Copyright 2014 American Scientic Publishers

All rights reserved

Printed in the United States of America
Review
Journal of
Nanoscience
and Nanotechnology
Vol. 14, 112, 2014
www.aspbs.com/jnn
CO
2
Adsorption by Functionalized Nanoporous Materials
Nicola Gargiulo
1
, Francesco Pepe
2
, and Domenico Caputo
1
1
Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale, Universit Federico II,
P.le Tecchio 80, 80125 Napoli, Italy
2
Dipartimento di Ingegneria, Universit del Sannio, P.zza Roma 21, 82100 Benevento, Italy
This review highlights the recent advances in the development of functionalized nanoporous adsor-
bents for CO
2
capture. Three main classes of materials are taken into account: zeolites, mesoporous
silicates, and metal organic frameworks (MOFs). Proper modication of the cation content of zeo-
lites, as well as the introduction of functional groups such as amine groups into ordered mesoporous
silicates and MOFs, greatly enhance the CO
2
adsorptive properties of these substrates. Specically,
cation-exchanged zeolites can be currently considered the benchmark for ordered nanoporous CO
2
adsorbents, nding application also on a plant scale. Amino-functionalized mesoporous silicates
tend to show a high afnity toward CO
2
: while this could be an advantage when pushed purication
is needed, it also implies that full regeneration of the adsorbent can be achieved only by putting
its surface in contact with a completely CO
2
-free environment. On the contrary, similarly modied
MOFs show higher CO
2
adsorption working capacities: this potentially makes them even better
candidates than their mesoporous inorganic homologues for a plant scale use. However, the per-
sisting lack of reliable methods for the pelletization of both ordered mesoporous silicates and MOFs
creates a care for further development efforts in the next future.
Keywords: Nanoporous Materials, Zeolites, Mesoporous Silicates, Metal Organic Frameworks,
Functionalization, Cation Exchange, Amine Groups, CO
2
Capture, Adsorption.
CONTENTS
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. CO
2
Adsorption by Modied/Functionalized Zeolites . . . . . . . . 3
3. CO
2
Adsorption on Functionalized Mesoporous Silicates . . . . . 5
3.1. Synthesis of Mesoporous Silicates . . . . . . . . . . . . . . . . . . . 5
3.2. Functionalization of Mesoporous
Silicates for CO
2
Adsorption . . . . . . . . . . . . . . . . . . . . . . . 6
4. CO
2
Adsorption on Functionalized Metal Organic Frameworks 8
5. Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
References and Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1. INTRODUCTION
Carbon dioxide (CO
2
) is the most relevant contributor to
the greenhouse effect. However, more than 15 years after
the Kyoto protocol (1997), emissions of CO
2
and other
greenhouse gases continue to increase.
1
Therefore, it is
necessary to set up adequate technologies to avoid CO
2
production in the rst place and to avoid its release into the
atmosphere when no practical alternatives to its produc-
tion exist. Anthropogenic CO
2
emissions are mainly due
to combustion processes, even though a number of other

Author to whom correspondence should be addressed.

