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PII: S0169-4332(17)32408-X
DOI: http://dx.doi.org/10.1016/j.apsusc.2017.08.075
Reference: APSUSC 36912
Please cite this article as: Eunji Jang, Seung Wan Choi, Seok-Min Hong,
Sangcheol Shin, Ki Bong Lee, Development of a cost-effective CO2
adsorbent from petroleum coke via KOH activation, Applied Surface
Sciencehttp://dx.doi.org/10.1016/j.apsusc.2017.08.075
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Development of a cost-effective CO2 adsorbent from
Eunji Jang†, Seung Wan Choi†, Seok-Min Hong, Sangcheol Shin, Ki Bong Lee*
*Corresponding author
Tel.: +82 2 3290 4851; FAX: +82 2 926 6102; E-mail: kibonglee@korea.ac.kr (K.B. Lee)
1
Graphical abstract
KOH
activation
Highlights
Abstract
The capture of CO2 via adsorption is considered an effective technology for decreasing global
warming issues; hence, adsorbents for CO2 capture have been actively developed. Taking into account
cost-effectiveness and environmental concerns, the development of CO2 adsorbents from waste
materials is attracting considerable attention. In this study, petroleum coke (PC), which is the carbon
residue remaining after heavy oil upgrading, was used to produce high-value-added porous carbon for
CO2 capture. Porous carbon materials were prepared by KOH activation using different weight ratios
of KOH/PC (1:1, 2:1, 3:1, and 4:1) and activation temperatures (600, 700, and 800 C). The specific
surface area and total pore volume of resulting porous carbon materials increased with KOH amount,
reaching up to 2433 m2/g and 1.11 cm3/g, respectively. The sample prepared under moderate conditions
with a KOH/PC weight ratio of 2:1 and activation temperature of 700 C exhibited the highest CO2
2
adsorption uptake of 3.68 mmol/g at 25 C and 1 bar. Interestingly, CO2 adsorption uptake was linearly
correlated with the volume of micropores less than 0.8 nm, indicating that narrow micropore volume is
crucial for CO2 adsorption. The prepared porous carbon materials also exhibited good selectivity for
CO2 over N2, rapid adsorption, facile regeneration, and stable adsorption–desorption cyclic performance,
Keywords: CO2 adsorption; porous carbon; petroleum coke; KOH activation; narrow micropore
3
1. Introduction
Global warming and the related climate change issues, attributed to the increase of greenhouse gas
(GHG) emissions, have attracted significant attention worldwide [1]. In particular, CO2 is a major GHG,
and its emissions from the combustion of fossil fuels as well as industrial processes account for 78% of
the total increase of GHG emissions [2]. According to the International Energy Agency (IEA), CO2
emissions have significantly increased since the industrial revolution. Currently, the concentration of
CO2 in the atmosphere is greater than 400 ppm, which is ~40% greater than that in the mid-1800s, with
an average growth of 2 ppm per year in the last ten years [3]. For reducing the CO2 emissions from the
energy sector, many studies have been conducted on the development of CO2 capture and storage (CCS)
technology. As the CO2 capture step accounts for two-thirds of the total cost of CCS [4,5], lots of studies
have been conducted to improve capture technologies. Currently, absorption using an aqueous amine
solution is commercially utilized for CO2 capture [6]; however, this approach is limited by several
disadvantages, such as the corrosion of process equipment and high consumption of energy. To
overcome these drawbacks, alternative technologies need to be developed. Membrane separation is one
of potential techniques for CO2 capture because of the advantages of high compactness and continuous
operation. However, the commercialization of membrane separation was hindered by low separation
efficiency at low feed concentration and low thermal stability in case of polymeric membrane and
vulnerability to cracking in case of inorganic or carbon membrane [7]. Recently, various studies have
been conducted to develop highly efficient membranes: e.g. thermally stable polymeric membrane
based on polybenzimidazole and mixed-ion conducting membrane for fast mass transport [8–10].
