Research Article

Cite This: ACS Appl. Mater. Interfaces 2018, 10, 769−775 www.acsami.org

Molecular Layer Deposition-Modified 5A Zeolite for Highly Efficient

CO2 Capture
Zhuonan Song,† Qiaobei Dong,‡ Weiwei L. Xu,† Fanglei Zhou,‡ Xinhua Liang,§ and Miao Yu*,‡
†
Department of Chemical Engineering, University of South Carolina, Columbia, South Carolina 29208, United States
‡
Department of Chemical and Biological Engineering, Rensselaer Polytechnic Institute, Troy, New York 12180, United States
§
Department of Chemical and Biochemical Engineering, Missouri University of Science and Technology, Rolla, Missouri 65409,
United States
*
S Supporting Information

ABSTRACT: Effective pore mouth size of 5A zeolite was engineered by depositing an ultrathin layer of microporous TiO2 on
its external surface and appropriate pore misalignment at the interface. As a result, a slightly bigger N2 molecule (kinetic
diameter: 0.364 nm) was effectively excluded, whereas CO2 (kinetic diameter: 0.33 nm) adsorption was only influenced slightly.
The prepared composite zeolite sorbents showed an ideal CO2/N2 adsorption selectivity as high as ∼70, a 4-fold increase over
uncoated zeolite sorbents, while maintaining a high CO2 adsorption capacity (1.62 mmol/g at 0.5 bar and 25 °C) and a fast
CO2 adsorption rate.
KEYWORDS: molecular layer deposition, pore misalignment, CO2 capture, CO2/N2 adsorption selectivity, CO2 adsorption rate

1. INTRODUCTION effective, large-scale separation technologies play a crucial role

Carbon dioxide is considered as one of the major greenhouse
gases that contribute to global warming, ocean acidification,
and other environmental concerns.1−3 The concentration of
CO2 in the atmosphere has increased by 40% from 280 to 400
ppm over the past century.4 In 2013, the Intergovernmental
Panel on Climate Change predicted that by 2100, the global
temperature will increase by another 1.9 °C.4 The rapid
increasing trend of CO2 emission, resulting from our heavy use
of fossil fuels,5 may not be alleviated within the next several
decades if appropriate CO2 capture strategies are not adopted.
To reduce CO2 emission, CO2 can be captured depending on
different processes: postcombustion capture, where CO2 is
separated from the other components of the flue gas,
precombustion capture with the removal of CO2 from the
fuel prior to combustion, and oxy-combustion, where the fuel
is burned in an oxygen stream.6 Among them, postcombustion
CO 2 capture from flue gases (predominantly CO 2 /N 2
separation) has been identified as an attractive and immediate
route for mitigating the escalating concentration of atmos-
pheric CO2 and may also be readily retrofitted to existing
power plants.3,7−9 However, the biggest challenges at present
are large energy requirement and high cost.2 Thus, cost-
in CO2 mitigation to become viable.10
Absorption processes using aqueous alkanolamine solutions
(amine scrubbers) have been extensively studied and widely
employed in conventional CO2 removal. The amine scrubbing
captures CO2 with a high selectivity, but an intensive energy
input is required to break the C−N bond formed between CO2
and the amine functionality for regeneration.9,11 Additionally,
amine solutions are also severely corrosive toward the vessels
in which they are contained.12 Membrane-based separation
processes have emerged as an effective alternative in
postcombustion CO2 capture.13 Membrane performance,
however, still needs to be improved to overcome the trade-
off between permeability and selectivity.13 Meanwhile, the low
pressure of CO2 in the feed stream and thus the low driving
force for its permeation may limit the application of
membranes in postcombustion CO2 capture.2 Relative to the
abovementioned methods, selective CO2 adsorption using
porous adsorbents has demonstrated great potential for
Received: October 31, 2017
Accepted: December 14, 2017
Published: December 14, 2017

