 2018).
3.1.3. Surface chemistry
The functional groups of CCB were clarified by FT-IR analysis
(Supplementary Fig. S2). Fig. S2 exhibits the FT-IR spectrum of the CCB
and presents the eight main functional groups. Peaks between 873 and
741 cm−1 represented the aromatic CeH, this disclosed the aromatic
benzene rings existing on the CCB surfaces (Tran et al., 2017). The band
at 1045 cm−1 was attributed to the CeO stretching of alcohol (Saffari
et al., 2015). The 1215 cm−1 peak was assigned to the CeO stretching
of phenolic hydroxyl (Chun et al., 2004). The 1572 cm−1 band was
ascribed to the aromatic hydrocarbon (C=C) (Saffari et al., 2015). The
1730 cm−1 peak was ascribed to the carbonyl group (C=O) disclosing
the carboxylic acid, ketone, and ester existed the surfaces of CCB (N. Liu
et al., 2015). The 2388 and 2296 cm−1 peak regions showed the ex-
istence of the ketone groups (C=O) (Nuithitikul et al., 2010). The 2917
to 2840 cm−1 peak areas represented the alkyl group (Kinney et al.,
2012). The 3615 to 3000 cm−1 peak areas and the peak at 3792 cm−1
were attributed to the stretching vibrations of hydroxyl group (OH)
(Tran et al., 2017).
From the FT-IR results, the primary functional groups of the CCB
including carbonyl, hydroxyl group, ketone, and aromatic hydrocarbon.
The hydroxyl groups are also the predominant molecule on the CCB,
they can bring on the H-bonding interaction of CCB and pollutants (N.
Liu et al., 2015). Additionally, the aromatic groups of the CCB can
produce the π-π EDA interaction between CCB and pollutants (N. Liu
et al., 2015).
3
Bioresource Technology Reports 11 (2020) 100520
Highest
removal
Lowest
removal
Fig. 1. The influence of pH on the efficiency of 2,4-D removal.
3.2. Effect of pH on 2,4-D removal
The pH values effected to the 2,4-D removal and were signified in
Fig. 1. The result showed that the competence of 2,4-D removal de-
creased when the pH values increased. The electrostatic force was
conducted by 2,4-D and the biochar surface, depending on the adjust-
ment of pH values. The greatest removal of 2,4-D was at pH 2.0
(95.0%), which was engendered by the electrostatic attraction. At
pH 2.0, the 2,4-D was generated as positively charged, because of the
solution pH is lower than the pKa of 2,4-D (2.8) (Herold et al., 2003;
Essandoh et al., 2017). Whereas, the surface charge of the CCB is ne-
gatively charged when the pH values are greater than the pHpzc value
of CCB. Consequently, the electrostatic attractiveness occurred among
the negatively charged CCB and the positively charged 2,4-D at pH 2.0,
which brought on the highest removal of 2,4-D for CCB.
When the pH values were adjusted from 4.0 to 12.0, the percentage
of 2,4-D removal decreased gradually (Fig. 1). This was demonstrated
by electrostatic repulsion. When the pH value increased (pH > 2.8),
the 2,4-D was changed in a large fraction to the anionic form (Njoku
and Hameed, 2011). In addition, the surface charge of the biochar was
negatively charged due to the solution pH is greater than the pHpzc of
CCB (pHpzc ≈ 1.1). Therefore, at pH from 4.0 to 12.0, electrostatic
repulsion was created among the anionic form of 2,4-D and the nega-
tively charged biochar surface, leading to the decrease of 2,4-D re-
moval. This result is similar to the previous work of Essandoh et al.
(2017).
In addition, at pH 12.0, the percentage of 2,4-D removal by biochar
was the lowest. If the pH values are higher than 8.0, the phenolic hy-
droxyl groups of biochar increased deprotonation, causing an aug-
mentation in the density of negative charges on the biochars (Essandoh
et al., 2017). This led to the repulsion that occurred between the phe-
nolate anions of biochar and the carboxylate anion of 2,4-D (Essandoh
et al., 2017) (Supplementary Fig. S3a). However, the carboxylate an-
ions of both biochar and 2,4-D were generated and caused the repulsion
between them (Essandoh et al., 2017) (Supplementary Fig. S3b).
Therefore, the pH of the solution at highest value caused the efficiency
of 2,4-D removal to be the lowest. This should be considered for ap-
plication in future research in 2,4-D removal.
3.3. Adsorption isotherm models of 2,4-D adsorbed on corn cob biochar
The parameters of Langmuir and Freundlich isotherm models for
2,4-D and CCB were presented in Table S3 (Supplementary Materials).
Q.A. Binh and H.-H. Nguyen Bioresource Technology Reports 11 (2020) 100520

