Adsorption (2016) 22:581–588
DOI 10.1007/s10450-015-9734-0
Equilibrium isotherms and isosteric heat for CO2 adsorption
on nanoporous carbons from polymers
Jerzy Choma1 • Kamila Stachurska1 • Michal Marszewski2 • Mietek Jaroniec2
Received: 27 September 2015 / Revised: 24 November 2015 / Accepted: 26 November 2015 / Published online: 8 December 2015
Ó Springer Science+Business Media New York 2015
Abstract Four nanoporous carbons obtained from dif-
ferent polymers: polypyrrole, polyvinylidene fluoride, sul-
fonated styrene–divinylbenzene resin, and phenol–
formaldehyde resin, were investigated as potential adsor-
bents for carbon dioxide. CO2 adsorption isotherms mea-
sured at eight temperatures between 0 and 60 °C were used
to study adsorption properties of these polymer-derived
carbons, especially CO2 uptakes at ambient pressure and
different temperatures, working capacity, and isosteric heat
of adsorption. The specific surface areas and the volumes
of micropores and ultramicropores estimated for these
materials by using the density functional theory-based
software for pore size analysis ranged from 840 to
1990 m2 g-1, from 0.22 to 1.47 cm3 g-1, and from 0.18 to
0.64 cm3 g-1, respectively. The observed differences in
the nanoporosity of these carbons had a pronounced effect
on the CO2 adsorption properties. The highest CO2
uptakes, 6.92 mmol g-1 (0 °C, 1 atm) and 1.89 mmol g-1
(60 °C, 1 atm), were obtained for the polypyrrole-derived
activated carbon prepared through a single carbonization-
KOH activation step. The working capacity for this
adsorbent was estimated to be 3.70 mmol g-1. Depending
on the adsorbent, the CO2 isosteric heats of adsorption
varied from 32.9 to 16.3 kJ mol-1 in 0–2.5 mmol g-1
range. Overall, the carbons studied showed well-developed
microporosity and exceptional CO2 adsorption, which
& Mietek Jaroniec
jaroniec@kent.edu
1
Institute of Chemistry, Military Technical Academy,
00-908 Warsaw, Poland
2
Department of Chemistry and Biochemistry, Kent State
University, Kent, OH 44242, USA
make them viable candidates for CO2 capture, and for other
adsorption and environmental-related applications.
Keywords Nanoporous carbons  Polymer-derived
carbons  CO2 adsorption  Isosteric heat of adsorption 
Microporosity
1 Introduction
The newest report of ‘‘The International Panel on Climate
Change’’ clearly indicates the ongoing and deepening cli-
mate change (IPCC, Climate Change 2013). The report
states the anthropogenic greenhouse gas emissions con-
tribute mostly to the climate change, and the resulting
changes already have a negative impact on human health,
agriculture, water resources, and ecosystems on land and
ocean. The main source of greenhouse gases—primarily
CO2, water vapor, CH4 and N2O (Piacentini and Mujumdar
2009)—is burning of fossil fuels, in industrial processes or
otherwise. The IPCC stressed the importance of reduction
of greenhouse gas emissions, particularly the anthro-
pogenic CO2 emissions, and proposed carbon capture and
storage (CCS) as a viable solution. Adsorption on nano-
porous solids is one of the possible implementations of
CCS.
So far various materials for CO2 adsorption and CCS
were explored such as nanoporous carbons (Ludwinowicz
and Jaroniec 2015a; Seredych et al. 2014), modified porous
silica (Heydari-Gorji et al. 2011) and organosilica (De
Canck et al. 2013), zeolites (Su and Lu 2012), porous
polymers (Patel et al. 2012), and organometallic networks
(Liu et al. 2012). Among these materials, activated carbons
commonly have high surface areas, large pore volumes,
and proper pore sizes; all beneficial for CO2 adsorption. In
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582
addition, carbons can be prepared in variety of morpholo-
gies, tailorable surface chemistry, and high chemical (wa-
ter, acids and bases) and thermal stability (Liu et al. 2015).
Activated carbons are commonly prepared from natural
precursors, such as coal, lignite, peat, wood, fruit pits, coal
tar, and various biomasses (Jankowska et al. 1991; Marsh
and Rodriguez-Reinoso 2006).
Alternatively, synthetic wastes can be used as carbon
precursors as well. For instance, polymers or polymeric
wastes used as carbon precursors include: polyethylene (PE),
polypropylene (PP), polystyrene (PS), poly(vinyl chloride)
(PVC), poly(ethylene terephtalate) (PET), poly(methyl
metacrylate) (PMMA), polyacrylonitrile (PAN), and more
(Mishra et al. 2003; Arienillas et al. 2005; Migahead et al.
2010; Gupta et al. 2014; Choma et al. 2014a). These, and
other polymers, are used every day for production of com-
mon objects, e.g., building components, household appli-
ances, textiles, CDs and DVDs, and computer equipment.
Carbons prepared by carbonization of polymers typically
require subsequent activation to develop their surface area
and porosity to be viable adsorbents. Activation is typically
classified as either physical or chemical, with the first
including activation with CO2 or water vapor (Górka and
Jaroniec 2011), and the second, activation with KOH (de
Souza et al. 2013) or ZnCl2 (Ludwinowicz and Jaroniec
2015b). Wickramaratne and Jaroniec (2013) found that the
CO2 activation of carbon spheres prepared by Stöber method
resulted in the development of microporosity and high CO2
uptake of 8.05 mmol g-1 (0 °C, 1 atm). Activated carbons
are effective CO2 adsorbents mainly due to the large amount
of ultramicropores (micropores with size \1 nm), which
were shown to enhance CO2 adsorption (Lee and Park 2013;
Liu et al. 2015).
In this article, we examine four carbon adsorbents pre-
pared by carbonizing and activating different polymers,
study their structure and CO2 adsorption properties at dif-
ferent temperatures ranging from 0 to 60 °C. This study
aims to explore the opportunities in the development of
microporosity in the polymer-derived carbons for enhanc-