© 2017 American Chemical Society 769 DOI: 10.1021/acsami.7b16574

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Figure 1. Illustration of pore misalignment at the interface between the MLD coating and the zeolite surface (a), transmission electron microscopy
(TEM) image of the MLD-coated 5A zeolite (the inset image shows the optical photograph of the MLD-coated 5A zeolite pellets) (b), EDS
spectrum of the MLD-coated 5A zeolite (c), and XPS spectrum of the MLD-coated 5A zeolite (d).
reducing energy and cost for CO2 capture.14,15 In adsorption
processes, the separation is usually based on the size and shape
of the molecules to be separated and/or their interaction with
the adsorbent.16 With regard to postcombustion CO2 capture,
various materials have been prepared and studied as
adsorbents. For instance, amine-grafted silica was found to
exhibit high affinity toward CO2 and good stability.17,18
However, these materials are typically prepared as powder,
which can be difficult to implement on a viable industrial scale
for CO2 capture owing to the high pressure drop and poor heat
and mass transport.19 In recent years, considerable efforts have
been expended on the synthesis of metal organic frameworks
(MOFs) for use as CO2 adsorbents.20 MOFs, an emerging
class of hybrid materials with a porous structure, combine the
metal centers with the bridging organic ligands. Conceptually,
MOFs can be synthesized to possess tunable pore sizes, large
surface areas, and specific adsorption affinities based on how
the building blocks bond together.21 For example, a series of
CO2-selective MOF adsorbents prepared by the research
groups of Matzger and Eddaoudi showed excellent CO2
selectivity and uptake at low pressures and ambient temper-
ature.22−24 The high cost of the organic ligands may limit the
large-scale applications of MOFs. The retail prices of the recent
four commercialized MOFs from BASF are $10 000−15 000/
kg.25 As a significantly cheaper porous material ($0.03−0.12/
kg),26 zeolites have drawn a great deal of attention as
adsorbents for CO2 capture for decades. Among them, small-
pore zeolites, such as CHA and NaA, have shown a decent
CO2/N2 separation selectivity (15−60) for a hypothetical flue
gas stream, but the slow diffusion of gases throughout the
materials may limit their practical applications.27 Medium-
sized-pore zeolites, especially 5A and 13X, are considered as
promising adsorbents because of their high CO2 adsorption
capacity at low pressures, fast kinetics, and excellent thermal,
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Research Article
chemical, and mechanical stabilities.28−31 Their adsorption
selectivity of CO2 over N2, however, is still low, typically in the
range of 15−22 at 50 kPa and 25 °C.14,32 In this study, we are
interested in optimizing the adsorptive separation performance
of medium-sized-pore 5A zeolite by improving its CO2/N2
selectivity through pore mouth engineering while maintaining
a high CO2 capacity and fast uptake kinetics.
In previous work, our group has shown a new method to
improve the adsorption selectivity of zeolites using the
molecular layer deposition (MLD) technique.33,34 MLD, a
gas-phase deposition method, is a subset of atomic layer
deposition, which is capable of depositing ultrathin conformal
organic−inorganic hybrid coatings on various substrates. The
obtained hybrid coatings can be converted into porous
coatings by removing the organic compounds.35,36 The
improved adsorptive separation performance of MLD-coated
zeolites was attributed to the narrowed zeolite pore mouth,
resulting from the misalignment between MLD coating pores
and zeolite pores, as shown schematically in Figure 1a. The
pore misalignment originates from the thermal interfacial shear
stress during calcination, resulting from the different thermal
expansion coefficients between the zeolite and the MLD
coating. We have shown that the extent of pore misalignment
(or relative displacement) at the interface can be controlled by
the MLD coating thickness when the calcination condition was
fixed. This is consistent with the Nassar’s analytical modeling
study for composite materials.37 However, when the resistance,
