Expanded organic building units for the construction of highly porous metal-organic frameworks

Article abstract of DOI:10.1002/chem.201302515

Two new organic building units that contain dicarboxylate sites for their self-assembly with paddlewheel [Cu₂(CO₂)₄] units have been successfully developed to construct two isoreticular porous metal-organic frameworks (MOFs), ZJU-35 and ZJU-36, which have the same tbo topologies (Reticular Chemistry Structure Resource (RCSR) symbol) as HKUST-1. Because the organic linkers in ZJU-35 and ZJU-36 are systematically enlarged, the pores in these two new porous MOFs vary from 10.8A in HKUST-1 to 14.4A in ZJU-35 and 16.5A in ZJU-36, thus leading to their higher porosities with Brunauer-Emmett-Teller (BET) surface areas of 2899 and 4014m² g^-1 for ZJU-35 and ZJU-36, respectively. High-pressure gas-sorption isotherms indicate that both ZJU-35 and ZJU-36 can take up large amounts of CH₄ and CO₂, and are among the few porous MOFs with the highest volumetric storage of CH₄ under 60bar and CO₂ under 30bar at room temperature. Their potential for high-pressure swing adsorption (PSA) hydrogen purification was also preliminarily examined and compared with several reported MOFs, thus indicating the potential of ZJU-35 and ZJU-36 for this important application. Studies show that most of the highly porous MOFs that can volumetrically take up the greatest amount of CH₄ under 60bar and CO₂ under 30bar at room temperature are those self-assembled from organic tetra- and hexacarboxylates that contain m-benzenedicarboxylate units with the [Cu₂(CO ₂)₄] units, because this series of MOFs can have balanced porosities, suitable pores, and framework densities to optimize their volumetric gas storage. The realization of the two new organic building units for their construction of highly porous MOFs through their self-assembly with [Cu ₂(CO₂)₄] units has provided great promise for the exploration of a large number of new tetra- and hexacarboxylate organic linkers based on these new organic building units in which different aromatic backbones can be readily incorporated into the frameworks to tune their porosities, pore structures, and framework densities, thus targeting some even better performing MOFs for very high gas storage and efficient gas separation under high pressure and at room temperature in the near future. Copyright

Full text of DOI:10.1002/chem.201302515

DOI: 10.1002/chem.201302515
Expanded Organic Building Units for the Construction of Highly Porous
Metal–Organic Frameworks
Guo-Qiang Kong,[a] Zhi-Da Han,[a] Yabing He,[b] Sha Ou,[a] Wei Zhou,[c, d]
Taner Yildirim,[d, e] Rajamani Krishna,*[f] Chao Zou,[a] Banglin Chen,*[b] and
Chuan-De Wu*[a]
Abstract: Two new organic building
units that contain dicarboxylate sites
for their self-assembly with paddle-
are among the few porous MOFs with
the highest volumetric storage of CH4
under 60 bar and CO2 under 30 bar at
room temperature. Their potential for
high-pressure swing adsorption (PSA)
hydrogen purification was also prelimi-
narily examined and compared with
several reported MOFs, thus indicating
the potential of ZJU-35 and ZJU-36
for this important application. Studies
show that most of the highly porous
MOFs that can volumetrically take up
the greatest amount of CH4 under
60 bar and CO2 under 30 bar at room
temperature are those self-assembled
from organic tetra- and hexacarboxy-
lates that contain m-benzenedicarboxy-
because this series of MOFs can have
balanced porosities, suitable pores, and
framework densities to optimize their
volumetric gas storage. The realization
of the two new organic building units
for their construction of highly porous
MOFs through their self-assembly with
wheel [Cu
cessfully developed to construct two
isoreticular porous metal–organic
2ACHTUNGTRENNUNG(CO2)4] units have been suc-
frameworks (MOFs), ZJU-35 and
ZJU-36, which have the same tbo top-
ologies (Reticular Chemistry Structure
Resource (RCSR) symbol) as HKUST-
1. Because the organic linkers in ZJU-
35 and ZJU-36 are systematically en-
larged, the pores in these two new
porous MOFs vary from 10.8 ꢁ in
HKUST-1 to 14.4 ꢁ in ZJU-35 and
16.5 ꢁ in ZJU-36, thus leading to their
higher porosities with Brunauer–
Emmett–Teller (BET) surface areas of
2899 and 4014 m2 gÀ1 for ZJU-35 and
ZJU-36, respectively. High-pressure
gas-sorption isotherms indicate that
both ZJU-35 and ZJU-36 can take up
large amounts of CH4 and CO2, and
[Cu2ACTHUNGTRNEUNG(CO2)4] units has provided great
promise for the exploration of a large
number of new tetra- and hexacarboxy-
late organic linkers based on these new
organic building units in which differ-
ent aromatic backbones can be readily
incorporated into the frameworks to
tune their porosities, pore structures,
and framework densities, thus targeting
some even better performing MOFs
for very high gas storage and efficient
gas separation under high pressure and
at room temperature in the near
future.
late units with the [Cu2ACTHNUGTRNEUNG(CO2)4] units,
Keywords: adsorption · gas storage ·
metal–organic frameworks · self-as-
sembly · surface analysis
Introduction
quite straightforward: it makes use of metal–organic coordi-
nation bonds to assemble framework solids, the crystalline
structures of which can survive under vacuum and/or ther-
mal activation to generate pore spaces for the recognition of
substrates, energy storage, and chemical transformations.
