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Review on CO2 Capture Using Amine-Functionalized Materials

Jannis Hack, Nobutaka Maeda,* and Daniel M. Meier*

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ABSTRACT: CO2 capture from industry sectors or directly from the atmosphere is drawing
much attention on a global scale because of the drastic changes in the climate and ecosystem
which pose a potential threat to human health and life on Earth. In the past decades, CO2 capture
technology relied on classical liquid amine scrubbing. Due to its high energy consumption and
corrosive property, CO2 capture using solid materials has recently come under the spotlight. A
variety of porous solid materials were reported such as zeolites and metal−organic frameworks.
However, amine-functionalized porous materials outperform all others in terms of CO2 adsorption
capacity and regeneration efficiency. This review provides a brief overview of CO2 capture by
various amines and mechanistic aspects for newcomers entering into this field. This review also
covers a state-of-the-art regeneration method, visible/UV light-triggered CO2 desorption at room
temperature. In the last section, the current issues and future perspectives are summarized.

1. INTRODUCTION monoethanolamine solution (20−30 wt % in water) and then

Since the onset of the Industrial Revolution in the 18th released at 100−120 °C. Amine scrubbing produces a huge
century, the atmospheric concentration of carbon dioxide amount of degraded solvent as waste. Therefore, the current
scrubbing technologies are energy intensive and therefore not
increased from ca. 280 ppm1 to 417 ppm in 2022. The climate
very economical. To improve CO2 capture technology, two
change and sea level rise of 1−3 mm per year arise from the
major drawbacks of amine scrubbing need to be overcome: (1)
record-high level of atmospheric CO2 concentration. Besides,
energy-inefficient regeneration at high temperature and (2)
CO2-induced ocean acidification is considered to have an
waste management of the degraded solvent containing amines.
impact on organisms and the ecosystem.2,3 Provided that no
In light of this, CO2 capture using solid materials has recently
action is taken, the atmospheric CO2 concentration is
come under the spotlight.10 CO2 adsorption on solid materials
estimated to rise up to 450 ppm by 2050.4 Because of surging
occurs at solid−gas interfaces and thus requires no solvent,
public concerns about potential environmental damage, carbon
leading to the complete elimination of the solvent disposal
capture and storage/sequestration (CCS)5 or utilization
process. Normally, CO2 adsorption on solid materials is carried
(CCU)6 became one of the key research topics in the 21st
out at ambient temperature, followed by regeneration of the
century. CCS aims at geological storage of CO2 in the deep
materials at 80−120 °C to release CO2. Therefore, high energy
underground. On the other hand, CCU is a concept in which
input during the regeneration process is still inevitable. Solid
captured CO2 is utilized as a carbon source for chemical
adsorbent-based technology can be applied for two different
feedstocks such as fuels and fine chemicals. The scientific capturing concepts. One is the direct air capture (DAC) which
community and industry are gradually coming to a conclusion captures CO2 directly from the atmosphere. The other is CO2
that CCS has limitations, taking into account the economic capture from the off-gas of industrial sectors such as power
feasibility. Hence, industries are shifting toward exploration of plants and factories for fine chemical synthesis. DAC is
CCU technologies.7 In any case, CO2 capture is the very first considered to be a “negative emission technology” because
step and thus the most critical technology to pave the way for already released CO2 in the air (417 ppm) has to be captured.
