A water stable metal-organic framework with optimal features for CO 2 capture

Article abstract of DOI:10.1002/anie.201302682

One flue over the cuckoo's nest: A novel porous Zr-based MOF combining a high chemical stability, easy green synthesis and scalability is prepared. This material incorporating carboxylic functions on its organic linkers has thermodynamically and kinetically very promising properties for CO₂ capture from post-combustion flue gas under real working conditions. Copyright

Full text of DOI:10.1002/anie.201302682

Angewandte
Chemie
Communications
Metal–Organic Frameworks
Q. Yang, S. Vaesen, F. Ragon,
A. D. Wiersum, D. Wu, A. Lago, T. Devic,
C. Martineau, F. Taulelle, P. L. Llewellyn,
H. Jobic, C. Zhong, C. Serre,*
G. De Weireld,*
G. Maurin*
&&&& — &&&&
A Water Stable Metal–Organic Framework
One flue over the cuckoo’s nest: A novel
porous Zr-based MOF combining a high
chemical stability, easy “green” synthesis
and scalability is prepared. This material
incorporating carboxylic functions on its
organic linkers has thermodynamically
and kinetically very promising properties
with Optimal Features for CO Capture
2
for CO capture from post-combustion
2
flue gas under real working conditions.
Angew. Chem. Int. Ed. 2013, 52, 1 – 6
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1
These are not the final page numbers!

.
Angewandte
Communications
DOI: 10.1002/anie.201302682
Metal–Organic Frameworks
A Water Stable Metal–Organic Framework with Optimal Features for
CO Capture**
2
Qingyuan Yang, Sꢀbastien Vaesen, Florence Ragon, Andrew D. Wiersum, Dong Wu, Ana Lago,
Thomas Devic, Charlotte Martineau, Francis Taulelle, Philip L. Llewellyn, Hervꢀ Jobic,
Chongli Zhong, Christian Serre,* Guy De Weireld,* and Guillaume Maurin*
The escalating level of atmospheric CO2 is a subject of
widespread public concern associated to global warming and
climate change. Flue gas emitted from power plants running
on carbon-based fossil fuels is a primary source for this
of: 1) a thermodynamically high selectivity of CO over other
2
gases, however, this approach is often questionable as this
parameter has been roughly estimated from simple macro-
scopic thermodynamic models, such as the ideal adsorbed
solution theory (IAST) or from the slopes of the adsorption
[
1]
worsening climatic issue. To decrease its impact on the
environment, the anthropogenic CO2 emission from post-
combustion flue gas must be minimized, however the great
challenge in doing this is achieving a selective adsorption of
CO over N . Pressure swing adsorption (PSA) technology is
[
6]
isotherms, and 2) a large CO uptake, however, this is not
2
necessarily of prime importance to efficiently purify gases
[
7]
under practical conditions. This assessment strategy led the
community to design many targeted MOFs combining extra-
large surface areas and the presence of specific adsorption
2
2
considered as an energetically efficient way for the industrial
[
2]
[8]
scale capture. For these physisorption-based processes, it is
indispensable to have porous adsorbents with good adsorp-
tion performance. In this context, porous crystalline materials,
as exemplified by zeolite 13X (also known as NaX), are very
sites that can strongly interact with CO2. In contrast, little
attention has been paid to the regeneration of such adsorb-
ents, and it is well established that an additional heating of the
column of a PSA process for the removal of the adsorbed
[
3]
[9]
attractive. During the past decades, a novel class of hybrid
nanoporous solids, metal–organic frameworks (MOFs) have
rapidly developed into one of the most fruitful research areas
in chemistry, materials science, and multiple branches of
species induces a significant extra-cost. Further, while the
thermal behavior of the envisaged MOFs is well-documented,
their stabilities under humidity have been poorly
[
10,11]
explored.