Given the fact that some very simple Werner complexes
The last two decades have witnessed the emergence of and
significant progress in porous metal–organic frameworks
(MOFs) and/or porous coordination polymers (PCPs).[1,2]
The concept for constructing such new porous materials is
[a] Dr. G.-Q. Kong, Z.-D. Han, S. Ou, Dr. C. Zou, Prof. Dr. C.-D. Wu
Center for Chemistry of High-Performance and Novel Materials
Department of Chemistry, Zhejiang University
Hangzhou, 310027 (P.R. China)
[d] Dr. W. Zhou, Prof. Dr. T. Yildirim
NIST Center for Neutron Research
Gaithersburg, MD 20899-6102 (USA)
[e] Prof. Dr. T. Yildirim
Fax : (+86)571-87951895
E-mail: cdwu@zju.edu.cn
Department of Materials Science and Engineering
University of Pennsylvania, Philadelphia, PA 19104-6272 (USA)
[b] Dr. Y. He, Prof. Dr. B. Chen
[f] Prof. Dr. R. Krishna
Department of Chemistry, University of Texas at San Antonio
One UTSA Circle, San Antonio, Texas 78249-0698 (USA)
Fax : (+1)210-458-7428
Van ꢀt Hoff Institute of Molecular Science
University of Amsterdam, Science Park 904
1098 XH Amsterdam (The Netherlands)
E-mail: r.krishna@uva.nl
E-mail: banglin.chen@utsa.edu
[c] Dr. W. Zhou
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201302515.
Department of Materials Science and Engineering
University of Maryland, College Park, MD 20742 (USA)
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FULL PAPER
such as [Ni(4-Me-pyridine)
G
and many others.[22] During the extensive studies on the
cules,[3] coordination polymers might be able to exhibit gas/
vapor sorption as well, as proposed by Hoskins and Robson
in 1989.[4] However, it took quite long time to realize the
first several porous coordination polymers and to introduce
the term metal–organic frameworks, the permanent porosi-
ties of which were established by gas-sorption isotherms
during 1997 to 1999.[5] This is mainly because most so-called
crystallographically “porous” coordination polymers are not
robust enough to sustain the vacuum/thermal activation:
once the solvent guest molecules are removed from the pore
spaces of the coordination polymers, the frameworks col-
lapse.[6] Such phenomena once again confirmed Aristotleꢃs
famous statement “Nature abhors the vacuum”.
The establishment of the permanent porosities of the first
several prototypic MOFs has immediately initiated much
more extensive research endeavors on functional MOF ma-
terials for gas storage, separation, heterogeneous catalysis,
photonics, and drug delivery.[7–11] From the structure point of
view, porous MOFs are self-assembled from metal ions and/
or metal-containing clusters (so-called metal-containing sec-
ondary building units (SBUs)) and organic building units
and/or linkers.[12] Such a MOF structure rationalization can
help us to readily understand the structures and pore dimen-
sions of MOF materials, and nowadays is widely practiced in
the rational synthesis of MOFs. This is particularly true for
[Cu
that some organic carboxylates such as BTB have a limited
capacity to assemble with [Cu2A(CO2)4] to construct highly
2ACHTUNGTRNEN(UNG CO2)4]-based porous MOFs, the community realized
CTHUNGTRENNUNG
porous MOFs because of the framework interpenetration
and/or the unstable frameworks. In fact, although the BTB
organic linker is quite large, the resulting MOF-14 is only
moderately porous with a BET surface area of 1502 m2 gÀ1
because of the framework interpenetration, whereas the
non-interpenetrated MOF-14 (MOF-143) from BTB and the
doubly interpenetrated MOF-388 from an even larger tricar-
boxylate (TAPB) are nonporous.[23] Studies, however, also
show that some organic carboxylates, particularly those con-
taining m-benzenedicarboxylate, are favorable to the forma-
tion of stable porous MOFs. The well-known porous MOF
constructed from [Cu2ACHTUNGTRN(ENUNG CO2)4] units and m-benzenedicarbox-
ylate containing carboxylates is HKUST-1 (Cu3ACHTUNGTRENNUNG(BTC)2;
BTC=benzene-1,3,5-tricarboxylate).[5d] The incorporation of
expanded organic linkers containing m-benzenedicarboxy-
late units into [Cu2ACHTNUGTRNEG(UN CO2)4] units, to a certain extent, was ini-
tiated by Chen et al. and subsequently by Lin et al. on m-
benzenedicarboxylate containing tetracarboxylates.[24] These
works immediately attracted wide attention in the MOF
community: not only a large number of tetracarboxylates,
but also a number of hexacarboxylates containing m-benze-
nedicarboxylate have been readily assembled with [Cu2-
those MOFs constructed from [Zn4O
(CO2)4] SBUs and organic carboxylates.
[Zn4O(CO2)6] and [Cu2A(CO2)4] SBUs are two of the most
A
(CO2)4] units to generate highly porous MOFs.[22] Although
ACHTUNGTRENNUNG
N
the mechanism as to why such m-benzenedicarboxylates
containing carboxylates can stabilize the frameworks is not
exclusively clear at this moment, the power of these m-ben-
zenedicarboxylate units to stabilize the cages of moderate
A
R
CHTUNGTRENNUNG
useful inorganic building units for the construction of highly
porous MOFs with BET surface areas over 2000 m2 gÀ1.
