Article

pubs.acs.org/EF

CO2 Capture with Activated Carbon Grafted by Nitrogenous

Functional Groups
Changming Zhang,†,‡ Wen Song,§ Guohua Sun,† Lijing Xie,†,‡ Jianlong Wang,*,† Kaixi Li,*,†
Chenggong Sun,*,∥ Hao Liu,∥ Colin E. Snape,∥ and Trevor Drage∥
†
Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, P. R. China
‡
Graduate University of Chinese Academy of Sciences, Beijing 100049, P. R. China
§
ShanXi XinHua Chemical Co., Ltd., Taiyuan 030008, P. R. China
∥
Energy and Sustainability Research Division, Faculty of Engineering, University of Nottingham, University Park, Nottingham NG7
2RD, United Kingdom

ABSTRACT: Amino/nitro groups were introduced onto the surface of the activated carbon (AC) with nitration followed by
reduction in order to improve its adsorption capacity toward CO2. These AC samples were characterized by N2 adsorption/
desorption, FTIR, and X-ray photoelectron spectroscopy (XPS). CO2 adsorption properties of the samples were investigated
using a self-regulating high-pressure adsorption apparatus. Results showed that the contents of nitrogen on the treated samples’
surface increased from 0% to 1.38 after modification. The maximum CO2 adsorption capacity of the modified samples can reach
19.07 mmol/g at 298 K and 36.0 bar. The adsorbed amounts of CO2 on all samples decreased with an increase in the adsorption
temperature, but the extent of the decrease with the modified samples was less than that of the raw AC sample. CO2 adsorption
capacities of the modified sample for five cyclic adsorption−desorption runs were found to be nearly identical.

1. INTRODUCTION performance.20−24 Several methods can be used to introduce

Carbon dioxide (CO2) is widely accepted as the most
important greenhouse gas that causes global warming.1−4 To
date, how to capture CO2 effectively has become a world issue.
Absorption, adsorption, membrane separation, and cryogenic
distillation are examples of the available methods for capturing
CO2.5−7 Amine-based regenerative chemical absorption pro-
cesses using aqueous solutions of amine, such as monoethanol-
amine (MEA), diethanolamine (DEA), diglycol-amine (DGA),
N-methyldiethanolamine (MDEA), and 2-amino-2-methyl-1-
propanol (AMP) have been widely practiced for several years
for CO2 capture from gas streams in natural gas, refinery off-
gases, and synthesis gas processing. Although absorption by
means of amine solutions is the most mature CO2 capture
technology in commercial applications, it has serious draw-
backs, such as a high energy requirement and corrosion of
process equipment.8−12
Adsorption is proposed as one of the most promising options
for CO2 capture due to its potential of having a lower cost and
less corrosion than amine scrubbing. Among all solid
adsorbents, activated carbons (ACs) are well-known adsorbent
materials, so it is no surprise that they have been studied in
CO2 separation applications. These meso- or microporous
carbonaceous structures have an advantage over other
adsorbents, such as ease of regeneration, lesser sensitivity to
moisture, and high CO2 adsorption capacity at ambient
pressure.13−15 CO2 adsorption capacity of AC depends not
only on its textural characteristics but also on its surface
chemistry, which can be modified with different method-
ologies.16−19 CO2 is a weak acidic gas, so it has been recognized
that the introduction of basic nitrogen functionalities onto the
surface of activated carbon can enhance its CO2 capture
basic nitrogen functionalities onto the carbon surface. One of
the most common procedures is the reaction with nitrogen
containing reagents (such as NH3 and amines), while another
way is surface impregnation with amine-containing compounds.
In addition, amino groups can be grafted on the surface of AC,
using techniques such as nitration followed by reduction,
anchoring diamines/polyamines, and surface-oriented polymer-
ization of ethylene imine.25−30
Up to now, few have reported on the efficacy of nitration-
reduction treatment in enhancing the performance of AC in
CO2 capture. In the present work, a facile method of nitration/
reduction was investigated as a means to graft amino groups to
the surface of AC. The surface of AC is first tailored with nitro
groups via nitration reaction by sulfuric/nitric acid mixture
which is one of the basic organic reactions. The surface nitro
groups can then be efficiently transformed into amino groups
via a simple reduction reaction by acetic acid and iron powder.
The textural structures of the modified ACs were characterized
by the N2 adsorption isotherm at 77 K. The surface nitrogen-
containing groups and the contents of elements were analyzed
by Fourier transform infrared spectroscopy (FTIR) and X-ray
photoelectron spectroscopy analysis (XPS). The adsorption
capacity of the modified activated carbons as CO2 adsorbents
was investigated at different temperatures and pressures.
Furthermore, the potential regeneration of the sorbents and
their suitability for application in cyclic processes were also
evaluated.
Received: March 22, 2013
Revised: June 19, 2013
Published: June 28, 2013