This is clearly a limiting factor for a potential
[4]
engineering. The chemical features of such materials allow
their structural properties to be finely tuned over an
extremely broad range. Indeed, a number of recent studies
have claimed that MOFs could serve as an ideal platform for
application of such materials for CO recovery as certain
2
amounts of water vapor are usually present in gas-separation
processes, which can contribute to dramatically alter the
performance of the adsorbents. The questions of cost/
production scale of the best MOFs have also been mostly
avoided so far for such related applications. Typically, the
the removal of CO from a series of gases (e.g. natural gas,
2
[
5]
syngas, biogas) and in particular from flue gas.
[
11b]
To date, the performances of most of the promising MOFs
MOF-type SIFSIX-2-Cu-i
material which has been very
for CO capture have been assessed primarily on the criteria
recently reported as an ideal candidate for the capture of CO2
2
[*] Prof. Q. Yang, D. Wu, Prof. C. Zhong
Prof. G. Maurin
State Key Laboratory of Organic-Inorganic Composites, Beijing
University of Chemical Technology, Beijing, 100029 (China)
Institut Charles Gerhardt Montpellier
UMR CNRS 5253, UM2, ENSCM
Place E. Bataillon, 34095 Montpellier cedex 05 (France)
E-mail: guillaume.maurin@um2.fr
Dr. S. Vaesen, Prof. G. De Weireld
Thermodynamics Department, Facultꢀ Polytechnique
Universitꢀ de UMONS
Place du Parc 20, 7000 Mons (Belgium)
E-mail: guy.deweireld@umons.ac.be
[**] This research was funded by the European Community’s Seventh
Framework Programme (FP7/2007-2013) under grant agreement
No. 228862, the Natural Science Foundation of China (21136001,
2
1276009), and the Beijing Nova Program (No. 2008B15). We thank
Dr. A. D. Wiersum, Dr. P. L. Llewellyn
Laboratoire MADIREL, Aix-Marseille Univ. - CNRS, UMR 7246
Centre de Saint Jꢀrꢁme, 13397 Marseille (France)
Dr. M. M. Koza for his help during the measurements on the IN6
spectrometer at the Institut Laue Langevin, Grenoble, France.
Supporting information for this article (the synthetic procedure for
F. Ragon, Dr. A. Lago, Dr. T. Devic, Dr. C. Martineau, Dr. F. Taulelle,
Dr. C. Serre
the preparation of the UiO-66(Zr)-(COOH) , together with details
2
on its computational assisted structure determination, thermal and
humidity resistance. Thermodynamic co-adsorption and QENS
measurements as well as regeneration are also described) is
available on the WWW under http://dx.doi.org/10.1002/anie.
Institut Lavoisier, UMR CNRS 8180-Universitꢀ de Versailles
St Quentin en Yvelines
45 avenue des Etats-Unis, 78035 Versailles (France)
E-mail: serre@chimie.uvsq.fr
201302682.
Dr. H. Jobic
Institut de Recherches sur la Catalyse et l’Environnement de Lyon,
Universitꢀ de Lyon, CNRS
2. Av. A. Einstein, 69626 Villeurbanne (France)
2
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Chemie
from flue gas is only synthesized at the laboratory scale (ca.
00 mg). Finally, the recycling and environmental issues of
1
such novel materials have been not prioritized in the choice of
the metal precursors and the synthesis route.
All these factors put together still call for the development
of novel porous hybrid solids as to our knowledge, there is still
not a MOF combining outstanding separation performance
[
12a]
[12b]
[12c]
(
such as IRMOFs,
Cu-BTC
or DMOFs,
CPO-27/
[
12d]
[11b,12e]
[4a]
MOF-74,
SIFSIX,
MIL-53 ) with a high chemical
resistance and easy “green” synthesis and scalability associ-
ated to the absence of toxicity or environmental concerns (e.g.