Since the discovery of MOF-5 (or IRMOF-1),[5c] the [Zn4O-
sizes surrounded by m-benzenedicarboxylate–[Cu2ACHTUNGTRENNUNG(CO2)4]
A
framework surfaces certainly plays a very important role.
The meta position of the two carboxylates within the organic
linkers can also minimize the possibility of the framework
interpenetration. The implementation of supercritical
carbon dioxide activation has now led to two extremely
porous MOFs with BET surface areas over 7000 m2 gÀ1,
which have been generated from two hexacarboxylate or-
ganic linkers built from three m-benzenedicarboxylate
units.[25]
of bicarboxylates to synthesize a series of isoreticular MOFs
whose pore spaces can be systematically varied by the
length of the bicarboxylates,[13] but have been also connected
with tricarboxylates such as 1,3,5-tris(4-carboxyphenyl)ben-
zene (BTB) to generate another highly porous MOF-177.[14]
Matzger and Kaskel have even been able to assemble two
different types of organic carboxylates such as benzene-1,4-
dicarboxylate (BDC) and BTB with [Zn4O
leading to
a
Motivated by the power of this basic m-benzenedicarbox-
ylate organic building unit to construct highly porous MOFs,
we have been working on the expanded organic units, as
shown in Figure 1a (II and III), for the design of new organ-
ic linkers and thus porous MOFs through their self-assembly
MOFs.[15] For example, MOF-200 and -205 developed by
Yaghi have BET surface areas of 4530 and 6240 m2 gÀ1, re-
spectively.[16]
G
(CO2)4] SBUs have been even more widely utilized
(CO2)6] ones to generate highly porous MOFs.
A
with the paddle-wheel [Cu2ACHTUNGRETNNU(G CO2)4] SBUs. To the best of our
C
knowledge, such expanded organic units have never been
utilized before. If such organic building units, particularly
unit III as shown in Figure 1a, can assemble with [Cu2-
CTHUNGTRENNUNG
with linear bicarboxylates led to the formation of two-di-
mensional (4,4) square-planar nets.[17] When the bicarboxy-
late is twisted, as in the case of 2-bromobenzene-1,4-dicar-
boxylate, a three-dimensional NbO type of porous MOF-
101 can be constructed.[18] It is understandable that self-as-
AHCTUNGTREN(GNUN CO2)4] units to construct porous MOFs, the incorporation
of this new organic unit into the rich organic aromatic back-
bones will lead to an abundance of new organic linkers for
the construction of highly porous MOFs (Figure S2 in the
Supporting Information). Theoretically speaking, all the aro-
matic backbones utilized for the syntheses of tetra- and hex-
acarboxylic acids containing m-benzenedicarboxylate organ-
sembly of [Cu2ACHTUNGTRENNUNG(CO2)4] units with organic carboxylates of
three dimensions can lead to three-dimensional porous
MOFs, as exemplified in MOF-11,[19] MOF-14,[20] PCN-6,[21]
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R. Krishna, B. Chen, C.-D. Wu et al.
ganic linkers and thus highly porous MOFs will lead to
a number of highly porous MOFs for gas storage and sepa-
ration in the near future.
Results and Discussion
As shown in Scheme 1, the two new tricarboxylate organic
linkers 5-(2-carboxyvinyl)isophthalic acid (H3L1) and 3,3’-
(5-carboxy-1,3-phenylene)diacrylic acid (H3L2) were simply
Scheme 1. The synthetic schemes for the organic linkers H3L1 and H3L2.
synthesized by Heck cross-coupling reactions of methylated
bromophenylcarboxylate and methyl acrylate, followed by
hydrolysis and acidification. Reactions of these two organic
Figure 1. a) m-Benzenedicarboxylate organic building unit I and two new
expanded ones (II and III). Self-assembly of b) H3BTC and c,d) two new
organic linkers with paddle-wheel [Cu2ACTHNUTRGNENUG(CO2)4] units leading to the con-
struction of isoreticular porous MOFs: b) HKUST-1, c) ZJU-35, and
d) ZJU-36, the pores of which (small and large spheres) are systematical-
ly enlarged (Cu, polyhedral,H atoms are omitted for clarity).
linkers with CuACTHNUTRGNE(UNG NO3)2·3H2O in acidified DMF/H2O at 658C
for two days afforded blue crystals of ZJU-35 and ZJU-36,
respectively. The compositions of the as-synthesized MOFs
were based on the elemental analyses, thermogravimetric
analyses (TGA), and single-crystal structures.
