Journal of Environmental Chemical Engineering 10 (2022) 108815

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Journal of Environmental Chemical Engineering

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

Preparation of activated carbon from spent coffee grounds and

functionalization by deep eutectic solvent: Effect of textural properties and
surface chemistry on CO2 capture performance
Alivia Mukherjee , Biswajit Saha , Catherine Niu , Ajay K. Dalai *
Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical and Biological Engineering, University of Saskatchewan, Saskatoon, Saskatchewan,
Canada

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

Editor: Dong-Yeun Koh Spent coffee grounds have been selected as a potential feedstock to synthesize activated carbon (AC) through
physical activation. The activation parameters were optimized by employing the Box-Behnken design method.
Keywords: The impact of input activation parameters included the activation temperature (600–800 ℃), holding time
Spent coffee grounds (60–120 mins) and CO2 flow rate (150–250 mL/min). Accordingly, at the optimum conditions obtained at 800
Activated carbon
℃, 90 min and 150 mL/min, the predicted response of specific surface area (1202.1 m2/g) was in good
Deep eutectic solvent
agreement with the actual response 1224 m2/g. Furthermore, natural deep eutectic solvent (DES) has been used
Post-combustion capture
Adsorption to tailor the surface functionalities of the optimized AC (pristine). The change in textural characteristics, surface
chemistry and morphology of the pristine and DES-AC samples were characterized by using complementary
analytical techniques, including ultimate analysis, ash content, textural characteristics, XRD, CO2-TPD, TGA, XPS
and SEM analyses. The studies highlighted change in physicochemical properties after the DES impregnation. For
instance, the specific surface area of the DES-functionalized AC reduced to 1033 m2/g, but more basic functional
moieties developed on the surface. The DES functionalised AC has shown adequate CO2 capture performance of
5.5 mmol/g compared to pristine AC (4.34 mmol/g) at 25 ℃ and 15 vol% of CO2 (in N2). Furthermore, DES
functionalized AC has shown excellent selectivity in a dynamic mixture stream of CO2/N2 and facile regeneration
(92% retention) after multiple adsorption-desorption runs. Hence, preparing AC from SCG derived biochar via
physical activation and DES impregnation could be proposed as a promising valorization strategy to alleviate the
CO2 emission problem.

1. Introduction
In the last few decades, anthropogenic emission of greenhouse gases,
mainly carbon dioxide (CO2) in the ambient air, has been considered as
one of the primary driving forces due to the assertion that it triggers
global warming [1]. The emission of CO2 accounts for about
three-quarters of total greenhouse gas emissions and is one of the critical
factors in the worldwide climate change scenario and ocean acidifica­
tion. Owing to the mass combustion of the most utilized energy source
such as fossil fuel resources (petroleum or coal) to sate the global energy
demand due to the abundant availability and economic efficiencies, the
emission of CO2 and the global warming issues have triggered [2].
Presently, the atmospheric concentration of CO2 has approached a level
of approximately 415 ppm from the pre-industrial time, which is already
beyond the earth’s total capacity [3]. The rise in global average tem­
perature by more than 2 ℃ would lead to serious environmental con­
sequences. Foreseen detrimental consequences of this phenomenon can
be observed globally, such as extreme forest fires and heatwaves,
melting of ice sheets and glaciers in the Antarctic, and rising sea levels. It
can be attributed to the increased atmospheric concentration of CO2 to
approximately 570 ppm in 2100 [4].
Carbon capture and storage (CCS) technologies would help to evade
the disastrous impacts on the eco-system strategically and combat car­
bon dioxide emissions [5]. Among all the available CO2 capture tech­
nologies, the post-combustion CO2 capture technique has comparatively
gained popularity owing to its low technological risk. It can be easily

* Correspondence to: Distinguished Professor and Canada Research Chair, Department of Chemical and Biological Engineering, University of Saskatchewan, 57
Campus Drive, Saskatoon, Saskatchewan, S7N 5A9, Canada.
E-mail address: ajay.dalai@usask.ca (A.K. Dalai).

