Partitioning MOF-5 into Confined and Hydrophobic Compartments for Carbon Capture under Humid Conditions

Article abstract of DOI:10.1021/jacs.6b06051

Metal-organic frameworks (MOFs), by virtue of their remarkable uptake capability, selectivity, and ease of regeneration, hold great promise for carbon capture from fossil fuel combustion. However, their stability toward moisture together with the competit

Full text of DOI:10.1021/jacs.6b06051

Subscriber access provided by Northern Illinois University
Communication
Partitioning MOF-5 into confined and hydrophobic
compartments for carbon capture under humid conditions
Nan Ding, Haiwei Li, Xiao Feng, Qianyou Wang, Shan Wang, Li Ma, Junwen Zhou, and Bo Wang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.6b06051 • Publication Date (Web): 01 Aug 2016
Downloaded from http://pubs.acs.org on August 1, 2016
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Journal of the American Chemical Society is published by the American Chemical
Society. 1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
Partitioning MOF-5 into confined and hydrophobic compartments
for carbon capture under humid conditions
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
‡
‡
Nan Ding, Haiwei Li, Xiao Feng,* Qianyou Wang, Shan Wang, Li Ma, Junwen Zhou, Bo Wang*
†Key Laboratory of Cluster Science, Ministry of Education of China, School of Chemistry, Beijing Institute of Technology, 5 South
Zhongguancun Street, Beijing 100081, P. R. China
Supporting Information Placeholder
ABSTRACT: Metal-organic frameworks (MOFs), by virtue
of their remarkable uptake capability, selectivity and ease of
regeneration, hold great promise for carbon capture from
fossil fuel combustion. However, their stability towards
moisture together with the competitive adsorption of water
Increasing MOF surface area and pore size is one of the
most efficient approaches to maximize CO uptake and can
dramatically enhance the storage capacity under high pres-
2
[
5]
sure (> 3-5 MPa). But such high adsorption is often not
viable when used in a post-combustion power plant where
the pressure of the flue gas from smoke stacks usually main-
molecule against CO drastically dampens their capacity and
2
[6]
selectivity under real humid flue gas conditions. In this work,
an effective strategy was developed to tackle the above ob-
stacles by partitioning the channels of MOFs into confined
and hydrophobic compartments by in-situ polymerization of
aromatic acetylenes. Specifically, polynaphthylene was
formed via radical reaction inside the channels of MOF-5
and served as partitions without altering the underlying
structure of the framework. Compared with pristine MOF-5,
tains below 0.3 MPa. Indeed, pore surface functionaliza-
tion of MOFs is the most widely used method for the effi-
cient and selective carbon capture. Generally, functional
groups with high polarity, such as pyridine, -OH, -NO
-SH, etc., and/or open metal sites decorating the walls of
MOFs pores are favorable, since CO molecule processes a
large quadrupole moment and these functional sites are able
2
, -CN,
2
[
3a,3b,7]
to induce polarization and enhance affinity.
effective way to improve the CO capacity and selectivity is
to anchor basic amine groups onto the skeleton of MOFs to
Another
the resultant material (PN@MOF-5) exhibits a doubled
2
3
CO
higher CO
proved moisture stability. The dynamic CO
2
capacity (78 vs. 38 cm /g at 273 K and 1 bar), 23-times
[
8]
mimic the chemisorption in the liquid absorbents. Never-
theless, aside from ~75% N and ~15% CO , a typical post-
2
/N
2
selectivity (212 vs. 9), and significantly im-
adsorption ca-
2
2
2
pacity can be largely maintained (> 90%) under humid con-
dition during cycles. This strategy can be applied into other
MOF materials and may shed light on designing new MOF-
polymer materials with tunable pore sizes and environment
to promote their practical applications.
combustion flue gas also contains 5%~7% water, which must
be thoroughly took into consideration for real
[2c,3a,3b,9]
applications.
During the separation process, water
molecules with higher polarity and binding energy will
strongly compete against CO , and therefore, the active ad-
2
sorptive sites in MOFs are easily poisoned by only small
amount of water. Consequently, the capacity and selectivity
will be dramatically dampened under real humid flue gas
Fossil fuel combustion from stationary sources makes up
[10]
conditions.
the majority of the total anthropogenic CO
raising huge environmental challenges facing our planet.