namely, the chemical bonding between the MLD coating and
the zeolite surface, balances the thermal shear force, the
relative movement between the MLD coating and the zeolite
surface stops, and thus no further relative displacement was
observed.34 In Pan’s recent study,38 it was found that the
interfacial displacement of composite materials can be further
influenced by varying the calcination conditions.
DOI: 10.1021/acsami.7b16574
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In this work, we selected 5A zeolite as a promising CO2
capture sorbent and explored the potential of MLD coating in
fine-tuning the pore entrance of 5A zeolite by controlling the
calcination temperature and calcination residence time and the
adsorptive separation performance of the resulting MLD-
modified composite 5A sorbent.
2. EXPERIMENTAL SECTION
2.1. Materials. Ethylene glycol (EG) (99%, HO(CH2)2OH) was
obtained from Alfa Aesar. Titanium tetrachloride (99.9%, TiCl4) was
obtained from Sigma-Aldrich. 5A zeolites were obtained from W. R.
Grace & Co.-Conn.
2.2. Characterization. A field emission scanning electron
microscope (Zeiss Ultra Plus) was used to observe the structure of
5A zeolite crystals. Elementary composition of the zeolites before and
after MLD was analyzed by energy-dispersive spectroscopy (EDS)
using an FESEM coupled with an EDAXS detector and an X-ray
photoelectron spectroscope (Kratos Axis Ultra DLD instrument
equipped with a monochromated Al Kα X-ray source and a
hemispherical analyzer capable of an energy resolution of 0.5 eV).
Infrared (IR) spectra were taken on a Bruker equinox 55 in a diffuse
reflection mode. A Praying Mantis diffuse reflection compartment was
used to allow the IR beam to be reflected on powder samples. For
each spectrum, 64 scans were collected to ensure a high signal-to-
noise ratio. The IR spectra were scanned in the range of 4000−1000
cm−1 with a resolution of 4 cm−1. Pore size distribution of the MLD-
coated zeolite adsorbents was calculated using an Ar adsorption
branch of the isotherms measured at −196 °C using a Micrometeritcs
ASAP 2020 unit. Prior to the adsorption measurement, the samples
were degassed in situ at 170 °C overnight.
2.3. Titanium Alkoxide MLD Coating. Zeolites were first
outgassed at 200 °C for 4 h to remove the adsorbed water. The
titanium alkoxide MLD coatings (−Ti−O−CH2−CH2−O−Ti−)
were prepared by using TiCl4 and EG as precursors. Each MLD
cycle started with 240 s vacuum. TiCl4 was then introduced into the
reactor until a pressure of 150 mTorr and settled for 120 s, and then
240 s vacuum was applied to evacuate the extraunreacted TiCl4.
Ultrahigh purity N2 (Airgas) was used to further clean the reactor at a
flow rate of 20 sccm for 30 s, which is controlled by a mass flow
controller. Then, 240 s vacuum was applied to evacuate N2. After that,
EG was diffused into the reactor until a pressure of 50 mTorr and
then settled for 120 s, followed by 240 s vacuum to evacuate the
extraunreacted EG. Ultrahigh purity N2 was used as the purge gas
again. Then, 240 s vacuum was applied to evacuate N2. This whole
process finishes one MLD cycle, and totally 60 cycles of titanium
alkoxide MLD coatings were deposited on the zeolites at 100 °C.
Then, the coated samples were heated in air from room temperature
to different elevated temperatures (200, 250, and 350 °C) at a rate of
1 °C/min, kept at an elevated temperature for different residence
times (1 min, 2 h, 4 h, and 8 h), and then cooled to room temperature
at the same rate.
2.4. CO2 and N2 Adsorption Isotherm Measurements.
Ultrahigh purity CO2 (99.999%) and N2 (99.999%) were purchased
from Airgas. Gas adsorption isotherms were measured by a volumetric
method using a home-built adsorption system. The sorbent was first
outgassed at 200 °C for 2 h. Helium was then used to calibrate the
volume of the adsorption cell with the sorbent at 25 °C. After vacuum
to remove the residue gases in the adsorption system, gases of interest
were introduced at 25 °C. The pressure change was recorded in real
time using a Swagelok E model transducer and LabVIEW 2012
software.
2.5. CO2 Adsorption Kinetics Measurement. 5A and 5A-MLD-
250-2h (∼0.065 g) samples were placed in the adsorption system.
