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Understanding the Effect of Water on CO2 Adsorption

Joel M. Kolle, Mohammadreza Fayaz, and Abdelhamid Sayari*

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ABSTRACT: Carbon capture from large sources and ambient air is one of the most
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promising strategies to curb the deleterious effect of greenhouse gases. Among different
technologies, CO2 adsorption has drawn widespread attention mostly because of its low
energy requirements. Considering that water vapor is a ubiquitous component in air and
almost all CO2-rich industrial gas streams, understanding its impact on CO2 adsorption is of
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critical importance. Owing to the large diversity of adsorbents, water plays many different
roles from a severe inhibitor of CO2 adsorption to an excellent promoter. Water may also
increase the rate of CO2 capture or have the opposite effect. In the presence of amine-
containing adsorbents, water is even necessary for their long-term stability. The current
contribution is a comprehensive review of the effects of water whether in the gas feed or as
adsorbent moisture on CO2 adsorption. For convenience, we discuss the effect of water
vapor on CO2 adsorption over four broadly defined groups of materials separately, namely (i) physical adsorbents, including carbons,
zeolites and MOFs, (ii) amine-functionalized adsorbents, and (iii) reactive adsorbents, including metal carbonates and oxides. For
each category, the effects of humidity level on CO2 uptake, selectivity, and adsorption kinetics under different operational conditions
are discussed. Whenever possible, findings from different sources are compared, paying particular attention to both similarities and
inconsistencies. For completeness, the effect of water on membrane CO2 separation is also discussed, albeit briefly.

CONTENTS 3.4.5. Effect of Framework Flexibility S

3.4.6. Comparative Studies S
1. Introduction B 4. Amine-Functionalized Adsorbents V
2. Measuring CO2 Uptake Under Humid Conditions C 4.1. Amine-Impregnated Adsorbents Y
2.1. Thermogravimetric Analysis D 4.2. Amine-Grafted Adsorbents AD
2.2. Column Breakthrough Technique (Open 4.2.1. Amine-Grafted Mesoporous Silicas AD
System) D 4.2.2. Amine-Grafted Nanofibrillated Cellu-
2.3. Multicomponent Equilibrium Adsorption lose AF
(Closed System) D 4.2.3. Amine and Ammonium-Containing Pol-
3. Physical Adsorbents E ymers AG
3.1. Carbons E 4.2.4. Amine-Functionalized Zeolites AI
3.1.1. Effect of Water on CO2 Adsorption at 4.3. Hydrophobic Amine-Containing Adsorbents AI
Subatmospheric Pressure E 4.4. Effect of Water on the Regeneration Heat AJ
3.1.2. Effect of Water on CO2 Adsorption at 5. Membranes AL
High Pressure G 6. Reactive Adsorbents AQ
3.1.3. Theoretical Studies G 6.1. Alkali Metal-Based Adsorbents AQ
3.2. Zeolites and Zeolite-like Materials H 6.1.1. Sodium Carbonate AQ
3.3. Metal−Organic Frameworks I 6.1.2. Potassium Carbonate AQ
3.3.1. Degradation Mechanisms of MOFs in 6.2. Alkaline Earth Metal-Based Adsorbents AR
Contact with Water J 6.2.1. Calcium Oxide and Hydroxide AR
3.3.2. Thermodynamic Stability of MOFs J 6.2.2. Magnesium Oxide AS
3.3.3. Kinetic Stability of MOFs K
3.4. Effect of Water on CO2 Adsorption over
MOFs L Received: July 21, 2020
3.4.1. Effect of Coordinatively Unsaturated
Sites L
3.4.2. Effect of Other SBU Features N
3.4.3. Effect of Hydrophobicity N
3.4.4. Effect of MOF Functionalization P

© XXXX American Chemical Society https://doi.org/10.1021/acs.chemrev.0c00762

A Chem. Rev. XXXX, XXX, XXX−XXX
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Table 1. Typical Compositions of Flue Gases from Different Sources69
components pulverized coal waste incineration
O2 (vol %) 6 7−14
N2 (vol %) 76 balance
CO2 (vol %) 11 6−12
H2O (vol %) 6 10−18
Ar (vol %) 1 1
SO2 (ppm) 300−5000 200−1500
NOx (ppm) 500−800 200−500
6.3. Other Metal Oxides
7. Conclusions and Outlook
Author Information
Corresponding Author
Authors
Notes
Biographies
Acknowledgments
References
1. INTRODUCTION
The threat of climate change and global warming to the planet
Earth has become one of our most intractable challenges.
Because of the sheer volume of anthropogenic carbon dioxide
(CO2) emissions, i.e., more than 36 gigatons per year, CO2 was
recognized as the largest greenhouse gas (GHG) contributor
to global warming.1 The atmospheric CO2 concentration
increased by more than a third since the Industrial Revolution
era, and continues to rise at an alarming pace, despite the
temporary relief due to the exceptional circumstances of the
Covid-19 coronavirus pandemic.2,3 In particular, the rapid
increase of atmospheric CO2 concentration from 378 to 411
ppm in the short period between 2005 and 2019 is a clear sign
of more severe weather events to come.4 Therefore, urgent
actions are needed to curb GHG emissions, culminating in
global accords such as the 2015 Paris Agreement, adopted at
the 21st session of the United Nations Framework Convention
on Climate Change (UNFCCC) Conference of the Parties
(COP21), requiring limitation of the global average temper-
ature rise over the 21st century to below 2 °C.5 In 2018, an
updated assessment by the Intergovernmental Panel on
Climate Change (IPCC) urged rapid, far-reaching and drastic
changes in energy, industry, buildings, transport, and cities to
limit global warming to 1.5 °C, requiring a 45% reduction in
anthropogenic CO2 emissions by 2030, relative to 2010 levels.6
Therefore, unprecedented efforts are being deployed for the
development of materials and processes to achieve more
efficient CO 2 capture capabilities 7−16 as well as CO 2
storage17,18 and utilization.19−21
Absorption of CO2 by alkanolamine solutions is a mature
technology that has been practiced on large scale for decades,
but mostly for gas purification, e.g., natural gas and hydrogen.22
Despite its widespread implementation, amine scrubbing has
several drawbacks. In particular, the regeneration step is highly
energy demanding.23 Moreover, amine solutions eventually
lead to the release of toxic pollutants such as nitrosamine,
nitramines, and ammonia,24−26 and extensive corrosion of the
equipment.27,28 Therefore, amine absorption for only the sake
of CO2 capture is cost-prohibitive. Nonetheless, CO2 capture
from flue gas using hindered amine solvents, in particular, the
proprietary KS-1 by Mitsubishi Heavy Industries, has been
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coal-fired IGCC natural gas-fired CC cement rotary kiln
12 14 7
66 76 59
7 3 19
14 6 13
1 1 1
10−200 5−1200
10−100 10−300 100−1500
AU implemented in several fossil fuel power plants.29 Compared to
AU conventional mono- and diethanolamine, KS-1 exhibits higher
AW CO2 loading, lower corrosion, limited degradation, and amine
AW loss and less energy consumption for solvent stripping. As an
AW alternative CO2 capture technology, adsorption using a variety
AW of materials capable of reversibly or permanently removing
AW CO2 has been proposed as a more viable approach, with lower
AW energy requirements.30 A wide variety of CO2 adsorbents were
AW developed for CO2 capture,15,31−34 including metal−organic
frameworks (MOFs), 35−43 covalent organic polymers
(COPs),44−46 zeolites,47,48 clays,49−51 carbons,52−56 silica,57,58
basic oxides,59,60 and amine-containing porous materials.61−68
Water vapor is a ubiquitous component in flue gas and in
many other CO2-rich industrial gases. Depending on their
origin, flue gases may contain 6−18% water vapor (Table 1),69
whereas the water content of biogas is typically 6−7%.70
Because of its chemical properties and large dipole moment,
water has a wide range of effects on CO2 adsorption depending
on the nature of the adsorbent and the separation conditions.
Therefore, it is critically important to understand the different
roles that water may play with respect to CO2 adsorption, and
their implications on the selection of materials and processes.
In some instances, water may strongly compete with CO2,
particularly in the presence of physical adsorbents,71−73 while
in others it may have a promoting effect on CO2 uptake
through more favorable surface chemistry, formation of CO2
hydrate, or through decreasing diffusion resistance and
enhanced CO2 adsorption kinetics.74−76 In other circum-
stances, water may have a unique stabilization effect on the
adsorbent during repeated adsorption−desorption cycling.77,78
As for the effects of other flue gas components such as O2, SOx,
and NOx on the performance of amine-containing adsorbents,
as well as their CO2-induced deactivation under dry
conditiona, they were addressed in a recent review.79
In the presence of physical adsorbents, interactions between
CO2 and the material surface are governed by van der Waals
forces.80 Some physical adsorbents, such as zeolites, exhibit
very high affinity toward water vapor,73,81,82 therefore, water
can significantly reduce their CO2 uptake through competitive
adsorption.83,84 As for hydrophobic adsorbents such as
activated carbons (ACs), the negative effect of water on CO2
uptake is not as drastic as for zeolites, particularly at low
relative humidity (RH). Nevertheless, at high RHs, CO2
adsorption over ACs often decreases in favor of water uptake,
but at high pressure, CO2 uptake may increase significantly due
to the formation of CO2 hydrate.85 For physical adsorbents
with more complex behavior such as MOFs, the effect of water
on CO2 capture is strongly dependent on the interactions
between the different components of the adsorbent and water
versus CO2. With MOFs emerging as a highly promising class
of adsorbents, numerous investigations dealt with the effect of
water not only on CO2 adsorption but also on their structural
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Figure 1. (a) Water uptake followed by humid CO2 uptake at the same temperature (30 °C) and relative humidity (20% RH) over NOTT-401.
Reproduced with permission from ref 198. Copyright 2016 American Chemical Society. (b) CO2 and water uptake on InOF-1 at 30 °C in the
presence of 20% RH. Reproduced with permission from ref 196. Copyright 2015 Royal Society of Chemistry.
integrity, depending on the nature of their ligands and metal
nodes. In early studies, several MOFs were found to collapse
upon exposure to water vapor, even at low RH and room
temperature.86−89 Nevertheless, many MOFs with high
hydrolytic stability are now readily available,90−97 particularly
once the underlying criteria for MOFs hydrolytic stability were
fully understood.88,96−98 In addition to water stability, there are
diverse effects of moisture on CO2 adsorption over MOFs. For
some types of MOFs, limited water preadsorption enhances
CO2 uptake and its selectivity versus N2 and CH4.99 However,
further increase in water content often has the opposite
effect.99−101 In some other instances, interactions between
water molecules and ligands can trigger the reversible
deformation of the material framework, a phenomenon
known as the breathing effect, with direct implications on
CO2 adsorption.102,103 All of these findings, some of which are
counterintuitive, indicate that the effect of humidity on CO2
capture performance of MOFs should be investigated almost
case by case. Note that there are other unrelated effects of
water on MOFs, such as single-crystal to single-crystal
transformation upon hydration−dehydration.104,105
In addition to CO2 physisorbents, chemical adsorbents
based on amine-functionalized porous materials were devel-
oped to combine the high affinity of amine groups toward CO2
and the low energy requirement for regeneration of solid
adsorbents. Amine-containing adsorbents are prepared using
different methodologies, including impregnation of amines or
polyamines on porous supports, particularly silicas,106−119 and
less frequently, activated carbons,120−122 zeolites,123−125 and
MOFs126−128 or covalent bonding of amines through surface
silylation, 76,129−143 tethering, 144−153 ligand modifica-
tion,154−156 in situ polymerization,157,158 and other strat-
egies.159−161 CO2 adsorption over amine-functionalized
materials involves chemical interactions mostly with primary
and secondary amines, typically to produce ammonium
carbamate.61,62,66 Remarkably, not only water is tolerated by
such adsorbents,162 but the presence of water vapor in the feed
gas often promotes CO2 adsorption, typically through the
formation of carbonate and bicarbonate with more favorable
CO2/N stoichiometric ratio than ammonium carbamate.61,62,66
Water vapor can also trigger CO2 adsorption by tertiary amines
via bicarbonate formation.163,164 More importantly, water
vapor was found to be necessary to ensure long-term stability
of amine-containing adsorbents against CO2-induced deacti-
vation, which takes place under dry condition through the
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formation of stable urea linkages by an overall dehydration
reaction.77,165 In addition to the above-mentioned materials,
the gas phase humidity and/or prehydration of materials affects
other adsorbents such as metal oxides, hydroxides, and
carbonates in a variety of ways.166−170
There are review articles on the effect of water vapor on CO2
adsorption performance of MOFs.171−173 However, there are
no comprehensive reports critically reviewing the effect of
water vapor on CO2 capture over the whole range of adsorbent
materials. Such a report would be highly informative because
different types of adsorbents exhibit distinct behaviors when
CO2 adsorption is conducted under humid conditions, and/or
when the material is prehumidified. The current review aims at
filling this gap, starting with discussion of water effect on CO2
uptake over physisorbents, such as zeolites and MOFs, then
over amine-containing adsorbents and reactive materials. To
facilitate comparison of literature data, whenever possible, the
water content of the feed gas was also expressed in RH at the
adsorption temperature. Nonetheless, it would be informative
to first discuss the different methodologies that are commonly
used to investigate the effect of moisture on CO2 adsorption,
with emphasis on their advantages and shortcomings.
Although membrane gas separation is distinctly different
from adsorption, both technologies use solid separating agents.
Moreover, because CO2 separation membranes often contain
actual CO 2 adsorbents, such as amines and poly-
amines,171,174,175 MOFs,176−178 zeolites,177,179,180 carbon,181
ionic liquids,182,183 enzymes,184 and enzyme mimics,185,186
they are bound to have similarities with adsorbents. Although
progress in this area has been reported in several authoritative
reviews,171,174,187−190 the effect of water on CO2 transport and
selectivity across membranes will be discussed succinctly.
2. MEASURING CO2 UPTAKE UNDER HUMID
CONDITIONS
Experimental studies investigating the effect of humidity on
CO2 adsorption involved different methods to measure
multicomponent CO2 uptake. This includes (i) thermogravi-
metric analysis (TGA), alone76,162,191−202 or combined with
other analytical techniques such as mass spectrometry (MS),
infrared spectroscopy (IR), gas chromatography (GC), or
other specific detectors for CO2 and/or RH measurements
with additional calibrations and validation proce-
dures,139,155,203 (ii) dynamic column-breakthrough technique
with accurate flow measurements in combination with different
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analytical tools,204 and (iii) static multicomponent equilibrium
adsorption.100,205
2.1. Thermogravimetric Analysis
When using TGA alone, the sample is often prehumidified
at a desired temperature in the presence of an inert gas
with a constant relative humidity, then exposed
to the CO2-containing feed with the same RH, at the same
temperature, while monitoring the weight gain
(Figure 1a).76,139,162,191−194,196−198,201,202,206 Alternatively,
both measurements can been undertaken separately (Figure
1b).196 Assuming that the adsorption of water at a given RH is
not affected by CO2, and the adsorption of the inert gas, often
N2, is negligible, the sample weights at both equilibria would
yield the corresponding water and CO2 uptakes. However, on
the basis of adsorption measurements using, in addition to the
method described above, independent measurements of CO2
uptake by MS during temperature programmed desorption
(TPD), these assumptions were found to be questionable.131
Using a triamine-grafted silica in the presence of 5% CO2/N2
with 27−74% RH, CO2 uptakes measured by TGA only, were
lower by as much as 50% compared to the combined TGA-MS
procedure, thus severely underestimating the actual uptake. It
was surmised that preadsorbed water is in part, displaced by
CO2 adsorption, which cannot be detected by TGA. In
addition, the CO2 uptake after prehumidification was found to
be as much as 10% higher compared to humid CO2 uptake
over fresh material, particularly at high RH, indicating that it is
difficult to reproduce the same equibrium conditions.131
Furthermore, to measure CO2 uptake by TPD, the gas phase
has to be flushed, altering the actual equilibrium state.
In another variation of this method applied to a large
number of MOFs, Chanut et al.195 first saturated their
materials with water vapor (100% RH) at room temperature
for 2 days, using an airtight vessel containing liquid water. The
sample was then loaded in the TGA instrument and submitted
to a five-step procedure as illustrated in Figure 2. It was first
treated in nitrogen at 30 °C for 8 h to remove weakly held
water, followed by CO2 adsorption in the presence of dry pure
CO2. The desorption step was conducted for 90 min, while the
sample was heated to a desired temperature to remove all CO2
and a portion of preadsorbed water. Finally, the sample was
cooled down to 30 °C while purging with nitrogen, and a new
Figure 2. Consecutive CO2 adsorption−desorption cycles conducted
by TGA. (a) Temperature and (b) mass profiles. Steps (1), (2)/(6),
(3), (4), and (5) represent sample pretreatment, CO2 adsorption,
CO2 desorption, partial water desorption, and sample conditioning,
respectively. Reproduced with permission from ref 195. Copyright
2013 John Wiley and Sons.
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CO2 adsorption−desorption cycle was conducted on the
adsorbent with lower moisture content. For each cycle, the
CO2 uptake was determined based on the difference between
the mass after and before CO2 adsorption. Here also, the
displacement of water by CO2, particularly for hydrophobic
adsorbents, with less strongly held water, cannot be ignored.
2.2. Column Breakthrough Technique (Open System)
As schematically shown in Figure 3a, in breakthrough
experiments, a gas mixture is flowed through a packed bed
of adsorbent until the outlet gas stream reaches the same
composition as the inlet feed.205,207 In the course of
adsorption, the outlet gas composition is continuously
measured using a variety of techniques such as gas
chromatography−thermal conductivity detection (GC-
TCD)75,208−215 MS207,216−219 or CO2 detectors.111,163,220−227
The CO2 uptake is calculated based on the gas composition
and flow rate and the breakthrough curve versus time.
Alternatively, the composition of the adsorbed phase may be
determined by TPD in an inert gas, coupled with MS
measurements.131 Although accurate determination of the
equilibrium amounts of adsorbed species based on break-
through experiments is not trivial,205 this technique is
extremely useful for comparative evaluation of adsorbents.
Pertinent to this review is the use of CO2−water−inert gas
mixtures, with or without prehydration of the materi-
al.75,111,157,163,208−229
In many instances, the outlet concentration of CO2 reaches
the same level as the inlet gas, yet the water front is still very
close to the column entrance, while most of the adsorbent is in
the presence of a desiccated gas mixture. This may lead to the
hasty conclusion that water has a limited or no effect on CO2
adsorption. If the experiment proceeds for longer time, the
advancing water front may displace some of the already
adsorbed CO2, leading to lower CO2 capacity under near-
equilibrium conditions. Moreover, if water is not completely
removed during regeneration, consecutive adsorption−desorp-
tion cycles, lead to decreasing CO2 working capacity as the
amount of adsorbed water builds up over time.
2.3. Multicomponent Equilibrium Adsorption (Closed
System)
In a typical closed system multicomponent equilibrium
adsorption measurement (Figure 3b), a gas mixture with
known volume, pressure, temperature, and composition is
dosed to a weighed sample, placed in an evacuated space.100,205
The gas is often recirculated continuously to improve mixing.
Once the equilibrium is established, the gas phase is analyzed,
typically by GC or MS, and the composition of the adsorbed
phase is deduced by material balance knowing the dead volume
or the total amount adsorbed. Contrary to the open system
where the gas composition at equilibrium is the same as the
inlet gas, in the closed system, the equilibrium state is difficult
to predict.
Among the three methods, the closed-system multi-
component adsorption with independent measurements of
gas phase composition before and after adsorption provides the
most accurate measurements of actual thermodynamic
equilibria. This is particularly important for multicomponent
adsorption isotherms to be used for modeling, process
optimization, and scale-up purposes.
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Figure 3. Schematic representation of systems for multicomponent equilibrium adsorption measurements (a) column-breakthrough (open system),
and (b) closed recirculation system. Reproduced with permission from ref 205. Copyright 2015 American Chemical Society.
Figure 4. Breakthrough data for a mixture of CO2, N2, O2, and H2O on a biomass-derived AC, at 25 °C and 130 kPa; (a) outlet concentration on
dry basis; (b) partial pressure of H2O in the outlet gas. Reproduced with permission from ref 209. Copyright 2014 American Chemical Society.
3. PHYSICAL ADSORBENTS
3.1. Carbons
Because of their often large surface area and pore volume and
their low cost, ACs have been traditionally used for separation
purposes,230,231 including CO2 capture.54,56,232−236 They are
often prepared through carbonization of different low-cost
precursors, including coal and a wide range of biomass
materials, e.g., wood, fruit stones, nut, and coconut shells,
followed by chemical or physical activation.232,237,238 Depend-
ing on their preparation conditions, ACs may be microporous
and/or mesoporous in nature. It should be noted that in
addition to ACs, other carbon-based materials such as carbon
nanotubes (CNTs),239 carbon molecular sieves,240 and
graphene241 were also investigated for CO2 capture. Two
properties were recognized to be of critical importance for CO2
adsorption over carbon materials, namely the occurrence of
nitrogen species and favorable pore structure.55,242 For
example, Sethia and Sayari,55 and others243,244 reported CO2
uptakes exceeding 5 mmol/g at 25 °C and 1 atm over nitrogen-
doped carbons with high ultramicropore (0.7−0.9 nm)
volume.
ACs often exhibit type I CO2 adsorption isotherms,
indicating their high affinity toward CO2 at low partial
pressures.240 In addition, they often have low affinity toward
water vapor at low RH; however, at high RH levels, water
uptake increases significantly. This is reflected in the “S”
shaped adsorption isotherms of water on ACs, corresponding
to type V.245,246 According to the model proposed by Do and
Do,247 because of strong affinity of water to surface functional
groups, water adsorbs first over such sites, then on top of the
chemisorbed water molecules through hydrogen bonding, to
eventually form water clusters that move into the micropores.
The formation of such clusters on the surface of activated
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carbon was proposed earlier based on experimental248,249 and
theoretical250 data. In some instances, the structural properties
of ACs can be adjusted to increase CO2 selectivity over water.
Koresh et al.251,252 found that mild thermal activation of a
fibrous carbon molecular sieve (TCM-128) resulted in a
controlled enlargement of the pores, with tiny hydrophobic
entrances (constrictions), possibly due to nonoxidized graphite
interlayers. Despite the smaller size of water molecules relative
to nitrogen and CO2, water was not able to penetrate such
constrictions due to the formation of water clusters; however,
the other two gases did penetrate. Therefore, the presence of
such hydrophobic adsorption sites significantly increased the
selectivity of CO2 over water.
3.1.1. Effect of Water on CO2 Adsorption at Subatmo-
spheric Pressure. Most studies on carbon-based materials
conducted at subatmospheric pressures reported a negative
impact of humidity on CO2 uptake as a result of competitive
adsorption of water. Duran et al.208 used a commercial-grade
(Norit R) and two biomass-derived (IH2 and IH3) ACs for
CO2 capture from a flue gas stream generated in a solid waste
incinerator. Single-component adsorption isotherms of N2,
CO2, and H2O were used to estimate the selectivity of CO2
versus water and nitrogen for all adsorbents at 30−70 °C. In
the presence of all carbons, water was found to preferentially
adsorb compared to CO2, particularly at the lowest temper-
ature. Using 2% H2O/N2 and 2% H2O/8% CO2/N2 gas
mixtures, corresponding to 48 and 16% RH at 30 and 50 °C,
respectively, water uptake was found to be hardly affected by
CO2. However, the presence of humidity reduced CO2 uptake
significantly, particularly at the highest RH. Moreover,
prehydration of the adsorbent at 30 °C reduced the CO2
uptake by as much as 46%. Younas et al.223 studied the effect of
activation method on the competitive adsorption of CO2 and
water vapor on a palm shell activated carbon (PSAC). Both
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Figure 5. (a) Gas phase concentration and (b) amount of adsorbed CO2 and water versus axial position. Reproduced with permission from ref 256.
Copyright 2015 John Wiley and Sons.

Figure 6. (a) CO2 adsorption isotherms at 2 °C on a microporous carbon with different moisture contents: (1) Rw = 0, (2) Rw = 1.74, (3) Rw =
1.32, and (4) Rw = 1.65. (b) CO2 adsorption isotherms using Rw = 1.31 at (1) 8 °C, (2) 6 °C, (3) 4 °C, and (4) 2 °C, while (5) is the CO2
desorption isotherm at 2 °C. Reproduced with permission from ref 85. Copyright 2007 Elsevier.

chemical activation using 20−50% NaOH solutions and
thermal activation were performed on the material. The
presence of water vapor (20% RH) was found to reduce CO2
uptake; however, the negative effect of humidity was more
severe for the thermally than the chemically activated PSAC,
with 45% and 13% decline, respectively. Similarly, water vapor
(94% RH) in 15% CO2/N2 at 30 °C led to ca. 14% decrease in
CO2 uptake over KOH-treated AC.253
Some studies reported that humidity has no effect on CO2
uptake of carbonaceous materials. Using vacuum swing
adsorption (VSA) to investigate the effect of humidity on
CO2 adsorption on an activated carbon bed, Xu et al.222
observed that increasing the water vapor content in a 12%
CO2/air inlet gas mixture up to 7.2% did not change the CO2
recovery and purity, presumably because this was a kinetic
separation and CO2 adsorbed much faster than water vapor. At
the time the outlet and inlet CO2 concentrations became
equal, all water was essentially adsorbed at the entrance of the
reactor, forming a cone with rapidly decreasing concentration
along the bed length. In a series of reports, Plaza et al.209,254,255
carried out a comprehensive investigation on the effect of
water on CO2 adsorption in a fixed-bed unit under different
conditions using a biochar obtained by carbonization of olive
stones. In agreement with others,210,222 they found that CO2
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adsorption on fresh or fully regenerated carbon material was
not affected by the presence of water in the feed. Dynamic
adsorption at 25 °C under dry 1% CO2/N2 or humid (40−
50% RH) conditions over a fresh adsorbent showed that the
CO2 breakthrough time and the saturation uptake were the
same.254 Moreover, using 15% CO2/N2 at 25 °C, the CO2
breakthrough and saturation occurred at ca. 17 and 48 min,
respectively (Figure 4a), regardless of the presence of moisture
(ca. 50% RH).209 However, water took about 470 min to break
through, while adsorption continued for well over 24 h (Figure
4b). This indicates that at the time of CO2 apparent saturation,
because of the much-delayed water adsorption front, most of
the adsorbent was in the presence of a dried CO2/N2 gas
mixture. Nonetheless, as the experiment proceeded further,
there was evidence of a roll-up phenomenon, indicating that as
the water front advanced, it displaced part of the CO2 initially
adsorbed. The ideal adsorbed solution theory (IAST)
predicted that over this time, 60% of adsorbed CO2 would
be displaced. 254 This finding has important practical
implications because it indicates that the effect of water on
CO2 adsorption over carbon depends on the degree of the
adsorbent hydration. Moreover, because the isosteric heat of
water adsorption is significantly higher than CO2, it is likely
that in a cyclic operation, water will not be completely
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removed because of its slower desorption and high heat

