Chemical Engineering Journal 437 (2022) 135378

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Chemical Engineering Journal

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

Development of high-performance adsorbent using KOH-impregnated rice

husk-based activated carbon for indoor CO2 adsorption
Shuang Wang, Yu-Ri Lee, Yooseob Won, Hana Kim, Se-Eun Jeong, Byung Wook Hwang,
A. Ra Cho, Jae-Young Kim, Young Cheol Park, Hyungseok Nam *, Dong-Ho Lee, Hyunuk Kim,
Sung-Ho Jo
Korea Institute of Energy Research, Daejeon 34129, Republic of Korea

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

Keywords: Relatively high indoor CO2 concentration (greater than 1000 ppm) has a negative impact on human health. In
Rice husk this work, a cost-effective CO2 adsorbent (DKOH-AC) was developed by impregnating KOH on rice husk-based
Activated carbon KOH activated carbon (KOH-AC, 1439 m2/g). KOH can be successfully loaded on the surface of KOH-AC and
KOH activation and impregnation
significantly changed its surface properties. DKOH-AC still remained a considerable surface area (206 m2/g) and
CO2 adsorption
Indoor air purification
showed a similar Smicro/SBET ratio. In-situ FTIR analysis confirmed that the major CO2 adsorption mechanism of
KOH-AC was based on physisorption while that on DKOH-AC involved both chemisorption and physisorption.
DKOH-AC showed a higher heat of adsorption (34 ~ 41 KJ/mol) and gas selectivity (16.6) than these of KOH-AC.
KOH-AC quickly reached an adsorption equilibrium (about 50 min) as compared to that of DKOH-AC. In addi­
tion, DKOH-AC exhibited an excellent adsorption performance of 2.1 mmol/g for a low concentration of CO2
(2000 ppm ~ 500 ppm) under indoor conditions. Both the CO2 adsorption isotherm on KOH-AC and DKOH-AC
well followed the Langmuir and Freundlich models. The CO2 adsorption kinetics on KOH-AC followed the
pseudo-first order model whereas that on DKOH-AC obeyed the pseudo-second order model. The adsorption
process was controlled by the intraparticle diffusion combined with the film diffusion model.

1. Introduction Harvard‘s research team showed that elevated CO2 levels have direct
negative impacts on human cognition and the biggest victims are those
The current concentration of CO2 in the atmosphere exceeds 410 who are often exposed to confined or unventilated spaces such as
ppm, which is 46.4% higher than the pre-industrial level [1]. Unfortu­ classrooms, workshops, homes, planes, and cars [8]. Therefore, suffi­
nately, the growing trend will continue due to fossil fuels, which ac­ cient attention must be paid to indoor CO2 issues and a cost-effective
counts for the largest portion of human energy demand for a long time in method for indoor CO2 capture is urgently required.
the future [2]. Consequently, the global warming and climate change Carbon dioxide (CO2) capture and storage (CCS) has been widely
issues, caused by greenhouse gas (GHG) emissions (CO2 is a major GHG, regarded as a very promising strategy for mitigating CO2 emission
accounting for 78% of the total GHG emission), have attracted a wide­ [9,10]. However, since the capture process accounts for approximately
spread attention worldwide [3,4]. Indoor CO2 is actually a very serious 70 ~ 80% of the total cost of CCS technology, cost-efficient CO2 capture
problem, but unfortunately, it has not attracted enough attention as methods are strongly required [11]. Absorption of CO2 using aqueous
compared to global warming and climate change issues. Many studies amine solutions is a very mature technology and has been widely used in
have shown that the safety threshold of indoor CO2 concentration for industry [12]. Nevertheless, several critical shortcomings restrict its
human is determined to be 1000 ppm. People will feel fatigued, inat­ wide applications in different fields, including high energy consump­
tention, headache, and drowsiness above 1000 ppm whereas it will tion, equipment corrosion, poor thermal stability, and possible second­
cause direct harm to humans including inflammation, a decline in ary pollution [13]. In addition, CO2 membrane separation technique has
advanced cognitive abilities, kidney calcification, bone demineraliza­ also attracted considerable attention due to its low energy consumption,
tion, and endothelial dysfunction above 5000 ppm [5–7]. In addition, high compactness and continuous operation, and environmental

* Corresponding author.
E-mail address: [email protected] (H. Nam).

https://doi.org/10.1016/j.cej.2022.135378
Received 23 November 2021; Received in revised form 14 February 2022; Accepted 17 February 2022
Available online 21 February 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
S. Wang et al. Chemical Engineering Journal 437 (2022) 135378

Fig. 1. Schematic diagram of the manufacturing process of KOH-AC and DKOH-AC filters for an indoor chamber test.

Fig. 2. Schematic diagram of (a) fixed bed adsorption setup and (b) chamber adsorption test setup.

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S. Wang et al. Chemical Engineering Journal 437 (2022) 135378

