See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/45801397

Can Metal-Organic Framework Materials Play a

Useful Role in Large-Scale Carbon Dioxide
Separations?

Article in ChemSusChem August 2010

DOI: 10.1002/cssc.201000114 Source: PubMed

CITATIONS READS

314 114

3 authors, including:

Seda Keskin
Koc University
83 PUBLICATIONS 2,539 CITATIONS

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Gas Separation Peformances of Metal Organic Frameworks View project

All content following this page was uploaded by Seda Keskin on 18 September 2014.

The user has requested enhancement of the downloaded file. All in-text references underlined in blue are added to the original document
and are linked to publications on ResearchGate, letting you access and read them immediately.
DOI: 10.1002/cssc.201000114
Can MetalOrganic Framework Materials Play a Useful
Role in Large-Scale Carbon Dioxide Separations?
Seda Keskin,[a] Timothy M. van Heest,[b] and David S. Sholl*[b]
Metalorganic frameworks (MOFs) are a fascinating class of
crystalline nanoporous materials that can be synthesized with
a diverse range of pore dimensions, topologies, and chemical
functionality. As with other well-known nanoporous materials,
such as activated carbon and zeolites, MOFs have potential
uses in a range of chemical separation applications because of
the possibility of selective adsorption and diffusion of mole-
cules in their pores. We review the current state of knowledge
1. Introduction
Any serious effort to reduce anthropogenic CO2 emissions
must contend with the geopolitical and economic reality that
fossil fuels will continue to make a dominant contribution to
the worlds energy supply for decades to come. This observa-
tion implies that scalable, cost-effective technologies for cap-
turing CO2 from conventional uses of fossil fuels are of great
importance. In many cases, the key technical challenge is to
achieve the seemingly prosaic task of separating CO2 from
other gases. CO2 capture from power plant flue gas, a mixture
composed mainly of water-saturated N2 with smaller amounts
of O2 and other species, is the best-known example. Other gas
separations that could have relevance to mitigating CO2 emis-
sions include removing CO2 from sour gas,[1] a process that
could increase supplies of natural gasthe fossil fuel with the
lowest carbon intensityand purification of O2 from air, a key
element in oxyfiring;[2] an attractive alternative to conventional
combustion. In each of these areas, there is a tremendous in-
centive to achieve the relevant separations on very large scales
with low cost in terms of capital outlay, maintenance, and the
energy requirements of the separation.
In this paper, we review studies considering metalorganic
frameworks (MOFs) for CO2-related gas separations. MOFs are a
relatively new class of crystalline nanoporous materials that
combine metal organic centers with organic ligands to create
extended crystals with permanent porosity. For the purposes
of this Minireview, we include in this class materials that are
variously described in the more detailed literature as coordina-
tion polymers, ZIFs (zeolite imidazolate frameworks), COFs (co-
valent organic frameworks), and others. Multiple reviews al-
ready describe the rapid developments in the synthesis of
these materials in approximately the last decade.[318] Many
MOFs have exceptionally high surface areas: examples with
> 4000 m2 g 1are known. Relative to more traditional nanopo-
rous crystals such as zeolites, the synthesis of MOFs is typically
more versatile and can be approached in a way that at least
ChemSusChem 2010, 3, 879 891  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
surrounding the possibility of using MOFs in large-scale carbon
dioxide separations. There are reasons to be optimistic that
MOFs may make useful contributions to this important prob-
lem, but there are several critical issues for which only very
limited information is available. By identifying these issues, we
provide what we hope is a path forward to definitively answer-
ing the question posed in our title.
approximates the concept of rational materials design. Molecu-
lar modeling can play an important role complementing exper-
imental studies of MOFs, as described in two recent re-
views.[19, 20] In this article, we focus primarily on what is known
about CO2 separations using MOFs from experiments.
To set the stage for discussing uses of MOFs for CO2 separa-
tions, we first briefly consider how any nanoporous material
could be used in these applications. It is useful to distinguish
between two fundamentally different concepts for these sepa-
rations: adsorption-based processes and kinetic separations.
Adsorption-based separations rely on the fact that gases rever-
sibly adsorb in nanopores at densities that far exceed the den-
sities of gases in equilibrium with the porous solid. To give a
representative example, the density of adsorbed CO2 in zeolite
13X, a widely available adsorbent, in equilibrium with gaseous
CO2 at 1 atm pressure and 298 K is 4.7 mmol g 1; this means
that at these conditions the density of CO2 in zeolite 13X is
73.7 times larger than the gas density.[21] Adsorbed gases can
be removed either by reducing the gas phase pressure or by
increasing the temperature (or both). Sophisticated cyclic pro-
cesses based on varying these quantities are already used
widely in industrial gas separations.[22] Although process design
for these applications is influenced by multiple factors, one key
metric is the adsorption selectivity for the desired gas relative
[a] Dr. S. Keskin
Department of Chemical and Biological Engineering
Ko University
Rumelifeneri Yolu, 34450, Saryer, Istanbul (Turkey)
[b] T. M. van Heest, Prof. D. S. Sholl
School of Chemical and Biomolecular Engineering
Georgia Institute of Technology
311 Ferst Dr., Atlanta, GA 30332-0100 (USA)
Fax: (+ 1) 404 894 2866
E-mail: david.sholl@chbe.gatech.edu
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.201000114.
879

to an undesired gas. For an arbitrary bulk phase composition,
this quantity is simply Sads = (q1/q2)/(y1/y2) where qi (yi) is the
mole fraction of species i in the adsorbed (bulk) phase. A
second key metric is the heat of adsorption, DHads, which con-
trols the temperature required to release an adsorbed gas.
Kinetic separations use differences in adsorption affinities
and differences in diffusivities of adsorbed species in a porous
material. Although kinetic separations can be performed with
appropriate operation of a packed-bed adsorber,[22] they are
easiest to appreciate for membrane-based separations. When
permeation through a membrane occurs via a solutiondiffu-
sion mechanism, the membrane selectivity can often be ap-
proximated by Smembrane = (q1/q2)  (D1/D2), where Di is the diffu-
sion coefficient of species i in the membrane. It is useful to
note that Smembrane = Sads  (D1/D2).[23] That is, efforts to select ma-
terials for kinetic separations have two variables that can con-
ceptually be adjusted independently, namely the adsorption
and diffusion selectivities, unlike adsorption-based processes,
which have only the former. Impressive examples of this idea
are already known. The pure silica zeolite DDR has Sads ~ 4 for
CO2/CH4 at room temperature, but DDR membranes have se-
lectivities > 100 because of the large values of DCO2/DCH4.[24]
We illustrated the concepts of adsorption-based and kinetic
separations using data from zeolites. This choice highlights the
fact that nanoporous materials, most notably activated carbons
and zeolites, have been used for gas separations for decades.
These materials are often physically robust and their prices
vary with quality. For example, the price of natural zeolites
ranges from US$ 0.50 to US$ 4.50 per kilogram.[25, 26] The unde-
niable aesthetic appeal of MOFs, as well as their status as de-
signable nanomaterials, means that the level of research activ-
ity for MOFs in recent years is far higher than for traditional
materials. In taking a pragmatic view towards commercial ap-
plications, however, it is important to inquire with an open
mind whether the properties of MOFs genuinely improve upon
(or seem poised to improve upon) the older materials.
In the remainder of this Minireview, we examine the current
state of knowledge for MOFs applied to CO2 separations. Sec-
tion 2 considers adsorption-based separations, where the ma-
jority of work in this field has focused. Section 3 turns to the
relatively less explored realm of kinetic separations. We are
cautiously optimistic that MOFs will make a useful impact on
future CO2 separation technologies, but it is clear from the cur-
rent literature that critical issues remain open, that must be ad-
dressed for the field to move towards realistic applications. We
describe these challenges in Section 4.
2. MOFs for Adsorption-based Separations of
CO2
In this Section, we review experiments that have been used to
examine adsorption of CO2 in MOFs under equilibrium condi-
tions. In assessing the potential of an adsorbent for an adsorp-
tion-based separation, information on the heat of adsorption
of the species of interest, the adsorption capacity for the spe-
cies of interest, and the selectivity for the species of interest
relative to other components are needed. An ideal adsorbent
880 www.chemsuschem.org  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
D. S. Sholl et al.
would have a moderate or low heat of adsorption, a large ca-
pacity, and high selectivity. In Section 2.1 we examine experi-
ments that probed adsorption of CO2 as a pure component in
MOFs. In Section 2.2, we look at experiments that have studied
the selectivity of CO2 adsorption relative to other gases.
2.1. Single-component adsorption of CO2 in MOFs
A large number of studies have examined single-component
adsorption of CO2 in MOFs. For example, in our survey of the
available literature, we found > 260 unique isotherm measure-
ments for > 130 MOFs.[11, 17, 27107, 108] A list of these materials and
the conditions for available isotherm data is tabulated in
Table S1 of the Supporting Information. In light of this large
amount of available data, we discuss carbon dioxide adsorp-
tion data in terms of two characteristic quantities: the heat of
adsorption and the adsorbed amount at atmospheric pressure.
2.1.1. Heat of adsorption
Although the heat of adsorption is not always reported when
CO2 adsorption isotherms are measured, the heats of adsorp-
tion of CO2 in MOFs are available for a large collection of mate-
rials.[17, 31, 34, 37,38, 42, 43, 45, 55,57, 58, 62, 64, 6669, 74, 76, 82,92, 94, 97, 98, 109111] This data
is summarized in Figure 1. In instances where a loading-depen-
dent heat of adsorption was reported, Figure 1 shows the
value reported for the lowest loading. In essentially all cases,
Figure 1. Heat of adsorption for carbon dioxide in MOFs (blue) near ambient
conditions (298 K, 1 atm). Non-MOF materials (red) are included for compari-
son. The heat of liquefaction of bulk CO2 is presented as a horizontal dashed
line at 17 kJ mol 1. See also Table S2 and S3 in the Supporting Information.
the data in Figure 1 are from experiments performed close to
room temperature. Although the heat of adsorption and the
isosteric heat of adsorption are slightly different quantities,[20]
many studies are unclear as to which quantity they report. For
this reason, we did not attempt to distinguish between these
two quantities in Figure 1. All of the data in Figure 1 is tabulat-
ed in Table S2. The ten MOFs with the highest reported heats
of adsorption are listed in Table 1. For comparison, Figure 1
also indicates the heat of adsorption of CO2 in a range of non-
MOF materials, including liquid-phase amines and zeolites. This
data is listed in Table S3.
ChemSusChem 2010, 3, 879 891
Can MOF Materials Play a Useful Role in Large-Scale CO2 Separations?