ing CO2 uptake at ambient conditions.
2 Experimental
2.1 Materials
2.1.1 Activated carbon from polypyrrole (AC-PPy)
One of the samples studied, namely polypyrrole-derived
activated carbon (AC-PPy), was reported by Choma et al.
(2015). This carbon (AC-PPy) was obtained by a single-
step carbonization-KOH activation of a self-made poly-
pyrrole (PPy). First, polypyrrole was prepared by
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Adsorption (2016) 22:581–588
polymerization of pyrrole (3.8 g) in the presence of FeCl3
(200 mL of 0.5 M FeCl3 aqueous solution) under stirring
for 2 h at room temperature; afterwards, the product was
filtered, washed with distilled water, and dried at 80 °C for
12 h. The resulting polymer was mixed with KOH (1:4
C:KOH weight ratio) and heated at 700 °C for 2 h using
3 °C min-1 temperature ramp in nitrogen flow
(40 dm3 h-1). The resulting activated carbon was washed
with a 1 M HCl aqueous solution and distilled water, and
dried at 110 °C for 12 h.
2.1.2 Activated carbon from polyvinylidene fluoride (AC-
PVDF)
Another activated carbon studied, AC-PVDF, was reported
by Choma et al. (2015). In this case, polyvinylidene fluo-
ride granules were carbonized at 450 °C for 30 min in
flowing nitrogen (heating rate = 5 °C min-1 and nitrogen
flow = 100 dm3 h-1). Then, the resulting carbon was
mixed with KOH (1:5 C:KOH weight ratio) and activated
at 700 °C for 1 h using the same heating rate and nitrogen
flow as in the case of carbonization. Finally, the activated
carbon was washed with a 35 wt% HCl aqueous solution
and distilled water, and dried at 100 °C for 24 h.
2.1.3 Activated carbon from sulfonated styrene–
divinylbenzene resin (AC-SDVB)
The third activated carbon studied, AC-SVDB, was pre-
pared according to the recipe of Choma et al. (2014b) using
a commercially available sulfonated styrene–divinylben-
zene resin Amberjet 1200H (Rohm and Haas, Philadelphia,
USA). The resin beads (d & 5 mm; 120 g) were dried at
100 °C for 3 h, immersed in 300 cm3 of 50 wt%
orthophosphoric acid, and evaporated in a rotary evapora-
tor at 180 °C. Next, the cooled down sample was car-
bonized at 350 °C for 90 min under static conditions (i.e.,
no gas flow), followed by activation with KOH (1:4
C:KOH weight ratio) at 700 °C, washing and drying as
reported by Choma et al. (2014b).
2.1.4 Ordered mesoporous carbon from phenol–
formaldehyde resin (OMC-PF)
OMC-PF ordered mesoporous carbon was prepared by
soft-templating procedure reported by Choma et al. (2012).
The XRD patterns and TEM images for phenolic resin-
based OMCs, confirming their mesostructural ordering, are
already available in literature (de Souza et al. 2013; Wang
et al. 2008). The synthesis was carried out under acidic
(HCl) conditions using resorcinol and formaldehyde as the
carbon precursors, and Pluronic F127 triblock copolymer
(polyethylene oxide-polypropylene oxide-polyethylene
Adsorption (2016) 22:581–588
oxide) as the structure-directing agent. First, 2.5 g of
resorcinol and 2.5 g of Pluronic F127 block copolymer
were dissolved in a mixture of 11.9 mL of ethanol and
6.6 mL of distilled water. After complete dissolution,
2.2 mL of HCl (35–38 wt% aqueous solution) was added
and the mixture was stirred for 30 min. Then, 2.5 mL of
formaldehyde (37 wt% aqueous solution) was added and
the stirring was continued until the solution separated into
two layers. The bottom organic layer was collected,
transferred to a Petri dish, and dried at 100 °C for 24 h.
The resulting organic–organic composite was carbonized
in nitrogen flow (20 dm3 h-1) using the following tem-
perature program: first, temperature was ramped to 180 °C
using 2 °C min-1 and dwelled for 5 h, then, temperature
was ramped to 400 °C using 2 °C min-1, and immediately
(no dwell), temperature was ramped to 850 °C using
5 °C min-1 and dwelled for 2 h. The procedure yielded
&1 g of the carbon product.
2.2 Measurements
Nitrogen adsorption–desorption isotherms at -196 °C and
carbon dioxide adsorption isotherms at 0, 10, 20, 25, 30,
40, 50, and 60 °C were measured on an ASAP 2020 surface
area and porosity analyzer manufactured by Micromeritics
Instrument Corp., Norcross, GA, USA. Each sample was
degassed at 200 °C for 2 h in vacuum before every
measurement.
2.3 Calculations
The apparent specific surface area (SBET) was determined
based on the low-temperature nitrogen adsorption by the
Brunauer–Emmett–Teller method (Brunauer et al. 1938) in
the relative pressure range 0.05–0.20 using the nitrogen
cross-section area of 0.162 nm2. Total pore volume (Vt)
was calculated by converting the volume of nitrogen
adsorbed at the relative pressure &0.99 to the volume of
liquid nitrogen at the experiment’s conditions. Pore size
distributions (PSD) and specific surface areas (SDFT) were
calculated based on the low-temperature nitrogen adsorp-
tion using the non-local density functional theory method
(NLDFT) for carbon slit-shaped pores with energetic
heterogeneity and geometrical corrugation developed by
Jagiello and Olivier (2013a, b) and implemented in
SAIEUS software by Jagiello. Volumes of micropores and
small mesopores (V2) were calculated by integration of the
PSD curves under the first and second peak in the range
from zero to the endpoint of the second peak. Volumes of
small micropores (V1) were calculated by integration of the
PSD curves under the first peak in the range from zero to
the PSD minimum after the first peak. The sizes of small
(w1) and large (w2) micropores were estimated at the
583
maxima of the first and second PSD peaks, respectively.
Microporosity was calculated as the ratio of V2 to Vt and
expressed in %. Isosteric heats of CO2 adsorption (qst) were
calculated based on the CO2 adsorption isotherms at 0, 10,
20, 25, 30, 40, 50, and 60 °C using the Clausius–Clapeyron
equation:
 
