materials
Article
CO2 Adsorption Behaviors of Biomass-Based Activated
Carbons Prepared by a Microwave/Steam Activation Technique
for Molecular Sieve
Jin-Young Lee 1 , Byeong-Hoon Lee 2 , Dong-Chul Chung 3, * and Byung-Joo Kim 1,4, *
Citation: Lee, J.-Y.; Lee, B.-H.; Chung,
D.-C.; Kim, B.-J. CO2 Adsorption
Behaviors of Biomass-Based
Activated Carbons Prepared by a
Microwave/Steam Activation
Technique for Molecular Sieve.
Materials 2023, 16, 5625. https://
doi.org/10.3390/ma16165625
Academic Editors: Qigang Han and
Ce Liang
Received: 27 July 2023
Revised: 10 August 2023
Accepted: 14 August 2023
Published: 15 August 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Materials 2023, 16, 5625. https://doi.org/10.3390/ma16165625
1 Material Application Research Institute, Jeonju University, Jeonju 55069, Republic of Korea;
akdah1tkf@naver.com
2 Convergence Research Division, Korea Carbon Industry Promotion Agency (KCARBON),
Jeonju 54853, Republic of Korea; bhlee@kcarbon.or.kr
3 Department of Organic Materials & Fiber Engineering, Jeonbuk National University,
Jeonju 54896, Republic of Korea
4 Department of Advanced Materials and Chemical Engineering, Jeonju University,
Jeonju 55069, Republic of Korea
* Correspondence: sonagiii0523@gmail.com (D.-C.C.); kimbyungjoo@jj.ac.kr (B.-J.K.)
Abstract: In this study, the activated carbon was prepared with superior CO2 selective adsorption
properties using walnut shells, a biomass waste, as a precursor. The activations were conducted
at various times using the microwave heating technique in a steam atmosphere. The surface mor-
phology and chemical composition of activated carbon were analyzed using a scanning electron
microscope and energy-dispersive X-ray spectroscopy. The textural properties were investigated
using the N2 /77K isothermal method, and the structural characteristics were examined using X-ray
diffraction analysis. The CO2 and H2 adsorption properties of activated carbon were analyzed using a
thermogravimetric analyzer and a high-pressure isothermal adsorption apparatus, respectively, under
atmospheric and high-pressure conditions. Depending on the activation time, the specific surface area
and total pore volume of the activated carbon were 570–690 m2 /g and 0.26–0.34 cm3 /g, respectively.
The adsorption behaviors of CO2 of the activated carbon were different under atmospheric and
high-pressure conditions. At atmospheric pressure, a significant dependence on micropores with
diameters less than 0.8 nm was observed, whereas, at high pressure, the micropores and mesopores
in the range of 1.6–2.4 nm exhibited a significant dependence. However, H2 adsorption did not occur
at relatively low pressures. Consequently, the prepared activated carbon exhibited superior selective
adsorption properties for CO2 .
Keywords: walnut shell; activated carbon; selective adsorption; H2 /CO2 ; microwave; steam
1. Introduction
The rapid advancement of technology since the industrial revolution in the mid-
18th century has caused greater comfort and affluence. However, this progress has led
to a significant increase in CO2 emissions [1,2]. CO2 , a prominent greenhouse gas, is a
major contributor to global warming, accounting for approximately 75% of greenhouse
gas emissions [3]. The increase in global temperatures resulting from global warming has
intensified the frequency and severity of natural disasters, including droughts, typhoons,
and floods [4,5]. Moreover, they have detrimental effects on the environment and organisms
of the earth [6,7]. The international community has realized the severity of global warming
caused by CO2 and is making efforts to secure CO2 removal technologies with superior
performance including strengthening CO2 emission-related regulations [8]. Furthermore,
as the market for fuel cells and automobiles that directly use hydrogen as fuel has expanded,
the importance of separating and removing CO2 has increased.
https://www.mdpi.com/journal/materials
Materials 2023, 16, 5625 2 of 15

Currently, various CO2 removal technologies are available, including liquid amine-
based absorption processes and those that utilize chemical looping combustion [9,10].
However, these methods suffer from issues such as high energy consumption, high costs,
and the potential for secondary pollution [11]. In contrast, activated-carbon-based adsorp-
tion technology offers several advantages such as including low cost, superior capture
capacity, renewability, and selective adsorption of CO2 based on its textural properties [12].
Activated carbon can effectively control atmospheric CO2 emissions and possesses selective
adsorption properties, making it suitable for application as a carbon molecular sieve (CMS).
In particular, high-purity hydrogen, which is currently attracting attention as an energy
source, can be separated from a H2 /CO2 mixture [13,14].
Methods of separating specific materials using activated carbon typically include
pressure swing adsorption (PSA) and temperature swing adsorption (TSA). Among them,
the PSA method was devised by Skarstrom in the 1960s and applied to separation pro-
cesses such as air separation and hydrogen purification due to low energy requirements
compared to other process methods [15–17]. The performance of the PSA process depends
on the selective adsorption characteristics of the adsorbent, and zeolite has been mainly
studied as an adsorbent widely used in the PSA process [18]. However, zeolite has limited
separation performance due to its relatively low selective adsorption performance [18].
Therefore, research on activated carbon and metal organic frameworks (MOFs) has been
conducted to find adsorbents more suitable for the PSA process (advantages and disad-
vantages of each adsorption material are shown in Table S1) [19–21]. MOF has a high
CO2 adsorption capacity and a high specific surface area, but it is limited in its applica-
tion to PSA based on expensive synthesis processes [19,22]. Activated carbon, another
adsorbent, can be a good solution for the PSA process based on advantages such as a
wide range of precursors, relatively low costs, and low energy consumption [19–21]. The
adsorption of CO2 by activated carbon is mainly due to physical adsorption based on
Van der Waal’s interaction, and the CO2 adsorption performance increases as the pressure
increases [19]. However, the post-combustion gas is emitted at a temperature in the range
of 40 to 160 ◦ C and an overall pressure of about 1 atm, where CO2 has a relatively low
partial pressure of 0.05–0.15 atm [23]. Therefore, activated carbon with excellent selective
adsorption performance of CO2 at relatively low pressure is required.
Lee et al. [24] successfully prepared high-quality microporous activated carbon using
a chemical activation method involving KOH. This method produces activated carbon with
outstanding CO2 adsorption performance. However, chemical activation has limitations
that hinder its practical applications in industrial settings. These disadvantages include the
need for an additional washing process, increased processing costs due to the generation
of chemical residues, and the potential for equipment corrosion [25]. In contrast, physical
activation offers an eco-friendly alternative because it does not generate chemical residues.
In addition, physical activation is well suited for large-scale production of activated carbon
in industrial fields because of its simplicity and the lack of equipment damage [26].
The commonly employed electric-resistance-heating furnace method for activation
relies on conduction, radiation, and convective energy transfer. However, it has the disad-
vantage of high energy consumption because the processing time is extended owing to the
relatively low heat-transfer rate of the material. Alternatively, researchers have employed
the microwave heating method [27,28]. This method involves ion conduction and dipole
rotation, where microwaves are directed toward the material, transforming them into heat
within the material itself. This enables rapid heating and reduces the processing time and
energy consumption [29].
In this study, activated carbon was prepared from walnut shells, a biomass waste,
through efficient energy consumption and eco-friendly activation processes. Various
microwave heating activation times were employed to control the textural properties of
walnut shell-based activated carbon. The effect of changes in the structure of activated
carbon over the activation time on the textural properties of activated carbon was evaluated.
Further, changes in the textural properties of activated carbon were examined through
Materials 2023, 16, 5625 3 of 15

changes in the pore volume and diameter. The CO2 and H2 adsorption capacities of the
prepared activated carbon according to pressure were also analyzed to determine the
applicability of H2 /CO2 separation in the PSA process.