industrial processes, such as hydrogen production, give
signicant contributions.
2
One possible way to avoid CO
2
emissions from these processes is to remove this species
from the gaseous streams in which it is contained in order
to safely dispose of it in deep underground areas, such as
exhaust oil reservoirs or ocean sediments. Moreover, it is
important to observe that the issue of CO
2
removal from
a gaseous stream arises in other situations apart from con-
trol of CO
2
release into the atmosphere. Examples in this
sense are the processes for cryogenic air separation and
NH
3
synthesis. Indeed, in cryogenic air separation plants,
air sent to liquefaction must be de facto CO
2
-free; oth-
erwise, a blockage due to freezing in the heat exchange
equipment could result.
3
Similarly, in NH
3
synthesis by
the reaction between H
2
and N
2
, CO
2
is present in very
large amounts in the H
2
stream coming from the steam
reforming or the partial oxidation steps, and its concentra-
tion must be reduced to parts per million levels in order
to avoid problems with the synthesis reactor.
3
CO
2
removal from gaseous streams has been histori-
cally carried out by physical or chemical absorption, using
aqueous solvents, such as moderately concentrated amine
J. Nanosci. Nanotechnol. 2014, Vol. 14, No. xx 1533-4880/2014/14/001/012 doi:10.1166/jnn.2014.8893 1
CO
2
Adsorption by Functionalized Nanoporous Materials Gargiulo et al.
solutions, or potassium carbonate solutions. An impor-
tant alternative technology is represented by adsorption,
usually carried out as pressure swing adsorption (PSA)
or sometimes as vacuum swing adsorption (VSA).
4
The
materials more often considered for PSA/VSA processes
are nanoporous adsorbents,
525
in particular microporous
adsorbents (whose pore sizes do not exceed 2 nm) and
mesoporous adsorbents (whose pore sizes are between 2
and 50 nm).
26
To be considered a suitable material for the
adsorption of a specic gas species, there are three main
functionalities that an adsorbent should feature:
(1) High adsorption capacity toward the target species,
i.e., the value of the amount of adsorbed substance reached
in saturation conditions;
7
Nicola Gargiulo obtained his M.Eng. degree in Chemical Engineering in 2003 from Fed-
erico II University of Naples, Italy. He did his postgraduate studies at the Materials and
Production Engineering Department of the Federico II University of Naples, where he
completed his Ph.D. in Chemical, Materials and Production Engineering in 2006. He
then worked as a postdoc fellow for several academic institutions, including the Depart-
ment for Technologies of the Parthenope University of Naples (20072008), the Engi-
neering Department of the University of Sannio (20092010) and the Interdisciplinary
Research Center on Biomaterials of the Federico II University of Naples (20112012).
He is currently a postdoc fellow at the Chemical, Materials and Industrial Production
Engineering Department of the Federico II University of Naples. His research inter-
ests include the synthesis, modication, and characterization of nanoporous materials for
adsorption/separation/purication applications, controlled release, and bioactivity-related processes. He has published
over 30 scientic publications in refereed journals and conference proceedings.
Francesco Pepe graduated cum laude in Chemical Engineering in 1990 from Federico
II University of Naples, Italy, and in 1994 he got his Ph.D. in Chemical Engineering
from the same university. In 19921993 he held a fellowship from the Department of
Chemical Engineering of the University of Texas at Austin. From 19941998 he has been
Research Professor of Chemical Engineering with the Second University of Naples. From
19982002 he was an Associate Professor of Chemical Engineering with the Alma Mater
University of Bologna, Italy. Since 2002 he has been an Associate Professor of Chemical
Engineering with the University of Sannio, Italy. From 20072012 he sat on the board
of that university. His scientic activity focuses mainly on the modeling of the coupling
between mass transfer and chemical reactions, and on reactive processes in the context
of environmental applications of Chemical Engineering. He has published more than 40
papers in refereed journals and more than 50 papers in conference proceedings.
Domenico Caputo graduated in Chemical Engineering at Federico II University of Naples
in 1993. He obtained his Ph.D. in Materials Engineering at La Sapienza University of
Rome in 1998. From November 1999 to October 2002, he was a Research Associate at
the Department of Materials and Production Engineering of the Federico II University of
Naples. Since November 2002 he has been Associate Professor of Materials Science and
Technology in the same department, now merged (from January 2013) into the Department
of Chemical, Materials and Industrial Production Engineering (DICMAPI) of Federico II
University. His research activity and scientic coordination are essentially devoted to the
science and technology of microporous and mesoporous materials, as demonstrated by an
international patent and over 160 papers in refereed journals and conference proceedings,
mostly on the synthesis and characterization of nanostructured microporous and meso-
porous materials and their use as adsorbents and/or ion exchangers for energy and environmental applications, such as
gas separation/purication, energy and gas storage, wastewater treatment, and the stabilization-solidication of toxic
and noxious sludges.
(2) High selectivity toward the target species, which can
be dened, e.g., for a binary mixture, as the ratio of
adsorbed amounts of each component normalized by the
bulk compositions;
8
(3) Full regeneration capacity, which implies the possibil-
ity of removing the previously adsorbed molecules from
the substrate by means of simple, non-expensive opera-
tions, in order to prepare the adsorbent for its successive
adsorption cycle.
High adsorption capacities can be roughly achieved by
using adsorbents endowed with high textural properties:
this is one of the reasons that, during recent years,
pushed the research toward the design and the synthesis
of nanoporous materials whose values of specic surface
2 J. Nanosci. Nanotechnol. 14, 112, 2014
Gargiulo et al. CO
2
Adsorption by Functionalized Nanoporous Materials
area are continuously increasing.
29
This approach clearly
reveals itself inadequate when it comes to selectivity:
indeed, when no distinct adsorbent/adsorbate interaction
is taken into account, a high specic surface area implies
high adsorbed amounts of both the target species and the
rest of the to-be-treated gas mixture. This limit can be
challenged either by synthesizing high surface area mate-
rials that intrinsically contain specic adsorption sites in
their structures or by partially modifying the chemical
nature of substrates whose pristine adsorption capabilities
rely only on their textural properties. The latter approach
can be followed through several routes that generically
fall under the process category known as functionalization.
With respect to the direct synthesis of selective adsorbents,
functionalization procedures often choose a single optimal
substrate in terms of textural features and tune its physic-
ochemical properties in different ways, in order to make it
selective toward different target species.
This review will highlight the recent advances in the
development of functionalized nanoporous adsorbents for
CO
2
capture. Three main classes of materials will be
taken into account: zeolites, mesoporous silicates, and
metal organic frameworks (MOFs). Because functional-
ization procedures sometimes induce such strong adsor-
bent/adsorbate interactions that the regeneration of the
adsorbent is difcult, the rationale of the literature sur-
vey will consist in the search for the adsorbents that
do not only perform the best in terms of adsorption
capacity and selectivity, but also in terms of regeneration
capacity.
2. CO
2
ADSORPTION BY
MODIFIED/FUNCTIONALIZED ZEOLITES
Zeolites are porous crystalline aluminosilicates, whose
framework consists of interlocking SiO
4
and AlO
4
tetra-
hedra joined together in various regular arrangements
through shared oxygen atoms.
30
This framework contains
open cavities in the form of channels and cages, which are
usually occupied by guest molecules and extra-framework
exchangeable cations (namely Na
+
, K
+
, Ca
2+
, Mg
2+
) bal-
ancing the negative charge created by the isomorphous
replacement of Si
4+
by Al
3+
in the structure. Synthetic and
natural zeolites have been used for adsorption-based sep-
arations for many years, nding applications in numerous
elds.
3034
The adsorption and gas separation properties
of zeolites are heavily dependent on several factors,
35, 36
including:
Size, charge density, polarizing power, and distribution
and number of cations in the porous structure;
Si/Al ratio of the framework;
Size and morphology of the pores;
Polarity, size, and shape of the adsorbate molecules;
The presence of water and other molecules or com-
pounds in the pores and/or on the surface (either internal
or external).
General reviews on CO
2
adsorption on zeolites (and some-
times also on different sorbents) have been presented by
Bonenfant et al.
36
Hao et al.
37
Wang et al.
38
and Samanta
et al.
39
Taking into account the work done so far, the present
review draws attention to the possibilities of improving
CO
2
adsorption of zeolites by modication procedures
based on cation exchange or impregnation techniques.
Exchanged cations inuence the electric eld inside the
pores, as well as the available pore volume, and pro-
vide a convenient way for tuning the adsorptive proper-
ties of zeolites.
38
In general, the polarizing power of a
given cation is higher when its ionic radius is smaller.
For instance, the diameters of alkaline cations vary in
the following order: Cs
+
(3.3 ) > Rb
+
(2.9 ) > K
+
(2.7 ) > Na
+
(1.9 ) > Li
+
(1.4 ); conversely, their
polarity follows the sequence: Li
+
> Na
+
> K
+
> Rb
+
>
Cs
+
.
36
Therefore, energy of the interaction between CO
2
molecules and extra-framework cations in the zeolites, and
consequently the adsorption capacity, decreases with the
increase of the size of these cations, as conrmed by sev-
eral studies focused on the modication of zeolites via
the introduction of alkali (and alkaline-earth) cations to
enhance CO
2
adsorption.
4050
Walton et al.
40
studied CO
2
adsorption behavior of
faujasite-type zeolites, specically X and Y terms,
exchanged with Li
+
, K
+
, Na
+
, Rb
+
, and Cs
+
, and found
that the largest CO
2
capacity was obtained for the Li-
containing zeolite. It was suggested that this is due to the
fact that CO
2
molecules have a high quadrupole moment
(14.29 10
40
C m
2
), they can interact more strongly
with smaller cations, such as Li
+
. Adsorption of CO
2
on
Y and X zeolites exchanged with Cs
+
was tested with
fairly good results also at relatively high temperatures
(373473 K) by Diaz et al.
41, 42
Dunne at al.
43
Yamazaki et al.
44
Katoh at al.
45
and
Wirawan and Creaser
46, 47
studied the adsorption behav-
ior of cation-exchanged ZSM-5 zeolites, M-ZSM-5 (where
M = Li, Na, K, Rb, Cs, H, Ba) in CO
2
separation from
other gaseous species. They found a high CO
2
selectiv-
ity for most zeolites tested, probably due to the fact that
almost all CO
2
molecules are strongly adsorbed on the
cation sites. Compared to other cation-exchanged forms,
Ba-ZSM-5 exhibited the highest CO
2
adsorption capac-
ity and the adsorbed species also has a higher thermal
stability.
47
Zhang et al.
48
prepared a synthetic chabazite-type zeo-
lites and exchanged them with alkaline cations (namely
Li
+
, Na
+
, and K
+
) and alkaline-earth cations (namely
Mg
2+
, Ca
2+
, and Ba
2+
) to assess their potential for CO
2
capture from ue gas. It was found that Na- and Ca-forms
of chabazite have comparative advantages for high tem-
perature CO
2
separation. Recently Bae et al.
49
found that
CaA (i.e., the Ca-exchanged form of zeolite A) exhibits
better performance with respect to NaA and MgA for
CO
2
capture from dry ue gas of a coal-red power plant,
J. Nanosci. Nanotechnol. 14, 112, 2014 3
CO
2
Adsorption by Functionalized Nanoporous Materials Gargiulo et al.
displaying a highly selective uptake and rapid adsorption
kinetics. Fast and relevant CO
2
adsorption rates have been
also reported by Cheung et al.
50
for NaKA. Zeolites
exchanged with transition metal cations were also inves-
tigated, but poorer selectivities were found.
5156
Among
the rst, Coughlan and Kilmartin
51
and Coughlan and
McCann
52
showed a decrease of CO
2
afnity after an
introduction of trivalent cations (Fe
3+
, Y
3+
, Cr
3+
, Co
3+
,
and Tl
3+
) in the X, Y, A, and L zeolites. As indicated by
these authors, this result could be generalized to all the
polyvalent cations of transition metals.
52
Khelifa et al.
53, 54
conrmed a decrease of the CO
2
adsorption afnity when
Na
+
cations of an X-type zeolite are exchanged by Zn
2+
,
Cu
2+
, Mg
2+
, and Sr
2+
. Khelifa et al.
55
also observed that
Na-X zeolite exchanged with Ni
2+
and Cr
3+
showed a
decrease in CO
2
adsorption capacity, compared to that
of the parent Na-X zeolite. They attributed this effect to
a general decrease in the adsorbate-adsorbent interaction.
However, other results appear to indicate that the substi-
tution of Na
+
with some divalent cations or with Cr
3+
cations has a signicant effect on CO
2
adsorption only
when the exchanged amount is higher than 4050%.
53, 55, 56
Although to a lesser extent, also natural zeolites, mostly
clinoptilolites, have been studied as adsorbents for CO
2
capture.
33, 57, 58
The inuence of cation exchange on CO
2
adsorption kinetics were studied by Aguilar et al.
57
for
Na-, K- and Ca-exchanged clinoptilolite-rich volcanic tuff.
Adsorption rate values decreasing in the order Ca
2+
>
K
+
> Na
+
as cation-exchanged form were obtained.
A clinoptilolite and its K- and Ca-exchanged forms were
also investigated by Rege et al.
58
The experimental and
modeling study of both adsorption isotherms and kinetics
revealed that K-clinoptilolite was an ideal sorbent for CO
2
removal as well as Na-X zeolite.
Table I reports a synopsis of some of the most rele-
vant results mentioned above. An important research topic
in the use of zeolites for post-combustion CO
2
removal
is represented by the selection of the kind of appara-
tus to be used, and by the individuation of the optimal
operating conditions for this apparatus. Most authors con-
sidered the use of a Pressure Swing Adsorption (PSA)
apparatus
59
and worked on the individuation of the opti-
mal operating conditions (working temperature, number of
cycles, etc.) for the minimization of energy costs associ-
ated with CO
2
removal and the production of high purity
streams. Siriwardane et al.
60
suggested a rather high oper-
ating temperature (493 K) for the optimization of the sep-
aration process.
Ho et al.
61
estimated the costs connected to PSA
applications for post-combustion CO
2
capture, concluding
that, under specic conditions, these costs can be lower
than those associated with traditional amine scrubbing,
a result that has been later conrmed by Lively et al.
62
who mentioned the crucial role of heat integration for cost
reduction. Li et al.
63
and Xiao et al.
64
proposed a lower
Table I. CO
2
adsorption capacity of selected cation-exchanged zeolites.
CO
2
adsorption
Temperature Pressure capacity Experimental
Zeolite (K) (kPa) (mol/kg) procedure Ref.
Li-X 298 100 5.62 Gravimetric [40]
Na-X 4.98
K-X 4.44
Rb-X 4.08
Cs-X 3.09
Cs-X 373 100 0.23 TPD* [41]
Li-Y 298 100 5.21 Gravimetric [40]
Na-Y 5.18
K-Y 4.40
Rb-Y 4.48
Cs-Y 2.57
Cs-Y 373 100 0.03 TPD

[42]
H-ZSM-5 323 80 1.30 Mass [43]
Na-ZSM-5 1,70 spectroscopic
Ba-ZSM-5 1.85
Li-CHA 273 100 5.17 Volumetric [48]
Na-CHA 4.92
K-CHA 4.41
Mg-CHA 4.25
Ca-CHA 4.58
Ba-CHA 3.45
Na-A 298 100 3.10 Volumetric [49]
Mg-A 3.90
Ca-A 5.00
Note:

