Journal of Environmental Chemical Engineering 7 (2019) 103344

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

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

Carbon dioxide adsorption studies on modified montmorillonite clay/ T

reduced graphene oxide hybrids at low pressure
⁎
Sona Stanlya, E.J. Jelmya, C.P.R. Naira, Honey Johna,b,
a
Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology, Kerala 682022, India
b
Inter University Centre for Nanomaterials and Devices, Cochin University of Science and Technology, Kerala 682022, India

A R T I C LE I N FO A B S T R A C T

Keywords: The effect of modification of Montmorillonite clay (MMT) and the development of its hybrid with reduced
Clay modification graphene oxide was studied for CO2 adsorption at low pressure. Novel polyphosphoric acid modified mon-
Polyphosphoric acid tmorillonite (PMMT) clay was synthesized by cation exchange reaction to improve the surface area and thereby
Clay graphene hybrids improving the carbon dioxide adsorption capacity. The MMT clay, polyphosphoric acid modified clay (PMMT),
CO2 adsorption
and amino modified clay (AMMT) were hybridized with reduced graphene oxide (rGO) by in-situ hydrothermal
reduction of graphite oxide for CO2 adsorption studies. The hybrids were characterized using X-ray diffraction
(XRD) analysis, Fourier Transform Infrared (FTIR) analysis, Field Emission Scanning Electron Microscopic
(FESEM) and Transmission Electron Microscopic (TEM) analyses. The Brunauer–Emmett–Teller (BET) surface
area analysis confirmed a surface area of 50.7709 m²/g for PMMT/rGO hybrid, which was higher than that of
MMT/rGO and AMMT/rGO hybrids. In general, all hybrids were active in CO2 adsorption at comparatively low
pressure [ranging from 0 to 900 mmHg]. PMMT/rGO hybrid showed highest CO2 adsorption of 0.49 mmol/g and
this was 42% more in CO2 adsorption when compared to other materials studied in this paper. The low pressure
CO2 adsorption values obtained for PMMT/rGO hybrid was substantially good when compared to the literature
results and this shows the importance of clay based materials for the development of efficient adsorbent for CO2.

1. Introduction
Now-a-days scientific society has great concern about the CO2 level
as it touched 410.79 ppm in June 2018 according to the Global mon-
itoring division of earth system research laboratory of U.S department
of commerce and it is forecasted to reach more than 550 ppm by 2050
[1]. The main sources of CO2 emission are burning fossil fuel, thermal
power plants, industries like cement, steel industry etc. [2–4]. Carbon
dioxide gas is a greenhouse gas and it is considered as the major victim
for global warming and ocean acidification [5,6]. In this contest CO2
capture and storage grab great attention in recent days [7]. There are
different approaches to develop efficient materials to capture and store
CO2 from process streams include chemical adsorption, physical ad-
sorption on the solid surface, solvent absorption, membrane separation,
cryogenic distillation etc. [8,9]. Among these, adsorption on solid ad-
sorbent has great attention because of its economical compatibility and
ease of operation with low energy consumption [10,11].
Carbonaceous materials like highly porous activated carbon, carbon
nanotubes (CNT) etc are conventionally used as adsorption material
because of its easy adsorption –desorption of carbon dioxide due to its
high surface area, porosity etc. [12–14]. Graphene is also a promising
material for the present century because of its exceptionally high sur-
face area (2630 m2 /g) that led to potential adsorption property. Hence
it is a good adsorbent of gases, dyes, metals etc. and it possess fabulous
mechanical properties, flame resistance, barrier properties and elec-
trical conductivity [15,16]. Clays like montmorillonite (MMT) and
zeolites are another class of potential adsorbent possessing better sta-
bility and economic viability [17].
Montmorillonite clay, one of the members in 2:1 clay, composed of
octahedral sheets of aluminium or magnesium oxide, which creates a
negative charge, is sandwiched between tetrahedral silicone layers and
the charges are balanced by the counter cations located in between the
interlayer space [18,19]. The high cation exchange capacity of mon-
tmorillonite makes it important in the applications of adsorption, en-
ergy storage, catalysis, drug delivery and contaminant removal. It is an
appropriate material for adsorption of CO2 gas too due to its high
porous nature and large amount of cations which make electrostatic
attraction between symmetric CO2 due to its high electric quadruple
moment. But the neat MMT is showing low pollutant removal by ad-
sorption due to its low surface area. CO2 adsorption of clay is depending

⁎
Corresponding author at: Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology, Kerala 682022, India.
E-mail address: honey@cusat.ac.in (H. John).

