pubs.acs.

org/IECR Article

High Adsorption Capacity Fe@13X Zeolite for Direct Air CO2 Capture
Xiaoju Xiang, Tuo Guo, Yinmei Yin, Zhuxian Gao, Yanxia Wang, Ruotong Wang, Mei An,*
Qingjie Guo,* and Xiude Hu*
Cite This: Ind. Eng. Chem. Res. 2023, 62, 5420−5429 Read Online

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ABSTRACT: The efficient separation of CO2 from air remains an important

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and challenging goal for direct air capture (DAC). Herein, iron-containing 13X
zeolite (Fe@13X) with an efficient separation of CO2 from the air was
synthesized via a simple one-step in situ crystallization method. The results
demonstrate that Fe@13X exhibited outstanding DAC performance (the CO2
capacity of Fe@13X was 0.64 mmol/g, much higher than the 13X zeolite
under simulated air), which was attributed to the introduction of Fe atoms,
effectively narrowing the 13X micropore channel. Moreover, the DAC
adsorption performance of Fe@13X in the temperature range from 25 to 75
°C was explored by combined thermogravimetric analysis and differential
scanning calorimetry. The results revealed that low temperatures were more
favorable for the adsorption of CO2 with a high adsorption rate but less
selectivity. Furthermore, Fe@13X showed a 3 times higher CO2 production
(0.003 kgCO2/kgads·h) and 3.6 times lower desorption energy (0.005 kW h/kgCO2) than 13X zeolite in 400 ppm CO2 in N2. Finally,
d

Fe@13X exhibited excellent cycle stability in simulated air and maintained its initial CO2 uptake in 10 consecutive cycles, showing
the broad application prospects of materials in industrial adsorption and separation.

1. INTRODUCTION resulting in a drastic reduction in the regeneration energy

A series of serious problems caused by the continuous
intensification of global warming have caused great concern
regarding anthropogenic CO2 emissions and promoted the
development and application of various technologies for
reducing carbon emissions.1−3 As one of the most developing
prospective emission technologies, direct air capture (DAC)
can play a key role in achieving carbon neutrality.4 Compared
to the conventional carbon capture and storage, the DAC of
CO2 (low concentrations, 400 ppm) can effectively address
global CO2 emissions from point and nonpoint sources, thus
eliminating the need for storage and transport infrastruc-
ture.3,5,6
The core of DAC technology is the design of adsorbent
materials.7 Currently, alkaline aqueous solutions and porous
solid adsorbents are the two main media for capturing low
concentrations of CO2.8 Among them, alkaline aqueous
solution has been promoted by several companies such as
Carbon Engineering and Climeworks for their high capacity
and simple process.9,10 Unfortunately, the regeneration of the
solution requires high energy consumption, and the solution is
corrosive to the equipment and highly volatile, thereby causing
environmental pollution. To address these issues, different
porous solid adsorbents have been developed extensively.
These adsorbents are mainly carbon-based materials,11−13
zeolites,14−16 and metal−organic frameworks (MOFs).17,18
Compared with alkaline aqueous solutions, the heat of
adsorption of porous solid adsorbents is remarkably lower,
consumption. However, MOF materials are unstable in humid
air, and the ligand bonds are easily hydrolyzed. Carbon-based
materials such as activated carbon and carbon nanotubes are
more stable than MOF materials but have a low selectivity for
CO2.13
Zeolites have been extensively studied in the fields of
catalysis, adsorption, and separation owing to their low cost,
stability, and easy preparation.19,20 In particular, 13X zeolites
have been used for the adsorption and separation of
CO2.19,21−23 Studies have shown that the adsorption selectivity
of 13X zeolites for CO2 is much greater than that of ZIF-8 or
activated carbon,24,25 making them the best candidate for DAC
systems. Further, 13X zeolites mainly rely on high micro-
porosity and uniform pore size to bind CO2 molecules and
cannot efficiently adsorb and separate CO2.26 Therefore, to
further improve the adsorption performance of zeolites,
researchers have introduced different types of heteroatoms
into the framework structure of zeolites19,27 and precisely
adjusted the pore or channel structure to meet the
Received: December 9, 2022
Revised: February 23, 2023
Accepted: March 2, 2023
Published: March 13, 2023