facilitating the industrialization of CCS and CCU. In the However, DAC is much less cost-effective compared to CO2
industrial sector, pressure swing adsorption (PSA) and amine capture from exhaust streams because of the low concentration
scrubbing have traditionally been applied for some decades.8
PSA, which has been the main technology in the last a few
decades, separates hydrogen out of other gases, including CO2. Received: May 31, 2022
Since PSA aims at purification of H 2 , the resulting Accepted: October 5, 2022
concentration of CO2 collected from off-gas is too low to Published: October 28, 2022
utilize CO2 for further chemical processes.8 On the other hand,
amine scrubbing has been applied since 1930 and allows CO2
collection with high purity (>99%).9 CO2 is captured by using
© 2022 The Authors. Published by
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Table 1. Summary of CO2 Adsorption Performance of Different Adsorbents

Amine Adsorption Adsorption Desorption
loading capacity temperature temperature
Support Absorbent [wt %] [mmol/g] [°C] [°C] Adsorption conditions Reference
SBA-15 functionalized by different - 2.2 to 3.2 25 95 to 105 pure CO2, static Boukoussa et
aminosilanes al.31
SBA-15 and fumed TEPA, impregnated - 3.25 to 3.97 75 115 15% CO2, no Chao et al.32
silica information about gas
flow
β-zeolite TEPA, impregnated 38.4 2.90 30 135 10% CO2, 30 mL/min Fischer et
al.12
protonated titanate TEPA, impregnated 60 4.13 75 100 10% CO2, 10 mL/min Guo et al.13
nanotubes
(PTNTs)
nanoporous titanium TEPA, impregnated 60 3.1 60 100 1% CO2 and 1% H2O, Irani et al.33
oxyhydrate 300 mL/min
carbon nanotubes TEPA, impregnated 75 5.0 60 90 10% CO2 and 1% H2O, Irani et al.14
(CNTs) 300 mL/min
PMMA (HP2MG) TEPA and modified TEPA, - 2.58 to 4.30 25 100 pure CO2, 200 mL/min Jo at al.15
impregnated
silica gel TEPA and PEI, 40 2.64 to 3.32 75 100 pure CO2, 100 mL/min Jung at al.34
impregnated
PAN carbon fibers TEPA and TETA, 50 4.30 to 5.44 25 90 10% CO2, 30 mL/min Kuang at
impregnated al.35
mesoporous SiO2 EPA, DETA, TEPA, and 40 1.19 to 2.34 35 100 10% CO2, no Liu at al.17
(MCM-41) PEHA, impregnated information about gas
flow
TiO2 monoethanolamine, 40 1.09 45 90 1% CO2, 300 mL/min Sun at al.36
impregnated
MR10 (LDPE) BPEI, impregnated 50 2.64 25 70 different concentrations Wang at al.22
of CO2, 3 mL/min
fumed silica BPEI and IL, impregnated 30 and 10 - 25 50 5000 ppm of CO2, 200 Weisshar at
mL/min al.23
nanosilica LPEI, impregnated different 1.0 to 3.5 different 50−60 different concentrations Zhang at
loadings temperatures of CO2, 3 mL/min al.21
- IRMOF-74-III-(CH2NH2)2, - 1.2 25 120 pure CO2, static Flaig et al.29
alkylamine functionality
- N-containing polymer - 6.9 25 25 10% CO2 Geng et al.27
NUT-4, imine linker
- N-doped copolymer 3.1 0 - pure CO2, static Qi et al.

of CO2 in the air and thus the associated thermodynamic of impurities in off-gas streams and adsorption mechanisms
barrier.4 On the other hand, CO2 capture from industrial off- and process engineering.
gas is considered as “zero emission technology” in order not to
increase the current CO2 level any further. Depending on 2. AMINE-FUNCTIONALIZED SOLID
emission sources, the CO2 concentration differs in a wide Amine-functionalized solid adsorbents light a path for
range of 3−100%.11 For example, the off-gas from coal-fired mitigating the issues encountered by liquid amine scrubbing,
power plants contains 10−15% CO2, whereas fermentation such as the loss of volatile amines by vaporization. The support
plants for ethanol production emit 98−99% CO2.11 Hence, materials with high surface area and porosity are functionalized
CO2 capture from these plants is thermodynamically favored with amines, such that the amines are well-dispersed as
and can be cost-effective. Public concerns about global uniformly as possible. Hence, the functionalized materials
warming and awareness of the importance of CO2 removal possess the positive properties of both components (an amine
make both “negative emission technology” and “zero emission and a support). The support materials are often functionalized
technology” a high priority. Such an urgent demand has lately in two different ways: wet impregnation or anchoring on the
been extending the horizon of solid adsorbent materials with surface with covalent bonds. This chapter discusses what types
new concepts, and in the past decade we have witnessed of amines and solid support materials have already been
tremendous advance in this field.10 Porous materials have been explored. Table 1 lists adsorbent materials reported by
extensively explored, targeting high CO2 adsorption capacity different research groups in the last 15 years.
such as carbonaceous adsorbents, ionic liquids, zeolites, metal 2.1. Type of Amines. As described in the Introduction, the
oxides, and metal−organic frameworks (MOFs). The overview monoethanolamine solution has been used as a main sorption
of different adsorbents is summarized in a previously published component for amine scrubbing. Since monoethanolamine is
review article.10 not suitable for the functionalization of solids due to its high
In this review, we outline properties, advantages, disadvan- volatility and the small adsorption capacity of CO2, longer-
tages, and future perspectives of amine-functionalized materi- chain amines have often been employed in the past. A prime
als, foreseeing their potential for high CO2 adsorption capacity, example in this respect is tetraethylenepentamine (TEPA),
relatively low regeneration temperature, cost-effectiveness, and which contains five amine groups and thus has the theoretical
industrial applications. This article not only summarizes capacity of chemisorption of up to five CO2 molecules per one
different amine-based materials but also sums up the effects TEPA molecule. Because the past research mainly focused on
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the adsorption capacity, the high adsorption capacity of TEPA of amino groups.24 TEPA substituted with bulky alkyl groups
attracted much attention.12−16 As a result, TEPA has become was found to enhance the adsorption capacity and to lower the
one of the most widely used amines for the functionalization of regeneration temperature. They achieved 88% efficiency in the
solid materials. Besides, other ethyleneamines, such as desorption at 60 °C by sweeping an inert gas.