https://doi.org/10.1016/j.jece.2019.103344
Received 4 May 2019; Received in revised form 24 June 2019; Accepted 6 August 2019
Available online 10 August 2019
2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
S. Stanly, et al.
on the surface area especially the internal pore volume. The high cation
density in the interlayer of MMT clay makes them highly viable for
modification. Modification of MMT clay with polymeric modifiers with
functionalities such as amine and oxygen containing groups like −OH
increases the surface area and improves the adsorption capability
[20,21].
Studies were reported on clay-graphene hybrids for adsorption of
different pollutants including gases. Organic–inorganic hybrids can
improve the surface area by decreasing the restacking of graphene
layers and improve gas adsorption capability by forming highly porous
structure at low cost [22]. Garcia-Gallastegui et al. have studied the
adsorption capacity of Layered Double Hydroxide and GO (LDH/GO)
for CO2 at atmospheric conditions and was found to be 0.45 ± 0.02
molCO2/Kg of adsorbate (0.45 ± 0.02 mmol/g of adsorbate) [22].
Novacek et al. have attained a CO2 adsorption level of 3.54 mmol/g at a
pressure of 900 kPa (6750.554 mmHg) by using multiple oxidized
graphene oxide [23]. For zeolite 13X-K Garshasbi et al. have reported
the CO2 adsorption of 6.9 mmol/g at an equilibrium pressure of 20 bar
(15,001.2 mmHg) [24]. In general, the CO2 adsorption studies have
reported in high pressure. When the pressure increases the adsorption
level of the CO2 will increases [25]. In this particular study, we have
focused on the CO2 adsorption analysis at room temperature (25 °C) and
at comparatively low pressure in the range 0–900 mmHg which is close
to atmospheric pressure. Hence for the easy removal of CO2 from the
atmosphere, low pressure adsorption will be of interest.
In this paper we have demonstrated the synthesis and CO2 adsorp-
tion behavior of modified MMT - graphene hybrids for the removal of
CO2 at 25 °C at low pressures (0–900 mmHg). The modification of
montmorillonite using polyphosphoric acid (PPA), an oligomeric ma-
terial, and its hybrid with reduced graphene oxide (rGO) for CO2 ad-
sorption is detailed in the study. The hydrothermal method was
adopted for the preparation of the hybrid in which in-situ reduction of
GO in the presence of clay was carried out in tetrahydrofuran (THF)
solvent at 100 ºC. The CO2 adsorption was measured at 25 ºC from zero
to 900 mm of Hg. This paper also compares the CO2 adsorption prop-
erties of montmorilonite (MMT/rGO) and amino modified MMT
(AMMT/rGO) hybrids.
2. Materials and methods
2.1. Materials
Graphite powder, particle size < 20 μm, was purchased from Sigma
Aldrich. H2SO4 (98%), H2O2 (30%), tetrahydrofuran (THF), AMMT
(Nanoclay, surface modified with 0.5–5% amino propyl triethoxysilane,
15–35% octadecylamine), particle size ≤ 20 μm, and density
200–500 kg/m3 was obtained from Sigma Aldrich, India. KMnO4
bought from Universal laboratories. MMT (Na MMT, Cloisite 30B,
particle size of 2.0 μm and specific gravity of 1.98 g/cc) used was
purchased from Southern Clays, USA. Polyphosphoric acid was pur-
chased from Loba Chemie Ltd., Mumbai.
2.2. Modification of montmorillonite clay with polyphosphoric acid
In a typical synthesis procedure MMT (0.5 g) was dispersed in dis-
tilled water (100 mL) and stirred for 24 h. To this 0.2% of polypho-
sphoric acid (PPA) solution was added drop by drop and stirred for 5 h
to obtain PPA modified MMT. The resulted clay was washed to remove
excess acid, centrifuged, and dried under vacuum at 60 ºC, and it was
designated as PMMT. For optimizing the pre-stirring time with water,
0.5 g of MMT was stirred with water for 24 h, 48 h and 72 h. It was then
stirred with 0.2% PPA for 5 h and titrated with NaOH to estimate the
unreacted PPA, from which the reacted PPA was calculated. The re-
sidual amount of PPA was calculated at different time intervals in-order
to determine the minimum stirring time with maximum incorporation
of PPA in MMT. The concentration of PPA was varied from 0.05, 0.1,
2
Journal of Environmental Chemical Engineering 7 (2019) 103344
Scheme 1. Scheme for the modification of MMT using PPA.
0.2, 0.3, 0.4 and 0.5% and after 5 h of stirring the amount of PPA ad-
sorbed was calculated. A schematic representation of PMMT synthesis
from MMT is given in the scheme.1 .
2.3. Synthesis of graphite oxide
Graphite Oxide was synthesized from Graphite powder by an en-
vironmental friendly low temperature modified Hummers method [26].
In the typical process Graphite powder (0.5 g) was stirred with 50 ml of
98% H2SO4 for 12 h at room temperature and then the system was
cooled below 10 ºC. To this, KMnO4 crystals (2 g), was slowly added as
oxidizing agent and stirred for 2.5 h. To the reaction mixture, 25 ml of
distilled water was added and stirred for another 1 h. Finally, the re-
action was arrested by adding 5 ml of 30% H2O2 and 76 ml of water.
The GO obtained was washed with distilled water till it was free from
acid, centrifuged and dried under vacuum for 12 h at 60 ºC.
2.4. Synthesis of clay/rGO nanohybrids
The modified clay, PMMT and GO was taken in 1:1 proportion and it
was dispersed in THF by ultrasonication. It was then transferred into a
Teflon lined autoclave and then kept at 100 ºC for 7 h for hydrothermal
in-situ reduction of GO to rGO in the presence of clay. The solid ob-
tained was washed with distilled water and dried under vacuum at 60
º
C and named as PMMT/rGO. The schematic representation of PMMT/
rGO synthesis is given in the scheme.2 . The other two hybrids of clays
(MMT and AMMT) with GO were also synthesized by the same method
and the hybrids were designated as MMT/rGO and AMMT/rGO.
2.5. Characterization methods
Fourier Transform Infrared (FTIR) spectra were recorded using
Thermo Nicolet, Avatar 370 model instrument in the spectral range of
4000–400 cm−1 by KBr transmission mode. Powder morphology was
analyzed using Hitachi SU6600 Variable Pressure Field Emission
Scanning Electron Microscope (FE-SEM) and a JOEL 3010 Transmission
Electron Microscope (TEM). Thermo- gravimetric analysis (TGA) was
carried out at a heating rate of 20 ºC min−1 under nitrogen flow of
35 ml min−1 with a TGA Q 50 Thermal Analyzer (TA Instruments).
Raman spectra of GO and clay/rGO hybrids were obtained using Horiba
Jobin Yvon Lab Ram HR system by using excitation of 514.5 nm by
Argon ion laser at a resolution of 2 mm. X-ray diffraction (XRD) pattern
of the samples were recorded using XRP-Bruker AXS D8 Advances in the
2θ values from 5 to 80º using Cu Kα radiation (λ value is 1.5418 Å). X-
ray photoelectron spectroscopy (XPS) was used for the elemental
composition analyses of clay and modified clay powder samples and
was done using Kratos Axis Ultra Photoelectron Spectrometer with a
monochromatic Al Kα X-ray source (1486.6 eV). The surface area and
pore volume of the samples was analysed using Micromeritics TriStar II
surface area analyser. The average pore-size of hybrids were calculated
using the Barrett–Joyner–Halenda (BJH) method. The CO2 adsorption
of the samples were evaluated at 25 °C by volumetric gas adsorption
S. Stanly, et al.
Scheme 2. Synthesis of PMMT/rGO hybrid.
studies using surface area analyzer (Micromeritics Tristar II, USA) at a
pressure range of 0 to 900 mmHg. Prior to the measurements, the
samples were degassed for overnight at 150 °C in-order to remove all
the gases adhered from the atmosphere especially bound moisture.
3. Results and discussions
3.1. Optimisation of reaction condition and characterization of PMMT
The MMT modification with PPA was optimised by varying the
parameters such as pre-stirring time with water, concentration and
stirring time of PPA. The studies were carried out by titrating the re-