Single-crystal X-ray diffraction analysis revealed that the
two MOFs are isomorphous, and crystallize in the cubic
¯
ic building unit I (Figure 1) can be also explored for the syn-
theses of new organic linkers of tetra- and hexacarboxylic
acids containing organic building unit III (Figure 1) and thus
for the construction of highly porous MOFs. Herein we
report the first two examples of organic linkers (Figure 1c,d)
constructed from such new expanded organic building units
and correspondingly constructed highly porous MOFs
(ZJU-35 and ZJU-36; ZJU=Zhejiang University) self-as-
sembled from these two new tricarboxylates and [Cu2-
Fm3m space group. Both ZJU-35 and ZJU-36 are isoreticu-
lar with the very important prototype MOF HKUST-1 of
the tbo topology, although the new linkers H3L1 and H3L2
are apparently less symmetric than H3BTC. It has been ra-
tionalized that the self-assembly of tricarboxylate with
paddle-wheel [Cu2ACHTUNRGTNEG(UN CO2)4] either forms tbo or pto frame-
works, which are attributed to the different structural orien-
tation of tritopic carboxylates.[20,21,23,26] Because H3L1 and
H3L2 are larger than H3BTC, the pores within these isoretic-
ular MOFs are systematically enlarged: the small orange
pockets are 5.3, 6.4, and 7.5 ꢁ, and the large purple cages
are 10.8, 14.4, and 16.5 ꢁ in HKUST-1, ZJU-35, and ZJU-
36, respectively, taking into account the van der Waals
radius, as shown in Figure 1. PLATON calculations indicate
that the void spaces are 62.3 and 76.9% for ZJU-35 and
ZJU-36, respectively.[27]
Both activated ZJU-35a and ZJU-36a exhibit type I rever-
sible sorption isotherms and take up 747 and 1033 cm3 gÀ1 N2
at 77 K and 1 bar, respectively (Figure 2a). Accordingly,
ZJU-35a has a BET surface area of 2899 m2 gÀ1 and a pore
volume of 1.156 cm3 gÀ1, whereas ZJU-36a has a BET sur-
face area of 4014 m2 gÀ1 and a pore volume of 1.599 cm3 gÀ1.
ACHTUNGTRENNUNG(CO2)4] units. Because these two new organic linkers can be
considered as the expanded organic linkers of BTC, the re-
sulting porous MOFs ZJU-35 and ZJU-36 are isoreticular to
HKUST-1 and thus have the same tbo topology (Reticular
Chemistry Structure Resource (RCSR) symbol) (Fig-
ure 1b).[12c] Of course, ZJU-35 and ZJU-36 exhibit higher
porosities than HKUST-1 because of their enlarged pore
spaces, with BET surface areas of 2899 and 4014 m2 gÀ1, re-
spectively. Their potential applications for high-pressure gas
storage (H2, CH4, and CO2) and CO2/H2 separation were ex-
amined, showing high storage and separation capacities for
these gas molecules. The bright promise of the organic
building unit III for the construction of new expanded or-
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Porous Metal–Organic Frameworks
FULL PAPER
CH4 and CO2 volumetrically at room temperature. The com-
parison of some highly porous MOFs for CH4 and CO2 stor-
age and capture is summarized in Tables S2 and S3 in the
Supporting Information. Because little data are available for
CH4 storage above 60 bar, and for CO2 capture above
30 bar, we compare the CH4 and CO2 storage capacities of
our MOFs under 60 and 30 bar, respectively, at room tem-
perature.
As shown in Figure 3b, the gravimetric CH4-storage ca-
pacities of the MOF materials under 60 bar and at room
temperature are basically dependent on their BET surface
areas. The larger the surface area, the larger the absolute
CH4 uptake by the MOF. Accordingly, MOF-210 and DUT-
49 have the maximum gravimetric methane uptakes of 536
and 540 cm3 gÀ1, respectively, at RT and 60 bar because of
their extremely high BET surface areas of 6240 and
5476 m2 gÀ1, among those examined porous MOFs for meth-
ane storage.[16,28] Because the framework density is inversely
proportional to the pore volume of the MOF materials, as
shown in Figure 3d (1/(framework density) is basically line-
arly correlated to the pore volume of the framework)—the
larger the porosity, the smaller the framework density of the
MOF—those MOFs exhibiting high volumetric methane
storage should have balanced porosities and framework den-
sities to utilize the pore spaces efficiently. In fact, these
MOFs have absolute volumetric CH4 uptakes of over
220 cm3 cmÀ3 under 60 bar at room temperature and have
BET surfaces from 1218 m2 gÀ1 for NiMOF-74 to 3342 m2 gÀ1
for NOTT-102.[29,30] Of course, the M-MOF-74 series of
Figure 2. a) N2 and b) absolute H2 sorption isotherms of ZJU-35a and
ZJU-36a at 77 K. STP=standard temperature and pressure.
The porosities of both ZJU-35a and ZJU-36a are systemati-
cally higher than those of HKUST-1 with a BET surface
area of 1502 m2 gÀ1 and a pore volume of 0.76 cm3 gÀ1, and
are among the few highly
porous MOFs. The maximum
excess H2 uptake of ZJU-35a
and ZJU-36a is 5.2 and
6.2 wt% (Figure S9 in the Sup-
porting Information), respec-
tively, which correlates well
with their corresponding sur-
face areas. Their absolute H2-
storage capacities are 7.1 and
9.1 wt%, respectively, at 77 K
and 63 bar (Figure 2b), which is
moderately high. Their room-
temperature absolute hydro-
gen-storage values are 1.0 and
1.2 wt% for ZJU-35a and ZJU-
36a, respectively.
The CH4-storage capacities of
ZJU-35a and ZJU-36a are 227
and 203 cm3 cmÀ3, respectively,
at 300 K and 64 bar (Figure 3a).