o ln p
qst ¼ RT2
oT a
where R is the universal gas constant, T is the adsorption
temperature, p is the equilibrium pressure, and a is the
amount adsorbed (Myers 2002).
3 Results and discussion
The CO2 adsorption properties of four selected carbon
adsorbents derived from different polymers were investi-
gated to explore the opportunities in the development of
microporosity in the polymer-derived carbons for achiev-
ing high CO2 uptakes at ambient pressure and different
temperatures between 0 and 60 °C. A series of eight CO2
adsorption isotherms was measured for each of the four
carbon studied. The corresponding nitrogen adsorption
isotherms and PSDs are presented in Fig. 1. The isotherm
obtained for AC-PPy shows type I(a) according to the new
IUPAC classification (Thommes et al. 2015), indicating the
presence of small micropores. On the other hand, the iso-
therm recorded for AC-PVDF is type I(b), which also
indicates microporous structure, but one with broad pore
size distribution and possibly small mesopores. In contrast,
AC-SDVB and OMC-PF both have isotherms being a
combination of type I and IV (Kruk and Jaroniec 2001).
The PSD curves support these observations: AC-PPy has
exclusively pores \1 nm, AC-PVDF has a bimodal PSD
spanning from small micropores up to & 4 nm, and AC-
SDVB and OMC-PF have both micropores and mesopores
present, although of different sizes and quantities.
Table 1 lists the structural parameters calculated based
on nitrogen adsorption isotherms for all carbons studied.
These carbons feature very large specific surface areas,
SDFT, reaching 2000 m2 g-1 in all instances and the
apparent SBET surface areas from 1810 to 2920 m2 g-1,
except OMC-PF, which had a smaller surface area,
SDFT = 840 m2 g-1 and SBET = 660 m2 g-1. Similarly,
the total pore volumes are large for these carbons in the
range of 0.87–1.64 cm3 g-1, and slightly smaller for OMC-
PF, Vt = 0.65 cm3 g-1. All carbons possess ultramicrop-
ores (pores \ 1 nm, labeled as V1) ranging from 0.18 to
0.64 cm3 g-1 depending on the polymer used. The average
size of these pores (w1) varies from 0.6 to 0.9 nm, as
indicated by the position of the first PSD peak for each
carbon sample. The carbons possess larger micropores as
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584 Adsorption (2016) 22:581–588