Figure 1. The UiO-66(Zr)-(COOH) crystalline structure: a) tetrahedral
cage, b) octahedral cage. The large green spheres represent the void
regions inside the cages (Zr polyhedra; C black; O red, and H cyan).
2
[
12f]
MOFs containing toxic metals such as MIL-100(Cr)
or
[12d]
CPO-27(Ni) ).
Alternatively, tetravalent-based carboxylate MOFs have
been revealed to be very promising materials with excellent
[13]
chemical and mechanical resistance associated with a very
low toxicity. Some of them show interesting, although not
[
14a]
exceptional CO2 capture abilities.
To meet the above
IV
considerations, we report herein a new Zr water-stable
MOF of the UiO-66 type incorporating benzene-1,2,4,5-
tetracarboxylate (H BTEC) ligands. Its preparation (see
2
Supporting Information for details) specially emphasizes:
1
) the introduction of organic functionalities decorating the
pores: polar free carboxylic groups that are prone to
[13e,14]
strongly interact with CO molecules.
2
2
) the nature of the solvent: whereas Zr carboxylates-based
MOFs are prepared in N,N’-dimethylformamide (DMF)
solution, only water was used, both for the synthesis and
activation procedures. This approach is not only environ-
mentally friendly, but also beneficial in terms of cost and
regeneration issues.
3
) the scale: a simple round bottom flask, room-pressure
procedure, allowing readily scale up of the synthesis was
developed. As a proof of principle, the material was
prepared at the 40 g scale, without any loss of perfor-
mance, together with a significant space time yield (STY)
À3
À1
of approximately 96 kgm day .
Figure 2. a) PXRD pattern of UiO-66(Zr)-(COOH) : 1) theoretical;
2
The Lebail refinement of the experimental X-ray powder
2) as-synthesized; 3) after treatment in H
lCu ꢀ1.5406 ꢂ). b) Correlation between NMR-measured and DFT-
calculated C isotropic chemical shifts.
2
O at 373 K for 16 h
(
diffraction (XRPD) pattern (Figure S1 in the Supporting
Information) was performed using the software WinPlotR
included in the FullProf suite 2011 (lCu ꢀ 1.5406 ꢀ) to extract
the unit cell parameter (20.736 ꢀ) and possible space group
1
3
(
F23). The resulting cell dimension/symmetry are consistent
shifts and the DFT calculated ones (Figure 2b, and Support-
ing Information). Nitrogen sorption analysis on the synthe-
sized sample also confirmed a good accordance between the
BET surface area and the theoretical accessible surface area
with the UiO-66 type topology framework; the crystal
structure was then further constructed through the combined
use of this experimental information and computational
strategy based on density functional theory (DFT) calcula-
tions (see Supporting Information).
2
À1
(428 vs. 415 m g ) while the pore volume is slightly lower
3
À1
(0.21 vs. 0.26 cm g , see Supporting Information).
This new MOF labeled as UiO-66(Zr)-(COOH)2 or
It is noteworthy that UiO-66(Zr)-(COOH)2 is water
stable as shown by XRPD of the sample dispersed 16 h at
373 K in water (Figure 2a). This moisture stability was
confirmed through repetitive water adsorption isotherms at
303 K (Figure 3) which show the same uptakes for each
Zr O (OH) (O C-C H -CO -(CO H) ) ·xH O
(x ꢀ 16),
6
4
4
2
6
2
2
2
2
6
2
shows tetrahedral (Figure 1a) and octahedral (Figure 1b)
cages whose dimensions are, as expected, smaller than the
[15]
UiO-66(Zr) analogue (see Supporting Information), lead-
ing to a decrease of the theoretical accessible surface area
relative pressure. This result is a clear-cut advantage over
2
À1
[5a,10,17]
(
0
from 1018 to 428 m g ) and pore volume (from 0.45 vs.
most of the MOFs envisaged so far for CO capture.