action mixture with NaOH for calculating the residual amount of PPA at
different time intervals (Table 1).
Table 1 shows the effect of pre-stirring time on adsorption of PPA on
MMT. It was clear from the table that 24 h stirring with water showed
better adsorption of PPA on interlayer galleries of MMT. The MMT
swells in water and this significantly increases the distance between
inter layer galleries of MMT and thus PPA can easily get adsorbed [27].
When the pre-stirring time increases, the concentration of PPA inter-
calated into the clay galleries decreases due to the presence of higher
concentration of water molecules which inhibit further cation exchange
reaction [28]. Fig. 1.a showed the effect of stirring time on the PPA
adsorption after the addition of PPA to MMT- water system. The rate of
PPA adsorption was higher during the initial hour when compared to
the percentage adsorption after 2 h of stirring and it was found that 5 h
of stirring was enough to get good level of PPA adsorption. Fig. 1.b
shows the effect of PPA concentration on the percentage adsorption on
MMT clay and it was clear from the plot that 0.2% PPA was enough for
obtaining better adsorption on MMT. The mechanism of PPA adsorption
on MMT can be explained on the basis of cation exchange reaction
between phosphate group on PPA and calcium ions on MMT. Here PPA
molecules enters into the interlayer galleries of MMT by cation ex-
change reaction which was highly favoured by hard acid (sodium and
calcium ions of clay)–hard base (phosphate ions of PPA) interactions
(HSAB principle). This is accompanied by a change in enthalpy, such
that PPA will have a high affinity to enter into inter-layer galleries of
MMT.
The above proposed mechanism was confirmed via XPS analyses of
MMT and PMMT clay samples (Fig. 2). XPS analysis was giving
Table 1
Effect opre-stirring time with water.
Pre stirring Time with water (h) PPA adsorbed on MMT (%)
24 65.01
48 63.12
72 57.59
3
Journal of Environmental Chemical Engineering 7 (2019) 103344
evidences for the exchange of Na+ ions from the interlayer galley of
MMT during the modification. The signal at 1071.2 eV is assigned to 1S
orbital of Na+ ion and the intensity of this signal was remarkably re-
duced in PMMT (Fig.2.b). From the XPS data, the initial mass con-
centration of the Na+ (Na 1 s) was decreased from 12.2% to 1.11% due
to the exchange of sodium ions with phosphorous ions of PPA in PMMT
clay. An additional peak of phosphorous (P2p) was observed in PMMT
at 138.2 eV (Fig. 2.a) with a mass concentration of 0.19% further
confirms the modification of MMT with PPA.
The FTIR spectrum of polyphosphoric acid modified clay (PMMT)
showed all the characteristic bands of MMT (Fig. 3a). The additional
peak obtained at 798 cm−1 in PMMT was due to the PeO stretching of
phosphates containing −OH groups which ensures the presence of PPA
in the MMT [29]. Peak at 3630 cm−1 refers to the stretching vibrations
of −OH in silicates and 3448 cm−1 corresponds to −OH stretching of
water. The peak at 1637 cm-1 is assigned to −OH bending mode and
the peak at 1045 cm−1 is representing the SieOeSi stretching in sili-
cates in the clay. The peak at 917 cm−1 is attributed to Al-O-Al de-
formation of aluminate in the clay.
The crystal structure of MMT and PMMT were evaluated using X-ray
diffraction technique as shown in the Fig.3.b. The XRD pattern of
modified MMT showed a shift in d(001) plane from 2θ of 7.29° to a lower
2θ of 6.02°, indicates the increase in the inter- layer distance due to the
incorporation of olegomeric molecules such as polyphosphoric acid
[30]. The interlayer distance of MMT was increased from 1.21 nm to
1.46 nm after modification with PPA.
Morphology of MMT and PMMT was analyzed using TEM (Fig.4a
and b). TEM images of MMT revealed aggregated layered structures in
its morphology but the modification of the clay with PPA increases the
interlayer spacing there by reducing the aggregation. Among the
modified clays, the PMMT showed a good amount of exfoliation due to
the presence of polymeric modifier in it.
The TGA thermograms of MMT and PMMT samples were given in
the Fig.5. The thermal degradation stages of MMT and PMMT were
found to be comparable and mainly two major stages of weight losses
were identified. The first weight around 100 °C is attributed to deso-
rption of water from the clay and this was 10% for MMT and was 8% for
PMMT. A narrow weight loss of about 1.12% was observed in the range
of 280 °C–380 °C for PMMT but for MMT it was only 0.38%. This may
be due to the degradation of polyphosphoric acid in the interlayer
galleries [31]. The major degradation was initiated ˜600 °C and this is
due to the dehydration of −OH group bridged on AleOeAl bonds in
[AlO6] the octahedral sheet and was found to be similar the cases of
both MMT and PMMT [25]. The weight loss observed at this degrada-
tion temperature was 12% for MMT and PMMT. The percentages of
final residue remained after the analysis was 84.33% for PMMT and
85.14% for MMT. The slight decrease in the percentage of the final
residue of PMMT when compared to MMT might be due to the PPA
S. Stanly, et al.
Fig. 1. a) Effect of time of stirring PPA b) % of PPA adsorbed on MMT in different conc. of PPA.
modification carried out.
3.2. GO and clay/ rGO hybrids
The clay/ rGO hybrids such as PMMT/rGO and MMT/rGO were
prepared via in-situ hydrothermal reduction technique and these hy-
brids were compared with amino modified clay (AMMT)/rGO hybrid
prepared through same technique. The functional groups present in GO
and the clay/rGO hybrids were evaluated using Fourier Transform
Infrared (FTIR) spectra (Fig.6). FTIR spectrum of GO showed a peak at
3425 cm−1 in the high frequency area attributed to the stretching vi-
bration of −OH groups. The presence of absorption peak at 1716 cm−1
can be assigned to the stretching vibration of C]O of carboxylic acid
group and the peak at 1631 cm-1 is due to the unoxidiszed C]C
stretching and this confirms the formation of GO from graphite powder.
The hydrothermal treatment of clay/GO hybrid reduces GO to rGO. The
hydrothermal reduction of GO to rGO in all hybrids was confirmed by
the drop in the intensity of the absorption peak at 1716cm−1. All the
major peaks of clay and rGO were observed in the corresponding FTIR
spectra.
Fig. 2. XPS spectra of MMT and PMMT.
4
Journal of Environmental Chemical Engineering 7 (2019) 103344
X ray diffraction pattern of graphite, GO and hybrids were shown in
fig.7. The pristine graphite has the characteristic sharp peak of (001)
plane at 26.6° indicating a highly ordered structure graphite with an
inter layer distance 0.334 nm [32]. Upon chemical modification of
graphite the peak at 26.6° was disappeared and a new peak at 10.39°
was formed due to the (002) plane of graphite oxide [34]. The increase
in the inter planar distance from 0.334 nm to 0.766 nm is may be due to
the presence of oxygen containing functionalities such as carboxylic,
epoxy, hydroxy etc. In the x-ray diffraction pattern of clay/rGO hybrids
(Fig.7b), the characteristic peak of GO at 10º was almost extinct and a
new broad peak was formed at 2θ angle between 20º-30º and this in-
dicates a good level of hydrothermal reduction of GO to rGO and better
intercalation of clay and rGO in the hybrid. The existence of broad peak
at 2θ between 20° to 30° after the reduction indicates the restacking of
layers after functionalization and retention of the partial graphitic
structure [33].
Further structural characterization was done using Raman spectro-
scopy (Fig.8). There are two characteristic bands viz D-band
∼1335 cm−1 which assigned to sp3 carbon atoms of the defect struc-
ture and G band ∼1593 cm−1 for the sp2-hybridized carbon atoms. The
S. Stanly, et al. Journal of Environmental Chemical Engineering 7 (2019) 103344