capacity, leading to increasing moisture content and eventually
decreasing CO2 uptake.254
Likewise, using a microporous coffee-based AC,256 a much
shorter breakthrough time was observed for CO2 relative to
water at 52% RH (3 versus 200 min). Although CO2 uptake
was not reduced in the presence of humidity over short
adsorption durations, experimental and modeling data showed
that extended adsorption time led to displacement of CO2 by
water, eventually resulting in decreasing CO2 uptake from 1.25
to 0.6 mmol/g at t = 523 min, the equilibrium time for water
adsorption. CO2 and water concentration profiles in the gas
phase (Figure 5a) and adsorbed phase (Figure 5b) were
determined throughout the bed via simulation using Aspen
adsorption software at three different times, i.e., right before
and after CO2 breakthrough at t = 2.2 and 4 min and at
equilibrium (t = 523 min). After CO2 uptake reached the Figure 7. CO2 isotherms at 2 °C on a microporous/mesoporous
maximum, as time elapsed, the water concentration front carbon with different moisture contents: (1) Rw = 0, (2) Rw = 1.35,
moved through the adsorbent bed, leading to partial (3) Rw = 1.80, (4) Rw = 2.15, and (5) Rw = 2.36. Reproduced with
desorption of CO2, consistent with experimental data. Notice permission from ref 257. Copyright 2008 Elsevier.
that for two commercial ACs (Takeda and Norit), even when
homogeneously distributed throughout the material, the
limited amount of preadsorbed water of 3.5−4 wt % did not
affect CO2 uptake.195
3.1.2. Effect of Water on CO2 Adsorption at High
Pressure. There is a broad consensus regarding the beneficial
effect of water on CO2 adsorption over carbon at high
pressure. Using a microporous AC derived from coconut shells,
Sun et al.85 measured CO2 adsorption isotherms at 2 °C up to
40 bar over prehydrated adsorbents. The moisture content Rw,
was defined as the ratio of adsorbed water to carbon.
Compared to dry carbon, the CO2 uptake over moisturized
materials was lower at low pressure; however, at 15−20 bar,
the uptake increased dramatically (Figure 6a), which was
attributed to enhanced solubility of CO2 in water, correspond-
ing to the formation of CO2 hydrate. Figure 6b shows that at Figure 8. CO2 adsorption isotherms for uGil carbon prehydrated with
increasing temperatures, the inflection point occurs at higher different amounts of water. CO2 uptake is per gram of dry carbon
pressures, with values comparable to the pressure required for material. Reproduced with permission from ref 258. Copyright 2017
the formation of CO2 hydrate in pure water. However, unlike Springer Nature.
exclusively microporous carbons, CO2 adsorption isotherms
over a bamboo-derived carbon with microporous/mesoporous reported earlier.260 At 25 °C, the presence of 1% H2O (32%
bimodal pore structure in the presence of water, exhibited RH) resulted in the least CO2 uptake reduction of 13% for NQ
similar transitions, but did not reach a plateau associated with sites, followed by 25%, 28%, and 58% loss for pyrrolic,
the formation of CO2 hydrate (Figure 7).257 pyridonic, and oxidized pyridinic nitrogen species, respectively.
Jalilov et al.258 demonstrated that compared to dry Although water vapor content at 25 °C cannot exceed 3.1%,
condition, prehydration of asphalt-derived AC (uGil) led to calculations were made at 10%. This resulted in dramatic
remarkable increase in CO2 uptake at −15 °C and 20 bar, from reduction in CO2 adsorption capacity for all materials, with the
15 to 48 mmol/g, and enhanced the CO2/CH4 selectivity from highest loss being associated with the quaternary (98%) and
ca. 2 to 200, with equilibrium and kinetic data suggesting that pyridinic (97%) nitrogen. Because of the presence of high-
CO2 uptake proceeded via both physisorption and chem- energy surface sites, however, CO2 adsorption was competitive
isorption. Moreover, as the water content of the adsorbent with water at low pressure over oxidized pyridine, pyridonic,
increased, the shape of CO2 isotherm changed from type I to and quaternary nitrogen-containing carbons. Pyrrolic nitrogen
type V (Figure 8), consistent with the formation of CO2 exhibited completely different behavior as it adsorbed more
hydrate. water than CO2 at low CO2 partial pressure (<0.1 mbar), with
3.1.3. Theoretical Studies. Using density functional CO2 uptake going through a maximum at 0.25 mbar. This was
theory (DFT) and grand canonical Monte Carlo (GCMC) attributed to the steric and electronic properties of pyrrolic
simulations, Psarras et al.259 studied the adsorption of CO2 nitrogen, which enabled the material to adsorb CO2 despite
with different RHs over carbon containing pyrrolic (N5), prior adsorption of water. Similar simulations conducted at 60
oxidized pyridinic nitrogen (NO), pyridonic (NP), and °C showed that in the presence of 1% H2O (5% RH), the
quaternary nitrogen (NQ) species. The simulated CO2 relative CO2 capacity decreased in the order of NO > NP >
adsorption isotherms in the presence of humidity (1 and NQ > N5, which is different from the trend observed at 25 °C,
10%) at two temperatures (25 and 60 °C) were compared to i.e., NQ > NP > NO > N5, indicating that CO2 adsorption
the calculated isotherms under dry and humid conditions, over different nitrogen species exhibits different temperature
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dependence behaviors. Moreover, the negative effect of 1% Table 2. CO2 Uptake for Activated Carbon Adsorbents at
H2O (5% RH) was particularly severe for NQ, N5, and NO, Atmospheric Conditions
with 38%, 19%, and 19% CO2 adsorption decline, respectively.
CO2 uptake
Surprisingly, at 10% H2O (51% RH), an increase in CO2 (mmol/g)
capacity was observed over NQ, N5, and NO, with minor
CO2 adsorption
negative effect of ca. 10% for NP relative to adsorption at 25 content temperature RH
°C. material (%) (°C) (%) dry humid ref
You and Liu261 used a Langmuir-type empirical model to sawdust-based 10 50 22 0.35 0.32 208
simulate fixed-bed adsorption and desorption of CO2 from wet carbon (IH2)
flue gas over AC. Using 12% CO2/N2 at 60 °C with 0−100% sawdust-based 10 50 22 0.42 0.38 208
carbon (IH3)
RH at atmospheric pressure, the recovery of CO2 was found to commercial 10 50 22 0.31 0.29 208
decrease from 84% under dry condition to 61% at 100% RH. carbon
This was attributed to the fact that water uptake increases with (Norit R)
humidity, whereas CO2 shows the opposite behavior. More- olive stones-based 13 25 48 1.1 1.1 209
carbon
over, the increase in water uptake with humidity led to a rise in
the average temperature of the bed, owing to the heat of coffee-based 16 25 48 1.25 1.25a 256
adsorption, with adverse effect on CO2 uptake, notably beyond activated carbon
50% RH. 16 25 48 1.3 0.6b 256
In summary, water in the form of vapor or preadsorbed
moisture can adversely affect the equilibrium CO2 capacity of palm shell 15 30 20 0.80 0.70 223
carbonaceous materials at low pressures due to competitive activated carbon
(PSAC)
adsorption. The negative effect of water is particularly striking Ni-impregnated 15 30 20 0.97 0.66 223
for feed streams with high RHs. However, in fixed bed (24 wt %)
operations, because the CO2 adsorption front moves through PSAC
the bed much faster than water, the negative effect of water KOH-activated 15 30 20 1.09 0.83 223
PSAC
vapor may be circumvented by kinetic separation. In contrast,
thermally 15 30 20 0.98 0.84 223
for CO2 adsorption at high pressures, the presence of activated PSAC
preadsorbed water promotes CO2 uptake through mechanisms KOH-treated AC 15 30 94 0.84 0.72 253
other than adsorption, including dissolution and hydrate ACFCd 15 25 75 0.68 0.68 210
formation. Typically, in the presence of wet carbon, CO2 ACFC/KOH 15 25 75 0.84 0.84 210
adsorption isotherms change from type I to type V as the commercial AC 100 30 100 1.93 2.01c 195
moisture content of the adsorbent increases. Literature data on (Takeda)
CO2 uptake by carbon-based materials at atmospheric pressure commercial AC 100 30 100 1.65 1.70c 195
(Norit)
are summarized in Table 2. a
CO2 uptake after 15 from the beginning of breakthrough test. bCO2
3.2. Zeolites and Zeolite-like Materials uptake after 523 min from the beginning of breakthrough test.
Zeolites are microporous crystalline materials with a wide
c
Prehumified at 100% RH. dPolyacrylonitrile activated carbon fiber
range of applications, in particular gas separation and
purification.262−266 Their narrow micropore size distributions decreasing Si/Al ratios because of higher content of extra-
and extra-framework cations make them an appropriate choice framework cations.275 However, in the presence of water (5%
for separating small molecules via electrostatic interactions or H2O/5% CO2/N2), CO2 uptake showed the opposite trend,
size exclusion (molecular sieving).267 Several alkali and alkaline whereas water uptake increased at decreasing Si/Al ratios,
earth-exchanged zeolites were reported to be efficient CO2 presumably because of stronger interactions between water and
adsorbents because of the strong interactions between the extra the increasingly hydrophilic framework. Encapsulation of
framework cations and CO2 molecules.47,48,267−271 Never- zeolites in a hydrophobic support helps mitigate the adverse
theless, ion-exchanged zeolites with low Si/Al ratio tend to effect of moisture. A hierarchically structured composite
adsorb not only molecules with large quadrupole moments monolith consisting of 43 wt % zeolite in carbon, prepared
such as CO2, but also species with high dipole moments such by carbonization of zeolite-β/polymer foam, exhibited in the
as H2O, through electrostatic forces.271 In particular, when presence of 15% CO2/N2 with 50% RH at 25 °C, a stable
dealing with CO2 adsorption at low concentration, as in direct working capacity of ca. 0.7 mmol/g over 15 adsorption−
air capture (DAC), the presence of humidity reduces CO2 desorption cycles.276 In contrast, pure zeolite β showed higher
uptake significantly.272,273 Investigating CO2 adsorption over working capacity for the first cycle (1.37 mmol/g) but
13X zeolite in the presence of 5% CO2/N2, Sayari group218 negligible CO2 uptake thereafter, which was attributed to
found that at increasing RH, more water was adsorbed at the strongly bound water molecules.
expense of CO2, whose uptake at 25 °C decreased by 80% and Contrary to hydrophilic aluminosilicate zeolites, such as
93% at 27% and 74% RH, respectively. Likewise, Li et al.274 NaX and 5A, CO2 uptake over coppersilicate (SGU-29), a
found that at 30 °C, 13X zeolite adsorbed 99% less CO2 in the crystalline microporous material with a structure akin to AM-6
presence of 8.8% CO2 and 3.4% H2O in air (80% RH) vanadosilicate and Engelhardt ETS-10 titanosilicate,277 was
compared to dry conditions, indicating that the competitive found to be unaffected by moisture.278 Exposure of SGU-29 at
adsorption is strongly in favor of water. 25 °C to dry (9.9% CO2/18.8% O2/N2) and humid (9.6%
Consistent with the above-discussed findings, Monte Carlo CO2/18.3% O2/2.9% H2O/N2, 90% RH) gas mixtures led to
simulations for CO2 and water adsorption on faujasite zeolite CO2 uptake of 2.47 and 2.43 mmol/g, respectively. Fourier-
showed that, under dry conditions, CO2 uptake increases with transform infrared spectroscopy (FTIR) measurements
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Table 3. CO2 Uptake for Zeolites in the Presence of Water at 1 atm

CO2 uptake (mmol/g)
material CO2 content (%)/balance adsorption temperature (°C) RH (%) dry humid ref
zeolite 13X 5/N2 25 27 1.95 0.48 218
5/N2 25 74 1.95 0.12 218
0.04/air 30 49 NPa 0.03 272
15/N2 30 100 3.18 0.60 272
100 30 100 3.86 1.22 272
0.0395/air 25 80 0.32 0 273
100 30 2.4a NPa 0.51 195
100 30 25.7b NPa 0.05 195
20/N2 40 24 4.1 0 205

Na−Y 15/N2 60 61 1.23 0.03 281

Li-LSX 0.04/air 25 80 0.82 0.01 273
K-LSX 0.04/air 25 80 0.25 0.03 273
SGU-29 9.8% CO2/18% O2/N2 25 90 2.47 2.43 278
ETS-4 9.8% CO2/18% O2/N2 25 90 1.72 1.65 278
ETS-10 9.8% CO2/18% O2/N2 25 90 1.88 1.81 278
AM-6 9.8% CO2/18% O2/N2 25 90 2.09 2.05 278

zeolite NaX 9.8% CO2/18% O2/N2 25 90 1.85 1.50 278

15% CO2/3% H2O/2% Ar/N2 40 41 2.1 0.23 279

SGU-29 15% CO2/3% H2O/2% Ar/N2 40 41 1.3 0.18 279

ETS-10 15% CO2/3% H2O/2% Ar/N2 40 41 1.4 0.17 279
zeolite 5A 20/N2 40 23 4.1 0.3 205
a
Not provided. bWater content in prehydrated material in wt %.