2. Experimental Methods
2.1. Preparation of Activated Carbon
In this study, walnut shells were obtained from commercial walnuts as activated
carbon precursors. Walnut shells were dried at 105 ◦ C for more than 24 h. To carbonize the
walnut shell, 10 g of the walnut shell was filled in an alumina boat, placed in a cylindrical
quartz tube (diameter 90 mm × length 1000 mm), heated to 800 ◦ C at a heating rate of
10 ◦ C/min in an N2 (200 mL/min) atmosphere, and maintained for 1 h. After heating,
this was followed by natural cooling to 30 ◦ C. The yield of carbonized walnut shells was
observed to be 29.0%
To proceed with the activation, the walnut shell char was pulverized and sieved to less
than 2 mm (Figure S1 shows the particle size of walnut shell-based activated carbon). Then,
3 g of the sieved walnut shell char was filled into a home-made quartz reactor (diameter
70 mm × length 100 mm). The quartz reactor was placed in a modified microwave oven
(MW22CD9D, LG Electronics, Seoul, Korea). Before activation, the quartz reactor was
degassed with N2 (200 mL/min) gas. Activation was performed for 10–25 min at 1 kW
with the flow rate set to H2 O (0.1 mL/min). After activation, the gas flow was changed
from H2 O to N2 (200 mL/min), and the sample was cooled to 30 ◦ C. The activation reaction
between the carbon crystallites and H2 O is an endothermic reaction in stoichiometric form,
as shown in Equation (1).

C + H2 O → CO + H2 ∆H = +117 kJ/mol (1)

A schematic of the microwave steam activation technique used in this study is indi-
cated in Figure S3. Each sample name was a walnut shell (WS)-microwave (M) activation
time (walnut shell-based activated carbon activated by microwave for 20 min: WS-M20).

2.2. Characterization
Scanning electron microscope (SEM; S-4800, HITACHI, Tokyo, Japan) and energy-
dispersive X-ray spectroscopy (EDX; EMAX, HORIBA, Kyoto, Japan) were used for the
surface morphology and elemental analysis of the walnut shell-based activated carbon
(WS-AC). In the SEM-EDX analysis, WS-AC was coated with platinum to reduce charging
and to obtain clear images under operating voltage and pressure conditions of less than
10 kV and 1 × 10−5 Torr, respectively.
The crystal structure of WS-AC was investigated using X-ray diffraction (XRD; Empyrean,
Malvern Panalytical, Malvern, UK). XRD patterns were recorded in the 2θ range of 10–60◦
at a rate of 2◦ /min using Cu Kα (1.542 Å) radiation. The crystallite size and interplanar
spacing of WS-AC were calculated using the Scherrer’s equation and Bragg’s equation,
respectively [30].
The textural properties of WS-AC were analyzed using N2 /77K adsorption–desorption
isotherms obtained by BELSORP-Max II (Microtrac BEL, Osaka, Japan) and pretreated at a
pressure of less than 1 × 10−3 Torr. The specific surface area and micropore volume of the
activated carbon were calculated using the Brunauer–Emmett–Teller’s equation [31] and
the t-plot method [32], respectively. The nonlocalized density functional theory (NLDFT)
method was used to determine the pore-size distribution of WS-AC [33,34].

2.3. CO2 and H2 Adsorption Behaviors

Thermogravimetric analysis (TGA; TGA/DSC 3+, Mettler-Toledo, Columbus, OH,
USA) was used to evaluate the CO2 adsorption performance of WS-AC at atmospheric
pressure. Briefly, in the analyzer, 10 mg of WS-AC was placed in a 70 mL alumina pan and
degassed at 110 ◦ C in an N2 (50 mL/min) atmosphere until no change in weight occurred.
Then, after cooling to 25 ◦ C the gas flow inside the analyzer was changed from N2 to CO2
 and degassed at 110 °C in an N2 (50 mL/min) atmosphere until no change in weight oc-
curred. Then, after cooling to 25 °C the gas flow inside the analyzer was changed from N2
to CO2 (50 mL/min), and the weight change in activated carbon was evaluated correspond-
ing to the CO2 adsorption behavior.
Materials 2023, 16, 5625 4 of 15
The high-pressure gas adsorption system, BELSORP-HP (Microtrac BEL, Osaka, Ja-
pan) was used to evaluate the CO2 and H2 adsorption performances of WS-AC at high
pressure. Before the analysis, 0.5 g of all WS-ACs were treated at a temperature of 300 °C
(50 mL/min), and the weight change in activated carbon was evaluated corresponding to
and a pressure of less thanadsorption
the CO 1 × 10−3 Torr. The measurement pressure range was 0–30 bar,
behavior.
2
and the temperature was The maintained
high-pressure at
gas25 °C (in the
adsorption PSABELSORP-HP
system, process, adsorption was Osaka,
(Microtrac BEL, per- Japan)
formed five times to confirm
was used tothe stability
evaluate of 2CO
the CO and2 adsorption circulation
H2 adsorption of activated
performances of WS-AC carbon
at high pressure.
the analysis, 0.5 g of all WS-ACs were treated at a temperature of 300 ◦ C and a
BeforeS2).
and is shown in Figure
pressure of less than 1 × 10−3 Torr. The measurement pressure range was 0–30 bar, and
the temperature was maintained at 25 ◦ C (in the PSA process, adsorption was performed
3. Results and Discussion
five times to confirm the stability of CO2 adsorption circulation of activated carbon and is
3.1. Surface Morphology
shown and
in Chemical
Figure S2).Composition
The optical and SEM images of WS-AC are exhibited in Figure 1a. In the optical im-
3. Results and Discussion
age, the color of the
3.1.walnut shell (WS)and
Surface Morphology is black,
Chemicalwhich is attributed to the conversion of
Composition
WS into a material withThe an optical
abundant carbon
and SEM content
images through
of WS-AC decomposition,
are exhibited polyconden-
in Figure 1a. In the optical image,
sation, and cyclization during the carbonization process. The SEM image exhibits
the color of the walnut shell (WS) is black, which is attributed to the conversion that sur-
of WS into
face pores were formed on the
a material smooth
with surface
an abundant of thecontent
carbon char, and the decomposition,
through roughness increased as
polycondensation,
and cyclization
the activation progressed. This was during the carbonization
attributed process. Theof
to the decomposition SEM
theimage
carbon exhibits that surface
structure
pores were formed on the smooth surface of the char,
generated by steam at high temperatures during the microwave heating process. and the roughness increased as the
activation progressed. This was attributed to the decomposition of the carbon structure
Figure 1b shows the EDX mapping images of WS-AC. All WS-ACs have a high car-
generated by steam at high temperatures during the microwave heating process.
bon content of 85.58–91.09%,
Figure which
1b showsis also attributed
the EDX mapping to the conversion
images of WS-AC. of walnut
All WS-ACsshells to a high
have
materials with a high carbon content. Further, as the activation time increased, the carbon
carbon content of 85.58–91.09%, which is also attributed to the conversion of walnut shells
content of WS-AC todecreased, and athe
materials with highoxygen
carbon content
content. increased. Nabais
Further, as the et al.time
activation [35]increased,
con- the
carbon content of WS-AC decreased, and the oxygen content
firmed that the carbon content decreased, and the oxygen content increased as the activa- increased. Nabais et al. [35]
confirmed
tion process intensified that the carbon,
in activated carbon content
whichdecreased, and the
is ascertained oxygen
to the content of
formation increased
func- as the
activation process intensified in activated carbon, which is ascertained to the formation of
tional groups. Therefore, the decrease in the carbon content and increase in the oxygen
functional groups. Therefore, the decrease in the carbon content and increase in the oxygen
content of WS-AC are an effect
content of activation,
of WS-AC are an effectresulting in the
of activation, decomposition
resulting of the carbon
in the decomposition of the carbon
structure and the consequent formation of oxygen functional groups.
structure and the consequent formation of oxygen functional groups.