Fig. 3. (a) FTIR spectra (b) XRD patterns of MMT and PMMT.

ID/IG ratio is often used to evaluate the degree of reduction of GO to

rGO. In the Raman spectra of GO the intensity of the D band was
substantially high and this is due to the increase in sp3 domains after
oxidation (26, 34). The ID/IG value of GO (1.42) was reduced to 1.123,
0.95 and 0.71 for MMT/rGO, PMMT/rGO and AMMT/rGO respectively
due to the reduction of defective domain and the restoration of the
graphitic structure after the hydrothermal reduction of GO to rGO [35].
TGA thermogram of graphite, GO and clay/rGO hybrids were shown
in the Fig.9. It was observed that the graphite was highly stable up to
700 ºC. When compared to graphite, the thermal stability of GO was
less and the significant weight loss was initiated from 150 °C and was
continued upto 250 °C (33%) and this is due to the pyrolysis of the
oxygen-containing functional groups such as CO, CO2 etc present in GO.
The degradation around 650 ºC is due to the decomposition of carbon
skeleton of GO. The initial weight loss below 150 °C was mainly due to
desorption of bound water within the material and this was 12%. The
thermal stability of all clay/rGO hybrids were increased remarkably
when compared to GO alone and is due to the removal of oxygen
containing functionalities during the hydrothermal reduction of GO in
the presence of clay. In the case of clay-rGO hybrids, the initial weight Fig. 5. TGA curves of MMT and PMMT.
loss upto 100 °C was due to the removal of water and for PMMT/rGO it
was 17% where as for MMT/rGO it was 6% and least for AMMT/rGO 38.5% while for PMMT/rGO hybrid it was 57%. For AMMT/rGO hybrid
(2.3%). The second stage degradation started from 175 °C and the 62.5% and MMT/rGO hybrid 62% residue remains after degradation up
weight loss in the temperature range of 175 °C–250 °C was 12% for to 750 °C. The thermal stability of PMMT/rGO hybrid was slightly
AMMT/rGO and 10% for both PMMT/rGO and MMT/rGO. The re- lower when compared to MMT/rGO and AMMT/rGO and this could be
duction in the weight loss in the case of hybrids when comparing with due to the PPA evolution.
GO is due the reduction in the oxygen functionalities which in turn due Morphological analyses of hybrids were carried out using SEM and
to the hydrothermal reduction. The final residue obtained for GO was

Fig. 4. TEM micrographs of (a) MMT and (b) PMMT.