Table 1
Kinetic parameters for 2,4-D adsorption onto corn cob biochar.
Initial concentration (mg.L−1) qe, exp. (mg.g−1) PFO parameters PSO parameters

2
qe, calc. k1 R qe, calc. k2 R2
(mg.g−1) (h−1) (mg.g−1) (g mg−1 h−1)

20 12.66 5.19 0.41 0.943 13.15 0.15 0.998

30 18.68 7.26 0.36 0.905 19.50 0.09 0.998
40 24.28 10.88 0.36 0.975 25.06 0.07 0.998
50 28.97 13.94 0.29 0.980 30.36 0.04 0.997
60 31.87 16.31 0.29 0.991 33.33 0.04 0.997

From the results in Table S3, the isotherm model of 2,4-D and CCB
followed Langmuir model, because of the R2 of the Langmuir (0.999)
was higher than that of the Freundlich (0.948) models. This proved that
the adsorption of 2,4-D and CCB following monolayer adsorption. The
maximum adsorption capacity of biochar and 2,4-D was 37.40 mg.g−1,
which was higher than the cotton plant ash and char reported in the
previous studies (Trivedi et al., 2016). From the data indicated in Table
S3 (Supplementary Materials), the RL value was 0.0004 and illustrated
favorable adsorption of CCB for 2,4-D. The RL value < 1 was also re-
ported on the 2,4-D adsorption onto switchgrass biochar (Essandoh
et al., 2017).

3.4. The kinetics adsorption models of 2,4-D and corn cob biochar

The model of PFO and PSO were utilized to determine the experi-
mental results. The kinetic parameters of CCB and 2,4-D were probed
including the adsorption capacity, the rate constants, and R2, and are
displayed in Table 1. The qe value computed from the PFO was sig-
nificantly different compared to the qe value of the experimental data.
Whereas, the qe values of the PSO were substantiated as fitting the
experimental data. The PSO plot are straight lines (t/qt against t), and
the R2 values were ranged from 0.997 to 0.998. The R2 values of the
PFO were in the range of 0.905 to 0.991 and were lower than the R2
values of the PSO. The two values of qe and R2 that were discussed
above, are shown in Table 1 and Fig. 2. The adsorption kinetics for 2,4-
D and CCB completely fitted the PSO and agreed with previous ex-
perimental results (Trivedi et al., 2016; Essandoh et al., 2017).
The kinetic experimental data were fitted to the PSO, this mani-
fested the adsorption of 2,4-D and CCB was chemisorption (Hafshejani
et al., 2016). The representation of chemisorption for the PSO model
consists of the exchanges of electrons, covalent bonds, and ions (Ho,
2006). However, the chemisorption of 2,4-D and CCB was the H-
bonding, and π-π EDA interactions. The functional groups of CCB
consist of, phenol, alcohol, ketone, carbonyl, and aromatic hydro-
carbons, that causes interactions between 2,4-D and CCB, and will be
clarified in the following sections.

3.5. Effects of the initial 2,4-D concentration

The adsorption capacity and initial 2,4-D concentration were a Fig. 2. Adsorption kinetics of 2,4-D adsorption onto corn cob biochar: (a) PFO
parallel correspondence. The result indicated that the increase of the model, (b) PSO model.
2,4-D concentration created the increase of the adsorption proficiency
(Fig. 3.). When the initial concentration was heightened, the driving
3.6. The adsorption mechanism of corn cob biochar and 2,4-D
force of the concentration gradient was reinforced, which engendered a
greater adsorption capacity (Weng et al., 2009). The correlation be-
The interactions that contributed to the adsorption mechanism of
tween the initial 2,4-D concentrations and the adsorption rate constant
biochar and organic pollutants comprise of pore-filling, electrostatic, H-
of the PSO model was considered as the inverse relation. Table 1 proved
bonding, hydrophobic bonding, and π-π EDA interactions (Tan et al.,
the adsorption rate constant k2 (PSO) of 2,4-D at the lowest con-
2015). From the results of this study, the SSA, TPV and the FT-IR results
centration was higher than the other concentrations and this result
of CCB before and after 2,4-D adsorption were changed, which verified
agreed with those reported by Weng et al. (2009). The high initial
that the pore-filling and chemical adsorption were formed between
concentration generates a low rate constant k2 (PSO) and the high rate
them (Fig. 4).
constant k2 is the result of a low concentration.

