Accepted Manuscript

Title: CO2 capture and adsorption kinetic study of

amine-modified MIL-101 (Cr)

Authors: Suresh Mutyala, Madhavi Jonnalagadda, Harisekhar

Mitta, Raveendra Gundeboyina

PII: S0263-8762(19)30030-9
DOI: https://doi.org/10.1016/j.cherd.2019.01.020
Reference: CHERD 3497

To appear in:

Received date: 26 October 2018

Revised date: 14 January 2019
Accepted date: 22 January 2019

Please cite this article as: Mutyala S, Jonnalagadda M, Mitta H, Gundeboyina R,

CO2 capture and adsorption kinetic study of amine-modified MIL-101 (Cr), Chemical
Engineering Research and Design (2019), https://doi.org/10.1016/j.cherd.2019.01.020

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CO2 capture and adsorption kinetic study of amine-modified MIL-101 (Cr)

Suresh Mutyala a *, Madhavi Jonnalagadda b, Harisekhar Mitta c, Raveendra Gundeboyina b

a
Department of Chemistry and Key Laboratory for Preparation and Application of Ordered

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Structural Materials of Guangdong Province, Shantou University, Guangdong 515063 (China).
b
Inorganic and Physical Chemistry Division, Indian Institute of Chemical Technology, Hyderabad
– 500007, India.

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c
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of

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Sciences, Dalian 116023, China.

Corresponding author. Tel.: +86-754-86503786, E-mail address: suresh@stu.edu.cn,

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sureshm186@gmail.com
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Research highlights
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 MIL-101 (Cr) was modified with polyethylenimine by wet impregnation method.

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 High adsorption capacity 3.81 mmol g-1 was obtained on MIL-101 (Cr)-PEI-70.

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CO2 adsorption capacity increased in moisture condition.

 No loss of adsorption capacity in adsorption-desorption cycles.
 The adsorption process was chemical adsorption by Avrami kinetic model.
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Abstract
MIL-101 (Cr) was synthesized by a hydrothermal method and used as support to prepare a
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series of polyethylenimine (PEI) incorporated MIL-101 (Cr) by wet impregnation method. All
characterization results revealed that the structure of MIL-101 (Cr) was well-maintained by the
incorporation of polyethylenimine and confirmed the presence of PEI within MIL-101 (Cr). The
CO2 adsorption studies were carried out in a fixed bed reactor from 30 – 90 °C, 1 bar. The
adsorption of CO2 has been increased by the incorporation of PEI. It was due to the chemical

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interaction between the –NH2 and CO2 groups to form a carbamate. The high CO2 adsorption
capacity 3.81 mmol g-1 was shown by 70wt% PEI loaded MIL-101 (Cr) at 75 °C, 1 bar, because
of more number of –NH2 groups and a high number of CO2 molecules diffusion. Its adsorption
capacity was 4.7 times higher than the adsorption capacity of MIL-101 (Cr) (0.80 mmol g-1).
Moreover, in moisture condition, CO2 adsorption capacity was increased to 4.4 mmol g-1 by the
formation of ammonium bicarbonate and showed good adsorption stability throughout each

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adsorption-desorption cycle. The Avrami adsorption kinetic model was well fitted with
experimental breakthrough CO2 adsorption data of MIL-101 (Cr)-PEI-70. It suggested that the

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adsorption of CO2 on PEI incorporated material was chemical adsorption.

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Keywords:
MIL-101 (Cr); Polyethylenimine; CO2 capture; Fixed bed reactor; Adsorption kinetic models.