© 2013 American Chemical Society 4818 dx.doi.org/10.1021/ef400499k | Energy Fuels 2013, 27, 4818−4823
Energy & Fuels
2. EXPERIMENTAL SECTION
2.1. Preparation of Activated Carbon. The AC was prepared
following the method of Sun et al.31 Petroleum coke, obtained from
Guangzhou (China), was crushed, sieved to the desired size (less than
200 μm), and dried at 378 K for 24 h. Then the petroleum coke was
subjected to chemical activation with potassium hydroxide (KOH), at
a coke/KOH mass ratio of 1:6 at 1103 K for 1 h in a vertical cylindrical
furnace under a nitrogen flow. Finally, the obtained product was
washed with deionized water, until the pH value of filtrate reached 7
before it was dried at 378 K for 24 h.
2.2. Modification of ACs with Amine Groups. The AC was
functionalized with amine groups via a two-step process which
involved the use of sulfuric/nitric acid mixture as the nitrating agent in
the first step and iron powder as the reducing agent in the second step.
To prepare the acid mixture, 60 mL of concentrated sulfuric acid
(H2SO4, 98 wt %) was mixed with 54 mL of concentrated nitric acid
(HNO3, 65 wt %) in a 500 mL glass beaker to give 114 mL of the acid
mixture at a H2SO4/HNO3 volume ratio of 10:9. Then 114 mL of
deionized water was slowly added into the concentrated acid mixture
to yield 228 mL of diluted acid solution, which was then allowed to
cool down to ambient temperature and used as the nitrating agent.
However, for comparison purposes, 228 mL of a concentrated H2SO4/
HNO3 acid mixture was also used directly as the nitrating agent.
Nitration modification of the selected carbon was performed at 323 K
in a three-necked round-bottom flask containing 2 g of the carbon
suspended in 80 mL of H2SO4/HNO3 with dropwise addition of the
acid mixture via a filling funnel in 60 min. The reaction system was
maintained at this temperature for 90 min under stirring conditions.
The modified carbon was filtered and extensively washed with
deionized water until the filtrate was neutral. Modified carbon thus
obtained was then dried at 373 K overnight. The samples obtained
from using concentrated and diluted acid mixtures are denoted as AC-
NO2 (1:1) and AC-NO2 (strong), respectively.
Amination of the nitrated carbons was carried out as follows. A total
of 250 mL of deionized water and 10 mL of acetic acid were mixed in a
three-necked round-bottom flask, followed by the addition of 5 g of
iron powder. The mixture was refluxed for 15 min with stirring to help
activate elemental iron into ferrous acetate. A total of 1 g of ACs-NO2
was added into the reaction system with continuous refluxing for an
additional hour before the system was allowed to cool down to room
temperature. The removal of the superfluous iron was achieved by the
use of a magnet and aqueous hydrochloric acid (0.01 N) solution for
30 min. Finally, the resultant mixtures were washed with deionized
water and dried at 333 K overnight under vacuum conditions. The
aminated AC samples are termed AC-NH2 (1:1) and AC-NH2
(strong).
2.3. Textural Properties of the Samples. The textural
parameters of the as prepared ACs were investigated by N2
adsorption/desorption at 77 K using an ASAP 2020 instrument. The
samples were separately degassed at 523 K in a vacuum environment
for 4 h prior to measurements. Experimental adsorption data at a
relative pressure (P/P0) less than 0.3 were used to calculate surface
area values using the standard Brunauer, Emmett, and Teller (BET)
equation. The pore size distribution (PSD) was determined by
applying the density functional theory (DFT) method based on the
nitrogen adsorption data.
2.4. Chemical Characterization of Samples. The obtained
samples were characterized in terms of their surface chemical
composition and functionalities due to the modifications. The X-ray
photoelectron spectrum (XPS) was measured on a PHI5300 X-ray
photoelectron spectrometer. A monochromatic Al Ka source (1486.6
eV) was used at a power of 210 W. The resolution of the instrument is
0.55 and 0.70 eV for Ag 3d and Au 4f peaks, respectively. Survey scans
were collected for binding energy ranging from 1100 eV to 0 with an
analyzer pass energy of 160 eV with a step of 0.6 eV for a dwell time of
150 ms. For the high-resolution spectra, the pass-energy was 20 eV
with a step of 0.1 eV and a dwell time of 200 ms.
FTIR spectra of the carbon samples were obtained utilizing a
Perkin-Elmer Spectrum 100 FTIR spectrometer. A disk made of pure
4819
Article
KBr was used as a reference sample for background measurements.
The carbon-KBr mixtures at a ratio of 1:300 were ground in an agate
mortar and then pressed under vacuum conditions in a hydraulic press.
Before the spectrum of a sample was recorded, the background line
obtained was arbitrarily and automatically subtracted. The spectra were
recorded from 4000 to 400 cm−1 at a scan rate of 0.2 cm s−1, and the
number of interferograms with a nominal resolution of 4 cm−1 was
fixed at 100. The spectra were recorded in the range of 400−4000
cm−1 at a resolution of 4 cm−1.
2.5. CO2 Adsorption Measurements. The CO2 adsorption
performance of the samples was assessed using a self-regulating high-
pressure adsorption apparatus as shown in Scheme 1, which was based
Scheme 1. Schematic Apparatus for CO2 Adsorption
Experiment
on a volumetric principle. The working principles of the rig and the
methodologies used to measure the volumes of reference cell,
adsorption cell, and pipeline were the same as previously described.32
The reference cell, which functions as a meter to measure the
quantities of gas adsorbed, was placed in a thermostat in order to
guarantee the constancy of temperature within 289.15 ± 0.05 K.
Pressure in the reference cell was detected by a pressure transducer
within a pressure range of 0−4 MPa (PAA-23/8465.1−100, Keller,
Switzerland). The adsorption cell, where the adsorption was
conducted for the loaded samples, was put in another thermostat
maintained at different temperatures. Inching valves V7 and V9 were
used to control the gas flow during the charging/discharging process,
so as to control the equilibrium adsorption pressure. For a typical
experiment, about 5 g of the sample was first dried at 383 K for 24 h
before it was subjected to adsorption measurement. High purity
helium (99.999%) was conduced to determine the void space of the
adsorption cell. Systematic measurements of the adsorption capacity of
high purity CO2 (99.999%) on the samples were conduced using the
apparatus. CO2 adsorption capacity was evaluated after the adsorption
equilibrium was reached. Then, the whole system was vacuumed, and
the adsorption cell was heated to 353 K and held at this temperature
for 1 h to regenerate the sample.
3. RESULTS AND DISCUSSION
3.1. Textural Properties. Table 1 presents the surface
textural properties of the AC samples. It appears that the BET
surface areas and total pore volumes of the AC-NO2 (1:1) and
AC-NH2 (1:1) became considerably lower at varying degrees
compared to those of the original AC, following an order of AC
> AC-NO2 (1:1) > AC-NH2 (1:1) > AC-NH2 (strong). The
largest change in surface area was observed for the AC-NH2
(strong) with its surface area reduced to only 507 m2 g−1 from
2994 m2 g−1 of the original carbon material used. This drastic
decrease may be due to the oxidative ability of the concentrated
HNO3/H2SO4 acid mixture used in nitration, which led to
excessive oxidation and hence the collapse of the pore
dx.doi.org/10.1021/ef400499k | Energy Fuels 2013, 27, 4818−4823
Energy & Fuels Article

Table 1. Porous Structure Parameters of the ACs

SBET (m2 Smicro (m2 Vpore (cm3 Vmicro (cm3 DP
sample g−1) g−1) g−1) g−1) (nm)
AC 2994 509 1.76 0.15 2.35
AC-NO2 2630 602 1.50 0.20 2.42
(1:1)
AC-NH2 2413 810 1.33 0.24 2.59
(1:1)
AC-NH2 507 329 0.30 0.18 3.28
(strong)

structures of the AC. Similar results have also been reported by

Tamai et al.33 Indeed, only slight decreases in surface area were
obtained for the AC-NO2 (1:1) and AC-NH2 (1:1) samples
where a diluted acid mixture was used as the nitrating agent.
Although the formation of nitrogen-bearing functional groups Figure 2. DFT pore size distribution for ACs.
may potentially lead to pore entrance blockage,34 the results
presented in Table 1 indicate that the average pore diameter of
the modified samples was increased, suggesting that pore
widening, as opposed to pore entrance blockage, may play a
more important role in determining the surface textural
properties of the modified carbons via the nitration/reduction
treatment.
The nitrogen adsorption−desorption isotherms are shown in
Figure 1 for the AC, AC-NO2 (1:1), AC-NH2 (1:1), and AC-

Figure 3. FTIR spectra for the original AC and the modified ACs.

NO2 (1:1) were reduced to amino groups (NH2) by iron

powder in aqueous acetic acid solution. For the aminated AC-
NH2 (1:1) sample, it can be seen that the vibrational peaks of
NO2 almost totally disappeared while new bands appeared at
3357 cm−1, 883 cm−1, and 752 cm−1, which correspond to the
C−N stretching mode and in-plane and out-of-plane
deformation modes of NH2 groups,37−39 respectively. These
results indicate that nitro groups can be efficiently converted to
Figure 1. N2 adsorption−desorption isotherms of ACs. amino groups by a simple reduction process.
In order to examine the surface functionalities induced by the
nitration/reduction treatment, XPS characterization was also
NH2 (strong) samples. It is evident that the amount of N2 conducted for the modified carbons. The XPS spectra (Figure
adsorbed on the ACs decreases with increasing concentration 4) show that besides the strong C(1s) and O(1s) peaks, the
of acid solutions, with the sample (AC-NH2 (strong)) prepared
from using concentrated acid mixture having the lowest
capacity for N2 adsorption. The shape of the adsorption
isotherms of these samples are overall similar and can be
considered as an intermediate to types I and IV, except AC-
NH2 (strong) where the amount of N2 adsorbed, after a sharp
rise at very relative pressures, remained relatively constant with
further increasing pressures. Figure 2 shows the DFT pore size
distributions for the ACs. It can be seen that the ACs have
mainly mesopores with some level of microposity.
3.2. FTIR and XPS Analysis. Figure 3 presents the FTIR
spectra of the AC samples, including both the original and
surface-modified carbons. The FTIR spectra demonstrate that,
compared to the original carbon, the surface-modified carbon
with the diluted HNO3/H2SO4 acid mixture at 323 K shows
new vibrational bands at 1562 cm−1 and 700 cm−1, which can
be assigned to the symmetric and asymmetric stretching of Figure 4. XPS spectra of (a) the AC, (b) AC-NH2 (1:1), and (c) AC-
nitro functional groups (NO2).35,36 The nitro groups on AC- NO2 (1:1).

4820 dx.doi.org/10.1021/ef400499k | Energy Fuels 2013, 27, 4818−4823

Energy & Fuels
ones corresponding to N(1s) were clearly evidenced with
considerable intensities for both the nitrated and aminated
carbon samples. In addition, an Fe (2p) peak was also detected
in the aminated carbon (AC-NH2 (1:1)), highlighting the
presence of the residual Fe arising from the reduction
treatment. Table 2 shows the surface elemental composition
Table 2. Surface Composition from XPS Spectra
atomic concentration (%)
samples C (%) O (%) N (%) Fe (%)
AC 94.15% 5.85% 0.00% 0.00%
AC-NO2 (1:1) 82.69% 16.11% 1.20% 0.00%
AC-NH2 (1:1) 80.98% 15.75% 1.38% 1.89%
for these samples, which was obtained from calculations based
on the peak areas of individual elements and their sensitivity
factors (0.25 for C, 0.66 for O, 0.42 for N, and 2.0 for Fe). It
was found that compared to the original carbon, the relative
surface C content decreased to 82.69% for the AC-NO2 (1:1)
and 80.98% for AC-NH2 (1:1) sample while the relative surface
nitrogen content increased from virtually none in the original
carbon to 1.20 atom % and 1.38 atom %, respectively. At the
same time, the surface oxygen content in the modified carbons
was also increased significantly, being indicative of the
formation of oxygen functionalities during the nitration process.
Although peak deconvolution must be viewed with caution, an
attempt to further elucidate the nitrogen functionality was
made by decomposing the envelope N(1s) peak into different
bands corresponding to different nitrogen functionalities. It is
evident from Figure 5(a,b) that a range of nitrogen
functionalities of varying significance were present in the
modified carbons, such as nitro-type N at 406.30 ± 0.2 eV,
pyrrolic and pyridonic N at 400.35 ± 0.3 eV, and pyridine type
N at 398.2 ± 0.1 eV. The very strong peak at 399.17 eV, which
was only detected in the AC-NH2 (1:1) sample, is typical of
amino-type nitrogen associated with a carbon matrix, such as
imine, amine, and amide.40−42 It should be noted that the much
lower peak intensities at 406.30 and 400.35 eV observed for the
aminated sample, AC-NH2 (1:1), suggest that the amino
nitrogen was mainly from the reduction of nitro groups
followed by pyrrolic and pyridonic N.
The characterization results reveal that the nitration/
reduction treatment can be an effective way to functionalize
activated carbon materials with desirable basic nitrogen
Figure 5. N 1s peak of (a) AC-NO2 (1:1) and (b) AC-NH2 (1:1).
4821
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functionalities which are crucial for efficient CO2 capture with
carbon-based adsorbent materials.
3.3. CO2 Capture Measurement. CO2 adsorption
behaviors for the AC and modified AC samples have been
studied, and the isotherms obtained at 298 K in the range of the
pressures from 0 to 36.0 bar are shown in Figure 6. It can be
Figure 6. CO2 capture capacities of the raw sample and modified
samples at 298 K.
seen that the CO2 capture capacity of the carbon samples
except AC-NH2 (strong) increased markedly with pressure
increasing from 0 to 36.0 bar, particularly at the early stage of
adsorption with pressures lower than 10.0 bar. The equilibrium
adsorption capacities obtained at 298 K and 36 bar for AC-NH2
(1:1), AC-NO2 (1:1), and AC samples were 19.07 mmol/g,
17.34 mmol/g, and 16.67 mmol/g, respectively. The CO2
adsorption capacities of samples in the reported literature
were 10 mmol/g at 293 K and 17 bar, 8.4 mmol/g at 298 K and
30 bar, and 10.3 mmol/g at 298 K and 30 bar.43−45 Under the
same conditions, the modified AC samples were higher than
those reported previously. Clearly, the CO2 adsorption
capacities of AC-NO2 (1:1) and AC-NH2 (1:1) are both
higher than those of the raw AC sample. Interestingly, however,
the adsorbed amounts of CO2 by the aminated carbon (AC-
NH 2 (strong)), which was prepared from using the
concentrated HNO3/H2SO4 acid mixture, were found to be
much smaller than those of the raw AC sample. This drastically
decreased CO2 capacity obtained for the AC-NH2 (strong)
dx.doi.org/10.1021/ef400499k | Energy Fuels 2013, 27, 4818−4823
Energy & Fuels
sample was believed to be due to the collapse of the porous
structures of carbon due to excessive HNO3 oxidation, which
led to a great reduction in surface area (Table 1). It is known
that the CO2 capacity of carbon materials is not only
determined by the pore volume but also by the basic
functionalities present on the carbon surface (combination of
physical and chemical adsorption).20,46 Indeed, the higher CO2
uptake obtained for the AC-NO2 (1:1) and AC-NH2 (1:1)
samples, which had lower pore volumes and BET surface areas
than the raw carbon, highlights the importance of the nitrogen
functionalities on the surface of the modified carbons as
revealed by above FTIR and the XPS characterizations, such as
imine, amine, amide, pyrrolic, and pyridonic groups, which are
the active sites for CO2 adsorption. Previous studies on CO2
adsorption with amine-impregnated activated carbons have
shown that despite the strong basicity of amines, the CO2
retention performance of the impregnated carbons is not as
satisfactory as expected and, in some cases, even lower than the
original carbons, due to the drastic loss of carbon porosity.47
The results obtained in this work demonstrate that nitration
followed by reduction can be an effective way of introducing
desirable basic nitrogen functionalities to the carbon surface
without compromising significantly the vital porosity of the
carbon materials.
To study the effect of adsorption temperature on CO2
capture, the CO2 adsorption characteristics of the original
and aminated carbons were also examined at different
temperatures in the range of pressures from 0 to 36.0 bar. As
shown in Figure 7, the CO2 adsorption capacity of both the
Figure 7. CO2 capture capacities of the AC and AC-NH2 (1:1) at
different adsorption temperatures.
samples was found to be significantly affected by adsorption
temperatures. The CO2 adsorption capacity of AC-NH2 (1:1)
decreased from 19.07 mmol g−1 at 298 K to 15.05 mmol g−1 at
323 K and 7.28 mmol g−1 at 343 K, while the capacity of the
original raw AC decreased from 16.67 mmol g−1 at 298 K to
12.05 mmol g−1 at 323 K and 6.79 mmol g−1 at 343 K,
respectively. The observed decrease in the CO2 adsorption
capacity with temperature is expected due to the exothermic
character of physisorption where both the molecule diffusion
rate and the surface adsorption energy increase with temper-
ature.20 Similar behaviors have also been reported for other
modified carbons prepared from using different precursors.46
However, the AC-NH2 (1:1) was found to have significantly
higher CO2 capacities than the raw AC at all temperatures
4822
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examined, being indicative of the higher affinity of the modified
carbons for CO2. However, the similar adsorption capacities
observed for the original and aminated carbons at the higher
temperature of 323 K suggest that the affinity of the aminated
carbon, AC-NH2 (1:1), for CO2 is of moderate strength, which
is ideal for easy regeneration of the carbon adsorbent materials
in practical applications (e.g., pressure or temperature swing
adsorption cycles).
As well as the adsorption capacity, a stable cyclic operation
performance is also a critically important property when
evaluating the ultimate performance of an adsorbent for CO2
capture. Figure 8 presents the test results from multiple
Figure 8. Cyclic tests of CO2 adsorption on AC-NH2 (1:1) at 298 K.
adsorption−desorption cycles. It can be observed that the CO2
adsorption of the aminated carbons are fully reversible with
superior cyclic stability, and the CO2 adsorption uptake was
well maintained at 19.07 mmol/g for each adsorption−
desorption cycle conducted at 298 K and 36 bar.
4. CONCLUSIONS
A facile method of nitration followed by reduction was
examined as an effective way to introduce basic nitrogen
functionalities onto the surface of activated carbon. Character-
izations of the nitrogen-enriched carbons by FTIR and XPS
have confirmed that a range of desirable basic nitrogen-
containing functional groups, such as pyrrolic, pyridonic,
pyridinic, and, in particular, amino type nitrogen, could be
effectively introduced via the nitration-reduction treatment
onto the surface of activation carbon, which can greatly
improve the affinity of activated carbon for CO2 capture. The
modified carbons via the nitration-reduction method demon-
strated very high CO2 capture capacities of up to 19.07 mmol/g
at 298 K and 36 bar. Due to the moderate affinity of the
modified carbons for CO2 retention, the adsorption was fully
reversible, and the adsorbents could be easily regenerated with
superior cyclic stability. Although further investigations are
needed, the results obtained so far tend to suggest that the
nonsophisticated nitration and reduction method can be used
to effectively improve the performance of activated carbon
materials as the adsorbents for CO2 capture, using a pressure or
temperature adsorption process.
dx.doi.org/10.1021/ef400499k | Energy Fuels 2013, 27, 4818−4823
Energy & Fuels

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Article

AUTHOR INFORMATION
Corresponding Author
*Tel.: +86 351 4250292. Fax: +86 351 4250292. E-mail:
likx99@yahoo.com (K.X.L.), jianlong.wang@hotmail.com
(J.L.W.), cheng-gong.sun@nottingham.ac.uk (C.G.S.).
Notes
Disclosure: The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
This work is financially supported by National Nature Science
Foundation of China (No. 51002166, 51172251, and
51061130536), Shanxi Province Science Foundation for Youths
(No. 2010021023-3), Shanxi Province International Coopera-
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Cooperation Project of the Ministry of Science and Technology
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