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Mesoporous TiO2 as the support of

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tetraethylenepentamine for CO2 capture from simulated

Cite this: RSC Adv., 2013, 3, 23785
flue gas
Fujiao Song, Qin Zhong,* Jie Ding, Yunxia Zhao and Yunfei Bu

Received 15th June 2013
Accepted 1st October 2013
DOI: 10.1039/c3ra42998a
www.rsc.org/advances
Mesoporous TiO2 (MT) was prepared by a hydrothermal method and used as the supporting material for
the immobilization of tetraethylenepentamine (TEPA) to develop a new type of adsorbent for CO2 capture
from flue gas. The CO2 adsorption capacity increases with the increase of the TEPA loading amounts. With
the maximum TEPA loading of 31 wt% onto the MT sorbent, the maximum CO2 adsorption capacity
reached 2.52 mmol of CO2 g 1 of sorbent. In the presence of an appropriate amount of water vapor,
the formation of bicarbonate and hydroxylated surface on TiO2 can improve CO2 adsorption capacity
1
from 2.64 to 2.91 mmol g . However, an excess of water vapor leads to a decrease in the CO2
1
adsorption capacity from 2.91 to 2.65 mmol g , probably attributed to the adsorption competition
between water and CO2. The absorption/regeneration cycle was repeated and the CO2 adsorption
1
capacity decreased from 2.52 to 2.41 mmol g over 5 cycles, almost completely maintained its original
CO2 adsorption capacity. In addition, the effect of long-term storage on CO2 adsorption capacity is
studied. After approximately one year of storage, the CO2 capacity of the MT–TEPA-31 decreased by
28% compared with the fresh sample.

1. Introduction ammonium carbamates and/or carbonates during CO2

Concern over the potential impact of CO2 emissions due to
combustion of fossil fuels on global climate change has
spawned numerous efforts to reduce CO2. One way to reduce
CO2 emissions to the atmosphere is carbon capture and
sequestration (CCS). In this scheme, CO2 is captured from
power plant emissions, and sequestered underground in
geological structures for long periods of time. In the past two
decades, various CCS technologies, such as absorption,1–3
membrane separation,4,5 and adsorbents for adsorption,6–8 have
been employed for the separation and recovery of CO2 emitted
from power plants.
Different materials have been used for CO2 absorption.
Among them, amine solutions and ionic liquids9–11 show
excellent properties. However, absorption process has several
negative attributes that have hindered their scale-up, including
the large amount of energy for the regeneration of the used
solutions, equipment corrosion, and degradation of amine
solutions in the presence of oxygen. This will enhance the cost
of electricity by 80% dramatically.
Amino-modied mesoporous materials, including siliceous
and non-siliceous mesoporous materials, are potential adsor-
bents for capturing CO2 due to the reversible formation of
School of Chemical Engineering, Nanjing University of Science and Technology,
Nanjing 210094, PR China. E-mail: zq304@mail.njust.edu.cn; Fax: +86 025
84315517; Tel: +86 025 84315517
adsorption, as well as due to their uniform, large pore, and high
surface area. Recently, many research groups have investigated
the adsorption of CO2 on amino-modied mesoporous silicas
and mesoporous carbons. For example, Feng12 and co-workers
prepared tetraethylenepentamine (TEPA)-modied meso-
celullar silica foam (MCF) and studied their CO2 adsorption
properties. Zhou13 and co-workers synthesized ordered meso-
porous carbon molecular sieve and investigated adsorption
selectivity of CO2 over CH4. Song14 and co-workers reported that
the initial adsorption rate constant k0 increased obviously aer
TiO2 nanotubes were impregnated by TEPA, which conrmed
that aqueous TEPA would be superior kinetically.
Since Antonelli and Ying15 reported a modied sol–gel
synthesis of hexagonally packed mesoporous TiO2 (M-TiO2) in
1995, M-TiO2 has been paid much attention due to its high
specic surface area and porosity, and is widely used in the
elds of photocatalysis,16–19 highly specic chemical
sensors,20–23 catalyst support24,25 and solarcells.26–28 In addition,
M-TiO2 show exciting prospects for the adsorption of heavy
metal ions because of their high specic surface area and large
pore systems. León and co-workers29 investigated the adsorp-
tion of Ru-bpy dyes on mesoporous TiO2 lms and demonstrate
the adsorption force between them.
However, are mesoporous TiO2 appropriate for CO2 capture?
In this paper, CO2 adsorbents based on mesoporous TiO2 with
different TEPA loadings were developed and tested for CO2
capture. The physicochemical properties of raw and TEPA