© 2023 American Chemical Society https://doi.org/10.1021/acs.iecr.2c04458

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technological requirements. For basic cation-modified zeolites,
the stronger the ionic dipole, the more favorable it is to
promote CO2 adsorption. The exchange of Li+ with Si/Al = 1
low silica zeolite X (Li-LSX) is currently the best commercially
adopted adsorption technique. The adsorbent capacity of CO2
(298 K, 400 ppm) can reach 1.34 mmol/g, followed by Na+
and K+.28,29 Chen et al.30 also prepared a new type of LiPdAgX
zeolite by the ion exchange method with better adsorption
performance than the undoped metal X zeolite. The separation
coefficient of this zeolite at 10% CO2 concentration is 61,
which is the best selectivity so far. However, the strong
chemical adsorption between alkali metal ions and CO2
molecules leads to high desorption energy consumption of
these zeolites, which is not conducive to industrial applications.
In recent years, transition metals have gradually replaced
alkali metals because they have advantages such as many empty
d orbitals and small ionic radius.21,31 Zhou et al.32 developed
an unusual “acid co-hydrolysis route” to slowly co−condense
transition metal Fe with Si/Al precursors at the initial gel
phase. Fe atoms were successfully introduced into the MOR
framework, which improves the adsorption selectivity of the
zeolite. In addition, the transition metals Cu(II), Co(II),
Ni(II), Fe(III), and Ce(III) were doped into SSZ-13 and RHO
zeolites by ion exchange,14,33 and their CO2/N2 separation
performances were investigated by single-component static
isothermal adsorption experiments. Co(II)/SSZ-13 exhibited
the greatest CO2 uptake (4.49 mmol/g) and superior CO2/N2
separation (52.55) at 273 K and 1 bar. Recently, Wang et al.34
prepared a porous material adsorbent X zeolite from rice husk
ash and modified these materials into Ce and La zeolites by ion
exchange. The CO2/N2 selectivity of LaNaX zeolite was
improved by more than three times, and the initial adsorption
rate of LaNaX remained above 96.5% after 20 adsorption−
desorption cycles. Currently, applied adsorbent materials for
DAC usually have low CO2 driving force and high regeneration
energy consumption due to the low CO2 partial pressure in the
air. In addition, these research results only focus on their CO2
adsorption performance at room temperature (25 °C),
ignoring the DAC device operating at different temperatures
in the actual environment.35 Therefore, it is a major challenge
to design a transition metal-doped zeolite that can effectively
capture CO2 in the air and understand its adsorption
performance at different temperatures.
In this work, iron-containing 13X zeolite (Fe@13X) was
produced by a simple and efficient one-step in situ
crystallization method. The prepared zeolites were charac-
terized by different devices to confirm that the unsaturated
Fe3+ ligand was successfully constructed within the 13X zeolite
nanopore channels. The Fe@13X zeolite working at temper-
atures ranging from 25 to 75 °C was studied by
thermogravimetric analysis (TGA) to investigate the adsorp-
tion and regeneration performances of the material. Sub-
sequently, the desorption energy and actual production of CO2
of the Fe@13X zeolite were comprehensively analyzed in
combination with differential scanning calorimetry (DSC). In
addition, the cycle stability energy is explored in simulated air.
2. EXPERIMENTS
2.1. Materials. Sodium hydroxide (NaOH, AR, 98%),
sodium metasilicate nonahydrate (Na2SiO3·9H2O, AR, 98%),
Fe(NO3)3·9H2O, and sodium aluminate oxide (Na2Al2O4, AR,
98%) were purchased from Sinopharm Chemical Reagent Co.,
LTD., China. High-purity N2 (99.999%) and synthetic air (400