Fig. 1 Nitrogen adsorption–desorption isotherms at -196 °C (left
panel) and the corresponding differential pore size distributions
calculated using 2D-NLDFT method (right panel; inset shows the
mesopore range of PSD for AC-SDVB) for all carbons studied. AC-
PPy, AC-PVDF, AC-SDVB and OMC-PF denote carbons prepared
from polypyrrole, polyvinylidene fluoride, sulfonated styrene–di-
vinylbenzene resin, and phenol–formaldehyde resin, respectively.
Nitrogen adsorption isotherms for AC-PVDF, AC-PPy and AC-
SDVB were reported by Choma et al. (2015)

Table 1 Structural parameters of the carbons studied

Sample SDFT (m2 g-1) SBET (m2 g-1) Vt (cm3 g-1) V2 (cm3 g-1) V1 (cm3 g-1) w1 (nm) w2 (nm) Microporosity (%)

AC-PPy 1990 1810 0.87 0.78 0.62 0.6 – 90

AC-PVDF 1980 2920 1.64 1.47 0.46 0.9 2.1 90
AC-SDVB 1960 2480 1.33 1.07 0.64 0.8 1.6 80
OMC-PF 840 660 0.65 0.22 0.18 0.6 1.2 34
SDFT—specific surface area calculated using 2D-NLDFT method for carbons with slit-shaped pores under assumptions of energetic heterogeneity
and geometrical corrugation of the surface implemented in SAIEUS software; SBET—apparent specific surface area calculated by the Brunauer–
Emmett–Teller method using low-temperature nitrogen adsorption data in the relative pressure range of 0.05–0.20 and nitrogen cross-section
area of 0.162 nm2; Vt—single-point pore volume calculated by conversion of the nitrogen adsorption at a relative pressure &0.99 to the volume
of liquid nitrogen at the experiment temperature; V2—volume of micropores and small mesopores calculated by integration of PSD under the
first and second peak in the range up to the endpoint of the second peak; V1—volume of small micropores (ultramicropores) calculated by
integration of PSD under the first peak in the range up to the PSD minimum after the first peak; w1—size of small micropores (ultramicropores)
estimated as the maximum of the first PSD peak; w2—size of large micropores estimated as the maximum of the second PSD peak; Microp-
orosity-ratio of V2 to Vt expressed in %. Notation of the samples as in Fig. 1. Parameters for AC-PVDF, AC-PPy and AC-SDVB are taken from
Choma et al. (2015)