Table 1 over other solid adsorbents include low cost, large surface area and well-
Experimental conditions for CO2 adsorption test using three experimental developed micropores, high adsorption capacity, good chemical and
apparatus. thermal stabilities, and easy regeneration, making it more attractive.
Type Sample Gas Experimental Analysis Activated carbon can be synthesized using various carbon-containing
conditions Method precursors (e.g. agricultural and industrial wastes, petroleum coke, and
Fixed KOH-AC 15% CO2 (N2 Inlet flow: 50 cc/ CO2 IR plastic waste) via carbonization (300 ~ 600 ℃) under inert gas condi­
bed and balance) min analyzer tions, followed by activation at high temperature (700 ~ 900 ℃)
DKOH- Pre-treatment [19,22–27]. The utilization of these waste materials can not only solve
AC (regeneration):
the increasing environmental problems but also produce high value-
150℃ for 2hrs
Adsorption added products that contribute to the circular economy. In particular,
temperature: 10 ~ when biomass-based activated carbon is used for CO2 capture, a nega­
40 ℃ tive carbon balance can be achieved. The carbon, released during the
Regenerability test: preparation of activated carbon, can be regarded as neutral by consid­
4 cycles at 30 ℃
DKOH- 2000 ppm (N2 Inlet flow: 50 cc/
ering the carbon consumed during the formation of biomass. Further­
AC balance) with/ min more, CO2 capture using prepared activated carbon can reduce the total
without 1.0% H2O Pre-treatment carbon emissions [28]. Generally, activation includes physical activa­
(regeneration): tion (such as, air, steam and CO2) and chemical activation (e.g. KOH,
150℃ for 2hrs
H3PO4, ZnCl2, etc). Chemical activation can produce activated carbon
Adsorption
temperature: 30 and with a better-developed microporous structure as compared to physical
40 ℃ activation [29]. Among these activators, KOH is considered to be the
Regeneration test: most effective and frequently used agent as it can create a large specific
10 cycles test for surface area and a high total pore volume (especially, micropores)
DKOH-AC at 30 ℃
[22,30]. Many studies on the preparation of activated carbon from
TGA KOH-AC 15% CO2 (N2 Inlet flow: 50 cc/ Weight
and balance) min based biomass for CO2 capture have been reported. Choi et al. [31] synthesized
DKOH- Pre-treatment/ the activated carbon using pollens with a KOH activation for CO2
AC Desorption adsorption. The best activated carbon sample (Max. SBET: 1460 m2/g)
(regeneration):
was obtained with a KOH/carbonized pollen ratio of 3:1 at 800 ℃. It
150℃ for 2 hrs
Adsorption: 10, 20, exhibited the highest CO2 adsorption capacity of 5.63 mmol/g at 0 ℃
30 and 40 ℃ for 5 and 3.42 mmol/g at 25 ℃ (CO2 adsorption isotherms at 1 bar), high
hrs. CO2/N2 selectivity (15 ~ 12 in the range of 0 ~ 1.0 bar) and good
Regenerability test: regeneration. In addition, it was found that the narrower micropores
5 cycles at 20 ℃
(<0.8 nm) are very suitable for CO2 adsorption. The preparation of
2000 ppm (N2 Inlet flow: 50 cc/
balance) min activated carbon using packing peanuts via physical and chemical ac­
Pre-treatment/ tivations was conducted by Hong et al. [30]. Chemical activation (KOH)
Desorption can produce a higher microporous carbon structure and greater carbon
(regeneration):
yield than physical activation (CO2). The specific surface area and total
150℃ for 2 hrs
Adsorption: 20, 30
pore volume increase in proportion to the mass ratio of KOH/carbon and
and 40 ℃ for 5 hrs. the highest BET surface area of 2420 m2/g was obtained at a KOH/
Chamber KOH-AC Initial CO2 Pre-treatment CO2 IR carbon ratio of 5. However, the highest CO2 adsorption capacities of
and concentration: 2000 (regeneration): analyzer 6.51 mmol/g at 0 ◦ C and 4.07 mmol/g at 25 ◦ C were obtained by CO2
DKOH- and 500 ppm (Air 150℃ for 1hr (Air)
adsorption isotherms at 1 bar using an activated carbon sample with a
AC filters balance) Adsorption time:
500 min KOH/carbon ratio of 3 instead of 5. This was due to the CO2 adsorption
Regenerability test: capacity of activated carbon was significantly dependent on the volume
5 cycles (Air) of narrow micropores (<0.8 nm) rather than the BET surface area and
Temperature: 25.0
total pore volume. Yuan et al. [25] prepared N-doped microporous
~ 34.0 ℃
Relative humidity:
carbon using PET plastic waste with N-doping treatment and KOH
40.0 ~ 52.0% activation via one-pot synthesis methods for CO2 capture. The micro­
Absolute humidity: porous carbon (SBET = 1165 m2/g, Vtotal = 0.469 cm3/g, and Vmicro =
1.5 ~ 2.5% 0.460 cm3/g) was obtained at a mass ratio of 1:2:1 for PET, KOH, and
urea, respectively. It showed the highest CO2 adsorption capacities of
friendliness [14]. However, its large-scale commercialization is still 6.23 mmol/g at 0 ◦ C and 4.58 mmol/g at 25 ◦ C (CO2 adsorption iso­
limited by some technical obstacles such as, low separation efficiency therms at 1 atm). The Langmuir and pseudo-second-order models
under low CO2 concentration, poor thermal stability, and easy cracking. showed the best-fitting relationship with the adsorption isotherm and
Therefore, the recent research interests have turned to the adsorption kinetic experimental data, respectively. Moreover, CO2 adsorption ca­
approach using solid materials for CO2 capture because of its low energy pacity depended not only on the volume of micropores but also on the
consumption, high feasibility for scale-up applications, mild operating nitrogen and oxygen functional groups on the activated carbon.
conditions, easy regeneration and no pollutants or byproducts [15]. Regeneration is a very important technology for CO2 adsorption
Many solid adsorbents have been proposed and developed including, materials, because it can increase the cost-effectiveness of the adsorbent
zeolite [16], mesoporous silica [17], MOFs (metal–organic frameworks) by extending the service life and reducing the cost. The appropriate
[18] and activated carbon [19]. Silica mainly contains a large amount of regeneration mode mainly depends on the physical characteristic of
mesoporous structure although the microporous structure rather than adsorbent (eg. thermal conductivity, specific heat and diffusivity) and
mesoporous structure is more suitable for CO2 capture [20]. In addition the nature of adsorption (physical adsorption or chemical adsorption)
to the high cost, zeolite and MOFs also have a vital defect, that is, their [32,33]. The regeneration mode can be classified into temperature
adsorption capacity dramatically decreases under humid conditions due swing adsorption (TSA), pressure swing adsorption (PSA), vacuum
to their hydrophilic properties [21]. Advantages of activated carbon swing adsorption (VSA) as well as hybrid regeneration (VTSA/PTSA) by
changing temperature and pressure resulting at the same time [32,33].

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S. Wang et al. Chemical Engineering Journal 437 (2022) 135378

Fig. 3. SEM of (a) rice husk, (b) and (c) biochar, (d)-(f) KOH-AC and (g)-(i) DKOH-AC.