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ppm CO2 in N2) were procured from Guangli Gas Co., LTD.,
Ningxia, China.
2.2. Synthesis of 13X and Fe@13X. The preparation
method in this paper was improved using the hydrothermal
method reported by Khoramzadehet et al.36 First, 1.5 g of
NaOH, 0.5 g of Na2Al2O4, and 29 g of deionized water were
mixed. Subsequently, under vigorous stirring, 0.09 g of
Fe(NO3)3·9H2O solution was added to the mixed solution,
and the solution was stirred until completely dissolved.
Thereafter, 3.81 g of Na2SiO3·9H2O solution was slowly
added dropwise to the abovementioned solution, followed by
stirring for 6 h. The molar compositions of the synthesized gels
were n % Fe/1 SiO2/0.58 Na2O/33 H2O/0.06 Al2O3 (n = 0
and 0.03). Finally, the slurry was placed in a stainless-steel
autoclave and crystallized in an oven at 80 for 14 h. The
prepared solid was washed with deionized water to neutral,
dried under vacuum, and calcined at 500 °C in a pure N2
atmosphere for 4 h. The synthetic samples obtained were
named 13X (n = 0) and Fe@13X (n = 0.03).
2.3. Material Characterization. The morphology and
elemental distribution of zeolites were examined by field
emission scanning electron microscopy (FE-SEM, Quanta
400FEI, Nano Ports, USA). Transmission electron microscopy
(TEM, Tecnai G2 20, FEI NanoPorts, USA) and high-
resolution TEM were performed to distinguish the lattice
changes in the zeolites. The phase purity of zeolites was
assessed on an X-ray diffractometer (XRD, Bruker D8
Advanced, Germany). The forms of Fe atoms were analyzed
by X-ray photoelectron spectroscopy (XPS, ESCALAB 250Xi,
Thermo Fisher Scientific, USA), Fourier transform infrared
spectroscopy (FTIR, Bruker TENSOR37, Germany), ultra-
violet−visible spectroscopy (UV−vis, Shimadzu UV-2600,
Japan), and electron spin resonance (ESR) spectroscopy
(Bruker A300, Germany). The N2 isotherm at 77 K and CO2
isotherm at 273 K were determined by an automatic physical
adsorption analyzer (Autosorb-IQ, Quantachrome, USA).
Before measurement, the sample was kept in vacuum at 200
°C for 6 h to ensure complete removal of impurities. The
Brunauer−Emmett−Teller method was used to calculate the
specific surface area (SBET) of zeolites based on the N2
adsorption data with a relative pressure (P/P0) of 0.01−0.25.
The total pore volume (Vtotal) was calculated at P/P0 = 0.99.
The micropore (<2 nm) volume (Vmicro) and micropore
specific surface area (Smicro) were determined using the t-plot
method. The narrow micropore size distribution (NMPSD)
for micropore size <0.7 nm was obtained from the CO2
adsorption isotherm at 273 K by applying the Dubinin−
Radushkevich equation.
2.4. CO2 Adsorption Performance Measurements.
Dynamic adsorption experiments of CO2 were performed in
simulated air (400 ppm CO2 in N2) by using an STA 449F3
analyzer (NETZSCH, Germany). The thermal synthesis
analyzer can provide TGA and DSC signals simultaneously.
The calorimetric and gravimetric accuracies were 1 μW and 0.1
μg, respectively. TGA was used to analyze the weight change of
CO2, while DSC was performed to measure the energy change
of the CO2 adsorption/desorption process.35,37
In TGA, first, a 55 mg sample was weighed and spread in an
alumina pan. Then, it was heated to 110 °C in pure N2 (100
mL/min) and kept for 2 h. The temperature decreased to 25
°C at a rate of 2 °C/min, and the temperature was stabilized
for 1 h under a N2 atmosphere for pretreatment. Subsequently,
the gas was changed to simulated air (100 mL/min) for
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Figure 1. (a) SEM images and the corresponding EDS mapping images for Al, Na, Si, and Fe elements and (b) SEM elemental mapping images.