triethylenetetramine (TETA) and pentaethylenehexamine 2.2. Support Materials. The choice of an appropriate
(PEHA), are also suitable for the functionalization as they support material is driven by several factors. Two important
have similar performance in CO2 adsorption.17 Recently, the properties for the support material are the thermal stability and
amine-containing polymer, i.e., polyethylenimine (PEI), has chemical inertness. Accordingly, the support material should
also come to the forefront of research. PEI has two different not be decomposed at relatively high temperature and should
structures: branched polyethylenimine (BPEI) and linear not react with amines during functionalization so that the
polyethylenimine (LPEI).18−21 Due to the significantly lower amines remain available for the chemisorption of CO2. Table 1
price and availability in the market, BPEI was studied more shows the various support materials tested in recent years. It is
extensively compared to LPEI. Both PEI types have adsorption worth noticing that all supports reported fulfill the two criteria
capacity similar to or slightly lower than TEPA. However, the mentioned above. However, additional properties must be
regeneration temperature of PEI is much lower, especially considered to finely tune the adsorption and desorption
LPEI, compared to shorter ethyleneamines.21,22 Another performance. For example, additional decisive properties are
exciting aspect of the use of PEI is the influence of the specific surface area, porosity, and pore volume, whereby the
polymer size. Smaller PEI molecules are better suited for the adsorption performance is interrelated. The specific surface
impregnation of porous materials because they can diffuse area plays an important role in impregnating amines onto the
more uniformly into the pores than large PEI molecules. support material uniformly. Support materials with high
Larger PEI molecules, on the other hand, are less soluble in surface area can impregnate a larger amount of amines,
water, resulting in better regeneration stability under humid leading to higher adsorption capacity. Because BPEI is a highly
conditions. This is an important factor considering long-term viscous liquid, thick liquid BPEI layers are formed on support
operations. As shown in Table 1, different adsorption materials with low specific surface area. The thick liquid layers
temperatures 25−75 °C were chosen for each of the reports. inhibit gas diffusion, resulting in the low efficiency for CO2
The concept of such adsorption conditions was built upon the adsorption. Furthermore, the porosity and the pore volume are
exploitation of the off-gas heat from industrial sectors. The important for the diffusion of gaseous molecules through the
source of CO2 emission from the industrial sectors is normally support material. Materials with high porosity and large pore
higher than room temperature, e.g., coal and petroleum power volume are favored due to better mass transport through the
plants (40−65 °C).11 Therefore, the adsorption performance support material. Such a property can enhance the adsorption
in this temperature range is important for industrial capacity as well as rapid desorption of CO2. Thus, the choice of
applications. Due to the climate change and global concerns support material drastically influences the performance of the
about energy and the environment, the research direction is adsorbents.25 Furthermore, the number of acid sites on the
shifting toward how to lower the regeneration temperature surface also has an influence on the sorption properties of the
without compromising the high adsorption capacity. Weisshar amine. The beneficial effects of acidic sites of the support
et al. reported that a hybrid adsorbent of BPEI with ionic liquid material can be attributed to the interaction between the acid
released CO2 even at 50 °C.23 The zwitterions formed by the sites and the amine groups. The presence of strong surface
reaction of amines and CO2 interact with counterion pairs of acidity contributes to the formation of protonated amine
the ionic liquid, leading to the weakening of the C−N bond as species on which CO2 weakly adsorbs. This is beneficial to the
shown in Figure 1. repeated cycles of adsorption and desorption.26 On one hand,
Yogo et al. reported a different approach to improving both the higher thermostability of the entire system and better
adsorption and desorption properties by chemical medication distribution of the amine on the surface of the support material
result in more efficient adsorption.26
2.3. Functionalized Polymeric Adsorbents. There has
been a new strategy to add the CO2-capturing property to
polymeric compounds such as porous polymers27,28 and
metal−organic frameworks (MOFs)29,30 with amine-function-
alized linkers. MOFs are classified as coordination polymers
with a metal cation center and organic linker. Yagi and co-
workers reported that IRMOF-74-III was functionalized with
primary or secondary amines.30 IRMOF-74-III-CH3 without
amine functionalization also adsorbed CO2, but the adsorption
capacity dropped by 80% under humid conditions. This
behavior can be explained by the CO2 adsorption to the open
Mn sites where H2O competitively coordinates. On the other
hand, the moisture did not affect the performance of IRMOF-
74-III-CH2NH2, indicating that the CO2 uptake occurs with
the amine linkers and that the open Mn sites are not available.