provided evidence that CO2 and H2O adsorbed non-
competitively on distinct sites, whereas NaX has, in addition
to specific sites for CO2 and H2O, shared adsorption sites. The
isosteric heat of adsorption of CO2 over SGU-29 was higher
compared to that of zeolite NaX, while the isosteric heat of
water adsorption was lower, indicating that SGU-29 binds CO2
more strongly than does NaX but has a lower affinity to water.
Surprisingly, soon after, Kim et al.279 reported contradictory
findings. They claimed that all three zeolites, NaX, ETS-10,
and SGU-29, lost 85−90% CO2 uptake upon addition of 3%
water (41% RH) to the 25% CO2/N2 feed gas at 40 °C.
Computational screening of hundreds of pure silica zeolites
using GCMC simulations showed that, depending on the
CO2/H2O binding site separations and CO2−H2O interaction
energies, humidity may promote or impede CO2 adsorption.280
Enhancement in CO2 uptake occurs when the material exhibits
clearly distinct CO2 and water binding sites, with long-range
favorable CO2−H2O interactions. Conversely, for zeolites with
overlapping CO2 and H2O binding sites, the CO2 uptake is
significantly reduced in the presence of water because of
adsorption competition. If the binding sites for CO2 and H2O
are nearby, but not completely overlapped, water may affect
CO2 uptake either way, depending on whether the reduced
pore volume for CO2 adsorption due to the presence of water
is overcompensated by the enhanced CO2−H2O interactions
or not.
In summary, the strong electrostatic interactions between
extra-framework cations and water molecules result in
significantly higher affinity of zeolites toward water compared
to CO2, leading to less favorable CO2 adsorption. Short of
dehydrating the feed gas, one way to minimize the negative
impact of water on CO2 adsorption is to use high-silica
hydrophobic zeolites with less extra framework cations or to
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encapsulate the zeolite in a hydrophobic matrix. Moreover,
because of their lower affinity for water, zeolite-like materials
with neutral frameworks such as AlPOs may exhibit high CO2
to water selectivity. Functionalization of zeolites with amine-
containing compounds (vide infra) is another strategy for
increasing the selectivity of CO2 over water, even though
amine modification of zeolites instead of cheaper silicas may
not be justified. CO2 adsorption data for selected zeolites in
dry and humid condition are listed in Table 3.
3.3. Metal−Organic Frameworks
Metal−organic frameworks are crystalline porous materials
comprised of a three-dimensional network of metallic ions or
clusters, referred to as secondary building units (SBU),
connected by organic linkers or ligands.282−287 Because of
their porous structure, MOFs may develop extraordinarily large
internal surface area and pore volume.288,289 Owing to the
diversity of their structure and composition, they are ideal
candidates for a wide range of applications, including gas
storage,290−292 postcombustion CO2 capture,35,293−298 and
others.299−309 Although amine functionalization was used to
impart CO2 chemisorption, most MOFs behave as physical
adsorbents.
Unlike conventional physical adsorbents such as carbons and
zeolites, interactions between water and MOFs cannot be
described by a single mechanism because MOFs exhibit
different behaviors associated with the wide variety of their
structures and properties. Therefore, depending on the
composition and structure of MOFs as well as the nature
and strength of their interactions with water, the ultimate
outcome may vary considerably. This diversity also applies to
the effect of water on CO2 adsorption over MOFs. Therefore,
although the main focus of this review is on the effect of
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Chemical Reviews
Figure 9. HSAB theory for MOFs stability (BTP, benzenetripyrazolate; BDP, 1,4-benzenedipyrazolate. Reproduced with permission from ref 95.
Copyright 2018 John Wiley and Sons.
moisture on CO2 adsorption, for MOFs it is important to first
discuss, albeit briefly, the adsorption of water and its potential
effect on their structural integrity. More details on the behavior
of MOFs in the presence of water may be found in several
authoritative reviews.86,88,96−98,308,310
MOFs exhibit a wide range of water adsorption isotherms.
Hydrophilic MOFs such as Ni-DOBDC and Mg-DOBDC
(DOBDC4−: 2,5-dioxido-1,4-benzenedicarboxylate), also
termed M-MOF-74, contain coordinatively unsaturated metal
sites (CUS) that adsorb water strongly, very much like extra-
framework cations in zeolites. Therefore, such MOFs exhibit
water adsorption isotherms of type I. In contrast, hydrophobic
MOFs such as MIL-125-NH2 and Cr-MIL-101 do not adsorb
much water until the pressure for capillary condensation is
reached, leading to type V isotherms.88 In general, water
adsorption on MOFs occurs via three mechanisms,88,98,308
namely (i) chemisorption on high affinity metallic clusters with
CUS as in M-DOBDC (M = Zn, Ni, Co), leading to type I
isotherms. In some instances, adsorption and desorption of
water on CUS leads to local or global deformation of the
framework,311 and (ii) reversible cluster adsorption, similar to
the water adsorption mechanism in the presence of carbon,
discussed earlier.247−250 This mechanism takes place in MOFs,
with pores below the critical pore size for water capillary
condensation of ca. 2.1 nm. For example, in the presence of
MOF-801, the primary adsorption sites for water are the
bridging OH groups on the Zr6O4(OH)4 metallic clusters,
leading first to tetrahedral water clusters, confined within the
MOFs tetrahedral pores. Further adsorption gives rise to larger
cubic clusters, which facilitate water clustering in the larger
octahedral pores. Eventually, all water clusters coalesce, leading
to continuous pore filling,98 and (iii) capillary condensation
through pore-filling in MOFs with pore diameter ≥2 nm. This
is the most common physical adsorption mechanism in
mesoporous materials. At rising moisture content, reversible
multilayer adsorption takes place, followed by capillary
condensation at specific pressures, depending on the pore
structure, leading to type IV or type V isotherms.
In many instances, water vapor affects the structural integrity
of MOFs. The hydrolytic stability of a MOF is defined as the
preservation of its pore structure and crystallinity after
exposure to a certain level of humidity for a period of time
at a given temperature.312 Techniques such as powder X-ray
diffraction (PXRD) and nitrogen adsorption at 77 K are the
most common tools used to evaluate the stability of MOFs in
the presence of water vapor or, in some instances, liquid
water.313−315
3.3.1. Degradation Mechanisms of MOFs in Contact
with Water. The degradation of MOFs with vulnerable
pubs.acs.org/CR Review
frameworks in the presence of water occurs through two
mechanisms, namely ligand displacement and hydrolysis.316 In
ligand displacement reactions under neutral condition, water
molecules are inserted into the metal−ligand bond of the
framework, leading to the formation of hydrated cations and
the release of deprotonated ligands (eq 1). The mechanism is
slightly different under basic or acidic condition.317 For
instance, in the presence of water vapor, MOF-5 undergoes
complete structural collapse via ligand displacement (eq 2).318
Mm − Ln − + H 2O → Mm + − (OH 2) ···Ln − (1)
(Zn4O)(BDC)3 + 4H 2O
→ [(Zn4O)(H 2O)4 (BDC)2 ]2 + . . . BDC2 − (2)
Hydrolysis of MOFs is akin to an acid−base reaction, where
the metal−ligand species react with water molecules to form a
hydroxylated SBU and free protonated ligand (eq 3). For
instance, the disintegration of Cu(BDC)(TED)0.5 (BDC, 1,4-
benzene dicarboxylate; TED, triethylenediamine) takes place
through hydrolysis of Cu−O−C, as demonstrated by IR
measurements (eq 4).319
Mm + − Ln − + H 2O → Mm + − (OH)− + HL(n − 1) − (3)
Cu−O−C + H 2O → Cu−O−H + C − OH (4)
Understandably, the hydrolytic stability of MOFs depends on
thermodynamic factors such as the strength of the metal−
linker bond and on kinetic factors that impede the degradation
reaction with water such as increased steric hindrance or
hydrophobicity.
3.3.2. Thermodynamic Stability of MOFs. The
thermodynamic stability of MOFs is primarily due to the
strength of the metal−linker bond. This bond can be regarded
as the result of a reaction between the metallic cation acting as
a Lewis acid and the ligand anion acting as a Lewis base,
indicating the strong relationship between the strength of the
acid and base and the stability of the corresponding MOF.
Hence, it is expected that as pKa of the protonated ligand
increases, the thermodynamic stability increases. As for the
metal, the higher the charge and the smaller the size, i.e., the
higher the charge density, the stronger the metal−linker bond.
As shown in Figure 9, this relationship can also be explained
using the hard−soft acid−base (HSAB) concept, which
indicates that strong bonds occur between hard acid and
hard base or soft acid and soft base.95
Most MOFs use carboxylate or N-heterocycle-based linkers.
Carboxylate ligands, such as BDC and BTC (1,3,5-benzene
tricarboxylate), are strong Lewis bases as indicated by the low
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Figure 10. Stability of different MOFs as a function of temperature and percent steam. The red and magenta numbers indicate experimental and
simulated activation energy (in kcal/mol) for ligand displacement by water, respectively. Reproduced with permission from ref 316. Copyright
2009 American Chemical Society.
pKa of their conjugated acids of 3.9 and 3.6, respectively. They
can also be regarded as hard bases, which form stable MOFs
with high-valent metal ions (hard acids), such as Fe3+, Cr3+,
Al3+, Zr4+, Hf4+, and Ti4+. The MIL series is a typical example
of hydrolytically stable carboxylate-based MOFs, containing
Fe3+, Cr3+, or Al3+.102,320,321 Likewise, Zr-carboxylate MOFs
such as UiO-66 and derivatives are also known to be
extraordinarily stable.90,322−325 Nitrogen containing hetero-
cycles (high pKa), such as azolates,326 adeninates,315 and
pyrazolates,327,328 are soft bases. Their combinations with low-
valent metals (soft acids), such as Zn2+, Ni2+, Cu2+, and Mn2+
also give rise to water-stable MOFs. Guided by the HSAB
concept, many hydrolytically stable MOFs have been
assembled and investigated.95,96
Although the metal−ligand bond strength based on pKa
values and the HSAB principle are useful to predict the
stability of MOFs, another important thermodynamic factor is
the metal lability with water, i.e., its likelihood to undergo
hydrolysis, which depends on the energy difference between
the frontier orbitals of the metal and water. The larger the
energy gap between these frontier orbitals, the higher the water
stability. For example, Kang et al.329 investigated the effect of
metal ions on the stability of three isostructural MOFs with the
same ligand, namely, Cr-BDC, Al-BDC, and V-BDC, in pure
water and in basic and acidic aqueous solutions. In all cases,
the stability decreased in the order of Cr-BDC > Al-BDC > V-
BDC, which is different from the metal−ligand bond strength
order, i.e., Al-BDC > Cr-BDC > V-BDC. Moreover, the metal
ions in all three MOFs had the same oxidation state and
coordination geometry, ruling out the effect of such parameters
on the observed trend. The authors concluded that the stability
of these MOFs depends on the inertness or lability order of the
metallic ions, i.e., CrIII > AlIII > VIII > VIV. In another example,
the Walton group330 carried out partial substitution of Mg in
Mg-DOBDC with other metals such as Ni or Co, which are
less vulnerable to hydrolysis than Mg, and evaluated the
stability of the resultant materials under humid condition. After
exposure to water vapor at 95% RH, Mg-Ni-DOBDC,
containing as little as 16% Ni, retained 80% of its surface
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area versus 8% for Mg-DOBDC, although no further
improvement took place at higher Ni content. As for Mg-
Co-DOBDC, the retained surface area after water exposure
increased linearly with Co content. Further computational and
experimental studies331 indicated that in mixed metal materials,
distortion of the apical M−O bond length exceeded what
would be expected from simple metal size effects, suggesting
that the M−O bond length plays a key role in M-DOBDC
hydrolytic stability. Consistent with the prevailing under-
standing of H2O adsorption on MOFs,86,332 it was inferred that
the increased water stability of Mg-Ni-DOBDC arises from the
contraction of the apical M−O bond.
3.3.3. Kinetic Stability of MOFs. In a seminal
contribution, Low et al.316 investigated the hydrolytic stability
of a series of MOFs as a function of temperature and steam
content and calculated the free energy for their hydrolysis
(ΔGhyd) as well as the free (ΔGdisp) and activation (ΔE⧧disp)
energy for ligand displacement. As shown in Figure 10,
experimental data were in good agreement with calculated
activation energies for ligand displacement, indicating that the
observed hydrolytic stabilities are under kinetic control.
Kinetic factors include any feature that affects the activation
energy of hydrolysis. For example, increased hydrophobicity
has a positive effect on MOF stability by preventing water from
adsorbing in the pores or from clustering around the metal
center.96,98 Preventing water clustering in the SBU neighbor-
hood was achieved by alkyl functionalization.333 Actually, even
polar groups such as amines and alkoxy groups draw water
toward the new sites, thus precluding water clustering near the
SBU.334 Using water-repellent fluorinated ligands blocked
water adsorption altogether.335,336 Incorporation of polymers
can also increase the MOF hydrophobicity and thus their
hydrolytic stability.337,338 In addition to hydrophobicity, steric
factors may also reduce the rate of hydrolysis. This includes the
occurrence of well-protected metals with high coordination
numbers, such as Zr-based UiO-66339 and MIL-140,340
numerous porous coordination networks (PCNs),341−343 Hf-
based DUTs,344 phosphonate-based MOFs,345−347 and
others.348 Catenation, i.e., interpenetration of two or more
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identical and independent frameworks, is another steric factor
that improves water stability by locking labile ligands in
place.349−352 The higher water-stability of Zn(BDC)(BPY)0.5
or MOF-508 (BDY = 4,4′-bipyridine) with catenation,
compared to Zn(BDC)(DABCO)0.5 or DMOF (DABCO:
1,4-diazabicyclo[2.2.2]octane) without catenation, offers an
illustrative example.349 Nonetheless, although the zinc paddle
wheel in the parent DMOF hydrolyzes readily, 319,353
functionalization of H2BDC linker by methyl groups increased
the kinetic water stability, particularly for the tetramethyl
BDC.354,355 This finding could not be rationalized solely by
increased hydrophobicity; the additional methyl groups had a
steric shielding effect on the SBUs.98,355 In another example,
MOFs, prepared from alkaline-earth Mg and Sr, and tetrakis[4-
(carboxyphenyl)oxamethyl]methane acid as ligand showed
significant structural collapse after 24 h exposure to 98% RH,
whereas the Ca-based counterpart was stable even after two
weeks of exposure.356 The superior stability of Ca-derived
MOF was attributed to a more subtle steric effect as the ligand
distortion within the framework gave rise to a steric
conformation of benzene rings around Ca2+ ions, shielding
them from water.
Some MOFs such as Zr-based UiO-67 and NU-1000 are
stable toward linker hydrolysis, but collapse during dehy-
dration, because of the occurrence of capillary forces, strong
enough to bring about solid-phase compression, and ultimately
structural collapse.357,358 Because these forces increase with
increasing liquid−vapor interfacial energy, one way to
circumvent the material collapse would be to exchange water
with a more volatile solvent before drying.358 Freeze-drying or
supercritical CO2 drying are other options.
In addition to the effect of water on the structural integrity
of MOFs, adsorption−desorption of water vapor may bring
about reversible changes in their pore structure, known as the
breathing effect, with the most typical example being MIL-53
MOFs.102 Millange et al.359 reported that the breathing
properties of MIL-53 is metal-dependent. Variable-temperature
PXRD data indicated that unlike MIL-53(Cr), whose pores
expand upon dehydration, the loss of water initially caused
pore narrowing in MIL-53(Fe) structure, leading to the
formation of a metastable intermediate anhydrous phase.
Further heating resulted in smaller opening of the structure
until a final anhydrous phase was obtained. Figure 11 illustrates
the structural changes during dehydration of MIL-53(Fe) and
MIL-53(Cr).
3.4. Effect of Water on CO2 Adsorption over MOFs
Numerous studies were devoted to the effect of water vapor or
preadsorbed water on CO2 capture by different MOFs.171−173
As discussed below, such effects depend on a multitude of
parameters, including the nature of metal centers, functional
groups, framework structure, porosity, postsynthesis modifica-
tions, and the adsorption procedure.
3.4.1. Effect of Coordinatively Unsaturated Sites.
Upon proper activation, many MOFs, including M-DOBDC,
UiO-66, MIL-100, MIL-101, and HKUST-1 (Cu-BTC) exhibit
metal sites with unsaturated coordination, referred to as CUS,
which represent preferential adsorption sites with applications
in adsorption, catalysis, and sensing.360 Despite the limited
water-stability of HKUST-1,339,361 numerous studies were
devoted to the effect of water on CO2 adsorption over this
MOF, starting with the intriguing promoting effect of moisture
at low content.99 On the basis of molecular simulations and
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Figure 11. Structural changes upon hydration-dehydration of (left)
MIL-53(Cr), (right) MIL-53(Fe). Reproduced with permission from
ref 359. Copyright 2008 Royal Society of Chemistry.
experimental evidence, Yazaydin et al.99 found that the CO2
uptake over HKUST-1 at 25 °C increased by 75% (from 2.3
mmol/g) at 0.2 bar and by 37% (from 11.3 mmol/g) at ca. 5
bar, when the material was prehydrated to 4 wt % (2.2 mmol/
g), corresponding to an average of 0.5 H2O per Cu. Further
increase of the material moisture content to 8 wt % reduced
the CO2 uptake, presumably because of the presence of
uncoordinated water that blocked the pore space. Simulation
data revealed that stronger interaction between the quadrupole
moment of CO2 and the electric field created by adsorbed
water is responsible for the enhanced CO2 uptake. Using
molecular modeling, Yu et al.362 also found that CO2
adsorption on HKUST-1 was promoted by small amounts of
both coordinated (preadsorbed) and uncoordinated (in gas
phase) water. Consistent with the results reported by Yazaydin
et al.,99 DFT calculations indicated that the presence of small
amount of preadsorbed water increased CO2 uptake and CO2/
N2 selectivity through higher binding energy between CO2 and
water-coordinated CUS compared to direct CO2−CUS
interaction. Enhanced CO2/N2 selectivity by uncoordinated
water was attributed to competitive adsorption sites between
water and N2 in combination with higher CO2 uptake. On the
contrary, closed-system multicomponent equilibrium adsorp-
tion measurements over HKUST-1 at 40 °C in the presence of
16% CO2/N2 with different humidity levels, indicated no
major changes in the amount of adsorbed CO2 at a water
pressure of 1 and 4 mbar, corresponding to H2O uptake of 1.9
and 7.7 mmol/g.205 Using slightly different static H2O/CO2
equilibrium, Liu et al.100 did find that up to 3.4 mmol/g, water
had a minor promoting effect on CO2 uptake but not as high as
reported by Yazaydin et al.99 Nonetheless, at higher moisture
content, no CO2 adsorption took place.100,204,205
In contrast to HKUST-1, interaction of water with CUS in
M-DOBDC (M = Mg, Ni, Zn, and Co) gave rise to metal-
dependent adverse effects on CO2 uptake.100,205,363−366 Static
three-component equilibrium measurements indicated that the
CO2 uptake at about 0.2 bar, over Mg- and Ni-DOBDC at 40
°C, decreased by more that 75% in the presence of H2O partial
pressure of 2 mbar (0.2%), well below practical applications.205
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Figure 12. CO2, N2, and H2O multicomponent equilibrium measurements for MIL-100(Fe) at (a) 25 °C and (b) 40 °C. Green circles represent
pure CO2 adsorption isotherms, and the black line is the corresponding dual-site Langmuir fit. Square data points represent the CO2 uptake from a
mixture of CO2, N2, and H2O (color of the square indicates the equilibrium partial pressure of H2O). Reproduced with permission from ref 205.
Copyright 2015 American Chemical Society.
Similar findings for Ni-DOBDC were reported based on binary
equilibrium data.100 Breakthrough measurements indicated
that the CO2 uptake of Ni-DOBDC in the presence of 15%
CO2/N2 at 25 °C of 3.74 mmol/g dropped to 2.2 mmol/g at
RH as low as 3%.365 Even this residual uptake is most likely
overestimated because the adsorption state did not reach
equilibrium.205 PXRD data showed no loss of crystallinity
upon exposure to humidity. Moreover, no relationship was
found between the loss of CO2 uptake and physical properties,
including metal atom electronegativity and metal−benzoate
stability in aqueous medium, suggesting that kinetic and
thermodynamic parameters may be associated with the loss in
CO2 capacity with moisture.365 In other studies on M-
DOBDC, the focus was on steam conditioning and long-term
stability.363,364 Using breakthrough experiments in the
presence of 20% CO2/N2 with 9−70% RH, Kizzie et al.363
found that the CO2 capacity of Mg-DOBDC was similar to
that under dry conditions. However, upon regeneration at 150
°C, the material lost up to 81% of its initial CO2 capacity under
dry conditions. Similarly, after exposure to 20% CO2/N2 with
70% RH, and regeneration in N2 at 150 °C, M-DOBDC (M =
Ni, Zn and Co) adsorbed under dry conditions, 78%, 39%, and
15% less CO2, respectively, compared to pristine materials.363
Similar findings were reported by Liu et al.364 Interestingly,
PXRD showed that after steaming, the crystal structure of Mg-
DOBDC remained intact, whereas Ni-DOBDC broke down,
but both materials had drastically reduced surface areas. It was
surmised that the CO2 uptake of these MOFs was not
governed by crystallinity but by the density of their CUS. On
the basis of the standard reduction potential of Mg2+ and Ni2+
of −2.37 versus −0.26 eV, respectively, it was inferred that Mg-
DOBDC would react more readily with oxygen or water than
its Ni counterpart, leading to decreased density of CUS. This
interpretation seems also to apply to Zn- and Co-DOBDC.364
Smit and co-workers367 developed a methodology to derive
improved force fields from periodic DFT calculations, enabling
accurate prediction of CO2 and H2O adsorption isotherms
over M-DOBDC. They found that the CO2 uptake at 0.15 bar
over Mg-DOBDC at 40 °C decreased by 50% and 100% in the
presence of 0.2 and 0.5% water vapor (2.7 and 6.8% RH),
respectively. This finding was attributed to the strong binding
energy between CUS and water (70 kJ/mol) and the
substantial difference (>20 kJ/mol) in the isosteric heat of
adsorption of water compared to CO2. However, Zn-DOBDC,
with lower binding strength for water, showed a constant CO2
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capacity up to 1% water vapor (3.5% RH). The difference in
binding energies between CO2 and CUS with and without
coordinated water is a good indicator of the effect of water on
CO2 adsorption on the corresponding MOFs.99,364,366 Hence,
the higher binding energy between CO2 and water-coordinated
Cu in HKUST-1 resulted in beneficial effect of water on CO2
uptake,99,362 whereas for M-DOBDC (M = Mg, Ni, Zn and
Co), lower binding energies led to the opposite effect, with
varying intensity, depending on the nature of the metal.366
Soubeyrand-Lenoir et al.216 investigated the effect of
humidity on CO2 adsorption over MIL-100(Fe), another
MOF with uncoordinated metal sites, using breakthrough
measurements after hydration of the adsorbent at the same
relative humidity. At 20% and 40% RH, the CO2 uptake at 0.2
bar was found to increase by an impressive 3 and 5 times,
respectively, compared to dry conditions. This was attributed
to a combination of water displacement and CO2 adsorption in
microporous pockets created by the partial filling of mesopores
by water. Similarly, using equimolar CO2/CH4, Xian et al.368
found that at 50% RH, the CO2 uptake over MIL-100(Fe)
increased from 1.49 to 3.75 mmol/g and CO2 versus N2
selectivity from 8.6 to 16.3. In contrast, the CO2 capacity of
MIL-100(Cr) decreased from 2.44 to 1.37 mmol/g. The
beneficial effect of humidity was tentatively associated with the
dissociation of water on MIL-100(Fe), forming new hydroxyl
adsorption sites for CO2. This contention was supported by
the occurrence of two CO2 desorption peaks in the TPD
profile in humid condition versus a single peak in dry
condition. For MIL-101(Cr), however, the reduction of CO2
uptake was attributed to competitive adsorption of water.
Contrary to the aforementioned promoting effect of humidity
in the presence of MIL-100(Fe), static three-component
equilibrium measurements at 25 and 40 °C showed a rather
slight decrease in CO2 uptake at 0.2 bar in the presence of
humidity (Figure 12).205
Al-containing MOFs were also considered for wet CO2
adsorption.369,370 Prehydration of water-stable aluminum
fumarate in humid N2 (14% RH) had no effect on its CO2
uptake of 2.1 mmol/g at 30 °C and 1.0 bar.369 As for CO2
uptake in the presence of 75% CO2/He with 14% RH, it
decreased by only 17%, indicating a modest negative effect of
water. Further GCMC simulations showed that in the presence
of Al-fumarate, gas species such as CO2, N2, and CH4 adsorb in
the center of the pores, while water adsorbs in proximity of the
Al-O-Al-O units in the form of clusters.370 Similar to HKUST-
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1,99,363 at low concentrations, water was found to increase the
isosteric heat of CO2 adsorption, leading to higher CO2
uptake; however, high moisture content led to the opposite
effect due to the accumulation of water clusters in the one-
dimensional Al(OH) fumarate channels. In the presence of rht-
Type-MOF (Cu-TDPAT, TDPAT: 2,4,6-tris(3,5-dicarboxyl-
phenylamino)-1,3,5-triazine), although water adversely affected
CO 2 adsorption, it increased CO 2 /CH 4 and CO 2 /N 2
selectivity.371 Masala et al.372 reported that another CUS-
containing MOF, UTSA-16, retained 70% of its CO2 capacity
at 40 °C, i.e., 0.94 versus 1.3 mmol/g, in the presence of humid
CO2 feed gas (9.8% CO2/1.7% H2O/N2; 23% RH), which was
attributed to its high density of CUS and low affinity for water.
3.4.2. Effect of Other SBU Features. Ibarra and co-
workers made significant contributions highlighting the
beneficial effect of bridging hydroxo groups (μ2-OH) on
humid CO2 uptake of hydrolytically stable MOFs such as
NOTT-400,373 NOTT-401,198,374 InOF-1,196 CAU-100,375
and others.376 CO2 uptake was found to increase significantly
in the presence of humidity up to some level, depending on the
actual MOF, before it eventually decreased to zero. As an
example, the uptake in the presence of pure CO2 at 30 °C over
NOTT-400, increased by 100% and 150% in the presence of
10% and 20% RH compared to dry conditions.373 This was
attributed to the strong hydrogen bonding between water
molecules and μ2-OH, leading to the so-called confinement
effect.377,378 It was suggested that such water molecules
homogeneously distributed inside the pores, providing addi-
tional adsorption sites for CO2. At higher RH of 35% and 60%,
no CO2 adsorption took place, presumably because of pore
blocking by water. Likewise, in the presence of water-stable
NOTT-401,198 CO2 uptake at 30 °C increased by 3.2- and 1.6-
fold in the presence of 5% and 10% RH, respectively, but was
completely inhibited beyond 30% RH. Notice that these
findings seem at odds with an earlier report on NOTT-401,
indicating a 7-fold increase in CO2 capacity at 40% RH.374
With regard to the indium-containing MOF, InOF-1, also
possessing a binuclear [In2(μ-OH)] building block, similar
promoting effect of humidity on CO2 adsorption was observed,
with 2-fold increase at 20% RH.196 However, beyond 40% RH,
there was significant decrease in CO2 uptake, also attributed to
pore blocking by water. The humidity-induced CO2 adsorption
enhancement over CAU-10, another μ2-OH containing MOF,
was 30% in the presence of 3−20% RH.375 Similar behavior
was also reported for MOFs containing [Al2(μ2-OH)] and
[Mg3(μ3-OH)]5+ units such as MIL-53(Al)-YDC379 and Mg-
CUK-1,380,381 respectively. The effect of spatial confinement
and surface interaction of water in the pore volume was also
reported for MIL-53(Al), containing AlO4(OH)2 octahedra, as
the presence of 20% RH resulted in 50% increase in CO2
uptake at 30 °C, i.e., from 0.8 to 1.2 mmol/g.382,383
MOFs containing monodentate hydroxide ligands (M-OH)
with the ability to generate bicarbonate upon exposure to CO2,
much like carbonic anhydrase, represent a recent development
in the field.384−387 Liao et al.384 synthesized MAF-X25ox and
MAF-X27ox by partial substitution of the corresponding
metals Co2+ and Mn2+ by [CoIII(OH)]2+ and [MnIII(OH)]2+,
respectively. Likewise, Bien et al.386 used postsynthesis ligand
exchange to generate Zn-OH using Zn-OAc containing CFA-1.
They also synthesized bimetallic analogues of CFA-1
containing Ni-OH and Co-OH by metal and ligand
exchanges.387 All such materials showed high affinity toward
CO2 at low pressure because of particularly high isosteric heat
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of adsorption.384,387 Although information is scarce, there are
indications that the effect of humidity on CO2 uptake by such
materials is metal-dependent. In the presence of 0.25% CO2/
N2 with ca. 10% RH at 25 °C, the CO2 uptake over Zn-OH
containing CFA-1 did not change (2.18 mmol/g) but
decreased from 2.31 to 1.93 mmol/g for its Ni-OH
counterpart.387 Nonetheless, in the presence of 100% RH,
the Zn-OH containing MOF did not exhibit any CO2 uptake.
Interestingly, the breakthrough curves of MAF-X27ox in the
presence of dry or humid (82% RH) 10:90 CO2/N2 were
almost the same, whereas the OH-free MAF-X27 completely
lost its ability to adsorb CO2 from the humid gas mixture.
3.4.3. Effect of Hydrophobicity. Adjusting the hydro-
phobicity is an excellent strategy to control the effect of water
on CO2 uptake. A comprehensive summary on hydrophobic
MOFs can be found elsewhere.388,389 Some MOFs such as
zeolitic imidazolate frameworks (ZIFs) are inherently hydro-
phobic, and as a general rule, their CO2 uptake is insensitive to
moisture. The Yaghi group390 observed negligible difference
between dry and humid (80% RH) CO2 uptakes over ZIF-300,
ZIF-301, and ZIF-302. Molecular simulations by Liu and
Smit391 also indicated that water did not affect the CO2 uptake
and CO2/N2 selectivity of ZIF-68 and ZIF-69 at low pressure;
however, higher water vapor pressures resulted in competitive
adsorption of water with decreasing CO2 and N2 uptake and an
overall increase in CO2 versus N2 selectivity. GCMC and DFT
calculations also confirmed the behavior of ZIF-68.392 As for
other MOFs, a straightforward method to achieve hydro-
phobicity is to use fluorinated ligands or SBUs. Bhatt et al.393
investigated the use of fluorinated NbOFFIVE-1-Ni for low-
concentration CO2 capture. NbOFFIVE-1-Ni showed excellent
CO2 uptake of 1.3 mmol/g at 400 ppm of CO2, with
unprecedented selectivity attributable to the adsorption sites
being at the vicinity of the fluorine center. In the presence of
dry 1% CO2/N2, the CO2 uptake was 1.86 mmol/g; however,
at 75% RH, although water capacity was 10 mmol/g, the CO2
uptake was reduced only to 1.27 mmol/g. Nonetheless, the
amounts of adsorbed water and CO2 over multiple cycles were
constant, suggesting that no more competition took place.
Likewise, although AlFFIVE-1-Ni adsorbed a significant
amount of water (11 mmol/g at 95% RH and 25 °C), single
breakthrough experiments using humid 5/5/90:H2S/CO2/
CH4 with 65% RH, showed little effect of water on CO2 uptake
because water adsorption was negligible by the time CO2
adsorption was completed.394 Moghadam et al.395 investigated
CO2 and water coadsorption on a flexible hydrophobic
fluorinated MOF (FMOF-1), consisting of a network of
channels and small pockets decorated with −CF3 groups.
Interestingly, GCMC simulations showed that the presence of
humidity, even as high as 80% RH, did not affect the CO2
uptake, consistent with the hydrophobic nature of the material
(Figure 13).
Yu and Balbuena396 found that because of the hydrophobic
nature of Br-functionalized UiO-66 and its low binding energy
with water, its CO2 uptake was hardly affected by moisture,
whereas NH2- and OH-modified UiO-66 materials showed
strong interactions with water, with adverse effect on CO2
uptake and CO2/N2 selectivity. Other studies also demon-
strated that functionalization of MOFs with groups that
decrease their hydrophilic character, decreased water uptake,
thereby increasing CO2 selectivity over water. Bae et al.397
found that pyridine incorporation in Ni-DOBDC (Py-Ni-
DOBDC) lowered water uptake significantly more than CO2,
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Figure 13. Calculated CO2 and water uptake on FMOF-1.
Reproduced with permission from ref 395. Copyright 2017 Creative
Commons Attribution License.
decreasing the selectivity of water versus CO2 from 1844 to
308, most likely because pyridine coordinates to CUS at the
expense of water.
Coating MOFs with appropriate polymers is also a
promising approach to not only improve their hydrolytic
stability because of higher hydrophobicity, but to main-
tain398,399 or enhance400−402 their CO2 capacity under wet
conditions, Zhang et al.398 coated MOF-5, HKUST-1, and
ZnBT [Zn(BDC)(TED) 0.5 ] with polydimethysiloxane
(PDMS) by vapor deposition at 235 °C and exposed the
pristine and coated materials to humid conditions; MOF-5 and
ZnBT were exposed to air at 55% RH for 1 day, while
HKUST-1 was treated in liquid water for 3 days. The CO2
uptake under dry condition at 25 °C and 1 atm was the same
for pristine and coated MOFs, suggesting that the coating did
not affect the CO2 binding sites nor their accessibility.
Following exposure to water, the CO2 capacity of all coated
MOFs did not change significantly, while that of pristine
materials decreased by 80%, 75% and 98% for MOF-5,
HKUST-1, and ZnBT, respectively. Hong group400 reported
that coating N-ethylethylenediamine-functionalized
Mn2(dobpdc) (dobpdc4−: 4,4′-dioxidobiphenyl-3,3′-dicarbox-
ylate), denoted 1-een, with 20% hydrophobic PDMS (1-een@
PDMS20) significantly improved its water resistance. In the
presence of 15% CO2/He, 1-een had the same CO2 capacity
under both dry and humid conditions (Figure 14a), whereas 1-
een@PDMS20 exhibited higher CO2 capacity under humid
condition (Figure 14b). Prehydration of hydrophilic 1-een over
an extended period adversely affected its CO2 uptake as
diffusing water competed with CO2, resulting in over 40%
decrease in CO2 capacity and almost complete loss in
crystallinity after 6 h of exposure to water vapor. On the
contrary, only 10% loss in CO2 capacity was observed when 1-
Figure 14. CO2 adsorption versus time in dry (15% CO2/He) and wet (15% CO2/He, 30% RH) conditions at 50 °C over (a) 1-een and (b) 1-
een@PDMS20. Reproduced with permission from ref 400. Copyright 2019 Royal Society of Chemistry.
pubs.acs.org/CR Review
een@PDMS20 was prehydrated for 6 h, with marginal
decrease in crystallinity. Using 1-een under dry optimum
TSA cycling, with adsorption at 70 °C and desorption at 100
°C, a steady CO2 working capacity of ca. 3.18 mmol/g, was
achieved over 600 cycles. However, under moist conditions
(15% CO2/3.75% H2O/He, 30% RH), the CO2 uptake over 5
cycles for 1-een was only 0.66 mmol/g, compared to 2.27
mmol/g for 1-een@PDMS20 (Figure 15), further supporting
the transfer of the hydrophobic character of PDMS to 1-een@
PDMS20.
Figure 15. Cyclic CO2 adsorption capacity for (a) 1-een and (b) 1-
een@PDMS20 under wet condition (15% CO2/He, 30% RH).
Reproduced with permission from ref 400. Copyright 2019 Royal
Society of Chemistry.
Coating NH2-MIL-125(Ti), ZIF-67, and HKUST-1 with a
silicone resin by solution immersion gave rise to stable
materials after exposure to liquid water for 5 days, while the
pristine MOFs showed varying degree of structure collapse as
early as after 1 day.403 CO2 uptake of pristine MOFs at 25 °C
and 1 bar, decreased by at least 80% after water treatment,
while their coated counterparts retained 76−86% of their
original capacity. Fernandez et al.399 coated MIL-101(Cr) and
Ni-DOBDC by immersion in a chloroform solution of Pluronic
P123 and found that upon exposure to air at 95% RH, the
modified materials adsorbed ca. 50% and 60% less water than
the pristine MOFs. Moreover, the CO2 capacity of the water-
exposed materials at room temperature was similar to that of
the unmodified MOFs, suggesting that coating enhanced the
hydrolytic stability of the materials without compromising its
CO2 capacity. Ding et al.402 performed in situ polymerization
of 1,2-diethynylbenzene inside the pores of MOF-5 to afford a
hydrophobic polynaphthylene-containing material, PN@MOF-
5. Despite its significantly lower surface area, breakthrough
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Table 4. CO2 Adsorption of 0.15 atm CO2 over Diamine-Appended Mg2(dobpdc) under Dry and Humid Conditions at 40 °C
CO2 uptake (mmol/g)
diamine RH (%) dry humid ref
a
ethylenediamine (en) 100 4.30 2.88 149
N-methylethylenediamine (men) 100 3.95 3.63a 149

N-ethylethylenediamine (een) 30 4.52 4.25a 150

50 4.52 4.59 150
412
70 4.36 4.70
100 3.18b 2.45b,c 400
100 4.11d 4.25d 400

N-(propyl)ethylenediamine (pen) 70 4.43 5.16 412

N-isopropylethylenediamine (ipen) 50 3.09 2.90 150

70 3.09 3.23 150
100 4.11 4.86 412

N-(butyl)ethylenediamine (nBu-2) 70 4.14 4.82 412

N-(pentyl)ethylenediamine (nPen-2) 70 3.86 4.48 412
N-(3-pentyl)ethylenediamine (3-Pent-2) 70 3.39 4.50 412
N-(hexyl)ethylenediamine (nHex-2) 70 3.50 4.14 412
N-(cyclopentyl)ethylenediamine (cPent-2) 70 3.86 5.45 412

N,N′-dimethylethylenediamine (mmen) 27 2.73 2.54a 149

50 3.36 4.80 149
50 3.75 4.22 205
100 3.02 3.32 408

2,2-dimethyl-1,3-diaminopropane (dmpn) 27 3.00 2.70 153

2-(aminomethyl)piperidine (2-ampd)e 35 2.40 2.40 411
a
Sample was exposed to 100% RH for 48 h, then activated at 130 °C under Ar and exposed to 15% CO2/N2. bAdsorption at 70 °C. cMaterial was
exposed to 100% RH at room temperature for 1 h, then activated at 120 °C for 2 h under N2 and exposed to 15% CO2/N2. dAdsorption at 50 °C.
e
CO2 pressure of 0.04 atm

experiments using 16% CO2/N2 at 25 °C indicated that the
CO2 capacity for PN@MOF-5 was 50% higher compared to
MOF-5 because of stronger CO2 binding, presumably due to a
more favorable pore size distribution with subnanometer pores
and the occurrence of exposed aromatic surfaces. Under humid
condition (65% RH), only marginal decrease in CO2 capacity
was observed for PN@MOF-5, while MOF-5 displayed 40%
and 73% loss in CO2 uptake for cycle one and two,
respectively.
3.4.4. Effect of MOF Functionalization. In addition to
earlier examples of ligand modification aiming at increasing
hydrophobicity,393−396 other functionalization in view of
facilitating CO2 capture from humid streams were reported.
Nandi et al.404 designed IISERP MOFs using bifunctional
ligands comprised of basic azolyl and chelating groups in the
presence of metal acetates, the latter providing a hydrophobic
lining to the pore walls. This enabled selective adsorption of
CO2 even in the presence of 75% RH. Simulation data revealed
the occurrence of polarized CO2 molecules adjacent to the
azolyl moieties, which in addition to strong van der Waal
interactions between O(δ−) and C(δ+) led to the formation of
T-shaped CO2···CO2 configurations, thought to be at the
origin of the CO2 affinity of the material under humid
conditions. Shi et al.405 synthesized derivatives of ZnF(TZ), a
1,2,4-triazolate (TZ)-based MOF, using amino, diamino, and
dimethyl-azolate linkers, i.e., ZnF(aTZ), ZnF(daTZ), and
ZnF(dmTZ), respectively. In addition to their outstanding
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hydrolytic stability, breakthrough data at 25 °C using 15%
CO2/N2 with 33−95% RH revealed up to 20% enhancement
in CO2 uptake compared to dry conditions, which was
attributed based on DFT calculations, to the significantly
higher heat of CO2 adsorption in the presence of water.
GCMC simulations indicated the occurrence of distinct sites at
the channel center for CO2 adsorption and at the corner for
H2O, which seems to be a prerequisite for the promoting effect
of water on CO2 uptake in zeolites280 and MOFs.406 Using
functionalized IRMOF74-III with two primary amine groups,
Yaghi and co-workers155 found that unlike other amine-
containing adsorbents, typically adsorbing CO2 as ammonium
carbamate, IRMOF74-III-(CH2NH2)2 adsorbed dry CO2
primarily as carbamic acid, whereas the formation of
ammonium carbamate increased with the humidity level,
suggesting a change in the conformation of the MOF linkers
with humidity. Dynamic CO2 uptake of 1.2 mmol/g in the
presence of 16% CO2/N2 was obtained at 25 °C under dry and
humid (65% RH) conditions. It was suggested that under both
conditions, CO2 forms first carbamic acid, which undergoes
proton transfer in the presence of water to generate
ammonium carbamate.
In addition to amine-functionalized ligands,155,396,407 the
most common amine modification of MOFs is through
tethering to CUS. Although the behavior of amine-grafted
materials will be addressed in section 4.2, it is more
appropriate to discuss amine-tethered MOFs, within this
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Figure 16. Proposed mechanism for CO2 adsorption over mmen-M2(dobpdc) with four neighboring M−mmen sites: (a) nucleophilic addition of
CO2 and amine deprotonation, (b) carbamate rearrangement and destabilization of M−N bonds, and (c) formation of carbamate chains along the
pore channels. Reproduced with permission from ref 151. Copyright 2015 Springer Nature.

Figure 17. CO2 adsorption isotherms at 25 °C (blue), 40 °C (blue-violet), 50 °C (red-violet), and 75 °C (red) for (a) mmen-Co2(dobpdc) and
(b) mmen-Zn2(dobpdc). Reproduced with permission from ref 151. Copyright 2015 Springer Nature

section. The Hong148−150,408,409 and Long151−153,205,410−413
groups and others144−147,414−416 devoted much effort to
understanding the effect of amine-appended MOFs for CO2
capture under dry and humid conditions. Amine tethering
provides protection for electrophilic CUS, leading to less
competitive adsorption of water.144 With few exceptions, most
investigations dealt with grafting Mg2(dobpdc), with ethyl-
enediamines having a wide variety of alkyl groups, which are
often highly efficient adsorbents for humid CO2 (Table 4). As
shown in Figure 16, using typical N,N′-dimethyldiethylenedi-
amine (mmen)-appended M2(dobpdc), CO2 adsorption versus
pressure takes place in three steps. At low pressure,
nucleophilic addition of CO2 occurs concurrently with the
deprotonation of a metal-bound amine by an uncoordinated
amine of a neighboring mmen, acting as a strong base. This
leads to the formation of ammonium carbamate as in amine-
containing silicas (Figure 16a).151,205 At an appropriate
pressure, carbamate rearrangement occurs (Figure 16b), and
the ion pair destabilizes the M−N bonds on adjacent metal
sites, leading to the formation of carbamate chains along the
pore channels through a cooperative adsorption mechanism in
a cascade manner (Figure 16c). This gives rise to CO2
isotherms with abrupt steps,151−153,411 corresponding to a
sudden rise in CO2 uptake as both ends of the diamine become
involved in binding CO2. Such steps are both metal- and
temperature-dependent. Typical CO2 adsorption isotherms for
Q https://doi.org/10.1021/acs.chemrev.0c00762
(mmen)-M2(dobpdc) with M = Co and Zn, are shown in
Figure 17.151
At 25 °C and 0.15 bar CO2, the CO2 capacity of
Mg2(dobpdc) was 4.85 mmol/g,410 and generally decreased
following functionalization with different dia-
mines148,150,410,417,418 due to a decrease in CUS density and
surface area (Table 4). Nonetheless, the main advantage of
amine-tethered MOFs is their tolerance to moisture as
opposed to pristine MOFs. After exposure to humid N2
(100% RH) at 21 °C for up to 50 h, mmen-Mg2(dobpdc),149
men-Mg 2 (dobpdc), 149 ipen-Mg 2 (dobpdc), 150 and een-
Mg2(dobpdc)150 showed marginal loss in crystallinity and
CO2 uptake, compared to en-Mg2(dobpdc)149 and the pristine
MOF,148 which lost up to 65% in CO2 capacity, suggesting that
MOFs-containing diamines with side alkyl groups have
superior hydrolytic stability. As for CO2 adsorption in humid
gas mixture, the Hong group reported that for mmen-
Mg2(dobpdc) exposed to 15% CO2/He with 51% RH at 40
°C, the CO2 uptake was up to 43% higher compared to dry
conditions, with the material being stable over multiple
adsorption cycles.149,408 Under similar conditions, only
marginal increase in CO2 uptake was obtained for een- and
ipen-Mg2(dobpdc) compared to dry conditions, i.e., 4.59
versus 4.52 mmol/g and 3.23 versus 3.09 mmol/g,
respectively.150 Moreover, the rate of CO2 uptake was almost
two times higher under humid compared to dry conditions, i.e.,
1.27 versus 0.66 mmol/g·min for ipen-Mg2(dobpdc). In
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Figure 18. CO2, N2, and H2O multicomponent equilibrium data at 40 °C for (a) mmen-Mg2(dobpdc) and (b) mmen-Ni2(dobpdc). Green circles
represent pure CO2 adsorption data. Squares represent CO2 uptake from a mixture of CO2 (166 mbar), H2O (up to 30 mbar), and N2 (679 mbar),
and the color of the square indicates the equilibrium partial pressure of H2O. Reproduced with permission from ref 205. Copyright 2015 American
Chemical Society.