https://doi.org/10.1016/j.jece.2022.108815
Received 18 July 2022; Received in revised form 29 September 2022; Accepted 17 October 2022
Available online 19 October 2022
2213-3437/© 2022 Published by Elsevier Ltd.
A. Mukherjee et al.
retrofitted to the existing emission sources without excessive distur­
bance to their operational structure to combat global warming [6].
Commonly used post-combustion CO2 capture techniques include
amine-based or ionic-liquid-based absorption [7]. Although adsorption
on solid adsorbent has been proposed as a mature and promising capture
technique instead of chemical absorption using amine-based solvents
owing to its high heat of absorption, high energy demand for regener­
ation, corrosivity of the reaction medium and expensive economics [8].
Recently, intensive research interests have been observed to developing
carbon-based adsorbents with higher adsorption capacity, renewability,
and faster kinetics, such as zeolites [9], metal-organic frameworks
(MOFs) [10], and engineered carbonaceous porous materials [11]. A
strategy to promote a bio-based and sustainable economy could be
achieved by undertaking valorization of lignocellulosic biomass to
produce value-added products like biochar or activated carbon (AC)
could eventually minimize the accumulation of waste. In Canada,
biomass-derived from coffee industries mainly spent coffee grounds
(SCG) are underutilized and are arbitrarily disposed of in open landfills,
escalating severe environmental issues like methane generation. How­
ever, SCG has displayed interesting inherent physicochemical properties
that could be valorized to produce value-added products [12]. Valo­
rizing SCG to synthesize AC brings two-fold benefits from the commer­
cial perspective. Firstly, the volume of SCG generated can be reduced
and secondly, its outstanding physicochemical properties can be utilized
to produce carbonaceous adsorbent that can trap recalcitrant CO2. Our
previous study investigated the CO2 adsorption potential of torrefied
biomass derived from SCG from torrefaction [13] and biochar from slow
pyrolysis [11]. However, further thermal treatment at elevated tem­
perature or surface functionalization is necessary to enhance the CO2
adsorption performance [14]. Furthermore, the synthesis of AC utilizing
SCG can be proposed as a potential strategy to promote a bio-based
economy owing to its abundant availability at a low price with pro­
spective to compete with commercial AC, which is mainly synthesized
from non-renewable sources and are generally expensive [15,16].
Conversion of SCG to produce AC is executed through two activation
pathways: physical and chemical activation techniques. Amongst the
two activation techniques, the physical activation is preferable owing to
the absence of harsh chemical treatment. It doesn’t involve any addi­
tional corrosion problems and washing stage. Synthesis of ACs via
physical activation involves a twofold process of pyrolysis and subse­
quent activation in the presence of suitable oxidizing agents for instance
air, steam (H2O) or CO2 [17,18]. Amongst the oxidizing agents, H2O and
CO2 are widely applied as the activating agents that undergo endo­
thermic reaction with adequate temperature controllability. The steam
activation process involves generating steam using a steam generator
and a metering pump and is more energy-intensive than CO2 activation.
In CO2 activation, the activating agent can be consumed directly from
the gas tank [19]. Also, the CO2 activation process permits tailoring of
the pore structure and generates narrow microporosity compared to
steam activation [19]. This behaviour of developing different porosity
by steam or CO2 could be attributed to the way of interacting with the
active sites of the carbonaceous material located at the pore-centre and
pore-wall [20]. Hence, the CO2 activation process is an economical and
more convenient pathway to synthesize ACs for CO2 capture than steam
activation [16]. Accordingly, in this regard, physical activation using
CO2 has been explored as a more straightforward strategy. It has the
potential to synthesize porous AC with well-developed textural prop­
erties and surface functionalities.
CO2 being Lewis acidic in nature can be trapped well onto a surface
containing basic N/O-functionalities, resulting in a superior adsorption
performance. Several research initiatives are underway to modify the
surface functionalities of AC. In this regard, the natural deep eutectic
solvents (DES) can be considered as a suitable solvent owing to its
abundant availability, biodegradability, performance, and price, which
can enhance the surface functionalities by adding more basicity neces­
sary for superior CO2 capture performance. Literature available has
2
Journal of Environmental Chemical Engineering 10 (2022) 108815
shown the comparative performance of raw and functionalized AC with
DES derived from two-step physical activation. Recently, Hussin [21]
have studied and compared the CO2 capture performance of raw and
functionalized AC derived from palm shells. They synthesized DES using
choline hydroxide, glycerol, and urea to tailor the surface functionalities
with more N-containing functional moieties. They reported that DES
synthesized using choline hydroxide and urea has shown superior CO2
capture performance than other functionalized (choline hydroxide:
glycerol) and raw AC samples performed under a similar capture
scenario.
Furthermore, manipulating the activation pathway is crucial to
maximize the total AC yield and synthesize AC with higher specific
surface area. In this regard, the one-parameter factor at a time meth­
odology has been studied extensively and mainly reported to determine
the optimum activation conditions. However, with many process pa­
rameters, these single-dimensional searches become time-consuming
and uneconomical as it overlooks the interaction between independent
input parameters. In recent, response surface methodology (RSM) has
been employed to study optimizing the process parameters and their
interaction between different process parameters. The RSM, coupled
with the Box Behnken Design (BBD), has become an efficient statistical
tool to synthesize optimized AC. It is a well-established design meth­
odology that uses the least number of experiments but also analyses the
interaction between different process parameters towards the output
response but avoid treatment combinations at an extreme range [22].
This study aimed to synthesize AC from SCG-derived biochar (SCG-
600) using CO2-induced physical activation to have desired elemental
composition, well-developed textural properties, morphology, surface
basicity and availability of active sites of basic functional moieties
necessary for enhanced CO2 capture performance. For this reason, the
significant activation parameters influencing the activation process
were optimized using the RSM coupled with the BBD (Box Behnken
Design) methodology. The influence and interaction of three activation
input parameters, namely activation temperature (℃), holding time
(min) and CO2 flow rate (mL/min), were evaluated to generate AC with
optimised specific surface area (SBET, m2/g) and total AC yield (wt%).
Consequently, the novelty of this study is that it involves the preparation
of DES by using choline chloride (ChCl) and urea followed by DES
functionalization of SCG-derived optimised and pristine AC sample. The
physicochemical transformation of pristine and DES functionalized AC
samples were compared in terms of elemental content obtained through
ultimate analysis, ash content, textural properties (SBET, pore-size dis­
tribution and total pore volume), TGA analysis, CO2-TPD analysis, XPS
analysis, XRD and SEM analyses. Moreover, the effects of adsorption
temperature (℃) and CO2 concentrations in N2 (vol%) on the equilib­
rium CO2 adsorption capacities of the pristine and DES treated AC
samples were assessed through breakthrough adsorption performance to
obtain a co-relationship between the adsorption capacity and the
adsorption conditions under simulated feed conditions. Further, the
selectivity of the AC samples towards CO2 in a binary flue gas stream
(CO2/N2) were investigated and the stability of the AC samples were
analyzed through the multiple adsorption-desorption cycle technique.
Finally, the as-synthesized optimum AC (pristine and DES impregnated
AC) and data reported in the literatures were compared and tabulated in
terms of the CO2 adsorption capacity.
2. Box-Behnken experimental design and statistical analysis
The Box-Behnken design (BBD) in Response surface methodology
(RSM) is a strong statistical tool, which is adopted to evaluate the
relation between independent input process parameters and output re­
sponses for the determination of the optimum conditions by reducing
the number of experiments and thus the overall cost of experiment.
Owing to its simplicity and feasibility, it provides meaningful conclu­
sions with interactive effects of operating parameters on output re­
sponses [23]. In this research, three independent factors and three level
A. Mukherjee et al.
Box-Behnken design (BBD) method were utilized to investigate the
correlation between the combined and interaction effects of individual
input process factors (activation temperature, holding time and CO2
flow rate) to both responses (specific surface area and activated carbon
yield). The factors and levels examined in this research to perform the
CO2 activation is shown in Table 1. The activation temperature, holding
time and CO2 flow rate were chosen as the crucial parameters to be
optimized owing to their significant influence on the textural properties
(specific surface area, SBET, m2/g) and AC yield (wt%). The input pa­
rameters were designated as A, B and C varied from low to high values
and were coded as − 1, 0 and + 1 as summarised in Table 1. In this
regard, A represented the activation temperature (600–800 ◦ C), B the
holding time (60–120 min) and C, the CO2 flow rate (150–250 mL/min).
The complete design matrix in actual and coded values along with the
responses (actual and predicted) is summarized in Table 2. The
three-factors-three level BBD model comprises a total of 17 runs among
which 12 are factorial and 5 central runs. The responses chosen for this
study were specific surface area (Y1) and AC yield (Y2) at atmospheric
pressure condition.
3. Materials and methodology
3.1. Materials section
In this work, high-purity nitrogen (N2, 99%) and carbon dioxide
(CO2, 99%) cylinders were obtained from the Praxair Co. Saskatoon, SK,
Canada. High purity choline chloride (ChCl, 99% purity) and urea (98
+% purity) were obtained from the Thermo Scientific ™.
3.2. Physical activation process and activated carbon production
The physical activation setup included a lab-scale fixed-bed reactor
made of Inconel tubing, as shown in Fig. S1. The specification of the
fixed-bed reactor is presented in our previous work [11]. The biomass
collection, pre-treatment conditions and preparation of biochar from
SCG through the slow pyrolysis technique is mentioned in detail in our
previous work [11]. For this study, physical activation of SCG-600 was
conducted using CO2 as the activating agent. The biochar was sieved to
maintain the particle size of < 500 µm before undergoing the physical
activation. A sample (SCG-600) size of 20 ± 0.5 g was used per batch of
an experiment run. To ensure inert conditions maintained inside the
reactor system, N2 gas was initially fed inside the fixed-bed reactor for
30 min under a flow rate of 100 mL/min, controlled and monitored by
the mass flow controller (MFC). This is followed by subsequent heating
to activation temperatures in the range of 600–800 ◦ C increased from
the ambient temperature at a constant ramping rate of 5 ◦ C/min con­
ducted under N2 flow (100 mL/min). Once the peak temperature was
reached, the gas was switched from N2 to desired flow rates of CO2
maintained in the range of 150–250 mL/min, controlled and monitored
by the MFC. Once the desired activation temperature was reached, the
system condition was held in that state for 60–120 min to allow
CO2–carbon reaction, widening of unreachable pores and elimination of
carbon monoxide from the carbon matrix. After completion of the CO2
activation, the reactor was allowed to cool to ambient temperature by
Table 1
Factors and levels in CO2 activation.
Coded levels
Factors Name Symbol Unit Low Intermediate High
(− 1) (0) (+1)
A Activation X1 ºC 600 700 800
temperature
B Holding time X2 min 60 90 120
C CO2 flow rate X3 mL/ 150 200 250
min
3
Journal of Environmental Chemical Engineering 10 (2022) 108815
natural cooling performed under N2 flow. The resultant AC samples
were appropriately labelled and stored in glass vials and kept inside a
desiccator to avoid moisture absorption or contamination for further
analyses, functionalization, and CO2 adsorption experiments. Conse­
quently, the AC yield from each run was also measured according to Eq.
(1).
AC yield (%) = W2/W1*100 (1)
where, W2 is the final weight of the AC synthesized and W1 is the initial
weight of the biochar (SCG-600).
3.3. Preparation of natural deep eutectic solvent
In this regard, to functionalize the surface of pristine AC samples, the
natural deep eutectic solvent (DES) was prepared by mixing choline
chloride (ChCl) and urea in different molar ratios as shown in Table 2.
Firstly, to remove any excess moisture, urea was pre-dried at 45 ± 5 ℃
in a vacuum oven for 48 h before synthesizing the solvent. The deep
eutectic solvent was prepared according to the method reported by
Hussin [21]. Choline chloride and urea were stirred using magnetic
stirrer (350 rpm) at different molar ratios ranging from 1:0.1–1:0.5 and
maintained at a temperature of 80 ℃ for 2 h until a homogeneous and
transparent liquid phase was obtained after mixing, as demonstrated in
Fig. 1. Finally, all the as-synthesized DES samples were dried in a vac­
uum oven at 110 ℃ to remove the traces of excess moisture and
collected in a well-sealed glass container for further functionalization
and experiments.
3.3.1. Impregnation technique and preparation of DES functionalized
activated carbon samples
The optimized AC derived from SCG was thoroughly mixed with DES
at a fixed ratio of 1:2, at approximately 65 ± 5 ℃ for 2 h using ultra-
sonication. In this regard, impregnation has been defined as the mass
of optimized pristine activated carbon to the mass of DES that was used
to synthesize functionalized activated carbon. Fig. 1 demonstrates the
natural DES preparation technique and impregnation procedure. For the
impregnation to occur, the DES mixed AC samples were left at room
temperature for 24 h. Once the impregnation was over, the AC samples
were washed thoroughly with distilled water, filtered, and subsequently
oven dried over-night at 110 ℃. Once the drying was over, the samples
were collected, labelled accordingly, and kept in a desiccator for further
analyses and adsorption performances. The samples obtained were
labelled as AC-DES-x, where x denotes the corresponding molar ratios
used to prepare the DES. For instance, AC-DES-0.1 means activated
carbon sample functionalized using DES solution of choline chloride and
urea mixed at a molar ratio of 1:0.1. Table S1 demonstrates the list of
DES solvents used to tailor the surface of AC.
3.4. Characterizations
Following characterizations were performed to analyze the physi­
cochemical characteristics of the pristine and DES-functionalised AC
samples are described in the section below:
The amount of ash content (proximate analysis) in the tested samples
was assessed based on the standard ASTM method as described in our
previous study [11] and is presented below. Each analysis was carried
out on a dried basis and repeated in triplicates to estimate the error.
Ash content (ASTM E1755–01): Subsequently, the ash content was
evaluated by heating the AC samples at a temperature of 575 ± 10 ◦ C for
4 h in a muffle furnace. Ash content is estimated by calculating the
weight loss of the sample (before and after heat treatment).
Using the Vario EL III CHNS Analyzer, the elemental composition (C,
H, N and S) was determined in the tested sample. The mass balance was
used to determine the oxygen content (O), as shown in Eq. (2). Each
analysis was repeated in triplicate to estimate the error.
A. Mukherjee et al. Journal of Environmental Chemical Engineering 10 (2022) 108815

Table 2
Experimental and model predicted responses (Y1 and Y2) by varying the activation input parameters.
Std. Run No. Real Value Coded Value Specific surface area (m2/g) Activated carbon yield (wt%)

R1 R2 R3 C1 C2 C3 Actual Predicted Actual Predicted

4 1 800 120 200 1 1 0 1146 1152.8 55.3 55.6

15 2 700 90 200 0 0 0 767 764.6 61.7 61.2
6 3 800 90 150 1 0 -1 1224 1202.1 57.4 57.1
17 4 700 90 200 0 0 0 747 752.3 62.5 63.1
5 5 600 90 150 -1 0 -1 611 602 63.5 63.8
1 6 600 60 200 -1 -1 1 577 570.3 64.8 64.5
2 7 800 60 200 1 -1 1 982 988 58.7 59.1
10 8 700 120 150 0 1 -1 827 842.1 60.2 60.3
14 9 700 90 200 0 0 1 757 764.6 61.8 62.1
3 10 600 120 200 -1 1 0 582 576 63.8 49.7
11 11 700 60 250 0 -1 1 729 714 63 62.9
12 12 700 120 250 0 1 1 833 817 60.8 60.9
16 13 700 90 200 0 0 0 768 762 62.5 62.1
9 14 700 60 150 0 -1 0 759 774.9 62.8 62.7
13 15 700 90 200 0 0 0 784 764.6 62 62.1
7 16 600 90 250 -1 -1 1 640 662 64 64.3
8 17 800 90 250 1 0 1 1047 1056.1 57.9 57.6