The regeneration of IRMOF-74-III-CH2NH2 required 90 °C
Figure 1. Proposed interaction of BPEI and ionic liquid. Copyright to remove CO2. They extended the synthetic method toward
2016 American Chemical Society. Reprinted with permission from ref functionalization by diamine and reported that IRMOF-74-III-
23. (CH2NH2)2 adsorbed 2.33 times more CO2 than monoamine-
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functionalized IRMOF-74-III-CH2NH2.29 The complete re- primary and secondary amines react with CO2 and H2O to
generation was achieved at 120 °C in a vacuum. form ammonium ions and bicarbonate. Hence, the theoretical
Recently, Sun and co-workers have proposed nitrogen- value of moles of CO2 per mole of primary and secondary
doped porous carbons (NPCs) for CO2 capture.27,28 The amines doubles to 1.0 under humid conditions. Likewise,
NPCs were prepared through polymerization of 2,4,6-tris- under humid conditions, CO2 and water react with tertiary
(chloromethyl)mesitylene (TCM) and p-phenylenediamine amines by forming an ammonium ion and bicarbonate and by
(PD) to a polymer of NUT-4 (NUT stands for Nanjing Tech binding one mole of CO2 per mole of tertiary amine. These
University). The obtained NUT-4 was further carbonized at reactions schemes are examples out of all the potential reaction
elevated temperatures (400−700 °C) to obtain NPCs. The paths, e.g., the formation of carbamic acid. The actual reaction
CO2 adsorption capacity of 6.9 mmol/g was achieved with appears to be more complicated than the schemes described in
NPCs containing CO2-philic N sites. The complete regener- Figure 2.
ation of the adsorbent was possible under mild condition (25 According to the theoretical estimation, the presence of
°C, 30 mmHg, 60 min). moisture should double the CO2 adsorption capacity for
primary and secondary amines. Thus, the enhancement effect
3. MOISTURE EFFECT of moisture depends on the type of amines used and relative
Amine-functionalized solid materials are advantageous over humidity (RH). On PEI supported on resin22 or polymer,39
porous adsorbents because of their high tolerance against CO2 adsorption capacity increases proportionally with RH.
moisture. In most of the cases, the presence of moisture even With 100 RH % at a dew point of 25 °C, the CO2
enhances the CO2 adsorption capacity14,20,22,33,36−40 yet keeps breakthrough period was twice as long as that of dry
the regeneration temperature in the same range.23 The conditions.23 The recyclability test was also conducted using
atmosphere contains 18−60% humidity on average over the a triamine-grafted mesoporous material.38 Under dry con-
year. The exhaust gas from power plants also contains ditions, CO2 uptake dropped by 15% after 700 cycles because
moisture. Therefore, both DAC and CO2 capture from of the formation of a stable urea, whose reaction is not
industrial off-gas using amine-functionalized materials can reversible. Under humid conditions, the same CO2 adsorption
greatly benefit from the enhancement effect of CO2 adsorption capacity was kept over 700 cycles. H2O was reported to react
by moisture. Figure 2 shows typical examples of reaction with urea to form carbamate, leading to the long-term
durability of the adsorbent. Another striking feature of the
moisture effect is that the desorption temperature was never
influenced by the presence of moisture even though CO2
uptake was doubled.23 Normally, the desorption temperature
increases for samples with higher loading amount of amine.41 A
clear answer to this unique effect of the moisture was given by
quantum chemical calculations.37 As in Figure 3, a H2O-
stabilized zwitterion is formed during the CO2 adsorption
process, which helps CO2 transport through PEI. Therefore,
under humid conditions the diffusion barrier can be
minimized.

