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Amine-rich ionic liquid grafted graphene for sub-
ambient carbon dioxide adsorption
Cite this: RSC Adv., 2016, 6, 3032
P. Tamilarasan and S. Ramaprabhu*
Received 21st October 2015
Accepted 25th November 2015
DOI: 10.1039/c5ra22029g
www.rsc.org/advances
The present study describes the synthesis of the adsorptivity based
amine-rich ionic liquid (ARIL), namely, 3,5-diamino-1-methyl-1,2,4-
triazolium tetrauoroborate grafted graphene (HEG/ARIL), and its
application in carbon dioxide adsorption. This ionic liquid occurs in the
solid form at standard atmospheric temperature and pressure, and
forms solid-like short range ordering on a graphitic substrate.
Molecular vibrational spectroscopy suggests that the ARIL molecules
are physically adsorbed on the graphene surface with no detectable
chemical interactions. The CO2 adsorption on ARIL is not signicantly
accompanied by chemical interaction with the amine groups under
sub-ambient conditions. The adsorption capacity of ARIL attained
a signicant improvement when it was grafted onto graphene. The
favourability and energy of adsorption suggest that the cumulative
interaction of CO2 with ARIL moieties is weaker than that with residual
oxygen-containing functional groups in graphene. The adsorbate
retention of graphene is largely increased upon grafting ARIL. The
isosteric heat and entropy of CO2 adsorption on the HEG/ARIL is lower
than that found on pristine HEG. Conclusively, ARIL functionalization
improved the CO2 adsorption capacity and decreased the interaction
energy between CO2 and graphene, because it enhances the density
of the low anity adsorption sites.
1. Introduction
Ionic liquids (ILs), the room temperature molten salts, have
several applications in green physical chemistry due to their
unique physical and chemical properties. In particular, they
attained immense interest in carbon dioxide adsorption appli-
cations, because CO2 has a rapid and reversible solubility in
selective ILs.13 Xiong et al. reported a reversible interaction of
carbon dioxide with an ionic liquid by a hydrophobichydro-
philic transition.4 The advantages of ILs in CO2 adsorption
include their low vapour pressure, wide liquid range, and high
Alternative Energy and Nanotechnology Laboratory (AENL), Nano Functional
Materials Technology Centre (NFMTC), Department of Physics, Indian Institute of
Technology Madras (IITM), Chennai, India. E-mail: ramp@iitm.ac.in
3032 | RSC Adv., 2016, 6, 30323040
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thermal and chemical stability.5 Several ionic liquids have been
developed especially for CO2 adsorption applications. Although
conventional ILs show rapid CO2 uptake, their storage capacity
is not appreciable. The investigations showed that the anion
and substituents (side chains and atoms in the backbone of the
ILs) on the cation inuence CO2 solubility to a certain extent.3,6
CO2 is a weakly acidic gas, which can be reversibly adsorbed by
structures having weak base moieties such as amine groups or
nitrogen sites.7 Moreover, it has been reported that each mole of
amine can capture 0.5 to 1 mole of carbon dioxide.8,9 Attaching
amine functionalities to the ions of an ionic liquid is a possible
way to enrich the amine content.10,11
Amine-functionalized ionic liquids have been developed to
achieve high CO2 adsorption capacity with fast adsorption
kinetics.12 In addition, they can show good selectivity towards
CO2 in a mixture with nitrogen and oxygen. Gurkan et al. ach-
ieved equimolar CO2 absorption on phosphonium-based ionic
liquids by choosing amine containing anions such as prolinate
and methioninate.8 On the other hand, amine groups can
also be attached to the cations of an ionic liquid.1,13 Zhang
et al. synthesized a series of dual amino-functionalized
phosphonium-based ionic liquids to achieve equimolar CO2
adsorption capacity, where both anion and cation were func-
tionalized with amine moieties.14
Ammonium,12 phosphonium8,14 and imidazolium1 are widely
used backbones in task specic ionic liquids for CO2 adsorp-
tion. In particular, nitrogen atoms present in imidazolium
cation based ionic liquids make weak intermediates with CO2
molecules.15 The triazolium backbone has high nitrogen
content because its ring contains three nitrogen atoms and
mimics the imidazolium structure. Thus, it is expected that CO2
can have better solubility in triazolium based ionic liquids
compared to imidazolium based ILs.3,16 It is also expected that
an amine enriched triazolium-based ionic liquid can have high
CO2 adsorption capacity.
It is reported that the solubility of CO2 in ionic liquids can be
enhanced through connement due to a favourable negative
transferring energy, which can be achieved by supporting ILs
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with a porous solid substrate.17,18 The atomistic simulations on
CO2 sorption properties of ILs incorporated carbon nanotubes
reveals an improved CO2 solubility in a conned phase.19 Wang
et al. immobilized amino acid ionic liquids into nanoporous
polymethylmethacrylate microspheres for a robust CO2 adsor-
bent with fast kinetics and improved sorption capacity along
with good regenerability.20 In our previous studies, we observed
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metathesis reaction conducted at room temperature for 16 h
exchanges the bromine anion with tetrauoroborate and results
in [DAMT][BF4] as the dissolved phase and NaBr as a white
precipitate. The supernatant was separated from the precipitate
and the methanol was evaporated to obtain an amber-coloured
amine-rich [DAMT][BF4] ionic liquid as a solid material (at 298 K).