ZJU-35a and ZJU-36a have
high CO2 uptakes of 328 and
311 cm3 cmÀ3, respectively, at
300 K and 30 bar. ZJU-35a and
&
Figure 3. a) Absolute gas-sorption isotherms of CO2, CH4, and H2 of ZJU-35a ( ) and ZJU-36a (open–solid di-
amond) at 300 K; the relationship between the gravimetric b) CH4 and c) CO2 storage capacities of the MOF
materials with BET surface areas, and d) the plot of the 1/framework density versus the framework pore
ZJU-36a are among the few
best-performing MOF materials
for the storage and capture of volume. SA=surface area.
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R. Krishna, B. Chen, C.-D. Wu et al.
MOFs are very special because of their significantly high
densities of open metal sites for the CH4 storage. In terms
of deliverable methane capacities (60 to 5 bar), NU-125 and
NOTT-102 have the highest volumetric deliverable amounts
of methane of 183 and 182 cm3 cmÀ3, respectively.[30,31] ZJU-
35 is among the six MOFs whose volumetric deliverable
amounts of methane are over 175 cm3cmÀ3. It needs to be
mentioned that those MOFs with high densities of open
metal sites such as the M-MOF-74 series exhibit quite low
volumetric deliverable amounts of methane. This is because
even at a pressure of 5 bar, this type of MOF can take up
quite a large amount of methane, which limits their delivera-
ble amount of methane capacity.
The absolute gravimetric CO2 capture capacities of the
MOF materials under 30 bar and at room temperature are
also approximately linearly dependent on their BET surface
areas, as shown in Figure 3c. DUT-49 has the highest abso-
lute gravimetric CO2 uptake of 947 cm3 gÀ1 at RT and
30 bar.[28] To reach high volumetric CO2 uptake at RT and
30 bar, the MOF materials also need to have balanced po-
rosities and framework densities to maximize the pore-usage
efficiency. Until now, NU-111 had the highest absolute volu-
metric CO2 uptake of 350 cm3 cmÀ3 at RT and 30 bar.[32]
ZJU-35 is one of the six MOFs with absolute volumetric
CO2 uptake amounts of over 320 cm3 cmÀ3 at RT and 30 bar.
The BET values of these six MOFs are in the range of
1931 m2 gÀ1 in PCN-11 to 4930 m2 gÀ1 in NU-111 except the
significantly low one of 1218 m2 gÀ1 in Ni-MOF-74.[29,32,33]
Again, the significantly high volumetric CO2 uptake of Ni-
MOF-74 is attributed to the high density of open Ni2+ sites
within this porous MOF.
adsorber breakthrough simulation for a ternary 30:20:50
CO2/CH4/H2 gas mixture (Figure S20 in the Supporting In-
formation), which is typically encountered in H2-purification
processes. Because very few porous MOFs have been com-
prehensively examined for their temperature- and pressure-
dependent sorption isotherms for all H2, CH4, and CO2 gas
molecules, we compared the performances of ZJU-35a and
ZJU-36a with other MOFs (HKUST-1, MgMOF-74, Cu-
TDPAT, and MIL-101) and zeolites (NaX and LTA-
5A).[36–38]
As shown in Figure 4a, the Qst values of CO2 systematical-
ly decrease from HKUST-1 to ZJU-35a and then to ZJU-
36a because the pores are enlarged while the densities of
the open metal sites are reduced gradually within these iso-
reticular MOFs. Cu-TDPAT has very high Qst values of CO2,
particularly at low loading of CO2, because of its amine
groups on the pore surfaces for their very strong interactions
with CO2. The very large Qst values of CO2 for MgMOF-74
are attributed to the strong electrostatic interactions be-
tween open Mg2+ sites and CO2 molecules. Zeolites NaX
and LTA-5A with smaller pores have larger Qst values of
CO2 than ZJU-35a and ZJU-36a.
HKUST-1 has the highest, and ZJU-36a has the lowest
CO2/H2 and CH4/H2 IAST adsorption selectivity among the
three isoreticular porous MOFs (Figures S21 and S22 in the
Supporting Information).[35] The performance of a PSA unit
is dictated both by the adsorption selectivity and by the ca-
pacity to adsorb both CO2 and CH4. Generally speaking,
higher capacities are desirable because the adsorber bed can
be run for longer lengths of time before the need for regen-
eration arises. The sum of the component loadings of CO2
and CH4 in the mixture is an appropriate measure of the ca-
pacity. Figure 4b presents data on the IAST calculations of
the (CO2 +CH4) uptake capacities, which indicate that ZJU-
35a and ZJU-36a have higher uptake capacities than other
examined materials for pressures exceeding 2 MPa.
Close examination of these data also indicates that those
MOFs exhibiting high absolute volumetric CH4 storage
under 60 bar and high deliverable amounts of methane (60
to 5 bar), and high absolute volumetric CO2 capture under
30 bar and at room temperature are mainly those MOFs
constructed from [Cu
(CO2)4] units with tetra- or hexacar-
Transient breakthrough calculations demonstrate that hy-
drogen breaks through earliest and it is possible to produce
pure hydrogen from this three-component mixture during
the adsorption cycles of both ZJU-35a and ZJU-36a (Fig-
ure 4c and Figure S23 in the Supporting Information).[39]
The most important feature is that ZJU-35a exhibits signifi-
cantly high gravimetric hydrogen productivity, as shown in
Figure 4d. For pressures exceeding 4 MPa, typical of hydro-
gen purification, the hierarchy of productivities is ZJU-
35a>MgMOF-74ꢀCu-TDPATꢀHKUST-1ꢀZJU-36a>
NaX>MIL-101>LTA-5A. The excellent performance of
ZJU-35a is due to the suitable combination of separation se-
lectivities and capacities optimized for H2 purification.