well, some with broad PSDs extending up to small meso-
pores. The peaks’ maxima in this range (w2) vary from 1.2
to 2.1 nm. The volume of all micropores and small
mesopores (if present, labeled as V2) range from 0.22 to
1.47 cm3 g-1. In addition, OMC-PF and AC-SDVB also
possess some amounts of mesopores, as apparent form their
PSDs.
Extensive CO2 adsorption studies were performed for all
carbons studied. CO2 adsorption measurements were done
at multiple temperatures from 0 to 60 °C and the results
were used to calculate the temperature dependence of CO2
uptake, working capacity of each adsorbent, and isosteric
heat of CO2 adsorption. Figure 2 shows all CO2 adsorption
isotherms and Table 2 lists the CO2 uptakes for all mate-
rials at each temperature. The CO2 uptakes recorded at
0 °C and 1 atm are in the range of 3.5–6.9 mmol g-1, and
those at 60 °C are in the range of 1.0–1.9 mmol g-1. AC-
PPy consistently scored the highest uptake at each tem-
perature, while the order of the other sorbents changed
depending on the temperature. To start with, the uptakes at
0 °C follow the order: AC-PPy [ AC-SDVB [ AC-
PVDF [ OMC-PF, but at higher temperatures, OMC-PF
slowly moves from the fourth to the third place at 10 °C,
and then to the second position at 50 °C. The final uptake
order, at 60 °C, ends up being AC-PPy [ OMC-PF [ AC-
SDVB [ AC-PVDF. These interesting changes are

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Adsorption (2016) 22:581–588 585

A 8 B 5
0oC
o
0C
o
AC-PPy 10 C 4 AC-PVDF o
10 C

CO 2 adsorption (mmol g )
CO2 adsorption (mmol g )

-1
-1

20oC o
20 C
25 C o 3 o
25 C
4 30ooC 30 C
o
40 C
2 o
50oC 40 C
o
60oC 50 C
o
2 60 C
1

0 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Pressure (atm) Pressure (atm)
C 7 o
0C D 4 o
0C
o
6 10 C
AC-SDVB CO2 adsorption (mmol g ) 20 C
o
OMC-PF
-1
CO2 adsorption (mmol g )

3 o
-1

o
5 10 C 25 C
o
30 C
o
4 20 C 40oC
25oC 2
30oC 50oC
3 60oC
40oC

2 50oC
o 1
60 C
1

0 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Pressure (atm) Pressure (atm)

Fig. 2 CO2 adsorption isotherms measured at 0–60 °C for a AC-PPy, b AC-PVDF, c AC-SDVB, and d OMC-PF. Notation of the samples as in
Fig. 1

Table 2 CO2 uptakes in

Sample CO2 uptake (mmol g-1)
0–60 °C temperature range for
the carbons studied 0 °C 10 °C 20 °C 25 °C 30 °C 40 °C 50 °C 60 °C

AC-PPy 6.92 5.69 4.64 3.92 3.70 2.98 2.32 1.89

AC-PVDF 3.79 3.09 2.62 2.30 1.95 1.46 1.22 0.96
AC-SDVB 5.78 4.19 3.34 2.99 2.65 2.23 1.64 1.28
OMC-PF 3.46 3.19 2.84 2.59 2.32 1.92 1.65 1.38
CO2 uptake at the specified temperature and pressure of 1 atm; Notation of the samples as in Fig. 1

attributed to the presence of extremely small micropores in
the OMC-PF carbon that retain CO2 much stronger and
result in much slower decay of the CO2 adsorption with
temperature. This is supported by much higher isosteric
heat of CO2 adsorption for OMC-PF at low values of
adsorption as compared to the values obtained for other
carbons (see Fig. 4).
Figure 3 shows the CO2 uptakes at 0.0013 atm
(1 mmHg) and 1 atm (760 mmHg) as functions of tem-
perature for all carbons studied. The uptakes show almost

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586 Adsorption (2016) 22:581–588

10 To complement the CO2 adsorption studies, the isosteric

1 atm
heats of adsorption were calculated based on the CO2
adsorption and the Clausius–Clapeyron equation. Figure 4
1 shows the calculated heats of adsorption as functions of the
CO2 uptake (mmol g )
-1