4. TOLERANCE FOR IMPURITIES

In this section, the effects of SO2, NOx, CO, and O2 on CO2-
capturing property are summarized. The performance of liquid
amine scrubbing with monoethanolamine (MEA) is tremen-
dously deteriorated by the presence of impurities such as SO2
and O2 in flue gas streams.42 Therefore, it is of vital importance
to investigate the potential degradation of amine-function-
alized materials under such conditions for industrial
applications. Xu et al. investigated the effects of impurities in
a flue gas on CO2-capturing property using 50 wt % of BPEI
(Mn = 600) finely dispersed in the pores of MCM-41.43 They
employed the actual off-gas from a natural gas-fired boiler
containing 7.4−7.7% CO2, 14.6% H2O, ∼4.45% O2, 200−300
ppm of CO, 60−70 ppm of NOx, and 73−74% N2. N2, O2, and
CO had little influence on CO2 adsorption, while NOx slightly
Figure 2. Examples of reaction schemes of CO2 adsorption under dry decreased the amount of CO2 adsorbed. However, CO2 was
and humid conditions. captured 3000 times more than NOx, demonstrating that
BPEI/MCM-41 can efficiently separate CO2 from the flue gas.
Rezaei et al. reported single-component adsorption44 and
schemes of amines with CO 2 under dry and humid multicomponent adsorption45 using SO2, NOx, and CO2 with
conditions.14 Under dry conditions, two primary amines different amine types. They demonstrated that SO2 greatly
react with one CO2 molecule to form an ammonium ion and influenced CO2 adsorption at 35 °C but had much less
carbamate ion. The secondary amines follow the same reaction influence at 75 °C.44 This phenomenon originates from the
path. Therefore, the maximum efficiency can only be 0.5 mol fact that SO2 adsorption capacity decreases with an increase in
of CO2 per mole of amine. Under humid conditions, both temperature, while CO2 adsorption capacity increases. The
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Figure 3. Water-assisted formation of bicarbonate via a zwitterion. Copyright 2016 American Chemical Society. Reprinted with permission from ref
37.

coadsorption experiments showed that the presence of SO2 identify reaction pathways and surface species formed, such as
considerably deteriorates CO2 adsorption performance.45 carbamic acid, carbamate, bicarbonate, and urea. In particular,
Among all the amine types, secondary amine was less its combination with IR spectroscopy offers a firm under-
influenced by SO2. Coadsorption with NO has no impact on standing of molecular structure because the frequency
CO2 adsorption, whereas NO2 slightly suppressed CO2 difference between asymmetric and symmetric stretching
adsorption capacity.45 vibrations of carboxylate ions provides insight into the
The degradation of amine-functionalized materials by molecular interaction.64 REDOR NMR is useful to gain
oxygen was also extensively studied.46−51 Normally, the off- information about short- and long-range dipolar coupling
gas from power plants and some fine chemical factories contain between isolated pairs of heteronuclei. 15N(13C) REDOR
a certain concentration of oxygen. Therefore, O2 tolerance of NMR identified amide-like species such as carbamic acid and
the amine-based materials should be taken into account for carbamate. Together with its counterpart, 13C(15N) REDOR
industrial applications with long-term operation. The reason NMR, REDOR NMR indicated that carbamate species are
for the degradation by O2 has never been clearly demonstrated. isolated from each other.62 2D NMR with HETCOR sequence
Heydari-Gorji et al. carried out infrared spectroscopic and detects the correlation of two different nuclei (c.f., 13C and 1H)
NMR analysis of a triamine-grafted material (TRI).48,49 Upon via single-bond spin−spin coupling and thus unveils which
the TRI deactivation, a new IR band emerged at 1665−1680 proton is bonded to which carbon groups. Chen et al. reported
cm−1, but only a minor change was confirmed by 13C NMR that 13C and 1H HETCOR NMR detected two distinct
except for a weak peak at 158 ppm. What these changes bicarbonate species at 100 K, which are coupled to different
indicate remain uncertain. However, they assumed that the protons, respectively.63 Their follow-up study evidenced that
possible formation of imine, carbamic acid, and nitrone cannot one bicarbonate species is coupled to H2O molecules present
be ruled out. Further research is required to draw a solid on the walls of the mesoporous material, while another
conclusion on the oxidative degradation mechanism of TRI. bicarbonate species is coordinated to H2O molecules in the
Bali at al. thoroughly investigated the oxidative degradation of pores.61
PEI and poly(allylamine) (PAA) on mesoporous alumina DFT calculations contributed considerably to understanding
support employing infrared, Raman, and 13C NMR spectros- what species is favorably formed and what reaction path is
copy.47 Their data clearly proved the formation of a C�O reasonable for the reaction of amines with CO2.37,67−70 Early
bond associated with deactivation of PEI. They concluded that stage research was reported by Mebane et al. that the
undesirable formation of amides, acids, and imides leads to formation of a zwitterion was unstable in a polar environment
lower basicity of the nitrogen species in the polymer and thus of anhydrous PEI.67 However, a dielectric medium under
low CO2 adsorption capacity. According to their findings, PAA humid conditions stabilizes the zwitterion. They also proposed
may serve as a better adsorbent with high oxidative stability. linear and ring topologies to be responsible for CO2 diffusion
Ahmadalinezhad et al. also came to a similar conclusion by in the bulk PEI under humid conditions.37 DFT calculations in
using 1D and 2D NMR techniques.46 BPEI is the most combination with adsorption isotherms demonstrated that
unstable amine among the amines tested, and PAA and LPEI CO2 uptake caused the volume expansion of the amine layers
can be more resistant to the oxidative atmosphere. and thus the decrease in the pore volume.69 Therefore, sticky
amines with high viscosity might increase the diffusion
5. MECHANISTIC STUDIES resistance and have a negative impact on CO2 adsorption
The advance in spectroscopy, in situ techniques, and quantum property.