CO2 was introduced at an initial pressure of 0.78 and 0.74 bar. The
final pressure was ∼0.5 bar after CO2 reached adsorption equilibrium.
The system pressure change due to CO2 adsorption was recorded for
every 0.3 s using a Swagelok E model transducer and LabVIEW 2012
software.
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2.6. Obtaining Propylene Transport Diffusivities from
Uptake Data. The propylene diffusivity was estimated by fitting
the initial linear uptake data with an approximate analytical simplified
solution given by Kaerger and Ruthven for short times:
Mt 6 Dt
=
M∞ π r2
where D is the Fickian diffusivity, r is the edge length of the cubic
crystal (∼2 μm), Mt is the mass adsorbed at time t, and M∞ is the
mass adsorbed at equilibrium. Propylene (>99%) was purchased from
Sigma-Aldrich. 5A, 5A-MLD-250-2h, 5A-MLD-250-8h, and 5A-MLD-
350-2h (∼0.065 g) samples were placed in the adsorption system.
Propylene was introduced at an initial pressure of ∼1 bar. The system
pressure change was recorded for every 0.3 s using a Swagelok E
model transducer and LabVIEW 2012 software.
3. RESULTS AND DISCUSSION
The field emission scanning electron microscopy (FESEM)
image shows that 5A zeolite crystals are cubic with an average
size of 2 μm (Figure S1). A conformal hybrid MLD coating
with a thickness of approximately 70 nm was deposited on the
5A zeolite crystals by 60 cycles of MLD prior to calcination
(Figure 1b), which will be converted to a thinner porous
coating upon removal of the organic compound. The optical
image of the MLD-coated 5A zeolite pellets is shown as the
inset of Figure 1b. No apparent difference can be seen between
the uncoated 5A and the MLD-coated 5A by naked eyes
because of the thin thickness of the MLD coating. The
elemental composition of the MLD-coated 5A zeolite was
analyzed by EDS. For the uncoated 5A zeolite, O, Na, Al, Si,
and Ca signals were present (Figure S2). In contrast, for the
MLD-coated 5A zeolite, the presence of a Ti peak was clearly
seen at around 4.5 keV (Figure 1c). The MLD coating on the
5A zeolite was also confirmed by analyzing the surface
composition of 5A zeolites before and after MLD using X-
ray photoelectron spectroscopy (XPS). The spectrum of the
uncoated 5A zeolite (Figure S3) showed a strong O1s
photoelectron peak at 531 eV and NaAuger, Ca2s, Ca2p, C1s,
Si2s, Al2s, Si2p, and Al2p peaks at 500, 440, 349, 285, 151, 138,
99, and 73 eV, respectively. This is consistent with the EDS
results (Figure S2) and typical 5A zeolite chemical
composition.39 XPS is a surface characterization technique,
with a typical detection depth limit of around 10 nm.40
Therefore, it is understandable that after MLD, peaks of Na,
Ca, Si, and Al disappeared (Figure 1d). Instead, O, Ti, and C
signals were observed at 531 eV (O1s), 460 eV (Ti2p), 33 eV
(Ti3p), and 285 eV (C1s), suggesting that the entire zeolite
surface has been conformally covered by the MLD coating.
Successful removal of the organic compound from the
hybrid MLD coating by calcination was examined by IR
(Figure S4). Absorbance corresponding to the −CH 2
asymmetric and symmetric stretching vibrations41,42 in the
hybrid MLD coating (−Ti−O−CH2−CH2−O−Ti−) was
observed in the range of 2890−2950 cm−1 only for the
MLD-coated 5A zeolite without calcination (5A-MLD-Uncal).
After calcination at 250 °C for different times (1 min, 2 h, and
8 h), −CH2 stretching vibrations disappeared. Furthermore, a
small shoulder appeared at around 1580 cm−1, which is the
characteristic band for −OH on TiO2,43 suggesting that the
organic compound in the MLD coating was removed and the
hybrid titanium alkoxide was converted to TiO2.
Adsorption isotherms of CO2 (kinetic diameter: 0.33 nm)44
and N2 (kinetic diameter: 0.364 nm)44 were measured on the
5A zeolite and MLD-coated 5A zeolite up to 3 bars, as shown
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Figure 2. CO2 (left y-axis; black column) adsorption capacity and CO2/N2 adsorption selectivity (right y-axis; red column) at 0.5 bar and 25 °C on
the 5A and MLD-coated 5A zeolite calcined at different conditions (a) and CO2 adsorption kinetic uptake curve on the 5A zeolite (black symbol)
and 5A-MLD-250-2h (red symbol) (b).