that the integration of ionic liquids with high surface area
support materials oers an improved CO2 adsorption
capacity.21,22
Carbon nanomaterials, particularly graphene, have been
identied to be promising support material for various func-
tionalities, including nanoparticles, polymer and ionic
liquids.23,24 Their high surface area, porosity, low density,
chemical stability, fast adsorption/desorption kinetics and ease
of functionalization facilitates their applications in adsorp-
tion.2530 Moreover, the compatibility between a graphitic
carbon substrate and ionic liquid is found to be appreciable.31
In our previous studies, we observed the potential advantages of
ionic liquid functionalization for CO2 capture and conversion
applications.22,32,33
In this study, we have synthesized an amine-rich ionic liquid
and graed the material into a graphene substrate. The
isothermal and thermodynamic aspects of CO2 adsorption on
the amine-rich ionic liquid-graed graphene have been briey
discussed. To the best of our knowledge, this is the rst report
on the synthesis of an amine-rich ionic liquid-graed graphene
and its CO2 adsorption properties under sub-ambient
conditions.
2.3 Ionic liquid functionalized graphene synthesis
About 100 mg of pristine HEG was dispersed in 5 mL of ethanol
using ultrasonic irradiation followed by the addition of 100 mg
of [DAMT][BF4] ionic liquid. The mixture was thoroughly stirred
for 6 h under ambient conditions in a closed vessel. The
dispersion was ltered once using a nylon-66 membrane and
dried in a static vacuum (400 mbar) for 6 h at room temperature
without repeated washing. The material was denoted as HEG/
ARIL.
2.4 Characterization techniques
The surface morphology of the synthesized materials was
determined by transmission electron microscopy (TEM) using
Technai G-20. An X'Pert Pro PANalytical powder X-ray dirac-
tometer was employed to analyse the structure of the nano-
composite. A Perkin-Elmer FTIR spectrometer was used to
determine the vibrational characteristics of the synthesized
materials. Carbon dioxide adsorption properties of the adsor-
bents were determined at various temperatures using a Micro-
meritics ASAP 2020 V3.00 H surface area analyzer equipped with
a water bath.

2. Experimental section 3. Results and discussion

3.1 Morphological analysis
2.1 Graphene synthesis
The rapid removal of the functional groups from graphite oxide
Graphene was prepared from graphite using a two-step top-
results in exfoliation and introduces disorder in the graphite
down approach.34 Briey, graphite was oxidized using a water-
structure, which produces highly wrinkled few-layered HEG
free mixture of concentrated potassium permanganate, sul-
sheets.34,36 The TEM image (Fig. 1(a)) of HEG displays the
phuric acid, and sodium nitrate (Hummers' method35), which
wrinkled nature of the graphene sheets, where the wrinkles
resulted in graphite oxide (GO) as a brown powder. Further-
were produced by structural defects such as heptagons and
more, this GO was subjected to rapid heating at 200
C under
pentagons.37 These structural defects and residual functional
a hydrogen atmosphere in a tubular furnace, which resulted in
simultaneous exfoliation and reduction. The graphene synthe-
sized via the hydrogen-assisted exfoliation technique is labelled
as HEG and has a wrinkled structure due to the rapid removal of
the oxygen-containing functional groups.34

