Journal of Sol-Gel Science and Technology (2021) 97:382–392

https://doi.org/10.1007/s10971-020-05432-7

ORIGINAL PAPER: SOL-GEL AND HYBRID MATERIALS FOR ENERGY,

ENVIRONMENT AND BUILDING

Modification of MCM-41 type structures by carbon deposition and

acid washing for CO2 adsorption
Diogo P. S. Silva1 Julyane R. S. Solano1 Lenivaldo V. Sousa1 Bruno J. B. Silva
● ● ●
1 ●
Paulo H. L. Quintela2 ●

Antonio O. S. Silva1

Received: 11 July 2020 / Accepted: 20 October 2020 / Published online: 6 November 2020
© Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
A modification of the MCM-41 mesoporous materials through carbon deposition followed by acid washing has been studied
for application in carbon dioxide adsorption. Two routes were used to prepare pure silica (Si-MCM-41) and Al-containing
(Al-MCM-41) samples, through hydrothermal synthesis at 150 °C for 24 h. The post-synthesis treatment took place in two
stages: carbon deposition using commercial glucose, in the mass ratio of 1 g (support): 2.2 g (glucose): 3.5 g (water),
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followed by washing with 0.2 M hydrofluoric acid solution at 65 °C for 2 h. The samples were characterized by X-ray
diffraction, dispersive energy X-ray spectrometry, nitrogen adsorption–desorption, Fourier-transform infrared spectroscopy,
thermal analyzes, and scanning electron microscopy. CO2 adsorption tests were performed on a thermogravimetric balance at
40 °C under atmospheric pressure. Carbon deposition led to a drastic reduction in the surface area and pore volume values of
MCM-41 samples, possibly due to deposits of carbonaceous species blocking part of the mesopores and defect sites in the
pore wall as self-assembled monolayers. After acid washing, part of these deposits was removed, as well as the occurrence of
structural silicon leaching. The post-synthesis treatment allowed the generation of structures with a bimodal pore system,
providing a substantial increase in the CO2 adsorption capacity compared to the as-synthesized mesoporous materials (~66%
for pure silica and 44% for Al-containing MCM-41 sample), representing a significant improvement in the adsorbents
performance for CO2 capture.

Graphical Abstract

Keywords MCM-41 mesoporous material Post-synthesis treatment Carbon deposition Acid washing CO2 adsorption
● ● ● ●