The relative costs of regeneration of the bed will be large-
ly dictated by the desorption of the CO2 captured during the
interval 0–tbreak. As shown in Figure 4a, the energy required
for regeneration of adsorbed CO2 in fixed-bed adsorbers
will be lower for ZJU-35a and ZJU-36a than for HUKST-1,
MgMOF-74, and Cu-TDPAT. For pressures exceeding
4 MPa (Figure 4d), ZJU-35a and ZJU-36a have higher
gravimetric production capacities than other examined
boxylates containing m-benzenedicarboxylate units (building
unit I in Figure 1a) except M-MOF-74, MOF-205, MIL-
101c, and our reported ZJU-35 and -36.[16,29,34] Because
building unit III can be simply considered as the expanded
building unit I, this new organic building unit is expected to
produce a number of tetra- and hexacarboxylic acids with
different aromatic backbones as the organic linkers, and
thus to self-assemble with [Cu2ACHTNUTRGNEUNG(CO2)4] units to construct
a series of highly porous MOFs for their high CH4 storage
and CO2 capture at room temperature.
The high CH4 storage and CO2 capture of these two new
MOFs at room temperature also encouraged us to examine
their potential applications on hydrogen purification, which
is one very important industrial process for which optimized
adsorbents are urgently needed because small improvements
can result in significant energy savings and cost reduc-
tions.[36–38] To establish the feasibility of ZJU-35a and ZJU-
36a for high-pressure swing adsorption (PSA) purification of
hydrogen, we studied in detail their isosteric heats of ad-
sorption, Qst, of CO2, adsorption selectivity, and packed-bed
14890
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ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 14886 – 14894

Porous Metal–Organic Frameworks
FULL PAPER
Conclusion
In summary, we have success-
fully developed two new organ-
ic carboxylate building units
and realized two tricarboxylate
linkers for the construction of
isoreticular porous MOFs ZJU-
35 and ZJU-36 for their high
CH4 storage, CO2 capture, and
hydrogen purification under
high pressure and room temper-
ature, which have been com-
pared with the reported MOFs
comprehensively.
Because
a series of new organic linkers
can be readily synthesized from
such simple organic building
units through the incorporation
of different aromatic back-
bones, this work will stimulate
extensive research on the con-
struction of a variety of new
highly porous MOFs in which
their framework topologies and
porosities can be readily tuned
for their high-pressure gas stor-
age and separation. The fact
that the MOFs exhibiting very
high volumetric storage and
capture of both CH4 and CO2
are mainly those self-assembled
from organic linkers containing
m-benzenedicarboxylate units
Figure 4. a) Comparison of isosteric heats of adsorption, Qst, of CO2 in ZJU-35a, ZJU-36a, CuBTC (HKUST-
1), MgMOF-74, Cu-TDPAT, MIL-101, NaX, and LTA-5A. The calculations of Qst are based on the use of the
Clausius–Clapeyron equation. b) Calculations using ideal adsorbed solution theory (IAST) of Myers and
Prausnitz[35] (CO2 +CH4) uptake capacity, expressed as moles per kg of adsorbent, in equilibrium with a ternary
CO2/CH4/H2 30:20:50 gas mixture maintained under isothermal conditions at 298 K. c) Breakthrough charac-
teristics of an adsorber packed with ZJU-35a maintained at isothermal conditions at 298 K and 5 MPa. d) In-
fluence of the operating pressure on the number of moles of 99.95%+ pure H2 produced per kg of adsorbent
material during the time interval 0–tbreak. The breakthrough times, tbreak, correspond to those when the outlet
gas contains 500 ppm (CO2 +CH4).
with paddle-wheel [Cu2ACHTUNGTRENNUNG(CO2)4]
SBUs, the new organic building
units reported here will be very
promising to target some novel
highly porous MOFs with even
higher storage capacities for
CH4 and CO2 under high pres-
sure and room temperature.
MOFs. Among the three isoreticular MOFs, ZJU-35a has
the highest gravimetric hydrogen production capacity
whereas HKUST-1 has the highest volumetric hydrogen pro-
duction capacity (Figure S25 in the Supporting Information)
at high pressures. Overall, ZJU-35a can be ranked as one of
the few best porous MOFs for high-pressure hydrogen pu-
rification when regeneration cost, gravimetric and volumet-
ric production capacities need to be balanced. The pore and
channel sizes/curvatures, pore surface functionalities, pore
volumes, and framework densities should be equally consid-
ered and optimized to further realize better MOF materials
for high-pressure hydrogen purification in the near future.
With systematically enlarged pore sizes and porosities, ZJU-
35 and ZJU-36 are expected to be fully explored for other
diverse functions as well. In fact, their isoreticular HKUST-
1 is one of the most important prototype MOFs for their ap-
plications in gas storage, separation, heterogeneous catalysis,
drug delivery, as host materials for the encapsulation of
active catalysts and nanoparticles, and fabrication of film de-
vices.[40] The realization of ZJU-35 as a significant potential
material for high-pressure swing adsorption hydrogen purifi-
cation at room temperature indicates that it is practically
feasible to realize high-performance materials for such im-
portant industrial applications through the deliberate con-
trol of the pore space and metrics of the porous MOFs.