TPD =temperature programmed desorption.
pressure version of PSA (vacuum swing adsorption, VSA)
using 13 zeolite as adsorbent, and reported a very high
CO
2
removal efciency, even in the presence of water
vapor.
An interesting process, namely temperature swing
adsorption (TSA) with indirect heating, was suggested by
Merel et al.
65, 66
Also Tlili et al.
67
observed that TSA (in
this case with direct heating) can give very good perfor-
mances. Another interesting study on this subject was car-
ried out by Zhang et al.
68
who found that some kinds of
exchanged chabazites have better performances for PSA
applications that 13 at temperatures of 333 K and higher.
Going back to the use of zeolitic substrates for CO
2
adsorption, it is important to mention that, with the aim
of individuating adsorbing materials having better perfor-
mances, a signicant attention has been paid to the effect
of surface modications capable of increasing the CO
2
adsorption capacity and/or giving better performances at
higher temperatures. Since amine-based chemical absorp-
tion is one of the most common techniques for CO
2
removal used in industry,
69
several studies have explored
the integration of organic amines into porous supports for
CO
2
adsorption (also see the following sections of the
present paper). Birbara et al.
70
mentioned zeolites among
possible supports for amines already in 1999. Afterwards,
Jadhav et al.
71
and Chatti et al.
72
prepared novel function-
alized adsorbents by immobilizing various amine on 13
zeolite. Those authors showed signicant enhancements
4 J. Nanosci. Nanotechnol. 14, 112, 2014
Gargiulo et al. CO
2
Adsorption by Functionalized Nanoporous Materials
Table II. CO
2
adsorption capacity of selected amino-functionalized zeolites.
CO
2
adsorption
Zeolite Functionalizing agent Temperature (K) Pressure (kPa) capacity (mol/kg) Experimental procedure Ref.
Na-X Monoethanolamine (MEA) 348 100 1.11 Volumetric [72]
0.45 Breakthrough
Isopropanolamine (IPA) 0.52 Breakthrough
Y(60)

Tetraethylenepentamine (TEPA) 333 50 3.34 Breakthrough [76]

Note:

Zeolite Y with a Si/Al molar ratio of 60.
(up to 50% at ambient temperature) in the CO
2
adsorp-
tion capacity of these materials over that of the unmodied
13. Similarly, Xu et al.
73
indicated that functionalization
with amines induces a signicant increase in CO
2
selec-
tivity against N
2
, with obvious implications for possible
applications of the proposed sorbent. Zukal et al.
74
worked
on the comparison between functionalized zeolites and
functionalized mesoporous sorbents, showing that, under
given circumstances, functionalized zeolites can give bet-
ter performances (on this subject, see also Hao et al.).
75
One of the most complete studies to date on the sub-
ject of functionalization of zeolites with amines has been
presented by Su et al.
76
who used a Y-type zeolite with a
Si/Al molar ratio of 60 (Y60) modied with tetraethylene-
pentamine (TEPA). They noticed that the surface charac-
teristics of Y60 signicantly changed after TEPA grafting
and observed a signicant enhancement in CO
2
adsorption
capacity. Those authors also found that the CO
2
adsorp-
tion capacity of TEPA-Y60 increased with temperature in
the interval 303333 K (then decreasing for T > 333 K),
and also that it was positively inuenced by the presence
of water vapor. Repeated adsorptiondesorption cycles
showed that the physicochemical properties of TEPA-Y60
were kept almost unaltered, suggesting that it could be
considered for industrial applications as a possible cost-
effective sorbent for CO
2
capture from ue gas. Quite
recently Lee at al.
77
worked with a similar compound
(a Y-type zeolite with a Si/Al molar ratio of 8, named Y8,
modied with TEPA) for the capture and concentration of
CO
2
for indoor air quality control applications. Also in
this case the CO
2
adsorption features of TEPA-Y8 were
substantially higher than those of the original Y8 zeolite.
Table II reports a synopsis of some selected results con-
cerning CO
2
capture by amino-functionalized zeolites.
3. CO
2
ADSORPTION ON FUNCTIONALIZED
MESOPOROUS SILICATES
Ordered mesoporous silicates constitute a large class of
mainly amorphous materials having high surface area (usu-
ally, hundreds of m
2
/g) and long-range ordered pore struc-
tures suitable for catalysis and separation processes.
78
Table III summarizes the main sub-classes of mesoporous
silicates synthesized so far: the rst ordered mesoporous
silicates historically reported in the literature were grouped
in a family termed M41S,
79
whose discovery was soon
followed by that of the so-called folded sheet mesoporous
material-16 (FSM-16).
80
Their emerging applications in
catalysis, adsorption, and separation have boosted the
development of many other ordered mesoporous silicates
such as the Santa Barbara Amorphous (SBA) family,
81, 82
the Korea Advanced Institute of Science and Technology
(KIT) series,
83
and the anionic-surfactant-templated meso-
porous silicas (AMSs).
84
3.1. Synthesis of Mesoporous Silicates
Mesoporous silicates are usually synthesized by a micelle-
templating process, either following an electrostatically-
driven cooperative assembly route or a nonionic one
in the presence of surfactants as structure directing
agents.
85
Electrostatic interaction is, for example, the driv-
ing process leading to ordered mesoporous silicates such
as those belonging to the M41S family: in this case,
alkyltrimethylammonium cations are used to develop tem-
plating micelles under alkaline conditions.
86
The nonionic
pathway works with neutral oligomeric surfactants, tri-
block and star diblock copolymers for the synthesis of
mesoporous silicates such as SBA-11, SBA-12 and SBA-
15:
82
in this case, hydrogen bonding is the main driving
force for pairing inorganic and organic species in the pres-
ence of templating micelles under acid conditions.
86
More
recently, the massive production and relatively low cost of
anionic surfactants has attracted researchers focus on the
synthesis of ordered mesoporous silicates using anionic
surfactants as templates: in particular, Tatsumi and co-
workers
84, 87
reported the synthesis of anionic-templated
mesoporous silicates (AMSs) in which an organoalkoxysi-
lane with a positively charged (protonated amine) func-
tional group is introduced as an additional silica source
to interact with the negatively charged sulfate headgroups
of the anionic surfactant, thus forming the silica-micelle
composite.
Regardless of the chosen template and silica source,
hydrothermal treatment is the most used synthesis method
to obtain mesoporous silicates: it can be carried out by
means of both common oven heating
88
and microwave
assisted heating.
89
Alternatively, the solgel process is
another well-established route to obtain mesoporous sil-
icates involving the hydrolysis and condensation of the
silica precursor to form a colloidal sol for the synthe-
sis of these porous inorganic materials.
90
Finally, every
synthesis method envisages a following template removal
J. Nanosci. Nanotechnol. 14, 112, 2014 5
CO
2
Adsorption by Functionalized Nanoporous Materials Gargiulo et al.
Table III. Main families of mesoporous silicates.
Family of
mesoporous
silicates Silica sources Templating agents Synthesis environment Pore size range (nm) Refs.
M41S Sodium silicate,
tetraethylortosilicate
(TEOS), silica fume
Alkyltrimethylammonium halides,
gemini surfactants
Alkaline 210 [79]
FSM Layered silicates
(kanemite)
Alkyltrimethylammonium halides Alkaline 210 [80]
SBA Sodium silicate, TEOS Alkyltrimethylammonium halides,
ethylene oxide-based block
copolymers
Acid 530 [81, 82]
KIT Colloidal silica Alkyltrimethylammonium halides Alkaline 210 [83]
AMS TEOS, aminosilanes Anionic surfactants Alkaline 26 [84]
step, that can be performed either by a thermal treat-
ment or by extraction techniques: depending on the chosen
removal method, different surface chemical properties can
be obtained for the same structure.
91
3.2. Functionalization of Mesoporous
Silicates for CO
2
Adsorption
In mesoporous silicates, pure silica surfaces do not pro-
vide strong adsorption sites (i.e., strong afnity/selectivity)
for CO
2
due to the fact that the residual hydroxyl groups
attached to the silica surfaces after the template removal
step fail to induce signicant interactions with CO
2
. How-
ever, modication of mesoporous silicates with functional
groups is the gold standard for tuning their properties and
hence to increase the adsorbent-adsorbate interactions.
92
In the literature, there are already specic reviews, whose
reading is strongly suggested, about CO
2
adsorption on
functionalized mesoporous silicates:
93
from these sources,
it can be inferred how the functional group mostly used
to enhance CO
2
adsorption properties is the amino group.
Indeed, there are several studies on aminosilane-modied
silicates due to their different possible applications, rang-
ing from the adsorption of organic dye molecules
94
to
the release of pre-loaded chemically/biologically active
species.
95, 96
Owing to the steric hindrance of aminosilanes,
it is usually hard to use them for the pore functionalization
of microporous adsorbents (e.g., zeolites), whereas ordered
mesoporous silicates are highly suitable for surface mod-
ication with aminosilanes due to their large and uniform
pores.
97
Table IV shows the main studies on the amino-
functionalization of ordered mesoporous silicates for CO
2
adsorption and separation. Usually, the modication with
different aminosilanes or amino-functional polymers was
shown to decrease the textural properties of the meso-
porous silicates due to the partial/complete lling of pores
by the modifying agents;
109
however, the corresponding
increase in CO
2
adsorption capacity is often remarkable
(up to more than one order of magnitude when expressed
in mol/kg).
106
As shown in Table IV, functionalizing
agents can be either covalently attached to the previously
synthesized mesoporous substrates or added by impregna-
tion; one-step silylation, where amine groups are grafted
simultaneously to the mesophase assembly, can also be
considered:
122
in some cases, this appeared to be a better
functionalization method over post-synthesis grafting for
higher CO
2
adsorption capacity,
124
even though one-step
silylation was often proved to seriously compromise the
textural uniformity of the synthesized mesophase.
125
The different types of aminosilanes or polymers
containing amino groups that are used to functionalize
mesoporous silicates clearly lead to quite different CO
2
adsorption performances. In particular, it can be eas-
ily inferred how the CO
2
adsorption capacity increases
with increase in the amine content of the functionalized
substrate and how, in turn, it increases with the amine con-
tent in the single aminosilane molecule.
122
Since adsorp-
tion is an exothermic process, an increase in temperature
usually leads to a decrease in the adsorption capacity:
while this is basically conrmed for aminosilane-grafted
mesoporous silicates,
126
it is surprisingly contradicted for
polyethyleneimine (PEI)-impregnated adsorbents.
106, 123
As
an example, Figure 1 reports CO
2
adsorption isotherms
on PEI-functionalized TUD-1 mesoporous silicate at 298,
313, 328, and 348 K.
123
Inspection of Figure 1 shows
that the highest CO
2
adsorption capacity was observed
at 348 K, turning out to be about 3 mol/kg. This result
depends on the fact that when temperature increases, PEI
chains become more and more exible, leading to an
increase in the number of CO
2
-afnity sites.
120
It should
be noted that almost all papers regarding CO
2
adsorption
on PEI-functionalized mesoporous silicates consider 348 K
as the maximum temperature for performing adsorption
runs because, for temperatures higher than 350 K, sorbent
degradation usually starts to occur.
123
Such peculiarities of
PEI-functionalized mesoporous silicates radically change
the point of view for what is regarded as the operating tem-
peratures of the adsorption process: indeed, since xed-bed
adsorption is an essentially adiabatic operation, the isos-
teric heat of adsorption is responsible for the temperature
rise during the process. Once the working pressure range
is xed, adsorbent materials used in xed-bed adsorption
6 J. Nanosci. Nanotechnol. 14, 112, 2014
Gargiulo et al. CO
2
Adsorption by Functionalized Nanoporous Materials
Table IV. Amino-functionalized ordered mesoporous silicates for CO
2
adsorption. Where not explicitly reported in the cited papers, CO
2
adsorption
capacity values were extracted from plots using the DataThief software.
CO
2
adsorption
Mesophase Functionalizing agent Functionalization method capacity (mol/kg) Ref.
MCM-41 Diethanolamine Impregnation 2.36 [98]
3-[2-(2-aminoethylamino)ethylamino]propyl
trimethoxysilane
Post-synthesis grafting 1.411.52 [99]
2.65 [100]
N-p-(aminoethyl)--aminopropyl dimethoxy
methylsilane
Post-synthesis grafting 2.20 [101]
Tetraethylenepentamine Impregnation 5.39 [102]
(3-aminopropyl)trimethoxysilane Post-synthesis grafting 3.27 [103]
Tris(2-aminoethyl)amine Post-synthesis grafting 1.36 [104]
(3-aminopropyl)triethoxysilane Post-synthesis grafting 1.20 [105]
Polyethylenimine Impregnation 5.59 [106]
SBA-15 Tetraethylenepentamine Impregnation 3.93 [107]
Tetraethylenepentamine/diethanolamine mixture Impregnation 3.70 [108]
(3-aminopropyl)triethoxysilane Post-synthesis grafting 1.54 [109]
Aziridine-derived aminopolymers Post-synthesis grafting 5.55 [110]
(3-trimethoxysilylpropyl)diethylenetriamine Post-synthesis grafting 2.41 [111]
Octa(3-aminophenyl)octasilsesquioxane Post-synthesis grafting 1.89 [112]
3-chloropropyl amine hydrochloride Post-synthesis grafting 1.70 [113]
Tris(2-aminoethyl)amine Post-synthesis grafting 1.591.82 [114]
Polyethylenimine Impregnation 1.48 [115]
1.56 [116]
3.14 [117]
SBA-12 (3-aminopropyl)triethoxysilane Post-synthesis grafting 1.04 [118]
SBA-16 N-(2-aminoethyl)-3-aminopropyltrimethoxysilane Post-synthesis grafting 0.73 [119]
KIT-6 Polyethylenimine Impregnation 3.07 [120]
Tetraethylenepentamine Impregnation 2.90 [121]
Lauric acid-
templated AMS
3-[2-(2-aminoethylamino)ethylamino]propyl
trimethoxysilane
Co-condensation 1.74 [122]
TUD-1 Polyethylenimine Impregnation 2.93 [123]
processes usually tend to lose part of their adsorption
capacity as the working temperature increases. In the case
of PEI-functionalized mesoporous silicates, the operating
temperature must be kept below 350 K to preserve the
integrity of the adsorbent, but also as near as possible to
this limit in order to maximize the adsorption capacity of
the bed.
Figure 1. CO
2
adsorption isotherms on polyethyleneimine-
functionalized TUD-1 mesoporous silicate at 298 K (circles), 313 K
(squares), 328 K (diamonds) and 348 K (triangles).
The enhancement in CO
2
adsorption due to the func-
tionalization of mesoporous silicates with amine groups
relies on the acid-base chemical interaction between CO
2
and amine groups,
127
leading to formation of carbamate
or bicarbonate species. Under dry conditions, the reaction
between CO
2
molecules and amine groups or polymers
containing amino groups lead to the formation of carba-
mates as shown in the following equations:
123, 128
CO
2
+2RNH
2
RNHCOO