* Bruno J. B. Silva
brunojbarros@hotmail.com
1
Department of Chemical Engineering, Laboratory of Catalyst
Synthesis, Federal University of Alagoas, Maceió 57072-900 AL,
Brazil
2
Department of Chemical Engineering, Federal University of
Sergipe, São Cristóvão 49100-000 SE, Brazil
Journal of Sol-Gel Science and Technology (2021) 97:382–392
Highlights
● Hydrotermal synthesis of the MCM-41 mesoporous materials (pure silica and Al-containing).
● Post-synthesis treatment promotes in generation of structures with a bimodal pore system.
● Post-synthesis treatment results an increase of 44% and 66% in the CO2 adsorption capacity.
1 Introduction
Carbon dioxide (CO2) is an essential compound for the
photosynthesis process, and is undoubtedly of crucial
importance to the maintenance of life on Earth [1]. Despite
this indispensable effect, there is now a consensus that this
gas is the biggest promoter of the “greenhouse effect”
because it allows the passage of sunlight and retains the
radiant heat from the Earth [2]. Due to human activities,
such as burning of fossil fuels and deforestation, the con-
centration of CO2 in the atmosphere has increased drama-
tically since the industrial revolution. Therefore, several
processes have been studied and developed in order to
improve the capture, separation, and storage of this gas
[3–5].
Among the CO2 capture processes, the chemical
absorption using liquid amines stands out, but presents
some disadvantages such as solvent high viscosity and
degradation, regeneration energy requirements, and equip-
ment corrosion [6, 7]. On the other hand, selective gas–solid
adsorption is a more economical approach, as it allows easy
handling without environmental risks and recovery of the
adsorbent material [8].
Studies for obtaining more efficient adsorbents aimed at
CO2 capture have led to the development of various mate-
rials, for applications where both the physical and chemical
adsorption may occur. Among the various adsorbents pro-
duced are silica-based inorganic mesoporous materials, such
as MCM-41, MCM-48, and SBA-15. The interest in these
solids lies in their versatile structures, as they have one- or
three-dimensional pore systems with diameters ranging
from 20 to 100 Å, in addition to high specific surface areas
up to 1500 m2 g−1 [9–11].
The adsorption capacity of these mesoporous adsorbents
can be improved by inserting amino groups on the surface
and incorporating heteroatoms in the structure of such
silica-based materials [12, 13]. These methods have as main
disadvantages the high cost, the generation of amine-
containing wastes and the low adsorption capacity of the
structures with heteroatoms compared to surfaces modified
by amines. Several studies have been carried out with the
perspective of modifying mesoporous materials by depos-
iting carbon on their surface for application in different
adsorption processes, so that this methodology can be pre-
sented as an alternative route for CO2 capture [14–16].
In this context, the present work proposed a surface
modification of MCM-41 mesoporous material, through
383
carbon deposition using glucose as carbon source followed
by an acid washing with hydrofluoric acid, in order to
obtain structures with a bimodal pore system (micro-
mesopores). The samples were evaluated in the CO2
adsorption of under atmospheric pressure at a temperature
of 40 °C.
2 Experimental
2.1 Synthesis of mesoporous materials
2.1.1 Si-MCM-41
The following reagents were used in the synthesis experiment:
cetyltrimethylammonium bromide—CTMABr (Sigma-
Aldrich, 98%), sodium metasilicate (Alfa Aesar, 99%), sulfuric
acid (Sigma-Aldrich, 99%), ethanol (Lafare, 99%) and distilled
water.
Reagents were mixed in order to obtain the following
molar composition: 3.3CH3 CH2OH: 0.2CTMABr: 1SiO2:
1Na2O: 0.9H2SO4: 143H2O. The reaction mixture prepara-
tion was based on the work of Nascimento et al. [17],
consisting of the following steps: (i) dissolution of
CTMABr in ethanol and subsequent addition of 40% of the
total water required for the synthesis (Solution I); (ii)
dilution of sodium metasilicate in 40% of the total water
required (Solution II), and (iii) dilution of sulfuric acid in
the remaining 20% of water (Solution III). Solutions I and II
were mixed and stirred for 30 min, then solution III was
added and the entire mixture was homogenized for 90 min.
The synthesis gel was placed in teflon-coated stainless steel
autoclaves and heated in an oven at 150 °C for 24 h. The
solids were recovered by vacuum filtration, washed with
distilled water to neutral pH, and oven-dried at 80 °C for
24 h (Si-MCM-41-as-synthesized sample). Subsequently,
the material was calcined under 100 mL min−1 air flow and
a heating ramp of 2 °C min−1 at 550 °C for 6 h (Si-MCM-