Chem. Eur. J. 2013, 19, 14886 – 14894
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
14891

R. Krishna, B. Chen, C.-D. Wu et al.
ed HCl. The precipitate was collected by filtration, washed with water
several times, and dried at 508C to afford a white powder. Yield: 2.5 g
(95%); 1H NMR (500 MHz, [D6]DMSO): d=6.74 (d, J=16.0 Hz, 2H),
7.65 (d, J=16.0 Hz, 2H), 8.16 (s, 2H), 8.35 ppm (s, 1H); 13C NMR
(125 MHz, [D6]DMSO): d=121.4, 130.2, 130.4, 133.1, 135.3, 142.3, 166.7,
167.4 ppm; IR (KBr pellet): n˜ =1724 (s), 1703 (s), 1637 (s), 1557 (w),
1442 (m), 1408 (m), 1293 (m), 1254 (m), 1216 (s), 981 (s), 863 (m), 773
(m), 691 (w), 616 (w), 581 cmÀ1 (w).
Experimental Section
Materials and methods: All of the chemicals were obtained from com-
mercial sources and were used without further purification. IR spectra
were collected from KBr pellets on a FTS-40 spectrophotometer. TGA
was carried out under an N2 atmosphere on a SDT Q600 instrument at
a heating rate of 108CminÀ1. Elemental analyses were performed on
a ThermoFinnigan Flash EA 1112 Element Analyzer. Powder X-ray dif-
fraction (PXRD) data were recorded on a RIGAKU D/MAX 2550/PC
for CuKa radiation (l=1.5406 ꢁ). 1H and 13C NMR spectra were record-
ed on a 500 MHz spectrometer in CDCl3 or [D6]DMSO and the chemical
shifts were reported relative to an internal standard of TMS (0 ppm). A
Micromeritics ASAP 2020 surface-area analyzer was used to measure
gas-adsorption isotherms.
Synthesis of [Cu3(L1)
2ACTHNUGTREN(NUNG H2O)3]·2DMF·5.5H2O (ZJU-35): H3L1 (20 mg,
0.085 mmol), Cu(NO3)2·3H2O (40 mg, 0.17 mmol), 0.1m HCl (2.8 mL),
AHCTUNGTRENNUNG
DMF (20 mL), and H2O (12 mL) were mixed and heated at 658C for two
days. Blue crystals of ZJU-35 were collected by filtration, washed with
EtOH and Et2O, and dried in air. Yield: 75%; IR (KBr pellet): n˜ =1652
(s), 1614 (m), 1560 (m), 1497 (w), 1440 (m), 1378 (s), 1262 (m), 1107 (w),
984 (w), 874 (w), 777 (m), 730 (m), 628 cmÀ1 (w); elemental analysis
calcd (%) for C28H41N2Cu3O22.5: C 35.17, H 4.32, N 2.93; found: C 35.13,
H 4.15, N 2.87
Synthesis of dimethyl 5-(3-methoxy-3-oxoprop-1-enyl)isophthalate
(Me3L1): As shown in Scheme 1, dimethyl 5-bromo-1,3-benzenedicarbox-
ylate (13.65 g, 50 mmol), methyl acrylate (9 mL, 100 mmol), K2CO3
(10.35 g, 75 mmol), tetrabutyl ammonium bromide (TBAB) (3.22 g,
Synthesis of [Cu3(L2)
2ACTHNUGTREN(NUNG H2O)3]·5DMF·6.5H2O (ZJU-36): H3L2 (20 mg,
0.076 mmol), Cu(NO3)2·3H2O (40 mg, 0.17 mmol), 0.1m HCl (5.4 mL),
AHCTUNGTRENNUNG
10 mmol), PdACHTUNGTRENNUNG(OAc)2 (1.122 g, 5 mmol), and DMF (100 mL) were mixed
DMF (20 mL), and H2O (4 mL) were mixed and heated at 658C for two
days. Blue crystals of ZJU-36 were collected by filtration, washed with
EtOH and Et2O, and dried in air. Yield: 79%; IR (KBr pellet): n˜ =1652
(s), 1588 (m), 1497 (w), 1437 (m), 1397 (s), 1282 (m), 1165 (w), 1101 (m),
984 (m), 870 (m), 789 (m), 754 (w), 665 (w), 611 cmÀ1 (w); elemental
analysis calcd (%) for C41H68N5Cu3O26.5: C 39.53, H 5.50, N 5.62; found:
C 39.43, H 5.59, N 5.79.
in a 250 mL round-bottomed flask. The mixture was heated at 1308C
under stirring for 24 h. After the reaction was cooled down to room tem-
perature, the mixture was poured into water and extracted with ethyl
acetate three times. The combined organic phase was dried over anhy-
drous MgSO4 and concentrated under vacuum. The residue was subjected
to chromatography on silica gel (petroleum ether/CH2Cl2 5:1). The sol-
vent was removed under reduced pressure to give a white power. Yield:
8.3 g (60%); 1H NMR (500 MHz, CDCl3): d=3.83 (s, 3H), 3.97 (s, 6H),
6.58 (d, J=16.0 Hz, 1H), 7.73 (d, J=16.0 Hz, 1H), 8.36 (s, 2H), 8.67 ppm
(s, 1H); 13C NMR (125 MHz, CDCl3): d=51.9, 52.6, 120.4, 131.4, 131.8,
132.8, 135.3, 142.5, 165.8, 166.8 ppm; IR (KBr pellet): n˜ =1733 (s), 1644
(m), 1560 (w), 1448 (m), 1436 (m), 1342 (m), 1253 (s), 1207 (m), 1176 (s),
1130 (w), 994 (m), 860 (w), 755 (m), 596 cmÀ1 (w).