Generally speaking, VSA is more suitable for physisorption based activated carbon obtained (defined as KOH-AC) was further developed
adsorbent materials (especially suitable for high concentration CO2) into DKOH-AC (KOH impregnated on KOH-AC) by mixing it with KOH
whereas TSA is more suitable for chemisorption based adsorbent ma­ solution again (mass ratio of KOH-AC : KOH = 1:1). Then, the slurry was
terials (especially suitable for low concentration CO2) [32,33] dried in an oven at 120 ℃ overnight to produce the final DKOH-AC
The application of activated carbon to remove low-concentration sample. The manufacturing process of KOH-AC and DKOH-AC filters
CO2 still has some challenges and knowledge gaps, which are worthy for indoor chamber test is represented in Fig. 1. First, the high density
of further study such as poor stability, weak binding strength and low filter layer obtained from 3-Ply surgical face mask was used to make
adsorption capacity. Therefore, in order to further study and solve these activated carbon filter bags with a size of 77 × 77 mm. Then, to enhance
problems, the method of KOH modified activated carbon was used for the strength and compactness of the activated carbon bag, a PET non-
the low-concentration CO2 adsorption. Therefore, following to our woven fabric was adhered to one side of activated carbon bag. Finally,
previous work [22], the KOH activated-rice husk activated carbon (BET: about 3.0 g of KOH-AC and DKOH-AC powder was put into the bag and
2652 m2/g and micropores volume: 0.531 cm3/g) for VOC application then enclosed it using a heat sealing machine.
was further modified for an indoor CO2 adsorption application in the
current study. To the best of our knowledge, this is the first study of 2.2. CO2 adsorption and regenerability experiments
using rice husk activated carbon for indoor CO2 removals by impreg­
nating KOH. The specific objectives of this study were a) to evaluate and The CO2 adsorption and regenerability experiments were carried out
compare their adsorption capacity in TGA test, fixed bed test, and using a fixed bed (Dreamtech Co., Ltd, Korea), TGA (Thermo Gravi­
chamber test, b) to investigate the physical and chemical properties of metric Analyzer Model: N-1500, SCINCO), and self-designed enclosed
KOH-AC (KOH-activated rice husk activated carbon) and DKOH-AC chamber (volume: 0.1 m3). The experimental setups of fixed bed and
(KOH impregnated on KOH-AC), c) to understand and determine the chamber are shown in Fig. 2 and the experimental conditions are sum­
heat of adsorption and the reusability of DKOH-AC (filter), and d) to marized in Table 1. The fixed bed tests (15%CO2 or 2000 ppmCO2, N2
explore and compare their adsorption mechanisms. balance) were conducted with KOH-AC and DKOH-AC powders (about 2
g) in the temperature range from 10 to 40 ℃. In addition, the regener­
2. Experimental ability test for DKOH-AC was performed at 30 ℃ to evaluate its reus­
ability. TGA CO2 adsorption (15%CO2 or 2000 ppm, N2 balance)
2.1. Preparation of KOH-AC and DKOH-AC filters experiments were conducted using 10 mg samples (KOH-AC and DKOH-
AC powders). The adsorption temperature conditions were 10, 20, 30,
Activated carbon was produced by carbonizing rice husk at 450 ℃ and 40 ◦ C for 5 h. In addition, TGA adsorption tests at 20 ℃ (close to
and then activating it with KOH at 750 ℃ under argon gas. The prep­ room temperature) for 24 h were performed to evaluate its long-term
aration process is discussed in detail in our previous study [22]. The adsorption capacity. For the reusability (regenerability) evaluation of

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S. Wang et al. Chemical Engineering Journal 437 (2022) 135378

test was initiated by analyzing CO2 concentration using a real-time IR

CO2 gas analyzer (AO2020, ABB Ltd., Switzerland) with a sampling
frequency of 0.1 s and precision of < 1 % of span (0 ~ 5000 ppm) until
the CO2 gas equilibrium. All the experiments and technical analyses
were performed at least twice or more, and the average values were
reported. The actual adsorption capacity can be calculated using the
following equations (1):
V c Mw
CO2 adsorption capacity (mg/g) : q = ∙ ∙(Ci − Cf ) (1)
w Vm

where Vc: volume of chamber (0.1 m3)

w: the mass of adsorbent, (g)
Mw: CO2 molar mass (44 g/mol)
Vm: molar volume of gas 24.465 L/mol at 25 ℃
Ci or f: the initial and final CO2 concentration, (ppm)

2.3. Characterization of adsorbents

KOH-AC and DKOH-AC samples were comprehensively character­

ized with the following analytical methods. The surface morphology of
KOH-AC and DKOH-AC was observed with FE-SEM (Scanning Electron
Microscope; TESCAN (Czech), VEGA). SEM-EDS (scanning electron
microscopy with energy dispersive spectroscopy, QUANTAX 200,
Bruker) was used to identify the presence of the impregnated KOH on
KOH-AC and confirmed the changed surface morphology. N2 adsorp­
tion–desorption isotherms were performed at 77 K using an ASAP 2020
(BET Micromeritics) to determine and analyze the BET surface area and
pore size distribution based on NL-DFT method. Similarly, CO2
adsorption isotherms was also carried out at different adsorption tem­
peratures using an ASAP 2020 (BET Micromeritics) to calculate the heat
of adsorption and the selectivity of CO2/N2. Before the adsorption
measurements, the samples were pretreated at 150 ◦ C for 4 h under the
vacuum. The surface basicity of KOH-AC and DKOH-AC was measured
by temperature programmed desorption (TPD) method using CO2-TPD
as probe gas (BELCAT II, BELMASS (MicrotracBEL Co.), Japan). The in-

Fig. 4. (a) N2 adsorption/desorption isotherm and (b) pore size distribution of Table 3
KOH-AC and DKOH-AC. Comparison of CO2 adsorption isotherm uptakes of activated carbon derived
from different biomass.
KOH-AC and DKOH-AC, 5 cycles of TGA adsorption/desorption were Carbon precursor Activator BET CO2 uptake at 1 bar Ref.
carried out. (m2/ (mmol/g)
g)
To better understand and simulate the adsorption capacity of KOH- 0℃ 20 25
AC and DKOH-AC at the indoor CO2 concentration level, the chamber ℃ ℃
adsorption tests were performed under indoor conditions of a temper­ Rice husk KOH 1439 5.70 3.88 3.51 This
ature range of 25.0 ~ 34.0 ℃, a relative humidity range of 40.0 ~ 52.0% study
and an absolute humidity range of 1.5 ~ 2.5%. The experimental pro­ Waste packing peanuts KOH 1354 6.51 – 4.07 [30]
Petroleum coke KOH 1586 6.08 3.57 [24]
cedure of the indoor chamber test with an initial concentration of 2000
–
Pollens KOH 1460 5.63 – 3.42 [31]
ppm (high indoor concentration) and 500 ppm (low indoor concentra­ Coal tar pitch KOH 974 6.00 – 4.03 [41]
tion) CO2 is as follows. First, a pretreated DKOH-AC filter (or KOH-AC Nitrogen-free phenolic KOH 1171 5.07 – 3.47 [42]
filter) was placed on the electric fan kit inside the chamber. Then, the resin derived
activated carbon
chamber door is closed before injecting pure CO2 gas to make the initial
beads
CO2 concentration at round 2000 ppm or 500 ppm. Last, the adsorption