2
3
À1
.26 cm g ) as summarized in Table S1. In light of our recent
Based on the UiO-66(Zr)-(COOH)2 structure model,
preliminary Monte Carlo simulations were realized for each
single CO and N adsorbate (see Supporting Information) to
[16]
findings, this model was further validated by a very good
1
3
agreement obtained between the NMR C isotropic chemical
2
2
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Communications
apparatus and gas chromatograph analysis. The measure-
ments were realized at 303 K for a gas mixture CO :N =
2
2
1
5:85 at 1.0 bar, that is, the typical industrial concentration
and pressure conditions for the separation of flue gas emitted
from power plants. A CO /N2 selectivity of 56 was thus
2
obtained. This excellent performance was further supported
by Grand Canonical Monte Carlo simulations (GCMC; see
Supporting Information) based on our structure model and
a validated set of potential parameters that led to a predicted
selectivity of CO over N of approximately 90, which is again
2
2
higher than the experimental value under the same condi-
tions. While this comparison confirms the great promises of
this novel MOF, it also suggests that there is still a need to
optimize some parameters of the synthesis. In particular, the
formation of anhydride species cannot be fully excluded as
referred to a recent work reported on the MIL-53(Al)-
Figure 3. Water adsorption isotherms in UiO-66(Zr)-(COOH) at
2
3
03 K. P/P is the relative pressure of water with P =4.247 kPa.
0 0
first confirm that such a porosity can accommodate CO and
2
whether or not CO interacts more preferentially than N with
2
2
[
19]
the pore walls of the MOF. A detailed analysis of the
COOH.
that could be at the origin of a slightly lower
configurations so obtained indicated that CO molecules are
experimental pore volume compared to the simulated value.
This selectivity value surpasses the performances reported
for other MOFs under similar conditions that have been
determined by real CO /N co-adsorption (CID-3 (selectivity:
2
primarily distributed in the regions close to the m -OH group
3
of the Zr O (OH) oxo-cluster node and the -COOH organic
6
4
4
functions, while N does not lead to specific interactions with
2
2
2
[
20a]
the pore walls. Such a scenario illustrated in Figure 4 holds
39))
or breakthrough measurements (MOF-74(Ni)
[
20b]
(38) ), while it is only slightly below the top experimental
[
11b]
record reported recently for SIFSIX-2-Cu-i (72)
whose
water stability is expected to be significantly lower than our
sample as this Cu-based MOF is constructed from hexafluor-
[
21]
osilicate anions that shall be easily hydrolysable.
This great promise even holds true when this data is
compared with the performances of the majority of MOFs
that have been evaluated solely using simple macroscopic
models, such as IAST, or estimated from the simple consid-
eration of the initial slopes of the pure CO and N adsorption
2
2
isotherms. Indeed, our novel material outperforms a series of
Figure 4. Local views of the snapshots extracted from the GCMC
simulations at 1.0 bar and 303 K, emphasizing the interactions
between the CO molecule and: a) m -OH group of the inorganic node,
b) the -COOH organic functions. Some framework atoms are deleted
for clarity. The distances are reported in ꢂ. (Zr sky blue; O red; C gray,
and H white; ball and stick representation for the interacting CO2
[6a]
[6c]
MOFs, such as ZIF-78 (selectivity: 50),
PCN-80 (19),
[
22]
[23a]
Zn (BTetB)(py-CF ) (37),
Ca(SDB) (50),
Cu-BTC
2
3 2
2
3
[23b]
[23c]
(20),
and ZIF-8 (8),
while its selective ability remains
lower than those of some other MOFs, such as Bio-MOF-11
[
6b]
[6d]
(75)
and Cu-TDPAT (79),
for which however the
while stick representation for non-interacting CO molecules).
2
performances need to be confirmed by real co-adsorption
measurements. Finally, the selectivity so-obtained is much
higher than those previously reported for the conventional
[3a]
also true for the gas mixture. These observations clearly
emphasize that despite the relatively high degree of confine-
ment of its cages, this solid allows an optimal role of the
grafting functions by authorizing a direct interaction between
the -COOH groups and the gas we aim to selectively adsorb.