¯
Crystal data for ZJU-35: C22H16Cu3O15, Mr =710.97, cubic, Fm3m, a=
29.8307(6) ꢁ, V=26545.5(9) ꢁ3, Z=16, T=293 K, 1calcd =0.712 gcmÀ3
m=1.384 mmÀ1, F
(000)=5680, 8749 reflections, 999 independent reflec-
tions, Rint =0.0294, R1A[I>2s(I)]=0.0783, wR2 =0.2318, GOF=1.003.
Crystal data for ZJU-36: C26H20Cu3O15, Mr =763.04, cubic, Fm3m, a=
33.6167(7) ꢁ, V=37989.6(14) ꢁ3, Z=16, T=293 K, 1calcd =0.534 gcmÀ3
m=0.982 mmÀ1, F
(000)=6128, 7843 reflections, 1367 independent reflec-
tions, Rint =0.0783, R1A[I>2s(I)]=0.0682, wR2 =0.1560, GOF=1.037.
,
AHCTUNGTRENNUNG
CTHUNGTRENNUNG
¯
,
AHCTUNGTRENNUNG
Synthesis of 5-(2-carboxyvinyl)isophthalic acid (H3L1): Me3L1 (3.9 g,
14 mmol) and KOH (210 mmol, 11.7 g) in THF (50 mL) and H2O
(50 mL) were heated at 608C for 12 h. After the mixture was cooled
down to room temperature, THF was evaporated under reduced pres-
sure. The pH value of the mixture was adjusted to 1 by using concentrat-
ed HCl. The precipitate was collected by filtration, washed with water
several times, and dried at 508C to afford a white powder. Yield: 3.2 g
(97%); 1H NMR (500 MHz, [D6]DMSO): d=6.64 (d, J=16.0 Hz, 1H),
7.71 (d, J=16.0 Hz, 1H), 8.37 (s, 2H), 8.49 ppm (s, 1H); 13C NMR
(125 MHz, [D6]DMSO): d=121.5, 131.0, 131.9, 133.1, 135.0, 142.0, 166.6,
167.3 ppm; IR (KBr pellet): n˜ =1701 (s), 1641 (m), 1603 (w), 1420 (m),
1274 (s), 1220 (s), 1103 (w), 982 (m), 903 (m), 871 (w), 763 (s), 695 (m),
603 (m), 519 cmÀ1 (m).
CTHUNGTRENNUNG
CCDC-898168 (ZJU-35) and -900115 (ZJU-36) contain the supplementa-
ry crystallographic data for this paper. These data can be obtained free
of charge from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgements
Synthesis of dimethyl 3,3’-[5-(methoxycarbonyl)-1,3-phenylene]diacrylate
(Me3L2): As shown in Scheme 1, methyl 3,5-dibromobenzoate (14.7 g,
50 mmol), methyl acrylate (9 mL, 100 mmol), K2CO3 (10.35 g, 75 mmol),
This work was supported by the National Natural Science Foundation of
China (grant nos. 21073158 and J1210042), Zhejiang Provincial Natural
Science Foundation of China (grant no. Z4100038), the Fundamental Re-
search Funds for the Central Universities (grant no. 2013FZA3006) and
Welch Foundation AX-1730 (B.C.), and partially supported by DOE-
BES grant no. DE-FG02-08ER46522 (T.Y.). We thank Michael OꢃKeeffe
for the very constructive discussions.
tetrabutyl ammonium bromide (TBAB) (3.22 g, 10 mmol), PdACTHNUTRGNEUNG(OAc)2
(1.122 g, 5 mmol), and DMF (100 mL) were mixed in a 250 mL round-
bottomed flask. The mixture was heated at 1308C under stirring for 24 h.
After the reaction was cooled down to room temperature, the mixture
was poured into water and extracted with ethyl acetate three times. The
combined organic phase was dried over anhydrous MgSO4 and concen-
trated under vacuum. The residue was subjected to chromatography on
silica gel (petroleum ether/CH2Cl2 5:1). The solvent was removed under
reduced pressure to give a white power. Yield: 9.9 g (65%); 1H NMR
(500 MHz, CDCl3): d=3.83 (s, 6H), 3.96 (s, 3H), 6.53 (d, J=16.0 Hz,
2H), 7.70 (d, J=16.0 Hz, 2H), 7.79 (s, 1H), 8.20 ppm (s, 2H); 13C NMR
(125 MHz, CDCl3): d=51.9, 52.6, 120.1, 130.0, 131.5, 131.7, 135.6, 142.8,
165.9, 166.8 ppm; IR (KBr pellet): n˜ =1735 (s), 1712 (s), 1643 (s), 1597
(w), 1445 (s), 1346 (m), 1315 (m), 1290 (m), 1254 (s), 1173 (s), 1024 (w),
1003 (m), 920 (w), 860 (m), 769 (m), 666 (w), 562 cmÀ1 (w).
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Published online: September 23, 2013
14894
www.chemeurj.org
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 14886 – 14894