+RNH
+
3
(1)
CO
2
+2R
2
NH R
2
NCOO

+R
2
NH
+
2
(2)
CO
2
+R
2
NH+R

NH
2
R
2
NCOO

+R

NH
+
3
(3)
In the presence of water vapor, every mole of amino
moieties can react with half an additional mole of
CO
2
, forming bicarbonates as shown in the following
equations:
129
CO
2
+RNH
2
+H
2
O HCO

3
+RNH
+
3
(4)
CO
2
+R
2
NH+H
2
O HCO

3
+R
2
NH
+
2
(5)
This is another peculiarity of amino-functionalized
mesoporous silicates with respect to more traditional
adsorbents (e.g., zeolites), for which the presence of mois-
ture usually decreases their adsorption capacity.
J. Nanosci. Nanotechnol. 14, 112, 2014 7
CO
2
Adsorption by Functionalized Nanoporous Materials Gargiulo et al.
As regards the selectivity of amino-functionalized meso-
porous silicates toward CO
2
, interesting results were
reported about the separation of CO
2
from ue gas-type
streams. Indeed, Xu et al.
130
applied PEI-impregnated
MCM-41 in the separation of CO
2
from the ue gas of a
natural gas red boiler. The adsorbent adsorbed very few
N
2
, O
2
, and CO from the ue gas, while moisture had
a promoting effect on the adsorption of CO
2
. The adsor-
bent simultaneously adsorbed CO
2
and NO
x
from ue
gas: although the adsorbed amount of CO
2
was around
3000 times larger than that of NO
x
, very few NO
x
des-
orbed during the regeneration of the substrate, indicating
the need for pre-removal of NO
x
from ue gas before cap-
turing CO
2
. In general, amino-functionalized mesoporous
silicates (particularly PEI-impregnated materials) tend to
show high afnity toward CO
2
molecules, i.e., remarkable
amounts of CO
2
can be adsorbed even when CO
2
activity
is very low. While this could be an advantage when pushed
purication is needed, it also implies that full regenera-
tion of the adsorbent can be achieved only by putting its
surface in contact with a completely CO
2
-free environ-
ment, e.g., a completely CO
2
-free purge stream or high
vacuum.
As specically regards the regeneration capacities
of amino-functionalized mesoporous silicates for CO
2
adsorption, good results are reported for post-synthetically
grafted materials: as an example, Hicks et al.
131
success-
fully amino-functionalized SBA-type mesostructures by a
one-step spontaneous aziridine ring-opening polymeriza-
tion off of surface silanols. The adsorption measurements
were performed in a xed-bed ow reactor using humid-
ied CO
2
, and the stability of the organic groups cova-
lently bound to the silica support was veried to be higher
than that of tetraethylenepentamine molecules loaded by
impregnation in the same starting pristine substrate: in the
latter case, the longevity of the adsorbent appeared limited
due to leaching of the organics from the support. This issue
seems to be solved when using impregnating molecules
with signicantly higher molecular weight: as an exam-
ple, Qi et al.
132
developed PEI-impregnated mesoporous
silica capsules as a high efciency nanocomposite sorbent
for CO
2
capture; these adsorbents exhibited extraordinary
capture capacity up to 7.9 mol/kg under simulated ue
gas conditions and showed good reversibility and sta-
bility during cyclic adsorption-regeneration tests up to
50 cycles.
All these observations allow the conclusion that various
amino-functionalized mesoporous silicates show all the
features required for efcient CO
2
adsorption processes;
the actual issue that still limits their use on a plant scale is
the lack of reliable methods for their pelletization: indeed,
there are very few papers in the literature that specically
deal with the functionalization of mesoporous silica mono-
liths for CO
2
adsorption,
133
so further developments in this
sense are expected in the next future.
4. CO
2
ADSORPTION ON FUNCTIONALIZED
METAL ORGANIC FRAMEWORKS
Despite the potentialities of functionalized mesoporous
silicates in CO
2
adsorption still are under development,
many recent research efforts have been also lavished in
the study of adsorbent materials belonging to the class
of microporous metal organic frameworks (MOFs), which
showed to be good candidates for improving performances
of adsorption-based CO
2
sequestration processes.
MOFs are hybrid materials where metal ions or
small metallic nanoclusters are linked into one-, two- or
three-dimensional structures by multi-functional organic
linkers.
134
Several MOFs have been proposed as adsor-
bents for CO
2
separation processes,
135
and among these
are MIL-47 [polymeric vanadium(IV) benzene-1,4-
dicarboxylate], MIL-53 [porous chromium(III) benzene-
1,4-dicarboxylate] and Cu-BTC [polymeric copper(II)
benzene-1,3,5-tricarboxylate]. In particular, MIL-47
showed a good CO
2
adsorption capacity,
136
while MIL-53
showed a very high selectivity for CO
2
over CH
4
,
137
and Cu-BTC proved to be endowed with noticeable
CO
2
adsorption capacity and selectivity with respect to
N
2
.
138
More recently, CO
2
adsorption performances of
Cu-BTC were further investigated, proving the superiority
of this adsorbent with respect to more traditional ones
such as 13 zeolite.
139, 140
Being MOFs characterized by
extremely high specic surface area values,
29
they are
intrinsically endowed with high non-specic adsorption
capacities. In order to make them more selective toward
CO
2
, surface functionalization, and, in particular, surface
amino-functionalization can be performed through routes
that share different conceptual and experimental aspects
with those used for the amino-functionalization of meso-
porous silicates. Table V shows the main studies on the
amino-functionalization of MOFs for CO
2
adsorption and
separation: most of these papers deal with what may be
called in situ functionalization of the pristine material.
Such modication methods can be considered similar
to the co-condensation process used for mesoporous
silicates: indeed, the latter case envisages the partial sub-
stitution of the chosen silica source with an aminosilane
in the synthesis batch, in order to carry out the grafting
of the amine groups simultaneously to the mesophase
assembly.
122
Similarly, in situ functionalization of MOFs
relies on the fact that replacing part of the organic linker
with an amino-substituted homologue still allows the
same crystal structure to be obtained while gaining the
functionality of amine groups attached to the pore surface
of the framework. In some cases, such substitution is not
needed at all as the organic linker initially designed for the
synthesis already contains amine moieties that endow the
resulting material with good CO
2
adsorption features.
144
In contrast with what was reported in the previous
section for mesoporous silicates, very few papers deal with
post-synthesis amine grafting of MOFs for CO
2
adsorption.
It is worth noting that this kind of functionalization method
8 J. Nanosci. Nanotechnol. 14, 112, 2014
Gargiulo et al. CO
2
Adsorption by Functionalized Nanoporous Materials
Table V. Amino-functionalized MOFs for CO
2
adsorption. Where not explicitly reported in the cited papers, CO
2
adsorption capacity values were
extracted from plots using the DataThief software.
CO
2
adsorption capacity
(mol/kg) at working
MOF type Functionalizing agents Functionalization method temperature (K) Ref.
MIL-53 (Al terephthalate) Mono-amino-substituted terephthalic acid In situ 2.73 at 298
o
[141]
MIL-68 (In terephthalate) 1.79 at 298
o
MIL-53 (Al terephthalate) Mono-amino-substituted terephthalic acid In situ 6.75 at 303
l
[142]
Zn aminotriazolato-oxalate Mono-amino-substituted 1,2,4-triazole In situ 4.35 at 273
c
[143]
bio-MOF-11 (Co adeninate) Amine- and pyrimidine-containing
nucleobase as organic linker
In situ 6.00 at 273
o
[144]
MIL-101 (Al terephthalate) Mono-amino-substituted terephthalic acid In situ 17.33 at 283
l
[145]
Cd isonicotinate Mono-amino-substituted isonicotinic acid In situ 4.72 at 273
o
[146]
Co isonicotinate 3.84 at 273
o
CPO-27 (Ni 1,4-dioxido-2,5-
benzenedicarboxylate)
Piperazine Post-synthesis grafting 3.20 at 298
o
[147]
MIL-125 (Ti terephthalate) Mono-amino-substituted terephthalic acid In situ 3.09 at 298
o
[148]
ZIF-8 (Zn 2-methylimidazolate) 2-aminobenzimidazole In situ 4.59 at 308
J
[149]
Carboxaldehyde-2-
imidazole +ethylenediamine
In situ+post-synthesis grafting 4.79 at 308
J
Mg 4,4