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modied mesoporous TiO2 were studied. Effects of temperature
and water content in air on CO2 adsorption are also conducted
and discussed.
2. Experimental
2.1. Preparation of titanium-based adsorbents
The mesoporous TiO2 (MT) was prepared by hydrothermal
method.30,31 First, cetyltrimethyl ammonium bromide (CTAB,
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under the nitrogen ow, the simulated ue gas (15 vol% CO2 in
N2) was introduced at the desired ow rate of 40 mL min 1. The
concentration of CO2 in the effluent was monitored by online
GC at an interval of 0.5 min. Aer the sorbent was saturated, the
simulated ue gas was changed back to the nitrogen gas, and
simultaneously the sorbent bed temperature was increased to
100  C and held at this temperature for 1 h to perform the
desorption. The sorption capacity of CO2 was calculated based
on the breakthrough curve, which is described in our previous

3.98 g) was dissolved in anhydrous ethanol (16 g), and then study.
tetra-n-butyl titanate (TBOT, 11.93 g) was added into the solu-
tion at room temperature under stirring for 1 h, and a homo-
geneous transparent solution was obtained. Aer that, the pH 3. Results and discussion
of the solution was adjusted to 11 by using NaOH solution 3.1. Characterization
(1 mol L 1). The resulting solution was transferred into a
3.1.1. XRD analysis. The wide-angle XRD patterns of the
Teon-lined autoclave and aged at 100  C for 12 h. The
obtained MT-raw and TEPA-loaded MT are presented in Fig. 1.
precipitate was ltered, washed with distilled water, and dried
The main diffraction peaks are indexed as the (101), (004), (200),
at 100  C for 12 h. The dried sample was calcined at 350  C for
(105), (211), (204) and (116) reections of crystalline anatase
10 h, obtained mesoporous TiO2 sieve, designated as MT.
phase, corresponding to those shown in the JCPDS card no. 21-
1272.33,34 No reections of rutile and brookite phases are
2.2. Modication with TEPA observed in the prepared MT-raw. Aer MT was modied with
Mesoporous adsorbents were prepared by impregnation TEPA, the major peaks of MT-raw were almost replicated and no
method. Firstly, different amounts of TEPA were dissolved in 20 obvious change was observed.
mL water at room temperature, respectively. Aer stirring for 3.1.2. IR analysis. The FT-IR spectra of the MT-raw and MT
0.5 h, 2.0 g MT was added into the solution under stirring for 6 supported TEPA sorbents are shown in Fig. 2 to obtain further
h, were then dried in a natural convection oven at 80  C for 4 h, information about their nature. It can be seen that the defor-
to obtain TEPA-loaded titanium-based adsorbents. We denoted mation and stretching vibrations of the OH group of phys-
the sorbents as MT–TEPA-n, and “n” was related to the mass isorbed water at 1624 and 3426 cm 1 are present in the IR
ratio of the amine loaded onto the support. For instance, when spectrum of MT-raw. Because of the strong interaction between
0.5 g TEPA was loaded onto 2.0 g mesoporous TiO2, the adsor- Ti ions and OH groups within the tubular structure, a shoulder
bent was denoted as MT–TEPA-25. at 3200 cm 1 from Ti–OH bonds was observed. It conrmed
that not only Ti–OH bonds exist within the tubular structure but
2.3. Characterization of the samples also some physisorbed water exists on the MT surface.35 The
broad peak at 470 cm 1 is caused by stretching vibrations of the
The crystallite structures of materials synthesized were investi-
Ti–O–Ti bonds.14
gated by analyzing the X-ray powder diffraction (XRD) patterns
In the IR spectrum of MT–TEPA, major peaks of MT-raw are
obtained with a Bruker D8 Advance X-ray diffraction equipped
almost replicated, but the location of the peaks shis slightly.
with Cu Ka irradiation and a xed powder source (35 kV,
The stretching vibrations of C–H bonds are present at 2936 and
20 mA). The specic surface area and pore size distribution were
2834 cm 1. The peaks of N–H bonds and C–N bonds are present
determined by surface area and pore porosimetry analyzer (V-
Sorbet 2008S). The sample was in vacuum at 100  C prior for 5 h
to measurement. And then the sample was measured by using
N2 adsorption at 196  C. The morphologies of the materials
were synthesized were investigated by using transmission
electron microscopy (TEM, JEM-2100). Infrared (IR) spectra
were recorded on a MB154S-FTIR spectrometer (Bomem, Can-
ada). The samples were measured in the form of KBr pellets.

2.4. Adsorption of carbon dioxide

The CO2 adsorption performance of some samples from a
simulated ue gas was also investigated in a xed-bed ow
sorption system.32 The experimental procedure was same for all
of the samples. Prior to the adsorption, 1.5 g adsorbent (40–60
mesh powder) was added in a U-bend tube, then an initial
drying step was operated in nitrogen at 100  C for 30 minutes to
remove any moisture or pre-adsorbed CO2 from the sample,
followed by cooling to the adsorption temperature of 60  C Fig. 1 XRD patterns of MT-raw and TEPA-loaded MT.