mechanical modeling in the past decade promoted mechanistic In situ infrared spectroscopy is the most widely utilized
investigations to unveil the underlying mechanism of CO2 technique to follow the reaction path in this field because the
adsorption and desorption. Commonly used techniques in this setup is relatively cheap and can be operated easily.23,52−60,64,71
field are infrared spectroscopy,23,52−60 nuclear magnetic Since there is an extensive review on IR spectroscopic studies
resonance (NMR), 61−66 and density functional theory published in 2019,54 we only describe major findings briefly
(DFT).37,67−70 This chapter briefly summarizes what informa- and update that what has been newly reported since then. A
tion can be gained by each technique and major findings number of reports contributed to assign IR bands observed
related to CO2 adsorption mechanisms. during CO2 adsorption such as carbamic acid, carbamate-
NMR studies were mainly reported by the group of Jones physisorbed CO2, and ammonium ions. The detailed band
and colleagues,61−66 exploiting 1H NMR,66 13C NMR,64,65 15N assignment is given in a previous review article.54 The most
dynamic nuclear polarization (DNP) NMR,64 rotational-echo frequently used amine, TEPA, was also investigated by in situ
double-resonance 15N(13C) and 13C(15N) (REDOR) NMR,62 IR spectroscopy. By increasing the thickness of TEPA layers,
and two-dimensional 13C−1H heteronuclear correlation the interaction between amines was enhanced, forming
(HETCOR) NMR.61,63 13C NMR is a powerful tool to zwitterions with NH and NH2 groups.59 This phenomenon
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Figure 4. Water-assisted formation of bicarbonate via a zwitterion. Copyright 2016 American Chemical Society. Reprinted with permission from ref
72.

suppresses CO2 gas diffusion in a thicker layer of liquid TEPA 6. REACTOR AND PROCESS DESIGN
and leads to high-temperature desorption of CO2 at 100 °C. 6.1. Vacuum Swing Desorption. Temperature vacuum
The addition of polyethylene glycol (PEG) with low molecular temperature swing desorption (TVSD) is considered to be
weight TEPA was reported to increase the ratio of weakly useful because a high-level vacuum is not required.72 The
adsorbed CO2, whose band emerged at 2627 cm−1 (NH2− process optimization is critical to not waste time, energy, and
O).57 PEI also possesses similar characteristics of IR bands.56 CO2 gas during the desorption process so that the maximum
IR spectroscopy together with thermogravimetric analysis efficiency for collecting pure CO2 can be achieved. In the
(TGA) provided important information about BPEI behavior TVSD process, CO2 is first chemisorbed on an absorbent
at different temperatures. Due to the high viscosity of liquid material at atmospheric conditions (typically 25 °C and 1 bar).