Figure 19. Isobars under (a) dry and (b) humid (2.6% H2O, 0.7−36% RH) conditions at atmospheric pressure for pure CO2 (green), 4% CO2 in
N2 (purple), 0.4% CO2 in N2 (orange), and pure N2 (blue) in 2-ampd-Mg2(dobpdc). Solid lines depict adsorption (cooling), and dotted green
lines depict desorption (heating) for the pure CO2 isobars. The dashed horizontal lines indicate adsorption of 1 CO2 per diamine. (c)
Breakthrough data at 40 °C with 2-ampd-Mg2(dobpdc) using 4% CO2/N2 and ∼1.1 bar: overlay of dry and humid (third cycle) CO2 breakthrough
profiles. Reproduced with permission from ref 411. Copyright 2019 American Chemical Society.

another study, the amount of CO2 adsorbed at 14% CO2/N2
with 32% RH and 17% CO2/N2 with ca. 32% RH was found to
be 4.2 and 1.1 mmol/g for mmen-Mg2(dobpdc) and mmen-
Ni2(dobpdc), respectively.205 These capacities were 14% and
83% higher, respectively, compared to dry conditions (Figure
18), suggesting that H2O promotes CO2 adsorption over these
hybrid materials as opposed to the pristine MOFs, which lost
up to 95% of their CO2 capacity in the presence of 20% CO2/
N2 with 26−32% RH. Water capacity up to 9.5 mmol/g was
obtained for mmen-Mg 2(dobpdc), suggesting that the
adsorption sites for water and CO2 are different.205
Comparison of CO2 isobars in the presence of 2-ampd-
Mg2(dobpdc), showed significant enhancement in CO2 uptake
in humid (Figure 19b) versus dry (Figure 19a) conditions,
notably at 40 °C and low CO2 concentration, e.g., orange
curves.411 In addition, column breakthrough data at 40 °C
showed no CO2 slip, with a significant sharp breakthrough
profile even after three cycles (Figure 19c). It was suggested
that under humid conditions, hydrogen-bonding interactions
between carbamate and water led to enhanced CO 2
adsorption, notably at low CO2 concentration. For other
diamines, such as dmpn-Mg2(dobpdc), only marginally higher
CO2 uptake was obtained at 40 °C under humid (15% CO2/
N2, 27% RH) compared to dry condition, i.e., 3.0 versus 2.9
mmol/g.153 Cycling with adsorption at 40 °C in the presence
of 15% CO2/N2 with 27% RH for 5 min and desorption at 100
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°C in 100% CO2 with 2% RH for 1 min indicated that dmpn-
Mg2(dobpdc) exhibits a stable working capacity of ca. 2.8
mmol/g over 1000 cycles, with no amine leaching or material
degradation.
Although diamine-appended Mg2(dobpdc) was the most
investigated, other MOFs were also tethered with diamines,
including M2(dobpdc), with M = Mn, Fe, Co, Ni, and Zn.151
Impressively, mmen-CuBTTri (H3BTTri: 1,3,5-tri(1H-1,2,3-
triazol-4-yl)benzene) produced 250% increase in CO2 uptake
at 0.15 bar and 25 °C compared to the pristine MOF413 and
only minimal decrease in CO2 uptake when exposed to 19%
CO2/N2 at 40 °C with 31% and 43% RH compared to dry
conditions.205 Other examples include een-Mn2(dobpdc)400
and piperazine (ppz)-Mg2(dondc) (dondc4−: 1,5-dioxido-2,6-
naphthalenedicarboxylate).409
In addition to ethylenediamines, MOFs were also tethered
with other amines. Liao et al.147 appended hydrazine into
Mg2(dobdc) to achieve high amine loading of ca. 6 mmol/g.
Surprisingly, water vapor (82% RH) had no effect on CO2
uptake at 40 °C regardless of the CO2 concentration in the
feed (10% or 400 ppm). In contrast, TEPA-appended
Mg2(dobdc) exhibited higher CO2 uptake under humid
condition.146 In the presence of 15% CO2/N2 at 60 °C, the
adsorption capacity increased from 6.06 to 8. 31 mmol/g at ca.
16% RH. In a more recent contribution, Kim et al.419
investigated a series of tetraamine-appended Mg2(dobpdc)
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adsorbents for the removal of CO 2 , mostly at 4%
concentration, relevant to the treatment of natural gas
combined-cycle emissions. In particular, the material appended
with 3-3 [bis(3-aminopropyl)amine] referred to as
Mg2(dobpdc)(3-4-3) was tested under humid condition in
the presence of 4% CO2/2.6% H2O/N2 at 100 °C (2.6% RH)
for 1000 cycles with desorption at 180 °C under humid CO2,
or for 15 cycles with regeneration at 120 °C under simulated
steam, ca. 60% H2O/N2. In both cases, the material was found
to be stable in terms of both amine content and adsorption
performance.
3.4.5. Effect of Framework Flexibility. MIL-53(Al and
Cr) are known to undergo reversible structural changes from
closed to open pore structure upon hydration−dehydra-
tion.359,420 Adsorbed water within the pores leads to
hydrogen-bonding with carboxylic acid ligands, as well as μ2-
OH groups,103,420 bringing about the deformation of the pore
system (Figure 20). As illustrated in Figure 21a, upon exposure
Figure 20. Breathing effect of MIL-53(Cr, Al) upon adsorption and
desorption of water. Reproduced with permission from ref 103.
Copyright 2006 John Wiley and Sons.
to CO2, dehydrated MIL-53(Cr) shrinks into its closed form,
with limited adsorption. At higher pressure of about 5−6 bar,
the CO2 uptake increases abruptly as a result of the pore
structure reopening.421 Similarly, hydrated MIL-53(Cr)
exhibits its closed structure in the presence of CO2 up to ca.
11 bar, when gradual opening of the pores takes place, leading
to a dramatic rise in CO2 uptake (Figure 21b). Interestingly,
hydration of MIL-53(Cr) reduced CH4 uptake even at high
pressures, with ca. 0.2 mmol/g at 20 bar (Figure 21b), because
of the repulsive interactions between preadsorbed water and
methane, a nonpolar molecule with significantly lower
quadrupole moment than CO2.103
3.4.6. Comparative Studies. Several comparative studies
dealt with the effect of water on CO2 adsorption over large
numbers of different materials, mostly MOFs. These are
Figure 21. Adsorption isotherms of CO2 and CH4 at 31 °C on MIL-53 (Cr): (a) before and (b) after hydration. Reproduced with permission from
ref 103. Copyright 2006 Wiley and Sons.
pubs.acs.org/CR Review
discussed separately for easier understanding of the key
conclusions.
Zaworotko and co-workers investigated the effect of water
on CO2 adsorption over zeolite 13X, tetraethylenepentamine
(TEPA)-impregnated SBA-15, and a total of 13 microporous
and ultramicroporous MOF physisorbents, as shown in Figure
22.272,422 Gas mixtures with CO2 to H2O ratios from 1% to
100% and CO2 concentrations from 400 ppm to 100% were
used. With the exception of TEPA/SBA-15, water had an
adverse effect on CO2 uptake over all other materials,
presumably because of competitive adsorption. Mason et
al.205 also concluded that among the 15 different adsorbents
they investigated, including 13X and 5A zeolites, AX-21 AC,
and numerous MOFs and amine-appended MOFs, only amine-
functionalized materials showed any significant CO2 uptake in
the presence of water partial pressures that are relevant to CO2
capture processes. Among physical adsorbents, everything
being equal, the severity of water competition was dependent
on the nature of the material and H2O to CO2 ratio.272,422 For
example, compared to dry conditions, the CO2 capacity of
SIFSIX-3-Ni, HKUST-1, Mg-DOBDC, and Zeolite 13X
decreased by 30%, 82%, 71%, and 81%, respectively, upon
exposure to 15% CO2/N2 with ca. 55% RH, whereas, in the
presence of pure CO2 with the same RH, the capacity of
HKUST-1 and Mg-DOBDC was only 53% and 60% lower,
while SIFSIX-3-Ni was hardly affected.272 The deleterious
effect of water on CO2 adsorption over HKUST-1 and Mg-
DOBDC was attributed to the strong coordination of water by
CUS, as reported by others.363,364
As for the higher tolerance of SIFSIX-3-Ni to water, it was
ascribed to the strong electrostatic field generated by the
charged pillars in the material framework and the tight binding
sites within the micropores, leading to particularly strong
interaction with polarizable species such as CO2. SIFSIX-3-Cu
exhibited even better performance in DAC conditions (400
ppm of CO2/N2, 49% RH) due to the higher isosteric heat of
CO2 adsorption of 56 kJ/mol versus 51 kJ/mol for SIFSIX-3-
Ni.422 However, it was found to be inherently unstable at
higher temperature and humidity (40 °C, 75% RH). Further
optimization of SIFSIX series led to SIFSIX-18-Ni-β, with
exceptional trace-CO2 removal capacity at ambient conditions,
excellent hydrolytic stability, and lower water capacity than
hydrophobic ZIF-8.423 In the presence of dry 1000 ppm of
CO2, the capacity of SIFSIX-18-Ni-β was found to be 0.7
versus 1.6 mmol/g for the best performing material, TIFSIX-3-
Ni.424 However, under humid condition (74% RH), the CO2
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Figure 22. Representative structures of adsorbents investigated by Zaworotko and co-workers. (a) Reproduced with permission from ref 272.
Copyright 2015 Wiley and Sons. (b) Reproduced with permission from ref 422. Copyright 2017 Royal Society.

uptake of SIFSIX-18-Ni-β was 0.3 mmol/g, higher than the top

performing MOFs, NbOFFIVE-1-Ni, SIFSIX-3-Ni, and
TIFSIX-3-Ni. Molecular simulations revealed that unlike
CO2−CUS interactions, typical of MOFs, SIFSIX-18-Ni-β
interacts with CO2 like an enzyme, through C···F interactions
between CO2 and SIFSIX units and O···H−C interactions
between CO2 and methyl groups, thereby simultaneously
enhancing its CO2 affinity and hydrophobicity.423
Eddaoudi group investigated other SIFSIX MOFs as
potential materials for CO2 capture under humid condi-
tions.425,426 SIFSIX-Cu-i, an interpenetrated polymorph of
SIFSIX-2-Cu, exhibited only a marginal decrease in the CO2
uptake and selectivity under humid relative to dry conditions
(CO2/H2:30/70) (i.e., 1.61 mmol/g and 191 at 74% RH vs Figure 23. Schematic representation of the effect of preadsorbed
1.99 mmol/g and 237 at 0% RH), while its PXRD spectra water on CO2 uptake for different groups of MOFs. Adapted from ref
showed a reversible phase change with hydration/dehydration 195.
cycles.425 Moreover, at low CO2 concentrations (1000 ppm),
switching from dry to humid condition (74% RH) over undertaken. The moisture content for each cycle was
SIFSIX-3-Cu and SIFSIX-3-Zn, did not significantly change calculated by comparing the weight at the end of the previous
CO2 selectivity over water.426 cycle to the weight of dry material. As shown in Figure 23, all
Llewellyn and co-workers195 conducted a comprehensive materials fell into five groups based on trends of CO2 uptake
screening study on the effect of preadsorbed water on CO2 versus preadsorbed water. The first group of materials (group
uptake over 45 MOFs, in the presence of 100% CO2 at 30 °C I) included hydrophobic MOFs, whose CO2 uptake was not
using TGA measurements (Figure 23). The data were affected by the level of preadsorbed water, which did not
compared with conventional adsorbents such as zeolites and exceed 4 wt %. This group was composed of ZIFs, ScBDCs,
ACs. In a typical experiment, the material was prehydrated in and MIL-121s families as well as MIL-69(Al) and MIL-
air at 100% RH at room temperature for 2 days, then treated in 103(La). The lack of water effect on CO2 adsorption over ZIFs
N2 at 30 °C for 8 h to establish the initial moisture content. was also reported by others.390−392 Because most of these
Adsorption of pure CO2 under dry conditions was then carried MOFs contain rather small pores, e.g., MIL-69(Al) with one-
out, followed by regeneration for 90 min at a desired dimensional tunnel of 2.7 × 19.4 Å2,427 the authors postulated
temperature to remove CO2 and decrease the moisture that CO2 and H2O may occupy distinct adsorption sites or
content, before a new adsorption−regeneration cycle was CO2 displaces adsorbed H2O.
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Group II included materials whose CO2 uptake decreased
linearly with increasing preadsorbed water, indicating that CO2
and water compete for the same adsorption sites, akin to the
behavior of the reference zeolites (13X and Chabazite-Cs).
Some MOFs in this group, including MIL-102(Cr) and Ni-
DOBDC, have CUS, where water adsorbs more favorably than
CO2. The third group (group III) comprised of MIL-100(Cr),
MIL-101(Cr), MIL-130(Al), and MIL-68(Ga), exhibited
slightly decreasing CO2 adsorption capacity as the amount of
preadsorbed moisture increased, albeit with different slopes.
Group IV, containing MOFs with flexible structures, showed a
plateau region for low moisture content combined with
decreasing trend in CO2 uptake with increasing preadsorbed
water. In particular, for MIL-53(Cr) and MIL-53(Al), the
plateau was followed by a strongly decreasing trend, suggesting
dynamic changes in the MOFs’ pore size, which shrinks with
increasing amount of preadsorbed water. The strong
adsorption of water in the narrow pores, due to the
confinement effect,377,378 was at the origin of the significant
decrease in CO2 uptake. The last group (group V), comprised
of MIL-110(Al), MIL-163(Zr), HKUST-1, and UiO-66(Zr),
UiO-66(Zr)-nCF3 (n = 1 or 2), UiO-66(Zr)-nMe (n = 1 or 2)
and UiO-66(Zr)-2Et, showed a weak relationship between
preadsorbed water and CO2 uptake, with a maximum at
particular water loadings. The presence of optimum amount of
preadsorbed water for HKUST-1 is in agreement with other
reports.99
To rationalize the often adverse effect of water on CO2
uptake over MOFs, the Llewellyn group195 used water
adsorption data for 33 materials to calculate the corresponding
Henry law constants (KH), which reflect the strength of water
interaction with the materials. As shown in Figure 24, almost
Figure 24. CO2 capacity loss versus KH for water adsorption on
different MOFs. Reproduced with permission from ref 195. Copyright
2017 John Wiley and Sons.
all the data fitted a single semilog correlation between CO2
uptake loss and KH, indicating that the stronger the water
adsorption, the larger the CO2 uptake decline. Despite the
presence of few outliers, the correlation indicates that CO2
capture performance of many MOFs in the presence of water
can be predicted based on water adsorption data. The binding
strength of water in MOFs plays a determining role in
controlling the CO2 selectivity versus, e.g., CH4, with direct
pubs.acs.org/CR Review
implications on CO2 capture from natural gas and biogas.428
Molecular simulations dealing with a collection of 25 MOFs
indicated that for materials with weak interactions with water,
the latter moves freely throughout the materials with little
effect on CO2 adsorption. However, when the interaction is
sufficiently strong, water may either compete with CO2
adsorption or generate additional adsorption sites for CO2.
Therefore, strong water−framework interactions can lead to
increased or decreased CO2/CH4 selectivity.428 Similar
arguments can be made regarding CO2/N2 selectivity, relevant
to CO2 capture from flue gas.
The Henry constant for water adsorption was also used by
Boyd et al.406 as an important criteria for the selection and
design of appropriate MOFs for wet flue gas CO2 capture.
MOFs were selected from a library of 325 000 hypothetical
candidates by (i) screening each material for its CO2 working
capacity and CO2/N2 selectivity, (ii) selecting more than 8000
materials with CO2 working capacity greater than 2 mmol/g
and CO2/N2 selectivity greater than 50, i.e., better than zeolite
13X under dry conditions, (iii) characterizing the structure of
the three most common CO2 adsorption sites, referred to as
adsorbaphore, and (iv) calculating the Henry constant for
water adsorption over these high-performing materials.
Materials selected based on criteria (ii) and (iii) with low
water Henry constant would be suitable for wet flue gas CO2
capture. Among the three identified CO2 adsorbaphores, the
one consisting of parallel aromatic rings as depicted in Figure
25 provides a near optimum interaction with all three atoms of
Figure 25. CO2 adsorbaphore containing parallel aromatic rings as
identified by computational screening. Reproduced with permission
from ref 406. Copyright 2019 Springer Nature.
CO2, with lower affinity toward N2 and H2O. Moreover,
because adsorption of water at high partial pressures is
dominated by the energetics of hydrogen bond formation,
materials with high CO2 uptake at high humidity should be
endowed with pore shapes that frustrate the formation of
hydrogen bond network and limit the water binding energy.
On the basis of these findings, the authors designed,
synthesized, and successfully tested two new MOFs, namely
Al-PMOF and Al-PyrMOF, containing one-dimensional rods
of AlIII linked by TCPP (tetrakis(4-carboxyphenyl)porphyrin)
and TBAPy (1,3,6,8-tetrakis(p-benzoic acid)pyrene) ligands,
respectively (Figure 26). Not only both materials were found
to be water-stable, but their high CO2 uptake was hardly
affected by moisture. As anticipated, Rietveld refinement and
Fourier analysis of PXRD data for CO2-loaded materials
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Figure 26. Structural representation of (a) Al-PMOF and (b)
AlPyrMOF showing the adsorbaphore contained in 3D non-
interpenetrated structures (red box), originating from the orientation
of the tetracarboxylate ligands around the Al3+ rods. Reproduced with
permission from ref 406. Copyright 2019 Springer Nature.
indicated that CO2 adsorption occurs preferentially in the
adsorbaphore described above, whereas 13C nuclear magnetic
resonance (NMR) data showed that (i) the adsorbaphore was
not a preferential site for water adsorption, and (ii) even at
high humidity level, water had limited effect on CO 2
adsorption.
Furthermore, Llewellyn and co-workers195 investigated the
relationship between the CO2 uptake versus preadsorbed water
and the dipole−quadrupole interactions between water and
CO2 molecules and generated energy maps for different
orientations between the two molecules. It was found that
depending on the alignment of the water dipole moment and
the CO2 quadrupole moment, the interactions between two
adsorbates can be attractive, neutral, or repulsive. Therefore,
adsorbed water molecules can block the CO2 adsorption sites
or be displaced by CO2, depending on the orientation of the
CO2 molecular axis with respect to the dipole moment of water
molecules. Consequently, the presence of adsorbed water may
increase, decrease, or not affect CO2 uptake, depending on the
actual MOF.
In summary, water stability of MOFs is an important factor
when it comes to using them for carbon capture in a humid
environment. From a thermodynamic point of view, MOFs
with a combination of high charge density metals (e.g., Fe3+,
Al3+, Zr4+, and Ti4+) and carboxylate ligands (e.g., BDC and
BTC) or a combination of low-valent metals such as Zn2+,
Ni2+, Cu2+, and Mn2+ with weakly basic ligands, exhibit strong
metal−ligand bonding and thus possess high hydrolytic
stability. Kinetics-wise, any factor that increases the activation
energy of hydrolysis enhances the hydrolytic stability of MOFs,
e.g., increased hydrophobicity through coating or fluorinated
ligands and SBUs, catenation, and metal shielding from water
through high coordination number or steric effects. Although
water stability is a requisite for CO2 capture from humid
streams over MOFs, other considerations such as the strength
of the water−MOF interactions, and the relative orientation of
the dipolar and quadrupole moments of H2O and CO2, are of
critical importance in promoting or blocking CO2 adsorption.
Depending on the nature of their metals, functional groups,
and structures, different MOF families exhibit different
relationships between CO2 uptake and preadsorbed water.
Carbon capture of some MOFs such as MIL-102(Cr) and M-
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DOBDC is severely hampered with increasing amounts of
adsorbed water. For others, such as HKUST-1, MIL-53(Cr or
Al), NOTT400 and 401, InOF-1, and CAU-100, the CO2
uptake initially improves then decreases with increasing water
loading. For hydrophobic MOFs, including ZIFs and MIL-
121s families, adsorbed water does not have any significant
effect on CO2 uptake. Generally, the stronger the water
adsorption as reflected by higher KH, the more severe the CO2
adsorption loss. Understandably, for any given MOF, the
adverse effect of water is likely to be stronger at lower CO2 to
water ratio as typically observed for direct air capture.
Several investigations focused on the CO2 uptake versus
preadsorbed water. Although such studies are very helpful in
determining the general behavior of different MOFs, the
observed trends may not be representative for the behavior of
the material in actual CO2 capture from humid streams. During
CO2 adsorption on prehydrated materials, the moisture
content may not remain constant in the presence of dry
CO2-containing streams. This may lead to underestimated
CO2 uptake, particularly when only gravimetric methods are
used to monitor adsorption. Moreover, during water and CO2
coadsorption, the presence of other species in the gas feed may
also affect the working capacity of CO2. Therefore, the effect of
water coadsorption on CO2 uptake should ideally be assessed
by exposing MOFs to gas mixtures with different moisture
contents and monitor both H2O and CO2 independently.
Table 5 summarizes CO2 uptake data for MOFs under dry and
humid conditions, reported in the literature.
4. AMINE-FUNCTIONALIZED ADSORBENTS
CO2 scrubbing in aqueous amine solutions has long been
practiced for commercial-scale CO2 separation from gas
mixtures, particularly for purification purposes such as natural
gas sweetening and hydrogen purification.431 Although several
alkanolamine solutions have been used, monoethanolamine
(MEA), diethanolamine (DEA), and methyldiethanolamine
(MDEA) are the most popular for large-scale opera-
tions.432−434 Nonetheless, despite its widespread application,
this technology suffers a number of drawbacks, including high
energy consumption, excess foaming, corrosion, solvent loss,
amine degradation, and toxic emissions.22−28 The high energy
demand of amine scrubbing processes is associated with the
regeneration stage, which involves heating a relatively dilute
aqueous solution, with high heat capacity. These shortcomings
often make large-scale amine scrubbing operations for the only
purpose of CO2 capture cost-prohibitive. Nonetheless,
extensive efforts are being deployed to address some of the
above-mentioned drawbacks. One breakthrough achievement
is the development of KS-1, a proprietary sterically hindered
amine with lower energy consumption and solvent circulation
flow rate than typical 30 wt% MEA solutions.29,435,436 In
addition, the KS-1 solvent has better oxygen tolerance than
conventional MEA, with practically no corrosion issues.
Nonetheless, shortcomings associated with amine solutions
can be circumvented when amine is immobilized on a solid
support and utilized for CO2 capture via adsorption.61 In
particular, because of the lower heat capacity of adsorbents
compared to water (ca. 1.5 versus 4.1 kJ/kg·K), the required
energy for adsorbent regeneration is significantly lower than for
stripping amine solutions.30,437,438
In the absence of moisture, CO2 adsorption by primary or
secondary amines occurs primarily via carbamate formation
(eq 5), whereas, in the presence of humidity, interactions
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Table 5. CO2 Uptake Data for MOFs under Dry and Humid Conditions
CO2 uptake (mmol/g)
material CO2 pressure (atm) adsorption temperature (°C) RH (%) dry humid ref
Mg2(dobdc) 0.10 38 5 4.93 2.41a 364
0.10 25 90 3.94 1.39 278
0.14 45 1 2.13b 1.05b 429
0.14 45 10 2.13b 0.47b 429
0.15 30 100 5.34 1.54 272
0.17 25 9 5.36 1.79c 363
0.17 25 36 5.36 1.34c 363
0.17 25 70 5.36 0.85c 363
0.17 40 36 4.95 0.50 205
1.00 30 100 5.68 2.28 272

Co2(dobdc) 0.17 25 70 3.03 2.59c 363

Zn2(dobdc) 0.17 25 70 1.65 0.36c 363

Ni2(dobdc) 0.10 38 5 2.98 2.73c 364

0.10 25 90 2.38 1.86 278
0.15 25 3 3.74 2.69 365
0.17 25 70 2.86 1.74a 363
0.18 40 16 3.20 0.10 205
0.18 40 5 3.20 0.30 205

HKUST-1 0.15 30 100 1.59 0.29 272

0.18 40 37 0.67 0 205
0.20 25 3 0.91 0.80 216
0.20 25 10 0.91 1.18 216
0.20 25 20 0.91 0.93 216
0.20 25 40 0.91 0.45 216
0.20 25 3 2.3 4.03d 99
1.00 30 100 2.5 1.17 272
0.14 45 1 0.33b 0.25b 429
0.14 45 10 0.33b 0.18b 429

MIL-53(Al) 0.14 45 1 0.19b 0.14b 429

0.14 45 10 0.19b 0.02b 429
1.00 30 20 0.80 1.19 382

MIL-100(Fe) 0.20 25 3 0.5 0.59 216

0.20 25 10 0.5 0.50 216
0.20 25 20 0.5 1.50 216
0.20 25 40 0.5 2.39 216
0.20 40 31 0.67 0.30 205
0.50 30 50 1.49 3.75 368

MIL-100(Cr) 0.50 30 50 2.44 1.37 368

SIFSIX-3-Zn 0.10 25 90 1.49 1.43 278

SIFSIX-3-Ni 0.15 30 100 2.48 1.76 272

1.00 30 100 2.5 2.49 272

SIFSIX-3-Cu 0.10 25 90 2.03 1.90 278

0.15 30 75 51.4e 60.6e 422

SIFSIX-2-Cu-i 0.15 30 75 9.2e 15.6e 422

NOTT-400 1.00 30 20 0.95 2.32 373

NOTT-401 1.00 30 5 0.27 0.89 198

1.00 30 10 0.27 0.43 198
1.00 30 30 0.27 0.09 198
1.00 30 40 0.33 2.3 374

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Table 5. continued
CO2 uptake (mmol/g)
material CO2 pressure (atm) adsorption temperature (°C) RH (%) dry humid ref
198
1.00 30 5 0.27 0.89

ZnF(TZ) 0.15 25 53 0.29 0.30 405

0.15 25 99 0.29 0.33 405

ZnF(aTZ) 0.15 25 53 0.49 0.50 405

0.15 25 99 0.49 0.47 405

ZnF(daTZ) 0.15 25 53 0.90 0.99 405

0.15 25 99 0.90 0.88 405

MOF-177 0.14 45 1 0.02b 0.01b 429

0.14 45 10 0.02b 0.01b 429

IRMOF-1 0.14 45 1 0.05b 0.03b 429

IRMOF-1 0.14 45 10 0.05b 0.02b 429

ZIF-8 0.14 45 1 0.03b 0.03b 429

0.14 45 10 0.03b 0.02b 429
0.15 30 75 0.04 0.06 430

PCN-14 0.14 45 1 0.18b 0.13b 429

0.14 45 10 0.18b 0.01b 429

UiO-66(Zr) 0.14 45 1 0.08b 0.06b 429

0.14 45 10 0.08b 0.03b 429

UTSA-16 0.10 25 90 1.05 0.95 278

0.10 40 23 1.3 0.94 372

Zn-OH/CFA-1 0.25 25 10 2.18 2.18 387

0.25 25 100 2.18 0.00 387

Ni-OH/CFA-1 0.25 25 10 2.31 1.93 387

InOF-1 1.00 30 20 1.23 2.5 196

1.00 30 20 0.12 0.25 196

aluminum fumarate 0.75 30 14 1.71 1.45 369

1.00 30 14 2.1 2.1f 369

NbOFFIVE-1-Ni 0.01 25 75 1.86 1.27 393

CAU-10 1.00 30 5 1.23 1.66 375
MOOFOUR-1-Ni 0.15 30 75 1.32 0.89 430
DICRO-3-Ni-i 0.15 30 75 0.54 0.44 430
Ni-4-PyC 0.15 30 75 0.59 0.35 430
DMOF-1 0.15 30 75 0.39 0.22 430
UiO-66 0.15 30 75 0.72 0.19 430
Zn(pyrz)2(SiF6) 0.18 40 20 2.4 0.20 205

PCN-250(Fe3) 0.15 25 50 1.18 1.82 376

0.15 25 90 1.18 1.47 376

PCN-250(Fe2Co) 0.15 25 50 1.32 2.23 376

0.15 25 90 1.32 2.27 376
a
Adsorption of 10% CO2/N2 after conditioning the sample in 5% H2O/N2 at 100 °C for 2 h. bUptake in kmol/m3. cAdsorption in dry condition,
over samples that were exposed to simulated flue gas with the indicated RH, then regenerated in Ar at 150 °C. dThe material was prehydrated to 4
wt %. eUptake in L/kg. fAdsorption in dry condition, after prehydration in He with 14% RH at 30 °C.