Figure 3. Pore size distributions (a) for 5A zeolite, 5A-MLD-250-2h, 5A-MLD-250-8h, and 5A-MLD-350-2h and propylene diffusivity (b) on 5A
zeolite, 5A-MLD-250-2h, 5A-MLD-250-8h, and 5A-MLD-350-2h. Pore size distributions were shifted upward by 1, 2, and 3 cm3/(g·nm) for 5A-
MLD-250-2h, 5A-MLD-250-8h, and 5A-MLD-350-2h to better distinguish them in (a).

in Figures S5 and S6. Figure S5a shows the adsorption
isotherms on the uncoated 5A zeolite, which are consistent
with the literature data reported by Wang.45 For the MLD-
coated 5A zeolite, calcination was first carried out at different
residence times (1 min, 2 h, 4 h, and 8 h) while maintaining
the calcination temperature at 250 °C. These samples are
labeled as 5A-MLD-250-1min, 5A-MLD-250-2h, 5A-MLD-
250-4h, and 5A-MLD-250-8h. Corresponding abbreviations
were used in the following discussion. Figure S5b−d shows
that the adsorption loadings of CO2 and N2 decreased
gradually for the MLD-coated 5A zeolites as the calcination
residence time increased from 1 min to 4 h, although their
adsorbed amounts decreased at different rates. This led to a
complex adsorption selectivity change with calcination
residence time (see the discussion below). However,
adsorption loadings of CO2 and N2 increased again after 8 h
of calcination at 250 °C (Figure S5e). We then investigated the
effect of the calcination temperature (200 and 350 °C) while
maintaining the residence time at 2 h. We found that after
calcination at 200 °C for 2 h, the adsorbed amounts of CO2
and N2 were still very low (<5% of uncoated 5A) (Figure S6a),
indicating that 200 °C was not high enough to remove the
organic compound in the dense hybrid MLD coating and
772
convert it into a porous coating. In contrast with the low
adsorption capacity on the MLD-coated 5A zeolite calcined at
200 °C, high capacity of CO2 (>90% of uncoated 5A) on 5A-
MLD-250-1min (Figure 2a) suggested that the organic
compound in the MLD coatings started to decompose at a
temperature between 200 and 250 °C. This is also consistent
with the IR results (Figure S4). The adsorbed amounts at 0.5
bar for 5A, 5A-MLD-250-1min, 5A-MLD-250-2h, 5A-MLD-
250-4h, 5A-MLD-250-8h, 5A-MLD-350-2h, and 5A-MLD-
200-2h are summarized in Figure 2a for CO2 (1.88, 1.79, 1.62,
1.04, 1.65, 1.52, and 0.021 mmol/g, respectively) and in Figure
S7 for N2 (0.10, 0.090, 0.022, 0.019, 0.074, 0.035, and 0.005
mmol/g, respectively). Apparently, different calcination
conditions drastically influenced the adsorptive properties of
the MLD-coated 5A composite sorbents. Because the partial
pressure of CO2 in flue gases is approximately 0.15 bar and of
N2 is about 0.75 bar, the corresponding adsorbed amounts of
CO2 and N2 and ideal selectivity were calculated and are listed
in Table S1. At a lower CO2 pressure, the optimized 5A zeolite
sorbent (5A-MLD-250-2h) showed a slightly lower CO2
adsorption capacity than 5A but a significantly improved
CO2/N2 selectivity, demonstrating its great potential for highly
selective CO2 capture from flue gases.
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Figure 4. Comparison of the MLD-coated zeolite composite sorbents with porous adsorbents for CO2/N2 separation: CO2/N2 selectivity vs CO2
adsorption capacity at 0.5 bar. The blue squares (1−8) represent porous adsorbents from the literature;50−56 the black squares (9) are the uncoated
zeolite sorbents; and the red squares (10) indicate the MLD-coated zeolite composite sorbents from this study.
For the MLD-coated 5A zeolite with 2 and 4 h residence
times at 250 °C and with 2 h residence time at 350 °C, the
reduction of the adsorption capacity was much larger for N2
(78, 81,, and 65%) than for CO2 (14, 44, and 19%). As a result,
the ideal CO2/N2 selectivity (the adsorption capacity ratio of
CO2 to N2 at 50 kPa) increased significantly from 19
(uncoated 5A) to 43 (5A-MLD-350-2h), 55 (5A-MLD-250-
4h), and 74 (5A-MLD-250-2h) (Figure 2a). Although the pore
mouth size decreased, as suggested by the more effective
exclusion of N2 and thus higher CO2/N2 adsorption selectivity,
CO2 uptake rate did not decrease too much. As shown in
Figure 2b, for the sorbent 5A-MLD-250-2h, CO2 adsorbed
amount reaches 90% of its equilibrium amount at 0.5 bar after
1 min of adsorption, only about 20 s slower than that of the 5A
zeolite. This uptake time is still much shorter than those on
activated carbon (∼40 min),46 on HKUST-1 (∼12 min),47 and
on multiwalled carbon nanotubes (∼9 min),48 demonstrating
the favorable uptake kinetics of the MLD-modified 5A zeolite.
To understand the adsorption selectivity increase, we also