5
S. Stanly, et al.
Fig. 6. FTIR spectra of MMT/rGOPMMT/rGO and AMMT/rGO hybrids.
TEM (Fig.10a–h). The SEM analysis shows a highly porous structure for
the hybrids when compared with GO. Hybrids were showing non uni-
form sheets with sharp and distinct edge protruding out from the sur-
face [36]. The ordered layered morphology was disturbed after making
hybrids. The TEM image of GO shows the presence of wide, flat and less
agglomerated layers of GO nano sheets. The PMMT/rGO hybrid showed
significant decrease in agglomeration and more uniform distribution of
clay –graphene layers in comparison with MMT/rGO and AMMT/rGO.
3.3. BET surface area analysis of MMT, PMMT and hybrids
Surface area of the MMT, PMMT, GO, MMT/rGO, AMMT/rGO, and
PMMT/rGO were analysed (Fig.11) by the N2 adsorption-desorption
isotherm by The Brunauer–Emmett–Teller (BET) specific surface area
analysis. BET surface area of MMT nanoclay and GO were found to be
14.908 m2/g and 1.1443 m²/g respectively. Both MMT clay and GO
were showing a type IV adsorption according to IUPAC which indicates
the presence mesoporous structure in the material. Both the MMT and
GO have very large pore width and have no significant micro pore area.
After the modification of MMT with PPA, PMMT showed a very high
surface area of 545.53 m²/g with a curve of both types I and type IV
characteristic profile which indicates the presence of the wide range of
pores in the sample which varies from microporic size to mesoporic
range. For PMMT the internal surface was comparatively low when
compared to the external surface area and this was found to be 500 m2/
g. The micropore volume and pore area of PMMT was found to be
Fig. 7. XRD spectra of (a) Graphite, GO,(b)PMMT/rGO, MMT/rGO and AMMT/rGO.
6
Journal of Environmental Chemical Engineering 7 (2019) 103344
0.835 cm2/g and 45.3703 cm³/g respectively and these values were
higher when compared unmodified MMT (14.9 m2/g and 7.269 cm2/g
respectively). The details of the BET surface area analysis of GO, MMT,
PMMT and hydrids are included in the Table 2.
The surface area of hybrids (Fig.11d) exhibit a type IV adsorption
according to IUPAC which indicates mesoporous structure with strong
adsorbent adsorbate interaction [37]. The surface areas of MMT/rGO,
AMMT/rGO and PMMT/rGO were found to be 12.1608 m²/g, 5.9021
m²/g, 50.7709 m²/g and the average pore size are found to be
14.19 nm, 22.61 nm, 6.7 nm respectively. The surface area of the clay/
rGO hybrids were lower than that of clay alone and it may be due to the
presence of reduced GO in the interlayer galleries which may reduce the
available surface area of clay [22,33,37]. The surface area of PMMT/
rGO hybrid is 76% higher than MMT/rGO hybrid and the same trend
was observed for the mesopore volume. This may be due to the increase
in the interlayer distance of modified MMT and the good inter mixing of
both clay and rGO layers.
3.4. Carbon dioxide adsorption analysis
Carbon dioxide adsorption capacities of the PMMT and hybrid
samples were evaluated and the results were shown in the Fig.12. The
results show that all hybrids adsorb carbon dioxide at comparatively
low pressures [ranging from 0 to 900 mmHg]. The large quadruple
moment and polarizability of carbon dioxide help to interact strongly
with the cations of the clay [38]. The resultant high electro static force
of attraction and the large three dimensional pores and pore volume
make the hybrid possible to adsorb comparatively high quantity at
normal atmospheric conditions. Giesting et al. have reported that the
CO2 adsorption mechanism of montmorillonite based on the interaction
of CO2 with H2O present in interlayers of montmorillonite [21].
Even though the specific surface area has an important role in the
adsorption of CO2, the pore size along with the pore volume can in-
fluences the CO2 adsorption behavior of clay and its hybrids [33].
Smaller pores are more favorable in adsorbing the CO2 due to the better
CO2 pore wall interaction especially at low pressures [40]. Surface
functionalities are also play key role especially in oxygen containing
functionalities like carboxylic and hydroxyl groups of rGO due to the
higher electron density around oxygen atom which may lead to the
increase of CO2 interaction [39]. The surface area of PMMT is ten times
higher than the hybrid, the CO2 adsorption capability was observed as
low as 0.217 mmol/g for PMMT when compared to that of PMMT/rGO
hybrid. PMMT/rGO hybrid showed very high CO2 adsorption of about
0.49 mmol/g at low pressure which was higher than MMT/rGO
S. Stanly, et al.
Fig. 8. Raman spectra of (a) GO, (b) PMMT/rGO, (c) MMT/rGO and (d)AMMT/rGO hybrids.
Fig. 9. TGA curves of Graphite, GO and hybrids.
(0.28 mmol/g) and AMMT/rGO (0.204 mmol/g). PMMT/rGO hybrid
showed about 55.7% improvement in its CO2 adsorption capability than
that of PMMT and 42.8% improvement than that of MMT/rGO hybrid.
The presence of unreduced carboxylic groups and ketonic groups at the
plane of the rGO will increase the interlayer distance after the reduction
of GO which favours the higher CO2 adsorption in PMMT/rGO hybrid
[23,41]. It was clear from the SEM and TEM analysis of the hybrids
(Figs. 4 and 5) that the PMMT and PMMT/rGO hybrid was exfoliated
and intercalated to higher extend than MMT/rGO and AMMT/rGO
7
Journal of Environmental Chemical Engineering 7 (2019) 103344
hybrids and it supports CO2 adsorption.
The CO2 adsorption of PMMT is comparable with MMT/rGO and
higher than AMMT/rGO hybrids and it may be due to the presence of
−OH terminating polyphosphoric acid groups. High electron density
around the oxygen atom of −OH group of polyphosphoric acid can
interact and bound CO2 molecules which have high quadruple moment
[23,41]. 42.85% CO2 adsorption by the PMMT/rGO hybrid at com-
paratively low pressure [900 mmHg] is a remarkable result on com-
paring with the CO2 adsorption values reported in the literature
(Table 3).
4. Conclusions
Most suitable and effective hybrids based on clay and reduced
graphene oxide was synthesized and characterized successfully for low
pressure CO2 adsorption. GO was prepared via low temperature mod-
ified Hummer’s method and the hybrids such as MMT/rGO, AMMT
(amino modified MMT)/rGO and PMMT (polyphosphoric acid modified
MMT)/rGO were prepared by in-situ reduction of GO in the presence of
clay via hydrothermal method. The oligomeric polyphosphoric acid
(PPA) increases the interlayer galleries of MMT, which was evident
from XRD, SEM and TEM analyses. All hybrids showed good reduction
of GO and exfoliated structure with pores favorable for CO2 adsorption.
The PMMT hybrid showed a BET surface area of 50.7709 m²/g, which is
higher than that of MMT [12.1608 m²/g], AMMT [5.9021 m²/g] hy-
brids. Generally, the clay/graphene hybrids possess active adsorption
sites for carbon dioxide and the PMMT/rGO hybrid showed a high CO2
adsorption of 0.49 mmol/g at low pressure (900 mmHg). The developed
PMMT/rGO hybrid is an excellent material for the CO2 adsorption and
it can be used for reducing the CO2 level in the atmosphere.
S. Stanly, et al. Journal of Environmental Chemical Engineering 7 (2019) 103344