0.1
0.01
0.0013 atm
0.001
0 10 20 30
Temperature (°C)
Fig. 3 CO2 uptakes at 0.0013 atm (hollow symbols) and 1 atm (full
symbols) as functions of temperature for all carbons studied. The
ordinate axis is in logarithmic scale. Notation of the samples as in
Fig. 1
perfect exponential dependence on temperature in the
0–60 °C interval (note the ordinate axis is in logarithmic
scale). For all straight lines in Fig. 3 the correlation coef-
ficient exceeds 0.99. The exponential dependence has been
previously reported by Ludwinowicz and Jaroniec (2015a)
and used to estimate the working capacity in a CO2 pres-
sure-swing adsorption process (PSA). Aaron and Tsouris
(2005) described PSA where adsorption occurs at 30 °C
and 2 atm and desorption is carried out at 60 °C and
0.0013 atm. Here, we calculate the working capacity based
on this information, but instead of adsorption at 2, 1 atm is
used (the working capacity at 2 atm would be even higher).
Table 3 lists the adsorption and desorption uptakes and the
final working capacity.
As the result of very small uptake under desorption
conditions, the working capacities are virtually equal to the
CO2 uptakes at the adsorption conditions. Consequently,
AC-PPy scored the highest working capacity of
3.70 mmol g-1. The other materials achieved values in the
range 1.95–2.65 mmol g-1, which are comparatively high
as well (Samanta et al. 2012).
AC-PPy
CO2 uptake for all carbons studied. The noticeable small
AC-PVDF
AC-SDVB
steps in the plots at higher values of the CO2 uptake are due
OMC-PF to the decreasing number of the CO2 isotherms used to
AC-PPy calculate qst. These steps represent a sudden decrease in the
AC-PVDF
AC-SDVB
accuracy not the actual changes. As expected, the heats of
OMC-PF adsorption decrease with the amount of adsorbed CO2, but
the values and their decline are quite different among the
carbons studied. For instance, the highest initial heat of
adsorption (32.9 kJ mol-1 at CO2 uptake of 0.1 mmol) is
observed for OMC-PF, followed by those for AC-PPy
40 50 60 70
(29.2 kJ mol-1), AC-SDVB (25.5 kJ mol-1), and AC-
PVDF (24.9 kJ mol-1). However, the fastest decreases in
qst, 35 and 29 %, in the range of 0–2.5 mmol are observed
for AC-PVDF and OMC-PR, respectively, while the cor-
responding decreases for AC-PPy and AC-SDVB are about
14 %.
4 Conclusions
Four carbon adsorbents prepared from different polymers:
polypyrrole (AC-PPy), polyvinylidene fluoride (AC-
PVDF), sulfonated styrene–divinylbenzene resin (AC-
SDVB), and phenol–formaldehyde resin (OMP-PF) were
examined as potential adsorbents for CO2 capture. CO2
adsorption isotherms measured at different temperatures
between 0 and 60 °C range were used to evaluate the
adsorption properties such as CO2 uptakes at different
temperatures, working capacity, and isosteric heat of
adsorption in relation to the polymer used as carbon
precursor.
All carbons studied showed the well developed porous
structures, either exclusively microporous (AC-PPy and
AC-PVDF) or micro-mesoporous (AC-SDVB and OMC-
PF). The highest CO2 uptake at 0 °C, 6.92 mmol g-1, was
obtained for AC-PPy followed by those for AC-SDVB,

Table 3 Adsorption and desorption uptakes, and the working capacity for a CO2 pressure-swing adsorption process calculated for all carbons
studied
Sample Adsorption uptake (mmol g-1) Desorption uptake (mmol g-1) Working capacity (mmol g-1)

AC-PPy 3.70 0.0018 3.70

AC-PVDF 1.95 0.0006 1.95
AC-SDVB 2.65 0.0008 2.65
OMC-PF 2.32 0.0029 2.32
Adsorption uptake denotes CO2 uptake at 30 °C and 1 atm; Desorption uptake denotes CO2 uptake at 60 °C and 0.0013 atm; the working
capacity was calculated as a difference between adsorption and desorption uptakes; Notation of the samples as in Fig. 1

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Adsorption (2016) 22:581–588 587

A B 26

Isosteric heat of adsorption CO2 (kJ mol )

30

-1
Isosteric heat of adsorption CO2 (kJ mol )
-1

24
29 AC-PPy AC-PVDF

28 22

27 20

26 18

25
16

0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5
-1 -1
CO 2 uptake (mmol g ) CO2 uptake (mmol g )
C D

Isosteric heat of adsorption CO2 (kJ mol )

26
-1
Isosteric heat of adsorption CO2 (kJ mol )
-1

32
25 AC-SDVB OMC-PF

24
28

23

22 24

21

0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5
-1
CO2 uptake (mmol g ) CO2 uptake (mmol g-1)