Figure 2. TEM images of (a) 13X and (d) Fe@13X. HRTEM images and area magnification of (b,c) 13X and (e,f) Fe@13X.

adsorption, and the time was set to 10 h. Finally, the
temperature was again raised to 110 °C for desorption under
100 mL/min of pure N2. The abovementioned steps were
repeated to study the characteristics of CO2 adsorption profiles
of the samples at different adsorption temperatures for 5 h.
Cyclic stability experiments mainly comprised two steps of
adsorption and desorption, without any pretreatment.
For the adsorption experiments, the saturated adsorption
(qads, mmol/g) and desorption (WCO2, mmol/g) of CO2 were
d
where m0 is the initial weight of the adsorbent (mg); mt is the
mass of the adsorbent after saturation (mg); qremain is the
amount of CO2 still remaining on the material after the
desorption is completed.
An adsorption method similar to the TGA described above
was used in the DSC experiments. The adsorption (ΔHads) and
desorption (ΔHdes) heats (kJ/mol) of CO2 were calculated as
follows
( )·(
A ads mindium
)

calculated by the weight method, as shown in the following Hindium• A indium madsorbent
equation Hads =
qads (3)
1000(m t m0)
qads =
44m0 (1)
Hdes =
Hindium• ( )·(
Ades
A indium
mindium
madsorbent )
wCO2 (4)
1000(mt m0)
WCO2 = = qads qremain where madsorbent is the weight of the adsorbent after degassing
44m0 (2) (mg), Aads and Ades are the integrated area under the DSC test
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Figure 3. (a) Fe 2p XPS spectra of Fe@13X. Comparison of (a) FTIR spectra, (b) UV−vis spectra, and (c) ESR spectra of 13X and Fe@13X.
curve (mJ); ΔHindium is the heat of melting of indium (J/
gindium); Aindium is the integrated area of the heat absorption
peak for the melting of (mJ); and mindium is the weight of
indium (mg).
The CO 2 production (P TGA‑DSC , kgCO 2 /kgads ·h) and
d
desorption energy (ETGA‑DSC, kW h/kgCO2) were calculated as
d
follows
WCO2·MWCO2
PTGA DSC =
t ·1000 (5)
Hdes
E TGA DSC =
3.6· MWCO2 (6)
where t (h) is the total time measured and 3.6 is the
transformation coefficient to gain kW h.
3. RESULTS AND DISCUSSION
3.1. Structural Characterization. The morphologies of
13X zeolite with different structural properties before and after
Fe3+ modification were observed by SEM (Figures 1 and S1).
The particles of Fe@13X have an octahedral structure with a
nearly round appearance, which is consistent with the typical
crystalline state of 13X.15,30 This structure demonstrates that
the synthesized Fe@13X has excellent dispersibility and high
crystallinity. The uniform distribution of Fe species within the
newly formed 13X crystal was observed in the SEM images,
corresponding EDS mapping images (Figure 1a), and SEM
elemental mapping images (Figure 1b).
The TEM images of the zeolite are characterized as shown
in Figure 2a,c, and together with the EDS images in Figure 1a,
they indicate that the Fe@13X lattice edges are uniform, and
there are no Fe2O3 particles. In addition, XRD analysis shows
that the 2θ angle of the zeolite after Fe doping moves toward
the high angle direction and the lattice spacing decreases
(Figure S2). The HRTEM images of 13X and Fe@13X are
shown in Figure 2b,c,e,f, respectively. The interplanar spacing
of the (111) plane corresponding to 13X is reduced from 0.52
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to 0.49 nm. These results fully indicate that the Fe species
grow uniformly within the pores and regulate the internal pore
size of zeolites.
To clarify the form in which Fe atoms exist, the surface
metal state of Fe@13X were first analyzed by XPS. As shown
in Figure S3, the XPS spectra of both 13X and Fe@13X
showed the existence of Si 2p, Al 2p, O 1s, and Na 1s,
indicating that the 13X structure is retained.38 The Fe 2p
spectra (Figure 3a) indicate that the two characteristic peaks at
725.48 and 711.48 eV can be attributed to Fe 2p3/2 and Fe
2p1/2 of Fe3+, respectively. This finding demonstrates the Fe
species in Fe@13X exists only in the isolated Fe3+ form.
The existing state and coordination of Fe3+ were further
analyzed using the UV−vis and ESR spectra. Compared with
the UV−vis spectra (Figure 3b) of 13X, Fe@13X has two
strong absorption bands at 210 and 261 nm, which are mainly
attributed to the four-coordinated isolated Fe3+ in the zeolite
framework.32,39 Figure 3c shows the ESR spectra of 13X and
Fe@13X. The results show that Fe@13X has characteristic
signal peaks at g = 2 and g = 4.3. The signal peak at g = 4.3 is
the four-coordinated site Fe3+ (replacing the T atoms of the
zeolite framework) and the peak at g = 2 is attributed to the
extra-framework hexacoordinate Fe3+.32 In summary, the active
material iron exists mainly in the framework of 13X in the form
of four-coordination Fe3+, and a small amount of Fe3+ exists in
the micropore channels.
The FTIR spectra in Figure 3d provide further evidence. All
samples have clear absorption peaks at 981, 756, 679, 567, and
467 cm−1, which are in accordance with the FTIR spectra
reported in the literature for 13X. The peak at 467 cm−1 is
attributed to the bending vibration of metal−oxygen (T−O)
and that at 756 cm−1 is attributed to the Si(Al)−O
vibration.38,40 However, the intensity of each of the stretching
vibration peaks of Fe@13X at 467 and 981 cm−1 is remarkably
stronger than that of 13X. These findings indicate that Fe3+
occupies the 13X framework T sites, leading to an increase in
the difference in the electronegativity between the atoms
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Figure 4. (a) N2 Adsorption Isotherms at 77 K and (b) NMPSD curves for CO2 at 273 K for 13X and Fe@13X.