Table 2
Langmuir and Freundlich model parameters of CO2 adsorption on KOH-AC and DKOH-AC.
Isotherm models Parameters KOH-AC DKOH-AC

0℃ 20℃ 25℃ 0℃ 20℃ 25℃

Experimental qe (at 1 atm) 5.70 3.88 3.51 0.89 0.64 0.48

Langmuir KL 2.85 1.88 1.62 3.17 1.99 1.89
qm 7.29 5.89 5.67 1.11 0.95 0.74
H(qmxKL) 20.78 11.07 9.19 3.52 1.89 1.40
R2 0.9807 0.9870 0.9896 0.9757 0.9844 0.9839
Freundlich KF 5.68 3.90 3.53 0.90 0.64 0.49
n 2.10 1.96 1.87 2.18 2.01 1.99
R2 1.0 1.0 1.0 1.0 1.0 1.0

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Fig. 5. In-situ FTIR analysis of 15% CO2 adsorption on (a) KOH-AC and (b) DKOH-AC at 30 ℃ from 0 to 60 min.

situ FTIR test of CO2 adsorption on KOH-AC and DKOH-AC was con­ (b). In addition, no pores are detected on the magnification surface of
ducted using DiffusIR (PIKE Technologies, USA) to determine the biochar as presented in Fig. 3 (c). After further KOH activation at 750 ℃,
adsorption mechanism of chemical or physical adsorption. XRD (D/Max KOH-AC obtained consists of many flocculent lumps with different size
2500) was used to identify the presence of inorganics after CO2 and irregular surfaces, as shown in Fig. 3 (d). Many identical pores are
adsorption on DKOH-AC. The specific heat capacity (Cp,s) was also evenly distributed on the surface of KOH-AC (Fig. 3 (e)) and a huge
determined by DSC analysis using SDT Q600 (TA instruments, USA). number of pores with different sizes are clearly observed at a higher
magnification of 100 nm, as shown in Fig. 3 (f). This confirmed that the
3. Results and discussion formation of a large number of pores was attributed to the KOH acti­
vation. Compared with the KOH-AC (Fig. 3 (d)), DKOH-AC has a smaller
3.1. Characteristics of KOH-AC and DKOH-AC size and is close to powder (Fig. 3 (g)) and its surface is smoother and
more irregular (Fig. 3 (h)). This is due to the KOH-impregnation, which
Fig. 3 shows the SEM images of rice husk and its biochar, KOH-AC is supported by the SEM-EDS (Figure S1), especially the potassium
and DKOH-AC. A smooth surface with a regular shape was obtained content greatly increased from 2.1% on KOH-AC to 40.4% on DKOH-AC.
with rice husk, as shown in Fig. 3 (a). After carbonization at 450 ℃, the Furthermore, from Fig. 4 of BET analysis, DKOH-AC still remained some
smooth and regular surface disappeared and was replaced by many micropores (similar ratio of Smicro/SBET). Therefore, this indicates that
lumps with different sizes and irregular surfaces, as displayed in Fig. 3 KOH-impregnation significantly altered the surface properties, but still

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remained numerous microporous structures.

Fig. 4 shows the N2 adsorption/desorption isotherm and pore size
distribution of KOH-AC and DKOH-AC. The profile of KOH-AC showed a
Type-I with an H4 hysteresis according to IUPAC (International Union of
Pure and Applied Chemistry) classification, indicating that KOH-AC was
comprised of a large number of microspores and a few mesopores.
Although a smaller N2 adsorption amount was obtained with DKOH-AC
as compared to KOH-AC, the DKOH-AC exhibited a more standard Type-
I isotherm without any hysteresis. This indicated that DKOH-AC mainly
contained microporous structures. In addition, KOH-AC with a wider
knee and DKOH-AC with a narrower knee indicate the presence of large
micropores in KOH-AC and small micropores in DKOH-AC, respectively
[30]. This indicates that KOH-impregnation on KOH-AC changed the
textural properties (only the small microporous structure was retained)
by destroying the surface mesoporous structure and microporous
structure. This well agreed with the above SEM analysis and was also
supported by the pore size distribution as shown in Fig. 4 (b).
CO2 adsorption isotherms of KOH-AC and DKOH-AC at 0, 20 and 25
℃ were carried out as shown in Figure S2. The CO2 adsorption isotherm
data were fitted into Langmuir (Eq. (S1)) and Freundlich (Eq. (S2))
adsorption isotherm models. Table 2 shows the summary of isotherm
model parameters with two adsorbents. The adsorption capacity
decreased as the adsorption temperature increased, indicating that
increasing temperature is not conducive to CO2 adsorption. This finding
was consistent with other literatures [24,30]. Although the Langmuir
model provided a relatively high R2 (greater than 0.98) for CO2
adsorption on KOH-AC and DKOH-AC, an almost perfect fit (R2 = 1.0)
was obtained with Freundlich model, indicating heterogeneous surface
features. In addition, BET surface area and CO2 uptakes of KOH-AC are
comparable to those reported in other studies, as shown in Table 3.
However, CO2 uptakes of KOH-AC at 0 ~ 25 ℃ (3.51 ~ 5.70 mmol/g)
are much higher than those of DKOH-AC (0.48 ~ 0.89 mmol/g). Lower
adsorption capacity with DKOH-AC from CO2 adsorption isotherms is
due to its relatively low surface area with small pore volume by
impregnation with KOH on the pores. More importantly, since CO2
adsorption isotherm was measured using pretreated DKOH-AC (under
high vacuum at 150 ◦ C for 4 h) in a closed sample cell system with no
water, there is a limit to the carbonation reaction (ii step) in the for­
mation of KHCO3 by reacting with H2O and CO2 according to following
reaction steps; (i) 2KOH + CO2 → K2CO3 + H2O, (ii) K2CO3 + CO2 +
H2O → 2KHCO3 [34]. However, TGA analysis to measure CO2 adsorp­
Fig. 6. XRD analysis of (a) KOH-AC and (b) DKOH-AC before and after tion capacity was conducted in an open system using an unpretreated
CO2 adsorption. sample resulting in high CO2 adsorption capacity despite low surface
area (Fig. 4 and Table 2). This result implies that the presence of water
can promote carbonation reactivity and CO2 chemisorption. Previous
studies on CO2 uptake by K2CO3/support reported that CO2 adsorption
was increased in the presence of H2O, and the carbonated K2CO3 hy­
dration products such as K4H2(CO3)3⋅(1.5 H2O) and K2CO3⋅(1.5 H2O)
can react with CO2 in a fast kinetic rate [35,36]. In detail, carbonation
reaction mainly occurs at the interfaces of K2CO3/support including
bicarbonate formation from the reactions of CO2 with OH via H2O
dissociation and CO32– with transferred H via H2O dissociation
combining. Thus, it can be supported that DKOH adsorbent with high
population of K+ ions (K: 40.4 wt% detected by EDS as shown in
Figure S1) to form potassium carbonate hydrate in the presence of H2O
showed a high CO2 adsorption capacity. In addition, this also indicates
that CO2 adsorption on DKOH-AC highly depended on the chemical
adsorption which requires water, besides the physical adsorption. To
confirm this hypothesis, the in-situ FTIR tests of CO2 adsorption on KOH-
AC and DKOH-AC were further studied, as shown in Fig. 5. The in-situ
FTIR spectra of CO2 adsorption on KOH-AC from 0 to 60 min show
that the intensity of the major peak at about 2341 cm− 1 increased
sequentially as the CO2 adsorption time increased while no significant
difference was detected on other minor peaks. The peak at 2341 cm− 1
can be attributed to the asymmetric stretching mode caused by the
Fig. 7. CO2-TPD profiles of KOH-AC and DKOH-AC. physisorption of CO2 [37]. For CO2 adsorption on DKOH-AC, the peak at