BPEI, adsorption capacity increased with temperature because After saturation of the material with CO2, the chamber with
of the reduction of the viscosity.56 There are several reports on the adsorbent is closed and evacuated by a vacuum pump,
amine-grafted/-immobilized materials.52,53,58,60 The IR spec- removing the excess gas at the begging and weakly adsorbed
troscopic features and behavior were similar to that of TEPA CO2. In order to desorb further CO2, the absorbent bed is
and BPEI. Effects of NO2 and SO2 on CO2 adsorption were heated to the desorption temperature.73 Figure 4 displays the
also investigated by in situ IR spectroscopy.55 Those acidic schematic diagram of a typical TVSD setup. There is also an
attempt without any temperature swing, i.e., vacuum swing
gases form NH−NO2 and NH−SO2 complexes assigned at
desorption (VSD), operated at 90 °C.74 VSD can achieve 95%
1650 cm−1, leading to the deterioration of CO2 adsorption
CO2 purity and 90% recovery. Due to the high-temperature
performance. NO2 has less influence on the amount of CO2 operation, the degradation of CO2 adsorption capacity is
adsorbed even at 200 ppm, but the presence of SO2 leads to expected with repeated cycles. Hence, the fabrication of
the considerable reduction of CO2 adsorption above 50 ppm. thermally stable adsorbents must be taken into account.74
Weisshar et al. have recently demonstrated that in situ IR Compared to VSD, TVSD is more efficient when higher CO2
spectroscopy could be a useful tool to monitor the weakening concentration is required. In some cases, >99% CO2 can be
of the C−N bond of carbamic acid and carbamate.23 Such an achieved with 0.23 mmol/g/h of the desorption rate.72 Under
attempt would be beneficial for designing an adsorbent humid conditions during the vacuum process, the desorption
material with low-temperature regeneration. rate increased to 3.75 mmol/g/h, confirming the beneficial
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kinetics assisted by steam. However, additional energy is applicability of reactor systems with amine-functionalized
required for the desorption of water if H2O is coadsorbed with solids for large-scale CO2 capture from exhaust gases. This
CO2. The recyclability test revealed that 8% loss in CO2 included four different reactor types (fixed bed, fluidized bed,
adsorption capacity was observed after 50 cycles (>1500 h).72 moving bed, and rapid thermal swing) and was compared with
Gebald et al. also reported cyclic experiments using TVSD with the liquid amine scrubbing often used today. By integrating the
amine-functionalized cellulose.75 100 cycles of adsorption and adsorption/desorption and heating/cooling processes, TEA
regeneration at 90 °C caused 2% loss of the N content. estimated a cost of the process by each reactor which falls into
However, this report showed a high potential that TVSD can the range of 48.1−75.2 $/t-CO2 and a heating recovery of 45−
be well applied for DAC. 58%. These results support the use and need for CO2 capture
6.2. Steam-Stripping Regeneration. Instead of TVSD, for flue gas purification.88 The lowest price of 48.1 $/t-CO2
steam-stripping regeneration combined with temperature can be achieved with the fixed-bed adsorption configuration.
swing desorption (TSD) has been explored to collect pure Considering the current cost of 62.8 $/t-CO2 with amine
CO2.76−82 In the regeneration process, a stream saturated with scrubbing using 30 wt % of MEA, CO2 capture with amine-
H2O carries a mixture of CO2 and H2O, and then a functionalized solid materials has a high potential to compete
concentrated CO2 can be obtained by compression and in the market.
condensation.83 There is a report on studying how to minimize Zhao et al. designed and evaluated a 200 kWth pilot reactor
the energy consumption, employing superheated steam from for the energy balance of three different regeneration processes
low-pressure steam turbine and a heat exchanger.76 This so- (thermal regeneration with CO2 stream, vacuum regeneration,
called “direct steam-stripping process” was found to lower the steam-stripping regeneration).89 Amine-functionalized resin
energy consumption by 23.2% compered to a conventional was selected to evaluate the efficiency and energy needs for
stripping method. The steam stripping can also be combined each of the regeneration processes. The least energy is required
with vacuum swing adsorption, named steam-aided vacuum for the thermal regeneration. Compared to the liquid amine
swing adsorption (SA-VSA).77 Yogo et al. demonstrated highly scrubbing often used today, the energy consumption can be
efficient CO2 capturing performance using a system with three reduced by 30% or more. However, if the thermal regeneration
columns: the first column for adsorption, the second column is supported by an additional vacuum system, the energy
for rinsing, and the third column for desorption.77 The SA- consumption is higher than the thermal process itself but still
VSA process with an amine-impregnated mesoporous MSU-F much lower than the liquid amine scrubbing. In addition, the
silica can achieve >98% of CO2 purity and >93% of recovery whole reactor is complicated and more expensive when the
rate. They also estimated the required heat for the regeneration vacuum is applied. The steam-stripping regeneration requires
to be much lower than that of liquid amine scrubbing and the most energy, but the process can be greatly optimized
other amine-based solid adsorbents. when the steam condensation and heat recovery are taken into
A challenge for its industrial application is the H2O tolerance account.89 The total annual cost also depends on the plant size.
of amines at elevated temperature. After steam treatment, the Mazzotti et al. performed a techno-economic assessment and
adsorption capacity drops to a certain degree.83,84 For long- found that the cost of commercially available adsorbent
term operations, the fabrication of robust amine-based considered gas had much less impact on the process cost,
adsorbents is desired. Sayari et al. reported that amine-grafted but the size and shape of the adsorption system critically affect
SBA-15 showed high hydrothermal stability, and its exposure the investment cost.90 The adsorption-based process can be
to steam for 48 h caused no change in the adsorptive and competitive at the small scale (less than 100 tons of flue gas
structural properties.85 A choice of support materials is also a per day) and low recovery rate (less than 40%). However, the
key factor for the steam tolerance. Upon exposure to steam, classical liquid amine scrubbing is still the most cost-effective at
alumina support is partially transformed into boehmite, but it most of the plant sizes and recovery rates.