range of CO2 loadings that is ex-

Table 1. The ten MOFs with the highest reported values for the initial (low loading) heat of adsorption for CO2.
See Tables S2 and S3 in the Supporting Information for a listing of all values shown in Figure 1. pected to be relevant in the ap-
plications of interest.
MOF Heat of adsorption Ref. In many cases, the heat of ad-
[kJ mol 1]
sorption of CO2 in a specific
Cu-BTTri(en) 90 [97] MOF has only been reported
Zn2(tetrakis[4-(carboxyphenyl)oxamethyl] methane)(4,4-bipyridine) 84 [62]
once. There are several materials,
MIL-100 62 [68]
USO-1-Al-A 50 [113] however, where multiple meas-
[Cu(PF6)2(bpetha)2]n 50 [92] urements are available, and
Mg/DOBDC/MOF-74 (Mg)/CPO-27-Mg 47 [57] these results highlight some im-
bio-MOF-11 45 [67]
portant aspects of dealing with
MIL-101 44 [68]
[Pd(m-H-pymo-N1,N3)2(H2O)m]n 44 [43] these materials. The reported
Ni/DOBDC/MOF-74 (Ni)/CPO-27-Ni 41 [57] heats of adsorption for CuBTC
(also known as HKUST-1) range
from 35 kJ mol 1[76] down to
It is clear from Figure 1 that MOFs can exhibit a large range 12 kJ mol . For IRMOF-1, values from 34[34] to 15 kJ mol 1[66]
1 [66]

of heats of adsorption for CO2. The highest value of
90 kJ mol 1, for an ethylenediamine-functionalized material,[97]
exceeds the heat of adsorption for the best known liquid
amine, MEA.[112] Materials with heats of adsorption in this range
are unlikely to be satisfactory in practical applications because
of the large energy requirements associated with desorbing
CO2. Most MOFs have heats of adsorption between 20 and
50 kJ mol 1. This is not a surprising outcome; the data in
Table S3 shows that this statement is also true for zeolites. It is
useful to note that these heats of adsorption exceed the heat
of liquefaction of CO2, which is 17 kJ mol 1.
In a recent review of adsorbents for CO2 capture, Choi
et al.[113] reviewed adsorption on a wide variety of materials
and showed that temperature and loading have a significant
effect on both capacity and heat of adsorption. A subset of
the studies we listed above provides information on the exper-
imentally measured heat of adsorption for CO2 on MOFs as a
function of pressure[55, 98, 110, 113] or loading.[42, 43, 58, 67, 68, 76, 92, 97, 98, 111]
In many cases, the heat of adsorption decreases rapidly with
loading. For example, one amine-functionalized material has
an initial heat of adsorption close to 90 kJ mol 1, but the heat
of adsorption quickly drops to less than 40 kJ mol 1 as loading
increases.[97] Physically, this occurs because the adsorption sites
with the highest affinity for CO2 are occupied first and the sites
that are occupied at higher loadings have weaker affinities.
There are a small number of counterexamples to this general
phenomenon where the heat of adsorption varies non-monot-
onically[55] or even smoothly increases[58] as a function of load-
ing. Snurr et al.[66] used simulations to calculate the initial heat
of adsorption for HKUST-1 and found a negative dependence
of this quantity on temperature. They argued that in this case
the binding site that dominates the initial adsorption of CO2
changes as a function of temperature because of an interplay
between enthalpic and entropic effects. Bhatia and Myers have
argued persuasively that having a strongly loading-dependent
heat of adsorption, or equivalently, a strongly heterogeneous
distribution of binding site energies, is not a useful property in
the sense of allowing design of efficient adsorption cycles.[114]
One obvious implication of this idea is that for measurements
of the heat of adsorption to be useful in considering practical
applications, data must be available that describes the full
have been reported and for CPO-27-Mg values of 47[57] to
39 kJ mol 1 have been measured.[69] Some of this variation can
be attributed to differences in the methods used to extract a
heat of adsorption, or to the loading-dependence of the heat
of adsorption. Much of the variation, however, appears to be
associated with genuine differences between the nominally
identical materials that are being measured. The CuBTC results
mentioned above vary considerably in the approach used to
activate the MOF, that is, to remove residual solvent associat-
ed with the materials synthesis from the MOF pores and possi-
bly other adsorbed species associated with the history of the
sample prior to the experimental measurement. One implica-
tion of this situation is that the methods that are used for acti-
vating MOF samples should be carefully described in experi-
mental reports. A second implication is that caution must be
exercised in comparing atomistic models of gas adsorption in
MOFs, which almost always invoke a solvent-free MOF,[19] to ex-
perimental data for new materials where the possible role of
MOF activation has not yet been thoroughly explored.
2.1.2. Adsorption capacity for CO2 in MOFs
We now turn to the adsorption capacity of MOFs for CO2. The
high degree of porosity of many MOFs means that they can
hold very large amounts of CO2 or other gases if they are in
equilibrium with gas reservoirs at high pressures. That is, the
absolute saturation capacity for CO2 isotherms in many MOFs
is large. This fact is not particularly relevant for practical appli-
cations of CO2 capture, because the pressure of CO2 that is
available in these applications is modest. It is therefore consid-
erably more important to examine the adsorption capacity of
MOFs (or other potential porous sorbents) under relatively
mild conditions. To this end, we collected data from the litera-
ture that reports the adsorbed amount of pure CO2 in MOFs
at room temperature and 1 atm.[14, 3234, 36, 37, 3943, 4648, 5760,
62, 63, 65, 67, 70, 71, 83, 95, 9799, 104, 106, 108, 115]
This set of data includes experi-
ments ranging from 273 to 318.15 K, and pressures ranging
from 0.85 to 1 bar. When not explicitly stated in the original
source, room temperature was taken to mean 298 K and stan-
dard pressure was taken to be 1 atm. This data is listed in
Table S4 in the Supporting Information and is summarized vis-

ChemSusChem 2010, 3, 879 891  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 881
 D. S. Sholl et al.

ually in Figure 2. For ease of comparison, all adsorbed amounts
are given in mmol g 1. These values can be changed into cm3-
STP g 1 (wt %) by multiplying by 24.4 (4.4). For comparison,
Figure 2. Amount of carbon dioxide adsorbed in MOFs (blue) near ambient
conditions (298 K, 1 atm). Two non-MOF materials (red) are included for
comparison. The top 10 highest values for MOFs are included in Table 2 and
a full listing of all data is provided in Table S4 of the Supporting Informa-
tion.
Figure 2 also shows data from several traditional porous mate-
rials, including zeolite 13X[57] and the activated carbon Norbit
RB2,[14] which adsorb 4.7 and 2.5 mmol g 1 CO2 at these condi-
tions, respectively. The MOFs with the ten highest amounts of
adsorbed CO2 from Figure 2 are listed in Table 2.
As with the heat of adsorption of CO2, a wide range of ad-
sorption capacities at near-ambient conditions are seen in
MOFs. The values shown in Figure 2 range from 8.48 mmol g 1
(37.3 wt %, 207 cm3-STP g 1) for Mg/DOBDC[108] down to
0.16 mmol g 1 (0.7 wt %, 3.9 cm3-STP g 1) for ZIF-20.[106] For ma-
terials with relatively large heats of adsorption, the measured
adsorption capacity is of course closely related to temperature.
To give one example, changing the temperature from 273 to
298 K drops the adsorption capacity at standard pressure for
Bio-MOF-11[67] from 6 to 4 mmol g 1. The small number of
cases where adsorption capacity has been measured for one
material by multiple groups illustrated the importance of syn-
thesis and activation procedures on the overall outcome, as
discussed above for the heat of adsorption. A compilation of
data for MOF-5 in work by Zhao et al. brings together iso-
Table 2. The ten MOFs with the highest reported amount of CO2 adsorbed near ambient (STP) conditions. A
full list of the materials shown in Figure 2 is provided in Table S4 of the Supporting Information.
MOF Conditions
Mg/DOBDC/MOF-74 (Mg)/CPO-27-Mg] 298 K, 1 bar
HKUST-1/Cu-BTC 298 K, 1 bar, 4 % hydrated
Co/DOBDC/MOF-74 (Co)/CPO-27-Co 298 K, 1 bar
Ni/DOBDC/MOF-74 (Ni)/CPO-27-Ni 298 K, 1 bar
bio-MOF-11 273 K, 1 bar
Zn/DOBDC/MOF-74 (Zn)/CPO-27-Zn 296 K, 1 atm
CUK-1 298 K, 760 torr
YO-MOF 273 K, 1 atm
SNU-M10 273 K, 1 atm
H3[(Cu4Cl)3-(BTTri)8] 298 K, 1 bar
therms from several different studies, and shows variation
from 2.1 to 1.12 mmol g 1at 1 bar and 298 K.[34]
The adsorption of CO2 in CuBTC illustrates the potentially
powerful influence of co-adsorbed species on the behavior of
MOFs. In its completely dehydrated form, CuBTC features pairs
of unsaturated Cu atoms. These open metal sites form strong
bonds with water molecules, so a hydrated form of CuBTC can
be created by exposing the material to low partial pressures of
water. The crystal structures of both the hydrated and dehy-
drated crystals have been carefully characterized.[116] In the hy-
drated material, one water molecule is bound to each Cu site.
Hydrated CuBTC shows the second highest CO2 capacity of the
materials summarized in Figure 2, holding > 8 mmol g 1.[59] The
dehydrated form under the same conditions, however, holds
only 45 mmol g 1.[14, 48, 59] It is not accurate to view the results
from the hydrated material as being representative of CO2 ad-
sorption in CuBTC from a humid gas of the kind that may be
relevant in practical applications. The partial pressure of water
that is necessary to hydrate the Cu sites in this material is
almost vanishingly small from a practical point of view, so the
potential impact of additional physisorbed water that would
be present in more realistic scenarios cannot be deduced in a
simple way from the available data. Nevertheless, it is encour-
aging that at least in this one example, the addition of water
to the pores of the adsorbent improves the materials proper-
ties as a CO2 adsorbent.
Having compiled data for both the heat of adsorption and
the ambient adsorption capacity of CO2 in MOFs, it is interest-
ing to explore whether a correlation between these two quan-
tities exists. To this end, we show in Figure 3 and Table 3 the
values of these two quantities for materials where both the ini-
tial heat of adsorption and the amount of CO2 adsorbed under
ambient conditions were reported. Only studies that simulta-
neously reported both quantities for the same sample were in-
cluded in this comparison to eliminate any potential bias due
to synthesis methods or activation procedures. When heat of
adsorption values were reported as a range, this range was
plotted in Figure 3 using an error bar. It is evident from
Figure 3 that these two quantities are not strongly correlated;
for materials with heats of adsorption between 40 and
50 kJ mol 1, adsorbed amounts vary from 1.68 mmol g 1. Per-
haps the most interesting observation from this analysis is that
the materials with the highest
heat of adsorption show low ad-
sorption capacities at ambient
conditions. It seems likely that
Adsorbed amount Ref. this outcome is associated with
[mmol g 1] the rapid saturation of the high-
8.48 [108] est energy binding sites at low
8.18 [59] CO2 pressures. This idea is sup-
7.55 [108] ported by the rapid decrease in
7.15 [108] the heat of adsorption for CO2
6.00 [67]
5.54 [57] as the CO2 loading is increased
3.48 [63] in these kinds of materi-
3.39 [41] als.[42, 67, 68, 97]
3.30 [70] A recent study by Yazaydin
3.25 [97]
et al. examined 14 MOF struc-