-dioxido-3,3

-
biphenyldicarboxylate
N,N

-dimethylethylenediamine Post-synthesis grafting 3.14 at 313

e
[150]
MIL-101 (Cr terephthalate) Polyethylenimine Impregnation 5.00 at 298
o
[151]
Note: Maximum observed pressure:
o
100 kPa,
l
3000 kPa,
c
120 kPa,
J
1000 kPa,
e
15 kPa.
relies on very different chemical grounds for the two afore-
mentioned adsorbent classes: indeed, for mesoporous sili-
cates, post-synthesis grafting is a reaction between surface
hydroxyl groups (on silanol groups) of the mesostructure
and the alkoxy ligands of the to-be-attached silane, arrang-
ing a layer of tethered amine groups on pore surfaces.
152
In MOFs, the transition metal complexes at the bottom of
their building units can sometimes be partially saturated by
non-primarily bonded ligands (e.g., water molecules): such
species can be removed from the framework by activation
processes (e.g., thermal treatments under vacuum), giving
rise to coordinatively unsaturated sites (CUSs) on the metal
moieties. CUSs can act as specic CO
2
adsorption sites
per se,
140, 153
but can be also used as graft points for multi-
functional chelating reagents such as ethylenediamines,
154
that in turn can operate as enhanced CO
2
adsorption
sites.
149, 150
Anyway, it seems odd to observe how post-
synthesis amino-grafting of MOFs often leads to reduced
CO
2
adsorption capacities with respect to those noticed
for their non-functionalized counterparts: indeed, Das et al.
synthesized the Ni-bearing CPO-27 MOF, both as is and
piperazine-grafted, and reported how the CO
2
adsorption
capacity at 100 kPa almost halves itself after the function-
alization step.
147
Similarly, Thompson et al. rst modied
ZIF-8 MOF by partially substituting 2-methylimidazole
with carboxaldehyde-2-imidazole in the synthesis batch,
and then attached ethylenediamine molecules to the so-
produced adsorbent: also in this case, the pre-grafting
samples surpassed the amino-fuctionalized ones in terms
of CO
2
adsorption capacity.
149
It is worth noting that,
in both aforementioned cases, the decrease in the overall
CO
2
adsorption capacity is balanced by a pronounced
increase in CO
2
adsorption afnity: indeed, as suggested by
Siriwardane et al.
155
an empirical assessment of the afn-
ity of an adsorbent for CO
2
can be achieved by plotting
adsorption isotherms as adsorbed amounts per unit area
of adsorbent versus gas pressure.
140
For both piperazine-
functionalized CPO-27 and ethylenediamine-modied ZIF-
8, the post-grafting decrease in specic surface area fairly
exceeds that in CO
2
adsorption capacity, thus leading to a
strong increase in CO
2
adsorbed amounts per unit area of
adsorbent,
147, 149
i.e., in CO
2
adsorption afnity.
Also in contrast with a vast part of the literature on
amino-functionalized mesoporous silicates, there is a sig-
nicant lack of papers about MOFs impregnated by amino-
functional polymers, probably due to the usually small
pore sizes of these materials (with respect to those of
mesoporous silicates), that are not suitable for the load-
ing of high molecular weight species. One of the very few
works on this topic is related to CO
2
adsorption on PEI-
impregnated MIL-101:
151
indeed, this is one of the few
MOFs that is endowed with mesoporous cages
156
that can
at least host compounds whose molecular weight falls in
the order of magnitude of 100 Da. Quite interestingly, the
temperature dependence of the adsorption capacity for PEI-
impregnated MIL-101 follows the usual correspondence
between increasing temperature and decreasing adsorption
capacity,
151
in contrast with what is observed for similarly
functionalized mesoporous silicates: presumably, the MIL-
101 cavities are not enough large to allow the increasing
temperature-induced exibilization of hosted PEI chains,
thus denying the exposure of additional CO
2
-afnity sites.
As regards the selectivity of amino-functionalized MOFs
toward CO
2
, the results are comparable to what has already
been pointed out for similarly modied mesoporous sili-
cates: in particular, PEI-impregnated MIL-101 showed a
J. Nanosci. Nanotechnol. 14, 112, 2014 9
CO
2
Adsorption by Functionalized Nanoporous Materials Gargiulo et al.
strong CO
2
selectivity against N
2
, as primarily requested to
candidate adsorbents for the treatment of ue gas streams
produced by coal-red power stations.
151
Instead, as
regards the regeneration capacities of amino-functionalized
MOFs, fully reversible CO
2
adsorption was observed, as
an example, for porous mono-amino-substituted Cd and
Co isonicotinates,
146
while CO
2
adsorption cycling mea-
surements were performed on PEI-impregnated MIL-101,
revealing a signicantly good retention of the CO
2
cap-
ture capacity after several adsorption/desorption cycles.
151
With respect to amino-functionalized mesoporous silicates
(in particular, PEI-impregnated ones), similarly modied
MOFs show higher working capacities, i.e., the differ-
ence between the CO
2
adsorption capacities determined for
the high and low pressures of interest in a PSA separa-
tion process: this potentially makes amino-functionalized
MOFs even better candidates than their mesoporous inor-
ganic homologues for a plant scale use. However, as has
been already pointed out in the previous section, the still-
persisting lack of reliable methods for the pelletization of
such new generation adsorbents
157
warrants further devel-
opment efforts in the future.
5. CONCLUDING REMARKS
Functionalized nanoporous materials are proven to be good
adsorbents for CO
2
. Proper modication of the cation
content of zeolites, as well as the introduction of func-
tional groups such as amine groups into ordered meso-
porous silicates and metal organic frameworks, greatly
enhances the CO
2
adsorptive properties of these substrates.
Specically cation-exchanged zeolites can be currently
considered the benchmark for ordered nanoporous CO
2
adsorbents, nding application also on the plant scale.
As regards ordered mesoporous silicates, functionalizing
aminosilanes can be covalently attached to substrates either
by post-synthesis grafting or by one-step silylation. Alter-
natively, low molecular weight amines or amino-functional
polymers can be added by post-synthesis impregnation.
In particular, polyethylenimine-loaded mesoporous sili-
cates show an interesting behavior toward phenomena,
such as more-than-ambient adsorption temperatures and the
presence of moisture in the to-be-treated gas streams that
are usually considered detrimental for adsorption perfor-
mances. Indeed, PEI-functionalized mesoporous silicates
perform the best in terms of CO
2
adsorption capacities
under working temperatures near 350 K and in the presence
of humid streams. In general, amino-functionalized meso-
porous silicates tend to show high afnity toward CO
2
:
while this could be an advantage when pushed purication
is needed, it also implies that full regeneration of the adsor-
bent can be achieved only by putting its surface in contact
with a completely CO
2
-free environment.
On the contrary, with respect to amino-functionalized
mesoporous silicates, similarly modied metal organic
frameworks show higher CO
2
adsorption working
capacities: this potentially makes amino-functionalized
MOFs even better candidates than their mesoporous inor-
ganic homologues for plant-scale use. However, the per-
sisting lack of reliable methods for the pelletization of both
ordered mesoporous silicates and MOFs warrants further
development efforts in the future.
References and Notes
1. IPCC, Climate Change 2007: Synthesis Report. Contribution of
Working Groups I, II and III to the Fourth Assessment Report of the
Intergovernmental Panel on Climate Change, IPCC, Geneva (2007).
2. M. M. Halmann and M. Steinberg, Greenhouse Gas Carbon Diox-
ide Mitigation: Science and Technology, CRC Press, Boca Raton
(1999).
3. J. R. Anderson and M. Boudart, Catalysis: Science and Technology,
Springer, Berlin (1984), Vol. 5.
4. B. Crittenden and W. J. Thomas, Adsorption Technology and
Design, Butterworth-Heinemann, Oxford (1998).
5. R. Chakravarty and A. Dash, J. Nanosci. Nanotechnol. 13, 2431
(2013).
6. Y.-K. Park, J. W. Kim, S. H. Park, S.-S. Kim, J.-K. Jeon, and S. H.
Lee, J. Nanosci. Nanotechnol. 13, 718 (2013).
7. Y.-K. Park, H. W. Lee, J.-K. Jeon, J. Han, C.-U. Kim, S.-Y. Jeong,
and K.-E. Jeong, J. Nanosci. Nanotechnol. 13, 714 (2013).
8. H. Jin, M. B. Ansari, and S.-E. Park, Adv. Porous Mater. 1, 72
(2013).
9. A. Vinu and K. Ariga, Adv. Porous Mater. 1, 63 (2013).
10. N. A. Khan, Z. Hasan, and S. H. Jhung, Adv. Porous Mater. 1, 91
(2013).
11. B. Liguori, F. Iucolano, D. Caputo, and C. Colella, Adv. Porous
Mater. 1, 129 (2013).
12. Z. Lin, C. Guo, and W. Song, Nanosci. Nanotechnol. Lett. 5, 907
(2013).
13. T. Gan, J. Sun, W. Wu, K. Huang, and J. Zhu, Nanosci. Nanotech-
nol. Lett. 5, 673 (2013).
14. S. Sartori, K. D. Knudsen, A. Roth, M. Fichtner, and B. C.
Hauback, Nanosci. Nanotechnol. Lett. 4, 173 (2012).
15. Y. Ishii, K. Okamura, T. Matsushita, and S. Kawasaki, Mater.
Express 2, 23 (2012).
16. F. Huang, J. Wang, S. Wu, Y. Zhang, and T. Yang, Sci. Adv. Mater.
5, 1097 (2013).
17. H. X. Zhu and Z. B. Wang, Sci. Adv. Mater. 5, 677 (2013).
18. C. Dong, M. Zhong, L. Li, T. Huang, and M. Ma, Sci. Adv. Mater.
4, 204 (2012).