41-calcined sample).
2.1.2 Al-MCM-41
The same reagents described above were used, with the
addition of aluminum isopropoxide (Sigma-Aldrich, 98%).
The reaction mixture composition was as follows:
3.3CH3CH2OH: 0.2CTMABr: 1SiO2: 0.03Al2O3: 1Na2O:
0.9H2SO4: 143H2O. The preparation procedure of the
384
mixture was based on the study of Silva et al. [18], con-
sisting of the following steps: (i) dilution of sodium meta-
silicate in 40% of the total water required for the synthesis,
with subsequent addition of aluminum isopropoxide in 30%
of the required water (Solution I); (ii) dilution of sulfuric
acid in the remaining 30% of water (Solution II), and (iii)
dissolution of CTMABr in ethanol (Solution III). Solution II
was added dropwise to solution I and kept under stirring for
30 min. Then Solution III was added and the entire mixture
was homogenized for 60 min. Hydrothermal treatment,
separation, washing, drying, and calcination of the solids
were performed under the same conditions as described for
Si-MCM-41. The materials obtained after the drying and
calcination steps were named Al-MCM-41-as-synthesized
and Al-MCM-41-calcined samples, respectively.
2.2 Carbon deposition and acid washing of the
mesoporous materials
Commercial glucose (99%, Êxodo Científica) was used as
carbon source, and the deposition procedure was based on
Wang et al. [16]. The support: glucose: water mass ratios
were of 1:2.2:3.5; thus a support + glucose + water solution
was prepared under stirring and then oven-dried at 90 °C for
12 h. Finally, the were calcined under nitrogen flow of
30 mL min−1, with a heating ramp of 2 °C min−1 at 600 °C
for 1 h (Si-MCM-41-deposited carbon and Al-MCM-41-
deposited carbon samples).
The acid washing was performed using a 0.2 M HF solu-
tion at 65 °C for 2 h while stirring at 300 rpm. In all experi-
ments, the ratio of 1 g of carbon deposited support to 50 mL
of acid solution was used. After the treatment period, the
solids were recovered by centrifugation, washed with distilled
water to neutral pH, and oven-dried at 80 °C for 12 h (Si-
MCM-41-acid treated and Al-MCM-41-acid treated samples).
2.3 Characterization
X-ray diffraction analysis was carried out in a Shimadzu
XRD-6000 diffractometer, with CuKα (λ = 0.1542 nm)
radiation, Ni filter, 40 kV voltage, and 30 mA current. The
data were collected in the 2θ range of 1–10° and 3–40°,
with goniometer speed of 2° min−1 and step of 0.02°. Dis-
persive energy X-ray spectrometry (EDX) was used to
determine the Si/Al ratio of the Al-MCM-41-as-synthesized
sample in a Shimadzu—EDX—7000/8000 spectrometer.
Nitrogen adsorption-desorption measurements at −196 °C
were performed on a Micromeritics ASAP 2020 equipment
in the P/P0 range between 0.01 and 0.99. The surface area
(SBET) was calculated by the BET method, external area
(SExt), micropore area (SMicro) and micropore volume
(VMicro) by the t-plot method. The total pore volume (VPore)
was measured by the amount of N2 adsorbed at a relative
Journal of Sol-Gel Science and Technology (2021) 97:382–392
pressure close to unity (P/P0 = 0.995). The average pore
diameter (DPore) and pore size distribution curves were
determined by BJH method from the N2 desorption iso-
therms branch. FTIR spectra were obtained in a Fourier
transform infrared spectrometer Shimadzu IRTrace-100, in
the region of 400–4000 cm−1. Thermal analyzes were per-
formed in a Shimadzu DTG-60H thermobalance, with
heating rates of 5, 10, and 20 °C min−1 under air atmo-
sphere with a flow rate of 50 mL min−1, from ambient
temperature to 800 °C. The model-free kinetic proposed by
Ozawa–Flynn–Wall [19–21] was used to evaluate the acti-
vation energy (Ea) of glucose degradation in the impreg-
nated samples. The micrographs were obtained on a
Shimadzu Supercan SSX-550 scanning electron microscope
at 10.000 magnifications.
2.4 CO2 adsorption measurements
CO2 adsorption tests were carried out on a Cahn 2000
thermogravimetric balance at 40 °C, under atmospheric
pressure in a fixed bed system. Previously, samples were
treated to remove physisorbed species, under helium flow of
50 mL min−1 at 110 °C for 1 h. Adsorption experiments
were conducted under CO2 flow of 10 mL min−1 for 1 h,
and ~10 mg of sample were used in each analysis. All
adsorption tests were performed in triplicate and average
values are shown. The amount of CO2 adsorbed was
determined using the gravimetric method [22]. This method
is based on the direct quantification of carbon dioxide
adsorbed, which consists of the gas adsorption on the clean
adsorbent followed by the determination of the mass
increase of the material. The adsorption capacity of each
adsorbent was calculated in terms of mass of carbon dioxide
adsorbed per mass of adsorbent (Eq. 1).