(a)

Figure 1. Cont.
16, x FOR PEER REVIEW 5 of 15
Materials 2023, 16, 5625 5 of 15

(b)
Figure
Figure 1. Scanning 1. Scanning
electron electron image
microscope microscope imageenergy-dispersive
(a) and (a) and energy-dispersive
X-rayX-ray spectroscopy
spectroscopy mapping
map-
ping image (b) ofimage
walnut(b) shell-based
of walnut shell-based
activatedactivated
carbonscarbons as a function
as a function of activation
of activation time.
time.
3.2. Textural Properties and Structure
3.2. Textural Properties and Structure
The N2 /77K adsorption–desorption isotherm is a powerful tool for analyzing the
The N2/77Kpore
adsorption–desorption isotherm
structure of activated carbon. Figureis 2a
a powerful tool
exhibited the N2for analyzing
/77K the pore
adsorption–desorption
isotherms
structure of activated of WS-AC
carbon. as a2a
Figure function of activation
exhibited the N2/77Ktime.adsorption–desorption
All WS-ACs were categorized iso- as
Type I by the IUPAC classification [36], which primarily consists
therms of WS-AC as a function of activation time. All WS-ACs were categorized as Type of micropores. As the
activation time increased, N2 adsorption gradually increased at a relative pressure (P/P0 )
I by the IUPAC classification [36], which primarily consists of micropores. As the activa-
of less than 0.1, and the hysteresis also increased. This could be owing to the development
tion time increased, N2 adsorption
of micropores gradually
due to the oxidationincreased
of amorphousat a relative
and small pressure (P/PFurther,
crystallites. 0) of less
as the
than 0.1, and the hysteresis also increased. This could be owing to the development
activation time increased, the wedge-shaped micropores became pot-type mesopores owing of
micropores duetotothethe oxidation
oxidation of edges
of the amorphous and (Table
of crystallite small S2crystallites. Further,
lists the textural as theparameter
properties acti-
of walnutthe
vation time increased, shell-based activatedmicropores
wedge-shaped carbon). became pot-type mesopores owing
to the oxidation of the edges of crystallite (Table S2 lists the textural properties parameter
of walnut shell-based activated carbon).
Figure 2b shows the pore size distribution of WS-AC investigated using the NLDFT
method. WS-AC comprised pores with diameters of 1 nm or less and pores with diameters
 Materials 2023, 16, 5625 6 of 15

Figure 2b shows the pore size distribution of WS-AC investigated using the NLDFT
Materials 2023, 16, x FOR PEER REVIEWmethod. WS-AC comprised pores with diameters of 1 nm or less and pores with 6 of diameters
15
of approximately 1–2 nm. Pores less than 1 nm in diameter gradually developed until
20 min of activation time but decreased at 25 min. Meanwhile, the diameters of the
1–2
amorphous nm ispores gradually
decomposed byexpanded
activation, and developed
narrow microporesas the activation
developed, andtime increased.
as the acti- As
the amorphous is decomposed by activation, narrow micropores
vation proceeds, these micropores become wide owing to expansion in diameter and in- developed, and as the
activation
crease in volumeproceeds, these
due to the micropores
small crystallitebecome
oxidation wide
andowing
greatertodecomposition
expansion in diameter
of the and
increase in volume due to the small crystallite oxidation and greater decomposition of the
amorphous.
amorphous.
XRD is a useful analytical tool for examining changes in the crystal structure of acti-
XRDasis aafunction
vated carbon useful analytical tool
of activation for In
time. examining
Figure S4, changes
the XRD in the crystal
patterns of WS-ACstructure of
activated
exhibit the 002carbon as a function of23–24°),
peak (approximately activation time.
which In Figurefrom
is different S4, the 002
XRDpeak
patterns of WS-AC
(26.56°)
of graphite.
exhibit theFurthermore, a broad 10l peak
002 peak (approximately 23–24 ◦ ), which is different
(approximately 43°), which cannot
from peak (26.56◦ )
be sepa-
the 002
rated, was observed
of graphite. and was attributed
Furthermore, a broad 10lto peak
the effect
(approximately 43◦ ), which
of the disordered graphite-like
cannotstruc-
be separated,
turewas
andobserved
irregularly stacked carbon layer.
and was attributed to the effect of the disordered graphite-like structure and
irregularly stacked carbon layer.

250
Volume adsorbed (cm /g, STP)

200
3

150

100

50 WS-M10
WS-M15
WS-M20
WS-M25
0
0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure (P/P0)
(a)

8
WS-M10
WS-M15
WS-M20
6 WS-M25
dV/dlog(D) (cm /g)
3

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Pore diameter (nm)
(b)
Figure 2. Cont.
Materials 2023, 16, x FOR PEER REVIEW 7 of 15
Materials 2023, 16, 5625 7 of 15

LDCC MDCC

WS-M25

WS-M20
Intensity (a.u)
WS-M15

002 WS-M10

10l
Char
10 20 30 40 50
2θ (degree)
(c)

16 50

15
45
14

La (A)
Lc (A)

° 13 40
°
12
Lc(LDCC) 35
11 Lc(MDCC)
La
10 30
0
Char 5 10 15 20 25
Activation time (min)
(d)
2. (a)2.N(a)
Figure
Figure N2 /77K
2/77K adsorption–desorption
adsorption–desorption isotherm,
isotherm, (b) pore(b)sizepore size distribution
distribution by NLDFT,by (c)
NLDFT,
de- (c) de-
convoluted X-rayX-ray
convoluted diffraction pattern,
diffraction and (d)and
pattern, crystallites size of walnut
(d) crystallites size of shell-based activatedactivated
walnut shell-based carbons carbons
as a as
function of activation
a function time. time.
of activation