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1. Introduction N
Global warming is one of the environmental issues caused by the liberation of carbon
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dioxide which is produced by the consumption of fossil fuel, high growth of petrochemical,
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automobile industries, and power plants (Wang et al., 2016). It has a major impact on the
atmosphere. So, there is a need to reduce the concentration of CO2. Conventional technology for
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CO2 capture and separation (CCS) is absorption using liquid amines such as monoethanolamine
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and diethanolamine (Kim et al., 2016). But, high energy is required for the regeneration and
corrosion of the pipeline. Membrane separation has a high cost of design and synthesis (Brunetti
et al., 2010). Finally, the most convenient method for CCS is adsorption (Webley, 2014). It needs
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less energy for the regeneration and no equipment corrosion. So far, mostly used adsorbents for
CCS are activated carbon (Guo et al., 2006), carbon nanotubes (Cinke et al., 2003), Zeolites (Cho
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et al., 2015), alkaline based adsorbents (Bang et al., 2014), polymers (Zhao et al., 2016) and
mesoporous silica materials (Li et al., 2015).
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From last few decades, metal-organic frameworks (MOFs) are using in various fields such
as catalysis (Nguyen et al., 2015), gas adsorption and separation (Rada et al., 2015), drug delivery
(Della Rocca et al., 2011) and optical property studies (Liu et al., 2014) which are synthesized by
a combination of metal ion/cluster and an organic ligand (Sánchez-Sánchez et al., 2015). MOFs
have well-ordered crystallinity, high porosity, and tunable pore size. In 2005, Ferey et al have

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synthesized MIL-101 (Cr) by a hydrothermal method. It has high crystallinity with pentagonal and
hexagonal windows in the range from 20 – 45 A°, moisture, chemical and thermally stable (Férey
et al., 2005). Carbon dioxide is acidic in nature. Basic nature of the MOF is useful for the
adsorption of CO2. It can be obtained by the surface modification of MOF using amines by two
approaches. One is the utilization of amine-based ligands in the synthesis of MOF. Couck et al
have synthesized amine functionalized MIL-53 (Al) using 2-Amino terephthalic acid as a ligand

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has shown high adsorption of CO2 (Ge et al., 2016). Another approach is a post-synthetic
modification of the MOF by impregnation method. In this method, amine occupies the pores of

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the MOF, a high number of free amine groups are available which are effective to interact with
CO2 groups and can show high adsorption capacity (Fu et al., 2017).

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Polyethylenimine is one of the polyamines having a large number of amine groups. It was
first used by Satyapal et al for the removal of CO2 in space air crafts (Satyapal et al., 2001). To

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enhance adsorption capacity of this polymer, Song et al first developed a “molecular basket”

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method for the incorporation of PEI on MCM-41 has shown CO2 adsorption capacity of 3.0 mmol
g-1 at 75 °C, 1 bar (Ma et al., 2009). Later, some research groups have implemented the same
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method for the incorporation of PEI over the supports such as mesoporous carbon and KIT-6 to
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study CO2 adsorption (Kishor and Ghoshal, 2016; Wang et al., 2013a). Lin et al have studied CO2
adsorption on linear and branched polyethyleneimine incorporated MIL-101 (Cr) by volumetric
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method. 100wt% PEI (linear molecule) incorporated MIL-101 (Cr) has shown CO2 capacity 4.2
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mmol g-1 at 25 °C, 3.4 mmol g-1 at 50 °C, 0.15 bar (Lin et al., 2014; Lin et al., 2013). Carlos et al
have studied the adsorption of CO2 on ethylenediamine grafted MIL-100 (Cr). It has shown an
adsorption capacity of 2.4 mmol g-1 at 308 K, 1 bar, and good adsorption stability by cyclization
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(Cabello et al., 2015). Similarly, Demessence et al have reported an increase in adsorption of CO2
by immobilization of ethylenediamine on Cu-MOF, H3 [(Cu4Cl) 3-(BTTri) 8] with adsorption
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capacity of 1.25 mmol g-1 at 298 K, 1 bar (Demessence et al., 2009). These results have suggested
that an increase in adsorption capacity of CO2 on amine incorporated materials and good
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adsorption stability. In this article, we have studied adsorption of CO2 on MIL-101 (Cr) and linear
polyethylenimine incorporated MIL-101 (Cr) by fixed bed method at different temperatures in
atmospheric pressure. Apart from, the effect of PEI loading, moisture effect, multiple adsorption-
desorption cycles and adsorption kinetic models also have been studied.