nf  ni
q¼  100; ð1Þ
ni
where q is the adsorption capacity (mmolCO2/gadsorbent), ni is
the initial adsorbent number of mmoles, and nf is the final
adsorbent number of mmoles.
3 Results and discussion
3.1 Adsorbents characterization physicochemical
properties
3.1.1 X-ray diffraction and dispersive energy X-ray
spectrometry
The powder X-ray diffraction patterns of the samples are
shown in Fig. 1. As can be seen, the Si-MCM-41-as-syn-
thesized and Al-MCM-41-as-synthesized samples exhibited
Journal of Sol-Gel Science and Technology (2021) 97:382–392
Fig. 1 XRD patterns of the MCM-41 samples
Fig. 2 XRD patterns of the deposited carbon MCM-41 samples with
and commercial glucose
four well-resolved XRD peaks, which can be indexed as
(100), (110), (200), and (210) plans, characteristic of the
hexagonally-ordered mesoporous silica MCM-41 with
P6mm space group [23, 24]. The sample synthesized in the
presence of aluminum showed broader and less intense
diffraction peaks, indicating a less ordered hexagonal array
of pores in this sample in comparison to the Si-MCM-41-as-
synthesized material. After calcination, the peaks shifted to
higher 2θ values due to pore size contraction. Diffracto-
grams of the samples after acid washing demonstrate the
loss of ordering of the materials caused by structural Si
leaching. The XRD patterns illustrated in Fig. 2 show that
no crystalline glucose (JCPDS card n°09-0623) exists in the
silica materials indicating that glucose was well distributed
on the surface of the solids.
The result of the EDX measurements revealed that the
Al-MCM-41-as-synthesized sample had a Si/Al ratio =
385
17.34 ratio, indicating as a result of a partial aluminum
insertion of aluminum in the structure, which corroborates
the XRD result in the XRD for of this material.
Table 1 presents the interplanar distance values (d(100))
and the unit cell parameter (a0) of the materials. Com-
paring the as-synthesized samples, it can be seen that the
introduction of Al into the lattice resulted in a small
increase of d(100) and a0, due to the size difference
between the Al+3 (radius = 53 pm) and Si+4 (radius =
40 pm) ions, causing an expansion in the crystalline reti-
culum and pore size narrowing, as well as a decrease in
the intensity of the diffraction peaks [25, 26]. After cal-
cination (Si-MCM-41-calcined and Al-MCM-41-calcined
samples) both structural parameters increased compared
to the as-synthesized materials, due to removal of the
organic surfactant template and condensation of silanol
groups in the pore walls [27].
3.1.2 Nitrogen adsorption–desorption measurements
N2 adsorption-desorption isotherms are shown in Fig. 3. The
calcined samples presented type IV isotherm profiles, as
expected for the mesoporous molecular sieve MCM-41 con-
taining well-defined cylindrical mesopores. The adsorption
curves exhibited three well-defined stages: (i) a slight increase
in the N2 uptake observed at low relative pressures (P/P0 <
0.25), forming mono- and multilayers on the pore walls; (ii) a
marked inflection at intermediate relative pressures (0.25 < P/
P0 < 0.40), that is related to the capillary condensation occur-
ring within the small mesopores; and (iii) a plateau with a small
inclination at higher relative pressures (P/P0 > 0.4), corre-
sponding to multilayers of N2 adsorbed on the external surface
of the solids. The HI loop hysteresis type observed at relative
pressures between 0.4 and 0.9 is typical of cylindrical shaped
materials with uniform pore size or materials consisting of
spheroidal particle aggregates [28].
The acid treated samples presented type I isotherm pro-
files at relative pressures below 0.02, is related to the pre-
sence of micropores and type IV profiles with a capillary
condensation loop in the range of P/P0 = 0.5–1.0, char-
acteristic of the mesoporous indicating the presence of
mesoporous phase. Isotherms have a HIII loop hysteresis
type observed is usually found on, referring to an aggregate
particle structures with different geometries but uniform
sizes [29].
The textural properties obtained through nitrogen
adsorption-desorption are listed in Table 1. Due to the
removal of the organic template (CTABr), after calcination
there is a reduction in pore diameter values compared to the
as-synthesized materials (Si-MCM-41-as-synthesized =
2.9 nm to Si-MCM-41-calcined = 1.8 nm and Al-MCM41-
as-synthesized = 3.9 nm to Al-MCM-41-calcined =
2.3 nm). The purely siliceous MCM-41 calcined showed a
386 Journal of Sol-Gel Science and Technology (2021) 97:382–392