Adsorption using solid materials is promising as this approach exhibits advantages of low energy
requirement for regeneration, scale-up feasibility, and mild operating conditions. Among various
adsorbents, e.g., metal–organic frameworks [11,12], zeolites [13], activated carbon [14,15], and
mesoporous silica [16], activated carbon is attractive because of advantages, e.g., cost-effectiveness,
4
Activated carbon can be obtained from several carbon-containing precursors (e.g., bones, phenolic
resins, polyacrylonitrile, coals, and lignocellulosic materials) [17–20]. Several studies have investigated
the development of CO2 adsorbents from inexpensive waste materials, which are stockpiled. The
utilization of these waste materials can not only resolve increasing environmental concerns associated
with increasing amounts of landfilled waste but also produce cost-effective CO2 adsorbents with
enhanced competitiveness. Plaza et al. have prepared CO2 adsorbents from a cost-effective, relatively
abundant agricultural byproduct such as almond shells [21]. Porous carbon was synthesized by the
carbonization of almond shells, followed by CO2 activation, affording carbon with a CO2 capture
capacity of 2.7 mmol/g at 25 C and 1 bar; this value is comparable to that of commercial activated
carbons. Fan et al. have fabricated nitrogen-doped microporous carbon from chitosan using K2CO3 as
the activating agent, and their cost-effective and environmentally friendly adsorbent exhibited a capture
capacity of 3.86 mmol/g at 25 C and 1 bar [22]. Parchetti et al. have produced cost-effective
carbonaceous adsorbents from the empty fruit bunch of oil palm trees; it is otherwise used as mulch or
incinerated in mills, resulting in air pollution [23]. The activated carbon prepared by hydrothermal
carbonization coupled with chemical activation exhibited a CO2 adsorption capacity of 3.71 mmol/g at
25 C and 1 atm.
Petroleum coke (PC) is another type of waste residue remaining after heavy oil upgrading. For
meeting the increasing demands for light oil, heavy oil fractions must be converted into light and more
valuable products via various upgrading technologies [24]. During upgrading pyrolysis, heavy (residual)
oil fractions are thermally cracked to produce light products, which are present in the gas product stream,
and a solid carbon-rich byproduct (or PC) is left behind. As PC contains high carbon and low volatile
and ash contents [25], it can be a good carbon precursor for activated carbons. By adequate activation
processes, industrial waste PC can be transformed into cost-effective value-added products. Recently,
Yang et al. reported porous nitrogen-doped carbon developed by combining ammoxidation with KOH
activation, and it showed high CO2 adsorption uptake and CO2/N2 selectivity [26].
5
In this study, porous carbon was synthesized from waste PC via KOH activation for use as an
adsorbent for CO2. PC was obtained as a byproduct during the pyrolysis upgrading of vacuum residue
(VR) on a laboratory scale. By varying the KOH to PC weight ratio and activation temperature, samples
with various surface areas and pore volumes were prepared. Then, the prepared porous carbon samples
were tested for CO2 adsorption. From the experimental results, the relation between porosities and CO2
adsorption uptakes were investigated and the pore size crucial for CO2 uptake was determined.
Furthermore, CO2/N2 selectivity, adsorption kinetics, and cyclic stability measurements were conducted
2. Experiment
PC used herein was obtained from the pyrolysis of VR on a laboratory scale. First, 50 g of VR
produced from a commercial vacuum distillation process (SK Innovation, Republic of Korea) was
added into a semi-batch reactor. Then, the reactor was heated to 450 °C and maintained at that
temperature for 2 h for pyrolysis. During pyrolysis, N2 was flowed through the reactor to discharge
volatile products. PC was produced as a residual solid product, which remained in the reactor after the
experiment. According to the results obtained from elemental analysis (Flash EA 1112 series, CE
Instruments) shown in Table 1, carbon is mainly present in VR and PC, the content of which increases
after pyrolysis.