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S. Wang et al. Chemical Engineering Journal 437 (2022) 135378

Fig. 8. CO2 and N2 adsorption isotherms at 20 ℃ on KOH-AC and DKOH-AC.

Fig. 9. CO2/N2 selectivity for the (a) KOH-AC and (b) DKOH-AC using the ratios of the Henry‘s constant obtained by the initial slopes of the single-component gas
adsorption isotherms measured at low pressure coverage (<0.15 bar) and 293 K.

40 45
(a) KOH-AC (b) DKOH-AC
40
35
Qst, (KJ/mol)
Qst, (kJ/mol)

35
30
30

25
25

20 20
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 0 0.1 0.2 0.3 0.4 0.5 0.6
n (mmol/g) n (mmol/g)
Fig. 10. Isosteric heat of CO2 adsorption on (a) KOH-AC and (b) DKOH-AC.

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S. Wang et al. Chemical Engineering Journal 437 (2022) 135378

Fig. 12. Fixed bed adsorption results of 2000 ppmCO2 at different adsorption
temperatures on DKOH-AC (a) without H2O and (b) with 1% of H2O.

peaks at about 3670 and 3800 cm− 1 were related to the ν(OH) pattern of
the newly formed hydroxyl group of bicarbonate, corresponding to the
bidentate bicarbonate (b-HCO3-) and monodentate bicarbonate (m-
HCO3-) species [34]. This can be fully confirmed by the XRD analysis of
KOH-AC and DKOH-AC before and after CO2 adsorption, as shown in
Fig. 6. Similar XRD profiles (two major weak and broad peaks at 26 and
43◦ , respectively) were obtained with the KOH-AC before and after CO2
adsorption (Fig. 6 (a)), indicating a typical amorphous carbon structure
[38]. This is consistent with the discovery of physical adsorption on
KOH-AC discussed above. In addition, the intensity change in the minor
peak after CO2 adsorption on KOH-AC is attributed to KCl (mainly due to
the remaining K after KOH activation and the Cl produced from HCl
washing, as confirmed by EDS in Figure S1). For DKOH-AC before and
after adsorption (Fig. 6 (b)), the main peak of KHCO3 detected on DKOH-
Fig. 11. Fixed bed adsorption results of 15%CO2 at different adsorption tem­
peratures on (a) KOH-AC and (b) DKOH-AC; (c) regenerability test of 15%CO2 AC before CO2 adsorption is due to exposure to air causing KOH to react
adsorption on DKOH-AC at 30 ℃. with CO2 and moisture (H2O) from the air. Although the KHCO3 peak
also appeared on DKOH-AC after CO2 adsorption, it cannot be strongly
proved that DKOH-AC adsorbs CO2 by chemical adsorption. However,
2341 cm− 1 was found to be opposite to the CO2 adsorption trend on
the appearance of K4H2(CO3)3⋅1.5H2O only on DKOH-AC after CO2
KOH-AC, that is, the peak intensity decreased gradually as the CO2
adsorption is a strong evidence that CO2 was adsorbed by DKOH-AC
adsorption time increased. This shows that CO2 physisorption on DKOH-
through chemical adsorption. This is due to the K4H2(CO3)3⋅1.5H2O is
AC wakened with the extension of the adsorption time. In addition,
regarded as the intermediate composition of KHCO3 crystals [39,40].
other broad peaks at about 1250 ~ 2000 cm− 1 and 3500 ~ 4000 cm− 1
Therefore, based on these analyses, it can be concluded that CO2
gradually became stronger as the adsorption time increased, which are
adsorption on KOH-AC was mainly physisorption while that on DKOH-
due to the chemisorption of CO2 on DKOH-AC (2KOH + CO2 → K2CO3 +
AC was initially physisorption and then the physisorbed CO2 was con­
H2O; K2CO3 + CO2 + H2O → 2KHCO3) [34]. The peaks at around 1508
verted into chemisorption.
and 1720 cm− 1 were assigned to be bidentate carbonate (b-HCO3-) and
The surface basicity of the KOH-AC and DKOH-AC adsorbents was
bridged bidentate carbonate (br-CO32-), respectively [34]. Also, the
measured by a temperature programmed desorption (TPD) technique

9
S. Wang et al. Chemical Engineering Journal 437 (2022) 135378

Fig. 13. Cyclic stability test of 2000 ppmCO2 on DKOH-AC (with H2O) using fixed bed apparatus.