high area values (SBET = 885 m2 g−1), smaller pore diameter

VMicro /(cm3 g−1) (DPore = 1.8 nm) and pore volume (VPore = 0.72 cm3 g−1)
values, compared to the Al-MCM-41-calcined sample
(SBET = 853 m2 g−1, DPore = 2.3 nm, VPore = 0.83 cm3 g−1).
0.09

0.13
This would be an indication that N2 molecules adsorb more
–
–

–
–
strongly on MCM-41 silica surfaces than the ones on Al-
containing samples. Though, this last may also have been
VPore /(cm3 g−1)

due to changes of the three-dimensional structure of the

purely siliceous MCM-41 with the introduction of Al ions
[30].
0.72
0.43

0.83
0.24
–

The acid treated materials showed a drastic reduction in

surface area (SBET) and pore volume (VPore) values in
SMicro/(m2 g−1)

comparison to the calcined samples (Si-MCM-41-calcined

and Al-MCM-41-calcined). This possibly happened
because deposits of carbonaceous species blocked part of
224

320

the mesoporous and defect sites in the pore walls as self-

–
–

–
–

assembled monolayers, and after acid washing part of these

deposits were degraded together with structural Si leaching,
SExt/(m2 g−1)

resulting in the generation of micropores and a structure

with bimodal pore system (micro-mesopores).
439

91

The BJH pore size distribution curves (Fig. 3) reveal that

–
–

–
–

the calcined materials have similar distribution profiles with

two peaks between 1 and 4 nm. After acid leaching, there
SBET/(m2 g−1)

was a strong reduction in mesoporosity, with the dis-

appearance of the first peak and a decrease of the second
885
663

853
411

peak intensity, possibly due to the generation of micro-

–

porosity in the materials and/or partial blockage of the

mesoporous by carbonaceous residues.
DPore (nm)

3.1.3 Fourier transform infrared (FTIR) spectroscopy

2.9
1.8
2.6
3.9
2.3
2.3

FTIR spectra for the MCM-41 materials are illustrated in

a0b (nm)

Fig. 4. For all samples, bands observed at 1222 and

1075 cm−1 are characteristics of asymmetric Si-O-Si
4.55
5.10

4.64
5.20
–

stretching. The bands observed at 787 and 465 cm−1 are

due to the symmetric Si-O-Si stretching and Si-O-Si
Table 1 Structural and textural properties of MCM-41 samples
d(100)a (nm)

bending, respectively. The broad band around 3500 cm−1

are related to surface silanols groups and adsorbed water
3.94
4.42

4.02
4.51

molecules, indicating the hydrophilicity of the MCM-41

–

Unit cell parameter calculated as a0 = 2dð100Þ = 3.

pffiffiffi

framework [18, 27].