882 www.chemsuschem.org  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2010, 3, 879 891
Can MOF Materials Play a Useful Role in Large-Scale CO2 Separations?

ative to CH4, CO, and N2, respectively.[117] Zeolite 5A gives

higher CO2 selectivities for dry gases than BPL Carbon, with re-
ported selectivities of 196, 59, and 331 for the same three gas
mixtures.[117] Not all zeolites are this selective; the selectivities
of zeolite 13X[118] and zeolite b[119] for CO2/CH4 are 224 and 28,
respectively. These widely available materials define several
cautionary notes related to examining data for MOFs. For ex-
ample, the strong heats of adsorption in zeolites such as 5A
and 13X make it difficult to regenerate these adsorbents with-
Figure 3. Amount of carbon dioxide adsorbed in MOFs near ambient condi- out significant heating, leading to high process costs.[55] Anoth-
tions (298 K, 1 atm) relative to heat of adsorption for materials where both
er disadvantage of these two zeolites is that they adsorb water
quantities have been measured. The numerical data for each material is
listed in Table 3. very strongly, significantly changing their adsorption properties
relative to those for dry gases.
If both species of an adsorbed
Table 3. Listing of materials and numerical data shown visually in Figure 3. mixture are present at low load-
ings (more precisely, within the
MOF Ambient amount Ambient con- Heat of Ref.
adsorbed ditions 1
adsorption [kJ mol ]
Henrys regime), the adsorption
[mmol g 1] selectivity relative to an equimo-
bio-MOF-11 4.1 298 K, 1 bar 45 [67]
lar bulk mixture is simply the
Co/DOBDC/MOF-74 (Co)/CPO-27-Co 6.95 296 K, 1 atm 37 [57] ratio of the Henrys constants for
Mg/DOBDC/MOF-74 (Mg)/CPO-27-Mg 8.00 296 K, 1 atm 47 [57] each species adsorbed as a pure
Ni/DOBDC/MOF-74 (Ni)/CPO-27-Ni 5.82 296 K, 1 atm 41 [57] component.[120] At non-dilute
H3[(Cu4Cl)3-(BTTri)8] 3.25 298 K, 1 bar 21 [97]
H3[(Cu4Cl)3-(BTTri8]-(en) 1.25 298 K, 1 bar 90 [97]
loadings, however, more infor-
Mg/DOBDC/MOF-74 (Mg)/CPO-27-Mg 6.82 298 K, 1 atm 40 [42] mation is required to describe
Ni/DOBDC/MOF-74 (Ni)/CPO-27-Ni 6.82 298 K, 1 atm 37 [42] multicomponent adsorption.
Ni-STA-12 2.60 298 K, 1 bar 35 [98] One common approach to de-
[Pd(m-H-pymo-N1,N3)2(H2O)m]n 1.64 293 K, 650 torr 41  3 [43]
1 3
[Pd(m-F-pymo-N ,N )2(H2O)m]n 2.49 293 K, 650 torr 44  4 [43]
scribing multicomponent ad-
[Fe(pz)Ni(CN)4] 2.48 298 K, 1 bar 30 [58] sorption in MOFs is to use ob-
Zn2(tetrakis[4-(carboxyphenyl)oxamethyl] meth- 1.14 298 K, 1 bar 84 [62] served single component ad-
ane)(4,4-bipyridine) sorption isotherms to predict
MOF-5/IRMOF-1 1.92 298 K, 1 bar 34 [34]
multi-component adsorption iso-
therms and selectivities using
Ideal Adsorbed Solution Theory
tures and found that heat of adsorption, which was computed (IAST). IAST is a well-developed technique to describe adsorp-
in their studies, was the best indicator of adsorbent perfor- tion equilibria for components in a gaseous mixture using only
mance at 0.1, 0.5, and 1 bar.[108] They also examined adsorbed data for the pure component adsorption without requiring
amounts at 0.5 and 1 bar, and found that available surface direct experimental measurement or simulation of mixture ad-
area and free volume did not correlate with adsorbed amount. sorption.[121] This approximate theory is known to work accu-
Still, they did not examine any functionalized materials on rately in many nanoporous materials except in materials that
their study, and these materials seemed to be the main reason have strong energetic or geometric heterogeneity.[122, 123] In
for the lack of strong correlation between heat of adsorption almost all examples where molecular simulations of mixture
and adsorbed amount in our analysis. adsorption in MOFs have been compared to IAST, the predic-
tions of IAST have been found to be accurate. These compari-
sons include Yang and Zhongs examination of CO2/CH4 mix-
2.2. Adsorption selectivity for CO2 in MOFs
tures in IRMOF-1, the similar calculations of Babarao and co-
All of the data discussed above was for adsorption of pure workers for CO2/CH4 mixture in the same material, and the re-
CO2. To understand whether an adsorbent can be useful in sults of Yang and co-workers for CO2/N2 and CO2/O2 mixtures
chemical separations, it is obviously critical to characterize the in CuBTC.[124126] In all of these examples, the heat of adsorption
materials performance in the presence of gas mixtures. In this for each species is not strongly loading-dependent. It is impor-
section, we describe experimental efforts that have studied tant to note, however, that IAST does not give accurate results
this issue for MOFs. for some cases; Yang and Zhong[124] and Keskin and Sholl[23]
showed that IAST gave poor results for CO2/H2 mixtures in
CuBTC. The discrepancy observed for this mixture was attribut-
2.2.1. Direct measurement of adsorption equilibrium
ed to the differing adsorption sites accessible to the two mo-
Activated carbons and zeolites have been widely used for se- lecular species inside the MOF.
lective separation of CO2. Henrys law selectivities on BPL The applications of IAST we just discussed used single-com-
Carbon at 303 K were reported as 2.5, 7.5, and 11.1 for CO2 rel- ponent isotherms calculated from molecular simulations. These

ChemSusChem 2010, 3, 879 891  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 883