Fig. 14. Adsorption results of (a) 15%CO2 on KOH-AC, (b) 15%CO2 on DKOH-AC, (c) 2000 ppmCO2 on KOH-AC and (d) 2000 ppmCO2 on DKOH-AC at different
adsorption temperatures of 10 ~ 40 ℃.

using CO2-TPD as probe gas. The TPD analysis was performed within the was calculated based on the area of these peaks and as expected, larger
temperature range from 303 to 1173 K where the structure of the ad­ amount of CO2 desorption occur at DKOH-AC (7.871 mmol/g) compared
sorbents did not collapse. Fig. 7 showed the CO2-TPD profiles of the to KOH-AC (6.011 mmol/g), which indicated that higher KOH loadings
samples, and the distribution of the basic sites in different strength was in DKOH-AC enhance the surface basicity to improve CO2 adsorption.
estimated following the guideline of Jiang et al. [43]; weak (323–450 K) The selectivity of CO2 over N2 is a very critical factor in practical
and medium to strong (450–773 K) basicity groups. Overall, both KOH- applications because N2 is the major component of the atmosphere
AC and DKOH-AC exhibited medium to strong basicity. In detail, several (~78%). The selectivity of CO2/N2 for KOH-AC and DKOH-AC can be
peaks in the CO2 spectra were detected; a peak at low temperature calculated using Henry’s law [44] through the initial slopes of CO2 and
(200–400 ◦ C) corresponding to the decomposition of carboxylic acids, N2 adsorption isotherms as shown in Fig. 8. The initial slopes (Henry‘s
peaks at around 400 ~ 650 ◦ C associated with carboxylic anhydride and constants) of CO2 and N2 adsorption isotherms are obtained as shown in
the decomposition of lactones or CO2 via the secondary reactions in Fig. 9. Finally, the Henry‘s law selectivity of CO2/N2 of KOH-AC and
porous carbon structures as reported previously. The amount of basicity DKOH-AC were obtained as 11.30 and 16.64 respectively, based on the

10
S. Wang et al. Chemical Engineering Journal 437 (2022) 135378

Table 4
Comparison of CO2 adsorption capacity on different activated carbons.
Types of adsorbent Apparatus Adsorption Temp. CO2 concentration Adsorption capacity Ref.
(℃) (mmol/g)

AC from polyacrylonitrile (PAN) with KOH activation TGA 30 6 ~ 100% 1.7 ~ 2.5 [51]
K2CO3/AC TGA 20 ~ 60 1% 1.62 [52]
3D hierarchical carbon materials from polyisocyanurate (PIR) polymer TGA 40 15% 2.30 [53]
with KOH activation
AC from urea formaldehyde resin with KOH activation Fixed bed 30–100 5–12.5% Max: 1.4 [54]
AC impregnated with Cu and Zn Fixed bed 30–50 5–50% Max: 2.25 [55]
MC-PEI (mesoporous carbon-supported polyethylenimine) Fixed bed Ambient 5000 ppm 3.34 for 5000 ppm [56]
temperature 400 ppm 2.25 for 400 ppm
AC from rice husk with KOH activation (KOH-AC) Fixed bed 20 15% 1.39 This
study
DKOH-AC Fixed bed 20 15% 2.55 This
study
DKOH-AC Fixed bed 30–40 2000 ppm (1.0% 1.91 ~ 1.93 This
H2O) study
K2CO3-AC TGA 30 2000 ppm (1.0% 3.33 This
H2O) study

ratio of the initial slopes (Henry‘s constants) of CO2 and N2 adsorption affects the economics and market competitiveness of the adsorbent in
isotherms. They are comparable to or higher than that of other activated practical commercial applications. In this work, the regenerability tests
carbons [24, 25, 30, and 31]. A higher selectivity of CO2/N2 was ob­ of KOH-AC and DKOH-AC for 15%CO2 adsorptions at 20 ℃ were carried
tained with DKOH-AC as compared to KOH-AC, showing a stronger out and the results were shown in Figure S5. Good regenerability per­
ability to separate CO2 from N2 for DKOH-AC than that for KOH-AC. The formance means that KOH-AC and DKOH-AC have perfect reusability.
reason for the behavior is that more oxygen-containing functional Furthermore, the energy required for the regeneration process will be
groups (like –OH) on DKOH-AC produced by KOH impregnation further studied to evaluate the energy cost of regeneration. According to
increased the adsorption affinity to CO2 molecule [19], which was Zhang et al. [48], the regeneration heat is mainly composed of sensible
supported by EDS analysis (Figure S1, O content: 12.81% on KOH-AC heat, heat of CO2 adsorption, and latent heat. The calculation equation
and 45.91% on DKOH-AC). of regeneration heat can be expressed as (Eq. (S3)). The sensible heat
The heat of adsorption (Qst) of KOH-AC and DKOH-AC was calcu­ mainly depends on the temperature difference between the adsorption
lated using the Clausius-Clapeyron equation (Eq. (2)) based on the CO2 temperature and the desorption temperature as well as the specific heat
adsorption isotherms at three adsorption temperatures of 0, 20, and 25 of adsorbent. To reduce the sensible heat, a conductive heating method
℃ as shown in Figure S3 [45]. can be applied instead of using hot gas for the regeneration, which is
[ ] under development [49]. Similarly, the heat of CO2 adsorption primarily
∂ln(p)
ΔH = − R (2) depends on the nature of adsorbent (heat of adsorption). In addition, the
∂(1/T) n
latent heat is largely affected by moisture adsorbed. However, owing to
the moisture adsorption characteristics (~10 wt%) of carbon materials,
where R: gas constant (0.00831 KJ/mol.K)
the high latent heat ultimately increases the energy consumption for
P: pressure (Torr)
regeneration of the adsorbent. A hydrophobic silane coated activated
T: adsorption temperature (K)
carbon [50] can be a good candidate to reduce moisture adsorption
n: specific adsorption amount of CO2 (mmol/g)
without negatively affecting the CO2 adsorption performance.
The isosteric heat of adsorption can be calculated from the plots of ln
P Vs 1/T for the CO2 adsorption isotherms at 0, 20 and 25 ℃ as shown in
Figure S4 and the calculated values were represented in Fig. 10.
3.2. Fixed bed adsorption tests
Although the actual CO2 amount adsorbed on DKOH-AC through
chemical adsorption was higher than that of CO2 adsorption isotherm, it
Fig. 11 shows the results of adsorption and regeneration using a fixed
has no significant effect on the calculation of the isosteric heat of
bed setup. The amount of CO2 adsorption was calculated from the blank
adsorption. This is because the isosteric heat of adsorption mainly re­
area between the black line of empty bed and the color lines of CO2
flects the relationship between the adsorption pressure and the deriva­
adsorption at different temperatures. The breakthrough time of KOH-AC
tive of adsorption temperature under a certain adsorption amount. The
was extended from 18 s at 40 ℃ to 22 s at 10 ℃ while that of DKOH-AC
Qst of KOH-AC was found to be in the range of 27.3 ~ 34.9 KJ/mol,
was prolonged from 22 s at 40 ℃ to 26 s at 20 ℃, indicating the lower
which was similar to that of activated carbons in other previous studies
temperature helps on CO2 adsorption. When it comes to adsorption rate,
[24, 25, 30, and 31]. In addition, the relatively low Qst values (<40 KJ/
DKOH-AC was slower than that of KOH-AC at the point of 40 s (red dots)
mol) show that the CO2 adsorption on KOH-AC was physical adsorption
in Fig. 11 (a) and (b). This indicates that DKOH-AC had longer break­
[46], as confirmed by the above-mentioned in-situ FTIR analysis. A
through time but higher adsorption capacity than KOH-AC. To further
higher Qst of 33.8 ~ 41.3 KJ/mol was obtained with DKOH-AC as
evaluate the reusability of DKOH-AC, the regenerability tests were car­
compared to KOH-AC, indicating a stronger interaction between the CO2
ried out at 30 ℃ after CO2 desorption at 150 ◦ C as shown in Fig. 11 (c).
molecule and DKOH-AC surface than that of KOH-AC. In particular, in
Almost the same CO2 adsorption performance was observed over four
the initial stage of adsorption, Qst exceeded 40 KJ/mol, which indicated
continuous cycles, indicating a good regenerability. The shaded area in
that the chemisorption occurred during the process of CO2 adsorption by
Figure S6 showed the actual CO2 adsorption capacity at 30 ℃, which is
DKOH-AC. This is consistent with the in-situ FTIR and XRD analysis
about 9.0 wt% (2.05 mmol/g). In addition, to more realistically simulate
above. The Qst reduced as the CO2 uptake increased, indicating that the
the indoor CO2 concentration adsorption, and to further study and
adsorption surface of KOH-AC and DKOH-AC was heterogeneous [47].
confirm the effect of moisture on the adsorption performance, the fixed
This is in agreement with the fact that a perfect fit (R2 = 1.0) of CO2
bed adsorption tests of 2000 ppmCO2 using DKOH-AC without/with
adsorption isotherm was provided by Freundlich model discussed above.
1.0% moisture have been carried out. The fixed bed adsorption results
The reusability of adsorbent is an important factor as it significantly
obtained are shown in Fig. 12. As discussed by CO2 adsorption isotherm