2θ (degrees)

For the as-synthesized samples, the bands at 2925 and

2859 cm−1 refer to the stretching of the CH bonds of the
groups ѵCH(-CH3) and ѵCH(-CH2), respectively, and the
2.25

2.25

band at 1482 cm−1 is associated with deformation of the CH

2
–

2
–

(-CH3) and CH(-CH2) groups [18, 27].

Al-MCM-41- as synthesized

For the calcined samples, the bands at 1482, 2859, and

Si-MCM-41-as synthesized

Si-MCM-41- acid treated

2925 cm−1 disappeared, indicating that the organic template

Al-MCM-41-acid treated
Al-MCM-41- calcined
Si-MCM-41-calcined

Interplanar distance.

was completely removed due to the calcination process. The

band observed at 1639 cm−1 is due to water molecules
stretching, since MCM-41 tends to adsorb moisture upon
contact with air [18, 27]. After glucose deposition, both
Sample

samples (Si-MCM-41-deposited carbon and Al-MCM-41-

deposited carbon) presented bands at 618 and 1456 cm−1,
b
a
Journal of Sol-Gel Science and Technology (2021) 97:382–392
Fig. 3 Nitrogen
adsorption–desorption isotherms
and BJH pore size distribution
curves of the calcined and acid-
treated samples
Fig. 4 FTIR spectra of MCM-41 samples: a as-synthesized, b cal-
cined, c deposited carbon, and d acid treated
referring to vibrations of the C-O and C-C groups, and at
2926 cm−1, attributed to the vibrations of the CH groups
[31]. Acid washing led to the disappearance of the bands
around 618, 1456, and 2926 cm−1, indicating the partial
leaching of the carbon film deposited on the MCM-41
surface.
3.1.4 Thermal analyzes (TG/DTG)
Thermogravimetric (TG) and differential thermogravimetric
(DTG) curves of the as-synthesized samples (Fig. 5)
exhibited basically four major mass loss events: (i) deso-
rption of physisorbed water, in the temperature range from
35 to 125 °C; (ii) surfactant decomposition, between 125
and 325 °C; (iii) decomposition of surfactant residues and
silanol group condensation, from 325 to 425 °C and (iv)
residual silanol condensation, between 425 and 800 °C [32].
387
Figure 6 shows TG and DTG curves of the carbon
deposited MCM-41 samples and pure glucose. Similar
decomposition profiles are observed between the carbon-
containing materials and glucose, with evidence of four
well-distinguished reaction stages: (i) referring to surface
water removal (Si-MCM-41-deposited carbon 30–105 °C,
Al-MCM-41-deposited carbon 30–108 °C, and glucose
30–160 °C), (ii) part of glucose polymerizes with the for-
mation of oligo- and polysaccharides, where this process is
accompanied by the formation of water that evaporates (Si-
MCM-41-deposited carbon 105–409 °C, Al-MCM-41-
deposited carbon 108–397 °C and glucose 160–417 °C),
(iii) residual glucose decomposes with the formation of oxo
and other unidentified compounds, including brown color-
ing matter. The associated polysaccharide and brown col-
oring matter are decomposed, the former becoming
insoluble and the polysaccharide also being converted to
insoluble brown matter (Si-MCM-41-deposited carbon
409–494 °C, Al-MCM-41-deposited carbon 397–668 °C
and glucose 417–600 °C) and (iv) decomposition of the
products formed by the most diverse substances is ignited in
the air (Si-MCM-41-deposited carbon 494–800 °C, Al-
MCM-41-deposited carbon 668–800 °C and glucose
600–800 °C) [33].
The mass loss data from stages (II) and (III), obtained
from the curves in Fig. 6, were converted into conversions
data before being submitted to kinetics treatment by
Ozawa–Flynn–Wall model. Assuming that the total mass
loss corresponds to 100% of conversion, thus the mass
losses in temperature are smaller normalized in relation to
total mass loss originating the curve of conversion. Figure 7
presents a set of conversion curves of the glucose degra-
dation and the plots of the logarithms of the heating rates
against the reciprocals of the corresponding values of the
absolute temperatures that produce straight lines, whose
slope is proportional to the activation energy (Ea). The
388
Fig. 5 TG/DTG curves: a Si-
MCM-41-as-synthesized and b
Al-MCM-41-as-synthesized
samples
Fig. 6 TG/DTG curves: a Si-MCM-41-deposited carbon, b Al-MCM-41-deposited carbon and c commercial glucose
average Ea values obtained were Ea = 147 kJ mol−1 for Si-
MCM-41-deposited carbon and Ea = 145 kJ mol−1 for Al-
MCM-41-deposited carbon, indicating a similar surface
interaction between glucose and both MCM-41 materials.
3.1.5 Scanning electron microscopy
Figure 8 shows the micrographs of the MCM-41 samples.
Both calcined materials (Fig. 8a, d) consist of aggregate
Journal of Sol-Gel Science and Technology (2021) 97:382–392
structures of spherical particles smaller than 1 µm. After
glucose deposition and carbonization (Fig. 8b, e), there was
a change in morphological characteristics of these materials,
with the emergence of an interparticle amorphous phase,
which was partially removed after acid washing (Fig. 8c, f),
generating aggregate structures with irregular particles,
denoting a direct effect of post-synthesis treatment, not only
in the removal of the superficial carbon film but as of
structural Si.
Journal of Sol-Gel Science and Technology (2021) 97:382–392 389