Fig. 4 Isosteric heat of CO2 adsorption for a AC-PPy, b AC-PVDF, c AC-SDVB, and d OMC-PF calculated from CO2 isotherms adsorption
measured at 0, 10, 20, 25, 30, 40, 50 and 60 °C

AC-PVDF, and OMC-PF. At higher temperatures, AC-PPy
consistently scored best CO2 uptakes among carbons
studied, while the order of the remaining samples changed
with temperature. The temperature dependence of CO2
uptake in 0–60 °C range followed an exponential trend, as
previously reported by Ludwinowicz and Jaroniec (2015a).
Based on these data, the working capacities for all adsor-
bents were calculated assuming a pressure-swing CO2
adsorption process with adsorption at 1 atm and 30 °C and
desorption at 0.0013 atm and 60 °C. The resulting values
range from 1.95 to 3.70 mmol g-1, with the best result for
AC-PPy. Overall, the carbons studied were highly micro-
porous, which resulted in high CO2 uptakes at ambient
conditions, making them viable candidates for carbon
capture and other adsorption and environmental-related
applications.
Acknowledgments J.C. acknowledges the National Science Centre
(Poland) for support of this research under grant 2013/09/B/ST5/
00076.
References
Aaron, D., Tsouris, C.: Separation of CO2 from flue gas: a review.
Sep. Sci. Technol. 40, 321–348 (2005)