11
S. Wang et al. Chemical Engineering Journal 437 (2022) 135378

Fig. 15. Adsorption kinetics of pseudo first order model of (a) KOH-AC and (b) DKOH-AC, pseudo second order model of (c) KOH-AC and (d) DKOH-AC, and linear
driving force model of (e) KOH-AC and (f) DKOH-AC.

12
S. Wang et al. Chemical Engineering Journal 437 (2022) 135378

Table 5
Adsorption kinetic model parameters of CO2 adsorption on KOH-AC and DKOH-
AC.
Kinetic models Parameters KOH-AC DKOH-AC

Experimental data qe (mol/kg) 1.52 2.31

Pseudo-first order qe (mol/kg) 4.43 1.94
k1 (min− 1) 0.102 0.009
R2 0.8114 0.9856
SSE 56.98 15.53
RMSE 0.31 0.06
Pseudo-second order qe (mol/g) – 2.71
k2 (kg mol− 1 min− 1) 0.013 0.005
R2 0.7211 0.9903
SSE 36,761 75,675
RMSE 7.91 4.08
Linear driving force qe (mmol/g) 15754.3 2.24
k (min− 1) 2.13E-6 0.013
R2 0.9563 0.9885
SSE 7.89 18.41
RMSE 0.11 0.06
Intra-particle diffusion k1 (kg mol− 1 min− 1/2) 0.320 0.193
C1 − 0.803 − 0.337
R2 0.9089 0.9636
SSE 3.07 22.01
RMSE 0.10 0.11
k2 (kg mol− 1 min-1/2) 0.230 0.048
C2 − 0.061 1.320
R2 0.9452 0.9841
SSE 0.15 0.79
RMSE 0.03 0.02

higher CO2 uptake was obtained with DKOH-AC as compared to KOH-

AC at the same concentration and temperature. In addition, compared
with the adsorption of 2000 ppmCO2, the adsorption of 15%CO2 showed
higher adsorption capacity for KOH-AC and DKOH-AC. Furthermore,
CO2 adsorption on DKOH-AC still kept a strong increasing trend while
that on KOH-AC almost reached equilibrium as also found in the fixed
bed test above. That is, DKOH-AC requires a longer breakthrough time to
equilibrium as compared to KOH-AC. This can be explained by the fact
that KOH-impregnation results in the occurrence of chemisorption be­
Fig. 16. Intraparticle diffusion model of CO2 adsorption on (a) KOH-AC and (b) sides the physisorption of activated carbon, thereby increasing the
DKOH-AC. adsorption performance of DKOH-AC. This has been discussed in detail
earlier in Section 3.1. The TGA adsorption capacity of DKOH-AC for 15%
above, the moisture indeed play a significant role in adsorption per­ CO2 in the temperature range of 10 ~ 40 ℃ is 1.68 ~ 2.68 mmol/g,
formance of DKOH-AC. A lower adsorption capacity of 0.19 ~ 0.23 wt% which is comparable or even higher than those obtained by TGA or fixed
was obtained using DKOH-AC without moisture, while much higher bed using different activated carbon, reported in other studies [51–56],
adsorption capacity of 8.4 ~ 8.5 wt% was archived using DKOH-AC with as shown in Table 4. The TGA adsorption capacity of DKOH-AC for 2000
1.0% H2O. The effect of moisture on CO2 adsorption performance of ppmCO2 in the temperature range of 20 ~ 40 ℃ is in the range of 0.51 ~
DKOH-AC is mainly achieved by controlling the chemical reactions: (i) 0.97 mmol/g, which is lower than other previous studies as shown in
2KOH + CO2 → K2CO3 + H2O, (ii) K2CO3 + CO2 + H2O → 2KHCO3 [34]. Table 2. However, the fixed bed adsorption capacity of DKOH-AC for
For CO2 adsorption on DKOH-AC without H2O, although the presence of 2000 ppmCO2 with 1.0%H2O in the temperature of 30 ~ 40 ℃ is about
KOH in DKOH-AC initiated the first-step chemical reaction (i: 2KOH + 1.91 ~ 1.93 mmol/g, which is comparable or even higher than other
CO2 → K2CO3 + H2O), the absence of moisture inhibited the occurrence previous studies.
of the second step chemical reaction (ii: K2CO3 + CO2 + H2O →
2KHCO3), thereby greatly limiting the adsorption performance. This is 3.4. Adsorption kinetics
mainly because the process of the second-step chemical reaction re­
quires water, and the existence of related reaction products (KHCO3 and The adsorption kinetics of CO2 on KOH-AC and DKOH-AC as a
K4H2(CO3)3⋅(1.5 H2O)) can also be confirmed by XRD analysis as shown function of adsorption time are presented in Figure S7. A faster rate of
in Fig. 6. Furthermore, excellent regeneration and reusability of DKOH- adsorption was obtained with KOH-AC (approximately 50 min to reach
AC was obtained with cyclic stability test of 2000 ppmCO2 on DKOH-AC equilibrium) as compared to DKOH-AC (continue to maintain slow
using fixed bed apparatus, shown in Fig. 13. adsorption). This is consistent with the nature of physical adsorption and
chemical adsorption, that is, the time required for physical adsorption to
3.3. TGA adsorption tests reach equilibrium is shorter while that for chemical adsorption is rela­
tively longer [57]. For the adsorption kinetics properties, the TGA
Fig. 14 shows TGA CO2 (15% and 2000 ppm) adsorption results with adsorption data were fitted into four adsorption kinetics models of
KOH-AC and DKOH-AC at different temperatures (10 – 40 ◦ C). The pseudo first order (Eq. (S4)), pseudo second order (Eq. (S5)), linear
adsorption capacity of KOH-AC and DKOH-AC increased as the driving force model (Eq. (S6))and intraparticle diffusion model (Eq.
adsorption temperature decreased. This is in agreement with the find­ (S7)), as shown in Figs. 15 and 16. Some important constants of three
ings obtained in the above-mentioned fixed bed adsorption test. A models (pseudo first order, pseudo second order and intraparticle