Fig. 10. TEM and SEM micrographs of GO (a and e), PMMT/rGO (b and f), MMT/rGO (c and g) and AMMT/rGO(d and h).

Fig. 11. BET surface area curves of a) MMT, b) PMMT, c) GO and d) MMT/rGO, PMMT/rGO, AMMT/rGO hybrids.

8
S. Stanly, et al. Journal of Environmental Chemical Engineering 7 (2019) 103344

Table 2 1262–1271, https://doi.org/10.1016/j.apsusc.2015.08.101.

Details of BET surface area analysis of GO, MMT, PMMT and Hybrids. [3] S. Kumar, M.Y. Wani, J. Koh, J.M. Gil, A.J.F.N. Sobral, Carbon dioxide adsorption
and cyclo addition reaction of epoxides using chitosan – graphene oxide nano-
Name BET surf area Pore volume Pore width Micro pore area composite as a catalyst, J. Environ. Sci. China (China) 12 (2017) 1–8, https://doi.
m²/g cm³/g nm cm³/g org/10.1016/j.jes.2017.04.013.
[4] M. Pera-titus, Porous inorganic membranes for CO2 capture : present and prospects,
MMT 14.90 0.061923 16.07 7.2696 Chem. Rev. 114 (2014) 1413–1492, https://doi.org/10.1021/cr400237k.
PMMT 545.5 0.835634 4.84 45.3703 [5] Seul-yi, S. Park, A review on solid adsorbents for carbon dioxide capture, J. Ind.
PMMT/rGO 50.77 0.078786 6.7 18.1933 Eng. Chem. 23 (2015) 1–11, https://doi.org/10.1016/j.jiec.2014.09.001.
MMT/rGO 12.16 0.045687 14.19 * [6] X. Su, L. Bromberg, V. Martis, F. Simeon, T.A. Hatton, Postsynthetic functionali-
zation of Mg-MOF-74 with tetraethylenepentamine: Structural characterization and
AMMT/rGO 5.9021 0.035497 22.61 *
enhanced CO2 adsorption, ACS Appl. Mater. Interfaces 9 (2017) 11299–11306,
GO 1.1443 0.015925 55.47972 *
https://doi.org/10.1021/acsami.7b02471.
[7] D. Tiwari, H. Bhunia, P.K. Bajpai, Synthesis of nitrogen enriched porous carbons
* represent that MMT/rGO, AMMT/rGO and GO have no micro pore area de- from urea formaldehyde resin and their carbon dioxide adsorption capacity, J. CO2
tected using BET. Util. 21 (2017) 302–313, https://doi.org/10.1016/j.jcou.2017.08.002.
[8] L. Valenzano, B. Civalleri, S. Chavan, G.T. Palomino, C.O. Area, S. Bordiga,
Computational and experimental studies on the adsorption of CO, N2, and CO2 on
Mg-MOF-74, J. Phys. Chem. C. 114 (2010) 11185–11191, https://doi.org/10.1021/
jp102574f.
[9] M. Mofarahi, F. Gholipour, Materials Gas adsorption separation of CO2/CH4 system
using zeolite 5A, Microporous Mesoporous Mater. 200 (2014) 1–10, https://doi.
org/10.1016/j.micromeso.2014.08.022.
[10] A. Garcia-gallastegui, D. Iruretagoyena, M. Mokhtar, A.M. Asiri, S.N. Basahel,
S.A. Al-Thabaiti, A.O. Alyoubi, D. Chadwickd, M.S.P. Shaffer, Layered double hy-
droxides supported on multi-walled carbon nanotubes : preparation and CO2 ad-
sorption characteristics, J. Mater. Chem. 22 (2012) 4531–4539, https://doi.org/10.
1039/c2jm00059h.
[11] A. Policicchio, Y. Zhao, Q. Zhong, R.G. Agostino, T.J. Bandosz, Cu-BTC/aminated
graphite oxide composites as high-efficiency CO2 capture media, ACS Appl. Mater.
Interfaces 6 (2014) 101–108, https://doi.org/10.1021/am404952z.
[12] A.A. Alhwaige, H. Ishida, S. Qutubuddin, Carbon aerogels with excellent CO2 ad-
sorption capacity synthesized from clay-reinforced biobased chitosan- poly-
benzoxazine nanocomposites, ACS Sustain. Chem. Eng. 4 (2016) 1286–1295,
https://doi.org/10.1021/acssuschemeng.5b01323.
[13] L. Hauchhum, P. Mahanta, Carbon dioxide adsorption on zeolites and activated
carbon by pressure swing adsorption in a fixed bed, Int. J. Energy Environ. Eng. 5
(2014) 349–356, https://doi.org/10.1007/s40095-014-0131-3.
[14] A. Ganesan, M.M. Shaijumon, Activated graphene-derived porous carbon with ex-
ceptional gas adsorption properties, Microporous Mesoporous Mater. 220 (2015)
21–27, https://doi.org/10.1016/j.micromeso.2015.08.021.
[15] S. Gadipelli, Z.X. Guo, Graphene-based materials: synthesis and gas sorption, sto-
Fig. 12. Carbon dioxide adsorption performance of PMMT, MMT/rGO, PMMT/ rage and separation, J. Prog. Mater. Sci. 69 (2015) 1–60, https://doi.org/10.1016/j.
rGO, AMMT/rGO. pmatsci.2014.10.004.
[16] R. Kumar, V.M. Suresh, T.K. Maji, C.N.R. Rao, Porous graphene frameworks pillared