2.2 Amine-rich ionic liquid synthesis

3,5-Diamino-1-methyl-1,2,4-triazolium tetrauoroborate ([DAMT]-
[BF4]) ionic liquid, denoted as ARIL, was synthesized via a two-
step method. In the rst step, 3,5-diamino-1,2,4-triazole (Sigma
Aldrich, 98%) was dissolved in acetonitrile followed by the
addition of an excess amount of methyl bromide under stirring.
The solution was reuxed at 333 K for 24 h under a nitrogen
atmosphere. Evaporation of the acetonitrile resulted in a highly
viscous, amber-coloured liquid. Similar reactions have been re-
ported in the literature.16 This liquid was dissolved in ethanol
followed by the addition of sodium tetrauoroborate. The Fig. 1 TEM images of (a) HEG and (b) HEG/ARIL.

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groups eectively interact with CO2 molecules and provide great
advantages for CO2 adsorption.38 It was dicult to record the
ARIL moieties on the HEG surface, because they were uniformly
coated over the surface. However, the morphology of HEG
signicantly changed upon ARIL functionalization, which can
be clearly seen in Fig. 1(b). The presence of ARIL can be
conrmed by the inhomogeneous shades over the surface and
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inside the channels formed by the wrinkled morphology of
HEG. Moreover, the amount of wrinkles reduced upon ARIL
functionalization. Further persuasive evidence to conrm the
presence of ARIL moieties on HEG surface can be obtained from
molecular vibrational analysis.
3.2 Structural analysis
The X-ray diraction pattern (XRD) pattern of HEG shows
a broad diraction peak (002) centered at 24
, corresponding to
an inter-layer distance of 0.37 nm. The inter-layer distance of
HEG was slightly higher than that of graphite (0.34 nm) due to
the disorder introduced by the rapid removal of its functional
groups. The broadening and weak intensity of the (002) peak
conrms the high degree of disorder in the graphitic structure
and the formation of few layered graphene.
The XRD pattern of ARIL was acquired at room temperature
in a moisture-free atmosphere. ARIL was coated as a thick layer
on a glass plate and dried under static vacuum prior to analysis,
because it was hydroscopic at room temperature. The pattern
shows a peak around 12
corresponding to a periodicity of 0.7
nm, which was comparable to the length of a triazolium cation
(Fig. 2).39,40 Here, the alkyl chain of the cation interacts in
parallel with the plane of the ordering and the triazolium rings
are tilted upon solidication. In a similar study, Bovio et al. had
observed the existence of ordered structures of ionic liquids on
atomically at surfaces using atomic force microscopy.41 In
addition, the absence of peaks corresponding to NaBF4 and
NaBr indicate the purity of the ionic liquid.
The XRD pattern of the ARIL functionalized HEG was
acquired at room temperature in a moisture-free atmosphere
aer drying, which shows the conventional graphitic peak cor-
responding HEG at 24
. In addition, a weak signal was observed
at around 12
, which can be assigned to the solid-like short
Fig. 2 X-ray diraction patterns of HEG, ARIL and HEG/ARIL.
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range ordering of the ARIL moiety on the HEG surface. This
observation is in good agreement with our previous studies.39,40
3.3 Molecular vibrational analysis
The FTIR spectra of HEG, ARIL and HEG/ARIL are shown in
Fig. 3. The modes are assigned based on the Colthup's table of
infra-red absorption bands.42 The FTIR spectrum of HEG
(Fig. 3(a)) shows a broad band in the high wavenumber region
(3450 cm1), corresponding to the stretching vibrations of the
hydroxyl group from carboxylic acid, alcoholic and phenolic
groups. In addition, anti-symmetric and symmetric stretching
vibrations of ]CH2 occur at 2925 and 2853 cm1, respectively.
The stretching vibration of the aromatic rings from the hexag-
onal honeycomb lattice was found at 1630 cm1. The peaks in
the low wavenumber region (5002000 cm1) can be assigned to
the residual functional groups (]CH2, OH, COOH, and pC]
O), where the stretching mode of CO (1210 cm1) and vibra-
tions of ketones (1060 cm1) have merged along with other
modes to form a broad pattern between 10401240 cm1.42
The FTIR spectrum of dry ARIL (Fig. 3(b)) conrms the
structure and shows no signicant peak associated with hydroxyl
groups, suggesting the purity of the material. The molecular
structure of 3,5-diamino-1-methyl-1,2,4-triazolium tetra-
uoroborate is given in Fig. 4. The attached NH2 (primary
amine) groups produce NH stretching vibrations between 3100
and 3500 cm1, while the ring nitrogen (tertiary amine) produces
no signal in this region. The strong NH stretching mode at 2427
cm1 and the NH deformation mode at 1543 cm1 also conrm
the presence of amine moieties. Moreover, the signal at 1121
cm1 corresponding to CN stretching from CNH2 conrms
that the amine groups are attached to the carbon atoms of the
triazole ring. The stretching vibration of CH from CH3 (2972
cm1) and CH3 deformation vibrations (1373 and 1344 cm1)
conrm the attachment of methyl group, while the signal at
2773 cm1 (CH stretching from NCH3) suggests that the
methyl group was attached to a nitrogen atom. The scissor
bending vibration of CH2 at 1461 cm1 was a conformational
signal from the CH3 group.
Fig. 3 FTIR spectra of (a) HEG, (b) ARIL and (c) HEG/ARIL.
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(m2  m1) with 1 mg accuracy. The sample temperature was