Figure 2c exhibits
Figure the XRD
2c exhibits deconvolution
the XRD deconvolutioncurves of WS-AC
curves according
of WS-AC to thetoactiva-
according the activation
tionconditions.
conditions. The
The 002 peaks were deconvoluted using Gaussian
002 peaks were deconvoluted using Gaussian fitting and fitting and separated
separated into
intoless-developed
less-developedcrystalline
crystallinecarbon
carbon(LDCC)
(LDCC)and andmore-developed
more-developedcrystalline
crystallinecarbon
carbon(MDCC).
(MDCC). Meanwhile,
Meanwhile, the correlation
the correlation coefficient
coefficient ofofthe
thedeconvolved
deconvolved peakpeakisismore
more than 0.990.99 (the
than
(thestructural
structural parameters
parametersare arelisted
listedinin
Table
TableS3). In WS-AC,
S3). In WS-AC, LDCCLDCCand and
MDCC,
MDCC,constitut-
constituting
ing the
the 002
002peaks,
peaks,shifted
shiftedin in
a direction
a directioncloser to that
closer to of crystallinity
that as the activation
of crystallinity time
as the activation time
increased, including char, and the change in LDCC was observed more clearly
increased, including char, and the change in LDCC was observed more clearly than that than that
of MDCC.
of MDCC.Physical activation
Physical is preceded
activation by theby
is preceded development of micropores
the development due to the
of micropores due to the
decomposition of amorphous and small crystallites. As the activation
decomposition of amorphous and small crystallites. As the activation continues, thecontinues,
edges the
of large crystallites constituting the carbon domain are oxidized to develop into meso-
edges of large crystallites constituting the carbon domain are oxidized to develop into
pores. Therefore, the change in the XRD pattern is due to the amorphous phase preferen-
mesopores. Therefore, the change in the XRD pattern is due to the amorphous phase
tially decomposed by physical activation and it is considered that a tendency to improve
preferentially decomposed by physical activation and it is considered that a tendency to
crystallinity has been observed.
improve crystallinity has been observed.
Figure 2d exhibited the change in Lc (LDCC and MDCC) and La of WS-AC according
to the activation time calculated from the XRD deconvoluted curve. A tendency to in-crease
both La and Lc was observed with increasing activation time. In addition, the change in
Materials 2023, 16, x FOR PEER REVIEW 8 of 15

Materials 2023, 16, 5625 Figure 2d exhibited the change in Lc (LDCC and MDCC) and La of WS-AC according 8 of 15
to the activation time calculated from the XRD deconvoluted curve. A tendency to in-
crease both La and Lc was observed with increasing activation time. In addition, the change
in thethe
lateral size
lateral (La(L
size ) was
a ) wasgreater
greaterthan thethe
than change
change in in
thethe
stacking
stackingheight
height (L(L
c). cThis is be-
). This is because
causethethelayer
layerofofthe
the(002)
(002)plane
planein inthe
thecrystal
crystalstructure
structure isis composed
composed of of strongly
strongly hybridized
hybrid- sp2
ized sp 2 bonds,
bonds, andandthethe verticalπ-bond
vertical π-bondon onthe
the (002)
(002) plane
plane results
resultsininweak
weakinterlayer
interlayer bonds
bonds [37].
[37]. Furthermore,
Furthermore, a relatively
relatively larger
largerchange
changeininthe theLcLof
c of LDCCthan
LDCC than that
that of of MDCC
MDCC was was
observed,
observed,
whichwhich is considered
is considered to be
to be an an effect
effect of the of the preferential
preferential decomposition
decomposition of LDCC. of LDCC.
Lee et al. [38]
Lee etreported
al. [38] reported
that uponthat uponactivation,
physical physical activation,
the amorphous the amorphous region is preferen-
region is preferentially decomposed,
tially the
decomposed,
crystallites size increases, and micropores develop. Accordingly, it is considereditthat the
the crystallites size increases, and micropores develop. Accordingly,
is considered
change in that
thethe change in
crystallite theofcrystallite
size WS-AC issize not of
dueWS-AC
to the is not due
growth of to the growth
carbon of
crystallites, but
carbon crystallites,
rather but rather
the increase in thethe increase
relative in the relative
crystallite size duecrystallite size due to the decom-
to the decomposition of amorphous
position of amorphous
regions regions and
and the oxidation of the
smalloxidation of small
crystallites crystallites
[39,40]. [39,40].
Therefore, it isTherefore,
expected itthat the
is expected that the
micropores of micropores
WS-AC develop of WS-ACdue to develop due to the decomposition
the decomposition of the amorphous of the amor-
region of the
phouscarbon
regionstructure,
of the carbonand as structure, and as progresses,
the activation the activation theprogresses, the small
small crystallites arecrystal-
oxidized, and
lites are
theoxidized, and theexpands
pore diameter pore diameter
(schematicexpands (schematic
diagram of thediagram
change of in the
thechange
crystalin the
structure of
crystal structure of carbon by steam activation
carbon by steam activation is shown in Figure S5). is shown in Figure S5).

3.3. Adsorption
3.3. Adsorption Behaviors
Behaviors and Correlation
and Correlation
FigureFigure 3a shows
3a shows the COthe2CO 2 adsorption
adsorption curvecurve of WS-AC
of WS-AC at atmospheric
at atmospheric pressure,
pressure, obtained
ob-
tainedusing
usinga aTGA.
TGA.The TheCOCO22adsorption
adsorption capacities are recognized in in the
the order
orderof ofWS-M20
WS-M20 > WS-
M15 >> WS-M10
> WS-M15 WS-M10 >>WS-M25.
WS-M25.InIn addition,
addition, thethe adsorption
adsorption rate,
rate, according
according to slope
to the the slope of
the CO adsorption
of the CO2 adsorption
2 curve, was in the order of WS-M20 > WS-M15
curve, was in the order of WS-M20 > WS-M15 > WS-M10 > WS-M25, > WS-M10 > WS-M25,
whichwhich
was thewas the as
same same
the as the adsorption
adsorption capacity.
capacity. In all WS-ACs,
In all WS-ACs, the adsorption
the adsorption equilibrium
equilibrium
was observed
was observed for COfor 2 atCO 2 at approximately
approximately 10 min. 10 Leemin.
et al.Lee
[24]etandal. Jagiello
[24] andetJagiello et al. [25]
al. [25] re-
portedreported
that thethat the effective
effective pore diameter
pore diameter of activated
of activated carbon for carbon for the adsorption
the adsorption of CO2 at at-of CO2 at
atmospheric
mospheric pressurepressure
was lesswas thanless
0.8than
nm.0.8Thenm. Thediameter
pore pore diameter distribution
distribution of WS-AC of WS-AC
is is
shown shown in Figure
in Figure 2b, and2b,WS-20
and WS-20has thehasmost
the most
porespores
with with a diameter
a diameter of lessofthan
less than
1 nm.1 This
nm. This is
based
is based on the
on the micropore
micropore filling
filling theory,
theory, in which
in which the the
COCO 2 adsorption
2 adsorption performance
performance of WS-AC
of WS-
is preferentially adsorbed in micropores with diameters less than
AC is preferentially adsorbed in micropores with diameters less than 1 nm, and the diameter 1 nm, and the diameter of
pores
of pores effective
effective for2CO
for CO 2 adsorption
adsorption mightmight increase
increase as theas the pressure
pressure increasesincreases [39]. Therefore,
[39]. Therefore,
activated
activated carboncarbon requires
requires the development
the development of narrowof narrow micropores
micropores with a with a diameter
diameter of less of less
than 1than
nm to1 nm to achieve
achieve superior superior CO2 adsorption
CO2 adsorption performance
performance at atmospheric
at atmospheric pressure.pressure.