In light of such favorable features, a step further consisted
of carefully characterizing the adsorption performances of
this novel porous solid. Based on our previous conclusions
from the study of a series of MOFs, such as the MIL-
zeolite 13X (ca. 20 corresponding to the ideal selectivity)
and the activated carbon Norit R1 Extra (13).
[
23d]
To assess the regeneration of UiO-66(Zr)-(COOH)2,
microcalorimetry experiments were performed using a mano-
metric dosing apparatus linked to the sample cell housed in
a Tian-Calvet type microcalorimetrer (see Supporting Infor-
mation). It is generally desirable for the strongly adsorbed
species to have a relatively low adsorption enthalpy for
minimizing the amount of heat required for regeneration. The
measurements evidenced that the zero-coverage adsorption
[
18]
1
00(Cr), for which we have established that the complexity
À1
of the host–guest interactions sometimes render the use of
macroscopic co-adsorption models including IAST inaccu-
rate, special attention has been paid to realize direct co-
adsorption measurements using a large amount of sample at
the laboratory level (ca. 20 g) to minimize experimental
deviations. Such real co-adsorption data, only scarcely
reported in the literature, were collected by using an
advanced home-made device which combines a volumetric
enthalpies at 303 K are À34.8 and À17.8 kJmol for the
single gases CO and N , respectively, which agree well with
2
2
À1
the GCMC simulated values of À36.4 and À19.7 kJmol . The
energetic value for CO is very similar to those reported for
2
À1
SIFSIX-2-Cu-i (CO : À31.9 kJmol ), while it remains lower
2
than those reported for most of the MOFs, that is, MOF-
À1 [24]
À1 [6b]
74(Ni) (À41.0 kJmol ), Bio-MOF-11 (À45.0 kJmol ),
À1 [6d]
Cu-TDPAT (À42.2 kJmol ),
as well as zeolite 13X
4
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À1
(
À45.0 kJmol ), suggesting a regeneration of this material
Keywords: CO separation · flue gas · green synthesis · metal–
2
organic frameworks · zirconium
.
under relatively mild conditions. Complementary experi-
ments (see Supporting Information) have shown that a full
regeneration is obtained at only 708C (see Supporting
Information) which is much lower than the temperature
required for zeolite 13X (1608C).
Further, the working capacity defined as the difference
between the CO amount taken up at the adsorption (high)
pressure and the amount remaining in the bed at the
desorption (low) pressure of the process, is a much more
significant factor regarding separation applications than the
[1] J.-R. Li, J. Sculley, H.-C. Zhou, Chem. Rev. 2012, 112, 869.
[2] B. A. Wells, A. L. Chaffee, Adsorption 2011, 17, 255.
[
3] a) S. Cavenati, C. A. Grande, A. E. Rodrigues, J. Chem. Eng.
Data 2004, 49, 1095; b) D. Ko, R. Siriwardane, L. T. Biegler, Ind.
Eng. Chem. Res. 2003, 42, 339.
2
[
4] a) G. Fꢂrey, C. Serre, T. Devic, G. Maurin, H. Jobic, P. L.
Llwewllyn, G. De Weireld, A. Vimont, M. Daturi, J.-S. Chang,
Chem. Soc. Rev. 2011, 40, 550; b) M. OꢃKeeffe, O. M. Yaghi,
Chem. Rev. 2012, 112, 675.
[
6b,8b]
absolute uptake most commonly reported for MOFs.
For
post-combustion CO capture from flue gas by a PSA process,
[5] a) K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D.
Bloch, Z. R. Herm, T.-H. Bae, J. R. Long, Chem. Rev. 2012, 112,
724; b) R. Babarao, J. Jiang, Ind. Eng. Chem. Res. 2011, 50, 62;
c) A. L. Dzubak, L.-C. Lin, J. Kim, J. A. Swisher, R. Poloni, S. N.