Fig. 7 Conversion and fitting

curves: a, b Si-MCM-41-
deposited carbon—R2 =
0.93–1.00, c, d Al-MCM-41-
deposited carbon—R2 =
0.90–1.00

Fig. 8 Micrographs of MCM-41 samples: a Si-MCM-41-calcined, b Si-MCM-41- deposited carbon, c Si-MCM-41-acid treated, d Al-MCM-41-
calcined, e Al-MCM-41-deposited carbon and f Al-MCM-41-acid treated

MCM-41-calcined = 0.30 mmol g−1), and this low

3.2 CO2 adsorption measurements
The CO2 adsorption isotherms are shown in Fig. 9. The
calcined samples had very similar adsorption capacity
values (Si-MCM-41-calcined = 0.33 mmol g−1 and Al-
adsorption can be attributed to the weak interaction between
the surface of the calcined MCM-41 materials and the CO2
molecules [34]. Santos et al. [35] measured the CO2
adsorption on MCM-41 (SBET = 856 m2 g−1, VPore =
0.95 cm3 g−1 and DP = 2.7 nm) at 1 bar and 30 °C, reporting
390
Fig. 9 CO2 adsorption isotherms of different MCM-41 samples at
40 °C
an adsorption capacity of 0.5 mmol g−1. Rao et al. [36]
describe that the unmodified MCM-41 (SBET = 992 m2 g−1
and VPore = 0.691 cm3 g−1) provided an adsorption capacity
of 0.75 mmol g−1 at 25 °C and 1 atm. Uyen et al. [37]
obtained an approximate adsorption capacity value of
0.25 mmol g−1, at 40 °C and atmospheric pressure, for the
unmodified MCM-41 (SBET = 985 m2 g−1, VPore =
3 −1
0.707 cm g , and DP = 2.87 nm). The difference in the
adsorption capacity values reported in our study and in the
literature can be related to variations in the textural
properties of the materials (which directly affect the
transport of CO2 molecules), accessibility and number of
basic sites in the structure. Furthermore, the CO2
adsorption is an exothermic process that involves dynamic
and thermodynamic phenomena, being favored by lower
temperatures [38].
The carbon deposition on the MCM-41 materials led to
different performances in CO2 adsorption. The pure silica
samples exhibited a small increase in the CO2 adsorption
capacity, from 0.33 mmol g−1 (Si-MCM-41-calcined) to
0.36 mmol g−1 (Si-MCM-41-deposited carbon), indicating a
low affinity of the adsorbate for the carbon layer. On the
other hand, the Al-containing solids showed a significant
increase in CO2 adsorption after carbon deposition, from
0.30 mmol g−1 (Al-MCM-41-calcined) to 0.42 mmol g−1
(Al-MCM-41-deposited carbon). This is possibly due to the
blocking of acidic sites generated by the Al atoms, which
reduced the repulsion between the surface of the solid and
the CO2 molecules and thus increased the adsorption
capacity.
After acid washing the opposite behavior was observed.
The small change in the adsorption capacity of Al-containing
samples between the steps of carbon deposition and acid
treatment (Al-MCM-41-deposited carbon = 0.42 mmol g−1 to
Al-MCM-41-acid treated = 0.44 mmol g−1). This fact is
probably the result of a greater availability of acidic sites
Journal of Sol-Gel Science and Technology (2021) 97:382–392
caused by acid leaching of carbonaceous species, leading to a
decrease in CO2 adsorption. In contrast, the performance of