are the only examples where direct comparisons to multicom-
ponent adsorption are currently possible. We now turn to ap-
plications of IAST involving experimentally measured single
component isotherms. This approach has been used for CO2/
CH4 adsorption in a number of MOFs. Mu et al.[32] predicted a
CO2/CH4 selectivity of 12.4 at 1 bar for an equimolar gas mix-
ture for a structure with unsaturated Cu2 + ions, [Cu2(HBTB)2-
(H2O)(EtOH)]H2OEtOH. Lee et al.[99] incorporated an organic azo-
lium salt as a strut in a microporous MOF material to form a
metalazolium framework and activated this material at differ-
ent temperatures. IAST predictions showed that the MOF
which was activated at a higher temperature for a short time is
the most selective for adsorbing CO2 from equimolar CO2/CH4
mixtures, showing a CO2 selectivity of 20 at 1 bar at room tem-
perature. Bae et al.[44] examined the potential of a carborane-
based MOF for separating mixtures of CO2 and CH4 at room
temperature at pressures up to 20 bar. Combining measured
single-component isotherms with IAST predicted CO2 selectivi-
ties of 731 for bulk gases that are 95 % CH4 and 510 for
equimolar bulk gases. The relatively high CO2 selectivity of this
MOF was attributed to its open metal sites. Bae et al.[93] also
studied adsorption-based separation of CO2/CH4 mixtures in a
mixed ligand paddlewheel MOF, (Zn2(NDC)2(DPNI), using a
combination of experimental measurements, IAST, and molecu-
lar simulation. IAST predicted CO2 selectivities for a bulk mix-
ture of 50 % CH4 in the range of 430, higher than carborane-
based MOF, IRMOF-1, CuBTC, zeolites 13X and b.
The experiments listed above focused on co-adsorption of
CO2 from CH4. Bae and co-workers[60] studied separation of CO2
from N2 by measuring single-component adsorption isotherms
and predicting multicomponent adsorption by IAST. They ex-
amined post-synthesis modification of a MOF[Zn2(1)(DMF)2]n-
(DMF)m, where (1) is 4,4,4,4- benzene-1,2,4,5-tetrayltetraben-
zoic acidby replacing coordinated solvent molecules with
highly polar ligands to enhance CO2/N2 selectivity. They modi-
fied a 3D non-catenated Zn-paddlewheel MOF to form open
metal sites and to make a py-CF3 modified MOF. Single-compo-
nent adsorption isotherms for CO2 and N2 were measured ex-
perimentally in the original MOF and in its modified versions
to make a comparison. IAST was used to predict the adsorp-
tion selectivities up to 8 bar at room temperature. The py-CF3
modified MOF showed CO2 selectivities of 1741.
2.2.2. Multicomponent breakthrough experiments
The experiments described above drew conclusions related to
adsorption selectivity based on measurement of single-compo-
nent adsorption isotherms and application of IAST; none of
them directly observed multicomponent adsorption. Another
useful measure of a materials CO2 separation capacity can be
obtained by exposing a bed packed with the material of inter-
est to mixed gas streams including CO2 and detecting the ap-
pearance or breakthrough of CO2 from the material. Qualita-
tively, a clear difference in breakthrough time between two
species indicates the bed is selective for the gas that has a
longer retention time. To draw quantitative conclusions from
these experiments, the adsorbed amounts of each species of
884 www.chemsuschem.org  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
D. S. Sholl et al.
the mixture can be estimated by integration of breakthrough
curves. An average selectivity is then defined as the ratio of
the adsorbed amounts normalized by the initial composition
of the bulk gas mixture.
A number of multicomponent breakthrough experiments
with MOFs give only qualitative conclusions. Hayashi et al.[106]
reported breakthrough for a CO2/CH4 gas mixture using ZIF-20,
showing that this material preferentially adsorbs CO2 from the
mixture. Dietzel et al.[42] studied members of the CPO-27-M
(M = Ni, Mg) series for separation of CO2/CH4 and CO2/N2 mix-
tures. For both mixtures the material preferentially adsorbed
CO2. Yoon et al.[63] explored separation of light gases over a
column packed with CUK-1, showing that CO2 had the longest
retention time among the gases in a mixture of H2, O2, N2, CH4,
and CO2. None of the conclusions from the breakthrough ex-
periments we have just mentioned are surprising; essentially
all nanoporous materials show preferential adsorption of CO2
relative to other light gases.
Some of the multicomponent breakthrough experiments
with MOFs that have been analyzed quantitatively showed low
levels of CO2 selectivity relative to other porous materials.
Bastin et al.[31] examined separation of CO2 from CO2/N2, CO2/
CH4 and CO2/CH4/N2 mixtures by MOF-508b. The reported se-
lectivity of CO2 from CH4 and N2 at 303 K was 3-6, lower than
selectivity of activated carbon. Finsy et al.[127] studied separa-
tion of CO2/CH4 mixtures using a fixed-bed packed with MIL-
53(Al). A CO2/CH4 selectivity of ca. 7 was found at pressures up
to 5 bar. Adsorption of CO2 in MIL-53(Al) at higher pressures
leads to expansion of the framework and an increase in the ad-
sorbed amount of both gases.[128] As a result, the CO2 selectivi-
ty as assessed by breakthrough experiments decreased from
ca. 7 to ca. 4 at pressures above 5 bar.
A number of experiments showed that the adsorption selec-
tivity of several MOFs for CO2 outperforms traditional nanopo-
rous materials such as BPL Carbon. Wang et al.[47] carried out
breakthrough experiments with ZIF-95 and ZIF-100 by expos-
ing these materials to streams containing binary mixtures of
CO2/CH4, CO2/CO, or CO2/N2. In both ZIFs, only CO2 was re-
tained in the pores while the other gas passed through with-
out hindrance; supporting the idea of using ZIF-95 and ZIF-
100 as selective CO2 reservoirs. They calculated CO2 selectivities
of ZIF-100 (ZIF-95) based on the ratio of Henrys constants of 6
(4), 17 (11), and 25 (18) from CH4, CO, and N2, respectively.
Banerjee et al.[71] studied ZIF-68, 69 and 70 for separation
of CO2 from CO. Their preliminary breakthrough experiments
showed complete retention of CO2 and passage of CO through
the pores of ZIF-68, 69, and 70 when they were exposed to
streams containing a binary mixture of CO2/CO at room tem-
perature. The CO2 selectivities from CO were reported based
on the ratio of Henrys constants as 19.2, 20.9, and 37.8 for
ZIF-68, 69 and 70, respectively. Banerjee and co-workers[49]
also studied separation of CO2/CH4, CO2/N2, and CO2/O2 using
ZIF-78, 79, 81, and 82. They concluded that ZIF-78 and
82 have higher selectivities than the other ZIFs and BPL
carbon for separation of CO2 from CH4, N2, and O2. For exam-
ple, the selectivity for CO2 over N2 (CH4) was estimated based
on the ratio of Henrys constants as ca. 50 (45) and ca. 35 (32)
ChemSusChem 2010, 3, 879 891
Can MOF Materials Play a Useful Role in Large-Scale CO2 Separations?
for ZIF-78 and ZIF-82, respectively. This was attributed to the
presence of NO2 and CN groups in ZIF-78 and 82, respec-
tively, which have significant dipole moments that create
dipolequadrupole interactions with CO2. Breakthrough experi-
ments with CO2/CH4 mixtures for ZIF-78 and ZIF-82 showed
that these materials had longer retention times for CO2 than
BPL Carbon under the same conditions.
Britt et al.[69] performed breakthrough experiments using a
20 % mixture of CO2 in CH4 to test Mg-MOF-74. The resulting
breakthrough curve showed that CO2 is highly preferred over
CH4. The separation capacity was determined by subtracting
the average CO2 concentration prior to breakthrough from the
amount of CO2 fed through the bed during that time. This
gave a separation capacity of Mg-MOF-74 for CO2 of 8.9 wt %,
very similar to the result obtained with zeolite NaX under iden-
tical conditions. To test the importance of the metal ion in CO2
adsorption, Britt et al.[69] also performed CO2 breakthrough
measurements on Zn-MOF-74, which differs from Mg-MOF-74
by substitution of the metal. Zn-MOF-74 took up just 0.35 wt %
CO2, a reduction of 96 % from Mg-MOF-74. Curiously, the ad-
sorbed amount of CO2 in these two materials measured in
other experiments do not differ so strongly (see Table 2)[57] .
The resolution of this apparent disagreement is unclear. Suc-
cessive breakthrough experiments revealed that Mg-MOF-74
retains a capacity of 7.8 wt %, 87 % of its intrinsic capacity,
after room temperature regeneration and further cycling did
not lead to further reduction of capacity.
In addition to the experiments by Finsy et al. with MIL-53(Al)
mentioned above, other experiments have examined other var-
iants of MIL-53. Several studies have reported breakthrough
curves for variants of MIL-53. This class of materials is known
to have a bistable crystal structure, with a narrow pore struc-
ture at low CO2 pressures and a wider pore structure being
stable at higher CO2 pressures.[55, 110] Hamon et al.[46] examined
MIL-53(Cr) for separation of mixtures of CO2 and CH4 by grav-
imetry and by breakthrough curves. Their gravimetric experi-
ments suggested that the narrow pore form of MIL-53(Cr) has
stronger affinity for CO2 and virtually excludes CH4. The selec-
tivity of MIL-53(Cr) measured experimentally is expected to be
correlated to the large pore/narrow pore fraction, which de-
pends on both pressure and initial composition of the gas
feed. Specifically, the exclusion of CH4 from the narrow pore
structure should lead to very high CO2/CH4 selectivities in
breakthrough experiments carried out under conditions in
which the narrow pore form should dominate. This outcome
was not observed, however; breakthrough experiments
showed CO2 selectivities in the range of 216 for different
CO2/CH4 compositions. It seems likely that this was due to a ki-
netic barrier for the large pore to narrow pore transition,
which was not completed during the breakthrough experi-
ments. Couck et al.[39] tested an amine-functionalized MIL-
53(Al) in breakthrough experiments using an equimolar CO2/
CH4 mixture. They concluded that CH4 travels rapidly through
the column, weakly adsorbing in the pores without causing
framework contraction, whereas CO2 adsorbs in the open
pores and replaces pre-adsorbed CH4 molecules. Beyond a cer-
tain CO2 intrapore concentration, pore contraction occurs, re-
ChemSusChem 2010, 3, 879 891  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
sulting in a rapid elimination of excess CH4 molecules from the
pores. Their mass balance calculation showed that essentially
no CH4 was adsorbed while 0.83 mmol g 1 of CO2 was ad-
sorbed, indicating that a very high CO2 selectivity could be ob-
tained at 1 bar. Experiments showed the retention time for CO2
and CH4 is 5.65 min and less than 0.1 at 30 8C, respectively.
Another interesting material that exhibits a high CO2 selec-
tivity associated with framework flexibility is SNU-M10. Choi
and Suh[70] showed that the adsorption selectivity of SNU-M10
for CO2 from N2 at room temperature is strongly pressure-de-
pendent. Specifically, the CO2/N2 selectivity of SNU-M10 at
298 K was reported as 24:1 (v/v) at 0.61 atm and 98:1 (v/v) at
1.0 atm, based on the ratio of volumetric gas uptakes. This
phenomenon occurs due to CO2-induced gate opening and
closing in the pores. This work also reported data on reversible
capture of CO2 in SNU-M10 at 298 K from a gas cycling experi-
ment on a thermogravimetric apparatus using a flow of 15 %
(v/v) CO2 in N2.
2.2.3. Open issues for adsorption-based separations with
MOFs
We have summarized the large literature that now exists char-
acterizing CO2 adsorption in MOFs. We conclude this section
by briefly commenting on what information is not currently
available. Very little is known about the co-adsorption of CO2
with water, despite the ubiquitous nature of water vapor in
large-scale applications. We feel that this is the most critical
shortcoming of work to date in this area, and we return to it in
Section 4. In addition to water vapor, realistic gas streams also
typically contain trace levels of potentially reactive species
such as SOx and NOx. It appears that almost nothing is current-
ly known about the effects of these species on MOFs, particu-
larly in humid environments. This situation will need to be re-
solved before the full potential of MOFs for large scale applica-
tions can be fully assessed.
The large amount of adsorption data that is now available
for dry gases in MOFs hopefully means that the research com-
munity can move towards a nuanced view of future experi-
ments. The fact that a new MOF preferentially adsorbs CO2 rel-
ative to CH4 or N2 is not intrinsically interesting; this is what es-
sentially all nanoporous materials do. Similarly, if a new MOFs
adsorption selectivity and/or capacity do not substantially im-
prove upon well-known and inexpensive adsorbents such as
activated carbon, then it can be concluded without exhaustive
analysis that the new material will not find widespread com-
mercial use.
3. MOFs for Kinetic Separations of CO2
We described in Section 1 how chemical separations with
porous materials can be broadly divided into adsorption-based
methods and kinetic separations. Kinetic separations can be
achieved using packed beds, but the most important applica-
tion of this concept is in membranes. Compared to the efforts
that have been devoted to characterizing adsorption in MOFs,
exploration of the use of MOFs in membranes is only just be-
www.chemsuschem.org 885