Note: (R: Real value) R1: Activation temperature; R2: Holding time; R3: CO2 flowrate and (C: Coded value) C1: Activation temperature C2: Holding time and C3: CO2
flow rate

Fig. 1. Deep eutectic solvent preparation and impregnation technique.
Oxygen content (O) wt% = 100- (C+ H + S+ N + ash)
Where, C (carbon, wt%); H (hydrogen, wt%); N (nitrogen, wt%) and S
(sulphur, wt%).
The textural properties of the tested samples were determined using
a Micromeritics instrument (Model ASAP-2020). The surface area (SBET)
of the tested sample was determined by using the BET method, whereas
to assess the pore volume and pore size of the tested samples, the BJH
model was used. The IUPAC classification (International union of pure
and Applied Chemistry) was considered for the pore size distribution.
Before the analysis, the tested sample was degassed at 300 ◦ C for 4 h
under vacuum maintained at 500 mm Hg to eliminate excess moisture
and traces of absorbed gases present on the surface of the tested samples.
This is followed by N2 adsorption-desorption analysis performed at a
temperature of − 196 ◦ C. To determine the micropore size distribution
of the tested sample, the Nonlinear Density Functional Theory (NLDFT)
model as provided by the software was applied using N2 adsoprtion at
77 K on slit-pore carbon. The software provided the micropore-size
distribution from 0.7 nm onwards and the corresponding cumulative
and incremental pore volume. The TGA analysis was performed to
examine the devolatilization behaviour of the tested samples. Using the
TGA Q500 instrument the analysis was executed. About 10 − 20 mg of
the tested sample was heated in an inert environment at a temperature
range of 25 − 600 ◦ C in the presence of Nitrogen gas (N2) purged at
60 mL/min of flow rate. The heating rate during the thermal degrada­
tion was maintained at 10 ◦ C/min. The X-ray diffraction (XRD) tech­
nique was used to analyze the X-ray diffractogram of the tested samples.
The analysis was performed using an Advance Diffractometer (Bruker
D8) equipped with Cu K-α source of radiation (λ = 1.54 Å). In this re­
gard, the powder XRD data were collected in the two-theta range of
10–80◦ and a scan rate of 1.36◦ min− 1. The X-ray photoelectron spec­
troscopy (XPS) analysis was collected using a Kratos AXIS Supra in­
strument. The spectrometer is equipped with a Rowland circle (500 mm,
Al K-α source) and a combined hemispherical and spherical mirror
analyzer. To conduct a high-resolution analysis, an accelerating voltage
and current of 15 keV and 10 mA was maintained. The CO2-Tempera­
ture-programmed desorption (TPD) study of the activated carbon sam­
ples (pristine and DES-functionalized) was performed with the aid of a
Micromeritics chemisorption Analyzer (AutoChem, 2950 HP). In a
typical CO2-TPD experiment, before the TPD analysis, the sample was
first degassed at 300 ◦ C under He flow maintained for 30 min. With
anhydrous CO2 gas (5.21% CO2 in He), the adsorption was performed at
100 ◦ C and held for 30 min. This is followed by flushing the sample with
He for 30 min to remove the physically adsorbed CO2 and recording the
(2)
desorption profile at 100–700 ◦ C in presence of He purged at a rate of
50 mL/min. The morphologies of the tested samples were acquired
using a scanning electron microscope (SEM, Hitachi SU8010). The im­
aging of the tested samples functioned at a voltage of 3 kV voltage
maintained under a high vacuum. Prior to SEM imaging, gold was used
to coat the tested samples with the aid of A Q150T ES sputter coating
instrument. Details regarding the analytical techniques mentioned
above are also provided in the previous work done by our research group
[11–13,24].
3.5. Breakthrough carbon dioxide adsorption setup
Breakthrough carbon dioxide adsorption experiments were per­
formed in an isothermal Inconel tubular reactor. The schematic diagram
of the fixed-bed CO2 adsorption setup (as also presented in our previous
work) is demonstrated in Fig. 2. Specification of the fixed-bed labora­
tory-scale reactor is summarized in Table S2. Inside the middle of the
fixed bed reactor, a K-type thermocouple was placed coupled with a
temperature controller (2416, Eurotherm). Silicone rubber insulated
heating tape was used to supply heat to the reactor. The binary mixture
of pure CO2 and N2 were fed through the reactor, and the flow rates
(maximum 200 mL/min) were controlled by using mass-flow controllers
(MFCs) and a metering valve coupled with a mass flow meter (maximum
flow rate of 500 mL/min). The dynamic gas concentration was measured
using a micro-GC analyzer equipped with a thermal conductivity de­
tector (µTCD).
3.5.1. Breakthrough adsorption experiments and regeneration study
Before assessing the breakthrough CO2 capture performance, the

4
A. Mukherjee et al.
Fig. 2. Schematic of CO2 adsorption setup (temperature swing adsorption, TSA).
fixed-bed reactor was loaded with 2 ± 0.1 g of AC samples and pre-
heated at 120 ºC for 2 h under a nitrogen (N2) environment to remove
the traces of moisture. This was followed by cooling down the reactor to
the desired column temperatures (25–70 ºC), and the feed gas was
switched to a mixture of CO2/N2, and the adsorption process continued
until a point of saturation was reached when the CO2 concentration in
the outlet became equal to the CO2 concentration in the inlet. CO2
adsorption capacity in this study was determined using the equation
stated in our previous work [11]. The adsorption process at 25 ºC and
desorption process at 120 ºC was repeated several times to assess their
durability under multiple cycles. The AC samples were subjected to 15
consecutive cycles of adsorption and desorption to examine their ability
to regenerate and stability.
3.5.2. Selectivity
The selectivity of binary mixture of CO2: N2 was measured according
to the IAST method using the breakthrough adsorption capacities [25].
The gas phase mixture contained CO2 and N2 at 0.15:0.85 molar ratio
(15 vol% of CO2 in N2, flue gas composition of the coal fired boiler) and
the following Eq. (3) was used to determine the selectivity of the AC
samples as also mentioned by Serafin [26]:
qCO2 @0.15bar 0.85
S(CO2/N2) = ×
qN2 @0.85bar 0.15
Where, qCO2@0.15 and qN2@0.85 represents the breakthrough adsorption
capacities of CO2 and N2 expressed in mmol/g evaluated at 25 ºC and at
the corresponding partial pressures of CO2 (0.15) and N2 (0.85),
respectively.
4. Results and discussions
4.1. Development of regression model equation
The complete three-factor-three-level design matrix for the activated
carbon production with the respective experimental (actual) and pre­
dicted values of specific surface area (Y1) and AC yield (Y2) are sum­
marized in Table 2. The findings demonstrate that the specific surface
area (Y1) ranges from 577 to 1224 m2/g while the AC yield (Y2) is found
in the range of 55.3–64.8 wt%. In this regard, the sequence of these
experimental runs was randomly accomplished to avoid bias errors due
to inessential factors. Also, the 5 central runs were performed to esti­
mate the experimental errors and data reproducibility of the experi­
mental runs [23]. It can be observed from the Table 2, that the predicted
values and the experimental findings are close, demonstrating that the
Journal of Environmental Chemical Engineering 10 (2022) 108815
developed model could identify the co-relationship between the com­
bined effect of the process parameters toward both the responses. The
sequential model sum of square formed the basis of selection of the
appropriate model to predict the responses based on the highest order
polynomial term in which the additional terms are not aliased but sig­
nificant [16]. Accordingly, the findings revealed that quadratic models
suitable to describe the responses to specific surface area (Y1) and AC
yield (Y2) owing to the lower standard deviation and higher R2 value.
The final empirical models for the responses Y1 (specific surface area)
and Y2 (AC yield) are represented by the following Eqs. (4) and (5) in
terms of coded factors.
Y1 = 746⋅60 +248⋅63 A + 42⋅63 B − 21⋅50 C +39⋅75 AB-51⋅50 AC +9⋅00
BC +75⋅33 A2 − 18⋅18 B2 +40⋅58 C2 (4)
Y2 = 62⋅10–3⋅35 A - 1⋅15B +0⋅22 C - 0⋅60 AB − 5⋅4×10-17AC +0⋅100 BC -
1⋅23 A2 − 0⋅23 B2-0⋅17 C2 (5)
Using the abovementioned equations, the predicted responses of the
specific surface area (Y1) and AC yield (Y2) were evaluated. The type of
effect each term has on the model is determined by observing the sign in
front of each coefficient. Referred to the regression Eqs. (4) and (5), the
plus sign in front of each coefficient revealed a synergistic or a positive
(3) impact, whereas the minus sign characterized the antagonistic or
negative effect on the value of the responses (Y1 and Y2). From Eq. (4), it
can be observed that the constant 746.60 was independent of any factors
either independent or interactions. It can also be observed from Eq. (4)
that the linear terms, A and B (except C), interactive terms AB and BC
(except AC) and quadratic terms A2 and C2 (except B2) had a positive
impact on the specific surface area (response: Y1) of the AC samples. The
findings denote that with increasing the magnitude of the parameters
with a positive sign would have a positive influence on the specific
surface area. Similarly, from Eq. (5) it was evident that the linear terms
except C, interactive terms (except BC) and the quadratic terms have
negative influence on the AC yield (response: Y2). Consequently, with
increasing magnitude of the corresponding parameters there will be a
negative impact on the AC yield (wt%).
4.2. Statistical analysis
The model appropriateness and significance can be further validated
through the analysis of variance (ANOVA) [27]. In this regard, ANOVA
was conducted to corroborate the stability of the quadratic model as
suggested by the Design Expert software® (version 9.0.6) for both the
responses specific surface area (Y1) and AC yield (Y2) and summarised in
5
A. Mukherjee et al. Journal of Environmental Chemical Engineering 10 (2022) 108815