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2. Experimental
2.1 Materials
Chromium nitrate nonahydrate (Cr(NO3)3.9H2O, 99%), terephthalic acid (C8H6O4, 99%),
hydrofluoric acid (HF, 48%), ammonium fluoride (NH4F, 95%), methanol (CH4O, 99.7%) and
ethanol (C2H6O, 99.8%) were purchased from Aladdin Chemicals Pvt. Ltd, China.
Polyethylenimine (M.Wt. = 800) was purchased from Aldrich Chemicals Pvt. Ltd, China. All

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chemicals were used without further purification.

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2.2 Synthesis of adsorbents
MIL-101 (Cr) was prepared by the reported method (Férey, 2005) Briefly, chromium

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nitrate nonahydrate (4.0 g), terephthalic acid (1.66 g), hydrofluoric acid (0.5 mL) and water (48
mL) were placed in a stainless steel autoclave at 220 °C for 8 h. The reaction mixture was cooled

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to room temperature and filtered using G2 fritted glass filter, again filtrate was filtered using

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Whatman filter paper to get MIL-101 (Cr). It was purified using 95% (vol.) ethanol and 1M NH4F
solution at 80 °C for 24 h. Finally, we got purified MIL-101 (Cr). PEI incorporated MIL-101 (Cr)
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was prepared by the impregnation method. In a typical procedure, a desired quantity of PEI was
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dissolved in 10 mL methanol, stirred for 30 minutes until a homogenous solution was obtained
then 1 g of MIL-101 (Cr) was added. The mixture was stirred for 1 h at room temperature and
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dried at 70 °C for 12 h. It was labeled as MIL-101 (Cr)-PEI-x, where x represents the mass ratio
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of PEI loaded on the support. For instance, 0.5 g of PEI was loaded on 1 g of MIL-101 (Cr) then
it was denoted as MIL-101 (Cr)-PEI-50. Similarly, MIL-101 (Cr)-PEI-30, MIL-101 (Cr)-PEI-70
and MIL-101 (Cr)-PEI-100 were prepared (Song et al., 2013a).
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2.3 Characterizations
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Powdered X-ray diffraction patterns were recorded on Rigaku Ultima-IV X-ray

diffractometer in the 2θ range from 0.7 to 20° having tube voltage 40 KV and current 15 mA.
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Surface area, total pore volume, and pore size were calculated from the N2 adsorption-desorption
isotherms. Micromeritics ASAP 2020 surface area analyzer was used to measure the N2
adsorption-desorption isotherms. The specific surface area was calculated using the BET method
in the relative pressure range of 0.05 – 0.3, total pore volume at P/P0 = 0.99 and pore size
distribution was plotted using the NLDFT method. FT-IR spectra were recorded on Nicolet IR200

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FT-IR spectrophotometer in the frequency range from 400 – 4000 cm-1 with a resolution of 4 cm-
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using KBr. Thermogravimetric analysis was carried out on TGA Q50 analyzer from 30 - 800 °C
in nitrogen flow 30 mL min-1 with a heating rate of 10 °C/min. Scanning electron microscopy
images were obtained from JEOL JSM-6360LA instrument. Elemental analysis was conducted on
Elementar, Vario EL Cube analyzer.

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2.4 CO2 adsorption/desorption measurements
CO2 adsorption/desorption studies were carried out using a fixed bed reactor at different

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temperatures in atmospheric pressure. About, 1 g of adsorbent was loaded in a stainless steel
reactor of 12 mm ID and 420 mm length between two quartz plugs. Prior to adsorption of CO2, the

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adsorbent was heated at 110 °C for 1 h in helium flow with a flow rate of 30 mL min-1 to remove
the physisorbed gases or moisture then cooled to desired adsorption temperature for the study of

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CO2 adsorption. 10 vol. % CO2 balanced helium was passed over the adsorbent with a flow rate of