Maximoff, B. Smit, L. Gagliardi, Nat. Chem. 2012, 4, 810; d) S.
Keskin, Ind. Eng. Chem. Res. 2011, 50, 8230.
2
the working capacity is usually calculated between the
[
2]
adsorptions at 0.1 and 1 bar. According to this definition,
despite its relatively low pore volume, the experimental CO2
3
working capacity reaches here approximately 42 cm -
À3
(
STP)cm , which is slightly higher than that reported for
[
6] a) R. Banerjee, H. Furukawa, D. Britt, C. Knobler, M. OꢃKeeffe,
O. M. Yaghi, J. Am. Chem. Soc. 2009, 131, 3875; b) J. An, S. J.
Geib, N. L. Rosi, J. Am. Chem. Soc. 2010, 132, 38; c) W. Lu, D.
Yuan, T. A. Makal, J.-R. Li, H.-C. Zhou, Angew. Chem. 2012,
3
À3
[3a]
the zeolite 13X (34 cm (STP)cm ) used commercially.
Further as our new material shows a relatively bulky
environment of the cages due to the presence of the two
carboxylic functions, at first sight it would be intuitionally
thought that the separation process could have some kinetic
limitations. Therefore, the kinetic behaviors of both confined
gases have been investigated by quasi-elastic neutron scatter-
ing (QENS) measurements. This experimental technique is
124, 1612; Angew. Chem. Int. Ed. 2012, 51, 1580; d) B. Li, Z.
Zhang, Y. Li, K. Yao, Y. Zhu, Z. Deng, F. Yang, X. Zhou, G. Li,
H. Wu, N. Nijem, Y. J. Chabal, Z. Lai, Y. Han, Z. Shi, S. Feng, J.
Li, Angew. Chem. 2012, 124, 1441; Angew. Chem. Int. Ed. 2012,
51, 1412.
[7] A. D. Wiersum, J.-S. Chang, C. Serre, P. L. Llewellyn, Langmuir
013, 29, 3301.
2
a valuable tool to follow the diffusivity (D ) of various guest
t
[15b,25]
[8] a) O. K. Farha, C. E. Wilmer, I. Eryazici, B. G. Hauser, P. A.
Parill, K. OꢃNeill, A. A. Sarjeant, S. T. Nguyen, R. Q. Snurr, J. T.
Hupp, J. Am. Chem. Soc. 2012, 134, 9860; b) S. Xiang, Y. He, Z.
Zhang, H. Wu, W. Zhou, R. Krishna, B. Chen, Nat. Commun.
2012, 3, 954.
molecules in MOF type materials.
The in situ QENS
measurements were performed at 230 K on a deuterated
sample loaded with 12 and 3 molecules per unit cell for CO2
and N respectively, using the time-of-flight spectrometer IN6
2
at the Institut Laue-Langevin (see the Supporting Informa-
tion). As both species are totally coherent scatterers, the
collective mobilities, that is, the transport diffusivities are
extracted from these QENS data. It was found that in this low
[9] a) J. Liu, P. K. Thallapally, B. P. McGrail, D. R. Brown, J. Liu,
Chem. Soc. Rev. 2012, 41, 2308; b) J. A. Mason, K. Sumida, Z. R.
Herm, R. Krishna, J. R. Long, Energy Environ. Sci. 2011, 4, 3030.
10] a) S. Han, Y. Huang, T. Watanabe, Y. Dai, K. S. Walton, S. Nair,
D. S. Sholl, J. C. Meredith, ACS Comb. Sci. 2012, 14, 263;
b) G. D. Pirngruber, L. Hamon, S. Bourrelly, P. L. Llewellyn, E.