ginning. Below, we review what is currently known about
MOF-based membranes for CO2 separations in two categories:
Hybrid (composite) membranes with MOFs and pure MOF
membranes.
3.1. Hybrid membranes with MOFs for separation of CO2
Hybrid membranes are heterogeneous membranes in which
organic/inorganic fillers are embedded into a polymer matrix
to enhance the selectivity and/or permeability of a pure poly-
meric membrane. Hybrid membranes have been prepared with
various fillers such as zeolites and carbon molecular sieves in
the past to exceed the selectivity/permeability upper bound
established for polymeric membranes.[129, 130] The most signifi-
cant advantage of hybrid membranes is that fabricating these
membranes on large scales can readily be envisioned with rela-
tively minor adaptation of existing commercial technology.
Polymer membranes with active surface area of hundreds of
thousands of square meters are already routinely used in in-
dustrial applications such as water desalination and reverse os-
mosis,[131, 132] and significant research efforts are already in
place to study methods of economical implementation of this
technology for flue gas capture.[132, 133]
Several groups have used MOF particles as fillers in polymer-
ic membranes and examined the performance of these hybrid
membranes for CO2 separations. The hybrid membranes are
typically described in terms of the loading of filler particles in
the polymer matrix. Car et al.[134] characterized MOF-based
hybrid membranes using a time lag apparatus. They studied
two different polymers, poly(dimethylsiloxane) (PDMS) and
polysulfone (PSf), and two MOFs, CuBTC and Mn(HCOO)2, as
filler particles in the polymers for separation of CO2 from N2
and CH4. Very slight improvements in the ideal selectivity for
CO2 over N2 at 10 % MOF loading and CO2 over CH4 up to 30 %
MOF loading of CuBTC in PDMS were observed. For example,
the selectivity for CO2 over N2 (CH4) was increased from 8 (3) in
PDMS membrane to 9 (4) in the hybrid membrane. Hybrid
membranes with a 5 % loading of Mn(HCCO)2 in PSf showed
essentially the same CO2 selectivity (ca. 20) with the pure PSf
membrane.
Zhang et al.[135] examined membranes composed of the MOF
Cu-BPY-HFS and Matrimid, a commercial polymer, for separa-
tion of CO2/CH4 and H2/CO2 mixtures. A hybrid membrane with
20 % Cu-BPY-HFS loading had a lower CO2 selectivity (20.5)
than a pure Matrimid membrane (36.3) for an equimolar CO2/
CH4 mixture. This decrease in CO2 selectivity was attributed to
high CH4 affinity of Cu-BPY-HFS. No significant change was ob-
served for selectivity of H2/CO2 mixtures relative to a pure Ma-
trimid membrane. Perez et al.[136] combined IRMOF-1 with Ma-
trimid to study separation of CO2/CH4 and H2/CO2 mixtures.
The results from this hybrid membrane were similar to the Cu-
BPY-HFS/Matrimid membrane discussed above: the MOF de-
creased the selectivity of the membrane for CH4/CO2 mixtures
and caused no appreciable change in selectivity for an H2/CO2
mixture. Although the MOF did not lead to an increase in the
membranes CO2 selectivity, the CO2 permeability of the hybrid
886 www.chemsuschem.org  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
D. S. Sholl et al.
membrane was up to 120 % larger than the pure polymer due
to the porosity of IRMOF-1 crystals.
Adams et al.[137] incorporated CuTPA MOF particles into PVAc
(polyvinyl acetate) to create 15 % (w/w) CuTPA-PVAc hybrid
membranes. Both CO2 permeability and ideal selectivity were
enhanced with hybrid membranes. The hybrid membrane
showed a slightly higher CO2 permeability (3.26 Barrer) than
the pure PVAc membrane (2.44 Barrer). The ideal selectivity for
CO2 over N2 (CH4) increased from 32.1 (34.9) in polymeric mem-
brane to 35.4 (40.4) in the hybrid membrane. Diaz et al.[138]
used pulse field gradient NMR techniques to study transport of
CO2 in a pristine poly(1,4-phenylene ether-ether-sulfone) mem-
brane and hybrid membranes including ZIF-8 particles in this
polymer. They also performed permeation experiments and re-
ported an increase in CO2 permeation relative to the pure poly-
mer.
Although these initial studies of MOFpolymer hybrid mem-
branes have not delivered a device with spectacular properties,
they do hint that this direction will be productive in the future.
Extensive previous studies of hybrid membranes using zeolites
as fillers have shown that achieving good compatibility be-
tween filler particles and the polymer matrix is both crucial
and challenging to achieve.[129, 130] The results from MOF-poly-
mer hybrid membranes to date suggest that these compatibili-
ty issues may be easier to handle with MOFs than with other
kinds of filler particles. For example, Zhang et al.[135] reported
that it was relatively easy to make defect free hybrid mem-
branes with MOFs due to the good compatibility between the
MOF crystals and the polymer matrix.
A critical question for the future development of this area is
whether MOF-polymer hybrids can be found whose properties
greatly improve on the polymer alone. Two of us have recently
introduced the first quantitative models of MOFpolymer
membranes,[139] and our results suggest that the observations
from the materials that have been studied to date are not (in
retrospect) surprising because the intrinsic kinetic selectivity
for the MOFs used to date is low. This outcome does not
appear to be true for all MOFs, however. Detailed models of
small pore MOFs have predicted that materials exist that have
very high kinetic selectivities for CO2/CH4 separations based on
large differences in the diffusion coefficients of the two spe-
cies.[140] Models that combine this information with experimen-
tal data from readily available polymers suggest that hybrid
MOFpolymer membranes made from these materials will
have both selectivity and permeability for CO2 that strongly ex-
ceeds the pure polymer membrane[139] .
3.2. Thin-film MOF membranes for separation of CO2
An alternative to using nanoporous materials as fillers in poly-
mer membranes is to fabricate membranes in which the active
layer is a dense film of the nanoporous material alone. This ap-
proach has been widely studied for zeolite membranes, where
intergrown films of zeolite crystals are typically fabricated on
top of a porous support such as alumina or stainless steel.[141]
The scale-up of thin-film membranes of this type to the very
large surface areas that will be required for large-scale applica-
ChemSusChem 2010, 3, 879 891
Can MOF Materials Play a Useful Role in Large-Scale CO2 Separations?
tions remains a severe challenge. Nevertheless, these mem-
branes continue to receive a great deal of attention because of
their excellent performance in CO2 separations (among other
chemical separations). Several zeolite membranes with very
high CO2 selectivity for CO2/CH4 mixtures are known. For exam-
ple, DDR (SAPO-34) membranes have been demonstrated with
a CO2 selectivity of 100 (270) from equimolar CO2/CH4 mixtures
at 303 (255) K and 5 (2.22) bar.[142, 143]
The fabrication of thin-film MOF membranes has only been
explored very recently. The first continuous and well-inter-
grown IRMOF-1 membrane was prepared on a porous alumina
support by in situ solvothermal synthesis by Liu et al.[144] Gas
permeation results showed that diffusion of CO2, CH4, H2, N2,
and SF6 through an IRMOF-1 membrane mainly follows a
Knudsen diffusion scaling. Bux et al.[145] prepared a continuous
intergrown layer of ZIF-8 on a porous titania support and mea-
sured the volumetric flow rates of single gases: CO2, H2, O2, N2,
and CH4. The permeance of H2 was almost five times faster
than that of CO2. Ranjan and Tsapatsis[146] prepared films of Cu-
(hfipbb)(H2hfipbb)0.5 on porous alumina discs and tested this
membrane for single-gas permeation of CO2, N2, H2, He, n-
butane, and iso-butane. Their Cu(hfipbb)(H2hfipbb)0.5 mem-
brane exhibited an ideal selectivity of ca. 4 for H2 over CO2 be-
tween 25200 8C. The net gas fluxes through this membrane
were low for all of the species tested, and the authors specu-
lated that efficient molecular transport through the films may
be severely reduced by misoriented crystals that block the
one-dimensional pore channels in the membrane.
The experiments listed above examined pure gas permea-
tion through MOF thin films. A limited number of MOF mem-
branes have been tested for separation of gas mixtures. Guo
et al.[28] prepared a Cu(BTC) membrane on a porous copper
support using a twin copper source method to study separa-
tion of H2/CO2 mixtures. They reported a H2 selectivity of 6.84
from equimolar H2/CO2 mixtures, a value somewhat higher
than the ideal selectivity of 4.52. Li et al. studied H2/CO2 per-
meation through ZIF-7 films using membranes fabricated with
seeded secondary growth method on an alumina support. The
H2/CO2 ideal selectivity and mixture selectivity were 6.7 and
6.5, respectively.
The large body of work associated with development of
thin-film zeolite membranes makes it clear that the overall per-
formance of these membranes is affected by both the intrinsic
properties of the zeolite crystals that make up the membrane
and the microstructure of the intergrown crystals that form
the membrane.[141] The same set of issues will also be critical in
membranes made from thin films of MOFs. The development
of these membranes is currently in its earliest stages, so it is
not yet possible to draw any definitive conclusions about
whether thin-film MOF membranes will be viable for practical
separations.
3.3. Characterizing CO2 diffusion in MOFs
For both kinds of membranes addressed above, the current ex-
perimental state of the art is that initial demonstrations that
MOFs can be used in membranes have been made, but no ex-
ChemSusChem 2010, 3, 879 891  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
amples with truly outstanding properties have yet been found.
If work in this area is to progress rapidly, it will be important
to use knowledge about the diffusion rates of molecules inside
MOFs to guide choices of which MOFs are the most likely to
be useful. Unfortunately, accurate characterization of molecular
transport inside nanoporous materials using experimental
techniques is very challenging. As a result, most of what is cur-
rently known about molecular diffusion of CO2 in MOFs has
come from molecular simulation studies.[147150]
Recently, several experimental techniques have been used
to assess CO2 diffusion in MOFs. Salles et al.[151] used a combi-
nation of quasi-elastic neutron scattering (QENS) measure-
ments and molecular dynamics simulations to examine the
transport diffusivity of CO2 in MIL-53 (Cr). Their experiments
and simulations were in fair agreement, and indicated that CO2
has a one-dimensional diffusion mechanism in both the
narrow pore and large pore structures of MIL-53(Cr). Salles and
co-workers[152] used the same methods to characterize the self
and transport diffusivities of CO2 in the rigid MOF MIL-47(V). In
both of these materials, the magnitude of the transport diffu-
sivities were found to be 10 8 m2 s 1. Zhao et al.[34] studied the
kinetics of adsorption and diffusion of CO2 in IRMOF-1, obtain-
ing CO2 diffusion coefficients of 511  10 13 m2 s 1 at 295
331 K. The difference between the diffusivities measured in
IRMOF-1 and MIL-47 is surprisingly large. For comparison, a
typical diffusivity for a small molecule in a liquid is 10 9 m2 s 1.
A critical lesson from the successful examples of highly se-
lective zeolite membranes for CO2 separations has been that
an effective membrane shows rapid diffusion of one species
(typically CO2) but very slow diffusion of other gases such as
CH4.[24, 142, 143] For the use of MOFs as components in mem-
branes to be successful, the identification of MOFs that have
this property is highly desirable. It appears that many, perhaps
most, MOFs do not have this property because the pore vol-
umes that control overall molecular diffusion are significantly
larger than typical gas molecules.[153] There are examples, how-
ever, where MOFs can be expected to have large differences in
diffusion coefficients among adsorbed gases. A recent model-
ing study that combined molecular simulations with quantum
chemistry calculations gave one example of this kind.[140] All as-
pects of the use of MOFs in membranes for CO2-related separa-
tions will move forward more quickly if experimental and mod-
eling efforts are focused on materials that have the pore char-
acteristics that allow the possibility of strong diffusion-based
selectivity rather than on large pore materials where the diffu-
sion coefficients of adsorbed gases can vary only relatively
weakly from species to species.
4. Conclusion and Outlook
There are several reasons to be optimistic about the potential
of MOFs for CO2 separations. A huge diversity of MOFs is
known. Avenues towards scalable applications in packed beds
or as components in high-surface-area membranes can be rea-
sonably envisaged. Computational tools for focusing searches
through the large space of possible materials to find the small
fraction of the best-performing materials are becoming avail-
www.chemsuschem.org 887