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30 mL min-1 until the adsorbent was saturated. The CO2 concentration in outlet of the reactor was
analyzed for every 5 minutes using online gas chromatography Agilent GC 7820A system, USA
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equipped with thermal conductivity detector having porapak Q packed column 3 m length and 3
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mm ID. CO2 adsorption capacity was calculated by integration of breakthrough curve using
equation (1) (Wang et al., 2015).
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t
1 C0 -C T0
q = Q [∫ dt] (1)
MVm 0 1-C T
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Where q is the amount of CO2 adsorbed in mmol g-1, M is the mass of adsorbent in grams,
Q is the gas flow rate in mL min-1, t is the adsorption time in minutes, C0 and C are the influent
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and effluent gas concentrations in volume (%), To is the absolute temperature in K, T is the gas
temperature in K and Vm is 22.4 mL mmol-1. In moisture condition, helium gas was passed through
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water bubbler maintained at room temperature for 1 h over adsorbent bed then it was switched to
dry helium for 1 h followed by CO2 adsorption similar to dry condition (Upendar et al., 2012).
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Multiple adsorption-desorption cycles were carried out at 75 °C, after desorption of adsorbed CO2
at 110 °C for 1 h in helium flow.

3. Results and discussion

3.1 Structural characterizations

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 Figure 1 shows the X-ray diffraction patterns of MIL-101 (Cr) and PEI incorporated MIL-
101 (Cr). The diffraction peaks of MIL-101 (Cr) were 2θ = 1.74°, 2.82°, 3.3°, 3.98°, 5.18°, 8.45°,
9.08°, 10.36°, and 16.56°. All diffraction peaks were well matched with simulated one (Hong et
al., 2009). In PEI incorporated MIL-101 (Cr), the major diffraction peaks of MIL-101 (Cr) were
appeared and no additional peaks. It represented that the structure of MIL-101 (Cr) was well
maintained by the incorporation of PEI. Moreover, the intensity of diffraction peaks below 2θ =

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5° was decreased. It suggested that PEI was present within MIL-101 (Cr). Similar results have
been reported by Kuwahara et al on PEI incorporated Zirconiasilicate (Kuwahara et al., 2012).

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Figure 2 shows the N2 adsorption-desorption isotherms and pore size distribution of MIL-
101 (Cr) and PEI incorporated MIL-101 (Cr). Adsorption-desorption isotherms of all synthesized

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samples were well merged and no hysteresis loop was observed. It indicated that most of the
adsorbed N2 molecules were completely desorbed. From the IUPAC classification of porous

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materials, the isotherm pattern belongs to Type-IV. It indicated that existence of mesopores (Wang

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et al., 2012). Textural properties of all samples were shown in table 1. MIL-101 (Cr) has shown
BET surface area 3324 m2 g-1, total pore volume 1.75 cm3 g-1 and average pore size 2.11 nm
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respectively. These values were matched with the reported literature (Chowdhury et al., 2009).
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The amount of N2 adsorbed was decreased with the increase of PEI loading. Consequently, the
change in textural properties has been observed. The specific surface area was decreased to 566
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m2 g-1 and total pore volume to 0.44 cm3 g-1. But, the average pore size was increased to 3.10 nm.
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It was due to the incorporated PEI, occupies the smaller pores of MIL-101 (Cr). Song et al have
reported similar results in amine incorporated Titania Nanotubes (Song et al., 2013b).
Surface functional groups of the MOFs can be found by FT-IR spectroscopy. Figure 3a
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shows the FT-IR spectra of PEI, MIL-101 (Cr) and PEI incorporated MIL-101 (Cr). The
vibrational band at 1398 cm-1 represented the symmetric stretching of (O-C-O) group. Other bands
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in the range from 600 – 1600 cm-1 were related to the benzene ring. It indicated that both groups
(dicarboxylate and benzene) were present in the framework of MIL-101 (Cr) (Liu et al., 2013). In
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PEI incorporated MIL-101 (Cr) samples, the major vibrational bands of MIL-101 (Cr) appeared.
Along with, new vibrational bands of PEI also appeared. The bands at 2837 cm-1 and 2944 cm-1
represented the symmetric and asymmetric vibrational bands of a methylene group. Similarly, the
bands at 3418 cm-1 and 3270 cm-1 represented the symmetric and asymmetric vibrational bands of
–NH2 group (Li et al., 2014). The intensity of the major vibrational bands of PEI was increased