19. D. Prabhakar, V. Kumari, and S. S. Islam, Sci. Adv. Mater. 4, 121
(2012).
20. P. Sui, X. Meng, Y. Wu, Y. Zhao, L. Song, Z. Sun, L. Duan,
A. Umar, and Q. Wang, Sci. Adv. Mater. 5, 1132 (2013).
21. V. G. Bairi, S. E. Bourdo, U. B. Nasini, S. K. Ramasahayam,
F. Watanabe, B. C. Berry, and T. Viswanathan, Sci. Adv. Mater.
5, 1275 (2013).
22. D. Jing, J. Shi, S. Shen, and L. Guo, Sci. Adv. Mater. 5, 982 (2013).
23. X. Liu, Q. Ge, A. Rawal, G. Parada, K. Schmidt-Rohr, M. Akinc,
and S. K. Mallapragada, Sci. Adv. Mater. 5, 354 (2013).
24. Z. Xu, Y. Wang, P. Dai, and W. Kong, Sci. Adv. Mater. 4, 1065
(2012).
25. M. Vaseem, K. M. Lee, and Y.-B. Hahn, Sci. Adv. Mater. 4, 687
(2012).
26. S. Lowell, J. E. Shields, M. A. Thomas, and M. Thommes, Charac-
terization of Porous Solids and Powders: Surface Area, Pore Size
and Density, Kluwer Academic Publishers, Dordrecht (2004).
27. A. D. McNaught and A. Wilkinson, IUPAC. Compendium of
Chemical Terminology (the Gold Book), Blackwell Scientic
Publications, Oxford (1997).
28. I. Erucar and S. Keskin, Ind. Eng. Chem. Res. 52, 3462 (2013).
10 J. Nanosci. Nanotechnol. 14, 112, 2014
Gargiulo et al. CO
2
Adsorption by Functionalized Nanoporous Materials
29. H. Furukawa, N. Ko, Y. B. Go, N. Aratani, S. B. Choi, E. Choi,
A. . Yazaydin, R. Q. Snurr, M. OKeeffe, J. Kim, and O. M.
Yaghi, Science, 329, 424 (2010).
30. D. W. Breck, Zeolite Molecular Sieves: Structure, Chemistry, and
Use, Wiley, New York (1974).
31. R. M. Barrer, Zeolites and Clay Minerals as Sorbents and Molecular
Sieves, Academic Press, London (1978).
32. D. M. Ruthven, Principles of Adsorption and Adsorption Processes,
Wiley, New York (1984).
33. M. W. Ackley, S. U. Rege, and H. Saxena, Microporous Meso-
porous Mater. 61, 25 (2003).
34. D. Caputo, F. Iucolano, F. Pepe, and C. Colella, Microporous
Mesoporous Mater. 105, 260 (2007).
35. D. Zhao, K. Cleare, C. Oliver, C. Ingram, D. Cook, R. Szostak,
and L. Kevan, Microporous Mesoporous Mater. 21, 371 (1998).
36. D. Bonenfant, M. Kharoune, P. Niquette, M. Mimeault, and
R. Hausler, Sci. Technol. Adv. Mater. 9, 013007 (2008).
37. G.-P. Hao, W.-C. Li, and A.-H. Lu, J. Mater. Chem. 21, 6447
(2011).
38. Q. Wang, J. Luo, Z. Zhong, and A. Borgna, Energy Environ. Sci.
4, 42 (2011).
39. A. Samanta, A. Zhao, G. K. H. Shimizu, P. Sarkar, and R. Gupta,
Ind. Eng. Chem. Res. 51, 1438 (2012).
40. K. S. Walton, M. B. Abney, and M. D. LeVan, Microporous
Mesoporous Mater. 91, 78 (2006).
41. E. Daz, E. Muoz, A. Vega, and S. Ordoez, Chemosphere
70, 1375 (2008).
42. E. Daz, E. Muoz, A. Vega, and S. Ordoez, Ind. Eng. Chem.
Res. 47, 412 (2008).
43. J. A. Dunne, M. Rao, S. Sircar, R. J. Gorte, and A. L. Myers,
Langmuir, 12, 5896 (1996).
44. T. Yamazaki, M. Katoh, S. Ozawa, and Y. Ogino, Mol. Phys.
80, 313 (1993).
45. M. Katoh, T. Yoshikawa, T. Tomonari, K. Katayama, and
T. Tomida, J. Colloid Interface Sci. 226, 145 (2000).
46. S. K. Wirawan and D. Creaser, Microporous Mesoporous Mater.
91, 196 (2006).
47. S. K. Wirawan and D. Creaser, Sep. Purif. Technol. 52, 224 (2006).
48. J. Zhang, R. Singh, and P. A. Webley, Microporous Mesoporous
Mater. 111, 478 (2008).
49. T. H. Bae, M. R. Hudson, J. A. Mason, W. L. Queen, J. J. Dutton,
K. Sumida, K. J. Micklash, S. S. Kaye, C. M. Brown, and J. R.
Long, Energy Environ. Sci. 6, 128 (2013).
50. O. Cheung, Z. Bacsik, Q. Liu, A. Mace, and N. Hedin, Appl. Energy
(2013), http://dx. doi.org/10.1016/j. apenergy.2013.01.017.
51. B. Coughlan and S. J. Kilmartin, J. Chem. Soc. Faraday Trans.
1, 1809 (1975).
52. B. Coughlan and W. A. McCann, J. Chem. Soc. Faraday Trans.
1, 1969 (1979).
53. A. Khelifa, Z. Derrich, and A. Bengueddach, Microporous Meso-
porous Mater. 32, 199 (1999).
54. A. Khelifa, A. Hasnaoui, Z. Derriche, and A. Bengueddach, Ann.
Chim. Sci. Mater. 26, 55 (2001).
55. A. Khelifa, L. Benchechida, and Z. Derriche, J. Colloid Interface
Sci. 278, 9 (2004).
56. T. M. Amelitcheva, A. G. Bezus, L. L. Bogomolova, A. V. Kiselev,
N. K. Shoniya, M. A. Shubayeva, and S. P. Zhdanov, J. Chem. Soc.
Faraday Trans. 1, 74, 306 (1978).
57. G. A. Armenta, G. H. Ramirez, E. F. Loyola, A. U. Castaneda,
R. S. Gonzalez, C. T. Munoz, A. J. Lopez, and E. R. Castellon,
J. Phys. Chem. B, 105, 1313 (2001).
58. S. U. Rege, R. T. Yang, and M. A. Buzanowski, Chem. Eng. Sci.
55, 4827 (2000).
59. D. M. Ruthven, S. Farooq, and K. S. Knaebel, Pressure Swing
Adsorption, Wiley & Sons, New York (1993).
60. R. V. Siriwardane, M. S. Shen, and E. P. Fisher, Energy Fuels
19, 1153 (2005).
61. M. T. Ho, G. W. Allinson, and D. E. Wiley, Ind. Eng. Chem. Res.
47, 4883 (2008).
62. R. P. Lively, R. R. Chance, and W. J. Koros, Ind. Eng. Chem. Res.
49, 7550 (2010).
63. G. Li, P. Xiao, P. Webley, J. Zhang, R. Singh, and M. Marshall,
Adsorption 14, 575 (2008).
64. P. Xiao, J. Zhang, P. Webley, G. Li, R. Singh, and R. Todd,
Adsorption 14, 415 (2008).
65. J. Merel, M. Clausse, and F. Meunier, Envir. Progr. 25, 327 (2006).
66. J. Merel, M. Clausse, and F. Meunier, Ind. Eng. Chem. Res. 47, 209
(2008).
67. N. Tlili, G. Grevillot, and C. Vallieres, Int. J. Greenhouse Gas
Control 3, 519 (2009).
68. J. Zhang, R. Singh, and P. A. Webley, Microporous Mesoporous
Mater. 111, 478 (2008).
69. G. T. Rochelle, Science 325, 1653 (2009).
70. P. J. Birbara, T. P. Filburn, and T. A. Nalette, United States Patent
5,876,488 (1999).
71. P. D. Jadhav, R. V. Chatti, R. B. Biniwale, N. K. Labhsetwar,
S. Devotta, and S. S. Rayalu, Energy Fuels 21, 3555 (2007).
72. R. Chatti, A. K. Bansiwal, J. A. Thote, V. Kumar, P. Jadhav, S. K.
Lokhande, R. B. Biniwale, N. K. Labhsetwar, and S. S. Rayalu,
Microporous Mesoporous Mater. 121, 84 (2009).
73. X. Xu, X. Zhao, L. Sun, and X. Liu, J. Nat. Gas Chem. 18, 167
(2009).
74. A. Zukal, I. Dominguez, J. Mayerova, and J. Cejka, Langmuir
25, 10314 (2009).
75. S. Hao, Q. Xiao, H. Yang, Y. Zhong, F. Pepe, and W. Zhu, Micro-
porous Mesoporous Mater. 132, 552 (2010).
76. F. Su, C. Lu, S. C. Kuo, and W. Zeng, Energy Fuels 24, 1441
(2010).
77. S. C. Lee, C. C. Hsieh, C. H. Chen, and Y. S. Chen, Aerosol Air
Qual. Res. 13, 360 (2013).
78. D. Zhao, Y. Wan, and W. Zhou, Ordered Mesoporous Materials,
Wiley-VCH, Weinheim (2012).
79. C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli, and J. S.
Beck, Nature 359, 710 (1992).
80. S. Inagaki, Y. Fukushima, and K. Kuroda, Stud. Surf. Sci. Catal.
84, 125 (1994).
81. D. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B. F.
Chmelka, and G. D. Stucky, Science 23, 548 (1998).
82. D. Zhao, Q. Huo, J. Feng, B. F. Chmelka, and G. D. Stucky, J. Am.
Chem. Soc. 120, 6024 (1998).
83. S. Ruthstein, J. Schmidt, E. Kesselman, R. Popovitz-Biro, L. Omer,
V. Frydman, Y. Talmon, and D. Goldfarb, Chem. Mater. 20, 2779
(2008).
84. S. Che, A. E. Garcia-Bennett, T. Yokoi, K. Sakamoto, H. Kunieda,
O. Terasaki, and T. Tatsumi, Nat. Mater. 2, 801 (2003).
85. P. Yang, The Chemistry of Nanostructured Materials, World Scien-
tic, Singapore (2003).
86. T. Yokoi and T. Tatsumi, J. Jpn. Petrol. Inst. 50, 299 (2007).
87. T. Yokoi, H. Yoshitake, and T. Tatsumi, Chem. Mater. 15, 4536
(2003).
88. T.-W. Kim, R. Ryoo, M. Kruk, K. P. Gierszal, M. Jaroniec,
S. Kamiya, and O. Terasaki, J. Phys. Chem. B 108, 11480 (2004).
89. B. L. Newalkar and S. Komarneni, Chem. Mater. 13, 4573 (2001).
90. S. A. Bagshaw, E. Prouzet, and T. J. Pinnavaia, Science 269, 1242
(1995).
91. A. G. S. Prado and C. Airoldi, J. Mater. Chem. 12, 3823 (2002).
92. C. Knfel, J. Descarpentries, A. Benzaouia, V. Zelek, S. Mornet,
P. L. Llewellyn, and V. Hornebecq, Microporous Mesoporous
Mater. 99, 79 (2007).
93. T.-L. Chew, A. L. Ahmad, and S. Bhatia, Adv. Colloid Interface
Sci. 153, 43 (2010).
94. A. Andrzejewska, A. Krysztafkiewicz, and T. Jesionowski, Dyes
Pig. 75, 116 (2007).
J. Nanosci. Nanotechnol. 14, 112, 2014 11
CO
2
Adsorption by Functionalized Nanoporous Materials Gargiulo et al.
95. N. Gargiulo, I. Attianese, G. G. Buonocore, D. Caputo,
M. Lavorgna, G. Mensitieri, and M. Lavorgna, Microporous Meso-
porous Mater. 167, 10 (2013).
96. M. Manzano, V. Aina, C. O. Aren, F. Balas, V. Cauda, M. Colilla,
M. R. Delgado, and M. Vallet-Reg, Chem. Eng. J. 137, 30 (2008).
97. N. R. E. N. Impens, P. van der Voort, and E. F. Vansant, Microp-
orous Mesoporous Mater. 28, 217 (1999).
98. R. S. Franchi, P. J. E. Harlick, and A. Sayari, Ind. Eng. Chem. Res.
44, 8007 (2005).
99. P. J. E. Harlick and A. Sayari, Ind. Eng. Chem. Res. 45, 3248 (2006).
100. P. J. E. Harlick and A. Sayari, Ind. Eng. Chem. Res. 46, 446 (2007).
101. H. Zhao, J. Hu, J. Wang, L. Zhou, and H. Liu, Acta Phys.-Chim.
Sinica 23, 801 (2007).
102. M. B. Yue, L. B. Sun, Y. Cao, Y. Wang, Z. J. Wang, and J. H. Zhu,
Chem. Eur. J. 14, 3442 (2008).
103. R. Serna-Guerrero, E. Dana, and A. Sayari, Ind. Eng. Chem. Res.
47, 9406 (2008).
104. M. Bhagiyalakshmi, L. J. Yun, R. Anuradha, and H. T. Jang,
J. Hazard. Mater. 175, 928 (2010).
105. S. Loganathan, M. Tikmani, and A. K. Ghoshal, Langmuir 29, 3491
(2013).
106. X. Xu, C. Song, J. M. Andrsen, B. G. Miller, and A. W. Scaroni,
Microporous Mesoporous Mater. 62, 29 (2003).
107. M. B. Yue, Y. Chun, Y. Cao, X. Dong, and J. H. Zhu, Adv. Funct.
Mater. 16, 1717 (2006).
108. M. B. Yue, L. B. Sun, Y. Cao, Z. J. Wang, Y. Wang, Q. Yu, and
J. H. Zhu, Microporous Mesoporous Mater. 114, 74 (2008).
109. V. Zeleka, M. Badaniov, D. Halamov, J.