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between amine groups and CO2 lead, often partially, to the

formation of bicarbonate and carbonate (eq 6), alongside
carbamate.61,439,440 It is widely believed that the formation of
bicarbonate is associated with the hydrolysis of ammonium
carbamate (eq 7). Recent study, however, indicated that the
direct formation of bicarbonate according to eq 6 is more
favorable than the carbamate hydrolysis.441
2(RNH 2) + CO2 ⇋ RNHCO2−RNH3+ (5)

RNH 2 + CO2 + H 2O → RNH3+HCO3− (6)

RNHCO2−RNH3+ + H 2O ↔ RNH 2 + RNH3+HCO3−

(7)
Although ammonium carbamate forms only in the presence of
primary and secondary amines, carbonate and bicarbonate may
form regardless of the type of amine, including tertiary amines, Figure 27. Effect of water content in simulated flue gas on CO2
uptake over 50% PEI-impregnated MCM-41 at 75 °C. Reproduced
provided water is present.163 According to the stoichiometry of
with permission from ref 75. Copyright 2005 American Chemical
the reactions, the maximum amine efficiency, i.e., CO2/N ratio, Society.
in the absence of moisture is 0.5, and 1 in humid conditions.
Therefore, the presence of humidity often promotes CO2
uptake over supported amines through more favorable surface
chemistry.131 In addition to bicarbonate formation, DFT
calculations442 and experimental data 443 indicated the
formation of hydronium carbamate (R2NCOO−H3O+) during
humid CO2 adsorption on supported amines, which also
corresponds to a CO2/N stoichiometry of 1.
As mentioned earlier, the most common methods
for the preparation of supported amine adsorbents are
(i) impregnation of amines on porous materials such as
silica,107,112−114,117,197,201,213,444,445 alumina,446
activated carbon,121,447,448 MOFs,127 zeolites,448,449 and
clays,450 and (ii) surface grafting of amine-containing species
mostly on silica,76,129,136−138 but occasionally on alumina451
and other supports.452 Other procedures such as amine Figure 28. CO2 and water uptake over 2.0 g of 50% PEI-impregnated
tethering 144,145,148−153,205,408−416 and ligand modifica- MCM-41 at 75 °C using 13.55% CO2/3.86% O2/9.87% H2O/N2.
tion154−156,453 have also been used, particularly for MOFs. Reproduced with permission from ref 75. Copyright 2005 American
Accordingly, the effect of water vapor on the CO2 adsorption Chemical Society.
over these classes of materials will be discussed separately.
Note that amine-tethered MOFs have already been discussed
after 30 min seems to indicate the occurrence of a consecutive
in section 3.4.4.
carbamate to bicarbonate reaction according to eq 8. Water
4.1. Amine-Impregnated Adsorbents uptake decreased much more rapidly after 75 min but
Although impregnated polyethylenimine (PEI) CO2 adsorb- remained higher than the corresponding CO2 uptake.
ents were reported in the 1980s,454 they gained prominence
only since 2002, when Song’s group455 reported on CO2 RR′NCOO− + 2H 2O + CO2 ↔ RR′NH 2+ + 2HCO3−
adsorption over PEI-impregnated MCM-41 adsorbent, referred (8)
to as “molecular basket”. As for the effect of water, they found Many other reports confirmed the promoting effect of
that in the presence of 7.5% CO2/N2 with ca. 38% RH at 75 humidity on CO2 capture by PEI-impregnated materials. The
°C, CO2 uptake increased by 50%, demonstrating the extent of such promotion depends on the properties of the
promoting effect of water.113 Furthermore, using 14.9% adsorbent, including the PEI content and molecular weight,
CO2/4.25% O2/N2 with 0−15.5% H2O (up to 40% RH) at the porosity of the support, as well as the RH and CO2
75 °C, it was shown (Figure 27) that even though the CO2 concentration. Using 55 wt % PEI-silica monolith (Mw =
content in the feed gas was reduced gradually as the humidity 10 000) in the presence of 0.5% CO2/N2 at 25 °C, the CO2
level increased, the CO2 uptake increased significantly, uptake increased from 1.33 to 2.28 mmol/g at 90% RH.456
indicating the positive effect of humidity. It should be noted Likewise, Chen et al.201 reported that the uptake of a PEI-
that beyond a CO2/H2O ratio of 1 (ca. 13% H2O, 34% RH), impregnated hierarchical silica monolith in the presence of
further increase in humidity did not result in a noticeable pure CO2 at 60 °C increased from 4.8 to 5.9 mmol/g upon
increase in CO2 uptake.75 addition of 10% H2O (ca. 50% RH) to the feed stream. Using
Moreover, CO2 adsorbed quantitatively at the beginning of PEI on CARiACT silica or polymethylmethacrylate in the
the experiment (Figure 28), whereas water adsorption was not presence of 10% CO2/He at 45 °C, under dry and humid (73%
as effective, indicating that at this stage, CO2 adsorption was RH) conditions, Gray et al.219 found that the presence of
mainly governed by carbamate rather than bicarbonate humidity promoted CO2 uptake by ca. 45%, i.e., from about
formation.75 The significant increase in water adsorption 2.55 to 3.65 mmol/g. CO2 uptake of 50 wt % PEI-impregnated
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macroporous silica at 40 °C was also found to increase from

2.44 to 3.84 mmol/g when switching from dry to humid gas
mixture (15% CO2/3% H2O/N2, 41% RH).457 The CO2
uptake of PEI-impregnated clays at 45 °C also increased by
20% upon addition of 5% H2O (53% RH) to the 15%CO2/5%
O2/N2 feed gas.450 SBA-15 containing hyperbranched PEI
obtained by in situ polymerization of aziridine, with an amine
loading of 9.78 mmol N/g, also exhibited in the presence of
water-saturated 10% CO2/N2 at 25 °C an impressive CO2
uptake and amine efficiency of 5.55 mmol/g and 56%,
respectively.157,229 All improvements of CO2 uptake in the
presence of humidity were attributed to higher CO2 diffusion,
enhanced amine accessibility, and the partial formation of
bicarbonate alongside carbamate.99,100,201,219,456,457
Other investigations used prehumidified materials to
delineate the effect of water on CO2 uptake.197,445,458 Using
60 wt % PEI-impregnated SiO2 with 3%, 10%, and 15 wt %
preadsorbed water, in the presence of 15% CO2/N2 with 30%
RH at 70 °C, the Abu-Zahra group445 reported moderate
improvement of less than 10% compared to the dry material.
Zhang et al.458 also investigated the effect of water on CO2
uptake over a series of linear and branched PEI on
hydrophobic and hydrophilic silicas at 25−100 °C. Materials
were prehumidified in N2 with specific humidity up to 17.2 mg
H2O/g of adsorbent, then exposed to 10% CO2/N2 at the
same humidity. Notice that the authors used specific humidity
instead of the more common relative humidity. The promoting
effect of moisture was most pronounced at 25 °C, when the
water adsorption was the highest. As shown in Figure 29, for
Figure 30. Effect of specific humidity on CO2 uptake over
prehumidified 44.8 wt % branched PEI on hydrophilic and
hydrophobic silica in the presence of 10% CO2/N2. Reproduced
with permission from ref 458. Copyright 2017 Elsevier.
prehydrated adsorbent. Water uptake up to 100% RH was
found to increase linearly with humidity. A generalized model
consisting of a rapid nucleation stage followed by a slow
growth period provided the best fit for the adsorption rate of
water vapor. It is worth mentioning that during exposure to
moisture, PEI underwent several water-induced phase
transitions to form hemihydrate, sesquihydrate, dehydrate,
and anhydrate, consistent with earlier time-resolved infrared
measurements.459 Similar to water, adsorption of humid CO2
on prehydrated materials was also described by a two-step
mechanism. The first rapid stage corresponded to surface
adsorption, whereas the second slower step was associated with
bulk diffusion within PEI. Notice that increasing humidity led
to a decrease in the rate of CO2 adsorption for both fast and
slow stages. Further adsorption measurements on materials
prehydrated in humid nitrogen up to 16 wt % moisture, in the
presence of 10% CO2/N2 at 60 °C with the same RH as the
pretreatment nitrogen, showed an increase in CO2 uptake from
3.16 to 5.86 mmol/g.197 This enhancement was attributed to
possible carbamate hydrolysis in addition to direct bicarbonate
formation by reaction of PEI, water, and CO2.
Molecularly imprinted unsupported PEIs referred to as MIP-
PEI-Mw, with Mw = PEI molecular weight, were prepared as
shown in Figure 31 by bubbling CO2 through aqueous PEI

Figure 29. Effect of temperature on CO2 uptake over prehumidified

44.5 wt % linear PEI on hydrophilic silica in the presence of 10%
CO2/N2 with different specific humidities, as indicated. Reproduced
with permission from ref 458. Copyright 2017 Elsevier.

45 wt % PEI on hydrophilic fumed silica, beyond 50 °C,

humidity had little effect on CO2 uptake. Notice that at low
specific humidity, the CO2 uptake versus temperature
exhibited the usual bell shape,117,444 indicating that at low
temperature, adsorption was kinetically controlled because of
excessive diffusion limitation. At high specific humidity, CO2
uptake decreased over the whole temperature range, a clear
indication that water facilitated CO2 diffusion. Figure 30 shows
that the optimum effect corresponded to a specific humidity of
11.5 and 15.3 mg H2O/g for PEI-impregnated hydrophilic and
hydrophobic silicas, respectively.
In a comprehensive investigation, Monazam et al.197 studied Figure 31. Synthesis process for molecularly imprinted solid amine
the uptake and adsorption kinetics of water at 60 °C on PEI- adsorbent. Reproduced with permission from ref 461. Copyright 2018
impregnated CARiACT G10 and humid CO2 on the Royal Society of Chemistry.

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Figure 32. (a) Column-breakthrough curves for CO2 adsorption on nOH-HBPA (n = OH to N ratio) and (b) cumulative CO2 adsorption capacity.
Reproduced with permission from ref 465. Copyright 2018 American Chemical Society.
solution, followed by cross-linking PEI chains using
glutaraldehyde and reduction of the imine groups,460 or glycol
diglycidyl ether,461 and finally CO2 desorption at 90 °C. In the
presence of 10% CO2/N2 at 25 °C, the CO2 uptake over dry
MIP-PEI-70000 was only 0.61 mmol/g compared to 8.56
mmol/g for prehydrated (75 wt %) material.460 In addition to
bicarbonate formation, the remarkable enhancement of CO2
uptake was attributed to the swelling of MIP-PEIs (Figure 31)
in contact with water, facilitating the diffusion of CO2 deeper
into the material, whereas in dry conditions, PEI chains were
extensively coiled, limiting the reaction of CO2 to surface
amine groups. Koutsianos et al. 462 also used almost
unsupported PEI (91 wt % PEI/C60) and reported a 10-fold
increase in CO2 uptake after prehydration and exposure to
100% CO2 with 21% RH at 25 °C. Notice that in both
examples, not only the PEI was basically unsupported, but the
CO2 adsorption was carried out at 25 °C, explaining the very
low uptake under dry conditions and the remarkable
improvement in the presence of moisture.460−462 Likewise,
using a combination of PEI cross-linking in the presence of a
diepoxide (bisphenol diglycidyl ether) and increased hydro-
phobicity using epoxides with hydrophobic chains, Hamdy et
al.463 found a significant increase in CO2 uptake in the
presence of water, particularly at low temperatures.
Moreover, Qi et al.464 polymerized 2-methyl-2-oxazoline
onto propyliodide-grafted silica to afford a tethered linear
polyethylenimine with high amine content (15.1 mmol N/g).
At 25 °C in the presence of 8% CO2/N2 with 18% RH, an
impressive CO2 capacity of 11.8 mmol/g, corresponding to ca.
14-fold increase compared to dry conditions, alongside an
amine efficiency of 80% was obtained. The observed
enhancement was attributed to the occurrence of less coiled
polymer chains, increased accessibility of amine sites and the
formation of bicarbonate under wet conditions, as reported for
other materials with high polyamine content.460−462 Hydroxy-
functionalized hyperbranched polyamine adsorbents with
different hydroxyl contents (nOH-HBPA, n = 0−0.38,
representing the molar ratio of hydroxyl to amino groups)
were also investigated for CO2 adsorption in dry and humid
conditions.465 In the presence of dry 10% CO2/N2 at 25 °C,
the lowest (1.08 mmol/g) and highest (1.60 mmol/g) CO2
uptake was obtained for HBPA and 0.38OH-HBPA,
respectively (Figure 32), which was attributed to higher
amine utilization efficiency (15% for HBPA vs 35% for
0.38OH-HBPA) as OH groups acting as Bronsted base,
assisted a 1:1 reaction of amine (1° or 2°) and CO2 to produce
AA
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carbamate via an oxonium intermediate. Interestingly, higher
CO2 capacities were obtained under humid conditions, due to
enhanced amine utilization efficiency (ca. 72%), but the
opposite order was observed, i.e., 5.26 and 3.28 mmol/g for
OH-free HBPA and 0.38-OH-HBPA, respectively. The
significantly higher CO2 capacity under humid conditions
was attributed to the 1:1:1 reaction between amine:CO2:H2O
compared to 2:1 reaction between amine:CO2 under dry
conditions.
TEPA-containing adsorbents were also investigated for
humid CO2 uptake.200,211,225 In the presence of 10% CO2/
N2 with 12% and 37% RH at 60 °C, the CO2 uptake of 50 wt
% TEPA-impregnated KIT-6 increased from 2.85 mmol/g to
2.92 and 3.2 mmol/g, respectively, with no further change at
higher RH.211 Liu et al.200 used 18 wt % TEPA-impregnated
as-synthesized mesocellular silica foam, i.e., containing both
P123 triblock copolymer (template) and the trimethylbenzene
pore-expander. Although at 6.7% RH, the CO2 uptake did not
change, increasing RH to 28% enhanced the CO2 uptake from
4.5 to 5.2 mmol/g.
Earlier findings on the promoting effect of humidity on DAC
over amine-impregnated materials were summarized in recent
reports.217,466−469 Sayari group reported a novel method for
improving amine efficiency in DAC through higher PEI
dispersion in a large-pore silica whose internal surface area was
covered with long carbon chains.217 In the presence of 400
ppm of CO2 with 64% RH, such materials achieved an
impressive CO2 uptake of 7.31 mmol/g PEI, 33% higher than
under dry conditions. Using 70 wt % PEI (Mw = 1200) over
mesoporous cellular silica foam for DAC, it was found that
addition of 2% H2O to 420 ppm of CO2/N2 at 58, 46, and 33
°C (11−42% RH) led to 20%, 30%, and 53% increase in CO2
uptake, respectively.470 This enhancement was associated with
improved accessibility of amine sites through decreasing
diffusion resistance and/or to the formation of bicarbonate.
Similar enhancement was reported for 72 wt % PEI on
hierarchical silica with 750 nm macropores and 5 nm
mesopores at 30 °C in the presence of 10% CO2/N2. The
CO2 uptake was 2.34 mmol/g under dry condition versus 3.36
in the presence of 19% RH.471 Using 44 wt % PEI-impregnated
nanofibrillated cellulose (NFC), Sehaqui et al.220 found that
increasing RH from 20% to 80% in the presence of 400 ppm of
CO2 increased the uptake from 0.5 to 2.2 mmol/g, which was
attributed to enhanced PEI dispersion and easier accessibility
to active amine sites by CO2 at higher RH. Similarly, exposing
anhydrous cellulose-acetate silica fiber impregnated with 26 wt
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Table 6. CO2 Uptake for Different Polyamine-Impregnated Adsorbents

CO2 uptake
(mmol/g)
support material amine (loading, wt %) CO2 content (%) adsorption temp (°C) RH (%) dry humid ref
Moderate to High CO2 Content
CARiACT G10 silica PEI (40) 1.2 40 28 2.5 2.75 199
1.2 80 5 1.1 1.11 199
10 40 97 2.55 3.65 29

LPEI (40) 10 60 15a 3.16 3.64 197

10 60 55a 3.16 4.58 197
10 60 100a 3.16 5.86 197

MCM-41 PEI (32) 14 40 28 1.7 2.5 205

PEI (50) 15 75 16 2.01 2.43 75
15 75 26 2.01 2.86 75
15 75 39 2.01 2.99 75,113

MCFb PEI (68.9) 15 75 0.6 1.18 0.86 202

15 105 0.8 1.83 2.09 202
50 75 2.6 2.50 2.98 202
50 105 0.8 3.37 3.04 202
50 115 0.6 3.00 2.61 202

LPEI (66.5) 15 105 0.8 0.28 0.28 202

50 75 2.6 3.20 3.34 202
50 105 0.8 1.41 1.23 202
50 115 0.6 0.59 0.57 202

MCFc PEI (71.4) 15 75 0.6 1.26 1.25 202

15 105 0.8 1.87 2.19 202
50 75 2.6 2.66 3.27 202
50 105 0.8 3.43 3.33 202
50 115 0.6 3.02 2.48 202

LPEI (68.4) 15 75 0.6 0.14 0.14 202

15 105 0.8 0.27 0.26 202
50 75 2.6 3.32 3.50 202
50 105 0.8 1.36 1.11 202
50 115 0.6 0.59 0.59 202

mesoporous silica PEI (60) 15 70 30 3.1 3.2d 445

15 70 30 3.1 3.4e 445
15 70 30 3.1 3.0f 445

macroporous silica PEI (50) 15 40 41 2.45 3.84 457

silica monolith PEI (55) 5 25 90 1.33 2.28 456
hierarchical silica monolith PEI (65) 100 75 26 4.80 5.90 201
PMMA PEI (40) 10 40 97 2.40 3.53 219
mesoporous carbon PEI (65) 15 75 80 4.82 5.36 473

C60 PEI (91) 100 25 21 0.04 0.18g 462

100 90 21 0.16 0.18g 462

KIT-6 TEPA (50) 10 70 12 2.85 2.92 211

10 70 37 2.85 3.20 211

SBA-15 and SiO2 gel TEPA (50) 15 75 60 5.05 5.86 225

as-synthesized MCF TEPA (18) 100 75 6.7 4.50 4.5 200

100 75 28 4.50 5.2 200

amorphous silica TEPA (9) 100 50 25 0.86 0.85 443

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Table 6. continued
CO2 uptake
(mmol/g)
support material amine (loading, wt %) CO2 content (%) adsorption temp (°C) RH (%) dry humid ref
Moderate to High CO2 Content
TEPA (20) 100 50 25 1.71 1.73 443
TEPA (35) 100 50 25 2.86 4.03 443
PEI (51) 100 50 25 2.68 3.25 443

atainless steel disk 0.8 μm TEPA film 100 50 25 6.13 11.3 443
3.5 μm TEPA film 100 50 25 5.68 10.2 443
10 μm TEPA film 100 50 25 5.25 9.00 443

SBA-15 HA (7.0)h 10 25 100 NP 3.11 157

HA (3.67)h 10 25 51 NP 2.76 229
HA (7.28)h 10 25 51 NP 4.24 229
HA (9.87)h 10 25 51 NP 5.57 229
HA (2.24)h 10 75 51 NP 0.97 229
HA (3.67)h 10 75 51 NP 1.74 229
HA (7.28)h 10 75 51 NP 2.92 229
HA (9.87)h 10 75 51 NP 4.17 229
HA (3.67)h 10 25 51 NP 2.76 229

mesoporous silica LPEIi 8 25 18 0.85 11.8 464

SBA-15 DEA (20) + TEPA (30) 100 75 100a 3.70 3.18 191

AC DBNj (40) 10 29 100 0 0.86 474

29.3 100 0 0.86 474
38.9 100 0 0.63 474
40.5 100 0 0.62 474
50.3 58 0 0.52 474
Ultralow CO2 Content
mesoporous AC BPEI (55) 4 25 80 2.25 2.58 212
50 25 80 3.34 4.05 212

PE-MCM-41 with CTMA+ PEI (40) 4 25 64 2.20 2.92 217

HP2MGL resin PEI (50) 4 25 10 1.96 3.16 213

4 25 20 1.96 2.88 213
4 25 40 1.96 2.75 213
4 25 60 1.96 2.34 213
50 25 10 2.13 3.15 213
50 25 20 2.13 3.27 213
50 25 40 2.13 3.74 213
50 25 60 2.13 3.51 213

nanofibrillated cellulose PEI (19) 4 25 80 NP 0.25 220

PEI (31) 4 25 80 NP 1.20 220
PEI (44) 4 25 20 NP 0.50 220
PEI (44) 4 25 80 NP 2.22 220
PEI (52) 4 25 80 NP 2.10 220
PEI (62) 4 25 80 NP 1.75 220

cellulose-silica fiber PEI (10) 4 35 47 0.36 0.64 472

fumed silica PEI (33) 4 25 67 1.23 1.77 115

fumed silica PEI (50) 4 25 67 1.70 1.41 115

PAA (30) 50 25 65 0.29 0.27 224
PAAk (30) 50 10 65 NP 0.39 224
a
The sample was prehydrated with the indicated RH. bMesostructured cellular foam (MFC) with average pore diameter and pore volume of 12.6
nm and 2.25 cm3/g, respectively. cMFC with average pore diameter and pore volume of 31.4 nm and 2.50 cm3/g, respectively. dThe material was
prehydrated to 3 wt %. eThe material was prehydrated to 10 wt %. fThe material was prehydrated to 15 wt %. gThe material was prehydrated to 68

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Table 6. continued
wt %. hHyperbranched amine with indicated amine content in mmol N/g. iAmine content of 15.1 mmol N/g. j1,5-Diazabicyclo[4.3.0]non-5-ene.
k
Polyallylamine. PEI = branched PEI. LPEI = linear branched PEI. CTMA+ = cetyltrimethylammonium cations. NP = not provided.
% PEI to dry 395 ppm of CO2/N2 at 35 °C led to CO2
breakthrough capacity of 0.59 mmol/g, compared to 1.6
mmol/g when prehydrated material was exposed to the same
feed with 47% RH.472
Wang et al.212 found that the effect of humidity on CO2
uptake at 25 °C over 55 wt % PEI-impregnated mesoporous
carbon using 400 and 5000 ppm of CO2 under dry and humid
(80% RH) conditions to be rather limited. Humidity increased
the CO2 uptake from 2.25 to 2.58 mmol/g and from 3.34 to
4.05 mmol/g for 400 and 5000 ppm, respectively. The role of
water over 50% PEI-impregnated HP2MGL resin was also
found to depend on the CO2 partial pressure, i.e., 400 vs 5000
ppm.213 At 400 ppm of CO2, as RH increased from 0% to 10%,
the uptake increased by more than 60%, from 1.96 to 3.16
mmol/g, then declined to reach 2.4 mmol/g at 60% RH. For
5000 ppm of CO2, increasing RH up to 40% led to significant
enhancement of CO2 uptake from 2.13 to 3.74 mmol/g.
Further increase of RH to 60%, however, resulted in a slight
decrease in CO2 uptake, which was attributed to the
competitive adsorption of H2O over CO2 at high RH. Zerze
et al.224 reported that for poly(allylamine) impregnated fumed
silica, CO2 uptake from air under humid condition was
enhanced by preadsorbed water because it was readily available
for bicarbonate formation. In fact, conducting adsorption on a
dry adsorbent hinders water build-up, which is required for
efficient formation of bicarbonate. Moreover, water inside the
pores facilitates the unfolding of the polymer network, thereby
enhancing the diffusion of CO2.221,224,458,460−462,464
While all the above-mentioned studies on DAC reported
beneficial effect of humidity on CO2 uptake, some workers
reported that water vapor has an adverse effect.115,213 Using
PEI-impregnated fumed silica for DAC in dry and humid (67%
RH) conditions, Goeppert et al.115 found that at low PEI
loading (33 wt %), the CO2 uptake increased from 1.18 to 1.77
mmol/g when switching from dry to humid gas feed but
decreased from 1.70 to 1.41 mmol/g over a material with 50 wt
% PEI loading. The explanation was somewhat tedious.
Considering that the material with higher PEI loading has
lower dispersion, the authors suggested that the detrimental
effect of water vapor on CO2 uptake was due to the water
blocking access to some of the already difficult to reach amine
groups.
As a general observation for amine-impregnated materials,
the presence of humidity improves CO2 uptake, regardless of
the feed CO2 content. Typical explanations involved the
formation of carbonate/bicarbonate in addition to carbamate,
as well as enhanced CO2 diffusion and amine accessibility.
Table 6 shows CO2 adsorption data for different amine-
impregnated adsorbents in dry and humid conditions.
4.2. Amine-Grafted Adsorbents
4.2.1. Amine-Grafted Mesoporous Silicas. Reports on
CO2 adsorption over grafted amines go back to the early
1990s.475,476 Leal et al.475 investigated CO2 adsorption over
propylamine-grafted amorphous silica and described the
formation of carbamate and bicarbonate under dry and
humid conditions, respectively. Nonetheless, even in the
presence of pure CO2, the uptake was limited to 0.41 and
0.89 mmol/g under dry and humid (100% RH) conditions,
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respectively. It was only a decade later that more seminal work
on amine-grafted CO2 adsorbents was reported.76,132,135,157,214
Huang et al.132 used propylamine-grafted MCM-48 silica with
amine content of 2.3 mmol/g. In the presence of 5% CO2/N2
at 25 °C, the adsorption capacity was 1.14 mmol/g,
corresponding to the quantitative formation of ammonium
carbamate (CO2/N = 0.5). Interestingly, under humid
conditions (100% RH), the CO2 uptake was doubled,
consistent with the quantitative formation of ammonium
bicarbonate and/or carbonate (CO2/N = 1). Nonetheless,
amine efficiency as high as 0.5 and 1 under dry and humid
conditions, respectively, have rarely been reported.76 In the
presence of moisture, the CO2 desorption temperature shifted
ca. 10 °C upward, indicating that the presence of humidity
leads to stronger CO2−amine interactions.132
Didas et al.477 investigated the effect of water on CO2
adsorption at ca. 1500 ppm over propylamine-grafted SBA-15
with different amine contents. Interestingly, the beneficial
impact of moisture was found to increase with decreasing
amine loading, indicating that surface amine coverage beyond a
monolayer hinders the ability of CO2 to interact favorably with
water. Alternatively, the presence of surface silanols on
materials with low amine loading offers an additional route
to CO2 adsorption through amine−silanol−water interaction.
Consistently, FTIR data confirmed the formation of
bicarbonate only at low amine loading.
The key role of silanol groups in facilitating proton transfer
reactions during CO2 adsorption over amine-grafted silica was
addressed in a theoretical contribution by Cho et al.478 In
addition to intermolecular and water-assisted CO2 adsorption
mechanisms, DFT calculations revealed the occurrence of a
surface hydroxyl-assisted mechanism or simply surface
mechanism (Figure 33), in which silanol groups act as proton
transfer species. Under dry conditions, the activation energy
for the surface mechanism (8.1 kcal/mol) was found to be
lower than the intermolecular mechanism (12.7 kcal/mol),
leading to the dominance of the former mechanism over the
Figure 33. Different reaction mechanisms for CO2 adsorption over
amine-grafted silica. The numbers indicate the corresponding
activation energy in kcal/mol. Reproduced with permission from ref
478. Copyright 2018 Royal Society of Chemistry.
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latter. Nevertheless, during the water-assisted mechanism,
water also acts as a proton acceptor (Brønsted base) and the
corresponding activation energy is lower than for the surface
mechanism, i.e., 6.0 kcal/mol. Therefore, in the presence of
humidity, both the surface and water-assisted intermolecular
mechanisms may take place. Other investigations on CO2−
amine interactions indicated that the nucleophilic attack of
CO2 carbon by amine is assisted or catalyzed not only by
another amine but also by other species such as
water441−443,479 or OH groups,442,478 playing the role of a
Brønsted base to achieve the proton transfer/exchange
required for the formation of ions pairs such as ammonium
carbamate.
Hiyoshi et al.214,281 also used monoamine-, diamine-, and
triamine-grafted SBA-15 for CO2 adsorption at 60 °C in the
presence of 15% CO2/N2 under both dry and humid (60%
RH) conditions. Surprisingly, they found that for grafted
monoamine, moisture had no effect on CO2 uptake, while
modest increases were obtained for the other materials, with
the highest increase of 14% being associated with triamine-
grafted SBA-15. In a similar study, Zheng and co-workers
found that using 2% water vapor (64% RH) in 15% CO2/N2 at
25 °C had no effect on CO2 capacity of diamine-grafted SBA-
15.480 The authors suggested that contrary to monoamine
adsorbents, where a 1 to 1 reaction between amine and CO2 is
possible in the presence of water, formation of stable
intramolecular ammonium carbamate between CO2 with
diamine adsorbents is the preferred pathway with or without
moisture.
As mentioned earlier, tertiary amines do not react with CO2
under dry conditions, yet in the presence of moisture, they
contribute to CO2 adsorption via bicarbonate formation, as
evidenced by FTIR and 15N NMR data.163,481 Interestingly, in
the presence of 1% CO2/He at 30 °C, humid CO2 (49% RH)
uptake over N,N-dimethyl-propylamine grafted SBA-15 was
lower in the presence of high versus low amine loading. This
behavior was attributed to the lesser tendency of the former
material to adsorb water (i.e., 1.5 vs 3.9 mmol water/g),
necessary for the formation of bicarbonate. Similar surface
density-dependence of amine−CO2−H2O interaction was also
reported for propylamine-grafted silica.477
Sayari group made significant contributions to elucidating
the different effects of humidity on CO2 adsorption over
amine-functionalized silicas. First, they showed that contrary to
conventional CO2 adsorbents such as zeolites and many
carbons, amine-containing materials are tolerant to water vapor
and do not require predried feed gas.162 To do so, they used
diethanolamine (DEA) impregnated pore-expanded MCM-41
(PE-MCM-41) in the presence of dry and humid (27% RH)
feeds containing 5% CO2 in N2. Note that at 5% CO2,
physisorption was found to be negligible, whereas the
chemisorption was almost complete; therefore, any effect on
CO2/N ratio corresponds to actual changes in amine−CO2
interactions.131 In the presence of 27% RH, CO2 uptake at 25
°C increased from 2.65 to 2.94 mmol/g and the amine
efficiency (CO2/N) from 0.33 to 0.37, indicating that water
vapor is not only tolerated but it promotes CO2 adsorption.76
In a more detailed investigation,131 they measured CO2 uptake
over propylamine-grafted PE-MCM-41 at different RHs (27%,
61%, and 74%) using a combination of TGA and MS
measurements (Figure 34). Increasing RH from 0 to low
(27%) and moderate (61%) levels resulted in modest increase
in CO2 uptake by 16% and 22%, respectively, most likely
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Figure 34. Temperature programmed desorption−mass spectrometry
(TPD-MS) profiles of CO2 after adsorption on propylamine-grafted
PE-MCM-41 in the presence of different levels of humidity.
Reproduced with permission from ref 131. Copyright 2008 American
Chemical Society.
through bicarbonate formation. However, at RH of 74%, CO2
uptake increased significantly by 60% to reach an amine
efficiency of 0.78. Because water adsorption at 74% RH
involved capillary condensation, it was surmised that under
such conditions, liquid-like water within the pores is more
effective at promoting CO2 adsorption than at lower pressures.
Notice that in all adsorption tests under humid conditions, the
amine efficiency increased but less than doubled, indicative of
the limited nature of bicarbonate formation. Figure 34 also
shows that at 74% RH, CO2 uptake over prehydrated material
was about 10% higher than dry material, possibly because of
more efficient formation of bicarbonate using water already
adsorbed. Moreover, CO2 desorption occurred at higher
temperatures after adsorption of humid versus dry CO2/N2,
indicating that the presence of humidity results in stronger
CO2−amine interactions, i.e., higher thermal stability of
bicarbonate compared to carbamate, as claimed by
others.132,193
In a series of contributions,77,78,165,482 Sayari’s group
investigated the effect of water vapor on CO2 adsorption
over different types of grafted amines and impregnated
polyamines, using TGA, infrared, and solid-state NMR
measurements to unravel the surface chemistry in the presence
of water. Figure 35a shows that under cyclic adsorption−
desorption experiments in dry conditions, in the presence of
grafted monoamine and triamine and PEI-impregnated PE-
MCM-41, all adsorbents deactivated gradually at different rates
depending on the severity of the adsorption−desorption
conditions and the nature of the amine.
13
C cross-polarization/magic angle spinning nuclear mag-
netic resonance (CP MAS NMR) and diffuse reflectance FTIR
measurements after CO2 adsorption−desorption cycling under
dry condition provided direct evidence for the formation of
stable urea linkages through dehydration involving CO2 and
two amine groups as shown in Scheme 1. Because the
formation of such linkages is irreversible under typical
regeneration conditions, urea species accumulate over time at
the expense of amines, giving rise to increasingly severe
deactivation. Interestingly, repeating all the experiments shown
in Figure 35a by bubbling the feed and purge gas in a water
saturator maintained at 20 °C, all other conditions being the
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Figure 35. CO2 uptake of different adsorbents during cyclic
adsorption−desorption operations under (a) dry and (b) humid
conditions (20 °C dew point). Mono and TRI stand for grafted
monoamine and triamine and PEI for impregnated PEI. X/Y-d and
X/Y-h indicate the adsorption and desorption temperatures under dry
and humid conditions, respectively. Reproduced with permission from
ref 77. Copyright 2010 American Chemical Society.
same, showed that none of the materials deactivated under any
of the conditions used (Figure 35b). Notice that the RH varied
Scheme 1. Proposed Mechanisms for CO2-Induced Degradation of Supported Aminesa
a
Reproduced with permission from ref 165. Copyright 2012 American Chemical Society.
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from 74% at 25 °C to as low as 0.4% at 105 °C, and yet it was
enough to inhibit the formation of urea linkages and prevent
deactivation. Hence, humidity plays a key role in stabilizing any
supported amine against CO2-induced deactivation.77,78
Notwithstanding the wide-ranging scope of CO2-induced
deactivation, its severity depends on the nature of the amine
groups involved.79,165,482 In general terms, primary amine-
containing adsorbents deactivate more readily than others,
whereas in the absence of primary amines, secondary amines,
as in LPEI, deactivate more slowly, with single secondary
amines such as grafted N-methyl propylamine being excep-
tionally resistant to CO 2 -induced deactivation in dry
conditions. It was inferred that in the presence of primary
amines, the loss of water takes place via dehydration of
carbamic acid into isocyanate, which then reacts with a
neighboring primary or secondary amine to form open chain or
cyclic urea as shown in Scheme 1, route 1 in mechanisms A
and B, respectively. Although the loss of water from the
primary amine-derived ammonium carbamate (Scheme 1,
mechanism A, route 2) cannot be completely ruled out, DFT
calculations showed that the isocyanate mechanism provides
the lowest energy route to urea formation.483 As for single
secondary amines, based on their high stability under dry
conditions, and the fact that no isocyanate can be formed from
the corresponding carbamic acid, it was surmised that the
associated ammonium carbamate does not dehydrate under
typical dry CO2 adsorption conditions. Nonetheless, although
single secondary amines are highly stable against CO2-induced
deactivation, LPEI, which contain ethylenediamine units with
only secondary amines, deactivates under dry condition, albeit
at a much lower rate than BPEI. It is thus inferred that the
corresponding intramolecular ammonium carbamate dehy-
drates into tetrasubstituted imidazolidinone (Scheme 1,
mechanism B, route 2).165,482
4.2.2. Amine-Grafted Nanofibrillated Cellulose. Cli-
meworks developed CO2 capture from ambient air using
amine-grafted NFC.221,484−486 Their first reported material,
diamine-grafted NFC exhibited a CO2 uptake and working
capacity of 1.39 and ca. 0.70 mmol/g in the presence of 506
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ppm of CO2/Ar with 40% RH at 25 °C and desorption at 95