able. There are, however, critical issues that will severely
hamper development of real applications if they are not ad-
dressed in a timely way. Below, we describe these issues.
By far the most critical issue is, to paraphrase Coleridges An-
cient Mariner, water, water everywhere, but not a drop of data.
Real CO2 separations must deal with gas streams containing,
and often saturated by, water. It is extraordinarily unlikely that
any process that dries flue gas before treating it for CO2 cap-
ture could be economically feasible.
The behavior of MOFs in hydrated conditions water varies
widely, from materials that irreversibly degrade due to water
under mild conditions[154] to examples that are highly stable in
boiling water,[15, 97] and the literature on systematic studies of
water adsorption in MOFs is limited. Experimental studies of Li
and Yang[155] indicated that MOF-177 can adsorb up to 10 wt %
H2O at room temperature, but this framework is not stable
upon H2O adsorption, and MOF-177 decomposes after expo-
sure to ambient air in 3 days. Kondo et al.[156] studied water ad-
sorption isotherms at 303 K on water-resistant three-dimen-
sional pillared layer MOFs.
Work specifically focusing on MOF stability has also been
sparse. Two notable studies are the high throughput analysis
of Low et al. and the modeling work of Greathouse and Allen-
dorf. Low et al.[157] found that the stability of MOFs in steam at
various saturations and temperatures corresponded well with
the dissociation energy of the metalligand bond. Greathouse
and Allendorf[154] found that ligand displacement at metal sites
is a likely mode of dissociation.
These studies have been beneficial in opening the door to
understanding MOF interactions with water, but more system-
atic studies are needed to gain understanding of the compet-
ing nature or assisting of water co-adsorption and the reasons
for MOF hydrothermal stability and instability. Multiple papers
have suggested that MOFs with open metal sites have favora-
ble properties for dry gas separations. In all examples we are
aware of, however, water binds strongly to these open metal
sites at bond strengths that are characteristic of chemisorption,
not physisorption. Unless convincing evidence is given to the
contrary for a particular material, it therefore appears reasona-
ble to assume that these open metal sites will be fully hydrat-
ed under essentially any conditions of practical interest for CO2
separations. One interesting report on this interaction comes
from the work of Yazadin et al.,[108] where the authors found
that adsorption of carbon dioxide actually increased at low
water vapor concentrations. Additionally, a number of studies
have pointed out the flexibility of MIL-53 (Cr) in the presence
of water, which results in a structural switching between a
large pore and a narrow pore form.
These observations of interactions with water provoke two
questions that should be answered for any MOF being consid-
ered for CO2 separations:
Question 1: Is the MOF stable under long term exposure to
low temperature steam?
If the answer to this question is no, further efforts to devel-
op the material for CO2 separations will be fruitless.
Question 2: How are the separation characteristics of the
material for CO2 affected by the presence of water vapor?
888 www.chemsuschem.org  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
D. S. Sholl et al.
Addressing this question should include both chemisorption
of water to open metal sites, if they exist, but also the coad-
sorption of physisorbed water in the MOFs pores. No serious
consideration of how a material could be used in a real appli-
cation is possible if this question is not answered. In our view,
progress in this field will stall unless these questions are tack-
led. Phrased more positively, research teams that successfully
resolve these questions will open up opportunities that may
permanently elude others who do not address them.
The interactions between water and CO2 inside pores of
MOFs will not necessarily prevent these materials from being
useful in practical applications. One example, CuBTC, has al-
ready been studied where the hydration of open metal sites in
the MOF framework increases the adsorbed amount of CO2 at
mild conditions relative to the dehydrated material (see discus-
sion in Section 2). In amine-containing materials, the presence
of water increases the variety of complexes that can form be-
tween CO2 and amines,[113] and there is no reason to suspect
that these interactions will always have a negative effect. The
lack of attention to these issues, however, is a critical limitation
of work to date in this area.
Aside from coadsorption of CO2 and water, it is striking how
little data is available regarding the coadsorption of any gas
mixtures in MOFs. Our literature survey did not find any meas-
urements that directly characterize multicomponent adsorp-
tion equilibrium involving CO2 in any MOF, although there are
a sizeable number of packed-bed breakthrough experiments
that give some insight into these issues. There is no doubt
that detailed measurements of multicomponent adsorption
equilibria are more challenging than pure component iso-
therms. For materials that are judged to be promising for real
applications, it would be fruitful to obtain data of this kind to
directly test the simple mixing theories such as IAST that are
typically assumed to be valid in current descriptions. This issue
may be especially important in materials where single-compo-
nent isotherms are strongly influenced by framework flexibility
in the MOF.
No experimental data at all is currently available regarding
multicomponent diffusion in MOFs. In our view, collecting data
of this kind for MOFs where diffusion of all components of an
adsorbed species is expected to be facile would have limited
value. If, in contrast, experiments to gather data of this kind
were performed on MOFs that are expected to show strong
diffusion-based selectivity for CO2 relative to other adsorbed
species could potentially play a key role in advancing develop-
ments of MOF-based membranes.
In considering MOFs for adsorption-based separations, infor-
mation on the reproducibility of sample properties and the re-
sponse of materials to cycling is urgently needed. We have al-
ready discussed several examples where careful studies by sev-
eral groups have highlighted the role of solvent removal and
activation of MOFs on their adsorption properties. Forward
progress in the field will be aided by clear descriptions of acti-
vation procedures and open discussion of challenges found in
reproducing data either within a single laboratory or when
making comparisons with literature data. The number of MOFs
for which detailed adsorption measurements have been per-
ChemSusChem 2010, 3, 879 891
Can MOF Materials Play a Useful Role in Large-Scale CO2 Separations?
formed by multiple groups is extremely limited compared to
the number for which a single published experiment is avail-
able. In studies of reversible hydrogen storage in solids, efforts
to characterize large number of loading/unloading cycles play
an influential role in demonstrating material stability.[158] Similar
efforts that demonstrate the stability of MOFs during cycling
for adsorption-based separations have considerable
value.[127, 159]
Attentive readers will note that our review jumped back and
forth between experiments aimed at CO2/H2, CO2/CH4, and
CO2/N2 mixtures. The clear economic incentives associated
with sour gas processing have motivated much of the work on
CO2/CH4 mixtures, but if the goal of a project is to consider
flue gas processing, then it is vital to collect data with CO2/N2
mixtures. Much can be inferred about CO2/N2 separations from
the CO2/CH4 data. CH4 typically adsorbs more strongly in nano-
pores than N2, so adsorption selectivities for CO2/N2 mixtures
will typically be higher than for CO2/CH4 mixtures. Neverthe-
less, having data at conditions similar to those of a particular
application will always be more valuable for making predic-
tions for that application than the kind of inference by analogy
just outlined.
Throughout this article, we have focused on the question
posed in our articles title: can MOFs play a useful role in large
scale CO2 related separations? No firm conclusion on this ques-
tion is currently possible. We hope that the next few years will
deliver information associated with the open issues we have
raised above that will enable the R&D community to resolve
this question in a definitive way.
We close by briefly suggesting a way in which MOFs may
enable breakthroughs in the broader area of porous adsorb-
ents for CO2 separations. It is possible that the best adsorbents
that will emerge for these applications will have high surface
areas but be intrinsically disordered on molecular length
scales.[113] Materials of this kind are difficult to optimize, at least
in part because the molecular-scale mechanisms that control
their behavior are hard to characterize. MOFs have potential to
play a useful role in this area because their highly ordered
structure makes them amenable to experimental and theoreti-
cal understanding. Efforts that seek to use MOFs as prototypes
to gain understanding of the important fundamental issues
that exist for more complex adsorbents could in the future
make significant contributions to this field.
Acknowledgements
This work was partially supported by the National Science Foun-
dation.
Keywords: adsorption carbon storage metal-organic
frameworks porous materials sustainable chemistry
[1] E. Drioli, M. Romano, Ind. Eng. Chem. Res. 2001, 40, 1277.
[2] T. Wall, Y. H. Liu, C. Spero, L. Elliott, S. Khare, R. Rathnam, F. Zeenathal,
B. Moghtaderi, B. Buhre, C. D. Sheng, R. Gupta, T. Yamada, K. Makino,
J. L. Yu, Chem. Eng. Res. Des. 2009, 87, 1003.
ChemSusChem 2010, 3, 879 891  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
[3] K. Uemura, R. Matsuda, S. Kitagawa, J. Solid State Chem. 2005, 178,
2420.
[4] T. Uemura, N. Yanai, S. Kitagawa, Chem. Soc. Rev. 2009, 38, 1228.
[5] G. Frey, C. Serre, Chem. Soc. Rev. 2009, 38, 1380.
[6] S. L. James, Chem. Soc. Rev. 2003, 32, 276.
[7] U. Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt, J. Pastre,
J. Mater. Chem. 2006, 16, 626.
[8] A. U. Czaja, N. Trukhan, U. Muller, Chem. Soc. Rev. 2009, 38, 1284.
[9] O. M. Yaghi, H. L. Li, J. Am. Chem. Soc. 1995, 117, 10401.
[10] H. Li, M. Eddaoudi, M. OKeeffe, O. M. Yaghi, Nature 1999, 402, 276.
[11] M. Eddaoudi, H. L. Li, O. M. Yaghi, J. Am. Chem. Soc. 2000, 122, 1391.
[12] O. M. Yaghi, M. OKeeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi, J. Kim,
Nature 2003, 423, 705.
[13] J. L. C. Rowsell, O. M. Yaghi, Microporous Mesoporous Mater. 2004, 73, 3.
[14] A. R. Millward, O. M. Yaghi, J. Am. Chem. Soc. 2005, 127, 17998.
[15] K. S. Park, Z. Ni, A. P. Cote, J. Y. Choi, R. D. Huang, F. J. Uribe-Romo,
H. K. Chae, M. OKeeffe, O. M. Yaghi, Proc. Natl. Acad. Sci. USA 2006,
103, 10186.
[16] O. M. Yaghi, Q. W. Li, MRS Bull. 2009, 34, 682.
[17] L. Pan, K. M. Adams, H. E. Hernandez, X. T. Wang, C. Zheng, Y. Hattori,
K. Kaneko, J. Am. Chem. Soc. 2003, 125, 3062.
[18] S. Kitagawa, R. Kitaura, S.-i. Noro, Angew. Chem. 2004, 116, 2388;
Angew. Chem. Int. Ed. 2004, 43, 2334.
[19] S. Keskin, J. Liu, R. B. Rankin, J. K. Johnson, D. S. Sholl, Ind. Eng. Chem.
Res. 2009, 48, 2355.
[20] T. Dren, Y. S. Bae, R. Q. Snurr, Chem. Soc. Rev. 2009, 38, 1237.
[21] E. D. Akten, R. Siriwardane, D. S. Sholl, Energy Fuels 2003, 17, 977.
[22] R. T. Yang, Gas Separation by Adsorption Processes, Butterworths,
Boston, 1987.
[23] S. Keskin, D. S. Sholl, Langmuir 2009, 25, 11786.
[24] S.-E. Jee, D. S. Sholl, J. Am. Chem. Soc. 2009, 131, 7896.
[25] S. Babel, T. A. Kurniawan, J. Hazard. Mater. 2003, 97, 219.
[26] R. L. Virta, C. H. Lindsay, Zeolites, US Geological Survey Minerals Year-
book, 1999.
[27] E. Ruiz-Agudo, S. Galli, J. A. R. Navarro, Inorg. Chim. Acta 2007, 360, 84.
[28] H. L. Guo, G. S. Zhu, I. J. Hewitt, S. L. Qiu, J. Am. Chem. Soc. 2009, 131,
1646.
[29] C. E. Willans, S. French, L. J. Barbour, J. A. Gertenbach, P. C. Junk, G. O.
Lloyd, J. W. Steed, Dalton Trans. 2009, 6480.
[30] T. M. Reineke, M. Eddaoudi, M. OKeeffe, O. M. Yaghi, Angew. Chem.
1999, 111, 2712; Angew. Chem. Int. Ed. 1999, 38, 2590.
[31] L. Bastin, P. S. Barcia, E. J. Hurtado, J. A. C. Silva, A. E. Rodrigues, B.
Chen, J. Phys. Chem. C 2008, 112, 1575.
[32] B. Mu, F. Li, K. S. Walton, Chem. Commun. 2009, 2493.
[33] Z. Y. Guo, J. B. Yu, G. H. Li, Z. J. Si, H. D. Guo, H. J. Zhang, CrystEng-
Comm 2009, 11, 2254.
[34] Z. X. Zhao, Z. Li, Y. S. Lin, Ind. Eng. Chem. Res. 2009, 48, 10015.
[35] A. J. Fletcher, E. J. Cussen, T. J. Prior, M. J. Rosseinsky, C. J. Kepert, K. M.
Thomas, J. Am. Chem. Soc. 2001, 123, 10001.
[36] P. D. C. Dietzel, R. E. Johnsen, H. Fjellvag, S. Bordiga, E. Groppo, S.
Chavan, R. Blom, Chem. Commun. 2008, 5125.
[37] B. Arstad, H. Fjellvag, K. O. Kongshaug, O. Swang, R. Blom, Adsorption
2008, 14, 755.
[38] R. Vaidhyanathan, S. S. Iremonger, K. W. Dawson, G. K. H. Shimizu,
Chem. Commun. 2009, 5230.
[39] S. Couck, J. F. M. Denayer, G. V. Baron, T. Remy, J. Gascon, F. Kapteijn, J.
Am. Chem. Soc. 2009, 131, 6326.
[40] C. Serre, S. Bourrelly, A. Vimont, N. A. Ramsahye, G. Maurin, P. L. Llewel-
lyn, M. Daturi, Y. Filinchuk, O. Leynaud, P. Barnes, G. Ferey, Adv. Mater.
2007, 19, 2246.
[41] K. L. Mulfort, O. K. Farha, C. D. Malliakas, M. G. Kanatzidis, J. T. Hupp,
Chem. Eur. J. 2010, 16, 276.
[42] P. D. C. Dietzel, V. Besikiotis, R. Blom, J. Mater. Chem. 2009, 19, 7362.
[43] J. A. R. Navarro, E. Barea, J. M. Salas, N. Masciocchi, S. Galli, A. Sironi,
C. O. Ania, J. B. Parra, J. Mater. Chem. 2007, 17, 1939.
[44] Y. S. Bae, O. K. Farha, A. M. Spokoyny, C. A. Mirkin, J. T. Hupp, R. Q.
Snurr, Chem. Commun. 2008, 4135.
[45] Z. J. Liang, M. Marshall, A. L. Chaffee, Energy Fuels 2009, 23, 2785.
[46] L. Hamon, P. L. Llewellyn, T. Devic, A. Ghoufi, G. Clet, V. Guillerm, G. D.
Pirngruber, G. Maurin, C. Serre, G. Driver, W. van Beek, E. Jolimaitre, A.
Vimont, M. Daturi, G. Ferey, J. Am. Chem. Soc. 2009, 131, 17490.
www.chemsuschem.org 889