Cejka, A. Zukal,
N. Murafa, and G. Goerigk, Chem. Eng. J. 144, 336 (2008).
110. J. H. Drese, S. Choi, R. P. Lively, W. J. Koros, D. J. Fauth, M. L.
Gray, and C. W. Jones, Adv. Funct. Mater. 19, 3821 (2009).
111. F.-Y. Chang, K.-J. Chao, H.-H. Cheng, and C.-S. Tan, Sep. Purif.
Technol. 70, 87 (2009).
112. M. Bhagiyalakshmi, R. Anuradha, S. D. Park, and H. T. Jang,
Microporous Mesoporous Mater. 131, 265 (2010).
113. M. Bhagiyalakshmi, L. J. Yun, R. Anuradha, and H. T. Jang,
J. Porous Mater. 17, 475 (2010).
114. M. Bhagiyalakshmi, S. D. Park, W. S. Cha, and H. T. Jang, Appl.
Surf. Sci. 256, 6660 (2010).
115. N. Gargiulo, D. Caputo, and C. Colella, Stud. Surf. Sci. Catal.
170, 1938 (2007).
116. Y. Kuwahara, D.-Y. Kang, J. R. Copeland, P. Bollini, C. Sievers,
T. Kamegawa, H. Yamashita, and C. W. Jones, Chem. Eur. J.
18, 16649 (2012).
117. A. Olea, E. S. Sanz-Prez, A. Arencibia, R. Sanz, and G. Calleja,
Adsorption 19, 589 (2013).
118. V. Zelenak, D. Halamova, L. Gaberova, E. Bloch, and P. Llewellyn,
Microporous Mesoporous Mater. 116, 358 (2008).
119. J. Wei, J. Shi, H. Pan, W. Zhao, Q. Ye, and Y. Shi, Microporous
Mesoporous Mater. 116, 394 (2008).
120. W.-J. Son, J.-S. Choi, and W.-S. Ahn, Microporous Mesoporous
Mater. 113, 31 (2008).
121. Y. Liu, J. Shi, J. Chen, Q. Ye, H. Pan, Z. Shao, and Y. Shi, Micro-
porous Mesoporous Mater. 134, 16 (2010).
122. S.-N. Kim, W.-J. Son, J.-S. Choi, and W.-S. Ahn, Microporous
Mesoporous Mater. 115, 497 (2008).
123. N. Gargiulo, F. Pepe, and D. Caputo, J. Colloid Interface Sci.
367, 348 (2012).
124. L. Wang, L. Ma, A. Wang, Q. Liu, and T. Zhang, Chinese J. Catal.
28, 805 (2007).
125. A. S. Maria Chong, and X. S. Zhao, J. Phys. Chem. B 107, 12650
(2003).
126. R. Serna-Guerrero, Y. Belmabkhout, and A. Sayari, Chem. Eng. J.
161, 173 (2010).
127. H. Y. Huang and R. T. Yang, Ind. Eng. Chem. Res. 42, 2427 (2003).
128. S. Satyapal, T. Filburn, J. Trela, and J. Strange, Energy Fuels
15, 250 (2001).
129. X. Xu, C. Song, B. G. Miller, and A. W. Scaroni, Ind. Eng. Chem.
Res. 44, 8113 (2005).
130. X. Xu, C. Song, B. G. Miller, and A. W. Scaroni, Fuel Process.
Technol. 86, 1457 (2005).
131. J. C. Hicks, J. H. Drese, D. J. Fauth, M. L. Gray, G. Qi, and C. W.
Jones, J. Am. Chem. Soc. 130, 2902 (2008).
132. G. Qi, Y. Wang, L. Estevez, X. Duan, N. Anako, A.-H. A. Park,
W. Li, C. W. Jones, and E. P. Giannelis, Energy Environ. Sci. 4, 444
(2011).
133. C. Chen, S.-T. Yang, W.-S. Ahn, and R. Ryoo, Chem. Commun.
3627 (2009).
134. J. L. C. Rowsell and O. M. Yaghi, Microporous Mesoporous Mater.
73, 3 (2004).
135. A. R. Millward and O. M. Yaghi, J. Am. Chem. Soc. 127, 17998
(2005).
136. S. Bourrelly, P. L. Llewellyn, C. Serre, F. Millange, T. Loiseau, and
G. Frey, J. Am. Chem. Soc. 127, 13519 (2005).
137. P. L. Llewellyn, S. Bourrelly, C. Serre, Y. Filinchuk, and G. Frey,
Angew. Chem. Int. Ed. 45, 7751 (2006).
138. Q. M. Wang, D. Shen, M. Bulow, M. L. Lau, S. Deng, F. R. Fitch,
N. O. Lemcoff, and J. Semanscin, Microporous Mesoporous Mater.
55, 217 (2002).
139. Z. Liang, M. Marshall, and A. L. Chaffee, Energy Fuels 23, 2785
(2009).
140. P. Aprea, D. Caputo, N. Gargiulo, F. Iucolano, and F. Pepe,
J. Chem. Eng. Data 55, 3655 (2010).
141. B. Arstad, H. Fjellvg, K. O. Kongshaug, O. Swang, and R. Blom,
Adsorption 14, 755 (2008).
142. S. Couck, J. F. M. Denayer, G. V. Baron, T. Rmy, J. Gascon, and
F. Kapteijn, J. Am. Chem. Soc. 131, 6326 (2009).
143. R. Vaidhyanathan, S. S. Iremonger, K. W. Dawson, and G. K.
H. Shimizu, Chem. Comm. 5230 (2009).
144. J. An, S. J. Geib, and N. L. Rosi, J. Am. Chem. Soc. 132, 38 (2010).
145. P. Serra-Crespo, E. V. Ramos-Fernandez, J. Gascon, and
F. Kapteijn, Chem. Mater. 23, 2565 (2011).
146. P. Pachfule, Y. Chen, J. Jiang, and R. Banerjee, J. Mater. Chem.
21, 17737 (2011).
147. A. Das, P. D. Southon, M. Zhao, C. J. Kepert, A. T. Harris, and
D. M. D