does not alter the amine efficiency.80 Therefore, γ-Al2O3 is To perform a cost estimation for CO2 capture and
considered to be a promising support material to impregnate concentration (CCC) technology, a model was created to
PEI. calculate the cost per ton of CO2 captured for a 500 MW
6.3. Reactor Design. The design of the adsorption− power plant. The absorbent used was zeolite 13X, which can
desorption chamber is also a crucial factor to achieve high also be replaced by an amine-functionalized material. Based on
efficiency with amine-functionalized solid materials. There are the calculations, a tremendous amount of energy can be saved
two flow-reactor types considered: (1) fixed-bed reactor86 and when the concentration of CO2 in the flue gas is high enough.
(2) fluidized-bed reactor.87 In the fixed-bed reactor. The solid Besides, the adsorption efficiency of the reactor can be
adsorbent is placed such that its position always remains the increased by shortening the reactor length with the larger
same when a gas stream flows through the fixed bed.86 On the diameter. At an off-gas CO2 concentration of 15%, the cost
contrary, in the fluidized bed reactor, the adsorbent powders estimate was $32.8 to $34.4 per ton of CO2 captured.91
are swirled up with a gas stream and fly around inside the
chamber.87 The advantage of the fixed-bed reactor is that the 7. LIGHT-TRIGGERED CO2 ADSORPTION AND
process engineering and reactor design are much simpler and DESORPTION
cheaper than the fluidized-bed reactor. Furthermore, a In this section, a state-of-the-art CO2 desorption method is
significantly larger quantity of adsorbent can be used per described. In the past decade, photosensitive functional groups
unit of space, which results in better process efficiency. are applied for low-temperature regeneration of adsorbents by
However, the fluidized-bed reactor benefits from high visible and/or UV light.92−94 This method allows CO2
adsorption rate and uniform heat distribution because the adsorption−desorption cycles to be operated under mild
adsorption process is exothermic.87 conditions (1 bar and room temperature). Lyndon et al.
6.4. Process Design and Cost Estimate. A techno- reported that a zinc-based MOF with 4,4′-dicarboxylate
economic analysis (TEA) was considered to assess the (AzDC) and trans-1,2-bis(4-pyridyl)ethylene (4,4′-BPE) as a
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framework released CO2 under UV light irradiation at 30−31 8400, Switzerland; orcid.org/0000-0001-5549-4982;
°C.92 In situ FT-IR spectroscopy detected the change in C− Email: [email protected]
C−C and C−C−N bending modes, originating from cis−trans Daniel M. Meier − Institute of Materials and Process
isomerization of Zn(AzDC)(4,4′-BPE)0.5 under UV irradi- Engineering (IMPE), School of Engineering (SoE), Zurich
ation. The desorption capacity was 42% under static irradiation University of Applied Sciences (ZHAW), Winterthur CH-
conditions and 64% under dynamic measurements. 8400, Switzerland; Email: [email protected]
Sun and co-workers reported photosensitive MOFs
functionalized with azobenzene for CO2 adsorption−desorp- Author
tion by UV and visible lights.93 Tetraethylenepentamine Jannis Hack − Institute of Materials and Process Engineering
(TEPA) was impregnated onto an UiO-type MOF function- (IMPE), School of Engineering (SoE), Zurich University of
alized with azobenzene (U-azo). Azobenzene changes its form Applied Sciences (ZHAW), Winterthur CH-8400,
between trans and cis under visible and UV lights, respectively. Switzerland
Exploiting this phenomenon, CO2 bound to TEPA is released Complete contact information is available at:
by UV light irradiation. U-azo has the CO2 adsorption capacity https://pubs.acs.org/10.1021/acsomega.2c03385
of 43.4 cm3/g (ca. 1.94 mmol/g), among which 45.6% of
adsorbed CO2 can be released. They also demonstrated that Notes
CO2 can be selectively separated using this principle out of gas The authors declare no competing financial interest.
mixtures of CO2/N2 and CO2/CH4. They further developed a
novel adsorbent which works only with visible light.94 MCM-
41 was functionalized with (3-aminopropyl)triethoxysilane
(APTES) and Disperse Red 1 (DR1). Without irradiation,
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