Table 3 confirm the sufficiency of the model with high F-value (64.10) and a
Specific Surface area (response: Y1). very low probability value. The main effect of linear factors (A and B),
Source Sum of df Mean F-value p- value double impact of the activation temperature and holding time (AB) and
squares square quadratic term (A2) are statistically significant terms for activated car­
Model 5.629 × 105 9 62,538.96 145.47 < 0.0001 bon yield (Y2). In addition, Lack-of-fit also determines the adequacy of
(Significant) the model and should be insignificant for the reliability of the model. As
A-Activation 4.945 × 10 5
1 4.945 × 1150.25 < 0.0001 can be observed from the Tables 3 and 4, the lack-of-fit of 3.94 and 1.71
temperature 10+5 infers that the lack-of-fit is insignificant compared to the pure error. It
B-Holding time 14,535.13 1 14,535.13 33.81 0.0007
C-Flow rate of 3698 1 3698 8.60 0.0219
also infers that there are 10.93% and 30.16% chance that lack of fit this
CO2 large could occur due to noise for response Y1 and Y2, respectively.
AB 6320.25 1 6320.25 14.70 0.064 Preferably, the large value of regression coefficient (R2), adjusted R2
AC 10,609.00 1 10,609.00 24.68 0.0016 (adj-R2) and predicted R2 (pred-R2) determines the model adequacy. The
BC 324 1 324 0.75 0.4141
goodness of fit (R2 and adj-R2) were evaluated further to validate the
A2 23,889.92 1 23,889.92 55.75 0.0001
B2 1390.87 1 1390.87 3.24 0.1151 reliability of the model. Regression coefficient (R2) is a significant
C2 6931.92 1 6931.92 16.12 0.0051 parameter that determines the extent of how well the model fits the
Residual 3009.45 7 429.92 – – observation data. Consequently, regression coefficient (R2) closer to
Lack of fit 2248.25 3 749.42 3.94 0.1093 unity is desirable to determine the goodness of fit. The model fit sum­
(Not
significant)
maries in Table 5 demonstrates specifically the regression coefficient
Pure error 761.20 4 190.30 (R2) of the model for responses Y1 and Y2 were 0.995 and 0.988,
Cor Total 5.65 × 10+5 16 respectively. The values of regression coefficient obtained for the re­
sponses (Y1) and (Y2) were very high to advocate for the significance of
the model. The findings demonstrate the response variation of 99.5%
Table 4 and 98.8% owing to the independent parameters. Although only 0.05%
Activated carbon yield (response: Y2). and 1.2% of the total response variation cannot be described by the
fitted model. In this regard, the obtained R2 value indicates a good
Source Sum of df Mean F- p- value
squares square value appropriateness of this model as it exceeds the minimum value of 0.8. In
addition, the adj-R2 of 0.9878 and 0.9726 were in reasonable agreement
Model 109.19 9 3.39 64.10 < 0.0001
(Significant) with the pred-R2 of 0.9343 and 0.8839 for response of Y1 and Y2. The
A-Activation 89.78 1 10.65 474.31 < 0.0001 findings also confirm the good predictability of the model, owing to the
temperature difference between adj-R2 and pred-R2 is within 0.2.
B-Activation time 10.58 1 0.0004 55.89 0.0001 Furthermore, the reliability of the suggested model can be further
C-Flow rate 0.40 1 0.3267 2.14 0.1869
assessed through the findings of additional influential parameters such
AB 1.44 1 0.0625 7.61 0.0282
AC 0.000 1 0.25 0.00 1.000 as coefficient of variation (C.V) and adequate precision (AP) as sum­
BC 0.040 1 0 0.21 0.6597 marised in Table 5 for both the responses. Adequacy precision evaluates
A2 6.32 1 2.91 33.38 0.0007 the ratio of signal to noise (S/N). For the suggested model to be
B2 0.21 1 0.0283 1.13 0.3238
adequate, AP should be equal to or above 4. AP responses for Y1 and Y2
C2 0.13 1 0.9698 0.68 0.4364
Residual 1.32 5 0.0405 noted were 39.73 and 26.97, respectively, which are far above the value
Lack of fit 0.74 3 0.0608 1.71 0.3016 of 4 which signifies an adequate signal, and the model could navigate
(Not significant) the design space. Furthermore, the CV is also an influencing factor that
Pure error 0.58 2 0.01 determines the significance of the model suggested by the Design
Cor Total 110.52 14
Expert® software. As can be seen from Table 5, the CV value of both
responses (2.6 and 0.7) are less than 10%, and consequently, it recom­
Tables (3) and (4), respectively. In ANOVA analysis, the statistical sig­ mends that this model is feasible and advocates the reproducibility of
nificance of the corresponding parameter can be evaluated from the the experiment.
model F value and p values. As can be observed in Table 3, for response
Y1, the model F-value of 145.47 and prob> F= <0.0001 verified the
4.3. Effects of process parameters on specific surface area
sufficiency and appropriateness of the model suggested by the Design
expert software. In addition, there is 0.001% chance that an F value
The effectiveness of activated carbon is determined by its specific
(145.47) this large could occur due to noise. Fundamentally, the sig­
surface area (SBET, m2/g). Referring to ANOVA analysis for response
nificance of the model term is indicated by the p-value and the value
specific surface area (Y1) in Table 3, the activation temperature is a
indicates the probability in getting results closer to the actual data with
significant parameter influencing the specific surface area with a p-value
small difference. For instance, p-value of < 0.05 indicates that the term
of < 0.0001 and F-value of 1150.25 followed by holding time (F-value:
is significant, otherwise the p-value higher than 0.1 means that the term
is irrelevant. Thereby for Y1 it was observed from the Table 3, taking F
Table 5
and p values into consideration of the parameters for response Y1, all
The model fit summaries for the responses specific surface area and activated
linear parameters A (activation temperature), B (holding time) and C
carbon yield.
(CO2 flow rate), the two-level interactions of AB and AC (except BC) and
Model fit summaries Specific surface area Activated carbon yield
quadratic interactions of A2 and C2 (except B2) are significant terms. The
(Y1) (Y2)
combined impact of activation temperature and holding time (AB) as
well as the interactive effect of activation temperature and CO2 flow rate Standard Deviation (S.D) 20.7 0.4
Mean 810.6 61.3
(AC) had a significant effect on the specific surface area (Y1). However, Coefficient of variance (C.V 2.6 0.7
for response Y1, the combined interaction between the holding time and %)
gas flow rate (BC) were insignificant and had no significant impact on R-squared (R2) 0.9947 0.9880
the response Y1. Adj-R2 0.9878 0.9726
Pred-R2 0.9343 0.8839
In addition, results of ANOVA in Table 4 (response Y2, AC yield)
Adequate Precision (AP) 39.73 26.97

6
A. Mukherjee et al.
33.81) and CO2 flow rate (F value: 8.60). The perturbation plot in Fig. 3
(a) corroborates the findings and reveals the significant impact of acti­
vation temperature on specific surface area owing to the greatest slope.
The specific surface area enhanced from 577 to 1224 m2/g with the
increasing temperature to 800 ℃. At higher activation temperature
(800 ℃) the endothermic reaction between the carbon-matrix and CO2
intensifies. Hence, release of volatile matter, elimination reactions and
dehydration reactions are accelerated leading to the pore development
and higher specific surface area. Furthermore, the micropore develop­
ment contributes to higher specific surface area is assisted by providing
adequate holding time of around 70–90 min. A similar finding was also
reported by Yuan [28] where they observed that with increasing the
carbonization temperature to 900 ºC, the specific surface area of the
activated carbon sample increased in the range of 1003–1317 m2/g. On
the other hand, extended holding time could cause widening of pores
and results in reduced specific surface area. Similarly, intensifying the
CO2 flow rate to the highest point could negatively impact the specific
surface area owing to the severe reaction between the carbon-skeleton
and CO2 resulting in pore shrinkage. In this regard, the maximum sur­
face area of the AC sample in the range of 982–1224 m2/g was obtained
at the activation temperature of 800 ºC and holding time in the range of
60-120 min. The findings are further validated by the design matrix
summarized in Table 2. In addition, referring to Table 3, the specific
surface area was mostly impacted by the interactive interaction effect of
activation temperature and holding time. A 3D response surface plot is
presented in Fig. 3(b) that demonstrates the double effect of the sig­
nificant factors (A and B).
4.4. Effects of process parameters towards activated carbon yield
Fig. 4(a) displays the perturbation plot response plot of the AC yield
(Y2) as a function of activation temperature (A), holding time (B) and
CO2 flow rate (C). From Fig. 4(a), it can be observed the activation
temperature significantly influences the variation in AC yield owing to
the steep curvature of the slope. On the other hand, hold-time and CO2
flow rate are less sensitive towards the response Y2 due to their moderate
straight line. The activated carbon yield (64.8 wt%) was maximum at
the lowest temperature (600 ℃) and reduces with the increasing tem­
perature to 55.3 wt% at 800 ℃. Referring to Table 4, the findings can be
further validated by the F-values (474.31) of the activation temperature.
The decline in the product yield is a predictable observation and the
plausible explanation of this could be accelerated dehydration and
elimination reaction to kick off the volatile matter at higher activation
temperature. Consequently, the amount of activated carbon yield is
impacted and reduces. The activated carbon yield is also negative
impacted by the extended holding time and intense CO2 flow rate.
Fig. 3. (a): Perturbation plot of specific surface area (response: Y1), (b): 3D response of specific surface area (CO2 flowrate constant).
7
Journal of Environmental Chemical Engineering 10 (2022) 108815
Although, the influence is not as apparent as activation temperature as
can be observed from the F-value of hold-time (55.89) and CO2 flow rate
(2.14) were not that apparent as can be seen from Table 4. This
behaviour can be attributed to the excessive carbon burn-off and tar
devolatilization with prolonged holding time and shrinkage in carbon
matrix with intense CO2 flow rate. A 3D response surface plot is pre­
sented in Fig. 4(b) that demonstrates the interactive effect of the sig­
nificant factors activation temperature (A) and holding time (B) on the
response of AC yield (Y2). Rashidi [29] has also reported a similar
findings of declining product yield with increasing temperature, reten­
tion time and CO2 flow rate.
4.5. Process optimization using desirability functions and validation
Relatively excellent textural properties (SBET) and higher activated
carbon (AC) yield are estimated to guarantee the effectiveness and
economic feasibility of the mass activated carbon production process.
Consequently, high specific surface area and high yield of AC is desirable
from economic point of view. Optimizing the activated carbon produc­
tion conditions are essential to determine the optimum process param­
eters to synthesize activated carbon with larger specific surface area and
high yield of activated carbon. Although, optimizing the responses by
applying the same conditions could be challenging owing to the differ­
ence in the region of interest of the process parameters. Hence, to
determine the optimum activated carbon production conditions, the
desirability approach in the Design-Expert® software was applied to
meet the initial objective to generate high specific surface area (Y1) with
adequate AC yield (Y2). Further, a confirmatory experiment was per­
formed to validate the reproducibility of the responses generated from
the software. In this regard, the optimization criteria were set to maxi­
mize in the response values within the actual domain for specific surface
area (577–1224 m2/g) and AC yield in the range of (55.3–64.8 wt%).
Based on the analysis the following conditions were obtained as the
optimised process conditions with the maximum value of the desirability
function (0.95): activation temperature (800 ℃), holding time (90 min)
and CO2 flow rate (150 mL/min). The validation runs at the optimum
levels were performed and the findings are summarized in the Table 6.
At the optimal condition, the predicted response values for surface area
and AC yield were 1202.1 m2/g and 57.1 wt%, respectively. It can be
observed from Table 8 that the experimental findings are in closer
proximity to the predicted values with relatively small differences of
± 3.3 and ± 0.4 for both the response Y1 and Y2, respectively. Also, the
errors associated with the AC yield (Y2) is less than the errors associated
with the specific surface area (Y1). In this regard, Rashidi [29] and
Abioye [30] have reported a similar findings and have confirmed that to
substantiate the model the difference between experimental findings
A. Mukherjee et al. Journal of Environmental Chemical Engineering 10 (2022) 108815