maintained using a water bath.
In a typical adsorption isotherm analysis, an accurately
known amount (n) of demoisturized high pure CO2 gas was
successively allowed into the sample cell. At equilibrium, the
free gas (neq) in the cell was calculated from the available
volume (V), equilibrium pressure (Peq) and sample temperature
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(T) using the van der Waals equation:43

 
n2 a

Peq 2 V  neq b neq RT (1)
V

Thus, the adsorbed amount, nad, can be calculated as nad n

Fig. 4 Molecular structure of 3,5-diamino-1-methyl-1,2,4-triazolium  neq. In the desorption analysis, a known amount of gas (n*)
tetrauoroborate. was successively removed from the cell. Thus, the total amount
of gas in the tube was n  n*, where n nad + neq. The amount of
unadsorbed free gas (n*eq) at the equilibrium desorption pres-
The asymmetric stretching vibration of NN]C from the 1, sure in the cell was determined using eqn (1). The equilibrium
2, 3 sites of the triazolium ring occur at 2111 cm1, while the amount of residual CO2 molecules present on the surface of the
CN compartment from the aromatic tertiary amine produces adsorbent, n*ad, was equal to n  n*  n*eq.
a stretching vibration at 1250 cm1. It was dicult to assign the The carbon dioxide adsorptiondesorption isotherms for
multiple peaks around 1636 cm1, because the stretching ARIL are shown in Fig. 5(a) and reveal the equilibrium
modes of C]N and deformation bending modes of NH groups adsorption capacity was 48, 46, 45 and 45 mmol g1 at 283, 288,
occur in the same region. However, it can be assumed that the 293 and 298 K, respectively, with 100 kPa CO2 pressure. As per
signal at 1636 cm1 belongs to C]N, because it produces the literature, each mole of amine moiety can absorb 0.5 mole of
a stronger signal compared to the deformation bending modes CO2 through carbamide formation.8 Here, the ARIL cation
of NH groups. contains two amine groups and three ring nitrogen atoms. The
Furthermore, a strong signal at 1670 cm1 was observed in amine groups adsorb CO2 with a high binding energy, while the
ARIL and HEG/ARIL even before the adsorption experiments, ring nitrogen can absorb through dipoledipole interactions
which can be assigned to the C]O stretching vibrations with the CO2 molecules. In this case, ARIL must absorb more
emerged from carbamate.1,9 We believe that this signal emerges
due to the interaction of amine moieties with ambient CO2
molecules. The strong signal at 1022 cm1 arises from the ring
breathing mode of the triazolium ring. Various modes of the
1,2,4 tri-substituted ring are observed at 863, 788 and 717 cm1
from the triazole backbone.
The FTIR spectrum of HEG/ARIL (Fig. 3(c)) shows no
signicant new vibrational signals other than those belonging
to ARIL and the residual functional groups of HEG, which
indicate that there is no signicant chemical interaction
between HEG and ARIL. The ionic liquid may be physically
adsorbed to form a thin layer of short range ordering on the
surface of graphene layers.