13
S. Wang et al. Chemical Engineering Journal 437 (2022) 135378

(a) (b)

2500
Adsorption Condition:
(c)
25%KOH
CO₂, Concentration( ppm )

Temp. 30.3~30.9; Hum. 45~52.3%

2000 50%KOH
75%KOH
1500

1000

500

0
0 100 200 300 400 500
Time( min )
Fig. 17. Chamber adsorption results of DKOH-AC with an initial concentration of (a) 2000 ppmCO2 and (b) 500 ppmCO2 at room temperatures; (c) effect of KOH
content on the adsorption performance.

for CO2 adsorption on DKOH-AC. Furthermore, the qe obtained from the

Table 6 pseudo second order model (2.71 mol/kg for 15%CO2) was close to that
Comparison of CO2 adsorption capacity of KOH-AC and DKOH-AC for the initial
obtained from the actual experiment (2.31 mol/kg for 15%CO2).
concentration of 2000 ppm and 500 ppm in an enclosed chamber under room
Therefore, the pseudo second order model was the best-fitted kinetic
temperatures.
model for the CO2 adsorption on DKOH-AC. According to Wang et al.
2000 ppmCO2 (mmol/gsample) 500 ppmCO2 (mmol/gsample)
[58], if the adsorption process follows the pseudo-first order model, the
KOH-AC 0 0 adsorption process is mainly controlled by physical adsorption. The
(50%) DKOH-AC 2.09 2.18 chemisorption involves the adsorption process when the pseudo second
25%DKOH-AC 0.64
order model provides a higher R2. This indicates that DKOH-AC (KOH-
–
75%DKOH-AC 1.19 –
impregnation on KOH-AC) allows both the physical and chemical CO2
adsorption mechanisms. The intraparticle diffusion model was also
diffusion model) can be obtained from the slope and intercept of the considered to study the adsorption mechanism by exploring the rate-
plots as summarized in Table 5. For the linear driving force model, some limiting step. Generally, the adsorption mechanism consists of three
important parameters can be obtained by nonlinear fitting and these major adsorption stages [58]. i) External film diffusion: transfer of CO2
values are also listed in Table 5.The pseudo second order model pro­ molecules from the bulk solution to the exterior surface of the adsorbent,
vided the lowest R2 for CO2 adsorption on KOH-AC (R2: 0.721 for 15% in which the rate of adsorption is very rapid due to the sufficient active
CO2), indicating that the CO2 adsorption on KOH-AC does not follow the sites available on the exterior surface of adsorbent as shown in I stage in
pseudo second order model. Although linear driving force model pro­ Fig. 16. ii) Intraparticle diffusion: transfer of CO2 molecules from the
vided high R2 (0.9563) for CO2 adsorption on KOH-AC, the values of qe exterior surface to the internal surface of the adsorbent. The adsorption
and k obviously cannot explain the adsorption process. In addition, a process is slow because most of the adsorption active sites are occupied
relatively higher R2 (0.8114) was obtained from the pseudo first order by CO2 molecules adsorbed in the fast external film diffusion state as
model, showing that CO2 adsorption on KOH-AC follows the pseudo first shown in II stage in Fig. 16. iii) Adsorption: adsorption of CO2 molecules
order model. Higher R2 was observed with CO2 adsorption on DKOH-AC onto the interior pores of adsorbent until the final equilibrium stage is
as compared to that with KOH-AC. In particular, among these kinetic reached (not shown in Fig. 16). In addition, when the plot of qt vs t1/2 is
models, the pseudo second order model yielded the highest R2 (0.9903) a straight linear line that passes the origin, the intraparticle diffusion is

14
S. Wang et al. Chemical Engineering Journal 437 (2022) 135378

the rate-limiting step according to Wang et al. [23]. However, Fig. 16 Declaration of Competing Interest
shows the straight linear line does not pass the origin of the plot. Rather,
multiple trend lines were observed, indicating that the rate-limiting step The authors declare that they have no known competing financial
is affected by both the intraparticle diffusion and the film diffusion interests or personal relationships that could have appeared to influence
adsorption process. From this, CO2 adsorption on KOH-AC and DKOH- the work reported in this paper.
AC was initially controlled by external film diffusion (rapid I stage),
followed by the intraparticle diffusion (gradual II stage) and finally Acknowledgement
reached equilibrium.
This work was conducted under the framework of the research and
3.5. CO2 chamber adsorption test development program of the Korea Institute of Energy Research (C2-
2440-01) and (C2-2438).
To better understand and simulate the adsorption capacity of KOH-
AC and DKOH-AC at the indoor CO2 concentration level, the enclosed
Appendix A. Supplementary data
chamber adsorption test of initial 2000 ppmCO2 (high indoor CO2
concentration) and 500 ppmCO2 (low indoor CO2 concentration) were
Supplementary data to this article can be found online at https://doi.
carried out under indoor conditions (Temperature: 25.0 ~ 34.0 ℃,
org/10.1016/j.cej.2022.135378.
relative humidity: 40.0 ~ 52.0% and absolute humidity: 1.5 ~ 2.5%).
Fig. 17 shows the chamber adsorption results and their CO2 adsorption
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