attached to the ends of the chemical bond, resulting in a porosity and narrowed micropore channels. Based on these
stronger absorption vibrational peak. observations, the four-coordinated Fe3+ in the framework
The entry of Fe species into the zeolite framework inevitably effectively narrows the microporous channels of 13X, allowing
affects the variation in the porosity of the material. From the CO2 with a relatively small kinetic diameter (3.3 Å) to enter
N2 adsorption isotherms of the samples at 77 K (Figure 4a), the channels and hindering the entry of the larger N2 (3.64 Å).
both 13X and Fe@13X exhibit type-I isotherms for micropores 3.2. CO2 Capture Performance. For practical applications
with remarkable N2 capacity at a relative pressure of P/P0 = in direct air conditions, we performed TGA to monitor the
0.01.41 From Table 1, the SBET of Fe@13X is 734 m2/g, which amount of CO2 adsorbed by 13X and Fe@13X. The results
showed that the CO2 uptake of Fe@13X was 0.64 mmol/g,
Table 1. Textural Properties of 13X and Fe@13X which was twice that of 13X at 25 °C and 400 ppm (Figure
5a,d and Table 2). Furthermore, Fe@13X exhibited faster
SBET Smicro Vtotal Vmicro
samples (m2/g) (m2/g) (cm3/g) (cm3/g) SBET/Smicro
13X 881 798.30 0.426 0.315 91%
Table 2. CO2 and N2 Capture Performance of 13X and Fe@
Fe@13X 734 650.76 0.349 0.251 89%
13X
N2 adsorption capacity
samples CO2 adsorption capacity (mmol/g) (mmol/g)
is lower than that of 13X (881 m2/g), indicating that the Fe3+
present in the micropores blocked the pore channels. The 298 K, 273 K, 298 K, 273 K, 298 K,
400 ppm 1 bar 1 bar 1 bar 1 bar
NMPSD in Figure 4b shows that the micropore pore sizes of
13X 0.29 6.89 5.79 0.95 0.44
both zeolites are concentrated around 0.35 and 0.48 nm.
Fe@13X 0.64 8.59 7.66 0.78 0.30
Compared with 13X, Fe@13X has a larger pore size
distribution area between 0.4 and 0.6 nm, mainly extending
to the small pore size direction. These findings combined with adsorption kinetics, as seen from the sharper adsorption rate
TEM images indicate that Fe@13X has well-developed curve for Fe@13X compared to 13X (Figure 5b). The

Figure 5. (a) CO2 capacity and (b) adsorption rate at 25 °C in simulated air. (c) Comparison of the adsorption capacity of Fe@13X under air
conditions. (d) Comparison of the saturation adsorption capacity of 13X at 1 bar and 298 K.