4
CO2 uptake (wt%)

WS-M10
WS-M15
WS-M20
WS-M25
0
0 5 10 15 20 25 30
Time (min)
(a)
Figure 3. Cont.
 Materials
Materials 16, 16,
2023,
2023, 5625PEER REVIEW
x FOR 9 of 159 of 15

21
H2
CO2

H2/CO 2 uptake (wt%)

14
10

H2/CO2 uptake (wt%)

6 WS-M10
7 4
WS-M15
WS-M20
2 WS-M25

0.10
0.05
0.00
0.0 0.2 0.4 0.6 0.8 1.0
0.10 Pressure (bar)
0.05
0.00
0 5 10 15 20 25 30
Pressure (bar)
(b)
1.0

0.8

0.6
2
R

0.4

0.2

0.0
0.0 0.8 1.6 2.4 3.2 4.0
Pore diameter (nm)
(c)
1.0

0.8

0.6
2
R

0.4

0.2

0.0
0.0 0.8 1.6 2.4 3.2 4.0
Pore diameter (nm)
(d)
Figure 3. (a)
Figure 3.CO storage
(a)2CO capacity of walnut shell-based activated carbons at 1 bar/298K, (b) CO2 and
2 storage capacity of walnut shell-based activated carbons at 1 bar/298K, (b) CO2 and
H2 storage capacity of walnut
H2 storage capacity of walnutshell-based activated
shell-based carbons
activated up toup
carbons 30 to
bar,
30(c) correlation
bar, coefficient
(c) correlation coefficient
between pore diameters and CO2 capacity at 1 bar, and (d) correlation coefficient between pore di-
between pore diameters and CO2 capacity at 1 bar, and (d) correlation coefficient between pore
ameters and CO2 capacity at 30 bar.
diameters and CO2 capacity at 30 bar.
Materials 2023, 16, 5625 10 of 15

Figure 3b exhibits the adsorption curves of CO2 and H2 of WS-AC measured at

0–30 bar conditions. The aforementioned CO2 adsorption behavior was similar to the CO2
adsorption behavior under atmospheric pressure conditions (Figure 3a) and 1 bar however,
the CO2 adsorption capacity under a pressure of further or more was different from the
CO2 adsorption under atmospheric pressure. In general, under atmospheric pressure, the
filling of the narrow micropore area precedes and saturates, and as the pressure increases,
wide micropores and narrow mesopores are filled. Casco et al. [41] reported that under
1 MPa conditions, activated carbon is almost saturated in narrow micropores and requires
a higher pressure to cause adsorption in wider pore diameters. Accordingly, WS-M25,
which has numerous wide micropores and narrow mesopores, exhibits superior CO2
capacity compared to the other activated carbon samples under high-pressure conditions.
In the case of H2 adsorption, an extremely small amount of H2 was adsorbed on all WS-
ACs. Lee et al. [37] reported that the hydrogen storage capacity of activated carbon was
affected by the micropore volume, and also inferred that the micropores in the range of
0.63–0.78 nm, controlled hydrogen adsorption under 25 ◦ C and 10 MPa conditions. These
results substantiate that a higher pressure is required or that the pore diameter of the
activated carbon needs to be further reduced for WS-AC to adsorb hydrogen. Therefore,
WS-AC is expected to be useful for separating high-purity H2 by selective adsorption of
CO2 from the H2 /CO2 mixture when applied as a CMS in the PSA process.
Figure 3c shows the correlation between the CO2 adsorption capacity and the pore
diameter of WS-AC under atmospheric pressure. The NLDFT data in Figure 2b were
used as the pore diameter data. CO2 adsorption at atmospheric pressure exhibited a high
correlation (R2 = 0.89) with pores having a diameter of 0.8 nm or less. CO2 adsorption is
mainly owing to Van der Waal’s interactions (physical adsorption) and is most suitable
when the pore diameter is approximately two to three times that of the adsorbate [25].
Therefore, at atmospheric pressure, WS-AC can remove CO2 molecules through strong
interactions with pores with a diameter of 0.8 nm or less.
Figure 3d shows the correlation between the CO2 capacity and diameter of WS-AC
at 30 bar. CO2 adsorption under high pressure has a high correlation (R2 = 0.93) with
wide micropores and narrow mesopores with diameters of 1.6–2.4 nm, and pore regions
with other diameters show a low correlation. Carsco et al. [41] reported that 4.5 MPa
was not sufficient to fill mesopores larger than 3.0 nm and were not suitable for capillary
condensation to occur. Therefore, pores with diameters of 1.6–2.4 nm generated capillary
condensation in WS-AC under 30 bar conditions, and it is effective in the adsorption
of CO2 .

3.4. Fitting of CO2 Adsorption Isotherms

The Langmuir [42], Freundlich [43], and Langmuir–Freundlich [44] models were
adopted to explain the CO2 adsorption behavior according to the pressure of activated
carbon, calculated by Equations (2)–(4), shown in Figure 4a–c, respectively (Table S4 showed
parameters according to Isotherm model star).

qm KL P
q= (2)
1 + KL P

1
q = KF P n (3)

1
q m KT P n
q= 1
(4)
1 + ( KL P ) P n
Materials 2023, 16, x FOR PEER REVIEW 11 of 15

Materials 2023, 16, 5625 11 of 15

25

20

CO2 uptake (wt%)

15

10

WS-M10
5
WS-M15
WS-M20
WS-M25
0
0 5 10 15 20 25 30
Pressure (bar)

(a)

25

20
CO2 uptake (wt%)

15

10

WS-M10
5
WS-M15
WS-M20
WS-M25
0
0 5 10 15 20 25 30
Pressure (bar)

(b)

25

20
CO2 uptake (wt%)

15

10

WS-M10
5
WS-M15
WS-M20
WS-M25
0
0 5 10 15 20 25 30
Pressure (bar)

(c)
FigureFigure
4. Comparison of theof
4. Comparison fitting resultsresults
the fitting by theby
(a)the
Langmuir, (b) Freundlich,
(a) Langmuir, and (c)
(b) Freundlich, Langmuir–
and (c) Langmuir–
Freundlich equations for the adsorption of CO 2 on walnut shell-based activated carbon.
Freundlich equations for the adsorption of CO on walnut shell-based activated carbon.
2