°C.484 The CO2 capture of monoamine-grafted NFC at 400
ppm of CO2 also increased in the presence of water (91% RH)
from 1.11 to 2.13 mmol/g at 23 °C and from 0.11 to 1.42 at 50
°C, with the effect of water decreasing at higher CO2
concentrations.221 This finding was attributed to the presence
of two different amine sites on the material, i.e., the ones that
are readily accessible to CO2 and those that are buried within
the bulk of the adsorbent, which can be reached only via
diffusion. In dilute CO2 streams, the amine sites within the
bulk were accessible only under humid conditions, with water
facilitating the diffusion of CO2 toward such sites, whereas, at
high CO2 pressure, both types of sites were accessible under
dry and humid conditions. Moreover, water was thought to Figure 36. CO2 and water uptake on Lewatit versus time under
contribute to the formation of diffusive intermediates as ambient air. Reproduced with permission from ref 203. Copyright
reported by others,442,462,487 thereby enhancing CO2 diffusion 2014 Elsevier.
and the accesibility of amine sites. This interpretation is
consistent with the oberved increase in amine efficiency at 25 CO2, (ii) amine catalyzed formation of carbamic acid, (iii)
°C from 0.26 under dry conditions to 0.51 at 91% RH. Under direct amine−water catalyzed formation of carbamic acid, and
otherwise the same conditions, the amine efficiency at 1 atm (iv) amine catalyzed formation of carbonic acid. DFT
CO2 and 25 °C increased only marginally from 0.54 to 0.60 calculations showed that reaction (ii) which does not involve
due to the much lower H2O/CO2 ratio. Using a similar water and reaction (iii) of water and CO2 catalyzed by amine,
material under temperature-vacuum swing (TVS) conditions, are both responsible for CO2 capture on Lewatit.
increasing RH from 20% to 80% was also found to increase The Lackner group468,491−493 developed moisture-swing
CO2 uptake at 20 °C from 0.39 to 0.65 mmol/g.485 At a given DAC materials, with water playing a key role in the CO2
RH, temperature had limited effect on CO2 and water uptakes. adsorption−desorption process. Such adsorbents consist of an
For example, CO2 (H2O) uptake at 40% RH was 0.42 (1.67), anion-exchange resin containing quaternary ammonium
0.44 (1.69), and 0.38 (1.74) mmol/g at 10, 20, and 30 °C, cations attached to a polymer network with hydroxide or
respectively. Column breakthrough data at 20 °C showed that carbonate anions as mobile counterions. As illustrated in
while water adsorption was complete between 0.5 and 4 h at Figure 37, for a fresh wet material (state 1), the more stable
20−80% RH, CO2 uptake in the presence of 455 ppm of CO2/
N2 did not reach equilibrium after 5 h at all RHs because of the
very low driving force.
4.2.3. Amine and Ammonium-Containing Polymers.
Amine-containing resins, including the highly hydrophilic
benzylamine-containing polymer Lewatit VP OC 1065 (or
Lewatit), were investigated for water and CO2 coadsorption.
Alesi Jr. and Kitchin474 found that exposure of prehydrated
(2.7 wt %) Lewatit to 11.1% CO2/N2 with 75% RH and 50 °C,
led to a CO2 capacity of 2.39 mmol/g, which was 30% higher
compared to dry conditions. The Brilman group carried out
extensive DAC investigations on Lewatit.203,226,227,488 Meas-
urements at 15−35 °C using 400 ppm of CO2/N2 with up to
60% RH showed that, while water adsorption was not affected
by CO2, higher CO2 uptake was recorded at increasing
humidity, reaching 47% increase at 15 °C and 60% RH.227
This was attributed to the formation of
bicarbonate, as reported for other amine-containing
materials.99,100,197,224,456,457,460,461,470,489 It was also reported
Figure 37. Moisture-swing sorbent for CO2 capture from ambient air
that the CO2 capacity of Lewatit in the presence of 500 ppm of over ion-exchanged resin. Reproduced with permission from ref 468.
CO2 at 20 °C increased by 216% at 79% RH compared to dry Copyright 2020 John Wiley and Sons.
conditions (0.6 vesus 1.3 mmol/g).488 Smal et al.203 exposed
Lewatit to ambient air for different periods of time up to 15 h
and monitored the effluent by TGA and IR spectroscopy (TG- carbonate anions are the dominant counterions. As the resin
FTIR) during regeneration of the material up to 130 °C. Water was dried, the carbonate evolved into bicarbonate and hydroxyl
adsorption was found to be dominant over CO2 in the early anion through reaction with water (state 2). Because of the
stages, mostly because of the high water to CO2 ratio (Figure occurrence of hydroxyl ions, state 2 had a strong affinity
36). After 450 min of air exposure, the water uptake began to toward CO2, even at very low concentrations. This led to state
decrease in favor of CO2, presumably because water is 3, with bicarbonate species as the dominant compensating
displaced by CO2 over time. As for the DAC mechanism anions. Wetting the material to full hydration led to state 4,
under humid condition over Lewatit, Buijs and de Flart490 used which evolved into state 1 with the release of CO2.
molecular simulations to investigate the following scenarios: Similar adsorbents were prepared by impregnating an amine-
(i) uncatalyzed formation of carbamic acid from an amine and containing polymer on carbon black and further quaternization
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Table 7. CO2 Uptake for Different Amine-Grafted Adsorbents

CO2 uptake
(mmol/g)
support material amine amine loading (mmol N/g) CO2 content (%) adsorption temperature (°C) RH (%) dry humid ref
Moderate CO2 Content
SBA-15 APTESa 2.60 15 60 60 0.66 0.65 214
MAPSb 1.92 15 60 60 0.25 0.25 214

AEAPSc 2.50 10 25 51 NP 0.71 157

4.14 15 60 60 0.87 0.98 281
2.25 15 60 60 0.26 0.34 214
3.75 15 60 60 0.87 0.90 214
4.62 15 60 60 1.36 1.51 214
2.65 15 25 64 0.45 0.45 480

TRId 5.00 15 60 60 1.10 1.28 281

2.73 15 60 60 0.35 0.39 214
4.84 15 60 60 1.10 1.21 214
5.79 15 60 60 1.58 1.80 214

DMAPSe 1.90 1 30 49 0.01 0.10 163

2.50 1 30 49 0.01 0.06 163

MCM-41 APTES 4.2 18 40 30 1.7 1.2 205

MAPS 3.7 18 40 27 1.4 1.5 205

TRI 5.78 5 25 27 1.04 1.12 76

5.97 5 25 27 1.08 1.18 76
5.84 5 25 27 1.01 1.09 76
5.70 5 25 27 0.97 1.01 135

PE-MCM-41 TRI 6.06 5 25 27 1.51 1.60 76

6.10 5 25 27 1.55 1.66 76
6.02 5 25 27 1.47 1.58 76
5.97 5 25 27 1.41 1.52 135
7.74 5 25 27 2.33 2.58 76
7.98 5 25 27 2.65 2.94 76
6.75 5 25 27 1.89 2.08 76
6.65 5 25 27 1.69 1.85 76
4.18 5 25 27 2.05 2.37f 131
4.18 5 25 61 2.05 1.31g 131
4.18 5 25 74 2.05 1.90g 131
4.18 5 25 27 2.05 2.46 131
4.18 5 25 61 2.05 2.64h 131
4.18 5 25 74 NP 3.67h 131

MCM-48 APTES 2.30 5 25 64 1.14 2.30 132

2.74 15 60 60 0.52 0.56 281
1.11 15 60 60 0.15 0.10 214
2.58 15 60 60 0.52 0.50 281

NFC APDES 3.21i 0.1 23 91 1.72 2.29 221

3.21i 1 23 91 2.03 2.37 221
3.21i 10 23 91 2.26 2.54 221
3.21i 0.1 50 21 1.51 1.97 221
3.21i 1 50 21 1.81 2.29 221
3.21i 10 50 21 2.05 2.37 221

HMS APTES 1.92 90 20 30 0.86 0.91 193

AEAPS 3.08 90 20 30 0.89 0.45 193
TRI 3.85 90 20 30 1.20 0.98 194

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Table 7. continued
CO2 uptake
(mmol/g)
support material amine amine loading (mmol N/g) CO2 content (%) adsorption temperature (°C) RH (%) dry humid ref
Ultralow CO2 Content
SBA-15 APTMSj 1.00 4 25 80 0.09 0.13 273

NFC APDES 3.21i 4 23 91 1.11 2.13 221

3.21i 4 50 21 0.11 1.42 221
3.86 4 10 20 NP 0.36 485
3.86 4 10 80 NP 0.63 485
3.86 5 20 20 NP 0.39 485
3.86 5 20 80 NP 0.65 485
3.86 5 30 20 NP 0.32 485
3.86 5 30 60 NP 0.50 485
a
(3-Aminopropyl)triethoxysilane. bN-Methylaminopropyltrimethoxysilane. cN-(2-Aminoethyl)-3-aminopropyltriethoxysilane. d(3-Trimethoxysilyl-
propyl)-diethylenetriamine. eN,N-Dimethyl-3-aminopropyltrimethoxysilane. fHumid CO2 adsorption was conducted on a dry material. gUptake is
in kmol/m3. hHumid CO2 adsorption was conducted on a prehydrated material. iTheoretical amine content. j3-aminopropyltrimethoxysilane.
HMS = hexagonal mesoporous silica. NFC = nanofibrillated cellulose. NP = not provided.

and ion-exchange of counterions with hydroxide.494 A cheaper

moisture-swing adsorbent was also developed from biomass-
derived amine-containing chitosan as starting material.495 The
biomass was cross-linked by poly(vinyl alcohol) in a three-
dimensional network to address the water solubility of chitosan
and increase the porosity of the material. The CO2 uptake
from air at 3% RH was 0.18 mmol/g at 20 °C. Exposing the
CO2-loaded material to 95% RH led to complete CO2
desorption, while decreasing the RH back to 3% led to a
100% CO2 readsorption. Table 7 shows selected CO2 uptakes
for different amine-grafted adsorbents in dry and humid
conditions.
4.2.4. Amine-Functionalized Zeolites. Although the
rational of combining zeolites and amines for the purpose of
CO 2 capture is questionable, several groups did
so. 123,279,496−501 Su et al. 123 conducted 15% CO 2 /N 2
adsorption on TEPA-modified Y zeolite in the presence of Figure 38. TPD-MS profiles of CO2 after adsorption on monoamine
different humidity levels at 60 °C. Increasing water content up impregnated zeolite β in dry and humid conditions. Reproduced with
to 17.4% (88% RH) led to an increase in CO2 uptake from permission from ref 496. Copyright 2016 Elsevier.
2.56 to 3.67 mmol/g with an optimum of 4.32 mmol/g in the
presence of 7% H2O (36% RH). Using APTES-impregnated
mmol/g over propylamine-functionalized hierarchical LTA
beta zeolite, Madden and Curtin496 found that addition of 2%
zeolite in the presence of 15% CO2/N2 at 60 °C decreased by
water to 15% CO2/He at 35 °C (36% RH) led to moderate
65% under humid conditions, which was attributed to the high
increase in CO2 uptake from 4.09 to 4.89 mmol/g. TPD-MS
affinity of LTA for water.
profiles of CO2-loaded adsorbent under humid condition
showed an increased amount of CO2 desorbing at 55, 69, and 4.3. Hydrophobic Amine-Containing Adsorbents
86 °C and a comparable amount at 98 °C (Figure 38).496 It As discussed earlier, water vapor promotes CO2 adsorption
was surmised that the carbamate decomposes at higher over amine-containing adsorbents and inhibits their CO2-
temperatures (98 °C) than bicarbonate. This finding is at induced degradation. Understandably, everything else being
odds with earlier reports on amine-containing mesoporous equal, adsorbed water increases the adsorbent regeneration
silicas, which indicated higher thermal stability of bicarbonate energy (vide infra). However, whether vapor or liquid, water
compared to carbamate.131,132,192 may have additional drawbacks, including decreasing amine
On the contrary, other groups found that CO2 adsorption on content and CO2 uptake. Because amines and polyamines are
amine-modified zeolites was adversely affected by moisture. mostly soluble in water, exposure of impregnated amine
Kim et al.279 reported that diamine-grafted Y zeolite exhibited adsorbents to liquid water, even at room temperature, leads to
a CO2 uptake of 1.9 mmol/g under dry flue gas (15% CO2/2% either amine leaching or surface segregation with increased
Ar/N2) compared to 1.6 mmol under humid conditions (41% diffusion resistance and pore blockage.457,502 Amine-grafted
RH), which was attributed to preferential water adsorption on adsorbents also undergo amine leaching or rearrangement via
the support over CO2. Interestingly, FTIR data showed that hydrolysis of the siloxane bridges, followed by dissolution or
due to strongly coadsorbed water on the zeolite support, not all regrafting, depending on whether liquid water is separated or
water was removed during desorption, which proved to be evaporated.138,503−505 In addition to leaching of active sites,
critical in obviating urea formation during cyclic operations. exposure to steam may lead to structural degradation of the
Nguyen et al.497 also reported that the CO2 uptake of 2.3 material, thereby inhibiting access to amine sites.506−508
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Developing adsorbents with hydrophobic character is a
promising option to overcome these shortcomings. Such
materials would reduce water uptake/working capacity, while
improving the stability of amine sites toward leaching and
surface mobility. Several adsorbents, consisting of either a
hydrophobic support509,510 or hydrophobic organic moi-
eties511,512 with improved behavior in the presence of
moisture, were reported in the literature. Guo et al.509 used
an amine-tethered polymer synthesized by copolymerization of
glycidyl methacrylate, tert-butyl methacrylate, and trimethylol-
propane triacrylate into microporous hydrophobic beads,
followed by covalent immobilization of TEPA via epoxy
groups. Primary amine groups on the resultant material were
converted into secondary amines by reaction with propylene
oxide. The material showed an uptake of 2.03 mmol/g in the
presence of pure CO2 at 60 °C, while under humid conditions
(6% O2/8% H2O/30 ppm of SO2/CO2; 41% RH), the CO2
uptake increased to 2.15 mmol/g (1.94 mmol/g after 1000
cycles) despite a lower CO2 concentration in the feed.
Moreover, the CO2 uptake under dry condition was unaffected
by steam treatment at 120 °C for 360 h. In contrast, upon
exposing triamime-grafted hydrophilic silica (CARiACT, P10)
to steam under similar conditions, Fayaz et al.508 reported 83%,
61%, and 26% decrease in CO2 uptake at 25, 50, and 75 °C,
respectively. The superior performance of the hydrophobic
copolymer framework was attributed to its ability to
significantly limit water uptake, while its macropores obviated
pore blocking. Although incorporating long alkyl chains is a
viable strategy to introduce hydrophobic character to amine-
containing adsorbents, the resultant material typically adsorb
less CO2 compared to their unmodified counterpart.
4.4. Effect of Water on the Regeneration Heat
The viability of CO2 capture processes depends on the overall
energy cost per tonne of CO2 removed. Regarding CO2
capture from typical humid industrial gases over solid
adsorbents, the key issue is the regeneration heat. To be
competitive, CO2 adsorption processes should achieve
significant energy reduction compared to ca. 4 GJ/tCO2
required for regeneration of the benchmark 30% MEA
solution.513
The regeneration energy includes many terms, depending on
the adsorption process, whether a pressure (PSA), vacuum
(VSA), or temperature (TSA) swing adsorption, and the gas−
solid contactor, such as fixed bed, structured bed, or fluidized
bed.514−516 In addition to the energy required to regenerate
the solid adsorbent as such, other terms associated, for
example, with heating the equipment, pumping, and steam
generation may be included. Whenever possible, this
discussion will be limited to the regeneration heat to bring
the adsorbent from the end to the beginning of the adsorption
step, typically in a TSA operation, and the adsorption will be
limited to CO2 and H2O. The regeneration heat for adsorbents
includes (i) the latent heat of desorption of CO2 and water,
(ii) the sensible heat to heat the material from the adsorption
to the desorption temperature, and (iii) the recovered heat, if
any.445,517,518 The most straightforward options to decrease the
regeneration heat include lower heat of adsorption, higher CO2
working capacity, lower water working capacity, and smaller
temperature swing between adsorption and desorption. Hence,
for amine-containing adsorbents, although water plays a pivotal
role as CO2 adsorption promoter and material stabilizer, its
removal during adsorbent regeneration may be more costly
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than the added benefit associated with enhanced CO2 working
capacity.445,517,519 In practice, the net regeneration heat should
take into account the thermal energy recovered from different
sources, such as the sensible heat from the adsorbent and
desorbed CO2 and the latent heat in moisture. Heat
management is a major component in the design and
optimization of adsorption processes.
Several groups used eq 9 or closely related equations to
calculate the regeneration heat, Qr (kJ/kgCO2) of amine-
containing adsorbents without considering water adsorption or
any heat recovery.
1
Qr = Cp,sΔT + ΔHa
qw (9)
where qw (kg CO2 per kg adsorbent) is the CO2 working
capacity, Cp,s (kJ/kg.K) is the adsorbent specific heat capacity,
ΔT (K) is the difference between the adsorption and
desorption temperature, and ΔHa (kJ/kg) is the absolute
value of the heat of adsorption. The first term on the right-
hand side of eq 9 is the sensible heat required to heat the
adsorbent over ΔT, and the second term is the latent heat to
desorb CO2. Another less important term, namely the sensible
heat for CO2, is often ignored. Sjostrom and Krutka30 reported
values mostly between 2 and 3 GJ/tCO2 for different
supported amine adsorbents. Similarly, applying eq 9 to PEI/
nanosilica adsorbents, Li et al.520 found regeneration heats in
the range of 1.7−1.8 GJ/tCO2. Veneman et al.521 calculated
the regeneration heat of TEPA-impregnated HP2MG as the
sum of the adsorption heat, considered to be constant at 1.5
GJ/tCO2, and the sensible heat as a function of CO2 working
capacity. At a working capacity in the range of 2.6− 3.1 mmol/
g, the regeneration heat was found to be ca. 1.8 GJ/tCO2. In
direct air capture applications, the regeneration heat is
necessarily higher because of the inherently lower CO2
working capacity. Using dry air in the presence of an amine-
containing adsorbent at 25 °C, Elfving et al.522 found
regeneration heats of 4.2 and 6.4 GJ/tCO2 for CO2 adsorption
at 60 and 100 °C, respectively, with working capacities of 0.47
and 0.55 mmol/g.
The presence of humidity in the gas has two opposing effects
on the regeneration heat, including a positive contribution
associated with the often observed increase in CO2 capacity,
indicating that a smaller amount of adsorbent is required to
capture a given amount of CO2, under otherwise the same
conditions. The negative contribution is associated with the
evaporation of adsorbed water445,517−519 and the higher
binding strength of CO2.131,132 Siegelman et al.411 found a
regeneration heat of 2.8 GJ/tCO2 for adsorption of 4% CO2/
N2 at 40 °C over 2-ampd-Mg2(dobpdc) and desorption in
100% CO2 at 140 °C. In the presence of water, at a rate of one
H2O and one CO2 per Mg2+ cation, the regeneration heat,
without heat recovery, increased by ca. 54% to 4.3 Gt/tCO2.
Zhang et al.517 proposed a more elaborate energy equation
to calculate Qr while including the latent heat for water
vaporization and taking into account the recovered heat (eq
10)
1−α Q f
Qr = Cp,s(ΔT ) + (1 − β)ΔHa + (1 − γ ) v H2O
qw qw
(10)
where α, β, and γ are the fractions of heat recovery from
sensible heat, latent heat of adsorption, and water vaporization
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heat, respectively, Qv (kJ/kg) is the vaporization heat of water,
and f H2O is the moisture uptake, which is evaporated during
regeneration. The authors determined many of the parameters
in eq 10 for cyclic adsorption−desorption of 15% CO2/N2 at
70 °C over 40 wt % PEI/silica adsorbent, using a combination
of fluidized bed adsorption data, TGA adsorption measure-
ments for CO 2 and water, and differential scanning
calorimetry. The recovery ratio α of sensible heat was assumed
to be 0.75, based on Veneman et al.,521 whereas β and γ were
estimated to be 0.25 and 0.5, based on other considerations.
For ΔT = 60 °C, ΔHa = 95 kJ/mol, Cp,s = 1.81 kJ/kg·K, qw =
1.35 mol/kg, and f H2O = 2 wt %, the heat of regeneration was
found to be 2.46 GJ/tCO2. Comparison of the different
contributions to Qr for this adsorption process and the
benchmark 30% MEA system (Figure 39) shows that the main
Figure 39. Comparison of regeneration heat requirement for CO2
capture over PEI/silica with the benchmark 30% MEA system.
Reproduced with permission from ref 517. Copyright 2016 Elsevier
Ltd.
advantage of adsorption resides in the much smaller sensible
heat corresponding to the difference between heating a solid
material and an aqueous solution. Notice that in this particular
example, qw and f H2O were somewhat low, and ΔHa was
particularly high. Sensitivity analysis of the influence of each
parameter, assuming that they are independent from each
Figure 40. (a) CO2 and H2O working capacities of the amine/silica composite adsorbents. The black solid line indicates the ratio of the CO2 and
H2O working capacity. (b) Heat required for adsorbent regeneration. Reproduced with permission from ref 519. Copyright 2018 American
Chemical Society.
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other, shows that the heat of regeneration is much more
sensitive to f H2O than qw or ΔHa, indicating the adverse effect
of water desorption on the energy requirement of the process.
To investigate the effect of adsorbed water on the
regeneration heat for supported PEI, Min et al.519 used a
series of adsorbents consisting of silica impregnated with PEI
and PEI functionalized with ethylene oxide or 1,2-epoxides
with C1−C4 alkyl chains. The CO2 and water working
capacities shown in Figure 40a were determined by TGA-MS
based on adsorption of 15% CO2/3%O2/10% H2O/2% Ar/N2
(51% RH) at 60 °C and desorption in the presence of 100%
CO2 at 110 °C. Although the CO2 working capacity decreased
as the PEI was modified by heavier epoxides, the water
working capacity decreased more strongly, particularly up to
1,2-epoxybutane (C2-E-PEI/SiO2). The heat of CO2 adsorp-
tion decreased from 1.83 GJ/tCO2 for PEI/SiO2 to about 1.48
GJ/tCO2 for C4-E-PEI/SiO2 with 1,2-epoxyhexane-modified
polymer. The heat of adsorption of water and the specific heat
capacity of the adsorbent also decreased from 2.62 GJ/tH2O
and 1.41 J/g·K for PEI/SiO2 to 2.22 GJ/tH2O and ca. 1.31 J/g·
K for C4-E-PEI/SiO2. The regeneration heat was calculated
using an equation similar to eq 10 but without any heat
recovery. Figure 40b shows that while the combined
contribution of the sensible and latent heat for CO2 desorption
was similar for all adsorbents, the regeneration heat depended
strongly on the latent heat for water desorption. These findings
are in general agreement with Quang et al.,445 who used a
similar relationship as eq 10, also without heat recovery. They
assumed that the latent heat of CO2 desorption does not
depend on the adsorbent moisture content, but the sensitive
heat increases somewhat with moisture content as a result of
increasing specific heat capacity. However, the most moisture-
sensitive contribution was the vaporization heat of water. In
summary, these three investigations showed that while the
CO 2 working capacity is important, managing water
adsorption−desorption is critical.445,517,519
It is clear that all other things being equal, the regeneration
heat decreases as the CO2 working capacity increases and/or
the water working capacity decreases. Because of their
hydrophilic nature, most amine-containing materials adsorb
significant amounts of water,75,135,162,227 which may increase
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the energy penalty to unacceptable levels. The penalty is
particularly severe when CO2 capture is conducted at low
concentration and temperature and high RH as in DAC and in
air revitalization in confined spaces, with pCO2 of 400 to ca.
5000 ppm.485,523 Bos et al.488 reported detailed energy
calculations for low concentration CO2 capture over Lewatit.
Figure 41 shows the regeneration heat for CO2 adsorption at
Figure 41. Regeneration heat for DAC over Lewatit. For conditions,
see text. The H2O to CO2 working capacity ratio is indicated on the
inner abscissa. Reproduced with permission from ref 488. Copyright
2019 Elsevier.
two different concentration versus RH. The conditions were as
follows: adsorption at 20 °C for 15 min, desorption at 116 °C
and 0.5 bar, and RH up to 86%. The CO2 working capacity was
calculated based on the amount of CO2 collected at 900 s of
desorption. It is seen that at 400 ppm, under dry conditions,
the regeneration heat is as high as 28 GJ/tCO2, mostly because
of the low qw, thus the high sensible heat required to heat the
large amount of adsorbent. Here, the presence of water in the
feed actually decreased the regeneration heat because the
additional energy required to evaporate adsorbed water was
overcompensated by the higher CO2 working capacity. At 5000
ppm, the overall regeneration heat was dictated by the
opposing effect of the water and CO2 adsorption capacities.
Similarly, Wurzbacher et al.485 reported a regeneration heat of
11−14.5 GJ/tCO2 for CO2 capture over APDES/NFC at 10−
30 °C in the presence of up to 80% RH. Kulkani and Sholl524
estimated the regeneration heat to be 6.7 GJ/tCO2 for DAC
over triamine-grafted PE-MCM-41 under dry conditions. Sinha
et al.525 reported a surprisingly low value of 3.3 GJ/tCO2 for
DAC with 25% RH over mmen-Mg2(dopdc) in a TVSA
process using a structured contactor.
Veneman et al.227 proposed several strategies to curb the
energy requirement for water desorption, either through the
adsorption process or the material design. These are as follows:
(i) Conducting adsorption at higher temperature with the
expectation that the relative decrease in the uptake of
physisorbed water would overcompensate the smaller decrease
in chemisorbed CO2, provided that the CO2 working capacity
remains within acceptable range, i.e., higher than ca. 2 mmol/g.
(ii) Using the difference in the adsorption kinetics of water and
CO2: the effectiveness of this strategy is contingent upon using
an adsorbent whose water adsorption is significantly slower
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than CO2 adsorption. (iii) Limiting the desorption of water
during regeneration: this technique would be applicable if the
purge medium has high humidity, such as steam. (iv)
Preconditioning the flue gas by decreasing its water content
via partial condensation. It was found that lowering the dew
point of the flue gas from 47 to 30 °C resulted in reduction of
water uptake from 0.85 to 0.25 mol H2O per mole of captured
CO2 from flue gas. This lowered the regeneration heat from 3
to 2.6 GJ/tCO2. Although this strategy seems to be the best
solution, adding a drying unit prior to CO2 capture can
significantly increase the operation costs. Instead of adjusting
the process parameters, Yogo and co-workers526−528 intro-
duced terminal alkyl groups to impregnated TEPA to facilitate
CO2 desorption and reduce the energy penalty associated with
regeneration. Steam-aided vacuum swing desorption (SA-VSA)
over isopropyl-substituted TEPA solid sorbents following
exposure to ca. 10.5% CO2/N2 with 50% RH required a
regeneration heat of 1.65 GJ/tCO2 to achieve more than 90%
CO2 recovery, compared to 80% for unsubstituted TEPA-
based adsorbents.526 Choi et al.529 reduced the regeneration
heat of PEI-impregnated silica by removing primary amine
groups in favor of secondary amines, through treatment with
1,2-epoxybutane. Not only epoxidation decreased the heat of
adsorption of both CO2 and H2O, but more importantly, it
inhibited water adsorption to a large extent without affecting
CO2 uptake significantly. As a result, the regeneration heat
calculated for a TSA operation with adsorption of 15% CO2,
10% H2O, 2% Ar in N2 balance at 60 °C (50% RH), and
desorption at 110 °C in pure CO2, decreased from ca. 4 to 2.67
GJ/tCO2 upon PEI epoxidation. By far, the main difference
was the latent heat of water desorption.
5. MEMBRANES
Membrane CO2 capture is beyond the scope of this
contribution. Nonetheless, because membranes often contain
actual CO2 adsorbents, such as amines,171,174,530 ionic
liquids, 182,183 enzymes 184 or mimic enzymes, 185,186
MOFs,176−178 carbon,181 and zeolites,177,179,180 the water
benefits or drawbacks on CO2 membrane separation will be
briefly discussed, with particular emphasis on water-facilitated
transport in polymeric membranes.171,188,189,530−532 Compre-
hensive reviews on membrane CO2 removal from large point
sources are readily available else-
where.174,176−181,187,190,530,533,534
In a typical membrane gas separation process, the feed gas
mixture is driven by a pressure (concentration) difference
across the membrane and separated into one or more gaseous
components by selective permeation, thus generating a specific
gas-enriched permeate or retentate. Permeability and selectiv-
ity are the most important parameters for evaluating the
performance of membranes.535 Note that there is often a
permeability/selectivity trade-off with an upper bound.536 An
ideal membrane for CO2 separation should have an optimum
combination of high CO2 permeability and selectivity, in
addition to other attributes, depending on the feed
composition, temperature, and pressure.537 CO2 separation
membranes are comprised of three major groups, namely
inorganic, polymeric (or organic), and mixed matrix
membranes.
Inorganic membranes are based on materials such as
MOFs,176−178 zeolites,177,179,180 carbon,181,538 and gra-
phene.539,540 They are typically porous, with high separation
factor due to well-defined pore sizes and molecular sieving
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properties. Similar to their adsorbent counterparts discussed in