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Figure 6. (a,b) CO2 adsorption capacity of Fe@13X at different temperatures. (c) Adsorption rate and (d) actual selective measurement of Fe@
13X at different adsorption temperatures.
exceptional CO2 adsorption performances of Fe@13X at low
partial pressures of CO2 are attributed to the stronger affinity
of the framework Fe3+ for CO2 and the smaller microporous
pore size.32 Since Fe3+ has many empty 4d and 4s orbitals,
electrons are easily transferred from the bonding π2p orbital of
the CO2 molecule to the 4s orbital of Fe3+ to realize the σ-
donation effect and from the empty 4d orbital of Fe3+ to the
π2p* of the CO2 molecule to complete the d−π2* back
donation. This π-coordination effect enhances the interaction
between CO2 molecules and Fe@13X.42−44 With excellent
CO2 adsorption performance and dynamics, Fe@13X is
considered one of the best candidates for DAC of CO2.
Note that the CO2 capacity of Fe@13X is better than or
comparable to that of previous high-efficiency adsorbents
(Figure 5c and Table S1), validating the reliability of the
zeolite.
Considering the fact that Fe@13X has high adsorption
capacity and adsorption rate, its static adsorption performance
and selectivity were studied by measuring the single-
component CO2 and N2 isotherms at 273 and 298 K (Figure
S4). CO2 adsorption capacities of Fe@13X greatly exceeded
those of 13X and reached up to 7.66/8.59 mmol/g (273/298
K, 1 bar; Table 2). The adsorption capacity of Fe@13X at 298
K was also compared with that of other zeolites and was found
to exceed or be equivalent to that of most zeolites (Figure 5d
and Table S2). Additionally, Fe@13X exhibited lower N2
absorption capacity than 13X, illustrating its selectivity
advantage. To predict the CO2/N2 selectivity, the IAST
method was used (eq S1). As shown in Figure S5, Fe@13X has
remarkably better selectivity than 13X and shows remarkable
selectivity at lower partial pressures, indicating that the zeolite
is highly promising for DAC.
3.3. Effect of Adsorption Temperature on CO2 and N2.
Most studies only dealt with the CO2 adsorption behavior of
adsorbents at ambient temperature and pressure, and DAC
systems operating at different temperatures were ignored.45,46
To further analyze the DAC adsorbent, an adsorption
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temperature of 25−75 °C was used for experimental
exploration. As shown in the adsorption isotherms (Figure
6a,c), the CO2 uptake of Fe@13X decreases with increasing
adsorption temperature. When the temperature rises from 45
to 55 °C, the adsorption of CO2 decreases the most and then
stabilizes. The highest adsorption of CO2 was observed at 25
°C with 0.54 mmol/g. More importantly, the adsorption
capacity of Fe@13X at 65 °C is equivalent to that of 13X at 25
°C. Even at a much higher temperature of 75 °C, the sample
still shows a CO2 uptake of 0.25 mmol/g.
Furthermore, the trend of the influence of temperature on
the adsorption rate is similar to that of CO2 adsorption. From
Figure 6c, the adsorption rate is seen to be negatively
correlated with temperature, and a high temperature leads to a
lower adsorption rate. The adsorption rate at 75 °C is still
higher than that of 13X at 25 °C. This trend is in agreement
with that reported in literature because adsorption is an
exothermic progress, and the higher the temperature, the less
likely are the CO2 molecules to be bound.35,46 Considering the
actual demand under different atmospheric temperature
conditions, Fe@13X exhibits superior adsorption capacity
and kinetics compared to 13X; hence, it is considered an
excellent CO2 capture material for DAC systems.
The CO2/N2 selectivity is an essential performance indicator
for evaluating adsorbents. According to the abovementioned
TAST calculations, Fe@13X has good selectivity at 25 °C, but
supporting data for practical applications in DAC systems are
still lacking. Therefore, the selectivity of Fe@13X was
measured at different simulated air temperatures. The variation
of the CO2 selectivity of Fe@13X at different temperatures can
be visualized from the adsorption and pretreatment data shown
in Figure 6d. The Fe@13X at different temperatures showed
obvious adsorption platforms, indicating that the N 2
adsorption of the adsorbent saturated within a short time
during the pretreatment process. Moreover, the plateau
gradually started to level off as the adsorption temperature
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Figure 7. (a) Regeneration of Fe@13X at different desorption temperatures and (b) amount of CO2 desorbed in step 1.

Figure 8. Energy consumption calculations for samples: (a) ΔHads and ΔHdes, (b) CO2 production and desorption energy.