[47] B. Wang, A. P. Cote, H. Furukawa, M. OKeeffe, O. M. Yaghi, Nature
2008, 453, 207.
[48] P. Chowdhury, C. Bikkina, D. Meister, F. Dreisbach, S. Gumma, Micropo-
rous Mesoporous Mater. 2009, 117, 406.
[49] R. Banerjee, H. Furukawa, D. Britt, C. Knobler, M. OKeeffe, O. M. Yaghi,
J. Am. Chem. Soc. 2009, 131, 3875.
[50] H. Furukawa, J. Kim, N. W. Ockwig, M. OKeeffe, O. M. Yaghi, J. Am.
Chem. Soc. 2008, 130, 11650.
[51] Y. K. Park, S. B. Choi, H. Kim, K. Kim, B. H. Won, K. Choi, J. S. Choi, W. S.
Ahn, N. Won, S. Kim, D. H. Jung, S. H. Choi, G. H. Kim, S. S. Cha, Y. H.
Jhon, J. K. Yang, J. Kim, Angew. Chem. 2007, 119, 8378; Angew. Chem.
Int. Ed. 2007, 46, 8230.
[52] J. Liang, G. K. H. Shimizu, Inorg. Chem. 2007, 46, 10449.
[53] M. Eddaoudi, H. L. Li, T. Reineke, M. Fehr, D. Kelley, T. L. Groy, O. M.
Yaghi, Top. Catal. 1999, 9, 105.
[54] A. C. Sudik, A. R. Millward, N. W. Ockwig, A. P. Cote, J. Kim, O. M. Yaghi,
J. Am. Chem. Soc. 2005, 127, 7110.
[55] S. Bourrelly, P. L. Llewellyn, C. Serre, F. Millange, T. Loiseau, G. Ferey, J.
Am. Chem. Soc. 2005, 127, 13519.
[56] H. Chun, J. Seo, Inorg. Chem. 2009, 48, 9980.
[57] S. R. Caskey, A. G. Wong-Foy, A. J. Matzger, J. Am. Chem. Soc. 2008,
130, 10870.
[58] P. D. Southon, L. Liu, E. A. Fellows, D. J. Price, G. J. Halder, K. W. Chap-
man, B. Moubaraki, K. S. Murray, J. F. Letard, C. J. Kepert, J. Am. Chem.
Soc. 2009, 131, 10998.
[59] A. O. Yazaydin, A. I. Benin, S. A. Faheem, P. Jakubczak, J. J. Low, R. R.
Willis, R. Q. Snurr, Chem. Mater. 2009, 21, 1425.
[60] Y. S. Bae, O. K. Farha, J. T. Hupp, R. Q. Snurr, J .Mater. Chem. 2009, 19,
2131.
[61] H. Li, M. Eddaoudi, T. L. Groy, O. M. Yaghi, J. Am. Chem. Soc. 1998, 120,
8571.
[62] P. K. Thallapally, J. Tian, M. R. Kishan, C. A. Fernandez, S. J. Dalgarno,
P. B. McGrail, J. E. Warren, J. L. Atwood, J. Am. Chem. Soc. 2008, 130,
16842.
[63] J. W. Yoon, S. H. Jhung, Y. K. Hwang, S. M. Humphrey, P. T. Wood, J. S.
Chang, Adv. Mater. 2007, 19, 1830.
[64] T. K. Maji, G. Mostafa, R. Matsuda, S. Kitagawa, J. Am. Chem. Soc. 2005,
127, 17152.
[65] J. A. R. Navarro, E. Barea, J. M. Salas, N. Masciocchi, S. Galli, A. Sironi,
C. O. Ania, J. B. Parra, Inorg. Chem. 2006, 45, 2397.
[66] D. Farrusseng, C. Daniel, C. Gaudillere, U. Ravon, Y. Schuurman, C. Mir-
odatos, D. Dubbeldam, H. Frost, R. Q. Snurr, Langmuir 2009, 25, 7383.
[67] J. An, S. J. Geib, N. L. Rosi, J. Am. Chem. Soc. 2010, 132, 38.
[68] P. L. Llewellyn, S. Bourrelly, C. Serre, A. Vimont, M. Daturi, L. Hamon, G.
De Weireld, J. S. Chang, D. Y. Hong, Y. K. Hwang, S. H. Jhung, G. Ferey,
Langmuir 2008, 24, 7245.
[69] D. Britt, H. Furukawa, B. Wang, T. G. Glover, O. M. Yaghi, Proc. Natl.
Acad. Sci. USA 2009, 106, 20637.
[70] H. S. Choi, M. P. Suh, Angew. Chem. 2009, 121, 6997; Angew. Chem. Int.
Ed. 2009, 48, 6865.
[71] R. Banerjee, A. Phan, B. Wang, C. Knobler, H. Furukawa, M. OKeeffe,
O. M. Yaghi, Science 2008, 319, 939.
[72] P. L. Llewellyn, S. Bourrelly, C. Serre, Y. Filinchuk, G. Ferey, Angew. Chem.
2006, 118, 7915; Angew. Chem. Int. Ed. 2006, 45, 7751.
[73] D. Li, K. Kaneko, Chem. Phys. Lett. 2001, 335, 50.
[74] J. T. Culp, M. R. Smith, E. Bittner, B. Bockrath, J. Am. Chem. Soc. 2008,
130, 12427.
[75] J. Seo, H. Chun, Eur. J. Inorg. Chem. 2009, 4946.
[76] Q. Min Wang, D. M. Shen, M. Bulow, M. L. Lau, S. G. Deng, F. R. Fitch,
N. O. Lemcoff, J. Semanscin, Microporous Mesoporous Mater. 2002, 55,
217.
[77] S. Q. Ma, X. S. Wang, E. S. Manis, C. D. Collier, H. C. Zhou, Inorg. Chem.
2007, 46, 3432.
[78] D. G. Samsonenko, H. Kim, Y. Y. Sun, G. H. Kim, H. S. Lee, K. Kim, Chem.
Asian J. 2007, 2, 484.
[79] X. F. Wang, Y. B. Zhang, H. Huang, J. P. Zhang, X. M. Chen, Cryst. Growth
Des. 2008, 8, 4559.
[80] H. J. Lee, W. Cho, S. Jung, M. Oh, Adv. Mater. 2009, 21, 674.
[81] H. Deng, C. J. Doonan, H. Furukawa, R. B. Ferreira, J. Towne, C. B. Kno-
bler, B. Wang, O. M. Yaghi, Science 2010, 327, 846.
890 www.chemsuschem.org  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
D. S. Sholl et al.
[82] P. Kanoo, R. Matsuda, M. Higuchi, S. Kitagawa, T. K. Maji, Chem. Mater.
2009, 21, 5860.
[83] A. Rossin, A. Ienco, F. Costantino, T. Montini, B. Di Credico, M. Caporali,
L. Gonsalvi, P. Fornasiero, M. Peruzzini, Cryst. Growth Des. 2008, 8,
3302.
[84] S. Galli, N. Masciocchi, G. Tagliabue, A. Sironi, J. A. R. Navarro, J. M.
Salas, L. Mendez-Linan, M. Domingo, M. Perez-Mendoza, E. Barea,
Chem. Eur. J. 2008, 14, 9890.
[85] R. Kitaura, K. Seki, G. Akiyama, S. Kitagawa, Angew. Chem. 2003, 115,
444; Angew. Chem. Int. Ed. 2003, 42, 428.
[86] M. Avila, L. Reguera, J. Rodriguez-Hernandez, J. Balmaseda, E. Reguera,
J. Solid State Chem. 2008, 181, 2899.
[87] J. Roque, E. Reguera, J. Balmaseda, J. Rodriguez-Hernandez, L. Reg-
uera, L. F. del Castillo, Microporous Mesoporous Mater. 2007, 103, 57.
[88] M. P. Suh, Y. E. Cheon, E. Y. Lee, Chem. Eur. J. 2007, 13, 4208.
[89] Z. X. Chen, S. C. Xiang, D. Y. Zhao, B. L. Chen, Cryst. Growth Des. 2009,
9, 5293.
[90] J.-R. Li, Y. Tao, Q. Yu, X.-H. Bu, H. Sakamoto, S. Kitagawa, Chem. Eur. J.
2008, 14, 2771.
[91] Y. E. Cheon, M. P. Suh, Chem. Commun. 2009, 2296.
[92] S. Noro, D. Tanaka, H. Sakamoto, S. Shimomura, S. Kitagawa, S. Takeda,
K. Uemura, H. Kita, T. Akutagawa, T. Nakamura, Chem. Mater. 2009, 21,
3346.
[93] Y. S. Bae, K. L. Mulfort, H. Frost, P. Ryan, S. Punnathanam, L. J. Broad-
belt, J. T. Hupp, R. Q. Snurr, Langmuir 2008, 24, 8592.
[94] P. S. Barcia, L. Bastin, E. J. Hurtado, J. A. C. Silva, A. E. Rodrigues, B. L.
Chen, Sep. Sci. Technol. 2008, 43, 3494.
[95] H. J. Park, M. P. Suh, Chem. Commun. 2010, 46, 610.
[96] H. Furukawa, O. M. Yaghi, J. Am. Chem. Soc. 2009, 131, 8875.
[97] A. Demessence, D. M. DAlessandro, M. L. Foo, J. R. Long, J. Am. Chem.
Soc. 2009, 131, 8784.
[98] S. R. Miller, G. M. Pearce, P. A. Wright, F. Bonino, S. Chavan, S. Bordiga,
I. Margiolaki, N. Guillou, G. Feerey, S. Bourrelly, P. L. Llewellyn, J. Am.
Chem. Soc. 2008, 130, 15967.
[99] J. Y. Lee, J. M. Roberts, O. K. Farha, A. A. Sarjeant, K. A. Scheidt, J. T.
Hupp, Inorg. Chem. 2009, 48, 9971.
[100] S. Surbl, F. Millange, C. Serre, T. Duren, M. Latroche, S. Bourrelly, P. L.