KL is K the Langmuir
L is isotherm
the Langmuir constant
isotherm constant ), qm−is
(bar−1(bar 1 ),the
qm maximum adsorption
is the maximum capacity,
adsorption capacity,
P is the
P isrelative pressure
the relative of theofadsorbate
pressure (bar),(bar),
the adsorbate KF isKtheF isFreundlich
the isotherm
Freundlich constant
isotherm constant
(bar−1(bar −1 ),
), and n and
is the
n Freundlich exponent.
is the Freundlich exponent.
Materials 2023, 16, 5625 12 of 15

The Langmuir model is based on monolayer adsorption on a homogeneous surface,

and the Freundlich model is based on multilayer adsorption on a heterogeneous surface.
The Langmuir–Freundlich model is a model that combines the previous two models. The
Langmuir model exhibited a high fit (R2 : 0.99), but the Freundlich model indicated a
relatively low fit (R2 : 0.96). It is inferred that the CO2 adsorption behavior of WS-AC
with narrow micropores is mainly adsorbed by the monolayer by filling the micropores.
Also, as the pressure increases, the adsorption of CO2 is considered to be caused by
additional multilayer adsorption. Accordingly, the highest fit (R2 : 0.9999) was observed in
the Langmuir–Freundlich model, which is a combination of the two models. Therefore, it
can be expected that the CO2 behavior of activated carbon mainly occurs in the relatively
low pressure part by monolayer adsorption by filling micropores, and multilayer adsorption
occurs as the pressure increases.

3.5. Comparison of CO2 Capture Capacity of Biomass Activated Carbon

To assess the applicability of the activated carbon used in this study, a comparison
was made with biomass-based activated carbon produced in other research, and the results
were presented in Table 1. In the case of physical activation, activated carbon produced by
conventional heating methods showed similar or up to 1.6 times enhanced CO2 adsorption
performance compared to microwave treatment. However, the activation time for these con-
ventional methods ranged from 60 to 240 min, which is 3 to 12 times longer than the method
used in this study. This leads to significant energy consumption and a subsequent decrease
in economy. For chemical activation, the CO2 performance was enhanced up to two times
compared to physical activation. However, despite relatively shorter activation times
compared to microwave methods, chemical activation still required 3 to 4.5 times longer
activation periods. Additionally, chemical activation has drawbacks such as wastewater
generation, equipment corrosion, and increased process costs due to additional washing
steps. Therefore, eco-friendly activated carbon in this study can reduce process costs due to
fast activation time, and problems arising from chemical activation do not occur, so it is
considered to be a superior adsorbent for CO2 capture in industrial processes.

Table 1. Comparison of activation method and CO2 adsorption capacity of biomass-based acti-
vated carbons.

CO2 Adsorption Amount (mmol/g) at Activation Time

Sample Heating Method Ref.
298 K and 1 Bar (min)
Microwave
Walnut shell 1.9 20 Our work
(physical)
Conventional heating
Coconut shell 1.8 60 [45]
(physical)
Conventional heating
Almond shell 2.7 240 [46]
(physical)
Conventional heating
Olive stone 2.9 240 [46]
(physical)
Conventional heating
Coffee residue 2.4 60 [47]
(physical)
Conventional heating
Almond shell 2.1 83 [48]
(physical)
Conventional heating
Olive stone 2.0 110 [48]
(physical)
Conventional heating
Amazonian waste 3.7 60 [49]
(Chemical)
Conventional heating
Cotton stalk 2.9 90 [50]
(Chemical)
Coconut shell 2.6 Conventional heating (Chemical) 60 [51]
DARCO FGD(Norit) 0.4 (291 K, l bar) - - [52]
Materials 2023, 16, 5625 13 of 15

4. Conclusions
In this study, activated carbon was prepared from walnut shells using a microwave
heating technique with low energy consumption and steam, an eco-friendly activator, and
the adsorption behavior of CO2 and H2 according to pressure was investigated to determine
the activated carbon suitable for the PSA process. The microwave/steam activation tech-
nique followed a typical physical activation mechanism, and through analysis of the crystal
structure and textural properties of activated carbon, it was confirmed that micropores
were developed due to preferential decomposition of Amorphous crystallite > amorphous.
WS-AC showed excellent selective CO2 adsorption performance and hydrogen separation
in all pressure ranges, especially in the relatively low pressure range. Narrow micropores
of 0.8 nm or less were effective in CO2 adsorption at atmospheric pressure, and effective
pore diameter for CO2 adsorption at high pressure (30 bar) was 1.6 to 2.4 nm. Therefore,
WS-AC manufactured as an eco-friendly activation means from walnut shells, which are
biomass waste, can be a good alternative as an adsorbent for the PSA process.

Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/ma16165625/s1, Table S1: Advantages and disadvantages of
CO2 adsorption by adsorbent; Figure S1: Particle size distribution of walnut shell-based activated
carbon; Figure S2: CO2 adsorption curve of activated carbon according to five times; Figure S3:
Schematic diagram of microwave steam activation system; (a) nitrogen storage, (b) H2 O-micro feeder,
(c) regulator, (d) heating zone temperature controller, (e) heating zone, (f) valve, (g) flow meter,
(h) quartz reactor, (i) walnut shell char, (j) microwave oven, (k) trap, and (l) vent. Figure S4: Original
X-ray diffraction of walnut shell-based activated carbon as a function of activation time; Figure S5:
Schematic diagram of carbon structure changes by steam activation; Table S2: Textural properties of
walnut shell-based activated carbons as a function of activation time; Table S3: Structural parameters
of walnut shell-based activated carbon as a function of activation time; Table S4: The correlation
parameters by adsorption isotherms model.
Author Contributions: Conceptualization, J.-Y.L., B.-H.L. and B.-J.K.; Methodology, B.-J.K.; Vali-
dation, J.-Y.L. and B.-J.K.; Formal analysis, J.-Y.L.; Investigation, J.-Y.L. and D.-C.C.; Data curation,
B.-H.L.; Writing—original draft, J.-Y.L.; Writing—review & editing, J.-Y.L., D.-C.C. and B.-J.K.; Super-
vision, D.-C.C. and B.-J.K.; Project administration, B.-J.K.; Funding acquisition, B.-J.K. All authors
have read and agreed to the published version of the manuscript.
Funding: This research was supported by project no. 20013038 by the Ministry of Trade, Industry, and
Energy. This research was also supported by the Nano-Material Technology Development Program
through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and
ICT (NRF-2019M3A7B9071501).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Samanta, A.; Zhao, A.; Shimizu, G.K.H.; Sarkar, P.; Gupta, R. Post-Combustion CO2 Capture Using Solid Sorbents: A Review. Ind.
Eng. Chem. Res. 2011, 51, 1438–1463. [CrossRef]
2. Iglina, T.; Iglin, P.; Pashchenko, D. Industrial CO2 Capture by Algae: A Review and Recent Advances. Sustainability 2022, 14, 3801.
[CrossRef]
3. Abbasi, F.; Riaz, K. CO2 Emissions and Financial Development in an Emerging Economy: An Augmented VAR Approach. Energy
Policy 2016, 90, 102–114. [CrossRef]
4. Li, Y.; Dong, Z.; Chen, D.; Zhao, S.; Zhou, F.; Cao, X.; Fang, K. Growth Decline of Pinus Massoniana in Response to Warming
Induced Drought and Increasing Intrinsic Water Use Efficiency in Humid Subtropical China. Dendrochronologia 2019, 57, 125609.
[CrossRef]
5. Khandekar, M.L. Are Extreme Weather Events on the Rise? Energy Environ. 2013, 24, 537–549. [CrossRef]
6. Norby, R.J.; Luo, Y. Evaluating Ecosystem Responses to Rising Atmospheric CO2 and Global Warming in a Multi-factor World.
New Phytol. 2004, 162, 281–293. [CrossRef]
Materials 2023, 16, 5625 14 of 15