by organic linkers with tunable surface area and gas storage properties, Chem.
Table 3 Comm. 1 (2017) 2015–2017, https://doi.org/10.1039/c3cc46907g.
Comparison of the CO2 adsorption capacites of different materials reported [17] Y. Chen, D. Lu, CO2 capture by kaolinite and its adsorption mechanism, Appl. Clay
Sci. 104 (2015) 221–228, https://doi.org/10.1016/j.clay.2014.11.036.
with PMMT/rGO.
[18] M. Tahir, N. Saidina, Photocatalytic CO2 reduction by CH4 over montmorillonite
Material CO2 adsorption Pressure Pressure in modified TiO2 nanocomposites in a continuous monolith photoreactor, Appl. Catal.
(mmol/g) mmHga B: Environ. 142–143 (2013) 512–523, https://doi.org/10.1016/j.apcatb.2013.05.
054.
Triply oxidized GO [23] 3.54 900 kPa 6750.554 [19] S. Christine, A. Mana, M.M. Hanafiah, A.J. Khan, Environmental characteristics of
clay and clay-based minerals, Geol. Ecol. Landscapes 9508 (2017) 1–7, https://doi.
Zeolite 13X-K [24] 6.9 20 bar 15,001.2
org/10.1080/24749508.2017.1361128.
MMT [25] 3.6 30 MPa 225018.46
[20] M. Atilhan, S. Atilhan, R. Ullah, B. Anaya, T. Cagin, C.T. Yavuz, S. Aparicio, High-
Amine modified MMT 0.8 8 bar 6000.49
pressure methane, carbon dioxide and nitrogen adsorption on amine-impregnated
[42] porous montmorillonite nanoclays, J. Chem. Eng. Data 61 (2016) 2749–2760,
PMMT/rGO (this work) 0.49 – 900 https://doi.org/10.1021/acs.jced.6b00134.
[21] P. Giesting, S. Guggenheim, A.F. Koster, V. Groos, Interaction of carbon dioxide
a
The authors have converted the reported pressure values to ‘mmHg’ for with Na-exchanged montmorillonite at pressures to 640 bars: Implications for CO2
better comparison with the present results. sequestration, Int. J. Greenh. Gas Control. 8 (2012) 73–81, https://doi.org/10.
1016/j.ijggc.2012.01.011.
[22] A. Garcia-gallastegui, D. Iruretagoyena, V. Gouvea, M. Mokhtar, A.M. Asiri,
Declaration of Competing Interest S.N. Basahel, S.A. Al-thabaiti, A.O. Alyoubi, D. Chadwick, M.S.P. Sha, Graphene
oxide as support for layered double hydroxides: enhancing the CO2 adsorption
There is no conflict of interest to declare. capacity, Chem. Mater. 24 (2012) 4531–4539, https://doi.org/10.1021/
cm3018264.
[23] M. Novacek, O. Jankovsky, J. Luxa, D. Sedmidubsky, M. Pumera, V. Fila, M. Lhotka,
Acknowledgements K. Klimova, S. Matejkovad, Z. Sofer, Tuning of graphene oxide composition by
multiple oxidations for carbon dioxide storage and capture of toxic metals, J. Mater.
Chem. A Mater. Energy Sustain. 5 (2017) 2739–2748, https://doi.org/10.1039/
We gratefully acknowledge IIST, Trivandram for conducting the C6TA03631G.
BET surface area analysis and CO2 adsorption analysis and CAM, [24] V. Garshasbi, M. Jahangiri, M. Anbia, Equilibrium CO2 adsorption on zeolite 13X
CUSAT for avail the facility for XRD analysis. prepared from natural clays, Appl. Surf. Sci. 393 (2017) 225–233, https://doi.org/
10.1016/j.apsusc.2016.09.161.
[25] Q. Wang, L. Huang, Molecular insight into competitive adsorption of methane and
References carbon dioxide in montmorillonite: effect of clay structure and water content, Fuel
239 (2019) 32–43, https://doi.org/10.1016/j.fuel.2018.10.149.
[26] M.K. Kavitha, H. John, P. Gopinath, R. Philip, Synthesis of reduced graphene oxide-
[1] Q. Wang, J. Luo, Z. Zhong, A. Borgna, CO2 capture by solid adsorbents and their
ZnO hybrid with enhanced optical limiting properties, J. Mater. Chem. C Mater.
applications : current status and new trends, Energy Environ. Sci. 4 (2011) 42–55,
Opt. Electron. Devices 1 (2013) 3669–3676, https://doi.org/10.1039/c3tc30323c.
https://doi.org/10.1039/c0ee00064g.
[27] D. Yi, H. Yang, M. Zhao, L. Huang, G. Camino, A. Frache, R. Yang, A novel, low
[2] N. Yang, S. Liu, X. Yang, Molecular simulation of preferential adsorption of CO2
surface charge density, anionically modified montmorillonite for polymer nano-
over CH4 in Na-montmorillonite clay material, Appl. Surf. Sci. 356 (2015)
composites, RSC Adv. 7 (2017) 5980–5988, https://doi.org/10.1039/