the pure silica materials increased significantly between these
steps, with Si-MCM-41-deposited carbon = 0.36 mmol g−1 to
Si-MCM-41-acid treated = 0.55 mmol g−1. This difference
can be attributed to the significant increase in the values of
external surface area and pore volume for the Si-MCM-41-
acid treated sample.
The changes in the CO2 adsorption behavior of the acid-
treated MCM-41 materials compared to the calcined sam-
ples may be related to the formation of adsorbate multi-
layers, capillary condensation in the mesopores and
micropores filling. The adsorption capacity was increased
by 66% (0.33–0.55 mmol g−1) for the pure silica MCM-41
and 44% (0.3–0.44 mmol g−1) for the Al-containing mate-
rial, representing a significant improvement in the perfor-
mance of the adsorbents for CO2.
The impregnation of organic amines on a mesoporous
support promotes a greater increase in adsorption capacity,
due to acid-base interactions/affinity between CO2 and the
immobilized amino groups on the external surface and
inside the pores of the adsorbent [12, 35, 36, 39, 40].
However, these organic groups are not stable at high tem-
peratures and start to decompose at 200 °C, limiting the
application of such mesoporous materials as recyclable
adsorbents that require high regeneration temperatures [41].
In this context, the micro-mesoporous structures generated
from carbon deposition and acid washing can represent an
alternative way to produce adsorbents with high thermal
stability and CO2 adsorption capacity, which are suitable for
application in cyclical separation processes for carbon
dioxide capture.
4 Conclusions
The characterization techniques showed that the as-
synthesized samples presented the characteristic properties
of the hexagonally-ordered silica MCM-41 mesostructure.
The post-synthesis treatment (carbon deposition and acid
washing) led to a loss of structural ordering in the materials,
causing a drastic reduction in surface area and pore volume
values, resulting in the generation of structures with bimo-
dal pore system (micro-mesopores).
The secondary porosity created by the treatment pro-
vided a significant increase in the CO2 adsorption capacity
when comparing calcined parents samples (Si-MCM-41-
calcined = 0.33 mmol g−1, Al-MCM-41-calcined =
0.3 mmol g−1) and modified samples (Si-MCM-41-acid
treated = 0.55 mmol g−1, Al-MCM-41-acid treated =
0.44 mmol g−1), which demonstrates the efficiency of the
methodology in improving the performance of MCM-41
material in CO2 adsorption.
Journal of Sol-Gel Science and Technology (2021) 97:382–392
Acknowledgements The authors are grateful for the financial support
of the Conselho Nacional de Desenvolvimento Científico e Tecnoló-
gico (CNPq), through a research grant and to CENPES/PETROBRAS
and ANP for the financial support.
Compliance with ethical standards
Conflict of interest The authors declare that they have no conflict of
interest.
Publisher’s note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.
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