Several samples were prepared by mixing 2 g of PC with a solution containing different amounts of
KOH (KOH/PC weight ratios of 1:1, 2:1, 3:1, and 4:1) and stirring the resulting mixture at 60 C for 2
h. The mixture was then placed into an alumina boat and dried at 110 °C for 24 h. After drying, the
alumina boat was inserted into a horizontal quartz tube furnace and heated at a rate of 5 °C/min to an
activation temperature of 600, 700, and 800 °C under N2. Next, the furnace was maintained at the
6
activation temperature for 1 h, followed by cooling to room temperature. The resulting sample was
washed with a 10% HCl solution to remove the remaining potassium, followed by washing several
times with deionized water until the pH of the filtrate was neutral. Finally, the sample was dried at 110
C for 24 h. The obtained activated porous carbon was referred to as PC-x:y-z (where, x:y represents the
2.3. Characterization
Scanning electron microscopy (SEM, Hitachi S-4800) and high-resolution transmission electron
adsorption analyzer to analyze the textural properties of porous carbon samples. Before each
measurement, samples were degassed under vacuum at 150 C for 12 h. The specific surface area was
calculated by the Brunauer–Emmett–Teller (BET) analysis from the adsorption data in the relative
pressure range of 0.01–0.1. The total pore volume was obtained from the adsorbed amount at a relative
pressure of 0.99, and the micropore volume was determined using the Dubinin–Radushkevich (D–R)
equation. Non-localized density functional theory (NLDFT) was employed to evaluate the pore size
distribution from the N2 adsorption data assuming a slit-pore model. Using the same volumetric
adsorption analyzer, the CO2 adsorption isotherms were measured at three temperatures of 0, 25, and
50 C, respectively, up to 1 bar. Thermogravimetric analysis (TGA, Q50, TA instruments) was used for
investigating the thermal decomposition of PC mixed with KOH. TGA was also employed for kinetic
and cyclic stability measurements of the adsorption of CO2 on porous carbon. The chemical surface of
samples was analyzed using Fourier transform infrared spectroscopy (FT-IR, LabRam Aramis IR2,
7
Fig. 1 shows the SEM images of the morphologies of pristine PC and activated PC. Pristine PC
exhibited a relatively smooth surface, while irregularly shaped activated PC exhibited a rough surface,
indicative of a reaction occurring between KOH and carbon atoms during activation. Depending on
activation conditions, activated PC exhibited different morphologies. In particular, PC-2:1-700 and PC-
3:1-700 exhibited many cavities as compared with those observed for PC-1:1-700 (Fig. 1b–d). During
activation under harsh conditions with a KOH/PC weight ratio of 4, small pieces of broken PC particles
with sharp edges were observed (Fig. 1e). The similar morphology characteristics were detected in the
samples activated at different temperatures. PC-2:1-600 showed relatively smoother edges than those
of samples activated at higher temperature, and PC-2:1-800 had similar morphology to that of PC-4:1-
700 because of harsh activation condition (Fig. 1f and g). As can be observed in the HRTEM image of
PC-2:1-700 (Fig. 1h), randomly distributed micropores were observed in the amorphous carbon
structure.
Fig. 2 shows the N2 adsorption–desorption isotherms of porous carbon samples prepared with
different KOH/PC weight ratios and activation temperatures. All samples exhibited type I isotherms
according to the IUPAC classification [27]. The isotherms exhibited significant N2 uptake at low
relative pressures of P/P0 < 0.1 and a plateau for P/P0 > 0.1, implying that micropores are predominantly
present in porous carbon samples. The adsorption–desorption curves were identical without any
hysteresis loop. The samples activated at a low KOH/PC weight ratio exhibited an abrupt knee in the
adsorption isotherm curves, indicative of narrow microporosity, and the samples activated at high
KOH/PC weight ratio presented a wider knee, attributed to broader microporosity (Fig. 2a). At a fixed