Alessandro, Dalton Trans. 41, 11739 (2012).

148. S.-N. Kim, J. Kim, H.-Y. Kim, H.-Y. Cho, and W.-S. Ahn, Catal.
Today 204, 85 (2013).
149. J. A. Thompson, N. A. Brunelli, R. P. Lively, J. R. Johnson, C. W.
Jones, and S. Nair, J. Phys. Chem. C 117, 8198 (2013).
150. T. M. McDonald, W. R. Lee, J. A. Mason, B. M. Wiers, C. S.
Hong, and J. R. Long, J. Am. Chem. Soc. 134, 7056 (2012).
151. Y. Lin, Q. Yan, C. Kong and L. Chen, Sci. Rep. 3 (2013), art. no.
1461.
152. P. J. E. Harlick and A. Sayari, Stud. Surf. Sci. Catal. 158, 987
(2005).
153. S. Xiang, Y. He, Z. Zhang, H. Wu, W. Zhou, R. Krishna, and
B. Chen, Nat. Comm. 3, art. no. 954 (2012).
154. Y. K. Hwang, D.-Y. Hong, J.-S. Chang, S. H. Jhung, Y.-K. Seo,
J. Kim, A. Vimont, M. Daturi, C. Serre, and G. Frey, Angew.
Chem. Int. Ed. 47, 4144 (2008).
155. R. V. Siriwardane, M. S. Shen, E. P. Fisher, and J. A. Poston,
Energy Fuels 15, 279 (2001).
156. G. Frey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour,
S. Surbl, and I. Margiolaki, Science 309, 2040 (2005).
157. T. Remy, S. A. Peter, S. Van der Perre, P. Valvekens, D. E. De Vos,
G. V. Baron, and J. F. M. Denayer, J. Phys. Chem. C 117, 9301
(2013).
Received: 29 July 2013. Accepted: 6 August 2013.
12 J. Nanosci. Nanotechnol. 14, 112, 2014