section 3, the CO2 separation performance of inorganic
membranes is often adversely affected in the presence of
water, particularly at low temperatures.541−544 Representative
behavior was reported by Gu et al.,542 using Y zeolite-based
membranes for separation of CO2/N2 mixtures under dry and
moist conditions in the temperature range of 23−200 °C. In
the presence of equimolar CO2/N2 at 23 °C and atmospheric
pressure, the CO2 selectivity in the presence of 94% RH (PH2O
= 2.64 kPa) was less than 1 versus 31.2 under dry conditions,
mostly because of decreasing CO2 permeance due to the
membrane pores being blocked by water. The N2 permeance
was low and hardly changed with humidity because the zeolite
pores were filled with either CO2 or H2O under dry and humid
condition, respectively. At increasing temperature up to 200 °C
(0.17% RH) using the same humid gas composition, the
permeance of all three components increased at different rates.
Below 80 °C, because of the decreasing affinity of water to Y Figure 42. CO2 permeability versus water content in hydrogel
zeolite, the CO2 permeance increased slowly, whereas beyond membranes at 23 °C and 5.15 bar (AGA, alginic acid; CE, cellulose;
80 °C, water desorbed significantly, and the CO2 permeance CEP, cellophane; CMC, carbonyl methyl cellulose; CS, chitosan;
increased rapidly. As a result, the CO2/N2 selectivity for the PVA, poly(vinyl alcohol); PVAm-X, polyvinylamine with X% PVA).
moist system increased and then decreased slightly with Reproduced with permission from ref 546. Copyright 2008 Elsevier.
temperature after reaching a maximum at ca. 140 °C. Above
110 °C, the CO2 versus N2 selectivity of the moist mixture was ment of the membrane polymer chains, similar to unsupported
significantly higher than that of the dry mixture, but their polyamine adsorbents.460−463
permeances were lower under humid condition over the entire Dai et al.547 investigated the CO2 separation properties of
range of temperature. Additional measurements carried out at sulfonated multiblock polymer membranes, referred to as
200 °C in the presence of equimolar CO2/N2 with up to 48 TESET, before and after submersion in water for 24 h and
kPa H 2 O (up to 3.1% RH), showed decreasing CO 2 drying under vacuum at room temperature as a function of RH.
permeance with increasing water partial pressure, whereas The membranes were casted from different solvents, including
the N2 permeance decreased up to 12.3 kPa of water (0.8% 50/50 v/v cyclohexane/heptane (CH), 85/15 w/w toluene/
RH) then remained practically constant. As a result, the CO2 isopropyl alcohol (TIPA), chloroform (CF), and tetrahydro-
selectivity reached a maximum value of 4.6 at 0.8% RH. furan (THF). Under dry condition, all membranes exhibited
Similarly, chabazite membrane grown on tubular alumina particularly low CO2 permeability (<30 Barrer) and CO2/N2
support showed limited decreases in CO2/N2 and CO2/CH4 selectivity (<30). With the exception of the THF-derived
selectivity of 11 and 15%, and CO2 permeance of 18% and membrane, before exposure to liquid water, all samples showed
similar separation properties with CO2 permeability in the
20% at 200 °C, in the presence of equimolar humid CO2/N2
range of 20−80 Barrer and CO2/N2 selectivity of 8 to ca. 60
and CO2/CH4 mixtures (8% H2O, 0.5% RH), respectively,
(Figure 43). The THF-cast membrane showed a CO 2
compared to dry condition.543 Bernal et al.544 also reported a
permeation of 300 Barrer at the highest RH of 95%. After
decrease in CO2 permeability through stainless steel-supported
submersion in water, all membranes showed significantly
boron-substituted ZSM5 membrane. However, the CO2 higher CO2 permeabilities, reaching 482 Barrer for the CF-
selectivity was not significantly affected by water, even at low derived membrane at 95% RH. All such improvements of the
temperatures, presumably because of the limited hydrophilicity membrane separation properties in the presence of water
of the B-ZSM-5 membrane.
With regard to polymeric membranes, the most straightfor-
ward effect of water on CO2 separation is associated with
polymer swelling. Water-swellable polymer membranes,
including nonreactive hydrogels and membranes containing
CO2 carriers (vide infra), such as polyamines, polyamides,
mixed matrix polymers, and polymer electrolytes, exhibit much
higher mass transfer in the presence of water due to diffusion
enhancement and other water-facilitated CO2 capture mech-
anisms. This is in contrast to the often prevailing solution-
diffusion mechanism545 under dry conditions, which is
governed by the permeability/selectivity trade-off mentioned
above.536 Swelling induced by water drastically increases the
polymer free volume, which is directly responsible for diffusion
enhancement, leading to higher CO2 permeance. Figure 42 Figure 43. CO2 separation performance of TESET membranes cast
shows the dramatic effect of water content in hydrogel from different solvents, as indicated, before and after submersion in
membranes, including polyvinylamine-poly(vinyl alcohol) liquid water (filled and open symbols, respectively). The dashed line
(PVAm-PAA) blends, on their CO2 permeability.546 In represents the Robeson upper bound. Reproduced with permission
addition, water swelling is often accompanied by disentangle- from ref 547. Copyright 2019 Springer Nature.

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vapor, and upon immersion in liquid water were associated
with morphological changes due to polymer swelling and the
formation of nanoscale channels promoting CO2 diffusion.
While optimum humidity promotes both CO2 permeability
and selectivity, often exceeding the upper bound Robeson
limit, excessive humidity may have an adverse effect on
selectivity through relaxation of the polymer network.548 Using
a nanofibrillated cellulose (NFC)-based membrane doped with
1-ethyl-3-methylimidazolium acetate ionic liquid (IL), as
shown in Figure 44, Janakiram et al.182 identified three
Figure 44. Mixed-gas CO2 permeability and CO2/N2 separation
factor for two hybrid NFC/IL membranes versus RH at 35 °C and 1.7
bar. R-I, R-II, and R-III indicate the three regimes of gas permeation
with the corresponding schematic morphologies. Reproduced with
permission from ref 182. Copyright 2020 Royal Society of Chemistry.
permeation regimes, depending on relative humidity. The first
regime (R-I) is dominated by low permeation of semicrystal-
line NFC nanofibrils because the humidity level is not
sufficient to swell the membrane and create continuous
water channels. In this regime, CO2 permeation occurs
through chemisorption on IL and diffusion along the NFC/
IL interface, explaining its strong sensitivity to IL content. The
next regime (R-II) occurs at RHs sufficient for NFC swelling
with decreased viscosity. Major morphological changes occur,
including physical separation of nanofibrils due to disruption of
interfibrillar hydrogen bonding by water and formation of
contiguous IL/water channels along the fiber surfaces. Hence,
CO2 permeation is promoted due to higher solubility and
faster diffusion compared to N2, leading to much higher CO2/
N2 selectivity for the 35% IL-containing membrane. As for the
membrane containing 50 wt % IL, the selectivity hardly
changed, presumably because of excessive swelling. In the third
regime, further swelling takes place, with the formation of
continuous pathways bulk water channels containing IL,
allowing fast diffusion of both CO2 and N2. Hence, while
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CO 2 permeability increased significantly, the CO 2 /N 2
decreased.
Reactive polymeric membranes may contain fixed-site and/
or mobile carriers that react reversibly with CO2. Examples of
CO 2 carriers include amines, 171,174,188,530,549,550 poly-
amines,171,174,530,540,550,551 ionic liquids (ILs),182,183,552 en-
zyme,184 and mimic enzyme.185,186 As shown schematically in
Figure 45, in polymeric membranes with fixed-site carriers,
Figure 45. Schematic diagram of transport mechanisms across
membranes.
CO2 diffuses across the membrane by hoping from one site to
another, from the high-pressure side to the permeate interface,
whereas for membranes with mobile carriers, CO2 reacts with
the carrier forming an intermediate product that migrates
through the membrane toward the low-pressure side, under the
concentration gradient driving force. In both cases, CO2-carrier
product dissociates at the permeate interface, leading to the
separation of CO2 and regeneration of the carrier. Such a
mechanism is referred to as a facilitated transport mecha-
nism.174,530−532,537 Occurrence of this mechanism is often
accompanied by enhancement of both permeability and
selectivity for the target species, thus providing a method to
overcome the above-mentioned permeability/selectivity trade-
off limitation.537 Moreover, in many instances, the CO2-carrier
reaction is either more efficient in the presence of water, or
requires water. Figure 46 illustrates the facilitated transport of
CO2 in the presence of carbonic anhydrase-inspired imidazole-
Zn(II).171 In the presence of this carrier, CO2 diffuses through
the membrane as bicarbonate, whose formation involves water.
In the presence of amine carrier sites, the reaction-
decomposition cycle takes place with the intermediacy of
ammonium carbamate (eq 5) or bicarbonate (eq 11),
depending on the humidity of the feed gas and/or the
membrane. Interestingly, using tertiary amines or sterically
hindered amines to inhibit the formation of ammonium
carbamate in favor of ammonium bicarbonate with higher
stoichiometric CO2/amine ratio proofed to be an excellent
strategy to achieve high CO2 permeability and selectivity in the
presence of water.175,549 Using poly-N-isopropylpolyallylamine
as a fixed-site carrier with hindered amine groups, at 110 °C
and 58% RH, Zhao and Ho549 achieved an impressive CO2
permeability of 6600 Barrer and CO2/H2 selectivity of 340,
compared to 3950 Barrer and 160, respectively, for unmodified
polyallylamine.
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Figure 46. CO2 hydration and deprotonation catalyzed by carbonic
anhydrase-inspired imidazole-Zn(II). Reproduced with permission
from ref 171. Copyright 2017 Royal Society of Chemistry.
R3N + CO2 + H 2O → R3NH+HCO3− (11)
Kim et al.489 demonstrated that hollow fiber-based membrane
containing hyperbranched aminosilica (HAS) obtained by in
situ polymerization of aziridine exhibit distinctly different
behavior in humid versus dry conditions, switching from CO2-
to N2-selective membrane, respectively. These findings were
associated with different interaction mechanisms between CO2
and amine, depending on the actual conditions (Figure 47). In
dry condition, CO2−amine interactions triggered polymer
chain cross-linking, which significantly decreased the CO2
permeability. However, in humid conditions, amine cross-
linking was limited, while the CO2 solubility was enhanced,
leading to improved CO2 permeation and near-quantitative
amine−water−CO2 reaction to form bicarbonate. Additional
data regarding enhancement of CO2 permeability and
selectivity in the presence of a variety of carriers and water
may be found elsewhere.171,537
While inorganic membranes are the most robust because of
their superior mechanical, thermal and chemical stability, and
offer higher selectivity and permeability, they are very brittle
and significantly more expensive. In contrast, polymeric
membranes are relatively cheaper and easier to process,
however, they are less stable, susceptible to physical aging
and CO2-induced plasticization, which may lead to loss of
selectivity and mechanical strength.553 An excellent trade-off
between membrane permeability, selectivity, and processability
can be achieved by mixed matrix membranes (MMM),
Figure 47. CO2 adsorption on grafted-polyethylenimine HAS membrane under dry condition. Reproduced with permission from ref 489.
Copyright 2015 American Chemical Society.
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consisting typically of a polymeric membrane with a dispersed
phase, which could be an inorganic filler such as MOFs, ILs,
zeolites, carbons, and metal oxides.554,555 or organic filler such
as polyaniline particles.556 Depending on the MMM design,
the polymer and the filler may play different roles in the CO2
separation process. In membranes consisting of an inert
polymer and an active dispersed phase, the filler adsorbs
significant amount of water, creating efficient CO2 transport
pathways. Liu et al.557 used a hydrophobic polyimide
membrane combined with carbon nanotubes functionalized
by polyzwitterions containing quaternary ammonium sulfonate
(Figure 48). Under humid conditions, the MMM showed
Figure 48. CO2 transport pathways within the hydration layer at the
polymer−filler interface. Reproduced with permission from ref 557.
Copyright 2014 American Chemical Society.
significantly enhanced CO 2 permeability compared to
unmodified polyimide membrane. It was argued that because
of the high hydrophilicity of the zwitterion, the filler adsorbs
significant amount of water. Moreover, the particles were
found to form an interconnected network morphology with
preferred CO2 transport pathways within the continuous
hydration layer. Further enhancement of CO2 permeability
under humid conditions was achieved by incorporating highly
hydrophilic nanohydrogel particles within the polyimide
membrane.558 Water-facilitated CO2 capture also takes place
in active membranes such as PVAm combined with fillers such
as polyaniline nanosheets556 or hydrotalcite particles,559 which
disrupt the polymer chain packing, creating transport channels.
Another important effect of water on CO2 separation by
membranes is the salting out affect introduced by Zhang and
Wang.560 Addition of aqueous solutions of salts to polymeric
membranes was found to decrease the solubility of nonreactive
gases, much more than the solubility of CO2, leading to
significantly higher selectivity for CO2 separation, albeit at
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Figure 49. (a) Permeability vs selectivity plot of Pebax electrolyte membranes with and without added salt (Ca1.5PW, calcium phosphotungstate;
CaLS, calcium lignosulfonate). (b) Corresponding CO2 permeability vs free water content and CO2/N2 selectivity vs bound water content.
Reproduced with permission from ref 171. Copyright 2017 Royal Society of Chemistry.

slightly lower permeability. For example, immersion of water-

swollen PVA membrane into 0.5 M NaF increased the CO2/
N2 separation factor from 79 to 500, while it decreased the
CO2 permeance from 0.79 GPU to only 0.53 GPU.560
Similarly, upon dipping a polyallylamine membrane in 0.5 M
of Na3[PW12O40], the CO2/N2 separation factor increased
from 50 to 1700, whereas the permeance decreased
considerably from 8.4 to 1.7 GPU. It was surmised that the
salting-out effect could be attributed to the preferential
attraction between the salt ions and the water-swollen polymer,
which would decrease the amount of “free water” and PVA
macromolecules to dissolve nonreactive gases, such as N2, as
opposed to the favorable water−CO2 interactions in the water-
swollen membrane.560 Li et al.561 found that not only
humidified poly(ether-b-amide) (Pebax) doped with calcium
chloride, calcium phosphotungstate, and calcium lignosulfo-
nate exhibits significantly higher CO2 permeability and
selectivity than their dry counterparts (Figure 49a), with a
ratio exceeding the traditional upper bound limit,536 but the
CO2 permeability and selectivity increase linearly with the total
water and bound water content, respectively (Figure 49b).
Consistent with Zhang and Wang’s proposal,560 they
hypothesized that bound water surrounding metal ions does
not have the ability to dissolve noncondensable gases and Figure 50. Schematic illustration of the effect of bound water on
disrupts the continuity of their transport routes. However, CO2/N2 separation for Pebax-containing calcium salts. Reproduced
with permission from ref 562. Copyright 2015 Royal Society of
water bound to the polar groups of Pebax may facilitate the Chemistry.
hydration of CO2 into bicarbonate anion and its permeation
through the membrane. Hence, as shown schematically in
Figure 50, the adverse effect of salt additives on the
permeability of noncondensable gases would be much more including increased CO2 solubility,565 enhanced CO2-complex
severe, in comparison to CO2 permeability, with calcium transport across the membrane,489,552 and occurrence of
phosphotungstate showing the highest amount of trapped preferential transport pathways.557,558,562 As the CO2 per-
water and the strongest salting-out effect.562
meation increases with higher membrane wetting, the
To sum up this section, while moisture has a limited or even
adverse effect on CO2 separation by inorganic membranes, it selectivity may go through a maximum value.546 In contrast,
plays a key role in facilitating CO2 transport across flexible in the presence of rigid polymers such as polymers of intrinsic
polymer membranes, through a multitude of mechanisms. microporosity567 and thermally rearranged polymeric mem-
Water is necessary for the reversible CO2 hydration.562,563 branes568 or in the presence of hollow fiber membrane
Moreover, water can swell the majority of polymer membranes, contactors,569 water may adversely affect CO2 permeability,
leading to enhanced CO2 permeability through decreased mostly because of competitive adsorption. Moreover, for flue
viscosity564,565 and high fractional free volume.546,566 Depend- gas containing NOx and SOx, the presence of water may lead to
ing on the nature and structure of the membrane, other water- permanent degradation of the membrane due to acid-catalyzed
facilitated CO2 transport mechanisms may also apply, hydrolysis of specific functional groups, e.g., nitrile.567
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6. REACTIVE ADSORBENTS
Because of the basic nature of some metal oxides, hydroxides
and carbonates, they react with acidic CO2, often at high
temperature, while demonstrating high CO2 uptake and
selectivity.62,570,571 Contrary to typical chemical adsorbents,
such as amine-functionalized materials, they interact with CO2
through a bulk as opposed to surface reaction. Alkali metal
carbonates 74,169,572−574 and alkaline earth metal ox-
ides74,575−578 are two important groups of metal-based
adsorbents, widely used for CO2 capture and sequestration.
6.1. Alkali Metal-Based Adsorbents
6.1.1. Sodium Carbonate. Alkali metal carbonates react
with CO2, but only in the presence of water to form
bicarbonates (eq 12).74,573,579,580 Sodium carbonate is a
common adsorbent that reacts with CO2 under humid
condition generating NaHCO3.580,581 Above 70 °C, the
material reacts with CO2 and water to produce preferentially
Wegscheider’s salt, according to eq 13, instead of bicarbon-
ate.582
M 2CO3(s) + H 2O(l) + CO2(g) ⇋ 2MHCO3(s)
(M = Na, K) (12)
Na 2CO3(s) + 0.6CO2(g) + 0.6H 2O(g)
⇋ 0.4[Na 2CO3 · 3NaHCO3](s) (13)
Dong et al.583
found that at 60 °C in the presence of 15%
CO2/15% H2O/N2 (76% RH), unsupported Na2CO3 gave rise
mostly to Wegscheider’s salt, whereas alumina-supported
Na2CO3 formed bicarbonate. Under specific conditions,
sodium sesquicarbonate, Na2CO3·NaHCO3·2H2O, can also
be produced in the presence of CO2 and moisture.582 While
humid CO2 adsorption at high concentration takes place on
the basis of eqs 12 and 13, PXRD data584 showed that at 30 °C
in the presence of 1−5% CO2/N2 with 74% RH, only Na2CO3·
H2O (eq 14) was detected due to unfavorable conditions for
the forward reactions of eqs 12 and 13 to take place at low
CO2 pressure. Increasing the CO2 concentration up to 10%
gave rise to Na5H3(CO3)4 (eq 15), eventually leading to the
formation of bicarbonate, according to eq 16.
Na 2CO3(s) + H 2O(g) ⇋ Na 2CO3 ·H 2O(s) (14)
5Na 2CO3 ·H 2O(s) + 3CO2(g)
⇋ 2Na5H3(CO3)4(s) + 2H 2O(g) (15)
Na5H3(CO3)4(s) + CO2(g) + H 2O(g) ⇋ 5NaHCO3(s)
(16)
The beneficial effect of the feed humidity on CO2 adsorption
kinetics and uptake over Na2CO3 was also reported by Luo
and Kanoh,584 as increasing RH from 38% to 74% reduced the
equilibrium time from 300 to 100 min, along with a slight
increase in CO2 uptake in the presence of 30% CO2/N2, i.e.,
from 7.21 to 7.39 mmol/g. In parallel, the intensity of the
diffraction peaks assigned to Na5H3(CO3)4 increased, indicat-
ing the favorable impact of water on the basis of eq 15.
Beside water vapor being an essential reactant for CO2
adsorption over Na2CO3, controlling the humidity of the
adsorbent was found to be of critical importance.585 Upon
exposure to pure CO2 at ambient pressure, materials with
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moisture content of 40−90 wt % at 30 °C had CO2 uptakes
below 0.74 mmol/g. Decreasing water content to 35 wt % led
to a dramatic increase in CO2 uptake to 3.55 mmol/g, in
addition to enhanced adsorption rate. At optimum water
content of 30 wt %, the material exhibited a CO2 uptake as
high as 6.41 mmol/g and the fastest kinetics. Further decrease
of the water content to 25 wt % slightly increased CO2 uptake
to 6.50 mmol/g, but the adsorption rate was about four times
lower. Figure 51 shows the efficiency of CO2 removal over
Figure 51. CO2 removal efficiency at 50 °C for Na2CO3 pre-exposed
to water vapor (100% RH) for different durations. Reproduced with
permission from ref 580. Copyright 2007 Elsevier Ltd.
Na2CO3 in the presence of 10% CO2/12.2% H2O/N2 (100%
RH) at 50 °C as a function of pretreatment time in water-
saturated nitrogen.580 It is clear that CO2 removal increased as
the duration of water pretreatment increased and leveled off at
ca. 15 min. Overexposure of the material to water vapor,
however, could result in agglomeration, hindering proper
fluidization of the adsorbent.
6.1.2. Potassium Carbonate. Potassium carbonate is
recognized as a more effective adsorbent than sodium
carbonate.573,586 Hayashi et al.586 impregnated K2CO3 on
AC and compared its CO2 capture performance in the
presence of 10% water to Li2CO3- and Na2CO3-based
adsorbents. As illustrated in Figure 52, below 80 °C, K2CO3
Figure 52. Effect of temperature on CO2 uptake of alkali metal
carbonates in the presence of 13.8% CO2/10% H2O/He. Reproduced
with permission from ref 586. Copyright 1998 American Chemical
Society.
reacted quantitatively with CO2 on the basis of eq 12.
Although CO2 uptake of K2CO3 decreased at higher
temperatures, it was still 82% of the maximum uptake at 100
°C. Similarly, CO2 uptake over Na2CO3 decreased with
temperature; however, the resulting NaHCO3 decomposed at
lower temperature compared to KHCO3. Moreover, CO2
uptake over Li2CO3 was very poor, irrespective of temperature.
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Adsorption of CO2 over K2CO3 between 40 and 80 °C is
believed to take place according to eq 12, in two steps
involving hydration into an active adsorption intermediate,
K2CO3·(1.5H2O), as shown in eq 17, followed by reaction with
CO2 (eq 17).573,586−588
K 2CO3 · (1.5H 2O)(s) + CO2(g) ⇋ 2KHCO3(s) + 0.5H 2O(g)
(17)
Nevertheless, PXRD data showed in addition to K2CO3·
(1.5H2O), the occurrence of K4H2(CO3)3·(1.5H2O) according
to eq 18, which ultimately gave rise to KHCO3 (eq 19).589
2K 2CO3(s) + 2.5H 2O(g) + CO2(g)
⇋ K4H 2(CO3)3 ·(1.5H 2O)(s) (18)
K4H 2(CO3)3 ·(1.5H 2O)(s) + CO2(g)
⇋ 4KHCO3(s) + 0.5H 2O(g)
(19)
Lee et al.74,169,573,588 carried out extensive work on CO2
adsorption over supported K 2 CO 3, demonstrating the
importance of the humidity of the gas feed and prehumidifi-
cation of the adsorbent. Increasing the pretreatment RH from
6% to 75% increased the CO2 uptake at 60 °C in the presence
of 1% CO2/N2 with 6% RH from 0.58 to 2.39 mmol/g while
equally enhancing the adsorption rate. The beneficial effect of
prehydration was attributed to higher conversion of K2CO3 to
the active K2CO3·(1.5H2O), as confirmed by PXRD measure-
ments. Moreover, at low humidity, the K2CO3·(1.5H2O)
intermediate phase could be easily converted into K2CO3
during thermal regeneration. Therefore, the RH should be
maintained sufficiently high to prevent the active phase from
transforming back into K2CO3.588
Unlike K2CO3/AC, K2CO3/Al2O3 deactivated over cyclic
operation with adsorption at 60 °C and regeneration at 150 °C
due to the formation of inactive mixed metal hydroxycar-
bonates, KAl(CO3)2(OH)2.573 In the presence of K2CO3/
MgO, CO2 adsorption took place between 200 and 320 °C and
above 600 °C, whereas under humid conditions, CO2 adsorbed
at temperature as low as 60 °C, up to 140 °C.74 Using 1%
CO2/N2 at 60 °C in the presence of 7%, 9%, and 11% H2O
(35%, 46%, and 56% RH), the CO2 uptake over 30% K2CO3-
impregnated MgO increased with humidity, reaching ca. 2.95
mmol/g at 56% RH. At 45% RH, the CO2 uptake over
K2CO3/MgO was 30% higher than the maximum uptake based
on CO2/K2CO3 = 1, indicating that the support contributed to
the overall CO2 adsorption. In addition to direct adsorption of
CO2 over MgO as discussed in section 6.2.2, MgO promoted
CO2 uptake of K2CO3 through the formation of mixed metal
carbonates, namely K2Mg(CO3)2 or K2Mg(CO3)2·4(H2O).
Similar to K2CO3/Al2O3, the decrease in CO2 capacity of
K2CO3/MgO over time was attributed to the formation of
inactive mixed metal carbonates.74,169
In contrast to the reports discussed above,573,580,586−588 the
Mahinpey group590,591 used a combination of TGA and MS to
simultaneously monitor the consumption of both water vapor
and CO2 on several potassium-based materials and demon-
strated that K2CO3 hydration (eq 17) and carbonation (eq 12)
are actually competitive reactions that take place in parallel,
with no direct conversion of K2CO3·(1.5H2O) into KHCO3
(eq 17). Their main objection was that the two-step
carbonation mechanism was based solely on TGA data
assuming that after carbonation, the material was composed
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of KHCO3 and K2CO3 only, without considering the possible
occurrence of hydrates.
6.2. Alkaline Earth Metal-Based Adsorbents
Chemical looping involving the carbonation of alkaline earth
metal-containing compounds, particularly Ca and Mg-rich
materials such as their oxides, hydroxides and mixed oxides,
and wollastonite (CaSiO3), was extensively investigated as a
means of CO 2 separation577 or permanent sequestra-
tion.18,592,593 Contrary to alkali metal-based materials,
adsorbents containing alkaline earth metal oxides or hydrox-
ides can react with CO2 in the absence of water, according to
eqs 20 and 21.62,594
MO(s) + CO2(g) → MCO3(s) (M = Mg, Ca) (20)
M(OH)2(s) + CO2(g) → MCO3(s) + H 2O(g)
(M = Mg, Ca) (21)
6.2.1. Calcium Oxide and Hydroxide. Among the oxides
studied for CO2 adsorption, CaO has received much attention
because it is readily available, cheap, and nontoxic, with
favorable thermodynamic properties and theoretical capacity of
0.78 g/g CaO.595−598 Calcium looping process (CLP) is a
promising technology for CO2 capture and release, involving
carbonation, typically at 600−700 °C, and calcination at ca.
900 °C (Figure 53).599 This process uses high temperature
Figure 53. Schematic of calcium looping process (CLP). Reproduced
with permission from ref 599. Copyright 2017 Elsevier Ltd.
streams with the potential of reducing the energy penalty
associated with CO2 capture.599,600 The merits and drawbacks
of water/steam on hydration of adsorbent, carbonation, and
calcination reactions were summarized by Zhang et al.601
Nonetheless, there is ample evidence that water has beneficial
effects on both carbonation and regeneration and even
reactivation of spent CaO.602−604
Carbonation of Ca−Al mixed oxide (Ca/Al = 2.5) at 600 °C
in the presence of 50% CO2/N2 showed that the initial CaO
carbonation increased with moisture, from 12.7 mmol/g under
dry conditions to a maximum of 16.1 mmol/g in the presence
of 1.6% water vapor, while further increase in water led to the
opposite effect.604 Moreover, the stability of the material
during multiple cycles of carbonation at 600 °C and calcination
in N2 at 700 °C in the presence of 1.6% water was higher than
cycling in dry condition. As for the mechanism of the water
effect, water may promote the initial reaction-controlled, fast
stage of CaO carbonation or the subsequent slow stage
controlled by diffusion of CO2 through the formed layer of
carbonate. It was also hypothesized that water may catalyze the
reaction, with the formation of a more active Ca(OH)2
intermediate.605 Literature data provide strong evidence that
water enhances diffusion in the product layer.604−606 For
example, the morphology of spent Ca−Al mixed oxide after 17
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cycles of carbonation at 600 °C and calcination at 700 °C with
up to 1.6% water vapor consisted of loose and porous particles
compared to compact particles under dry conditions or in the
presence of more water, suggesting enhanced mass transfer
during the diffusion-controlled stage of carbonation under
optimized moisture conditions. Interestingly, under dry
conditions, the CO2 uptake decreased from 12.5 to 8 mmol/
g after 17 cycles but the adsorbent could be reactivated by
introduction of 1% steam from the 18th cycle, leading to a
steady increase in CO2 uptake up to 13.6 mmol/g in the 28th
cycle.604
Zhang et al.607 reported that compared to dry conditions
(15% CO2/N2), carbonation at 650 °C followed by calcination
at 950 °C of 0.74 mol % Mn-doped CaO was ca. 100% higher
in the presence of steam (15% CO2/15% H2O/N2) over
multiple cycles. While steam brought about enhanced porosity,
Mn was thought to significantly reduce sintering of CaO
particles during calcination.604,606 Following CO2 adsorption at
650 °C over CaO derived from limestone, calcination in humid
nitrogen at 850 °C led to higher CO2 uptake in subsequent
adsorption cycles compared to calcination under dry
conditions.608 For instance, consistent with Guo et al.,604
CaO conversion to CaCO3 after 20 cycles was ca. 16%, 23.4%,
and 25.5% when calcination was carried out in N2 with 0%,
30%, and 80% RH, respectively, with RH calculated at room
temperature. This was attributed to the formation of larger
pores in the presence of water vapor, enabling CO2 to diffuse
deeper into the bulk material and enhanced carbonation due to
steam retained in the pores and interparticle voids after
calcination.
CaO-based materials were also investigated for CO2 capture
at low to moderate temperatures.166,609,610 Azmi et al.166
compared commercial CaO and a CaO derived from waste
seashell cockle for CO2 adsorption at 2 °C and pressures up to
36 bar. Moisturizing the commercial-grade and synthesized
materials to optimum water content of 32% and 67 wt %
increased CO2 uptake ca. 4 and 8 times, respectively. Beyond
these optimum water contents, lower CO2 uptake was
obtained, presumably due to the blockage of adsorbent pores
by water.
Theoretical studies to elucidate the promoting effect of
water on carbonation611−613 and calcination614 were also
reported. DFT calculations showed that CO2 adsorption on
CaO (001) is facilitated by the presence of water, suggesting
an Eley−Rideal type mechanism in which H2O preferentially
adsorbs on the CaO (001) surface and activates adjacent O
atoms, which are more reactive with CO2 compared to water-
free CaO surfaces.611,612 Consistent with TGA data, molecular
dynamic simulations using ReaxFF reactive force field showed
that water vapor improved CaO carbonation mainly through
enhanced diffusion, while the beneficial impact of water on the
kinetics of carbonation was negligible.613 As often reported, He
et al. 614 observed an increase in the rate of CaCO 3
decomposition and a decrease in the onset decomposition
temperature during calcination of CaCO3 with increasing
steam content, suggesting a reduction in activation energy
barrier, with water acting as a catalyst. Their DFT calculations
revealed that water splits into OH− and H+, then the proton
reacts with CO32− of CaCO3 to form HCO3−, which then
decomposes to CO2 and OH−. The activation energy for
CaCO3 decomposition was determined to be 342 kJ/mol,
compared to 263 kJ/mol for HCO3−, i.e., in the presence of
steam.
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6.2.2. Magnesium Oxide. Magnesium oxide received
much attention as a sorbent or additive for CO2 adsorption at
different temperatures.169,615,616 Although water is not required
for CO2 to react with MgO (eq 20), adsorption is strongly
promoted in the presence of humidity.74,167,594 For example, in
the presence of 15% CO2/N2 at 50 °C, increasing RH from 0%
to 50% and 70% enhanced CO2 uptake over MgO from 0.66 to
3.01 and 3.42 mmol/g, respectively, without the formation of
intermediate species as indicated by PXRD and FTIR data.167
Nonetheless, capillary condensation of water should be
avoided, as prehydrating MgO at 50 °C with moist N2 (70%
RH) led to 34% decrease in CO2 uptake compared to the
nonhydrated material. It was inferred that the presence of
capillary condensed water in the pores of MgO hindered the
diffusion of CO2 toward active sites. Moisture had no
noticeable effect on the initial rapid uptake of CO2 because
it is a surface-limited reaction. However, similar to CaO,604−606
the rate of the diffusion-controlled stage was enhanced by
moisture.167 PXRD and FT-IR data provided evidence that
water vapor not only increases CO2 uptake, but also the
adsorption kinetics, presumably through the formation of
MgO·H2O reactive intermediate.594 Zarghami et al.617 claimed
that the promoting effect of steam on the carbonation of MgO
was due to the formation of MgO·H2O/Mg(OH)2 inter-
mediates, which are more reactive than MgO, and to the fact
that these species have larger molar volume than MgO, leading
to pore expansion, thereby alleviating diffusion limitations.
CO2 uptake at 60 °C over mesoporous MgO/Al2O3 (Mg/Al =
1) was found to increase from 0.74 mmol/g under dry
condition (10% CO2/N2) to 1.74 and 2.0 mmol/g at 5% and
10% RH, respectively, which was attributed to the formation of
more reactive Mg(OH)2 phase.618 However, further increase in
RH led to a decrease in CO2 uptake, presumably due to
diffusion resistance for CO2 owing to high water uptake. With
regard to the carbonation of Mg(OH)2, it was found to be
much faster than the carbonation of MgO and less sensitive to
steam, as water is already obtained intrinsically by
dehydration.594
Calcination of layered double hydroxides (LDH), also
known as hydrotalcite, often leads to highly dispersed mixed-
metal oxides with remnant lamellar structures. This synthesis
methodology was used to design Mg-containing oxides for
CO2 adsorption. Ram Reddy et al.619,620 used Mg-Al oxides
nanoplatelets obtained by calcination of the corresponding
LDH at 200 °C. They found that at 200 °C, switching from
dry (14% CO2, 4% O2 in N2) to humid (12% H2O, 0.8% RH)
conditions increased CO2 uptake from 0.62 to 0.71 mmol/g.
Similarly, Hanif et al.621 carried out pure CO2 adsorption at
200 °C and 1.2 bar over Ni-Al-LDH nanosheets, prehydrated
at the same temperature. The CO2 uptake was found to be
1.22 mmol/g compared 0.66 mmol/g under dry conditions,
which was attributed to the formation of bicarbonate and
carbonate in the presence of water.621
In a series of studies, Coenen et al.622−626 investigated the
adsorption−desorption of CO2 under humid conditions over
potassium promoted hydrotalcite-derived mixed oxides,
consisting of ca. 20 wt % K and Mg/Al molar ratio of 0.54
(KMG30). Adsorption data in the presence of humid CO2 by
TGA-MS (400 °C, PH2O = 0.34 bar, PCO2 = 0.66 bar) and
column-breakthrough technique (400 °C, PH2O = 0.1 bar, PCO2
= 0.025 bar) were interpreted based on the occurrence of
multiple adsorption sites (A, B, C, and D) with different
affinities toward CO2 and water (Figure 54).623,624 In the
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Figure 56. Conversion of bidentate carbonate into bicarbonate along