7. Zhang, Y.; Gentine, P.; Luo, X.; Lian, X.; Liu, Y.; Zhou, S.; Michalak, A.M.; Sun, W.; Fisher, J.B.; Piao, S.; et al. Increasing Sensitivity
of Dryland Vegetation Greenness to Precipitation Due to Rising Atmospheric CO2 . Nat. Commun. 2022, 13, 4875. [CrossRef]
[PubMed]
8. Lai, J.Y.; Ngu, L.H.; Hashim, S.S.; Chew, J.J.; Sunarso, J. Review of Oil Palm-Derived Activated Carbon for CO2 Capture. Carbon
Lett. 2021, 31, 201–252. [CrossRef]
9. Dutcher, B.; Fan, M.; Russell, A.G. Amine-Based CO2 Capture Technology Development from the Beginning of 2013—A Review.
ACS Appl. Mater. Interfaces 2015, 7, 2137–2148. [CrossRef]
10. Hu, J.; Galvita, V.; Poelman, H.; Marin, G. Advanced Chemical Looping Materials for CO2 Utilization: A Review. Materials 2018,
11, 1187. [CrossRef] [PubMed]
11. Sjostrom, S.; Krutka, H. Evaluation of Solid Sorbents as a Retrofit Technology for CO2 Capture. Fuel 2010, 89, 1298–1306.
[CrossRef]
12. Cruz, O.F., Jr.; Campello-Gómez, I.; Casco, M.E.; Serafin, J.; Silvestre-Albero, J.; Martínez-Escandell, M.; Hotza, D.; Rambo, C.R.
Enhanced CO2 Capture by Cupuassu Shell-Derived Activated Carbon with High Microporous Volume. Carbon Lett. 2022, 33,
727–735. [CrossRef]
13. Rasool Abid, H.; Keshavarz, A.; Lercher, J.; Iglauer, S. Promising Material for Large-Scale H2 Storage and Efficient H2 -CO2
Separation. Sep. Purif. 2022, 298, 121542. [CrossRef]
14. Mendes, A.M.M.; Costa, C.A.V.; Rodrigues, A.E. Oxygen Separation from Air by PSA: Modelling and Experimental Results. Sep.
Purif. 2001, 24, 173–188. [CrossRef]
15. Tan, J.S.; Ani, F.N. Carbon Molecular Sieves Produced from Oil Palm Shell for Air Separation. Sep. Purif. 2004, 35, 47–54.
[CrossRef]
16. Shamsudin, I.K.; Abdullah, A.; Idris, I.; Gobi, S.; Othman, M.R. Hydrogen Purification from Binary Syngas by PSA with Pressure
Equalization Using Microporous Palm Kernel Shell Activated Carbon. Fuel 2019, 253, 722–730. [CrossRef]
17. Brea, P.; Delgado, J.A.; Águeda, V.I.; Gutiérrez, P.; Uguina, M.A. Multicomponent Adsorption of H2 , CH4 , CO and CO2 in Zeolites
NaX, CaX and MgX. Evaluation of Performance in PSA Cycles for Hydrogen Purification. Microporous Mesoporous Mater. 2019,
286, 187–198. [CrossRef]
18. Ko, D.; Siriwardane, R.; Biegler, L.T. Optimization of a Pressure-Swing Adsorption Process Using Zeolite 13X for CO2 Sequestra-
tion. Ind. Eng. Chem. Res. 2002, 42, 339–348. [CrossRef]
19. Raganati, F.; Miccio, F.; Ammendola, P. Adsorption of Carbon Dioxide for Post-Combustion Capture: A Review. Energy Fuels
2021, 35, 12845–12868. [CrossRef]
20. Plaza, M.G.; García, S.; Rubiera, F.; Pis, J.J.; Pevida, C. Post-Combustion CO2 Capture with a Commercial Activated Carbon:
Comparison of Different Regeneration Strategies. J. Chem. Eng. 2010, 163, 41–47. [CrossRef]
21. Ammendola, P.; Raganati, F.; Chirone, R. CO2 Adsorption on a Fine Activated Carbon in a Sound Assisted Fluidized Bed:
Thermodynamics and Kinetics. J. Chem. Eng. 2017, 322, 302–313. [CrossRef]
22. Younas, M.; Rezakazemi, M.; Daud, M.; Wazir, M.B.; Ahmad, S.; Ullah, N.; Inamuddin; Ramakrishna, S. Recent Progress and
Remaining Challenges in Post-Combustion CO2 Capture Using Metal-Organic Frameworks (MOFs). Prog. Energy Combust. Sci.
2020, 80, 100849. [CrossRef]
23. Mason, J.A.; Sumida, K.; Herm, Z.R.; Krishna, R.; Long, J.R. Evaluating Metal–Organic Frameworks for Post-Combustion Carbon
Dioxide Capture via Temperature Swing Adsorption. Energy Environ. Sci. 2011, 4, 3030–3040. [CrossRef]
24. Lee, S.-Y.; Park, S.-J. Determination of the Optimal Pore Size for Improved CO2 Adsorption in Activated Carbon Fibers. J. Colloid
Interface Sci. 2013, 389, 230–235. [CrossRef]
25. Jagiello, J.; Thommes, M. Comparison of DFT Characterization Methods Based on N2 , Ar, CO2 , and H2 Adsorption Applied to
Carbons with Various Pore Size Distributions. Carbon 2004, 42, 1227–1232. [CrossRef]
26. Kang, S.-H.; Lee, H.-M.; Kim, K.-W.; Kim, B.-J. Preparation and Characterization of Polyethylene-Based Activated Carbon Fibers
Stabilized at Low Temperatures. J. Ind. Eng. Chem. 2023, 121, 401–408. [CrossRef]
27. Lee, J.-Y.; Kim, B.-J. Surface-Modified Activated Carbon Fibers by a Facile Microwave Technique for Enhancing Hydrocarbon
Adsorption. Environments 2023, 10, 52. [CrossRef]
28. Karrab, A.; Bensimon, R.; Muller, D.; Bastide, S.; Cachet-Vivier, C.; Ammar, S. Photoelectrochemical and Electrochemical Urea
Oxidation with Microwave-Assisted Synthesized Co-Fe2 O3 @NiO Core–Shell Nanocomposites. Carbon Lett. 2022, 32, 999–1015.
[CrossRef]
29. Lee, J.-Y.; Lee, H.-M.; Kim, B.-J. Facile Microwave Treatment of Activated Carbons and Its Effects on Hydrocarbon Adsorp-
tion/Desorption Behaviors. Carbon Lett. 2023, 33, 1105–1114. [CrossRef]
30. Biscoe, J.; Warren, B.E. An X-ray Study of Carbon Black. J. Appl. Clin. Med. Phys. 1942, 13, 364–371. [CrossRef]
31. Brunauer, S.; Emmett, P.H.; Teller, E. Adsorption of Gases in Multimolecular Layers. J. Am. Chem. Soc. 1938, 60, 309–319.
[CrossRef]
32. Lippens, B. Studies on Pore Systems in Catalysts: V. The t Method. J. Catal. 1965, 4, 319–323. [CrossRef]
33. Lastoskie, C.; Gubbins, K.E.; Quirke, N. Pore Size Distribution Analysis of Microporous Carbons: A Density Functional Theory
Approach. J. Phys. Chem. 1993, 97, 4786–4796. [CrossRef]
34. Olivier, J.P.; Conklin, W.B.; Szombathely, M.v. Determination of Pore Size Distribution from Density Functional Theory: A
Comparison of Nitrogen and Argon Results. Stud. Surf. Sci. Catal. 1994, 87, 81–89. [CrossRef]
Materials 2023, 16, 5625 15 of 15