Lenoir, V. Guillerm, C. Serre, T. Devic, ChemSusChem 2012, 5,
[
À10
loading range, the D values for CO and N are 1.0 ꢁ 10 and
t
2
2
À9
2
À1
4
.0 ꢁ 10 m s respectively. Noteworthy, despite the bulky
nature of our sample, the resulting diffusivities for both
species are finally very similar to the values reported for the
conventional faujasite 13X for the same temperature range
7
62.
[11] a) A. C. Kizzie, A. G. Wong-Foy, A. J. Matzger, Langmuir 2011,
27, 6368; b) P. Nugent, Y. Belmabkhout, S. D. Burd, A. J. Cairns,
R. Luebke, K. Forrest, T. Pham, S. Ma, B. Space, L. Wojtas, M.
Eddaoudi, M. J. Zaworotko, Nature 2013, 495, 80.
À10
2
À1
À9
2
À1 [26]
(
CO :1.5 ꢁ 10 m s and N :2 ꢁ 10 m s ).
Indeed, it
2
2
can be considered that kinetics will not be a drawback for the
use of such a novel material in physisorption-based processes.
In summary, we have demonstrated that a new Zr-based
MOF, containing two carboxylic functions grafted on the
organic linkers, shows great promises for CO /N gas mixture
[
12] a) M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M.
OꢃKeeffe, O. M. Yaghi, Science 2002, 295, 469; b) S. S.-Y. Chui,
S. M.-F. Lo, J. P. H. Charmant, A. G. Orpen, I. D. Williams,
Science 1999, 283, 1148; c) Z. Q. Wang, S. M. Cohen, J. Am.
Chem. Soc. 2009, 131, 16675; d) P. D. C. Dietzel, V. Besikiotis, R.
Blom, J. Mater. Chem. 2009, 19, 7362; e) S. Noro, S. Kitagawa, M.
Kondo, K. Seki, Angew. Chem. 2000, 112, 2161; Angew. Chem.
Int. Ed. 2000, 39, 2081; f) G. Fꢂrey, C. Serre, C. Mellot-
Draznieks, F. Millange, S. Surblꢂ, J. Dutour, I. Margiolaki,
Angew. Chem. 2004, 116, 6456; Angew. Chem. Int. Ed. 2004, 43,
2
2
separation with not only a very good selectivity, relatively
high working capacity, a regeneration expected to occur
under mild conditions, and no kinetic limitations, but also
a water stability and a relatively high-scale production
involving an environmental friendly and cheap scalable
synthesis. All these considerations suggest that this material
can serve as a bona-fide alternative to conventional porous
solids involved in the physisorption-based processes for
6296.
[13] a) V. Guillerm, F. Ragon, M. Dan-Hardi, T. Devic, M. Vishnu-
varthan, B. Campo, A. Vimont, G. Clet, Q. Yang, G. Maurin, G.
Fꢂrey, A. Vittadini, S. Gross, C. Serre, Angew. Chem. 2012, 124,
9401; Angew. Chem. Int. Ed. 2012, 51, 9267; b) S. M. Cohen,
selective capture of CO from post-combustion gas mixture.
2
Chem. Rev. 2012, 112, 970; c) A. Schaate, P. Roy, A. Godt, J.
Lippke, F. Waltz, M. Wiebcke, P. Behrens, Chem. Eur. J. 2011, 17,
6643; d) H. Wu, T. Yildirim, W. Zhou, J. Phys. Chem. Lett. 2013,
Received: April 1, 2013
Published online: && &&, &&&&
4, 925; e) H. Jasuja, J. Zang, D. S. Sholl, K. S. Walton, J. Phys.
Chem. C 2012, 116, 23526.
Angew. Chem. Int. Ed. 2013, 52, 1 – 6
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

.
Angewandte
Communications
[
14] a) Q. Yang, A. D. Wiersum, P. L. Llewellyn, V. Guillerm, C.