Fig. 4. (a): Perturbation plot of activated carbon yield (response: Y2), (b): 3D response of activated carbon yield (CO2 flowrate constant).

Table 6
Validation of actual data evaluated at the optimum activation conditions.
Response Predicted Actual Standard
value value deviation
Specific surface area (SBET, 1202.1 1224 3.3
Y1)
Activated carbon yield (AC, 57.1 57.4 0.4
Y2)
and predicted value should not exceed 10%.
4.6. CO2 adsorption screening for DES treated AC samples
Adsoprtion is a transitory phenomenon, and the extent of adsorption
capacity of an adsorbent is dependent on the breakthrough adsorption
time. The CO2 adsorption test was performed to determine the break­
through time and CO2 adsorption capacity of DES functionalised AC
samples. The findings on the breakthrough time along with the
adsorption capacities of the functionalised AC samples are summarised
in Table 7.
The findings from Table 7 depicts that the type of adsorbent in­
fluences the breakthrough adsorption time and adsorption capacity. As
can be seen in Table 7, the longest breakthrough of 23 min was observed
in DES-AC-0.4. The identified breakthrough time for other DES treated
samples increased in the following order: AC-DES-0.1 (9 min), AC-DES-
0.2 (12 min) and AC-DES-0.3 (15 min). The highest adsorption capacity
of AC-DES-0.4 can be attributed to the availability of higher elemental N
and active sites on the surface of the sample that significantly influences
the CO2 adsorption performance. Based on its longest breakthrough time
and highest CO2 adsoprtion capacity, AC-DES-0.4 was selected as the
basis of functionalised AC sample for further comparative physico­
chemical analyses and CO2 capture performance with pristine and
optimised AC sample.
4.7. Ultimate analysis and ash content
The ultimate analysis was performed to estimate the value of
elemental carbon, hydrogen, nitrogen, and sulphur content in the AC
samples derived from SCG-600 that are summarised in Table 8. In this
regard, the oxygen is calculated by the difference. The results of the
analysis demonstrate that the hydrogen (H) and oxygen (O) content
decreased in both the AC samples compared to SCG-600 owing to the
release of the hetero-atoms in the form of gas at the high activation
temperature and the findings are consistent with the findings reported
by Hussin [21]. Accordingly, an enhancement in carbon (C) and nitro­
gen (N) content and declining trend of H and O content has been
detected upon CO2 activation and DES impregnation process in the
functionalised AC sample. Improved N content in DES treated sample
would also indicate successful doping of N atoms in the carbon matrix.
Enriched C and N content in AC-DES-0.4 sample would promote the CO2
adsoprtion owing to the improved Vander Waals force and acid-base
interactions [21]. Minimal ash content of the precursor is favourable
for optimal yield of AC production and the findings complement the
total AC yield reported in Table 2. From Table 8, it is observed that the C
content is considerably higher for both pristine and DES impregnated AC
samples and enriched in the range of 92.0–92.5 wt% after the CO2
activation and N-content improved to 4.1 wt% in AC-DES-0.4 after DES
functionalization than the precursor (SCG) or pyrolysed biochar samples
(SCG-600) as reported in our previous study [11].
4.8. XRD analysis
X-ray diffraction (XRD) pattern of the AC samples derived from SCG-
600 is illustrated in Fig. 5. The XRD-patterns have a substantial intensity

Table 8
Table 7
Ultimate analysis and ash content of pristine and DES-treated AC samples.
CO2 adsorption performance of DES-treated AC samples.
Sample Elemental analysis (wt%) Ash content
Sample Breakthrough time (min) Adsorption capacity (mmol/g) (wt%)
C H N S O*
AC-DES-0.1 9 3.8
AC-DES-0.2 12 4.2 AC-CO2 92.0 1.2 2.8 -N/A- 2.3 1.7
AC-DES-0.3 15 4.8 AC-DES-0.4 92.5 0.8 4.1 -N/A- 1.5 1.1
AC-DES-0.4 23 5.5 *
O content (by difference): 100- (C +H +N + S+ Ash) wt%

8
A. Mukherjee et al.
Fig. 5. XRD analysis of pristine (AC-CO2) and DES treated AC sample.
in low-angle scatter, indicating the presence of pores in the AC samples
as also evident from the SEM analysis. The XRD pattern exhibited two
broad diffraction peaks at about at about 2θ = 26◦ and 43◦ as illustrated
in Fig. 5, which correspond to the (002) and (100) plane interlayer
reflection of graphitic carbon in the AC samples [31,32]. Broad
diffraction peak at 26◦ indicate that the AC samples have a
semi-crystalline form structure in the local region and stacked aromatic
layer form structure of carbon matrix. However, after the impregnation,
the intensity of the diffraction pattern of DES treated AC sample
(AC-DES-0.4) reduced and gets weaker. Although, no significant dif­
ference could be observed in the XRD-diffraction pattern (Fig. 5). The
findings reveal the appearance of typical amorphous graphitic carbo­
naceous structure which could be due to the presence of
stacked-disordered carbon rings in the carbon samples. The develop­
ment of amorphous graphitic carbonaceous structure is favourable for
CO2 adsorption owing to the development of well-defined porous
structure as also evident from the textural characteristics. Hussin [21]
also reported a similar finding on the development of amorphous and
porous structure after the activation process and reduced peak-intensity
after the DES modification of the activated carbon samples.
4.9. Thermogravimetric analysis
The thermal degradation pattern of the precursor and selected AC
samples were studied under the N2 atmosphere, and the result is illus­
trated in Fig. 6. The TGA analysis was conducted between 25 and 600 ºC
to identify the mass reduction of each carbonaceous samples. The TGA
results of the AC samples indicated that activation occurs via a series of
processes including removal of surface-bonded moisture and volatile
matter, formation of carbon backbone and development of the porous
network in the carbon matrix. Accordingly, the temperature profile of
the samples is divided in three phases: (i) 25–100 ºC, (ii) 100–400 ºC and
(iii) 400–600 ºC. The first phase refers to the removal of moisture con­
tent from the carbonaceous samples. Minimal moisture content
(1.3–3.4 wt%) for pristine and DES treated AC sample could be benefi­
cial for CO2 adsorption. The AC samples also exhibited higher thermal
stability in phase (i) than the precursor (SCG) owing to the removal of
hydroxyl group (-OH) during the slow-pyrolysis and further during the
CO2 activation process [33]. Referring to Fig. 6, onset temperature of
both the AC samples were between 400 and 500 ºC. An appreciable shift
in the onset temperature in both pristine and DES treated AC samples
9
Journal of Environmental Chemical Engineering 10 (2022) 108815
Fig. 6. Thermogravimetric analysis of SCG and AC samples.
compared to the precursor could be attributed to an accomplishment in
de-volatilisation of the volatile components throughout the CO2 acti­
vation process. It can be observed that after the CO2 activation process
and DES-functionalization the thermal stability of the AC samples
improved dramatically compared to the precursor (SCG) in terms of total
weight loss as presented in our previous paper [11]. As can be observed
from Fig. 6, the stability of the carbonaceous adsorbents can be clearly
observed mainly in the phases (ii) and (iii). After CO2 activation, both
the AC samples exhibited negligible mass loss of 3.4 wt% and 4.3 wt% in
the range of 100–400 ºC and gradual mass loss of 8.9 wt% and 12 wt% at
400–600 ºC for pristine and DES functionalised AC samples. However,
the AC-CO2 displayed higher thermal stability compared to AC-DES-0.4
and that could be due to the evolution of vapour after the DES
impregnation process. A similar finding was reported by Jawad [34],
where they reported that compared to raw Malayasian Selantik-low rank
coal the activated Selantik coal (SC) displayed higher thermal stability
after KOH activation than the starting precursor.
4.10. Temperature-programmed desorption (TPD)
Temperature programmed desorption (TPD) technique using CO2 as
the probe gas is constantly performed to investigate the surface basicity
of carbonaceous materials and to characterize the oxygenated functional
species present on the surface of the carbonaceous sample [35]. The
temperature within which the programmed desorption by temperature
of the AC samples performed were within the range of 30–800 ºC. The
temperature range was selected to avoid collapse of the structure of the
carbonaceous samples. Fig. S2, demonstrates the CO2-TPD evolution
profiles the studied AC samples (pristine and DES functionalized sam­
ples). The distribution of basic sites in different strength of the AC
samples were estimated and summarized in Table 9.
Both the AC samples have demonstrated medium to strong basic sites
as can be observed from the Fig. S2. Furthermore, in the CO2 spectra,
multiple peaks were detected for both the carbonaceous samples. A peak
at low range of temperature (200–400 ºC) correspond to the decompo­
sition of carboxylic groups and the intensity is less in both the samples.
Peaks between the temperature ranges 450–650 ºC correspond to the
Table 9
Distribution of basic sites and temperature range.
Strength Temperature range (ºC)
Weak basicity 50–132
Medium-strong basicity 177–500
A. Mukherjee et al. Journal of Environmental Chemical Engineering 10 (2022) 108815