Figure 9. (a) CO2 adsorption/desorption curves and cyclic performance of Fe@13X at an adsorption temperature of 25 °C and a desorption
temperature of 110 °C.

increased. The N2 adsorption plateau remained almost
constant above 45 °C.
The differences in the CO2 adsorption between 25 and 75
°C, Qst values and FTIR analysis of Fe@13X before and after
CO2 adsorption indicate that Fe@13X is mainly physisorbed
(Figures S6 and S7). The low temperature favors adsorption,
and the CO2 concentration trapped at high temperatures
decreases, and the selectivity increases. Combined with the
previous analysis of the adsorption ability of CO2 and N2, the
selectivity at 45 °C is better than that at other higher
temperatures (55, 65, and 75 °C).
3.4. Study of Desorption Temperature. Desorption is
another important process in the DCA system. This process
can be observed to effectively assess the economic value of the
material. Therefore, experiments were performed by changing
the desorption temperature (from 50 to 110 °C) at an
adsorption temperature of 25 °C. The experimental design is
as follows. First, Fe@13X was kept for 2 h in pure N2 (100
mL/min) at 110 °C, and then the temperature was lowered to
25 °C at 2 °C/min. Subsequently, the gas was switched to
simulated air (100 mL/min) and was maintained for 3 h to
ensure that the adsorption of CO2 was saturated. Finally, the
5426
gas was replaced with pure N2, and the temperature was raised
to the target desorption value for 30 min. If the temperature
was set below 110 °C, another desorption experiment was
performed at 110 °C for 30 min to ensure that CO2 could be
completely removed from the adsorbent.
Figure 7a shows the desorption curves at different
temperatures. The weight loss of Fe@13X is smaller at lower
desorption temperatures, indicating that the desorption rate of
Fe@13X decreases with decreasing desorption temperature.
Figure 7b shows the desorption capacity of CO2 for desorption
step 1. When the temperature exceeds 90 °C, the weight
difference of the adsorbent changes from 0.01 to 0.04 mg, and
the desorption rate changes more rapidly. Almost no CO2
remains inside Fe@13X for both desorption temperatures of
100 and 110 °C, but the most effective removal efficiency of
100% is achieved at 110 °C.
3.5. Energy Consumption Calculation for the DAC
System. To further evaluate the practicability of Fe@13X in
DAC. In this section, 25 and 110 °C are selected as the
operating temperatures to measure the energy involved in
adsorption/desorption. The specific operating conditions of
this experiment are listed in Table S3.
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The Aads and Ades values of the adsorbent can be obtained by
integrating the DSC test results shown in Figure S8. The
performance indicators of 13X and Fe@13X were then
calculated according to eqs 1−4. The results show that the
ΔHads and ΔHads of 13X are higher than those of Fe@13X
(Figure 8a), which are 0.13 and 2.89 kJ/mol, respectively.
Combined with the Qst analysis (Figure S6), Fe@13X has a
moderate binding strength to CO2, and the regeneration
energy consumption is lower than that of 13X. Therefore, to
confirm the abovementioned analysis, the CO2 production and
desorption energy of 13X before and after the modification
were also calculated (Figure 8b). The CO2 production values
of 13X and Fe@13X were calculated by using eq 5 as 0.001
and 0.003 kgCO2/kgads·h, respectively. For the desorption
d
energy (eq 6), the values were 0.018 and 0.005 kW h/kgCO2
for 13X and Fe@13X, respectively. These results confirm that
Fe@13X has a higher CO2 production than 13X but requires
less desorption energy.
3.6. Cyclic Stability. CO2 adsorbents with excellent
regeneration capacity are critical for the industrial applications
of DAC. The prepared Fe@13X adsorbent was tested for 10
cycles to evaluate its stability. Here adsorption was performed
using simulated air at 25 °C for 1 h, and desorption was
performed for 30 min at 110 °C using pure N2. The CO2
working capacities in each cycle are shown in Figure 9a,b. At
the end of 10 cycles, the CO2 adsorption capacity of Fe@13X
remained at 0.24 mmol/g with almost no loss, demonstrating
that the zeolite has excellent stability and is suitable for
industrial applications.