4. Adsorption analysis
4.1 Adsorption isotherm analysis
The carbon dioxide adsorptiondesorption properties of ARIL
and HEG/ARIL were determined using a vacuum-swing
adsorption technique at low pressure (<100 kPa) and at four
dierent temperatures, viz., 283, 288, 293 and 298 K. Approxi-
mately 150200 mg of the adsorbent was loaded into a sample
cell of known mass (m1). The sample was degassed and acti-
vated under reduced pressure (7 Pa) at 373 K for 3 h. The
dierence between the total mass of the cell with the activated Fig. 5 CO2 adsorptiondesorption isotherms for the (a) ARIL and (b)
sample (m2) and that of the sample cell gives the sample mass ARIL functionalized HEG at multiple sample temperatures.

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than an equimolar amount (i.e., higher than 5 mmol g1) under
the given physical conditions. However, the obtained capacity
was almost two orders less than the expected values.
ARIL is a crystalline solid in a moisture-free atmosphere at
room temperature. Its crystallinity may prevent the accessibility
of the adsorption sites for molecules at the inner lattice points.
This may not be true at high pressures, because the CO2
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adsorption isotherms of ARIL closely follow a type-III isotherm,
according to IUPAC classication. Here, CO2 molecules may
chemically interact with only the surface ARIL molecules under
sub-ambient temperatures and at very low pressures, which
leads to a low adsorption capacity. The trends in the adsorption
and desorption isotherms indicate a high anity with the
adsorbate due to chemical interactions.
Surprisingly, we found no signicant change in the equilib-
rium adsorption with temperature, which needs further study to
justify the mechanism. However, we anticipate that this may be
due to the partial chemical interactions of the amine groups
with CO2 molecules.
Consequently, HEG supported ARIL (HEG/ARIL) shows
a signicant improvement in CO2 adsorption capacity,
compared to the neat ARIL. Numerically, HEG/ARIL adsorbs 882,
770, 680 and 557 mmol g1 at 283, 288, 293 and 298 K with a 100
kPa equilibrium pressure, respectively. Moreover, the values are
signicantly higher than those found for conventional ionic
liquids. For example, the 1-butyl-3-methyl imidazolium cation
based ionic liquids with tetrauoroborate, hexauorophosphate
and triuoromethylsulfonylimide anions adsorbs 84, 63 and 482
mmol g1 under similar conditions, respectively.44,45
The adsorption capacities of HEG/ARIL were signicantly
higher (1026%) than those found for pristine HEG under
similar conditions. It is also worth noting that the ARIL moie-
ties improve adsorption capacity relatively better compared to
1-butyl-3-methylimidazolium tetrauoroborate ([BMIM][BF4]).
In our previous study, we found that functionalization with
a conventional ionic liquid has a minimal inuence on the
adsorption capacity compared to a polymerized ionic liquid.22
However, ARIL shows a signicant improvement in its mono-
meric form itself, due to the rich amine content.
Henry's constant (kH) denes the anity of the adsorbent
towards an adsorbate, which assumes that the adsorbed mole-
cules exert no inuence on an approaching molecule at very low
surface coverage. Numerically, it is represented as
P interaction between the adsorbate and adsorbent. HEG sup-
kH lim (2)
x/0 x ported ARIL shows higher adsorption energy compared to the
where P is the partial pressure of CO2 and x is the amount of gas
adsorbed (in units of gram per gram of adsorbent). The number
of anchoring sites per unit mass of sample was not available.