9
S. Stanly, et al.
C6RA27562A.
[28] R.L. Anderson, I. Ratcliffe, H.C. Greenwell, P.A. Williams, S. Cliffe, P.V. Coveney,
Clay swelling — a challenge in the oil field, Earth. Rev. 98 (2010) 201–216, https://
doi.org/10.1016/j.earscirev.2009.11.003.
[29] W. Jastrzebsk, M. Sitarz, M. Rokita, K. Bułat, Infrared spectroscopy of different
phosphates structures, Spectrochim. Acta A: Mol. Biomol. Spectrosc. 79 (2011)
722–727, https://doi.org/10.1016/j.saa.2010.08.044.
[30] S. Kittinaovarat, P. Kansomwan, N. Jiratumnukul, Chitosan/modified montmor-
illonite beads and adsorption Reactive Red 120, Appl. Clay Sci. 48 (2010) 87–91,
https://doi.org/10.1016/j.clay.2009.12.017.
[31] A. Bozkurt, M. Ise, K.D. Kreuer, W.H. Meyer, G. Wegner, Proton-conducting
polymer electrolytes based on phosphoric acid, Solid State Ion. 125 (1999)
225–233, https://doi.org/10.1016/S0167-2738(99)00179-4.
[32] N.F. Attia, N.S. Abd El-Aal, M.A. Hassan, Facile synthesis of graphene sheets de-
corated nanoparticles and flammability of their polymer nanocomposites, Polym.
Degrad. Stab. 126 (2016) 65–74, https://doi.org/10.1016/j.polymdegradstab.
2016.01.017.
[33] Z.Y. Sui, B.H. Han, Effect of surface chemistry and textural properties on carbon
dioxide uptake in hydrothermally reduced graphene oxide, Carbon 82 (2015)
590–598, https://doi.org/10.1016/j.carbon.2014.11.014.
[34] N. Hong, L. Song, T.R. Hull, A.A. Stec, B. Wang, Y. Pan, Facile preparation of
graphene supported CO3O4 and NiO for reducing fire hazards of polyamide 6
composites, Mater. Chem. Phys. 142 (2013) 531–538, https://doi.org/10.1016/j.
matchemphys.2013.07.048.
[35] R. Wang, D. Zhuo, Z. Weng, L. Wu, X. Cheng, Y. Zhou, J. Wang, B. Xuan, A novel
nanosilica/graphene oxide hybrid and its flame retarding epoxy resin with si-
multaneously improved mechanical, thermal conductivity, and dielectric
10
Journal of Environmental Chemical Engineering 7 (2019) 103344
properties, J. Mater. Chem. A: Mater. Energy Sustain. 3 (2015) 9826–9836, https://
doi.org/10.1039/c5ta00722d.
[36] J. Zhang, C. Li, Z. Peng, Y. Liu, J. Zhang, Z. Liu, D. Li, 3D free- standing nitrogen-
dopped reduced graphene oxide aerogel as anode material for sodium ion batteries
with enhanced sodium storage, Sci. Rep. 7 (4886) (2017) 1–7, https://doi.org/10.
1038/s41598-017-04958-1.
[37] M.R. Vengatesan, S. Singh, S. Stephen, K. Prasanna, C.W. Lee, V. Mittal, Facile
synthesis of thermally reduced graphene oxide-sepiolite nanohybrid via intercala-
tion and thermal reduction method, Appl. Clay Sci. 135 (2017) 510–515, https://
doi.org/10.1016/j.clay.2016.09.006.
[38] T. Du, X. Fang, L. Liu, J. Shang, B. Zhang, Y. Wei, G. Kevin, An optimal trapdoor
zeolite for exclusive admission of CO2 at industrial carbon capture operating tem-
peratures, Chem. Comm. 54 (2018) 3134–3137, https://doi.org/10.1039/
c8cc00634b.
[39] N. Yang, S. Liu, X. Yang, Applied surface science molecular simulation of pre-
ferential adsorption of CO2 over CH4 in Na-montmorillonite clay material, Appl.
Surf. Sci. 356 (2015) 1262–1271, https://doi.org/10.1016/j.apsusc.2015.08.101.
[40] Y. Liu, J. Wilcox, Effects of surface heterogeneity on the adsorption of CO2 in
Microporous Carbons, Environ. Sci. Technol. 46 (2012) 1940–1947, https://doi.
org/10.1021/es204071g.
[41] A.A. Alhwaige, T. Agag, H. Ishida, S. Qutubuddin, Biobased chitosan hybrid aero-
gels with superior adsorption: Role of graphene oxide in CO2 capture, RSC Adv. 3
(2013) 16011–16020, https://doi.org/10.1039/c3ra42022a.
[42] J. Pires, J. Juźków, M.L. Pinto, Amino acid modified montmorillonite clays as
sustainable materials for carbon dioxide adsorption and separation, Colloids Surf.
A: Physicochem. Eng. Asp. 544 (2018) 105–110, https://doi.org/10.1016/j.
colsurfa.2018.02.019.