4
Q.A. Binh and H.-H. Nguyen
Fig. 3. The adsorption capacity plot of the corn cob biochar and 2,4-D (CCB
dosage = 1.5 g/L, and pH = 2.0).
The pore size results in Table S2 (Supplementary Materials) showed
that the CCB had an abundant distribution of micropores (20.29%) and
narrow mesopores (57.69%). The size of the molecular structure of 2,4-
D was 1.54 × 0.56 × 0.22 nm analysed by the calculation of
ChemBio3D software (H. Liu et al., 2015). The CCB pore size is rea-
sonably close to the dimension of 2,4-D molecular. Therefore, the 2,4-D
was able to be adsorbed inside the micropore sizes (< 2 nm) and small
mesopore sizes (2–20 nm) of CCB. The pore-filling adsorption partici-
pated in the adsorption process when the molecular dimension of ad-
sorbate is similar to the pore size of biochar (Lian et al., 2016).
Moreover, the TPV and SSA of the CCB specified before and after
2,4-D adsorption changes. The SSA of the CCB before and after ad-
sorption were 298.01 m2.g−1 and 159.80 m2.g−1, and the TPV of the
CCB were 0.126 and 0.068 cm3.g−1, respectively. The decrease of the
SSA and TPV of the CCB after 2,4-D adsorption due to the biochar pore
size and the 2,4-D molecular size expounding. This proved that the
pore-filling was the mechanism in the adsorption process of the CCB
and 2,4-D (Fig. 4a).
Chemical adsorption was generated by the interactions of the
functional groups of CCB and the 2,4-D. The proposed chemical inter-
action of 2,4-D and CCB consisted of π-π EDA interactions, H-bonding
and clarified by the FT-IR analysis (Supplementary Fig. S4 and Table 2).
H-bonding is an attractive interaction between a hydrogen (H) atom
and an electronegative atom such as oxygen (O), nitrogen (N), and
fluorine (F) (Arunan et al., 2011). Supplementary Fig. S4 and Table 2
displayed the creation of H-bonding and the alteration of FT-IR analysis
after the adsorption of 2,4-D. The peak and peak region were shifted
including peak at 1730 cm−1 (C]O of carbonyl group), peak at
1045 cm−1 (the CeO stretching of alcohol), peak at 1215 cm−1 (phe-
nolic hydroxyl), peak area 2388–2296 cm−1 (C]O of ketone group),
and peak area 3615–3000 cm−1 (OeH of carboxyl, phenol, and al-
cohol) (Supplementary Fig. S4 and Table 2). All of the peaks propose
that H and O atoms of these functional groups participated in H-
bonding. According to Essandoh et al. (2017), carboxylic acid and the
phenolic groups of CCB can act as hydrogen donors. Therefore, an H
atom from alcohol, phenol, and carboxyl groups of the biochar en-
gendered the H-bonding interaction with O atom from carboxylated
and carbonyl groups of 2,4-D (Fig. 4b and c). Moreover, the H-bonding
was formed between the O atom from alcohol, carboxyl groups of
biochar and H atom of 2,4-D (Fig. 4b and c) (Essandoh et al., 2017).
π-π EDA interactions were engendered between two π -electrons in
the aromatic rings of a carbonaceous adsorbent and an adsorbate (Tran
5
Bioresource Technology Reports 11 (2020) 100520
et al., 2017). The π-π EDA interactions between the CCB and 2,4-D are
exposed in Fig. 4d. The alteration of the peaks (1572 cm−1) proved that
the aromatic hydrocarbon (C=C) involved in the π-π EDA interactions
(Supplementary Fig. S4 and Table 2). The hydroxyl group (OH) of CCB
is an electron giving group, which generates the rich electron density (π
−
) in aromatic rings of CCB (Liao et al., 2008). The halogen (Cl) of 2,4-
D is able to perform electron-withdrawing, which brought on the nu-
cleus to hold a positive charge (π +) (Sykes, 1985). Therefore, π-π EDA
interactions were engendered between 2,4-D and the C]C (aromatic
hydrocarbon) of the CCB. Various effective groups of CCB include,
carboxylic acid groups, alcohol, and phenol, engendered the H-
bonding. Whereas, only the aromatic hydrocarbon compound of CCB
formed the π-π EDA interactions (Fig. 4d). Hence, the H-bonding was
the most important of chemical interaction.
In conclusion, the adsorption mechanism of CCB and 2,4-D consist
of the pore-filling, π-π EDA interactions, and H-bonding, however, the
H-bonding was the main contributor.
3.7. The financial assessment for corn cob biochar
Following recent research for estimating the price of biochar, the