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with the increase of PEI loading. Hence, FT-IR analysis has confirmed the existence of PEI within
MIL-101 (Cr).
TGA patterns of MIL-101 (Cr) and PEI incorporated MIL-101 (Cr) were shown in figure
3b. MIL-101 (Cr) has shown two-step weight loss. First step weight loss below 100 °C indicated
the removal of coordinated water and second step weight loss above 300 °C represented the
decomposition of the framework. It indicated MIL-101 (Cr) was stable up to 300 °C (Wang et al.,

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2013b). While PEI incorporated MIL-101 (Cr) samples have shown three-step weight loss. First
step weight loss was similar to MIL-101 (Cr) and two-step weight loss in the temperature range of

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250 - 500 °C was due to the decomposition of PEI and MIL-101 (Cr). Based on the thermal stability
of all synthesized adsorbents, CO2 adsorption-desorption can be studied up to 200 °C.

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Morphological images of MIL-101 (Cr), MIL-101 (Cr)-PEI-70 and CO2 adsorbed sample
MIL-101 (Cr)-PEI-70 at 75 °C were shown in figure 4. MIL-101 (Cr) has shown an octahedral

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shape (fig. 4a) (Darunte et al., 2016). Same morphology was obtained for MIL-101 (Cr)-PEI-70

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(Cr) (fig. 4b). It indicated that PEI has no impact on the change in morphology of MIL-101 (Cr).
Moreover, morphology of CO2 adsorbed sample MIL-101 (Cr)-PEI-70 at 75 °C was similar to
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fresh MIL-101 (Cr)-PEI-70 (fig 4c). The nitrogen content of PEI incorporated MIL-101 (Cr)
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samples was calculated by elemental analysis. The values were shown in table 2. Nitrogen content
was increased with the increase of PEI loading.
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3.2 CO2 adsorption study

Figure 5 shows the adsorption of CO2 on MIL-101 (Cr)-PEI-70 at different temperatures
in atmospheric pressure. With the increase of temperature from 30 – 75 °C, the breakthrough
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adsorption time and adsorption capacity were increased. The CO2 adsorption capacities were 2.51
mmol g-1 at 30 °C, 2.96 mmol g-1 at 50 °C and 3.81 mmol g-1 at 75 °C. Further increase of
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temperature to 90 °C, the breakthrough time was decreased and CO2 adsorption capacity was 2.61
mmol g-1. Theoretically, the adsorption of CO2 on amine incorporated materials depends on the
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active amine groups and motion of CO2 molecules. The adsorption of CO2 is most favorable at a
lower temperature. Because of adsorption of CO2 is an exothermic reaction. However, PEI is
highly viscous. It is more flexible for the adsorption of CO2 at a higher temperature of around 50
- 75 °C based on kinetic and thermodynamic studies (Guo et al., 2016). At 90 °C, some of the
adsorbed CO2 molecules desorbed. Hence, it has shown less adsorption capacity compared to the

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adsorption capacity at 75 °C. Sanz et al have reported CO2 adsorption capacity of 2.04 mmol g-1
on PEI incorporated SBA-15 at 75 °C (Sanz et al., 2010).
Figure 6 shows the breakthrough curves of MIL-101 (Cr) and PEI incorporated MIL-101
(Cr) at 75 °C, 1 bar and adsorption capacities were presented in table 2. MIL-101 (Cr) has shown
CO2 adsorption capacity of 0.80 mmol g-1. The adsorption of CO2 has been increased by
incorporation of PEI compared to adsorption capacity of MIL-101 (Cr). It was attributed to the

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chemical interaction between the –NH2 and CO2 groups. As the loading of PEI increased from 30
to 70 wt%, the adsorption of CO2 has been increased and the adsorption capacities were 2.21 mmol

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g-1 for MIL-101 (Cr)-PEI-30, 2.78 mmol g-1 for MIL-101 (Cr)-PEI-50 and 3.81 mmol g-1 for MIL-
101 (Cr)-PEI-70 respectively. The high adsorption capacity was shown by MIL-101 (Cr)-PEI-70.