Thus, Henry's constant was described as the pressure required
to store CO2 molecules equal to the mass of adsorbent, in this
study.
Henry's constant for the neat ARIL was much higher than that
for pristine HEG, as a consequence of low initial adsorption rate.
Moreover, the kH values did not change with temperature, which
suggests that the initial adsorption was accompanied by partial
chemical interactions. However, the adsorption rate increases
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with pressure and results in a type-III isotherm. The kH values for
HEG/ARIL are signicantly higher than those found for pristine
HEG. In other words, they approach the values found for the neat
ARIL and suggest that the surface chemistry of HEG has been
considerably changed upon ARIL functionalization.
The adsorption isotherms were modeled with Freundlich
adsorption isotherm, because graphene surface has variety of
adsorption sites with distributed adsorption energy. Briey,
HEG/ARIL possesses structural defects, residual functional
groups and ARIL functionalities, which may have dierent
adsorption energies.
Numerically, Freundlich model46 is represented as
1
Qeq KF Pn (3)
1
where Qeq (mol g ) is the amount of adsorbed CO2 molecules at
an equilibrium pressure P (Pa), KF is the Freundlich isotherm
constant (mol g1) and n is the adsorption intensity. The
Freundlich isotherm was in close agreement (R2 0.999) with
the experimental data at all the temperatures studied, con-
rming the heterogeneity of the surface.
The tting parameter n denes the favorability of CO2
adsorption, which is in good agreement with the trend in Hen-
ry's constant. The values of n were higher for pristine HEG
compared to ARIL under sub-ambient temperatures. This was
due to the high surface area and signicant amount of residual
functional groups in HEG, which were almost readily available
for interaction with CO2 molecules. Although ARIL has rich
amine groups, they may not be accessible to CO2 at low pressures
due to the predominant physisorption and inaccessibility at low
pressure. Moreover, the low reactivity of the amine functional-
ities at sub-ambient temperature also inuences the favorability.
Upon ARIL functionalization, the favorability attains an
intermediate value of pristine HEG and neat ARIL. Because kH
and n values depend on the low surface coverage (or low pres-
sure) phenomenon, they did not follow the trend of equilibrium
adsorption capacity at ambient pressure. It should be noted that
the n values for HEG and HEG/ARIL approach unity (or Henry
isotherm behavior) with temperature, i.e., the isotherms
become more linear with increase in temperature. Another
Freundlich constant, KF, is the specic adsorption constant
when the surface coverage tends to zero, which decreases with
temperature for HEG and HEG/ARIL. The value of KF/n reveals
the information about the adsorption energy, i.e., the energy of
neat ARIL, following a similar trend for the favorability of
adsorption with temperature. This was expected to be reected
in the isosteric heat of adsorption. From Table 1, it is clear that
the CO2 adsorption on HEG supported ARIL is highly favorable
than that found on the neat ARIL. Once again, we anticipate the
limited chemical interactions of ARIL with CO2 results in low
adsorption energy.
4.2 Adsorbate retention analysis
Generally, desorption isotherms do not follow the same trend as
adsorption due to the porosity and surface chemistry of the
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Table 1 Comparison of the adsorption isotherm parameters for