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Fig. 2 IR spectrum of MT-raw and MT–TEPA-n.
at 1554 and 1405 cm 1 respectively, indicating an interaction
between the basic –NH2 groups on TEPA and the acidic sites on
the MT support, such as Ti–OH bonds. Therefore, TEPA is
loaded into the pore channels of the MT support.
3.1.3. TEM analysis. The TEM images of adsorbents are
shown in Fig. 3. The obtained MT-raw samples consist of the
aggregation of nanoparticles, which possess an irregular
spherical morphology with sizes of 25–40 nm in the TEM image
shown in Fig. 3(a) and (b). Porous structure with pore size of
2–4 nm can be observed clearly, and disordered channels are
packed randomly forming a three-dimensional mesoporous
framework.36 TEPA-modied MT samples are shown in Fig. 3(c)
and (d). There is no obvious change in morphology, but the
Fig. 3 TEM images of mesoporous TiO2 (a), (b) and TEPA-impregnated MT (c), (d).
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samples get slightly larger in size. It was possibly caused by the
amine loaded onto MT particles.
3.1.4. BET analysis. Physical properties of the test sorbents
are listed in Table 1. The surface area of MT support is 159.16 m2
g 1, the pore volume is 0.31 cm3 g 1, and the pore diameter is
5.59 nm. Aer the MT support was modied with TEPA, the
surface area, pore volume and pore diameter became lower and
they decreased with the increase of the amount of TEPA loaded. It
conrms that TEPA is loaded into pore channels of the MT
support, which is consistent with IR and TEM analysis.
3.2. CO2 adsorption
3.2.1. Effect of TEPA loading amount on CO2 adsorption.
The TEPA loading can greatly affect the CO2 adsorption capacity
of the prepared sorbents because CO2 can be xed by amine
groups on TEPA.37,38 Aer the MT support was modied with
TEPA, all the other sorbents maintained the original state of dry
powders, while the sample MT–TEPA-40 showed a sticky state,
conrming that 40% was an excessive amount of loading. To
investigate the optimum TEPA loading amount, adsorption
experiments of sorbents were carried out at 60  C. The results of
experiments are given in Fig. 4. It can be seen that, the CO2
adsorption capacity increases with the increase of the TEPA
loading amounts. The sample MT–TEPA-31 reached the
maximal CO2 adsorption capacity of 2.52 mmol of CO2 g 1 of
sorbent.
The adsorption capacities of MT–TEPA-31 and other TEPA-
related materials39–43 from some literature are listed in Table 2.
As shown in Table 2, the adsorption capacities range from 0.68
mmol g 1 to 3.56 mmol g 1 and the performance of MT–TEPA-
31 is in the upper middle.
3.2.2. Effect of water vapor content on CO2 adsorption
from a simulated ue gas. There is 5–7% water vapor in ue gas
which may signicantly inuence the performance of CO2
capture. Liu found that CO2 adsorption on the Ni/DOBDC was
limited in the presence of trace amounts of water since water
molecules compete with CO2 for the adsorption sites.44
However, Wang reported that moisture addition in the ue gas
promoted the CO2 adsorption over the TEPA(50)/Ben_H2-
SO4_6M sorbents, which could be due to the formation of
bicarbonate with an ideal amine efficiency of 1 under a wet
condition, rather than carbamate with an ideal amine efficiency
of 0.5 under a dry condition.45 In addition, Yu concluded that
whether the water promote or limit CO2 adsorption on MOFs
with CUMs (coordinatively unsaturated metal sites) mainly
depend on the competition of the binding energies between
CO2/CUM and CO2/coordinated water.46 In this work, CO2
adsorption experiments of MT–TEPA-31 in the presence of
water vapor were carried out at 60  C to study the effects of water
on CO2 adsorption. The water vapor was generated by a ask
lled with 100 mL water in the water bath at different temper-
atures. The results of experiments are given in Fig. 5. It was
obvious that the adsorption capacity increased signicantly
from 2.64 to 2.91 mmol g 1 as the bath temperature increased
from 40 to 60  C due to the formation of bicarbonate mentioned
above. In addition, coordinatively unsaturated TiO2 can
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Table 1 Characterization details of the mesoporous TiO2 and TEPA-impregnated MT

Surface area Pore volume Pore diameter Adsorption capacity

Samples (BET) (m2 g 1) (cm3 g 1) (BJH) (nm) (mmol g 1)

MT-raw 159.16 0.31 5.59 0.84

MT–TEPA-11 101.21 0.22 4.98 1.67
MT–TEPA-24 48.62 0.16 4.64 1.92
MT–TEPA-31 14.47 0.11 4.12 2.52
MT–TEPA-40 10.21 0.06 3.48 2.17
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Fig. 4 Breakthrough curves of CO2 on MT-raw and MT–TEPA-n.