2
contributions,
[
1]
Needless to say that many MOF structures are vulnerable
under moisture conditions, and the collapse of the frame-
work by slow hydrolysis can significantly lower the separa-
tion performance and impede their practical
Although aqueous alkanolamine solutions are the state-of-
the-art capture absorbents that broadly implemented in
power plants for CO capture, the regeneration of them from
2
[
10c,11]
[
2]
application.
Alternatively, trapping CO in a confined
2
carbamates inevitably leads to a huge energy penalty. Met-
al-organic frameworks (MOFs), constructed from organic
space offers opportunities to separate gas molecules based on
size. Due to the difficulties in the design and synthesis of
links and metal ions or clusters, represent one of the most
[2c,3]
MOFs with pore openings that exactly match for CO
2
mole-
promising materials for CO
2
capture and storage.
Owing
cule in kinetic diameter, only few pioneering works have
to their high porosity, structural diversity, tunable pore envi-
ronment, and atomically well-defined skeleton, MOFs have
been extensively explored in various applications, such as gas
[
12]
been reported. Therefore, the demand of a facile method
to prepare moisture-stable MOF materials that can selec-
[
4]
tively adsorb CO
2
over other gas components and water
storage and separation, catalysis, and chemo-sensing.
molecules from flue gas is ever urgent yet largely unmet.
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 5
Recently, Cohen et al. reported polymer−metal−organic
CO
2
capacity under humid conditions (> 90% retention rate
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
frameworks that can selective adsorption of CO
2
against N
2
under RH = 65%).
[13]
and exhibited high water stability. Kitagawa et al. are pio-
neered in in-situ polymerization of vinyl monomers inside
the channels of MOFs.[ Inspired by their works, herein, we
report a strategy that can divide the open channels of MOFs
into confined and hydrophobic compartments by in-situ
polymerization of aromatic acetylenes inside MOF pores.
The details for the polymerization of DEB in MOF-5 were
described in Supporting Information. A significant color
change from white to brown was observed after heating
(Figures S3 and S4), indicative of the formation of highly
conjugated polymers. The powder X-ray diffraction pattern
(PXRD) of PN@MOF-5 is consistent with that of MOF-5
14]
Thus-obtained MOF material can capture and trap CO
2
(
Figure S5), revealing the crystalline structure is retained
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
molecules and effectively retard the diffusion and repel water
molecules. We intentionally selected MOF-5, a famous and
highly porous MOF structure that can also be produced in
13
during inclusion and polymerization of DEB. C solid state
NMR spectra of PN@MOF-5 as well as the PN polymer
isolated from PN@MOF-5 (Figure S7) display the signals of
aromatic carbons belonging to the polynaphthylene at ~128
ppm. The disappearance of C≡C-H stretching vibration at
[15]
industrial scale (> 1 ton per 30 mins) , to serve as the pro-
totype host material. 1,2-diethynylbenzene (DEB) as
monomer were adsorbed and encapsulated in MOF-5 and
further heated at elevated temperature to afford polynaph-
thylene (PN) inside the channels via Bergman cyclization
and subsequent radical polymerization (Scheme 1), and this
composite is denoted as PN@MOF-5. Due to its hydropho-
bic and linear nature, PNs in MOF-5 can act as partitions to
segregate the micropores with ~1.2 nm in width into ultra
micropores (≤ 0.7 nm) and simultaneously improve the sta-
bility of PN@MOF-5 towards moisture.
-1
-1
3
300 cm and C≡C-H bending vibration at ~700 cm in the
fourier transform infrared attenuated total reflection (FTIR-
ATR) spectrum of PN@MOF-5 (Figure S8) reflects the
high polymerization degree of acetylene. As determined by
elemental analysis, the loading amount of PN in the host-
polymer inclusion is 15.0 wt% (Table S1). The PN loading
can be adjusted by carefully altering the amount of solvent
used for washing before polymerization, and accordingly,
another three inclusion samples with a 3.2, 34 and 40 wt%
Scheme 1. (a) Illustration of competitive adsorption of
PN loading (denoted as PN @MOF-5, x means loading
x
CO
2
against H
2
O at the surface and edge of PN. (b)
amount%) were obtained. Scanning electron microscopy
(SEM) and optical microscopy images (Figures S9 and S10)
of the two PN@MOF-5 samples display their preserved crys-
tal morphologies. To address whether the PN polymers are
homogeneously existed in large domains (greater than a na-
nometer scale), each crystal was dissected into two segments.
The color is almost evenly distributed in each crystal, and the
higher the loading amount, the deeper the color.
Polymerization of DEB in MOFs.