carboxylic anhydride and decomposition of lactones. The amount of Table 10

surface basicity in the corresponding carbonaceous samples were Textural properties of the activated carbon samples.
calculated based on the area of the CO2-TPD profiles (Fig. S2). In this Sample Specific Micro-pore Total t-plot Average
regard, the amount the total amount of CO2 evolved during the surface surface pore micropore pore width
desorption for DES treated AC (AC-DES-0.4) was 39 mmol/g and for area area volume volume (nm)
(SBET, m2/ (m2/g) (VT, cm3/ (Vmic, cm3/
pristine AC (AC-CO2) was 29.9 mmol/g. As expected, the surface ba­
g) g) g)
sicity of DES treated AC sample improved considerably than pristine AC
owing to the functionalization with the mixture of choline chloride and AC-CO2 1224 1055 0.63 0.54 1.70
AC- 1033 880 0.52 0.37 2.14
urea. The higher surface basicity is prioritized for the removal of CO2 DES-
from flue gas stream owing to the enhanced Lewis acid to base in­ 0.4
teractions and is explained further through the CO2 adsorption
performances.
micropores mostly and AC-DES-0.4 has a pronounced hysteresis loop,
indicating a higher number of mesopores.
4.11. Textural properties of the activated carbon samples It can be observed from Fig. 7 that N2 adsorption increased signifi­
cantly for both the AC samples, which indicated an increase in both the
Nitrogen adsorption-desorption isotherm carried out at 77 K reveals surface area and pore-volume compared to the precursor (SCG) and
the textural properties such as SBET, pore volume, and average pore biochar (SCG-600) as mentioned in our previous work [11] as evident
diameter of the ACs (pristine and DES impregnated) derived from SCG. from the Table 10. As evident from the sharp N2 adsorption-desorption
The shape of the N2 adsorption-desorption isotherm could reveal the isotherm, AC-CO2 has shown the highest surface area and pore volume
preliminary qualitative information of N2 adsorption on the porous with a SBET of 1224 m2/g and pore volume of 0.63 cm3/g. The change in
structure and surface area of the AC samples. Fig. 7 shows full N2 porous structure and formation of pores, mostly takes place during the
adsorption-desorption isotherm of the AC samples. The textural char­ activation process as it induces surface release of heteroatoms and vol­
acteristics of the AC samples (SBET, micropore area, total pore-volume, atiles to form more pores in the structure. However, the surface area of
micropore-volume, and pore-width) and summarised in Table 10. DES impregnated AC reduced significantly to 1033 m2/g and
In accordance with the IUPAC classification, the N2 adsorption- pore-volume reduced to 0.52 cm3/g. The finding agrees with the result
desorption isotherm of the pristine AC sample (AC-CO2) followed type reported by Hussin [21]. The decline in BET surface area and total
IV isotherm with an H4 hysteresis loop, with closed fitting and it dem­ pore-volume of the DES treated AC sample could be attributed to the
onstrates the dominance of slit-shaped micropores over mesopores, DES impregnation process followed by DES particles absorbed in the
formed by layered structure of slit-shaped micropores over mesopores. most internal part of the pores, thereby, blocking the fine pores of the
In this regard, the hysteresis loop of the pristine AC sample is categorised impregnated AC sample. Although, many active sites were created on
as type H4 hysteresis loop that are associated with the presence of slit- the functionalised AC surface which could accelerate the CO2 capture
pores in the micro-pore region and is reported for numerous AC sam­ performance under post-combustion conditions. At this moment,
ples [36]. The findings reveal that the pristine AC investigated, exhibit adsorption of CO2 is influenced by both the textural properties of the AC
microporous structure, pore size distribution mostly in the micropore sample as well as on the reaction occurred between adsorbate (CO2) and
range and improved pore-volume than functionalised AC (AC-DES-0.4) the functionalised adsorbent surface (AC-DES-0.4).
and SCG-600 [11] as also evident from the Table 10. Additionally, for The pore-size distribution is one of the main characteristics of the AC
the DES impregnated AC sample, the adsorption-desorption isotherm at when explored for gas separation process. The pores of AC are divided
a low relative pressure between 0.4 and 0.9 corresponded to type IV into three major categories: micropores (diameters <2 nm), mesopores
isotherm with a prominent but displayed considerably wide H4 hyster­ (diameters 2–50 nm) and macropores (diameters >50 nm) Shahkarami
esis loop than pristine AC indicating the formation of mesopores along [45]. Traditionally, the pore-size distribution (PSD) is evaluated using
with micropores. Referring to the Fig. 7, isotherm of AC-CO2, exhibit the N2-isotherm at 77 K. However, the quantification of
very narrow hysteresis loops, which is a trait of the presence of

Fig. 7. N2 adsorption isotherms of AC samples: AC-CO2 and AC-DES-0.4.

10
A. Mukherjee et al.
narrow-micropores below 0.7 nm becomes difficult at 77 K as the N2
molecules couldn’t penetrate easily through the small micropores.
However, to keep the process conditions similar for both the AC samples,
N2 was used to determine the micropore size distribution below 1 nm as
it is inert in nature and will not undergo any unwanted reactions while
undergoing adsoprtion-desorption with the surface functional moieties
of the DES treated AC sample. Referring to Table 10, the average
pore-size of pristine AC and DES treated AC were 1.70 and 2.14,
respectively. Owing to the significant enlargement of the pore-space, the
average pore-diameter in DES treated AC sample was higher and was in
the mesoporous range compared to pristine AC sample. Furthermore,
the pore-size distribution of the AC samples obtained from the N2
adsorption at 77 K is displayed in Fig. 8(a) and (b). From the Fig. 8(a) it
was observed that the micropore-volume fluctuated in the range of
0.7–2.0 nm for pristine AC which indicated it is significantly dominating
in terms of microporous characteristics than AC-DES-0.4. It can be
observed from the Fig. 8(a) that the main peak is centered at around the
region of fine micropores (0.7 nm) with pore volume of 0.34 cm3/g
while the rest of the pores were within the range of micropores
0.8–2.0 nm. The microporous nature of the pristine AC sample is further
confirmed from the average pore-width (1.70 nm) as shown in Table 10.
Therefore, to obtain an adsorbent with desired textural characteristics in
terms of SBET and pore-diameter, for gas separation process needs crucial
monitoring while impregnating it with functionalizing agent.
Fig. 8. (a): Pore size distribution of the AC-CO2 and (b) AC-DES-0.4 obtained
using N2 at 77 K.
11
Journal of Environmental Chemical Engineering 10 (2022) 108815
4.12. XPS analysis
N1s spectra of the AC samples were deconvoluted into three main
peaks of different binding energies as shown Fig. 9(a) and (b) and are
summarized in Table 11. The peak at 398.1–398.4 eV is assigned to
pyridinic-type nitrogen (N-6), peak at 400.1–400.4 eV is assigned to
Pyrrolic type nitrogen (N-5) and quaternary (N-Q) at 400.7 - 401.5 eV
nitrogen, respectively [31]. It can be seen from Table 11 , that N-5 and
N-6 are higher for the DES functionalised AC sample. Upon activation,
the contribution of N-Q reduced for both the samples as evident from the
Table 11 [37]. Both pyridinic (N-6) and Pyrrolic (N-5) contributes to the
basicity of the carbonaceous surface, but N-5 has more pronounced
impact towards CO2 capture owing to the lower binding energy and the
ability to ameliorate the polarity of the carbon owing to its electron
donation ability [38]. The carbon’s basicity is enhanced from the
improved N-5 content and is prioritized as it provides more active sur­
face sites for its Lewis basic nature to interact with CO2 which Lewis
acidic in nature [37]. The Table 11 shows O1s spectra of samples
(deconvoluted into three peaks). In this regard, the O1s spectra after
deconvolution generated three peaks at 531.5 eV (O1), 532.5 eV (O2)
and 533.6 eV for (O3) [39]. It is observed that O-1 which is assigned to
carbonyl, or lactone groups and O-2 which represents the ether or
alcohol groups are maximum in AC-DES-0.4 compared to the pristine AC
sample (Table 11). For enhanced CO2 removal, presence of basic
oxygenated species (O-1) and (O-3) are necessary and hence O-1 and O-3
could favour the CO2 removal owing to the improved basicity of the
carbonaceous surface. Therefore, it can be observed that with improved
basic nitrogenated species and oxygenated species AC-DES-0.4 is more
basic in nature than AC-CO2.
4.13. Surface Morphology
SEM analysis is mainly performed to investigate the sample’s surface
morphology and it also provides high-resolution image for estimating
the surface fractures, flaws, pores shape and size. Fig. 10 (a) & (b) il­
lustrates the SEM micrographs of pristine and DES treated AC samples,
to examine and compare the change in surface morphology after the
impregnation process. The SEM micrographs corresponding to pristine
AC (Fig. 10 (a)) and DES treated AC (Fig. 10 (b)), showed a considerable
difference with respect to their surface morphology and external surface
texture pores. The surface morphology altered significantly and
exhibited remarkable change on the surface after undergoing CO2 acti­
vation. The SEM image for pristine AC in Fig. 10 (a), clearly displays the
irregular-shaped surface along with presence of many small fragments,
cracks, and crevices. In Fig. 10 (a), rough surface and high porous
structure indicate the evolution of pores owing to the release of volatile-
organic components and reaction between CO2 and the carbon-matrix
also assists in the pore-formation. Accordingly, the presence of abun­
dant pores of different size implies the enhancement in surface area and
accounting for better porous characteristics in pristine AC, which
eventually may have a significant impact on the CO2 capture perfor­
mance. On the contrary, after impregnating the carbon sample with DES,
the external surface seems to be eroded and pores have been clogged
owing to the agglomeration of DES on its external surface (Fig. 10 (b).
Consequently, there is a fall in the pore-volume as evident from the
findings of BET surface area analysis. The difference in SEM images of
pristine and DES impregnated AC samples with respect to their surface
morphology and arrangement of pores suggests the effectiveness of
activation process and confirms the change in surface morphology after
the DES impregnation as also reported by Hussin [21].
4.14. Breakthrough CO2 adsoprtion performance
In general, breakthrough curve that appears as an S shaped curve is
evaluated to determine the efficacy of a carbonaceous adsorbent in
terms of the CO2 removal capacity in a fixed bed reactor system under
A. Mukherjee et al. Journal of Environmental Chemical Engineering 10 (2022) 108815