Serre, G. Maurin, Chem. Commun. 2011, 47, 9603; b) A. Torrisi,
C. Mellot-Draznieks, R. G. Bell, J. Chem. Phys. 2010, 132,
[21] W. F. Finney, E. Wilson, A. Callender, M. D. Morris, L. W. Beck,
Environ. Sci. Technol. 2006, 40, 2572.
[22] Y.-S. Bae, O. M. Farha, J. T. Hupp, R. Q. Snurr, J. Mater. Chem.
2009, 19, 2131.
044705.
[
15] a) J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti,
S. Bordiga, K. P. Lillerud, J. Am. Chem. Soc. 2008, 130, 13850;
b) Q. Yang, A. D. Wiersum, H. Jobic, V. Guillerm, C. Serre, P. L.
Llewellyn, G. Maurin, J. Phys. Chem. C 2011, 115, 13768.
16] S. Devautour-Vinot, G. Maurin, C. Serre, P. Horcajada, D. P.
da Cunha, V. Guillerm, E. de Souza Costa, F. Taulelle, C.
Martineau, Chem. Mater. 2012, 24, 2168.
17] a) K. A. Cychosz, A. J. Matzger, Langmuir 2010, 26, 17198; b) J.
Liu, A. I. Benin, A. M. B. Furtado, P. Jakubczak, R. R. Willis,
M. D. LeVan, Langmuir 2011, 27, 11451.
[23] a) D. Banerjee, Z. Zhang, A. M. Plonka, J. Li, J. B. Parise, Cryst.
Growth Des. 2012, 12, 2162; b) Z. J. Liang, M. Marshall, A. L.
Chaffee, Energy Fuels 2009, 23, 2785; c) Z. Zhang, S. Xian, H.
Xi, H. Wang, Z. Li, Chem. Eng. Sci. 2011, 66, 4878; d) F.
Dreisbach, R. Staudt, J. U. Keller, Adsorption 1999, 5, 215.
[24] S. R. Caskey, A. G. Wong-Foy, A. J. Matzger, J. Am. Chem. Soc.
2008, 130, 10870.
[25] a) N. Rosenbach, Jr., H. Jobic, A. Ghoufi, F. Salles, G. Maurin, S.
Bourrelly, P. L. Llewellyn, T. Devic, C. Serre, G. Fꢂrey, Angew.
Chem. 2008, 120, 6713; Angew. Chem. Int. Ed. 2008, 47, 6611;
b) F. Salles, H. Jobic, T. Devic, P. L. Llewellyn, C. Serre, G. Fꢂrey,
G. Maurin, ACS Nano 2010, 4, 143; c) Q. Yang, H. Jobic, F.
Salles, D. Kolokolov, V. Guillerm, C. Serre, G. Maurin, Chem.
Eur. J. 2011, 17, 8882.
[
[
[
18] L. Hamon, N. Heymans, P. L. Llewellyn, V. Guillerm, A. Ghoufi,
S. Vaesen, G. Maurin, S. Serre, G. De Weireld, G. D. Pirngruber,
Dalton Trans. 2012, 41, 4052.
[
19] N. Reimer, B. Gil, B. Marszalek, N. Stock, CrystEngComm 2012,
1
4, 4119.
[26] a) D. Plant, H. Jobic, P. L. Llewellyn, G. Maurin, Eur. Phys. J.
Special Topics 2007, 141, 127; b) N.-K. Bꢄr, P. L. Mc Daniel,
C. G. Coe, G. Seiffert, J. Kꢄrger, Zeolites 1997, 18, 71.
[
20] a) K. Nakagawa, D. Tanaka, S. Horike, S. Shimomura, M.
Higuchi, S. Kitagawa, Chem. Commun. 2010, 46, 4258; b) J. Liu,
J. Tian, P. K. Thallapally, B. P. McGrail, J. Phys. Chem. C 2012,
116, 9575.
6
www.angewandte.org
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2013, 52, 1 – 6
These are not the final page numbers!