studied the pore size distribution of the 5A zeolite and MLD-
coated 5A composite sorbents after calcination under different
conditions by argon sorption measurements. The argon
sorption isotherms and Brunauer−Emmett−Teller (BET)
plots for 5A, 5A-MLD-250-2h, 5A-MLD-250-8h, and 5A-
MLD-350-2h are presented in Figures S8 and S9. The
isotherms showed a sharp argon uptake at a low relative
pressure, which was expected for the microporous zeolitic
materials. The MLD-coated zeolite sorbents showed a similar
surface area (Figure S9). The pore size distribution was
calculated by Horvath−Kawazoe method and is shown in
Figure 3a; the sharp peak at around 0.53 nm was assigned to
the 5A zeolite, and the pore diameter of the MLD coatings
after removing the organic compound was estimated to be
around 0.80 nm. Moreover, the pore diameter of the MLD
coating did not change obviously upon changing the
calcination condition. Therefore, we speculate that the
improved CO2/N2 selectivity should be attributed to the
different extent of pore misalignment occurred at the interface
between the MLD coating and the 5A zeolite surface under
different calcination strategies; the preferred extent of pore
misalignment is expected to result in a smaller effective pore
mouth size and thus increase the CO2/N2 adsorption
selectivity (Figure S10). The decreased CO2/N2 selectivity
after long-time calcination (8 h at 250 °C) might be due to the
unfavorable pore misalignment configuration generated at the
interface and thus larger pores at the interface. To prove this
assumption, we selected propylene (kinetic diameter: 0.40
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nm),49 a tight fit molecule for 5A zeolite, and used its
adsorption uptake kinetics to explore the small change of pore
misalignment at the interface (Figure S11). Compared with
that of 5A zeolite, the propylene diffusivity decreased by almost
2 orders of magnitude for the MLD-coated samples (Figure
3b), suggesting that the effective pore mouth size of the 5A
zeolite was effectively reduced by pore misalignment. For the
MLD-coated sorbents, different propylene diffusivities resulted
when the calcination conditions were different, with the lowest
propylene diffusivity of the sorbent 5A-MLD-250-2h. This
indicates that the extent of pore misalignment at the interface
between the MLD coating and the zeolite surface can be tuned
by controlling the calcination conditions.
We made a comparison of our MLD-coated zeolite sorbents
with other representative porous materials, including zeolites/
molecular sieves with medium-sized pores, MOFs, and zeolitic
imidazolate frameworks, for CO2/N2 adsorptive separation, as
shown in Figure 4. We did not compare the narrow-pore
zeolites, such as Li-ZK-5 and AlPO-53, because of their
relatively high resistance for CO2 diffusion. We found that our
MLD-modified 5A shows a much higher CO2/N2 selectivity,
whereas the CO2 adsorption capacity is still comparable and/
or superior to those of most of the porous sorbents.
4. CONCLUSIONS
We prepared microporous TiO2-coated zeolite composite
sorbents and optimized their pore sizes by optimizing the
calcination conditions. The resulting MLD-coated zeolites
showed greatly improved CO2 capture performance. Specifi-
cally, our sorbents showed a CO2/N2 selectivity as high as ∼70
and a CO2 adsorption capacity of 1.62 mmol/g at 0.5 bar and
room temperature. Considering their high adsorption
selectivity and adsorption capacity, the MLD-modified zeolites
are superior to most of the reported sorbents for CO2 capture.
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.7b16574.
Adsorption capacities of CO2 and N2, FESEM image,
EDS spectrum, XPS spectrum, IR spectra, adsorption
isotherms of CO2 and N2 at 25 °C, N2 adsorption
capacity, BET plots, adsorption of Ar at −196 °C for
BET surface area, pore size distribution characterization,
and adsorption kinetics of propylene at 25 °C (PDF)
DOI: 10.1021/acsami.7b16574
ACS Appl. Mater. Interfaces 2018, 10, 769−775
ACS Applied Materials & Interfaces
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: yum5@rpi.edu. Phone: +1-518-276-6808.
ORCID
Qiaobei Dong: 0000-0001-9219-6319
Weiwei L. Xu: 0000-0001-7671-4753
Xinhua Liang: 0000-0001-7979-0532
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We greatly acknowledge the financial support by the National
Science Foundation (NSF), United States, under grant no.
CBET-1402772.
■
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775 DOI: 10.1021/acsami.7b16574

ACS Appl. Mater. Interfaces 2018, 10, 769−775