Fig. 9. Deconvoluted N1s spectra of (a) pristine AC (AC-CO2) and (b) DES treated AC sample (AC-DES-0.4).

time. The breakthrough time (tb) and exhaustion time (tE) is defined as
Table 11
the contact time when the ratio of outlet to inlet CO2 concentration
N1s and O1s deconvoluted spectra of pristine and DES treated AC samples.
reaches to 0.1 and 0.9, respectively.
XPS (at% of total O)
Elements Binding energy (eV) AC-CO2 (at%) AC-DES-0.4 (at%)
4.14.1. Effects of adsorption temperature on CO2 capture performance
O-1 531.2–531.5 44.9 63.3
O-2 532.3–532.5 49.8 52.4 To study the influence of adsorption temperature on breakthrough
O-3 533.3–533.6 -N/D- 6.3 adsorption performance, the column temperature was varied inside a
XPS (at% of total N) fixed bed reactor under the dynamic adsorption condition. The
Elements Binding energy (eV) AC-CO2 (at%) AC-DES-0.4 (at%) adsorption temperature was varied from 25 to 70 ºC for both pristine and
N-6 398–398.8 16.8 26.5
DES functionalised samples. All the breakthrough experiments were
N-5 400.2–400.7 65.3 73.7
N-Q 401–401.5 15.5 9.4 conducted under a fixed inlet CO2 concentration (15 vol% in N2) and
standard atmospheric pressure. The breakthrough CO2 adsorption per­
formance of the AC samples are summarised in Table S3. Furthermore,
dynamic adsoprtion conditions. The breakthrough curve displays the the breakthrough curves as a function of varying column temperature of
breakthrough adsoprtion performance which depicts the co-relationship the AC samples are displayed in Fig. 11 (a) and (b), respectively. From
between the ratio of outlet to inlet CO2 concentrations and the contact Fig. 11 (a) and (b) it can be observed that all samples have displayed the

Fig. 10. SEM analysis of (a) AC-CO2 and (b) AC-DES-0.4.

12
A. Mukherjee et al. Journal of Environmental Chemical Engineering 10 (2022) 108815

Fig. 11. Effect of adsorption temperature on CO2 capture performance (a) AC-CO2 and (b) AC-DES-0.4.

ability to capture CO2 under all column temperatures. The initial outlet
Table 12
of CO2 was not detected in the effluent stream mainly owing to the
CO2 adsoprtion performance of prepared AC samples with other reported works
complete adsorption by the adsorbents. However, CO2 was detected
(under dynamic conditions).
gradually with the progress of contact time and reached saturation
Carbon sorbents Activating and Adsorption capacity Reference
where the adsorbent surface is saturated with adsorbate and the mass
functionalizing at 25 ºC and 1 bar
transfer zone (MTZ) reached the bed outlet [39]. As can be observed agent (mmol/g)
from Fig. 11 (a) and (b), the breakthrough curve is broad at 25 ºC for
AC-CO2 CO2 4.34 This
both the samples and show substantial CO2 uptake but slope varied and AC-DES-0.4 Choline chloride and 5.5 study
becomes steeper with increasing column temperature to 70 ºC due to urea (DES-1:0.4)
faster adsorption rate along with reduced saturation time and adsorption Palm kernel based CO2 2.3 [16]
capacity. Although the trend is similar for both the samples but activated carbon
Coffee grounds Ammoxidation 2.67 [41]
adsoprtion capacity of pristine AC reduces drastically to 2.90 mmol/g
(melamine) + KOH
compared to DES treated AC (3.7 mmol/g). The plausible explanation of Date fruits (seeds) CO2 3.3 [8]
declining adsoprtion capacity drastically from 4.34 to 2.90 mmol/g for Coconut shell CO2 1.8 [42]
pristine AC (AC-CO2) with increasing adsorption temperature to 70 ºC, Paper mill sludge N2 0.67 [25]
could be attributed to the influence of physisorption between the derived biochar
(PMS)
adsorbate-adsorbent. On the other hand, for the DES treated carbon
Pine sawdust (PSS) Steam 0.73
(AC-DES-0.4) the surface basicity, presence of active sites, basic nitro­ derived activated
genated/oxygenated functionalities are helpful in retaining the CO2 carbon
adsorption capacity through a combination of both physisorption and Bamboo CO2 2.52 [36]
Urea 2.63
chemical attraction even under higher column temperature (70 ℃).
Activated carbon Nitrogen doped 5.4 [43]
Increase in column temperature also causes shift of breakthrough point Birch activated Steam 4.06 [44]
towards lower saturation time for both the AC samples irrespective of carbon
the impregnation indicating exothermic nature of the capture process. CACs-2–800 (AC KOH 3.8 [31]
Even though, pristine AC displayed considerably higher SBET, but derived from coffee
grounds at 800 ºC)
AC-DES-0.4 showed a substantial difference in CO2 capture perfor­
Petroleum coke and K2CO3 2.4 [29]
mance. In this regard, AC-DES-0.4 displayed superior breakthrough palm shell
performance than pristine AC (AC-CO2) in terms of improved break­ Activated carbon Steam and MgO 49 mg/g [45]
through adsorption time from 18.4 min to 23 min and equilibrium from whitewood (1.1 mmol/g)
Palm shell activated Choline hydroxide 37.2 mg/g [46]
adsorption capacity from 4.34 to 5.5 mmol/g at 25 ºC in a binary
carbon and urea (0.9 mmol/g)
mixture of 15 vol% of CO2 in N2. Multiple factors influenced the Coconut shell-based Char + urea, and 4.8 [47]
enhanced CO2 capture performance of DES impregnated sample that AC KOH
includes developed textural characteristics, presence of elemental C and
N, higher surface basicity due to the presence of N-5, N-6 functional
species and basic-O functional groups (carbonyl/lactone) that have well-developed textural characteristics, morphology and surface
promoted the interaction among CO2 molecules (Lewis acid) through composition under a typical post-combustion scenario. Also, form the
acid-base interactions or Vander Waals force of attractions. Similar ob­ economic point of view the production of pristine and DES treated AC
servations were also reported by Hussin [21]. The data of CO2 adsorp­ samples displayed economic feasibility in terms of the MSP of the AC (U.
tion performance of different biomass derived carbon materials were S.D $/ kg) when compared with the data reported in the literature as
compared with the adsorbents prepared in this study as summarized in presented in our previous paper [40].
Table 13. Referring to Table 12, the adsorption capacities of both pris­
tine and DES treated samples are comparable with the findings stated in 4.14.2. Effects of inlet CO2 concentration on CO2 capture performance
the literature. From Table 12, it is evident that DES treated AC sample is Fig. 12 (a) and (b) displays the effect of initial CO2 concentrations in
a potential carbonaceous adsorbent synthesized from two-step physical the range of 10–20 vol% on the breakthrough adsorption performance
activation and functionalization technique that displayed a compatible carried under a fixed column temperature of 25 ºC and at standard at­
CO2 removal performance owing to the contribution of the mospheric pressure conditions. It can be observed from Table S4, that

13
A. Mukherjee et al. Journal of Environmental Chemical Engineering 10 (2022) 108815

Fig. 12. Effect of CO2 concentration of adsorption performance (a) AC-CO2 and (b) AC-DES-0.4.