123
588
Arienillas, A., Rubiera, F., Parra, J.B., Ania, C.O., Pils, J.J.: Surface
modification of low cost carbons for their application in the
environmental protection. Appl. Surf. Sci. 252, 619–624 (2005)
Brunauer, S., Emmett, P.H., Teller, E.: Adsorption of gases in
multimolecular layers. J. Am. Chem. Soc. 60, 309–319 (1938)
Choma, J., Kalinowska, A., Jedynak, K., Jaroniec, M.: Reproducibil-
ity of the synthesis and adsorption properties of ordered
mesoporous carbons obtained by the soft-templating method
(in Polish). Ochr. Srodowiska 34(3), 3–10 (2012)
Choma, J., Osuchowski, L., Jaroniec, M.: Properties and applications
of activated carbons obtained from polymeric materials: a review
(in Polish). Ochr. Srodowiska 36(2), 3–16 (2014a)
Choma, J., Osuchowski, L., Marszewski, M., Jaroniec, M.: Highly
microporous polymer-based carbons from CO2 and H2 adsorp-
tion. RSC Advances 4, 14795–14802 (2014b)
Choma, J., Stachurska, K., Osuchowski, L., Dziura, A., Jaroniec, M.:
Carbon dioxide adsorption on activated carbons obtained from
polymeric precursors (in Polish). Ochr. Srodowiska 37(4), 3–8
(2015)
De Canck, E., Ascoop, I., Sayari, A., Van Der Voort, P.: Periodic
mesoporous organosilicas functionalized with a wide variety of
amines for CO2 adsorption. Phys. Chem. Chem. Phys. 15,
9792–9799 (2013)
De Souza, L.K.C., Wickramaratne, N.P., Ello, A.S., Costa, M.J.F., da
Costa, C.E.F., Jaroniec, M.: Enhancement of CO2 adsorption on
phenolic resin-based mesoporous carbons by KOH activation.
Carbon 65, 334–340 (2013)
Górka, J., Jaroniec, M.: Hierarchically porous phenolic resin-based
carbons obtained by block copolymer-colloidal silica templating
and post-synthesis activation with carbon dioxide and water
vapor. Carbon 49, 154–160 (2011)
Gupta, V.K., Nayak, A., Agarwal, S., Tyagi, I.: Potential of activated
carbon from waste rubber tire for the adsorption of phenolics:
effect of pre-treatment conditions. J. Colloid Interface Sci. 417,
420–430 (2014)
Heydari-Gorji, A., Belmabkhout, Y., Sayari, A.: Polyethyleneimine-
impregneted mesoporous silica: effect of amine loading and
surface alkyl chains on CO2 adsorption. Langmuir 27,
12411–12416 (2011)
ICPP, Climate Change 2013: The Physical Science Basis. Contribu-
tion of Working Group I to the Fifth Assessment Report of the
Intergovernmental Panel of Climate Change, Cambridge Univer-
sity Press, Cambridge, United Kingdom and New York, 2013
Jagiello, J., Olivier, J.P.: 2D-NLDFT Adsorption models for carbon
slit-shaped pores with surface energetical heterogeneity and
geometrical corrugation. Carbon 55, 70–80 (2013a)
Jagiello, J., Olivier, J.P.: Carbon slit pore model incorporating surface
energetical heterogeneity and geometrical corrugation. Adsorp-
tion 19, 777–783 (2013b)
Jankowska, H., Swiatkowski, A., Choma, J.: Active Carbon. Ellis
Horwood Ltd., Chichester (1991)
Kruk, M., Jaroniec, M.: Gas adsorption characterization of ordered
organic–inorganic nanocomposite materials. Chem. Mater. 13,
3169–3183 (2001)
123
Adsorption (2016) 22:581–588
Lee, S., Park, S.: Determination of the optimal pore size for improved
CO2 adsorption in activated carbon fibers. J. Colloid Interface
Sci. 389, 230–235 (2013)
Liu, J., Thallapally, P.K., McGrail, B.P., Brown, D.R., Liu, J.:
Progress in adsorption-based CO2 capture by metal-organic
frameworks. Chem. Soc. Rev. 41, 2308–2322 (2012)
Liu, J., Wickramaratne, N.P., Qiao, S.Z., Jaroniec, M.: Molecular-
based design and emerging applications of nanoporous carbon
spheres. Nat. Mater. 14, 763–774 (2015)
Ludwinowicz, J., Jaroniec, M.: Potassium salt-assisted synthesis of
highly microporous carbon spheres for CO2 adsorption. Carbon
82, 297–303 (2015a)
Ludwinowicz, J., Jaroniec, M.: Effect of activating agents on the
development of microporosity in polymeric-based carbon for
CO2 adsorption. Carbon 94, 673–679 (2015b)
Marsh, H., Rodriguez-Reinoso, F.: Activated Carbon. Elsevier,
Amsterdam (2006)
Migahead, M.A., Abdul-Raheim, A.M., Atta, A.M., Brostow, W.:
Synthesis and evaluation of a new water soluble corrosion
inhibitor from recycled poly(ethylene terephthalate). Mater.
Chem. Phys. 121, 208–214 (2010)
Mishra, S., Goje, A.S., Zope, V.S.: Chemical recycling, kinetics, and
thermodynamics of poly(ethylene terephthalate) (PET) waste
powder by nitric acid hydrolysis. Polym. React. Eng. 11, 79–99
(2003)
Myers, A.L.: Thermodynamics of adsorption in porous materials.
AIChE J. 48, 145–160 (2002)
Patel, H.A., Karadas, F., Canlier, A., Park, J., Deniz, E., Jung, Y.,
Atilhan, M., Yavuz, C.T.: High capacity carbon dioxide
adsorption by inexpensive covalent organic polymers. J. Mater.
Chem. 22, 8431–8437 (2012)
Piacentini, R.D., Mujumdar, A.S.: Climate change and drying of
agricultural products. Drying Technol. 27, 629–635 (2009)
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. 51, 1438–1463 (2012)
Seredych, M., Jagiello, J., Bandosz, T.J.: Complexity of CO2
adsorption on nanoporous sulfur-doped carbons—is surface
chemistry an important factor? Carbon 74, 207–217 (2014)
Su, F., Lu, C.: CO2 capture from gas stream by zeolite 13x using a
dual-column temperature/vacuum swing adsorption. Energy
Environ. Sci. 5, 9021–9027 (2012)
Thommes, M., Kaneko, K., Neimark, A.V., Olivier, J.P., Rodriguez-
Reinoso, F., Rouquerol, J., Sing, K.S.W.: Physisorption of gases,
with special reference to the evaluation of surface area and pore
size distribution (IUPAC Technical Report). Pure Appl. Chem.
(2015). doi:10.1515/pac-2014-1117
Wang, X., Liang, C.D., Dai, S.: Facile synthesis of ordered
mesoporous carbons with high thermal stability by self-assembly
of resorcinol–formaldehyde and block copolymers under highly
acidic conditions. Langmiur 24, 7500–7505 (2008)
Wickramaratne, N.P., Jaroniec, M.: Activated carbon spheres for CO2
adsorption. ACS Appl. Mater. Interfaces 5, 1849–1855 (2013)