Fig. 5 Effect of water vapor generated at different temperatures on CO2

adsorption of MT–TEPA-31.
Table 2 TEPA-related materials for CO2 capture from literature and our work

T p p Capacity
Material ( C) (bar) CO2 (bar) (mmol g 1) Reference 3.3. Cycle test and stability toward storage
Fig. 6 depicts adsorption–desorption cycles for MT–TEPA-31.
MCM-48 25 1 1 0.68 39
MCM-41 25 1 1 0.90 39 The absorption–regeneration cycle was repeated for a total of 5
Beta zeolite 30 1 0.1 2.07 40 cycles. The adsorption was conducted at 60  C and regeneration
KIT-6 60 1 0.1 2.90 41 was performed at 100  C under 100% N2. The CO2 adsorption
SBA-15 75 1 1 3.36 42 capacity decreased from 2.52 to 2.41 mmol g 1 over 5
CNTs 40 1 0.02 3.56 43
Mesoporous TiO2 60 1 0.15 2.52 This work

coordinate with water and generate bridging and terminal

hydroxyl groups,47 and terminal hydroxyl groups are alkaline,
which can improve CO2 capture. However, the adsorption
capacity began to decrease from 2.91 to 2.65 mmol g 1 as the
bath temperature further increased from 60 to 80  C. It is
because that water molecules take up those specic adsorption
sites for CO2 molecules in the adsorbents.
Other strong acidic gases in ue gas such as SO2 and NOx
also have obvious effect on CO2 adsorption performance
because their strong acidity competes with CO2 for the
adsorption sites. It was reported that the coadsorbed acidic SO2
and NO2 can cause the degradation of amine-based sorbents
due to the formation of the heat-stable and irreversible amine
salts.48,49 Therefore, the strong acidic gases should be removed
prior to CO2 capture by amine-based sorbents from ue gas. Fig. 6 Adsorption–desorption behavior of MT–TEPA-31.

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Fig. 7 Breakthrough curves of CO2 on fresh and aged MT–TEPA-31.
adsorption–desorption cycles, almost completely maintained
its original CO2 adsorption capacity.
The lifetime of adsorbents is a key property of equal
importance as adsorption capacity, with direct impact on the
economics of commercial-scale operations. How about the
stability of the supported amine on mesoporous TiO2? Yu50 and
co-workers reported that the rst weight loss of mesoporous
TiO2 in the range 25–200  C was attributed to the loss of ethanol
and adsorbed water and hydroxyl groups linked to titanium
would not decompose at 200  C, which conrmed that meso-
porous TiO2 had good thermal stability. Song37 and co-workers
demonstrated that the TEPA loaded onto TiO2 nanotubes
decomposed from 200–600  C. Therefore, the supported amine
on mesoporous TiO2 also process a good thermal stability at the
range of 25–200  C.
MT–TEPA-31 was investigated to determine whether they
lose CO2 capacity over time with storage. CO2 breakthrough
curves were measured and shown in Fig. 7 compare the
capacities of fresh sample and aged sample which had been
stored in sealed containers for approximately one year. Even
though the sample had been stored in a desiccator, the CO2
capacity of the aged MT–TEPA-31 decreased from 2.52 to 1.81
mmol g 1, decreasing by approximately 28% compared with the
fresh sample. A longer storage time may lead to a larger
decrease in the CO2 adsorption capacity. Therefore, the MT–
TEPA-31 adsorbent cannot maintain a good chemical stability
over longtime storage.
4. Conclusions
A new type of adsorbent has been developed using mesoporous
TiO2 as the supporting material for the immobilization of
TEPA to capture CO2 from ue gas. With a maximal TEPA loading
of 31 wt%, the adsorption capacity can reach as high as 2.52
mmol of CO2 g 1 of sorbent. With appropriate amount of water
vapor addition in the ue gas, CO2 adsorption capacity can be
improved from 2.64 to 2.91 mmol g 1 due to the formation of
bicarbonate and hydroxylated surface on TiO2. However, an
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excess of water vapor can lead to a decrease in the CO2 adsorption
capacity from 2.91 to 2.65 mmol g 1 because of the competition
between water and CO2. Moreover, the MT–TEPA-31sorbents
show a good regeneration in 5 absorption–regeneration cycles.
The considerable CO2 adsorption capacity, positive effect of
moisture, and good regenerability suggest that TEPA modied
mesoporous TiO2 could be a promising cost-effective adsorbent
for CO2 capture from ue gas.
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