Figure 1. (a) Pore size distributions of PN@MOF-5,
PN3.2@MOF-5 and MOF-5 based on quenched solid-state den-
sity functional theory. (b) CO
PN@MOF-5 and MOF-5 at 273, 283 and 298 K.
2
sorption isotherms of
In contrast to MOF-5, which is water-sensitive,
PN@MOF-5 can retain its crystallinity and porosity upon
exposure to humid air (> 40 h, RH = 40%). More important-
ly, the ultra micropores and exposed large amount of aro-
matic edges and surfaces in PN@MOF-5 allow its efficient
Nitrogen sorption isotherm tests at 77 K were conducted
to access their porosities. Analyses of the sorption curves of
MOF-5, PN3.2@MOF-5 and PN@MOF-5 (Figure S11) by
the Brunauer-Emmett-Teller (BET) method give specific
surface areas of 3200, 2600 and 1200 m g , respectively
(Figures S12-S14). Quenched solid-state density functional
theory (QSDFT) was utilized to deduce the pore size distri-
butions (Figure 1a). Interestingly, along with the increasing
of PN loadings, the pores with 1.2 nm (MOF-5 pores) in
2
-1
capture of CO
the thermodynamic adsorption capacity of CO
and selectivity of CO /N (14/86, 1 bar, 273 K) is 23-times
2
(Scheme 1). Compared with pristine MOF-5,
2
is doubled
2
2
increased for PN@MOF-5. Furthermore, in breakthrough
experiments, PN@MOF-5 largely maintained its dynamic
ACS Paragon Plus Environment

Page 3 of 5
Journal of the American Chemical Society
CO /N selectivity at 1 bar and 273 K for PN@MOF-5 (212)
width are gradually diminished whereas the pores with 0.6
2
2
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
nm (partitioned pores) in width are emerged and boosted
significantly. These results demonstrate that the PN poly-
mers can act as partitions to segregate the channels of the
crystals into confined compartments. Although these anal-
yses do not preclude the presence of PN polymers wrapped
the surface of crystals, we believe that the overall considera-
tion of the pore size distribution analysis, PXRD measure-
ments and microscopy images strongly support that most
PN polymers are distributed inside the crystal channels and
serve as partitions.
is almost 23 times higher than that of MOF-5 (9) (Table S2).
MOF-5 is very sensitive to moisture, as a result of the
breakdown of the coordination bonds by the attack of water
[17]
molecule. In contrast to the hydrophilic nature of MOF-5
o
with a water contact angle close to 0 , PN@MOF-5 is hy-
o
drophobic and exhibits a water contact angle of 135 (Figure
2a). MOF-5 completely loses its porosities within 6 h and
[18]
transforms to MOF-69c within 40 h in a humid environ-
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
ment (RH = 40%), as evidenced by PXRD and N sorption
2
isotherm measurements (Figures 2b and S23). On the con-
trary, the BET surface area and crystallinity of PN@MOF-5
are preserved after 40-h moisture treatment (Figures 2b and
S23), indicating that the inclusion of aromatic PN into the
channels can effectively prevent the attack to the coordina-
tion bonds from water. Similar results are observed for
PN3.2@MOF-5 (Figures S24 and S25).
Figure 2. (a) Contact angle measurements. (b) Nitrogen sorp-
tion profiles of PN@MOF-5 and MOF-5 for exposure to hu-
midity for different times.
Compartments with confined space together with abun-
dant exposed surfaces and edges of aromatic rings in
PN@MOF-5 are supposed to be favorable for CO
2
capture.[ Considering a balance between partitioning the
16]
MOF channels and partially blocking (Figure S15 and S16),
we selected PN@MOF-5 to perform CO
2
sorption isotherm
test at different temperatures and calculated its adsorption
3
-1
enthalpy. Remarkably, compared with MOF-5 (38 cm g at
73 K, 760 Torr), the doubled CO capacity of PN@MOF-5
Figure 1b) with just one third of the BET surface area of
2
2
Figure 3. (a) Calculated IAST selectivity of CO
2
over N
2
at 273
(
K of a 14/86 gas mixture of CO /N . (b) Capacities and (c)
2
2
3
-1
MOF-5 is achieved (78 cm g at 273 K, 760 Torr). It is
worth noted that, derived from CO adsorption isotherm at
73 K by using NLDFT method, the pore size distribution
Figure S17) displays a maximum at about 0.5-0.6 nm as well
dynamic sorption curves of PN@MOF-5 and MOF-5 under dry
conditions (blue) and in the presence of water (red).