HEG,22 ARIL and HEG/ARILa

Freundlich coecients
Qeq
Material T (K) (@ 100 kPa) kH (bar) n KF KF/n R2

HEG* 283 695 13.3 1.479 30.93 21.04 0.999

288 609 15.9 1.470 27.64 18.80 0.999
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293 558 18.5 1.448 23.64 16.41 0.999

298 512 22.2 1.423 20.05 14.12 0.999
ARIL 283 48 30.4 0.595 0.22 0.37 0.999
288 46 34.9 0.623 0.31 0.49 0.999
293 45 32.8 0.620 0.28 0.45 0.999
298 45 33.5 0.622 0.31 0.49 0.999
HEG/ARIL 283 882 25.8 0.977 7.95 8.14 0.999
288 770 28.9 0.979 7.17 7.32 0.999
293 680 33.0 0.984 6.43 6.53 0.999
298 557 39.7 1.018 6.25 6.14 0.999
a
Units: Qeq (mmol g1) and KF (mmol g1 kPa(1/n)). * From our previous
study.22

adsorbent and show a hysteresis. The amount of adsorbate

retained when isothermally desorbed at the same pressure is
called the isothermal adsorbate retention (IAR) and is mathe-
matically represented as

IAR Qeq(des)  Qeq(ads) (4) Fig. 6 Isothermal adsorbate retention of ARIL and HEG/ARIL as
a function of equilibrium pressure.
where Qeq(ads) is the equilibrium adsorbate concentration at
a certain pressure on the adsorption isotherm and Qeq(des) is
the equilibrium adsorbate concentration at the same pressure all the adsorbents, as the CO2 molecules attain high kinetic
on the desorption isotherm.47 energy at high temperatures, which helps them to escape from
In the present case, desorption isotherms are unique for the surface. However, temperature has a signicant inuence
ARIL and show large hysteresis. The IAR values for ARIL are on the desorption of CO2 from HEG/ARIL compared to ARIL.
around 40 mmol g1 at 20 kPa in desorption, which slightly
varies with temperature (Fig. 6(a)). At low pressures (<2 kPa),
ARIL shows a 5070 mmol g1 residue, which may be attributed 4.3 Thermodynamic parameters of adsorption
to the possible chemical interactions with the amine groups. The adsorption isosteres and regression lines of ln(pressure) vs.
Nevertheless, IAR values rapidly fall with pressure at low pres- 1/T at a constant adsorbed amount of CO2 adsorption on HEG/
sures (<10 kPa). ARIL are shown in Fig. 7 and follow the Arrhenius relation,
The IAR values for HEG/ARIL (Fig. 6(b)) are signicantly
higher compared to neat ARIL and pristine HEG. For instance,
HEG/ARIL shows 215 mmol g1 IAR at 50 kPa desorption pres-
sure and at 298 K sample temperature, while it becomes 33 and
36 mmol g1 for the neat ARIL and pristine HEG, respectively.
This indicates the improved reactivity/adsorptivity of the func-
tionalized support and was a substantiation of the inuence of
ARIL on the CO2 adsorption capacity of HEG. It is also worth
noting that ARIL functionalization signicantly improves CO2
retention, compared to other conventional ionic liquids such as
[BMIM][BF4].22
Conclusively, both HEG and ARIL components of the
adsorbent contribute to the adsorption process. The adsorbate
residue at around 2 kPa pressure was much higher (70100
mmol g1) for HEG/ARIL compared to pristine HEG (<10 mmol
g1), which was additional proof for the inuence of ARIL. In
general, IAR values deceases with an increase in temperature for Fig. 7 CO2 adsorption isosteres (van't Ho plot) for ARIL-functional-
ized HEG at various adsorbed amounts.

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which suggests a temperature-dependent adsorption. This also

implies that the amine groups of ARIL moieties undergo no
predominant chemical interaction such as formamide forma-
tion at sub-ambient temperatures. Moreover, the regression
lines have a negative slope, which reveals that the CO2
adsorption on HEG/ARIL is an exothermic phenomenon
(physisorption). Because the adsorption isotherms for the neat
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ARIL show insignicant changes with temperature, it was

impossible to determine the adsorption isosteres.
The isosteric heat of adsorption (|DH|) is dened as the
dierence between the activation energies for adsorption and
desorption, and quanties the strength of the adsorbate
adsorbent interaction. Here, |DH| values were calculated from
the slope of adsorption isosteres in van't Ho plot for the range
of 50550 mmol g1 (Fig. 7) using the ClausiusClapeyron Fig. 8 Comparison of the isosteric heat of adsorption of HEG22 and
equation, HEG/ARIL as a function of adsorbed amount.
 