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It was due to the more number of active amine groups and a high number of CO2 molecules
diffusion. Further increase of PEI loading, CO2 adsorption capacity was decreased and reached

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2.85 mmol g-1 for MIL-101 (Cr)-PEI-100. At higher loading, the pores of MIL-101 (Cr) were

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mostly filled with PEI and less number of CO2 molecules diffusion. Hence, it has shown less
adsorption capacity. Chen et al have reported CO2 adsorption capacity of 1.07 mmol g-1 on PEI
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incorporated Bentonite at 75 °C, 1 bar which was higher than pristine Bentonite adsorption
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capacity of 0.14 mmol g-1 (Chen et al., 2013).

Amine efficiency in PEI incorporated MIL-101 (Cr) was presented in table 2. The values
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were 0.37 for MIL-101 (Cr)-PEI-30, 0.29 for MIL-101 (Cr)-PEI-50, 0.32 for MIL-101 (Cr)-PEI-
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70 and 0.19 for MIL-101 (Cr)-PEI-100 respectively. A high number of active amine groups and
number of CO2 molecules diffusion were helpful to show high amine efficiency for MIL-101 (Cr)-
PEI-70. Industrial flue gas contains less amount of water which can influence the CO2 adsorption
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capacity of an adsorbent. Figure 7a shows the breakthrough curves of MIL-101 (Cr)-PEI-70 in dry
and moisture conditions at 75 °C, 1 bar. The adsorption of CO2 in moisture condition was 4.4
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mmol g-1 which was higher than adsorption capacity of 3.81 mmol g-1 in dry condition. In amine
incorporated materials, one mole of CO2 reacts with two moles of primary or secondary amine to
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form a carbamate (Equ. 2 and 3) in dry condition. Similarly, in moisture condition, one mole of
CO2 reacts with one mole of amine to form ammonium bicarbonate (Equ. 4 and 5) (Khutia and
Janiak, 2014). Hence, high adsorption of CO2 has been observed in moisture condition.

2RNH2 + CO2 → R2NCOO− + NH4+ (2)

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 2R2NH + CO2 → R2NCOO− + R2NH2+ (3)

RNH2 + CO2 + H2O → RNH3+ + HCO3− (4)

R2NH + CO2 + H2O → R2NH2+ + HCO3− (5)

CO2 adsorption capacity of MIL-101 (Cr)-PEI-70 was compared with PEI incorporated on

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different supports such as MCM-41, mesoporous alumina, nanoporous carbon, single-walled
carbon nanotube and ZIF-8. The amount of PEI loaded and CO2 adsorption capacity were shown

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in table 3. Lowest CO2 adsorption capacity 1.09 mmol g-1 was obtained for 50wt% PEI
incorporated nanoporous carbon at 75 °C, 1 bar by thermogravimetric method (Tang et al., 2013).

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Among the reported adsorbents, MIL-101 (Cr)-PEI-70 has shown high adsorption of CO2
3.81mmol g-1 at 75 °C by fixed bed method. Hence, it is one of the adsorbents showed high CO2

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adsorption capacity. Adsorption-desorption cycle is an important study to know the adsorption

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stability of an adsorbent. Figure 7b shows the multiple adsorption-desorption cycles of MIL-101
(Cr)-PEI-70 at 75 °C. The initial CO2 adsorption capacity of MIL-101-PEI-70 was 3.81 mmol g-1.
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The same adsorption capacity was maintained in each adsorption-desorption cycle up to 6 cycles.
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It represented that no decomposition or loss of PEI group in adsorption-desorption cycles.

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3.3 Adsorption kinetics

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CO2 adsorption rate and type of adsorption process can be determined using different
adsorption kinetic models such as Pseudo-first order kinetic model, Pseudo-second-order kinetic
model, and Avrami adsorption kinetic model. Pseudo-first order kinetic model explains the
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physical adsorption process. It has a relationship between the adsorption rate and a number of
active sites present on the adsorbent (Equ. 6). Pseudo-second order kinetic model explains the
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chemical adsorption process. It has a relationship between the adsorption rate and square of the
number of active sites on the adsorbent (Equ. 7). Similarly, Avrami adsorption kinetic model
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explains both physical and chemical adsorption processes (Equ. 8) (Wang et al., 2015) (Serna-
Guerrero and Sayari, 2010).