4. CONCLUSIONS
An adsorbent with improved CO2 adsorption and separation
performances was developed by introducing doped transition
metal Fe into zeolite 13X using a simple one-step in situ
crystallization method. The DAC performance and energy
consumption calculation of Fe@13X were studied by a
combination of TGA and DSC. The results showed that
Fe@13X has a much faster adsorption rate and superior CO2
adsorption capacity of 0.64 mmol/g compared to the
corresponding values of 13X at 25 °C and 400 ppm CO2.
Furthermore, Fe@13X exhibited higher CO2 production
(0.003 kgCO2/kgads·h) and lower desorption energy (0.006
d
kW h/kgCO2) than the parent zeolite (13X) in simulated air.
d
Simultaneously, Fe@13X exhibited excellent stability under air.
The results presented here suggest that Fe@13X has extremely
high prospects for application in solid-adsorbent DAC systems.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.iecr.2c04458.
(PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Mei An − Key Laboratory of Coal Processing and Efficient
Utilization, Ministry of Education, China University of
Mining & Technology, Xuzhou, Jiangsu 221116, China;
orcid.org/0000-0002-4025-4756; Email: anmei_712@
163.com
pubs.acs.org/IECR Article
Qingjie Guo − State Key Laboratory of High-efficiency Coal
Utilization and Green Chemical Engineering, School of
Chemistry and Chemical Engineering, Ningxia University,
Yinchuan, Ningxia 750021, China; Key Laboratory of Clean
Chemical Engineering in Universities of Shandong, College of
Chemical Engineering, Qingdao University of Science &
Technology, Qingdao 266042, China; Email: qjguo@
qust.edu.cn
Xiude Hu − State Key Laboratory of High-efficiency Coal
Utilization and Green Chemical Engineering, School of
Chemistry and Chemical Engineering, Ningxia University,
Yinchuan, Ningxia 750021, China; Email: xiude_hu@
163.com
Authors
d
Xiaoju Xiang − State Key Laboratory of High-efficiency Coal
Utilization and Green Chemical Engineering, School of
Chemistry and Chemical Engineering, Ningxia University,
Yinchuan, Ningxia 750021, China; orcid.org/0009-
0009-2981-4458
Tuo Guo − State Key Laboratory of High-efficiency Coal
Utilization and Green Chemical Engineering, School of
Chemistry and Chemical Engineering, Ningxia University,
Yinchuan, Ningxia 750021, China
Yinmei Yin − State Key Laboratory of High-efficiency Coal
Utilization and Green Chemical Engineering, School of
Chemistry and Chemical Engineering, Ningxia University,
Yinchuan, Ningxia 750021, China
Zhuxian Gao − State Key Laboratory of High-efficiency Coal
Utilization and Green Chemical Engineering, School of
Chemistry and Chemical Engineering, Ningxia University,
Yinchuan, Ningxia 750021, China
Yanxia Wang − Chemical Science and Engineering College,
North Minzu University, Yinchuan 750021, China;
orcid.org/0000-0002-1225-3510
Ruotong Wang − State Key Laboratory of High-efficiency Coal
Utilization and Green Chemical Engineering, School of
Chemistry and Chemical Engineering, Ningxia University,
Yinchuan, Ningxia 750021, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.2c04458
Author Contributions
X.X.: conceptualization; methodology, validation, formal
analysis, data curation, investigation, visualization, writing�
original draft, and writing�review and editing. T.G.: Visual-
ization, formal analysis, and writing�review and editing. Y.Y.:
Visualization and formal analysis. Z.G.: Visualization. Y.W.:
Visualization. R.W.: Visualization. M.A.: Methodology, formal
analysis, visualization, writing�review and editing, and
supervision. Q.G.: Methodology, writing�review and editing,
project administration, funding acquisition, and supervision.
X.H.: Methodology, visualization, writing�review and editing,
and supervision.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported financially by the Joint Funds of the
National Natural Science Foundation of China (U20A20124),
the Natural Science Foundation Project of Ningxia
(2022AAC01001), and the Foundation of State Key
5427 https://doi.org/10.1021/acs.iecr.2c04458
Ind. Eng. Chem. Res. 2023, 62, 5420−5429
Industrial & Engineering Chemistry Research
Laboratory of High-efficiency Utilization of Coal and Green
Chemical Engineering (grant no 2022-K27).
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