biochar production cost includes the total capital investment, operating
costs, and electricity consumption. The capital investment consists of
the cost of the equipment, civil work, direct installation, and the aux-
iliary equipment. The operating costs included labor cost, storage cost,
feedstock purchase cost, transportation cost, and maintenance cost
(Ahmed et al., 2016). However, in this study, we synthesized a small
amount of biochar in the laboratory, therefore, the cost of biochar can
be estimated by feedstock purchase cost, HF acid cost, and electricity
consumption. Moreover, the feedstock of corn cob was collected from
agricultural waste, and HF acid was used in a small amount. Hence,
feedstock purchase cost and HF acid cost can be estimated as zero. The
electricity consumption of the furnace was estimated based on the en-
ergy consumption ($ (USD) 1.344/each of the pyrolysis, Vietnam
electricity prices). The furnace synthesized 24.0 g of biochar product
(6.0 g × 4 ceramic pots = 24.0 g) for each time. Therefore, the price
for corn cob biochar was $ 56 kg−1 (24.0 g of biochar costs $ 1.344).
The price of corn cob biochar is higher than those of biochar produc-
tions in the UK ($8.85 kg−1) and US ($13.48 kg−1) (Ahmed et al.,
2016). However, the corn cob biochar of this study was synthesized in a
small scale at the laboratory, if the corn cob biochar synthesis for a
large scale, the cost of corn cob biochar will be decreased. The biochar
cost was significantly reduced using the mobile pyrolysis units and
improved logistics (Ha et al., 2010). Moreover, corn cob biomass is in
large quantities, the corn production in Vietnam achieved 5.5 million
tons in 2013, corn farming was cultivated in northeastern and central
Vietnam (Viet et al., 2015). Therefore, the adsorbent from corn cob is a
low financial input. The plant origin is a source of raw materials pro-
viding from other industries (Machová and Vrbka, 2018). From this
study, the high adsorption proficiency in 2,4-D removal is achievable
using the CCB which is economic, abundant, and nature-friendly ad-
sorbent. The CCB product can be further applied in the wastewater
treatment plants as well as the water supply units.
4. Conclusions
This study demonstrated that corn cob biochar had a great profi-
ciency for 2,4-D removal; and explored the overview of their adsorption
mechanism. The pH parameter was a key factor for 2,4-D removal on
CCB. The experimental adsorption data followed the PSO model and
Langmuir isotherm. The adsorption mechanism between CCB and 2,4-D
consists of the pore-filling and the chemical adsorption including the π-
π EDA interactions and H-bonding. Nevertheless, the H-bonding was
the key adsorption mechanism. Overall, corn cob biochar was suc-
cessfully produced from inexpensive source and possessed a potential
quality to contribute for the purifying of pollutants.
Q.A. Binh and H.-H. Nguyen Bioresource Technology Reports 11 (2020) 100520

Fig. 4. The suggested adsorption mechanism of the corn cob biochar and 2,4-D.

CRediT authorship contribution statement Declaration of competing interest

Quach An Binh:Investigation, Writing - original draft, Writing - The authors declare that they have no known competing financial
review & editing.Hong-Hai Nguyen:Conceptualization, Data cura- interests or personal relationships that could have appeared to influ-
tion, Methodology, Software, Writing - review & editing. ence the work reported in this paper.

Table 2
The intensity change (% transmittance) of FT-IR of corn cob biochar before and after 2,4-D adsorption.
Wavenumber Ascribed to the type of vibration The functional group Intensity changes Proposed interactions
(cm−1) (% T)

1045 C-O C-O stretching of alcohol 0.48 H-bonding

1215 C-O C-O stretching of phenolic hydroxyl 0.62 H-bonding
1572 C=C Aromatic hydrocarbon 0.24 π-π EDA
1730 C=O Carbonyl group 0.60 H-bonding
2388–2296 C=O Ketone group 0.14 H-bonding
3615–3000 O-H Alcohol, phenol, carboxylic acid 0.84 H-bonding

6
Q.A. Binh and H.-H. Nguyen
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.biteb.2020.100520.
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