2
2
(
Given the high humid stability, hydrophobicity and good
CO
experiments to test the ability of PN@MOF-5 to separate
CO from N with and without moisture (see details in Fig-
ure S26 in the SI). A mixed N /CO gas with 16% CO con-
2
uptake capacity, we carried out dynamic separation
as partial pores at 0.37 and 0.81 nm. We further employed
the Clausius-Clapeyron formula to determine the isosteric
2
2
heats of adsorption (Qst) from CO
2
adsorption isotherms at
2
2
2
2
73, 283 and 298 K (Figures 1b and S18). At zero loading
tent was introduced to the bed, and the effluent was moni-
tored by a mass spectrometer (Figure 3b and 3c). Under dry
the Qst value (-ΔH) is 29 kJ/mol, and at higher loadings it
decreases to ~24 kJ/mol, the value of which is still one third
higher than that of MOF-5. The fact that twice amount of
conditions, PN@MOF-5 adsorbent bed shows a dynamic
3
CO
2
adsorption capacity of 34 cm /g, which is one-and-a-
CO
2
are adsorbed in the comparatively low-surface-area ma-
3
half times of MOF-5 (23 cm /g) prepared under similar
conditions. For humid condition test, a gas mixture
terial of PN@MOF-5 with larger Qst can be attributed to the
enhanced adsorbate-surface interactions to both sides or
(V(N
2
)/V(CO ) = 84:16) with a RH value of 65% was in-
2
ends of the CO molecules stemmed from confined pore size
2
troduced to the bed. The dynamic sorption capacity of
PN@MOF-5 under moisture almost retains the value ob-
tained under dry condition, while MOF-5 displays a 40% and
effect and the more exposed aromatic surfaces.
Ideal adsorption solution theory (IAST) was applied in
order to predict the expected selectivity of CO
the materials (Figure 3a). Under simulated post-combustion
flue gas composition (14% CO , 86% N ), the calculated
2
and N for
2
7
3
3% decrease in the first and second cycle (Figures 3b and
c), respectively, in the presence of water. In addition, the
2
2
topology of PN@MOF-5 remained intact after dynamic
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 5
[
4] (a) Li, H.; Eddaoudi, M.; O'Keeffe, M.; Yaghi, O. M. Nature 1999,
sorption, while the skeleton of MOF-5 was almost collapsed
Figure S29). For comparison, two representative MOFs,
MOF-199 and NH -UiO-66 significantly lost their CO ca-
pacity under humid conditions (Table S3).
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
402, 276. (b) Kitaura, R.; Kitagawa, S.; Kubota, Y.; Kobayashi, T. C.; Kindo,
K.; Mita, Y.; Matsuo, A.; Kobayashi, M.; Chang, H. C.; Ozawa, T. C.;
Suzuki, M.; Sakata, M.; Takata, M. Science 2002, 298, 2358. (c) Férey, G.
Chem. Soc. Rev. 2008, 37, 191. (d) Li, J. R.; Kuppler, R. J.; Zhou, H. C.
Chem. Soc. Rev. 2009, 38, 1477. (e) Yoon, M.; Srirambalaji, R.; Kim, K.
Chem. Rev. 2012, 112, 1196. (f) Guo, Y. X.; Feng, X.; Han, T. Y.; Wang, S.;
Lin, Z. G.; Dong, Y. P.; Wang, B. J. Am. Chem. Soc. 2014, 136, 15485. (g)
Wang, L.; Feng, X.; Ren, L. T.; Piao, Q. H.; Zhong, J. Q.; Wang, Y. B.; Li, H.
W.; Chen, Y. F.; Wang, B. J. Am. Chem. Soc. 2015, 137, 4920.
(
2
2
In conclusion, we have reported a new strategy to divide
MOF pores into confined compartments by in-situ polymeri-
zation of aromatic acetylene. For PN@MOF-5, a remarkable
3
increase in CO
CO /N
2
adsorption capacity from 38 to 78 cm /g and
[
5] (a) Millward, A. R.; Yaghi, O. M. J. Am. Chem. Soc. 2005, 127, 17998.
b) Farha, O. K.; Yazaydin, A. O.; Eryazici, I.; Malliakas, C. D.; Hauser, B.
G.; Kanatzidis, M. G.; Nguyen, S. T.; Snurr, R. Q.; Hupp, J. T. Nature Chem.