35. Nabais, J.M.V.; Nunes, P.; Carrott, P.J.M.; Ribeiro Carrott, M.M.L.; García, A.M.; Díaz-Díez, M.A. Production of Activated Carbons
from Coffee Endocarp by CO2 and Steam Activation. Fuel Process. Technol. 2008, 89, 262–268. [CrossRef]
36. Sing, K.S.W. Reporting Physisorption Data for Gas/Solid Systems with Special Reference to the Determination of Surface Area
and Porosity (Recommendations 1984). Pure Appl. Chem. 1985, 57, 603–619. [CrossRef]
37. Lee, H.-M.; Heo, Y.-J.; An, K.-H.; Jung, S.-C.; Chung, D.C.; Park, S.-J.; Kim, B.-J. A Study on Optimal Pore Range for High Pressure
Hydrogen Storage Behaviors by Porous Hard Carbon Materials Prepared from a Polymeric Precursor. Int. J. Hydrogen Energy
2018, 43, 5894–5902. [CrossRef]
38. Lee, H.-M.; Baek, J.; An, K.-H.; Park, S.-J.; Park, Y.-K.; Kim, B.-J. Effects of Pore Structure on n-Butane Adsorption Characteristics
of Polymer-Based Activated Carbon. Ind. Eng. Chem. 2018, 58, 736–741. [CrossRef]
39. Kim, J.-H.; Jung, S.-C.; Lee, H.-M.; Kim, B.-J. Comparison of Pore Structures of Cellulose-Based Activated Carbon Fibers and
Their Applications for Electrode Materials. Int. J. Mol. Sci. 2022, 23, 3680. [CrossRef]
40. Lee, H.-M.; Kwac, L.-K.; An, K.-H.; Park, S.-J.; Kim, B.-J. Electrochemical Behavior of Pitch-Based Activated Carbon Fibers for
Electrochemical Capacitors. Energy Convers. Manag. 2016, 125, 347–352. [CrossRef]
41. Casco, M.E.; Martínez-Escandell, M.; Silvestre-Albero, J.; Rodríguez-Reinoso, F. Effect of the Porous Structure in Carbon Materials
for CO2 Capture at Atmospheric and High-Pressure. Carbon 2014, 67, 230–235. [CrossRef]
42. Richter, E.; Wilfried, S.; Myers, A.L. Effect of Adsorption Equation on Prediction of Multicomponent Adsorption Equilibria by the
Ideal Adsorbed Solution Theory. Chem. Eng. Sci. 1989, 44, 1609–1616. [CrossRef]
43. Ghaemi, A.; Torab-Mostaedi, M.; Ghannadi-Maragheh, M. Characterizations of Strontium(II) and Barium(II) Adsorption from
Aqueous Solutions Using Dolomite Powder. J. Hazard. Mater. 2011, 190, 916–921. [CrossRef]
44. Manjare, S.; Ghoshal, A. Adsorption Equilibrium Studies for Ethyl Acetate Vapor and E-Merck 13X Molecular Sieve System. Sep.
Purif. Technol. 2006, 51, 118–125. [CrossRef]
45. Rashidi, N.A.; Yusup, S.; Borhan, A.; Loong, L.H. Experimental and Modelling Studies of Carbon Dioxide Adsorption by Porous
Biomass Derived Activated Carbon. Clean. Technol. Environ. Policy 2014, 16, 1353–1361. [CrossRef]
46. González, A.S.; Plaza, M.G.; Rubiera, F.; Pevida, C. Sustainable Biomass-Based Carbon Adsorbents for Post-Combustion CO2
Capture. J. Chem. Eng. 2013, 230, 456–465. [CrossRef]
47. Plaza, M.G.; González, A.S.; Pevida, C.; Pis, J.J.; Rubiera, F. Valorisation of Spent Coffee Grounds as CO2 Adsorbents for
Postcombustion Capture Applications. Appl. Energy 2012, 99, 272–279. [CrossRef]
48. Plaza, M.G.; González, A.S.; Pis, J.J.; Rubiera, F.; Pevida, C. Production of Microporous Biochars by Single-Step Oxidation: Effect
of Activation Conditions on CO2 Capture. Appl. Energy 2014, 114, 551–562. [CrossRef]
49. Serafin, J.; Ouzzine, M.; Cruz Junior, O.F.; Sreńscek-Nazzal, J. Preparation of Low-Cost Activated Carbons from Amazonian
Nutshells for CO2 Storage. Biomass Bioenergy 2021, 144, 105925. [CrossRef]
50. Singh, M.; Borkhatariya, N.; Pramanik, P.; Dutta, S.; Ghosh, S.K.; Maiti, P.; Neogi, S.; Maiti, S. Microporous Carbon Derived from
Cotton Stalk Crop-Residue across Diverse Geographical Locations as Efficient and Regenerable CO2 Adsorbent with Selectivity. J.
CO2 Util. 2022, 60, 101975. [CrossRef]
51. Yue, L.; Xia, Q.; Wang, L.; Wang, L.; DaCosta, H.; Yang, J.; Hu, X. CO2 Adsorption at Nitrogen-Doped Carbons Prepared by
K2 CO3 Activation of Urea-Modified Coconut Shell. J. Colloid Interface Sci. 2018, 511, 259–267. [CrossRef]
52. Rehman, A.; Park, S.-J. Comparative Study of Activation Methods to Design Nitrogen-Doped Ultra-Microporous Carbons as
Efficient Contenders for CO2 Capture. J. Chem. Eng. 2018, 352, 539–548. [CrossRef]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.