Figure 54. (a) Proposed model and (b) regeneration of adsorption with the corresponding wavenumbers. Reproduced with permission
sites for CO2 and H2O on hydrotalcite-based Mg-Al mixed oxide from ref 625. Copyright 2018 Creative Commons Attribution License.
adsorbent at 400 °C. Reproduced with permission from refs 623 and
624, respectively. Copyright 2017 and 2018 Creative Commons
Attribution License.

presence of pure water and pure CO2, weight gains of 0.44 and
0.27 mmol/g were obtained, corresponding to adsorption on
sites A and B, respectively. Upon exposure of CO2-loaded
material to dry N2, not all CO2 desorbed. However, the use of
moist N2 led to complete removal of the remaining CO2, which
was associated with adsorption site C (Figure 55). Further
exposure to N2 led to complete H2O desorption, but when
CO2 was reintroduced, the CO2 capacity exceeded 0.27 mmol/
g. This increase was attributed to the displacement of adsorbed
H2O by CO2.
Figure 57. Infrared bands associated with CO2 and/or water
Site D can adsorb CO2 only in the presence of water and can
adsorption on different sites of KMG30. Reproduced with permission
be regenerated completely by using water or partly by using from ref 625. Copyright 2018 Creative Commons Attribution License.
nitrogen.623 Moreover, the presence of humidity during
desorption increased CO2 working capacity from 0.3 to 0.53
mmol/g, suggesting that water facilitated the recovery of CO2 and water on the same sites may be different for different
strongly bound CO2 species, particularly from site C. FTIR materials. Increasing MgO content was found to enhance the
data provided direct evidence that the beneficial impact of CO2 working capacity on site B, a basic site that can be
water on CO2 working capacity was due to the transformation regenerated under flowing nitrogen. Furthermore, the working
of strongly bound bidentate carbonate species into bicarbonate capacity for water on site A was slightly higher for KMG
as shown in Figure 56.625 sorbents relative to alumina hydrotalcite. Figure 58 shows
The proposed mechanism was further investigated by in situ comparative data for the three adsorbents as measured by
FTIR during CO2 and water coadsorption on KMG30.625 TGA. The total working capacity of CO2 and water depends
Figure 57 indicates the main IR bands associated with CO2 primarily on the effect of adsorbate partial pressure on
and/or water adsorption over the proposed four sites in adsorption over site C. Decreasing temperature led to an
KMG30. increase in the cyclic capacity of water on site A and a decrease
Further work on other LDH-derived materials such as in CO2 cyclic capacity on site B for all materials. Moreover, site
KMG70 (with Mg/Al ratio of 2.95) and alumina hydrotalcite C in KMG70 exhibited the highest CO2 working capacity at
(KSORB),624 indicated that the cyclic working capacity for 300 °C.624

Figure 55. (a) TGA profile for CO2-loaded Mg−Al mixed oxide exposed to four gases in sequence at 400 °C with PH2O = 0.34 bar PCO2 = 0.66 bar.
(b) Corresponding fixed bed reactor experiment at 400 °C with PH2O = 0.1 bar and PCO2 = 0.025 bar. Reproduced with permission from ref 623.
Copyright 2017 Creative Commons Attribution License.

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Figure 58. CO2 and water working capacity for different materials as
measured by TGA at PCO2 = 0.66 bar and PH2O = 0.34 bar. EQ =
equilibrium. Reproduced with permission from ref 624. Copyright
2018 Creative Commons Attribution License.
TGA data for CO2 and H2O coadsorption over KMG
sorbents in the range of 300−500 °C were adequately
described by a modified Elovich equation.626 The model
consisted of two chemisorption sites for CO2 and H2O, with a
third site for interactions between CO2, H2O, and the
adsorbent. Unlike the two former sites that can be regenerated
by flowing nitrogen, regeneration of the latter site was by
displacement adsorption of CO2 or water, depending of the
partial pressure of each adsorbate.
6.3. Other Metal Oxides
Water also plays a determining role in the CO2 adsorption
mechanism and structural evolution of other metal oxide
adsorbents. In the absence of moisture, CO2 reacts with the
hydroxylated surface of iron oxide to form bicarbonate,
whereas in the presence of water, CO2 reacts in a stepwise
process, giving rise to surface carbonate.627 Occurrence of a
thin layer of adsorbed water on oxide surfaces can impact their
interaction with CO2. Baltrusaitis et al.628 used FTIR to
investigate dry and humid CO2 adsorption at 23 °C on
hydroxylated Fe2O3, γ-Al2O3, and TiO2 nanoparticles. The
main adsorption products were bicarbonate and monodentate
and bidentate carbonates. In dry conditions, CO2 adsorption
led to the formation of different surface species, depending on
the basicity of the adsorption sites. For Fe2O3 and γ-Al2O3,
CO2 adsorbed primarily in the form of bicarbonate, whereas
for TiO2, mostly carbonate was formed in addition to traces of
carboxylate species. In the presence of moisture (40% RH),
CO2 reacted with a layer of adsorbed water to form solvated
hydronium carbonate. The CO2 initial adsorption rate was
higher in dry versus humid condition, suggesting rapid water
uptake followed by slow CO2 diffusion to form solvated
carbonates. Irrespective of the presence of water or the lack
thereof, the initial rate of adsorption decreased in the order
Fe2O3 > γ-Al2O3 > TiO2.
Likewise, CO2 reacts with ZnO and CuO surface hydroxyl
groups in dry conditions to form bicarbonate.168 Additionally,
the reaction between CO2 and surface defect sites and lattice
oxygen in dry conditions was associated with the formation of
surface monodentate and bidentate carbonate as well as
carboxylate species. Bicarbonate formation was found to
decrease with increasing humidity. Beyond 20% and 70% RH
for CuO and ZnO, respectively, CO2 adsorbed in the form of
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solvated carbonate. In line with the finding of Baltrusaitis et
al.,627 CO2 adsorption in the presence of humidity was
suggested to take place through the intermediacy of carbonic
acid, which may undergo deprotonation and further react with
surface hydroxyl groups to generate adsorbed carbonate (eqs
23−24, where (a) indicates adsorbed species). Therefore,
consumption of hydroxyl groups was observed in both dry and
humid conditions.
MOH + H+ ⇋ M − OH 2+ (22)
MOH + H 2CO3(a) ⇋ M − OH 2+ + HCO3(a)− (23)
MOH + HCO3(a)− ⇋ MOCO2(a)− + H 2O(a) (24)
Reactions 22−24 occur at low RHs, where surface coverage of
water is limited. Higher RHs gave rise to competition between
CO2 and intermediate species (H2CO3 and HCO3−) for
adsorption sites, as evidenced by increased conversion of
surface-adsorbed carbonate to solvated carbonate. With
increasing RH, the higher water to CO2 molar ratio in the
gas phase increased the likelihood of water to interact with the
oxide surface and form a barrier for direct CO2 adsorption to
form bicarbonate and carbonate species. Hence, at high RHs,
CO2 was adsorbed mainly in the form of solvated carbonate.168
In summary, the presence of water is essential for CO2
adsorption on alkali metal carbonates into bicarbonates.
Depending on the adsorbent and adsorption conditions,
humid CO2 adsorption over Na2CO3 may give rise to several
intermediate compounds, including Wegscheider’s salt
(Na2CO3·3NaHCO3), sodium sesquicarbonate (Na2CO3·
NaHCO3·2H2O), Na2CO3·H2O, and Na5H3(CO3)4. The
presence of humidity equally promotes CO2 adsorption on
K2CO3, presumably through the formation of K2CO3·
(1.5H2O), considered as a highly active phase for CO2
adsorption. For both adsorbents, pre-exposure of the material
to water vapor and increasing humidity during CO2 adsorption
enhanced CO2 uptake. The presence of water during CO2
capture over CaO and MgO-based materials is beneficial to
carbonation by enhancing the diffusion of CO2 through the
carbonate layer as a result of increased porosity. It also
promotes the calcination of CaCO3 by reducing the temper-
ature for CaCO3 decomposition while increasing its rate. For
potassium-promoted Mg-Al mixed oxide derived from hydro-
talcite, multiple adsorption sites with different affinity with
water and/or CO2 were proposed. Moreover, FTIR data
showed the beneficial impact of humidity in increasing the
CO2 working capacity of the material by converting the
strongly bound bidentate carbonate species into bicarbonate
during CO2 desorption. As for metal oxides with surface
hydroxyl groups, CO2 adsorbs in the form of bicarbonate and/
or carbonate in dry conditions. Although water preferentially
adsorbs on these surfaces, CO2 adsorption in the form of
solvated carbonate is enhanced in the presence of partially
humid surfaces, however, higher RH has an adverse effect on
CO2 uptake.
7. CONCLUSIONS AND OUTLOOK
Water is a ubiquitous component in all potential CO2 sources,
including air and industrial large point sources, such as flue
gases, biogas, and natural gas. As far as adsorption is
concerned, the wide variety of CO2 separation materials
exhibit as many different behaviors in the presence of water.
Depending on the material, water may promote or impede
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Chemical Reviews
CO2 adsorption, enhance or decrease the rate of CO2 uptake,
or even affect the structural integrity of the adsorbent.
Therefore, understanding how water affects the performance
of different adsorbents is of paramount importance in terms of
material development and process design.
In the presence of physical adsorbents such as ACs, zeolites,
and MOFs, CO2 capture at low to moderate pressures is often
adversely affected by water, mostly because of competitive
adsorption of water on preferred sites such as functional
groups in carbons, extra-framework cations in zeolites, and
coordinatively unsaturated sites in MOFs, or simply by pore
blocking. However, there are several exceptions to this
statement. At relatively high pressure in the presence of
carbon, water plays a positive role through enhanced CO2
solubility and formation of CO2 hydrate. Some MOFs are
unaffected by water because they are highly hydrophobic or
have distinct sites for water and CO2 adsorption or they
possess very specific enzyme-like pockets for CO2 adsorption,
with little interaction with water. As a general rule, MOFs with
high CO2 capacity and low Henry constant for water
adsorption are potential candidates for CO2 capture from
humid gas streams. The lack of hydrolytic stability of some
MOFs is an additional complicating factor that can be
overcome through appropriate material design. Another
potential strategy to circumvent the competitive effect of
water is to achieve kinetic separation, where the adsorption
stage is terminated while the water adsorption front is still
located at the entrance of the adsorption bed.
Because of their tolerance to water, amine-containing
adsorbents are among the most promising materials for DAC
and postcombustion CO2 capture. In the presence of moisture,
such materials often exhibit higher CO2 uptake because of
more favorable surface chemistry, shifting from carbamate
(CO2/N = 0.5) to bicarbonate (CO2/N = 1) formation and/or
enhanced diffusion of CO2 within the bulk of the material,
particularly for impregnated amine-containing polymers with
high amine content. Higher CO2 diffusion may stem from
reduced cross-linking due to the formation of bicarbonate
versus carbamate, polymer swelling, unfolding of the polymer
chain, or removal of hydrogen bonding in the presence of
water. More importantly, water is necessary to maintain the
long term stability of amine-containing adsorbents, precluding
the formation of stable urea linkages at the expense of CO2
adsorption sites. Nonetheless, unexpected water condensation,
for example, during steam regeneration, may bring about
polymer leaching or trigger −Si-O-Si− bond cleavage in
amine-grafted silicas.
As for reactive adsorbents such as metal oxides, hydroxides,
and carbonates, occurrence of water during CO2 capture is
either required or strongly recommended. Water often
increases the carbonation efficiency and rate through different
processes such as the formation of reactive intermediates or the
promotion of the material porosity, facilitating mass transfer
deeper into the adsorbent.
As a general rule, water enhances CO2 permeation and, to
some extent, selectivity of polymer-based membranes through
a variety of mechanisms that may involve polymer swelling
with decreased viscosity and larger free volume, increased CO2
solubility, facilitated CO2−carrier interactions, or the creation
of preferential CO2 transport pathways. In the presence of
inorganic membranes, such as zeolites, water often has an
adverse effect on CO2 permeability, particularly at low
temperatures, because of unfavorable competitive adsorption.
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Even when it plays a beneficial role, the main drawback of
water in CO2 capture by adsorption remains the energy penalty
associated with water vaporization during adsorbent regener-
ation. Moreover, there is often an optimum amount of
moisture for maximum benefit. However, because adjusting the
humidity of the gas feed does not seem to be economically
viable, the solution lies in the design of either the adsorbent
and/or the process. Innovative materials should be designed to
take full advantage of the beneficial effects of water without
excessive adsorption. It would also be advantageous if as little
water as possible desorbs during regeneration.
Almost all investigations dealing with the effect of water on
CO2 adsorption were limited to three-component gas mixtures,
CO2/H2O/N2, often with humidity levels below the water
content of typical large point source emissions. Future
directions may include the following:
• To undertake the next stages of material and process
development, it is essential to focus on the effect of
water vapor under industrially relevant concentrations
and for significantly longer periods of time to gain new
insights into the long-term behavior of adsorbents.
• Other species that often occur in industrial flue gases,
such as SOx, NOx, and O2 should be included in future
studies to understand their impact and mutual
interactions with water on CO2 uptake and the stability
of the material. Such insights are needed for process
simulation, optimization, and scale-up.
• Another water-related issue that needs to be addressed is
the effect of liquid water that may occur accidentally in
cold spots in the presence of water-saturated feeds, or
during steam regeneration. Condensed water may have a
number of negative effects. Liquid water may not only
block the adsorption of CO2 for most adsorbents but
may also induce significant changes in the number and
spatial distribution of CO2 adsorption sites, particularly
for amine-functionalized materials. As all impregnated
and tethered amines and polyamines are water-soluble,
they can be easily lixiviated out of the support and either
segregate on the material outer surface or be completely
washed out, depending on whether liquid water is
evaporated or removed as such. Similarly, grafted
aminosilanes leach readily in the presence of liquid
water through hydrolysis of their surface siloxane
bridges, leading to either significant removal of amine
groups or segregation of grafted amines into islands that
form as the water is evaporated. Segregation of amine
groups has a negative effect at least on the rate of
adsorption because of increased diffusion resistance.
Therefore, innovative solutions to overcome the adverse
effects of liquid water on CO2 adsorption should be
developed. This may include material hydrophobization
through grafting of alkyl chains or coating with
appropriate polymers.
• Another area of intensive research activity that was not
addressed in this review is the combined CO2 capture
and catalytic conversion into a variety of value-added
products, including synthetic natural gas,629,630 syn-
gas,629,631 and other chemicals,632,633 over dual function
materials (DFM). In single capture-conversion oper-
ations, selection of appropriate adsorbents is dictated
primarily by the conditions of the catalytic reaction,
particularly the temperature window.629,633 Moreover,
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Chemical Reviews
the CO2 conversion may be affected not only by water
but also by other feed gas impurities such as O2, SOx,
and NOx. High temperature reactions at ca. 200−400
°C, such as CO2 methanation and syngas production,
require metal oxide adsorbents, typically CaO, combined
with a catalyst, often a transition metal such as Ni or
Ru.634 Although nickel is an excellent and less costly
methanation catalyst, it is readily deactivated through
oxidation in the presence of typical flue gas containing
water and oxygen.634,635 CO2 conversion at lower
temperature, below ca. 120 °C, requires low temperature
adsorbents such as MOFs, polymers, and amine-
containing materials.631,633 Under such conditions,
water may be present not only in the gas phase, but
also in liquid phase, if the reaction is carried out at high
enough pressure.636 For example, in the popular reaction
of CO2 with epoxides, water may adversely affect the
yield of cyclic carbonate through the formation of
diols.636,637 Overall, the area of combined CO2 capture
and conversion is still wide open, with many research
opportunities to explore the advantages and disadvan-
tages of single versus two-step operations and investigate
the role of water on the state of the catalyst under
working condition and the reaction outcome.
AUTHOR INFORMATION
Corresponding Author
Abdelhamid Sayari − Centre for Catalysis Research and
Innovation, Department of Chemistry and Biomolecular
Sciences, University of Ottawa, Ottawa, Ontario K1N 6N5,
Canada; orcid.org/0000-0002-5424-6466;
Email: abdel.sayari@uottawa.ca
Authors
Joel M. Kolle − Centre for Catalysis Research and Innovation,
Department of Chemistry and Biomolecular Sciences,
University of Ottawa, Ottawa, Ontario K1N 6N5, Canada
Mohammadreza Fayaz − Centre for Catalysis Research and
Innovation, Department of Chemistry and Biomolecular
Sciences, University of Ottawa, Ottawa, Ontario K1N 6N5,
Canada
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.chemrev.0c00762
Notes
The authors declare no competing financial interest.
Biographies
Joel M. Kolle obtained his B.S. (2007) and M.S. (2012) degrees in
Chemistry from the University of Buea, Cameroon. He obtained a
second M.S. degree in Advanced Materials and Processes (2015) from
the University of Erlangen−Nürnberg, Germany, and a Ph.D. degree
in Chemistry (2020) from the University of Ottawa under the
supervision of Prof. Abdelhamid Sayari. His doctoral work focused on
the synthesis of porous organosilicas for CO2 adsorption and fixation
to valued chemicals. He is currently a Research Associate in Prof.
Sayari’s group, where he is looking at enhancing the oxidation/
leaching stability and low-cost synthesis of solid amine CO2 sorbents.
Mohammadreza Fayaz completed his Ph.D. in Environmental
Engineering at the University of Alberta, where he studied the
methods used to minimize irreversible adsorption of VOCs on
activated carbon. Following his Ph.D., he joined Prof. Sayari’s research
AW
pubs.acs.org/CR Review
group at the University of Ottawa as a postdoctoral fellow to develop
cost-effective silica-based adsorbents for CO2 capture. Later, he joined
Enerkem as an industrial Postdoctoral Fellow to conduct research on
catalytic conversion of syngas to valuable chemicals. Currently, he is a
surface scientist at Ingevity, working on the characterization of a
variety of adsorbents using experimental and theoretical methods.
Abdelhamid Sayari is Professor of Chemistry at the University of
Ottawa since 2001. In 1983−1985, he was a Postdoctoral Fellow at
the University of Pittsburgh, working on Fischer−Tropsch catalysis.
Then he moved to the National Research Council of Canada
(Ottawa) as Research Associate to work on the genesis of metallic
nanoparticles in zeolites before joining Université Laval (Québec) as
Professor of Chemical Engineering. He was a Tier-1 Canada Research
Chair (2002−2015) in Catalysis by mesostructured materials and
founding Director of the University of Ottawa’s Center for Catalysis
Research and Innovation. Abdel is currently a leading scientist in
postcombustion CO2 capture. He published more than 280 papers on
porous materials, catalysis, and adsorption, in addition to eight
patents, and edited four books on nanoporous materials.
ACKNOWLEDGMENTS
A.S. thanks the Natural Sciences and Engineering Research
Council of Canada (NSERC) for a Discovery Grant and a
Collaborative R&D Grant (CRDPJ 543657-19).
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