vln P
DH R (5)
v1=T n
the primary anchoring sites in HEG/ARIL, while the residual
where DH is the dierential enthalpy of adsorption, P is the functional groups play a certain role in HEG. Oxygen-containing
pressure, T is the temperature, and R is the gas constant. The functional groups are stronger adsorption sites compared to
absolute value of DH gives the isosteric heat of adsorption ARIL moieties under sub-ambient conditions.
(|DH|). The intercept of extrapolated isosteres with ln P-axis The change in entropy (DS) for the adsorbent due to the
(DS/R) gives the change in entropy (DS) associated with adsorption of CO2 was calculated from the ln P-axis intercepts
adsorption.48 (DS/R) of the van't Ho plot at various adsorbed amounts. The
The carbon dioxide physisorption reaction on HEG/ARIL DS value for HEG/ARIL was found to be 80 J mol1 K1, while
surface shows a |DH| value of 17  2 kJ mol1 at 100 mmol it was 175 J mol1 K1 for HEG at 100 mmol g1 surface
g1 adsorbed amount, which was signicantly lower than that coverage.
observed with pristine HEG (25 kJ mol1) at low surface The pattern of entropy change upon surface coverage is
coverage. This was in good agreement with the trend observed presented in Fig. 9 and indicates that the DS value for CO2
in Henry's constant and favorability of adsorption. It is gener- adsorption on HEG/ARIL was lower compared to that found on
ally expected that HEG/ARIL should have a higher |DH| value HEG. The interaction of CO2 molecules with the oxygen-
compared to pristine HEG, because a chemical interaction is containing residual functional groups was stronger compared
possible for it. However, the low heat of adsorption suggests to that found with ARIL moieties, as concluded by adsorption
that the CO2 molecules predominantly interact with the isothermal analysis. This stronger interaction results in a larger
nitrogen atoms on the triazolium ring rather than with the change in the entropy of the system. Upon functionalization,
amine groups, due to the limited chemical interaction at sub- ARIL moieties cover the surface and screen the native adsorp-
ambient temperatures. tion sites (structural defects and residual functional groups),
The change in |DH| value with surface coverage was deter- which leads to weaker interaction and lower disorder in the
mined for 50550 mmol g1 of the equilibrium amount of system under sub-ambient conditions. Initially (<150 mmol g1),
adsorption, which follows an entirely dierent trend compared DS values were signicantly increased with surface coverage for
to pristine HEG. The |DH| value for HEG was observed to
decrease with surface coverage, but HEG/ARIL shows almost
unchanged |DH| values in the same range. This may be attrib-
uted to the coverage of HEG surface by ARIL moieties, which
predominantly adsorbs CO2 molecules. The surface of HEG was
heterogeneous, where the heterogeneity was introduced by
structural defects (wrinkles and edges) and residual functional
groups. This causes a continuous change in |DH| values with
surface coverage. Upon ARIL functionalization, the surface was
covered with ARIL and resulted in a narrow distribution of
adsorption energy. This can be correlated with the near unity n
values (Henry's behavior) observed in the adsorption isotherm
analysis.
It was interesting to note that the numerical value of |DH| for
both HEG and HEG/ARIL approaches the same value with Fig. 9 Comparison of entropy change upon the adsorption of CO2 on
surface coverage (Fig. 8). This suggests that ARIL moieties are HEG22 and HEG/ARIL as a function of adsorbed amount.

3038 | RSC Adv., 2016, 6, 30323040 This journal is The Royal Society of Chemistry 2016

Communication
HEG/ARIL, suggesting that the adsorption was accompanied by
partial chemical interaction from the amine functionalities.
5. Conclusions
In this study, we have synthesized an amine-rich ionic liquid
Published on 15 December 2015. Downloaded by Universidade Federal Fluminense on 28/11/2016 18:38:50.
graed graphene and found that the ARIL forms a solid-like
layer through physical interaction with graphene surface. The
ARIL-graed graphene shows an equilibrium CO2 adsorption
capacity of 882 mmol g1 at 283 K with 100 kPa equilibrium
pressure, while the neat ARIL and pristine HEG adsorb 48 and
695 mmol g1, respectively, under the same physical conditions.
The Henry's constant of graphene was increased upon ARIL
functionalization, while the Freundlich constant, n, was
decreased. Moreover, the adsorption energy (KF/n) of HEG was
decreased upon ARIL functionalization. This suggests that the
ARIL moieties were relatively less reactive compared to the
surface residual oxygen-containing functional groups under
sub-ambient conditions. Even though the equilibrium adsorp-
tion capacity of HEG was improved, the adsorption energy (or
head of adsorption) and favorability of adsorption was
decreased upon ARIL functionalization. This indicates the
introduction of low energy adsorption sites on the HEG surface.
The isosteric heat of CO2 adsorption on HEG/ARIL was found to
be 17  2 kJ mol1 at 100 mmol g1 adsorbed amount, while it
was 25 kJ mol1 for HEG at the same surface coverage. The heat
of adsorption was slightly increased with initial surface
coverage, due to the partial chemical interaction between CO2
and amine moieties. The change in entropy of CO2 adsorption
on HEG (175 J mol1 K1) was reduced to 80 J mol1 K1
upon ARIL functionalization. Conclusively, HEG/ARIL is an
adsorbent with high adsorption capacity and low interaction
energy, which facilitates easy adsorbent regeneration.
Acknowledgements
Authors acknowledge SAIF-IITM for FTIR analysis. One of the
authors (P. T.) acknowledges the Indian Institute of Technology
Madras (IITM) for nancial support (senior research fellowship).
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