with increasing the CO2 volume fraction from 10 to 20 vol%, the
breakthrough point appears earlier owing to the faster bed saturation.
Although, the adsorption capacity improves with the increasing CO2
concentration. For instance, when the initial CO2 concentration
increased from 10 to 20 vol%, the adsorption capacity of AC-CO2
increased from 4.17 mmol/g to 4.92 mmol/g and for DES-AC-0.4 it
increased from 5.2 mmol/g to 6.03 mmol/g, respectively (Table S4).
The plausible explanation of this enhancement in adsorption capacity
and reduced breakthrough time with the increasing inlet CO2 concen­
tration to 20 vol% can be attributed to the fall in the diffusion coefficient
in the system. Reduced CO2 concentration significantly influences the
CO2 removal efficacy owing to the increased concentration gradient
resulting in slower saturation of the system and increased exhaustion
time. Also, at higher CO2 concentration (20 vol%), large number of
active sites on the surface of the adsorbent are participating, thus,
limiting the adsorbent bed capacity, whereas lesser active sites are
involved at lower CO2 concentration. A similar finding was reported by
Tan [48] who stated that with increasing the CO2 concentration the
breakthrough time is reduced producing the highest adsorption
capacity.
developed textural properties played a significant role in exclusive
selectivity towards CO2. Also, it was observed from the ultimate,
CO2-TPD and XPS analyses that the surface functionalities improved
after the DES treatment that contributed towards higher selectivity of
CO2 over N2 owing to the stronger electrostatic or pole-pole interactions
[25]. Consequently, by using DES treated sample, CO2 molecule can be
selectively separated under the dynamic flow condition (CO2/N2) under
a typical post combustion conditions. Higher selectivity is one of the
imperative adsorption characteristics for being an efficient adsorbent in
removing CO2 under dynamic conditions.
4.14.4. Multiple adsorption-desorption study
Examining the regeneration ability of a saturated adsorbent is a
significant aspect to stimulate the adsorption capacity and in deter­
mining economic feasibility. To exhibit superior regeneration ability,
the adsorbent should display stability to CO2 adsorption in multiple
adsorption-desorption cycles. In this regard, to study the regeneration
stability of the AC samples (pristine and DES), 15 consecutive
adsorption-desorption experiments were performed using a binary

4.14.3. Selectivity
Measuring the selectivity of the carbonaceous adsorbents is imper­
ative to evaluate the CO2 removal performance under post-combustion
conditions. Based on the ideal adsorption solution theory (IAST) and
the adsoprtion data, the selectivity of the binary component gas mix­
tures (CO2/N2) of the pristine (AC-CO2) and AC-DES-0.4 samples were
evaluated at 25 ℃ and calculated by using the Eq. (3). The flue gas
mixtures studied in this regard is 15 vol% of CO2 balanced in N2 and is in
accordance with the composition of the coal fired boilers [26,41]. The
apparent adsorption selectivities calculated of the gas pair CO2/N2
(mixture of 15 vol% of CO2 with 85 vol% of N2) were (SCO2/N2) 48.7 and
(SCO2/N2) 60.2 for pristine (AC-CO2) and DES treated AC (AC-DES-0.4)
samples, respectively. Irrespective of the AC sample type, the N2
adsoprtion capacity was comparatively much smaller than CO2. The
findings revealed that DES treated AC sample (AC-DES-0.4) showed a
very high selectivity and a substantial difference in the adsorbed amount
of CO2 than N2 adsorption. The synergistic impact of the improved
elemental N content (wt%), surface basicity, higher proportion of basic
N functional moieties (Pyridinic or Pyrrolic-type N species), oxygenated
functional species (carbonyl or hydroxyl functional groups) and well Fig. 13. Multiple adsorption and desorption cycle of the AC samples.

14
A. Mukherjee et al.
mixture of CO2/N2 and the findings is displayed in Fig. 13. Referring to
Fig. 13 the CO2 adsorption capacity of pristine and DES functionalised
AC samples over 15 cycles. The Fig. 13 demonstrates that the adsorption
capacity for pristine AC at the first cycle was at 4.34 mmol/g and it
reduced at the subsequent cycles. It significantly reduced after the 14th
cycle. Meanwhile, on the other hand, the DES impregnated AC displayed
a good regeneration ability with insignificant decline in the adsorption
capacities till the 15th cycle. In this regard, DES-AC showed a superior
performance by retaining approximately 92% of the original adsorption
capacity compared to pristine AC that displayed 89% retainment in
adsorption capacity after 15 cycles. Initially, the adsorption capacity
was stagnant and is evident for both the AC samples which can be
attributed to the complete desorption of the CO2 molecules. However,
DES treated AC retained its adsorption capacity till six consecutive cy­
cles but displayed fall in the adsoprtion capacity and can be mainly
owing to the presence of enriched surface chemistry, presence of ni­
trogen functional species, entire adsorbed CO2 could not be desorbed
from the surface. The maximum adsorption capacities of DES treated
sample for the 1st, 2nd and 15th cycles were 5.5, 5.46, 5.06 mmol/g,
respectively. However, both the samples displayed a declining trend in
the adsorption capacities with the progress of multiple regeneration
cycles which can be mainly attributed to the incomplete desorption,
collapse of pore structure in the carbon matrix or decomposition of the
active sites during the consecutive cycles of adsorption and desorption.
5. Conclusions
In summary, pristine and DES treated AC samples prepared by CO2
activation and DES impregnation is investigated in this study. Firstly, a
series of SCG derived AC samples were prepared by undergoing two-
stage physical activation using CO2 as the activating agent. The acti­
vated carbon (AC) production conditions were optimized through the
Box Behnken Design (BBD) technique in terms of specific surface area
(Y1) and AC yield (Y2). In this research, both the responses were eval­
uated based on the activation temperature (600–800 ºC), holding time
(60–120 min) and CO2 flow rate (150–250 mL/min). From the ANOVA
analysis, it was evident based on the F-value and p-value that activation
temperature significantly influenced both the responses (Y1 and Y2).
Based on the desirability function, the optimum activated carbon pro­
duction condition was obtained at 800 ºC, 90 min and 150 mL/min with
desirability of 0.95. Maximum SBET of 1224 m2/g and yield of 57.4 wt%
were obtained at the optimum activation conditions. Furthermore, the
development of environmentally friendly and non-toxic AC agent is
imperative in terms of sustainability. Therefore, non-toxic, and
biocompatible natural deep eutectic solvent (DES) was prepared by
mixing choline chloride (ChCl) and urea at different molar ratios to
functionalize the surface of pristine AC sample and incorporate basic
functional groups on its surface. It was observed that, DES treated AC
sample had comparatively lower SBET (1033 m2/g) than pristine AC,
which is attributed to its recalcitrant chemical structure difficult to
decompose even at lower-thermal treatment conditions as well as
chemicals clogged the porous structure. The presence of nitrogenated
functional species was confirmed using the ultimate, CO2-TPD and XPS
analyses as the diagnostic analytical techniques. The presence of nitro­
genated species (N-5) is favourable for high adsorption capacity of acidic
CO2 molecules under dynamic adsorption conditions. The superior
performance of DES functionalised AC was attributed to the presence of
basic oxygenated (carboxylates, lactones and phenols) and nitrogenated
functional groups (N-6/N-5 or N-Q) on its surface as well as the porous
structure and morphology available that accelerated the removal of
acidic CO2 molecules under dynamic adsorption conditions. The
noticeably longer breakthrough time of 23 min and higher CO2
adsorption capacity (5.5 mmol/g) of DES treated AC sample compared
to pristine-AC (4.34 mmol/g) at 25 ºC and in presence of 15 vol% of CO2
in N2 can be attributed to the combination of developed textural prop­
erties, porous structure, morphology, and surface chemistry.
15
Journal of Environmental Chemical Engineering 10 (2022) 108815
Furthermore, the exclusive selectivity of CO2 from the binary mixture
(CO2/N2) and stability of DES treated sample (AC-DES-0.4) displayed in
multiple regeneration study represent it as a promising and potential
carbonaceous adsorbent with an effective retention of approximately
92% after 15 cycles of consecutive adsorption and desorption perfor­
mance. Compared to the conventional carbonaceous adsorbents’ CO2
removal performance reported in the literature and its functionalization
broadly stated in the literature, DES impregnated AC sample prepared
by using a mild and low-cost method retained high specific surface area
(SBET) irrespective of maintaining its basic characteristics in the form of
nitrogenated functional species and formation of active adsorption sites.
Furthermore, DES treated AC sample has also demonstrated a superior
adsorption capacity, selectivity and stability rendering as an effective
carbonaceous adsorbent for CO2 adsorption from the flue gas stream.
CRediT authorship contribution statement
Alivia Mukherjee and Ajay K. Dalai: Conceptualization. Alivia
Mukherjee and Biswajit Saha: Data curation. Alivia Mukherjee,
Biswajit Saha, Catherine Niu and Ajay K. Dalai: Formal analysis.
Alivia Mukherjee: Investigation. Alivia Mukherjee: Methodology.
Alivia Mukherjee, Biswajit Saha and Ajay K. Dalai: Project admin­
istration. Alivia Mukherjee and Biswajit Saha: Resources. Alivia
Mukherjee: Software, Supervision. Alivia Mukherjee, Biswajit Saha,
Catherine Niu and Ajay K. Dalai: Validation. Alivia Mukherjee,
Biswajit Saha and Ajay K. Dalai: Visualization. Alivia Mukherjee:
Roles/Writing – original draft. Alivia Mukherjee, Biswajit Saha,
Catherine Niu and Ajay K. Dalai: Writing – review & editing.
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 would like to gratefully acknowledge the financial
support received from the Natural Sciences and Engineering Research
Council of Canada (NSERC) and BioFuel Net towards the completion of
the current research work. The authors also express their sincere grati­
tude to Saskatchewan Structural Sciences Centre (SSSC, Saskatchewan,
Canada) for providing the XPS spectroscopy and XRD facilities to
investigate the change in surface composition and structure of the AC
samples. The authors also acknowledged Mrs. Eiko and Li for doing SEM
analysis of the AC samples.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jece.2022.108815.
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