Qt = Qe [1- exp(-k1 t)] (6)

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 k2 Q2e
Qt = t (7)
1+ k2 Qe t
Qt = Qe [1- exp (-ka t)na ] (8)
Where Qt is the adsorption capacity at time t (mmol g-1), Qe is the equilibrium adsorption
capacity (mmol g-1), k1 is the pseudo-first order rate constant (min-1), k2 is the pseudo-second-
order rate constant (g mmol-1 min-1), ka is the Avrami rate constant (min-1) and na is the order of

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kinetic equation. Figure 8 shows the fitting of experimental CO2 adsorption of MIL-101 (Cr)-PEI-
70 with adsorption kinetic models. The parameters of the adsorption kinetic models were presented

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in table 4. The fitted Qe value from all adsorption kinetic models was close to the experimental Qe.
But, R2 (0.9959) and adsorption rate constant (0.0432 min-1) values were higher in the Avrami

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kinetic model compared to the Pseudo-first order and Pseudo-second order kinetic models. It
suggested that the adsorption of CO2 on MIL-101 (Cr)-PEI-70 followed Avrami adsorption kinetic

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model.
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4. Conclusions
High surface area and pore volume of MIL-101 (Cr) were helpful for the incorporation of
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polyethylenimine. All PEI incorporated MIL-101 (Cr) samples have shown high adsorption of CO2
compared to MIL-101 (Cr), because of the chemical interaction between adsorbent and adsorbate.
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MIL-101 (Cr)-PEI-70 has shown CO2 adsorption capacity of 3.81 mmol g-1 at 75 °C, 1 bar. It was
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due to the more number of active amine groups and a high number of CO2 molecules diffusion.
Moreover, high amine efficiency was also found on the same adsorbent. Increase in adsorption of
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CO2 has been observed in moisture condition by the formation of ammonium bicarbonate and CO2
adsorption capacity was 4.4 mmol g-1 at 75 °C, 1 bar. Stable CO2 adsorption capacity was
maintained in each adsorption-desorption cycle. Avrami adsorption kinetic model was well fitted
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with experimental CO2 adsorption of MIL-101 (Cr)-PEI-70. It suggested that adsorption of CO2
on PEI incorporated MIL-101 (Cr) was chemical adsorption.
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Acknowledgment
We gratefully acknowledge financial support from NSFC (No. 21571122), the National
Basic Research Program of China (973 Program, 2013CB834803), and Department of Education
in Guangdong Province (No. 2014KCXTD012).

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Figure captions

Fig. 1. XRD patterns of MIL-101 (Cr) and PEI incorporated MIL-101 (Cr)

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Fig. 2. a) N2 adsorption-desorption isotherms and b) pore size distribution of MIL-101 (Cr) and

PEI incorporated MIL-101 (Cr)

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 A
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Fig. 3. a) FT-IR spectra of PEI, MIL-101 (Cr) and PEI incorporated MIL-101 (Cr) and b) TGA

patterns of MIL-101 (Cr) and PEI incorporated MIL-101 (Cr)

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Fig. 4. SEM images of a) MIL-101 (Cr), b) MIL-101 (Cr)-PEI-70 and c) CO2 adsorbed sample

MIL-101 (Cr)-PEI-70 at 75 °C

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Fig. 5. Breakthrough curves of MIL-101 (Cr)-PEI-70 at different temperatures.