Llewellyn, G. Ferey, J. Am. Chem. Soc. 2006, 128, 14 889.
[101] J. Y. An, R. P. Fiorella, S. J. Geib, N. L. Rosi, J. Am. Chem. Soc. 2009, 131,
8401.
[102] K. S. Walton, A. R. Millward, D. Dubbeldam, H. Frost, J. J. Low, O. M.
Yaghi, R. Q. Snurr, J. Am. Chem. Soc. 2008, 130, 406.
[103] A. A. Lemus-Santana, J. Rodriguez-Hernandez, L. F. del Castillo, M. Bas-
terrechea, E. Reguera, J. Solid State Chem. 2009, 182, 757.
[104] E. Neofotistou, C. D. Malliakas, P. N. Trikalitis, Chem. Eur. J. 2009, 15,
4523.
[105] S. Neogi, J. A. R. Navarro, P. K. Bharadwaj, Cryst. Growth Des. 2008, 8,
1554.
[106] H. Hayashi, A. P. Cote, H. Furukawa, M. OKeeffe, O. M. Yaghi, Nat.
Mater. 2007, 6, 501.
[107] T. Wu, J. Zhang, C. Zhou, L. Wang, X. H. Bu, P. Y. Feng, J. Am. Chem.
Soc. 2009, 131, 6111.
[108] A. O. Yazaydin, R. Q. Snurr, T. H. Park, K. Koh, J. Liu, M. D. LeVan, A. I.
Benin, P. Jakubczak, M. Lanuza, D. B. Galloway, J. J. Low, R. R. Willis, J.
Am. Chem. Soc. 2009, 131, 18 198.
[109] T. Loiseau, L. Lecroq, C. Volkringer, J. Marrot, G. Ferey, M. Haouas, F.
Taulelle, S. Bourrelly, P. L. Llewellyn, M. Latroche, J. Am. Chem. Soc.
2006, 128, 10223.
[110] N. A. Ramsahye, G. Maurin, S. Bourrelly, P. L. Llewellyn, T. Loiseau, C.
Serre, G. Ferey, Chem. Commun. 2007, 3261.
[111] C. Volkringer, T. Loiseau, M. Haouas, F. Taulelle, D. Popov, M. Burgham-
mer, C. Riekel, C. Zlotea, F. Cuevas, M. Latroche, D. Phanon, C. Knofelv,
P. L. Llewellyn, G. Ferey, Chem. Mater. 2009, 21, 5783.
[112] B. Metz, O. Davidson, H. de Coninck, M. Loos, L. Meyer, IPCC Special
Report on Carbon Dioxide Capture and Storage, Cambridge University
Press, Cambridge, United Kingdom, 2005.
[113] S. Choi, J. H. Drese, C. W. Jones, ChemSusChem 2009, 2, 796.
[114] S. K. Bhatia, A. L. Myers, Langmuir 2006, 22, 1688.
[115] C. C. Zheng, D. H. Liu, Q. Y. Yang, C. L. Zhong, J. G. Mi, Ind. Eng. Chem.
Res. 2009, 48, 10479.
ChemSusChem 2010, 3, 879 891
Can MOF Materials Play a Useful Role in Large-Scale CO2 Separations?
[116] S. S. Y. Chui, S. M. F. Lo, J. P. H. Charmant, A. G. Orpen, I. D. Williams, Sci-
ence 1999, 283, 1148.
[117] S. Sircar, T. C. Golden, M. B. Rao, Carbon 1996, 34, 1.
[118] S. Cavenati, C. A. Grande, A. E. Rodrigues, J. Chem. Eng. Data 2004, 49,
1095.
[119] P. Y. Li, F. H. Tezel, Microporous Mesoporous Mater. 2007, 98, 94.
[120] A. L. Myers, in Fundamental of Adsorption (Ed.: A. Liapis), Engineering
Foundation, New York, 1986.
[121] A. L. Myers, J. M. Prausnitz, AIChE J. 1965, 11, 121.
[122] H. Chen, D. S. Sholl, Langmuir 2007, 23, 6431.
[123] M. Murthi, R. Q. Snurr, Langmuir 2004, 20, 2489.
[124] Q. Y. Yang, C. L. Zhong, J. Phys. Chem. B 2006, 110, 17776.
[125] R. Babarao, Z. Q. Hu, J. W. Jiang, S. Chempath, S. I. Sandler, Langmuir
2007, 23, 659.
[126] Q. Y. Yang, C. Y. Xue, C. L. Zhong, J. F. Chen, AIChE J. 2007, 53, 2832.
[127] V. Finsy, L. Ma, L. Alaerts, D. E. De Vos, G. V. Baron, J. F. M. Denayer, Mi-
croporous Mesoporous Mater. 2009, 120, 221.
[128] N. A. Ramsahye, G. Maurin, S. Bourrelly, P. L. Llewellyn, T. Devic, C.
Serre, T. Loiseau, G. Ferey, Adsorption 2007, 13, 461.
[129] L. M. Robeson, J. Membr. Sci. 1991, 62, 165.
[130] C. M. Zimmerman, A. Singh, W. J. Koros, J. Membr. Sci. 1997, 137, 145.
[131] L. F. Greenlee, D. F. Lawler, B. D. Freeman, B. Marrot, P. Moulin, Water
Res. 2009, 43, 2317.
[132] T. C. Merkel, H. Lin, X. Wei, R. Baker, J. Membr. Sci. 2010, 359, 126.
[133] M. T. Ho, G. W. Allinson, D. E. Wiley, Ind. Eng. Chem. Res. 2008, 47, 1562.
[134] A. Car, C. Stropnik, K. V. Peinemann, Desalination 2006, 200, 424.
[135] Y. F. Zhang, I. H. Musseman, J. P. Ferraris, K. J. Balkus, J. Membr. Sci.
2008, 313, 170.
[136] E. V. Perez, K. J. Balkus, J. P. Ferraris, I. H. Musselman, J. Membr. Sci.
2009, 328, 165.
[137] R. Adams, C. Carson, J. Ward, R. Tannenbaum, W. Koros, Microporous
Mesoporous Mater. 2010, 131, 13.
[138] K. Diaz, L. Garrido, M. Lopez-Gonzalez, L. F. del Castillo, E. Riande, Mac-
romolecules 2010, 43, 316.
[139] S. Keskin, D. S. Sholl, J. Phys. Chem. C 2007, 111, 14055.
[140] T. Watanabe, S. Keskin, S. Nair, D. S. Sholl, Phys. Chem. Chem. Phys.
2009, 11, 11389.
ChemSusChem 2010, 3, 879 891  2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
View publication stats
[141] J. Choi, H. Jeong, M. A. Snyder, J. A. Stoeger, R. I. Masel, M. Tsapatsis,
Science 2009, 325, 590.
[142] T. Tomita, K. Nakayama, H. Sakai, Microporous Mesoporous Mater. 2004,
68, 71.
[143] S. Li, J. G. Martinek, J. L. Falconer, R. D. Noble, Ind. Eng. Chem. Res.
2005, 44, 3220.
[144] Y. Y. Liu, Z. F. Ng, E. A. Khan, H. K. Jeong, C. B. Ching, Z. P. Lai, Micropo-
rous Mesoporous Mater. 2009, 118, 296.
[145] H. Bux, F. Y. Liang, Y. S. Li, J. Cravillon, M. Wiebcke, J. Caro, J. Am. Chem.
Soc. 2009, 131, 16000.
[146] R. Ranjan, M. Tsapatsis, Chem. Mater. 2009, 21, 4920.
[147] A. I. Skoulidas, D. S. Sholl, J. Phys. Chem. B 2005, 109, 15760.
[148] A. I. Skoulidas, J. Am. Chem. Soc. 2004, 126, 1356.
[149] S. Keskin, J. C. Liu, J. K. Johnson, D. S. Sholl, Langmuir 2008, 24, 8254.
[150] L. Sarkisov, T. Dren, R. Q. Snurr, Mol. Phys. 2004, 102, 211.
[151] F. Salles, H. Jobic, A. Ghoufi, P. L. Llewellyn, C. Serre, S. Bourrelly, G.
Ferey, G. Maurin, Angew. Chem. 2009, 121, 8485; Angew. Chem. Int. Ed.
2009, 48, 8335.
[152] F. Salles, H. Jobic, T. Devic, P. L. Llewellyn, C. Serre, G. Ferey, G. Maurin,
ACS Nano 2010, 4, 143.
[153] S. Keskin, D. S. Sholl, Ind. Eng. Chem. Res. 2009, 48, 914.
[154] J. A. Greathouse, M. D. Allendorf, J. Am. Chem. Soc. 2006, 128, 10678.
[155] Y. Li, R. T. Yang, Langmuir 2007, 23, 12937.
[156] A. Kondo, T. Daimaru, H. Noguchi, T. Ohba, K. Kaneko, H. Kanob, J. Col-
loid Interface Sci. 2007, 314, 422.
[157] J. J. Low, A. I. Benin, P. Jakubczak, J. F. Abrahamian, S. A. Faheem, R. R.
Willis, J. Am. Chem. Soc. 2009, 131, 15834.
[158] J. Lu, Y. J. Choi, Z. Z. Fang, H. Y. Sohn, E. Ronnebro, J. Am. Chem. Soc.
2009, 131, 15843.
[159] A. C. McKinlay, B. Xiao, D. S. Wragg, P. S. Wheatley, I. L. Megson, R. E.
Morris, J. Am. Chem. Soc. 2008, 130, 10440.
Received: April 15, 2010
Published online on July 9, 2010
www.chemsuschem.org 891