KOH/PC weight ratio of 2:1, the knee in the adsorption isotherm curves became wider as the activation
temperature increased (Fig. 2b). Table 2 summarizes the textural properties of porous carbon samples
estimated from the N2 adsorption isotherms at 77 K. With increasing KOH/PC weight ratio, the specific
surface area and total pore volume of samples significantly increased from 915 m2/g and 0.38 cm3/g to
2433 m2/g and 1.11 cm3/g, respectively. Large amounts of KOH resulted in high carbon consumption
and created many micropores according to the following reaction: 6KOH + 2C 2K + 3H2 + 2K2CO3
8
[28]. These results indicate that the pore structure of porous carbon samples significantly depends on
the KOH/PC weight ratio during activation. Activation temperature is also an important factor to control
the textural properties of the samples. At a fixed KOH/PC weight ratio of 2:1, textural properties became
Fig. 3 shows the pore size distribution and cumulative pore volume as obtained from N2 adsorption
isotherms by NLDFT assuming a slit-pore model. With increasing KOH/PC weight ratio, the proportion
of large micropores increased (Fig. 3a). The samples activated under mild conditions (KOH/PC weight
ratios of 1:1, 2:1, and 3:1) were mainly composed of micropores centered at 0.6 and 0.8 nm. On the
other hand, the micropore size increased, and small mesopores were newly formed in PC-4:1-700. This
tendency was further confirmed from the curve of the cumulative pore volume (Fig. 3b). For the samples
activated with KOH/PC weight ratios of 1:1, 2:1, and 3:1, the cumulative pore volume increased with
increasing size of up to 1.5 nm and then reached a plateau. However, the cumulative pore volume
continuously increased in the microporous region for PC-4:1-700. At a fixed KOH/PC weight ratio of
2:1, micropores actively developed up to the activation temperature of 700 °C (PC-2:1-700) and larger
pores were detected at higher activation temperature than 700 °C (PC-2:1-800). For the cumulative pore
volume, PC-2:1-700 showed the highest value until the pore width of ~1.3 nm, however, PC-2:1-800
had the highest value at the pore width over ~1.3 nm (Fig. 3d). As activated PC comprises a large
volume of narrow micropores, it is expected to be an effective adsorbent for capturing CO2 [29, 30].
The thermal decomposition of PC mixed with KOH in the ratio of 2:1 was analyzed using TGA to
further understand the effect of activation temperature (Fig. 4). The weight decrease up to ~100 °C is
from the evaporation of moisture and the additional weight decrease until ~350 °C can be attributed to
pore development through the reaction with KOH. After that, no further weight decrease was detected
until ~600 °C. However, when temperature reached ~700 °C, the sample weight started to decrease due
to further development of pores resulting from the reaction with KOH. When the activation temperature
increased over 750 °C, a sharp decrease of sample weight was observed, relating to pore enlargement
9
and increasing surface area. Based on the thermal decomposition results, the optimum temperature for
The chemical surface of pristine PC and PC-derived porous carbons was investigated using FT-IR
(Fig. 5). Nitrogen, sulfur, hydrogen, and oxygen were detected as heteroatoms in the porous carbons
and various bonds of heteroatoms to carbon were observed. The absorption bands at the wavenumber
of 1562, 1750, and 2928 cm–1 are attributed to stretching vibrations of C=C, C=O, and C–H, respectively
[31–33]. Nitrogen and sulfur exist in the form of C=N, C–S, C–N, and S–H and their absorption bands
are observed at the wavenumber of 1640 (C=N), 855 (C–S), 1195 (C–S), and 2343 cm–1 (C–N or S–
H), respectively [31,33,34]. However, no distinct changes of FT-IR spectra were detected with changing
Also, the chemical surfaces were studied in detail by XPS (Fig. 6). In the S2p spectra (Fig. 6a), it can
be found that some of sulfur components originated from PC were oxidized after KOH activation.