010, 2, 944. (c) Furukawa, H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.;
2
2
selectivity from 9 to 212 at 273 K and 1 bar were
(
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
obtained. Due to its hydrophobic nature, not only the stabil-
ity of the framework toward moisture was significantly im-
proved but also the competitive adsorption of water against
2
Choi, E.; Yazaydin, A. O.; Snurr, R. Q.; O'Keeffe, M.; Kim, J.; Yaghi, O. M.
Science 2010, 329, 424.
[6] Yan, J. Handbook of Clean Energy Systems, 6 Volume Set; John Wiley
& Sons, 2015; Vol. 5.
[
CO
dynamic CO
4% retention rate. The improved stability towards moisture
2
molecule was effectively inhibited. Consequently, the
2
capacity under humid conditions reached a
9
7] (a) Caskey, S. R.; Wong-Foy, A. G.; Matzger, A. J. J. Am. Chem. Soc.
and increased adsorption capacity of PN@UMCM-8 (Figure
S32-S34) demonstrates the applicability of the present strat-
egy. The abundant combinations of porous materials (i.e.,
MOFs, covalent organic frameworks,[ porous polymers,
etc.) and conventional polymers will provide versatile mate-
rial platforms for achieving multi-functions and practical
applications.
2008, 130, 10870. (b) Li, B. Y.; Zhang, Z. J.; Li, Y.; Yao, K. X.; Zhu, Y. H.;
Deng, Z. Y.; Yang, F.; Zhou, X. J.; Li, G. H.; Wu, H. H.; Nijem, N.; Chabal,
Y. J.; Lai, Z. P.; Han, Y.; Shi, Z.; Feng, S. H.; Li, J. Angew. Chem. Int. Ed.
2
012, 51, 1412. (c) Cui, P.; Ma, Y. G.; Li, H. H.; Zhao, B.; Li, J. R.; Cheng,
19]
P.; Balbuena, P. B.; Zhou, H. C. J. Am. Chem. Soc. 2012, 134, 18892.
[8] (a) McDonald, T. M.; Lee, W. R.; Mason, J. A.; Wiers, B. M.; Hong,
C. S.; Long, J. R. J. Am. Chem. Soc. 2012, 134, 7056. (b) Arstad, B.; Fjellvag,
H.; Kongshaug, K. O.; Swang, O.; Blom, R. Adsorption. 2008, 14, 755. (c)
An, J.; Geib, S. J.; Rosi, N. L. J. Am. Chem. Soc. 2010, 132, 38. (d) Fracaroli,
A. M.; Furukawa, H.; Suzuki, M.; Dodd, M.; Okajima, S.; Gandara, F.;
Reimer, J. A.; Yaghi, O. M. J. Am. Chem. Soc. 2014, 136, 8863.
ASSOCIATED CONTENT
[
9] Nguyen, N. T. T.; Furukawa, H.; Gandara, F.; Nguyen, H. T.;
Supporting Information. The Supporting Information is avail-
able free of charge on the ACS Publications website. Experi-
mental details and data (PDF).
Cordova, K. E.; Yaghi, O. M. Angew. Chem. Int. Ed. 2014, 53, 10645.
[10] (a) Babarao, R.; Jiang, J. W. Energy Environ. Sci. 2009, 2. (b) Yu, J.
M.; Balbuena, P. B. J. Phys. Chem. C 2013, 117, 3383. (c) Kizzie, A. C.;
Wong-Foy, A. G.; Matzger, A. J. Langmuir. 2011, 27, 6368.
[11] Low, J. J.; Benin, A. I.; Jakubczak, P.; Abrahamian, J. F.; Faheem, S.
A.; Willis, R. R. J. Am. Chem. Soc. 2009, 131, 15834.
AUTHOR INFORMATION
Corresponding Author
[
12] (a) Nugent, P.; Belmabkhout, Y.; Burd, S. D.; Cairns, A. J.; Luebke,
bowang@bit.edu.cn; fengxiao86@bit.edu.cn;
R.; Forrest, K.; Pham, T.; Ma, S.; Space, B.; Wojtas, L.; Eddaoudi, M.;
Zaworotko, M. J. Nature 2013, 495, 80. (b) Xiang, S.; He, Y.; Zhang, Z.;