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Fig. 6. Breakthrough curves of MIL-101 (Cr) and PEI incorporated MIL-101 (Cr) at 75 °C

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Fig. 7. a) Breakthrough curves of MIL-101 (Cr)-PEI-70 in dry and moisture conditions and b)

Multiple adsorption-desorption cycles of MIL-101 (Cr)-PEI-70

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 A
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Fig. 8. Fitting of experimental CO2 adsorption of MIL-101-PEI-70 with adsorption kinetic

models

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Table 1. Textural properties of MIL-101 (Cr) and PEI incorporated MIL-101 (Cr)

Sample S BET a (m2 g-1) S Langmuir b (m2 g-1) Vt c (cm3 g-1) Dp d (nm)
MIL-101 (Cr) 3324 4214 1.75 2.11
MIL-101 (Cr)-PEI-30 1633 1929 0.87 2.13
MIL-101 (Cr)-PEI-50 1136 1351 0.62 2.18

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MIL-101 (Cr)-PEI-70 923 1098 0.53 2.29
MIL-101 (Cr)-PEI-100 566 711 0.44 3.10

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a
Surface area by BET, b Langmuir surface area, c Total pore volume at P/P0 = 0.99, d Average pore

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size (4Vt/SBET)

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Table 2. Elemental analysis, CO2 adsorption capacity and amine efficiency of MIL-101 (Cr) and
PEI incorporated MIL-101 (Cr)

Sample Na N CO2 adsorption Amine efficiency

(wt%) (mmol g-1) capacity b (mmol g-1) (mmol CO2/mmol N)

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MIL-101 (Cr) ND ND 0.80 ND
MIL-101 (Cr)-PEI-30 8.31 5.94 2.21 0.37

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MIL-101 (Cr)-PEI-50 13.63 9.74 2.78 0.29

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MIL-101 (Cr)-PEI-70 16.87 12.05 3.81 0.32
MIL-101 (Cr)-PEI-100 20.52 14.66 2.85 0.19

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a
From elemental analysis, b CO2 adsorption at 75 °C, ND: Not determined
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Table 3. Comparison of CO2 adsorption capacity with reported adsorbents.

Adsorbent Test condition Adsorption

CO2 adsorbed Reference
method (mmol g-1)
50wt% PEI/ MCM-41 15 vol.% CO2, 75°C Fixed bed3.18 (Ma et al.,

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method 2009)
a
45wt% PEI/ MA 100 vol.% CO2, 75 °C TGA 2.72 (Chen and
Ahn, 2011)

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b
50wt% PEI/NC 100 vol.% CO2, 75 °C TGA 1.09 (Tang et al.,
2013)

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c
30wt% PEI/SWCNT 100 vol.% CO2, 75 °C TGA 1.77 (Dillon et al.,
2008)
d
45wt% PEI/ZIF-8 50 vol.% CO2, 65 °C GC-MS 1.61 (Xian et al.,

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2015)
MIL-101 (Cr)-PEI-70
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10 vol.% CO2, 75 °C Fixed bed 3.81
method
Present work
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a
MA: mesoporous alumina, b NC: nanoporous carbon, c NC: single-walled carbon nanotube,
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d
ZIF: zeolite Imidazole framework.
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Table 4. Parameters of adsorption kinetic models for MIL-101 (Cr)-PEI-70

Kinetic models Parameters MIL-101 (Cr)-PEI-70

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Qe (mmol g-1) 3.81 (exp.), 4.06 (fit.)
Pseudo first order k1 (min-1) 0.0275

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R2 0.9829
Qe ( mmol g-1) 3.81 (exp.), 4.11 (fit.)

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Pseudo second order K2 (g mmol-1 min-1) 0.0022
R2 0.9792

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Qe ( mmol g-1) 3.81 (exp.), 3.89 (fit.)
Avrami model ka (min-1) N 0.0432
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na 1.4940
R2 0.9959
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Kinetic models Parameters MIL-101 (Cr)-PEI-70

Qe (mmol g-1) 3.81 (exp.), 4.06 (fit.)
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Pseudo first order k1 (min-1) 0.0275

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R2 0.9829
Qe ( mmol g-1) 3.81 (exp.), 4.11 (fit.)
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Pseudo second order K2 (g mmol-1 min-1) 0.0022

R2 0.9792
Qe ( mmol g-1)
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3.81 (exp.), 3.89 (fit.)

Avrami model ka (min-1) 0.0432
na 1.4940
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R2 0.9959

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