Therefore, the PC-derived porous carbons have both neutral sulfur (163.6 and 164.7 eV) and oxidized
sulfur (168.0 eV), while PC contains only neutral sulfur [35]. Since sulfur has weak acidity, it is
anticipated that sulfur-doped carbon has low affinity to CO2. However, when sulfur exists in an oxidized
form (-SO or -SO2), the acidity of sulfur makes oxygen negatively charged. The negatively charged
oxygen has high affinity to CO2 [36,37]. In the N1s XPS spectra (Fig. 6b), a weak C–N peak centered
Fig. 7a and b show the CO2 adsorption isotherms at 25 C and up to 1 bar for samples activated with
different KOH/PC weight ratios and activation temperatures, respectively. Table 3 summarizes their
adsorption uptake values. At 25 C and 1 bar, PC-2:1-700 exhibited the highest CO2 uptake of 3.68
mmol/g, indicating that an optimal amount of KOH and activation temperature are required for the
activation of PC to attain the maximum CO2 uptake. Although specific surface area and total pore
volume continuously increased with increasing KOH/PC weight ratio and activation temperature, the
10
CO2 adsorption uptake reached the maximum at a KOH/PC weight ratio of 2 and activation temperature
of 700 C. This result indicates that CO2 uptake is not directly related to the specific surface area or
total pore volume (Fig. 7c). Pore size increased, as well as pores were generated, at high KOH/PC
weight ratios and activation temperature, resulting in the increase of surface area and total pore volume,
but a large pore size is not adequate for the pore filling mechanism for CO2 adsorption at 1 bar. Several
studies have reported that narrow micropores less than 0.8 nm or 1 nm mainly contribute to the CO 2
adsorption uptake [39–41]. To investigate the effect of the narrow micropore volume on CO2 adsorption,
Fig. 7d plots the relationship between the volumes of narrow micropores less than 0.8 nm and the
amount of CO2 adsorbed at 25 C and 1 bar. With increasing volume of micropores less than 0.8 nm,
the CO2 uptake increased, with a correlation coefficient (R2) of 0.96, indicating that narrow micropores
significantly affect the CO2 adsorption uptake at 25 C and 1 bar. This is because narrow micropores
exhibit strong adsorption potentials, which can increase the strength of interaction between CO 2
molecules and pore walls [42]. Hence, to achieve high CO2 adsorption uptake, it is imperative to
synthesize adsorbents containing narrow micropores (<0.8 nm) by adjusting activation conditions.
Interestingly, the CO2 uptake for PC-4:1-700 was greater than that observed for PC-1:1-700 at
pressures greater than 0.5 bar, but the CO2 uptake for PC-1:1-700 was greater than that observed for
PC-4:1-700 at low pressures of less than 0.5 bar. This result was attributed to the reduced amount of
very small pores around 0.6 nm in PC-4:1-700 as shown in Fig. 3a. Another reason can be the effect of
nitrogen, which is known to serve as a basic site for attracting acidic CO2 molecules. Although samples
were not intentionally doped with nitrogen, raw PC as obtained from pyrolysis still exhibited low
amounts of nitrogen (Table 1). The amount of nitrogen in the sample decreased after activation as
nitrogen was oxidized and removed by KOH. As PC-1:1-700 (0.63%) exhibited a relatively high
nitrogen content as compared with that observed for PC-4:1-700 (0.21%), PC-1:1-700 can adsorb more
CO2 at low pressures. The nitrogen content has been reported to be crucial for the CO 2 uptake at low
pressures [43,44].
11
Fig. 8 shows the effect of temperature on the CO2 adsorption uptake of PC-2:1-700 at 0, 25, and 50
C. Depending on the adsorption temperature, different CO2 uptake values were observed at the pressure
of 1 bar: 6.08 mmol/g at 0 °C and 2.14 mmol/g at 50 °C. Low CO2 uptake at high temperature indicates
To investigate the adsorption of CO2 on porous carbon, CO2 adsorption isotherms of PC-2:1-700 at
0, 25, and 50 C were fitted with the Langmuir isotherm model (Fig. 8). The widely accepted Langmuir
isotherm model is a simple adsorption model, which is suitable for providing a thermodynamic basis to
describe adsorption equilibria [45]. The Langmuir isotherm model is expressed as follows:
qmax K L P
qe = (1)
1 + KL P
Here, qe is the adsorbed amount at equilibrium, qmax is the maximum adsorption capacity, KL is the
Langmuir constant, and P is the pressure. Table 4 summarizes the parameters obtained from the
Langmuir model fitting and correlation coefficients (R2). The CO2 adsorption isotherm data were well
As post-combustion flue gases comprise 15% of CO2, with the remainder being mainly N2 [46,47],
it is imperative to selectively capture CO2 over N2 for practical applications. To compare CO2 and N2
uptakes on PC-2:1-700, N2 adsorption isotherm was measured under the same conditions as those
measured for CO2 (25 C and up to 1 bar). As shown in Fig. 9a, the adsorption uptake for N2 was only
0.48 mmol/g at 25 C and 1 bar, which was significantly less than that of CO2 at any pressure. For
calculating the selectivity of CO2 over N2 in flue gas, the ideal adsorbed solution theory (IAST) model
was applied to predict the binary gas mixture equilibria using single-component isotherms [48–51]. The
qCO2 / qN 2
SCO2 /N 2 = (2)
pCO2 / pN 2
Here, qCO2 and qN2 are the adsorbed amounts of CO2 and N2, respectively, obtained from the single-
component adsorption isotherm. pCO2 and pN2 are the partial pressures of CO2 (0.15 bar) and N2 (0.85
12
bar) in flue gas, respectively. At a total pressure of 1 bar and 25 C, the selectivity of PC-2:1-700 for
CO2 over N2 was 13.7, indicating that CO2 is preferentially separated effectively from N2 (Fig. 9b).
Fig. 10 shows the adsorption kinetics of CO2 on PC-2:1-700 at 30 C and 1 bar. Kinetic analysis was
conducted by TGA. First, the sample was pretreated under N2 at 150 C for 4 h to remove any pre-
existing guest molecules. After pretreatment, the temperature was decreased to 30 C, and N2 was
switched to CO2 for adsorption. For CO2 adsorption, the change in weight over time was recorded for
6 h. Rapid adsorption of CO2 was observed; in particular, the initial adsorption rate was 4.72 wt%/min.
Because of rapid kinetics, approximately 85% of CO2 adsorption equilibrium capacity was attained
within 30 min.
To determine the binding strength between CO2 and PC-2:1-700, the isosteric heat of adsorption (Qst)
was calculated from the CO2 adsorption isotherms at 0 and 25 C by applying the Clausius–Clapeyron
equation [52]. As can be observed from Fig. 11, Qst values were 25–30 kJ/mol, characteristic of typical
physisorption. During physisorption, adsorption and desorption are typically facile, and the adsorbent
is easily regenerated, attributed to weak adsorbent–adsorbate interactions and a low energy requirement
for desorption.
The adsorption–desorption cyclic stability of PC-2:1-700 was further investigated by TGA. PC-2:1-
700 was pretreated at 150 C for 60 min under N2 before the cyclic stability test. During adsorption, the
sample was exposed to CO2 at 30 C for 40 min. During desorption, the sample was purged with N2 at
the same temperature for 60 min to eliminate the adsorbed CO2 molecules. Fig. 12a shows the change
in the weight of PC-2:1-700 during consecutive adsorption and desorption cycles. Rapid kinetics was
observed during adsorption and desorption. The initial adsorption uptake was well maintained during 9
cycles, demonstrating that the adsorbent is easily regenerated by N2 and exhibits excellent adsorption–
desorption cyclic stability. The cyclic stability of PC-2:1-700 was also confirmed in a repeated
13
4. Conclusions
Porous carbon materials with high microporosity were successfully prepared by the activation of
petroleum coke (PC) using KOH as the activating agent. The porosity of PC-based porous carbon
samples was easily controlled by changing the KOH/PC weight ratio and activation temperature. With
increasing KOH/PC ratio and activation temperature, the surface area and total pore volume increased,
reaching up to 2433 m2/g and 1.11 cm3/g for PC-4:1-700, respectively. The maximum CO2 adsorption
uptake was 3.68 mmol/g at 25 C and 1 bar for PC-2:1-700, implying that during activation, an optimal
KOH amount and activation temperature is necessary to prepare the CO2 adsorbent. The adsorbed CO2
amount is not directly related to the surface area or total pore volume, but it is significantly dependent
on the volume of micropores less than 0.8 nm, suggesting that a narrow micropore volume is crucial for
CO2 adsorption. Besides high CO2 uptake, PC-2:1-700 exhibited high selectivity of CO2 over N2, rapid
Acknowledgments
This study was supported by grants from the Basic Science Research Program [grant number
2015R1A1A1A05001363] and the Super Ultra Low Energy and Emission Vehicle Engineering
funded by the Korean Government (Ministry of Science, ICT and Future Planning).
14
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19
Table 1
Elemental analysis of vacuum residue (VR), petroleum coke (PC), and PC-derived porous carbon
samples.
20
Table 2
21
Table 3
CO2 adsorption uptake of the PC-derived porous carbon samples at different temperatures and at 1 bar.
22
Table 4
Parameters from the Langmuir model fitting for the adsorption of CO2 on PC-2:1-700.
H (= qmax b,
Temperature (C) qmax (mmol/g) b (1/bar) R2
mmol/g∙bar)
23
Figure captions
Fig. 1. SEM images of (a) pristine PC, (b) PC-1:1-700, (c) PC-2:1-700, (d) PC-3:1-700, (e) PC-4:1-700, (f)
Fig. 2. N2 adsorption (solid symbols) and desorption (open symbols) isotherms at 77 K for PC-derived
porous carbon samples (a) with different KOH/PC ratios and (b) with different activation temperatures.
Fig. 3. (a) Pore size distribution and (b) cumulative pore volume of PC-derived porous carbon samples with
different KOH ratios. (c) Pore size distribution and (d) cumulative pore volume of PC-derived porous
Fig. 4. Thermal decomposition of PC mixed with KOH (the ratio of KOH and PC was 2:1).
Fig. 6. XPS spectra of pristine PC and PC-derived porous carbon samples: (a) S2p and (b) N1s.
Fig. 7. CO2 adsorption isotherms at 25 C for PC-derived porous carbon samples (a) with different KOH
ratios and (b) with different activation temperatures. Relationship between CO2 uptake at 25 C and 1 bar
and textural properties: (c) BET specific surface area and (d) volume of micropores less than 0.8 nm.
Fig. 8. CO2 adsorption isotherms of PC-2:1-700 at 0, 25, and 50 C. Dots and solid lines represent
Fig. 9. (a) CO2 and N2 adsorption isotherms of PC-2:1-700 at 25 C. (b) The IAST selectivity of PC-2:1-
Fig. 11. Isosteric heat of adsorption for PC-2:1-700 calculated from CO2 adsorption isotherms.
Fig. 12. Cyclic stability test of PC-2:1-700 from (a) a gravimetric method at 30 C and (b) a volumetric
method at 25 C.
24
Fig. 1. SEM images of (a) pristine PC, (b) PC-1:1-700, (c) PC-2:1-700, (d) PC-3:1-700, (e) PC-4:1-700, (f)
25
Fig. 2. N2 adsorption (solid symbols) and desorption (open symbols) isotherms at 77 K for PC-derived
porous carbon samples (a) with different KOH/PC ratios and (b) with different activation temperatures.
26
Fig. 3. (a) Pore size distribution and (b) cumulative pore volume of PC-derived porous carbon samples with
different KOH ratios. (c) Pore size distribution and (d) cumulative pore volume of PC-derived porous
27
Fig. 4. Thermal decomposition of PC mixed with KOH (the ratio of KOH and PC was 2:1).
28
Fig. 5. FT-IR spectra of pristine PC and PC-derived porous carbon samples.
29
Fig. 6. XPS spectra of pristine PC and PC-derived porous carbon samples: (a) S2p and (b) N1s.
30
Fig. 7. CO2 adsorption isotherms at 25 C for PC-derived porous carbon samples (a) with different KOH
ratios and (b) with different activation temperatures. Relationship between CO2 uptake at 25 C and 1 bar
and textural properties: (c) BET specific surface area and (d) volume of micropores less than 0.8 nm.
31
Fig. 8. CO2 adsorption isotherms of PC-2:1-700 at 0, 25, and 50 C. Dots and solid lines represent
32
Fig. 9. (a) CO2 and N2 adsorption isotherms of PC-2:1-700 at 25 C. (b) The IAST selectivity of PC-2:1-
33
Fig. 10. CO2 adsorption kinetics of PC-2:1-700 at 30 C and 1 bar.
34
Fig. 11. Isosteric heat of adsorption for PC-2:1-700 calculated from CO2 adsorption isotherms.
35
Fig. 12. Cyclic stability test of PC-2:1-700 from (a) a gravimetric method at 30 C and (b) a volumetric
method at 25 C.
36