Wu, H.; Zhou, W.; Krishna, R.; Chen, B. Nat. Commun. 2012, 3, 954. (c) Li,
J. R.; Yu, J.; Lu, W.; Sun, L. B.; Sculley, J.; Balbuena, P. B.; Zhou, H. C. Nat.
Commun. 2013, 4, 1538. (d) Yang, S.; Lin, X.; Lewis, W.; Suyetin, M.;
Bichoutskaia, E.; Parker, J. E.; Tang, C. C.; Allan, D. R.; Rizkallah, P. J.;
Hubberstey, P.; Champness, N. R.; Thomas, K. M.; Blake, A. J.; Schroder,
M. Nat. Mater. 2012, 11, 710. (e) Chen, B.; Ma, S.; Zapata, F.; Fronczek, F.
R.; Lobkovsky, E. B.; Zhou, H. C. Inorg. Chem. 2007, 46, 1233.
Author Contributions
‡
These authors contributed equally.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
[
13] Zhang, Z. J.; Nguyen, H. T. H.; Miller, S. A.; Ploskonka, A. M.;
This work was financially supported by the 973 Program
DeCoste, J. B.; Cohen, S. M. J. Am. Chem. Soc. 2016, 138, 920.
2
013CB834704; the National Natural Science Foundation of
China (grant nos. 21471018, 21404010, 21201018, 21490570);
000 Plan (Youth).
[14] (a) Uemura, T.; Yanai, N.; Kitagawa, S. Chem. Soc. Rev. 2009, 38,
228. (b) Uemura, T.; Hiramatsu, D.; Kubota, Y.; Takata, M.; Kitagawa, S.
1
1
Angew. Chem. Int. Ed. 2007, 46, 4987. (c) Uemura, T.; Kitaura, R; Ohta, Y;
Nagaoka, M; Kitagawa, S. Angew. Chem. Int. Ed. 2006, 45, 4112.
REFERENCES
[15] (a) Czaja, A. U.; Trukhan, N.; Muller, U. Chem. Soc. Rev. 2009, 38,
284. (b) McKinstry, C.; Cathcart, R. J.; Cussen, E. J.; Fletcher, A. J.;
1
[
1] Pachauri, R. K.; Reisinger, A. Intergovernmental panel on climate
change; IPCC Secretariat Geneva, 2007.
2] (a) Rochelle, G. T. Science 2009, 325, 1652. (b) Haszeldine, R. S.
Science 2009, 325, 1647. (c) Schoedel, A.; Ji, Z.; Yaghi, O. M. Nature Energy
016, 1, 16034.
3] (a) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch,
Patwardhan, S. V.; Sefcik, J. Chem. Eng. J. 2016, 285, 718.
[16] (a) Rowsell, J. L. C.; Spencer, E. C.; Eckert, J.; Howard, J. A. K.;
Yaghi, O. M. Science 2005, 309, 1350. (b) Chae, H. K.; Siberio-Perez, D. Y.;
Kim, J.; Go, Y.; Eddaoudi, M.; Matzger, A. J.; O'Keeffe, M.; Yaghi, O. M.
Nature 2004, 427, 523.
[
2
[
[
17] (a) Guo, P.; Dutta, D.; Wong-Foy, A. G.; Gidley, D. W.; Matzger, A.
E. D.; Herm, Z. R.; Bae, T. H.; Long, J. R. Chem. Rev. 2012, 112, 724. (b)
Zhang, Z. J.; Yao, Z. Z.; Xiang, S. C.; Chen, B. L. Energy Environ. Sci. 2014,
J. J. Am. Chem. Soc. 2015, 137, 2651. (b) Zhang, W.; Hu, Y. L.; Ge, J.; Jiang,
H. L.; Yu, S. H. J. Am. Chem. Soc. 2014, 136, 16978.
7
, 2868. (c) Li, J. R.; Ma, Y. G.; McCarthy, M. C.; Sculley, J.; Yu, J. M.;
Jeong, H. K.; Balbuena, P. B.; Zhou, H. C. Coord. Chem. Rev. 2011, 255,
791. (d) Sreenivasulu, B.; Sreedhar, I.; Suresh, P.; Raghavan, K. V. Environ.
Sci. Technol. 2015, 49, 12641.
[
18] Hausdorf, S.; Wagler, J.; Mossig, R.; Mertens, F. O. R. L. J. Phys.
Chem. A 2008, 112, 7567.
[19] Feng, X.; Ding, X. S.; Jiang, D. L. Chem. Soc. Rev. 2012, 41, 6010.
1
ACS Paragon Plus Environment

Page 5 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
Table of Contents
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment