A highly stable zeotype mesoporous zirconium metal-organic framework with ultralarge pores

Article abstract of DOI:10.1002/anie.201409334

Through topological rationalization, a zeotype mesoporous Zr-containing metal-organic framework (MOF), namely PCN-777, has been designed and synthesized. PCN-777 exhibits the largest cage size of 3.8 nm and the highest pore volume of 2.8 cm³ g^-1among reported Zr-MOFs. Moreover, PCN-777 shows excellent stability in aqueous environments, which makes it an ideal candidate as a support to incorporate different functional moieties. Through facile internal surface modification, the interaction between PCN- 777 and different guests can be varied to realize efficient immobilization.

Full text of DOI:10.1002/anie.201409334

Angewandte
Chemie
DOI: 10.1002/anie.201409334
Metal–Organic Frameworks
A Highly Stable Zeotype Mesoporous Zirconium Metal–Organic
Framework with Ultralarge Pores**
Dawei Feng, Kecheng Wang, Jie Su, Tian-Fu Liu, Jihye Park, Zhangwen Wei, Mathieu Bosch,
Andrey Yakovenko, Xiaodong Zou, and Hong-Cai Zhou*
Abstract: Through topological rationalization, a zeotype
mesoporous Zr-containing metal–organic framework
MOF), namely PCN-777, has been designed and synthesized.
PCN-777 exhibits the largest cage size of 3.8 nm and the
highest pore volume of 2.8 cm g among reported Zr-MOFs.
Moreover, PCN-777 shows excellent stability in aqueous
environments, which makes it an ideal candidate as a support
to incorporate different functional moieties. Through facile
internal surface modification, the interaction between PCN-
variation of synthetic conditions in isoreticular structures,
framework interpenetration, and challenges in activation all
hamper the development of novel mesoporous MOFs. Most
importantly, when the size of the organic linker increases,
both the mechanical and the chemical stability of the frame-
(
3
À1
[
3]
work decrease gradually. Furthermore, the working envi-
ronments of those immobilized moieties are usually harsh,
which requires the frameworks to be chemically very stable.
The requirement of a combination of good chemical stability
and a large pore size means that very few candidates are
widely utilized. MIL-101 (MIL: Materials of Institut
Lavoisier) and MIL-100 are two extraordinary examples
that exhibit both properties and can be used as suitable
7
77 and different guests can be varied to realize efficient
immobilization.
M
esoporous metal-organic frameworks (MOFs) have been
[
4]
extensively studied as heterogeneous platforms to immobilize
functional moieties, such as organometallic catalysts, nano-
supports.
MIL-100 and MIL-101, both of which have zeotype
mtn topology (zeotype refers to structures sharing the same
topology as zeolites), contain super-tetrahedral cages to
[
1,2]
particles, polyalkyl amine chains, and enzymes.
As a result
of their readily adjustable structures and tunable function-
alities inside the frameworks, mesoporous MOFs facilitate the
performance of those materials through heterogenization or
isolation. However, the majority of reported MOFs are
microporous. Difficulty in the extension of organic linkers,
[
5]
substitute for the tetrahedral unit in zeolites. Thus, their
largest pores reach 31 ꢀ and 29 ꢀ, respectively, although the
organic linkers are relatively small. Moreover, the metal
nodes in these MOFs are based on trivalent metal species. The
strong interaction between carboxylates and high-valent
metal species accompanied with the small organic linker
endows these frameworks with excellent chemical stability.
Despite these advantages, the pore size still restricts
further application of these MOFs when it comes to larger
guests, such as nanoparticles or enzymes. Therefore, synthesis
of mesoporous materials with larger pore sizes which also
maintain excellent chemical stability is highly desired. The
use of a larger ligand than those employed in the MIL-100 and
MIL-101 MOFs to create zeotype frameworks would be an
effective way to generate extra-large pores, while avoiding
a complicated organic synthetic route to make very large
linkers. Unfortunately, several challenges must be addressed
to extend the series of mtn topological MOFs: a) the
[
+]
[+]
[
*] D. Feng, K. Wang, Dr. T.-F. Liu, J. Park, Dr. Z. Wei, M. Bosch,
Prof. Dr. H.-C. Zhou
Department of Chemistry, Texas A&M University
College Station, TX 77843 (USA)
E-mail: zhou@chem.tamu.edu
Homepage: http://www.chem.tamu.edu/rgroup/zhou/
Dr. J. Su, Prof. Dr. X. Zou
Berzelii Center EXSELENT on Porous Materials and
Inorganic and Structural Chemistry
Department of Materials and Environmental Chemistry
Stockholm University, 10691 Stockholm (Sweden)
Dr. A. Yakovenko
X-ray Science Division, Advanced Photon Source
III
III
III
III
[
M O(COO) ] building block (M = Fe , Al , Cr , In ,
Argonne National Laboratory, Argonne, IL 60439 (USA)
3 6
III
III
+
V , Sc ) is not the thermodynamically favored form, which
makes the controllable formation of target products diffi-
cult, b) even if the inorganic building block can be obtained,
competitive framework isomers, such as the MIL-88 struc-
[
] These authors contributed equally to this work.
[
**] Research Center funded by the U.S. Department of Energy (DOE),
Office of Science, Office of Basic Energy Sciences, and was also
supported by the Office of Naval Research as part of
[6]
[
6d]
N000141310753. Use of the Advanced Photon Source, an Office of
Science User Facility operated for the U.S. Department of Energy
ture, still dominate as the major products, and c) most of
the synthesis should be conducted under hydrothermal
conditions, which is infeasible for large organic linkers with
poor water solubility. Therefore, searching for other zeotype
frameworks, which can be more easily synthetically
controlled, is one promising strategy.
(
DOE) Office of Science by Argonne National Laboratory, was
supported by the U.S. DOE under Contract No. DE-AC02-
6CH11357. The structure characterization by PXRD and TEM was
0
supported by the Swedish Research Council (VR) and VINNOVA,
the Knut & Alice Wallenberg Foundation through the project grant
3
DEM-NATUR.
Through a topological analysis, we present herein a
zeotype mesoporous Zr-MOF, namely PCN-777, which has a
b-cristobalite-type structure (PCN = porous coordination net-
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201409334.
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work). PCN-777 exhibits the largest cage (3.8 nm) and the
3
À1
highest porosity (2.8 cm g ) among reported Zr-MOFs.
Moreover, it shows high stability in aqueous solution over
a wide range of pH values.
Zirconium MOFs have been extensively studied recently
[7]
as a result of their excellent chemical stability. One major
reason is the controllable synthesis of crystalline products or
[8]
even single crystals by using competing reagents. Moreover,
a Zr cluster [Zr O OH (COO) ] fully coordinated by twelve
6
6
4
4
12
carboxylates has O symmetry, which has many high-
h
symmetry subgroups. This means that it is possible to decrease
the connectivity and symmetry of Zr to make it compatible
6
with almost all kinds of organic linkers and form three-
dimensional (3D) periodic frameworks. As almost all the Zr-
MOFs contain the Zr cluster, tuning the symmetry and
6
connectivity of the Zr cluster into a suitable node in a zeolite
6
net would be an ideal approach to develop zeotype
mesoporous MOFs.
Considering that the [M O(COO) ] unit in MIL-100 and
3
6
MIL-101 has D3h symmetry, a direct way to make zeotype
Zr-MOFs is to lower the connectivity and symmetry of Zr to
6
D3h while using the same organic linker. However, as
D3h symmetry is not a subgroup of O symmetry, it is not
h
possible to obtain the same mtn network with Zr when using
6
Figure 1. a) Inorganic and organic building units and symmetry analy-
sis in the mtn type MOF MIL-100. The light-blue bar denotes an
eclipsed configuration between adjacent tetrahedra with D3h-connected
nodes. b) Super-tetrahedral rotation from the mtn network to the
b-cristobalite network. The dark-blue bar denotes a staggered config-
uration between adjacent tetrahedra with D -connected nodes.
only one type of organic linker. Fortunately, the major factor
resulting in the formation of diverse zeolite structures is the
variation of relative positions between adjacent tetrahedral
nodes, and the [M O(COO) ] unit with D symmetry in MIL-
3
6
3h
3
d
1
00 and MIL-101 only determines the eclipsed configuration
BTC=benzene-1,3,5-tricarboxylate.
between adjacent super-tetrahedra to generate the mtn
network (Figure 1a). When making a 608 rotation between
each super-tetrahedron to form a staggered configuration, a
b-cristobalite network can be constructed, which requires
a six-connected D3d node (Figure 1b). Coincidently, D3d is
In comparison, trigonal planar organic linkers with three
carboxylates in the same plane, which can form super-
a subgroup of O symmetry, showing the theoretical feasibil-
tetrahedra with six-connected antiprismatic D3d Zr clusters,
h
6
ity of using the Zr unit to build zeotype frameworks.
can topologically form only one type of edge-transitive
6
Topologically, both ditopic linear organic linkers and
tritopic trigonal-planar organic linkers can form super-tetra-
hedra with six-connected D -symmetric Zr clusters of anti-
binodal
network—the
b-cristobalite-type
network.
Zr clusters with all other reported connectivities and sym-
6
metries, such as twelve-connected O , eight-connected D ,
3
d
6
h
4h
prismatic configuration. Linear organic linkers could serve as
the edge while the trigonal-planar organic linkers could be the
face. However, the challenge is to guarantee the formation of
and six-connected hexagonal D , are not compatible with the
3d
formation of binodal edge-transitive networks with trigonal-
planar organic linkers. Therefore, it is more likely to obtain
mesoporous Zr-MOFs with a b-cristobalite network with
trigonal-planar organic linkers.
the Zr unit with reduced connectivity as well as the correct
6
symmetry to form the expected structures. With ditopic linear
organic linkers, the Zr cluster can form a fcu-a network with
Bearing such structural rationalization in mind, we
selected a relatively large 4,4’,4’’-s-triazine-2,4,6-triyl-tri-
benzoate (TATB) linker, which prefers the trigonal-planar
configuration, to construct the proposed Zr-MOF. To afford
6
a twelve-connected O node, a bcu-a network with an eight-
h
connected D4h node, an hxg-a network with a six-connected
hexagonal D3d node, and a b-cristobalite network with six-
connected antiprismatic D3d node. Although these frame-
works are topologically different, the other three are actually
the subnetworks of the twelve-connected fcu-a network,
which means that they can be obtained by simply decreasing
the connecting linkers in the fcu-a network. Therefore, it is
challenging to control the specific connectivity and symmetry
without controlling the inherent kinetic or thermodynamic
preference. All efforts to use higher zirconium to organic-
linker ratios and more competing reagents to realize con-
nectivity elimination have resulted in the formation of the
a partially substituted Zr cluster we used excess Zr starting
6
materials as well as trifluoroacetic acid (TFA) as a strong
competing reagent. Solvothermal reaction between TATB,
ZrOCl ·8H O, N,N-diethylformamide (DEF),and TFA gave
2
2
rise to the formation of the product PCN-77 as a white powder
(see the Supporting Information, section 3).
Synchrotron powder X-ray diffraction (PXRD) collected
at 17-BM beamline at Advanced Photon Source, Argonne
National Laboratory, shows that PCN-777 is cubic with unit-
cell length a approximately 55 ꢀ. This was further confirmed
[
9]
[10]
fcu-a network with defects.
by 3D rotation electron diffraction (RED)
(Figure 2a–c
2
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Figure 2. a) 3D reciprocal lattice of PCN-777 reconstructed from the
RED data. b,c) 2D slices cut from the reconstructed 3D reciprocal
lattice showing the b) h0L and c) hhl plane. d) Rietveld refinement of
PCN-777 using synchrotron PXRD data. The spectra from top to
bottom are simulated (red), detected (blue), and difference profiles
(
grey), respectively; the bars below the curves indicate peak positions.
Inset in (d): 80-fold magnification of the plots.
and the Supporting Information section 4). The reflection
conditions deduced from the RED data gave the following
five possible space groups: F23, Fm-3, F432, F-43m, and
Fm-3m. Considering that the ideal space group of b-cristoba-
lite is Fd-3m, the space group F-43m, which is the subspace
group of Fd-3m, was chosen for the further structural study. A
Figure 3. a) Six-connected D -symmetric Zr antiprismatic units and
trigonal-planar organic linker TATB. b) The structure of PCN-777 with
the large mesoporous cage (given in red).
3
d
6
structural model of PCN-777, with
a
formula of
[
Zr (O) (OH) (H O) (TATB) ], was built based on our
6
4
10
2
6
2
[11]
proposed b-cristobalite network using Material Studio 6.0
and further refined against the synchrotron PXRD data.
Rietveld refinement with soft restraints for the MÀO bond
distances and a rigid body for the ligands shows a precise
match between the experimental PXRD data and that
simulated from the proposed structure (Figure 2d).
Zr cluster results in the formation of a perfectly staggered
6
configuration of adjacent super-tetrahedra instead of the
eclipsed configuration in MIL-100. The overall topology of
PCN-777 changes from the mtn topology in MIL-100 to
b-cristobalite type.
The excess zirconium helps to form a six-connected
D3d Zr building block, while the remaining coordinating
6
positions are occupied by terminal OH and H O moieties.
Owing to the relatively small ligand size and strong
coordination bond between the organic linker and metal
struts, PCN-777 can be activated directly upon the removal of
solvent, while many other MOFs with such large pores and
high porosity must be carefully activated with supercritical
2
[
7g]
Unlike the D -symmetric Zr unit in PCN-224, the posi-
3
d
6
tions of the carboxylates and terminal OH/H O are switched
2
to form an antiprismatic connecting mode in PCN-777. The
overall structure of PCN-777 is built by sharing the vertexes of
[12]
the super-tetrahedra, which consists of four Zr units linked
CO2.
To assess the porosity of PCN-777, we performed
6
along the faces by the organic linkers (Figure 3a). The organic
linker TATB is almost twice the size of BTC (benzene-1,3,5-
tricarboxylate), which makes the size of the super-tetrahedra
in TATB-containing PCN-777 twice as large as those in MIL-
N sorption at 77 K (Figure 4a). PCN-777 shows N uptake of
2
2
3
À1
around 1460 cm g at 1 bar (Figure 4a). The experimental
Brunauer–Emmett–Teller (BET) surface area of PCN-777 is
2
À1
2008 m g . A steep increase at p/p = 0.4 on the N adsorp-
0
2
1
00. Consequently, a mesoporous cage of 38 ꢀ is formed in
tion isotherm corresponds to a mesoporous cage of 3.5 nm in
PCN-777 (Figure 4a, inset). The experimental void volume of
PCN-777 is 2.82 cm g , which is the highest among all the
reported Zr-MOFs (see Table S2 in the Supporting Informa-
tion).
PCN-777, which is the largest pore among all reported
Zr-MOFs. As a result of the high concentration of such
mesoporous cages, the calculated porosity of PCN-777
3
À1
3
À1
reaches 3.38 cm g . As expected, the D -symmetric
3
d
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direct physisorption, ionic trapping (in ionic MOFs), and
covalent attachment through the functional anchors. As the
Zr cluster is only partially occupied by organic linkers, there
6
are still positions available that can be functionalized for
further modification. On one hand, the terminal OH/
H O groups can interact strongly with guests through either
2
[15]
hydrogen or coordination bonding after deprotonation. On
the other hand, after one-step treatment, the terminal OH
and H O on the Zr cluster can be easily substituted by other
2
6
carboxylate-containing species under very mild conditions,
which is a convenient method to introduce many kinds of
[16]
anchors. Moreover, there are only six carboxylates coordi-
nating to the Zr cluster in PCN-777 and the empty positions
6
are all pointing into the mesoporous cages. Therefore, the
properties of the internal surface of the mesoporous cages in
PCN-777 can be easily adjusted for further applications.
In fact, the trapping and leaching of guests in porous
materials can be considered as equilibrium processes. When
trapped guests are heterogeneously used, leaching becomes
an entropically favored process. Therefore, to effectively
prevent or diminish the leaching process, trapping guests
inside the pores should be a highly enthalpically favored
process, which requires strong interaction between the guests
and supports.
Covalent attachment of guests can be thought of as an
extreme method to enhance the trapping enthalpy. However,
this approach always requires additional anchors on both the
MOF framework and the incoming guests, which requires
extra synthetic effort. In comparison, physical adsorption can
directly incorporate guests. Although the interaction is
usually weak, when the substrate is relatively large and
multiple interacting sites could be provided by the frame-
work, the overall interaction can still be strong enough to
effectively prevent the substrate leaching. Accordingly, by
postsynthetic modification of the internal surface, we exam-
ined the adsorption and leaching of different guests inside
PCN-777. Using 4-tert-butylbenzoic acid (denoted as tBu) and
4-carboxy-1-methylpyridinium iodide (denoted as Me-Py),
we altered the internal surface from having the originally
hydrophilic properties into being either highly hydrophobic
or ionic. Three guests, meso-tetra(4-sulfonatophenyl)-
porphyrin (TSPP), tris(2,2’-bipyridine) dichlororuthenium(II)
([Ru(bpy) ]Cl ), and tetra-amido macrocyclic ligand catalytic
Figure 4. a) N sorption isotherm of PCN-777. b) PXRD patterns of
PCN-777 after different treatments.
2
Remarkably, PCN-777 has very high stability in aqueous
solutions despite its high porosity. After soaking in distilled
water and in aqueous solutions with pH = 3 and 11, PXRD
patterns of PCN-777 are well maintained (Figure 4b). N2
adsorption isotherms of these samples after the different
treatments confirms the excellent stability of PCN-777 in pure
H O and the basic environment while showing relatively
2
3
2
weak stability in the acidic environment (Figure S2). The high
positive charge density (Z/r= charge/radius) on Zr causes
activators (TAML-NaFeB*, a catalyst for CÀH bond activa-
tion; see Supporting Information, section 7), all of which
having relatively large sizes but different functionalities, were
incorporated into the modified PCN-777 (Figure 5). TSPP, as
a porphyrinic derivative, can serve as a catalyst for different
reactions and light-harvesting species. It shows the highest
loading amount and slowest leaching in the pristine PCN-777
because of hydrogen bonding between the peripheral sulfonic
IV
a strong electrostatic interaction between the metal nodes and
ligand carboxylates, which endows the frameworks with
excellent stability towards attack by reactive species. Thermal
gravimetric analysis (TGA) indicates that the decomposition
temperature of PCN-777 is around 5008C (Figure S4), show-
ing that the framework has very high thermal stability. The
TGA curve also indicates that there are few or no missing-
linker defects in the structure (see the Supporting Informa-
groups and terminal OH/H O functionalities on the
2
Zr cluster. The system containing the anionic TAML-
6
[13]
tion, section 6).
NaFeB* (the major part) shows the highest volumetric
loading amount in Me-Py-modified PCN-777 despite having
the lowest porosity because of the strong electrostatic
interaction. In contrast, for [Ru(bpy) ]Cl , a light harvesting
As a mesoporous MOF with very large pores and
excellent chemical stability, PCN-777 is a suitable candidate
to incorporate functional moieties with relatively large size
3
2
[
14]
through postsynthetic modification. There are three major
approaches to introduce functional moieties into MOFs:
reagent as well as a photocatalyst, there is no preferential
loading in any framework as the functional part is cationic. As
4
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Figure 5. Color variation of pristine, tBu-modified, and Me-py-modified
PCN-777 when loaded with different guests (TSPP, [Ru(bpy) ]Cl , or
3
2
TAML-NaFeB*).
6
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[
1
expected, the tBu-modified PCN-777 shows the weakest
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(
see Supporting Information, section 8).
In conclusion, we designed and synthesized a zeotype
mesoporous Zr-MOF, PCN-777. PCN-777 exhibits cages as
large as 3.8 nm and excellent stability in aqueous environ-
ments, which make it an ideal candidate as a support to
incorporate different functional moieties. Through facile
internal pore surface modification, we can vary the inter-
action between PCN-777 and different guests to realize
efficient immobilization.
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Experimental Section
Synthesis of PCN-777: ZrOCl .8H O (360 mg), TATB (90 mg), and
2
2
trifluoroacetic acid (0.6 mL) in DEF (12 mL) were ultrasonically
dissolved in a 20 mL Pyrex vial. The mixture was heated at 1208C in
an oven for 12 h. After cooling to room temperature, a white powder
product of PCN-777 was collected by filtration.
Crystal data from PXRD of PCN-777: Zr O122C N H , M =
6
48
6
24
3
3
184.05, space group F-43 m, a = 55.568(3) ꢀ, V= 171583(5) ꢀ ,
Z = 16, total reflections = 514, GOF = 1.134, R = 0.0395, Rwp
=
p
0
.0564, Rexp = 0.0497 (see the Supporting Information, section 4).
CCDC-1013322 (PCN-777) contains the supplementary crystallo-
graphic data for this paper. This data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via www.ccdc.
cam.ac.uk/data_request/cif.
Full experimental details can be found in the Supporting
Information.
16997 – 17003; l) H. Fei, S. M. Cohen, Chem. Commun. 2014, 50,
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4
Received: September 21, 2014
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Published online: && &&, &&&&
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Keywords: carboxylate ligands · host–guest systems ·
mesoporous materials · metal–organic frameworks · zirconium
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Angew. Chem. Int. Ed. 2014, 53, 1 – 7
These are not the final page numbers!

Angewandte
Chemie
Communications
Metal–Organic Frameworks
D. Feng, K. Wang, J. Su, T.-F. Liu, J. Park,
Z. Wei, M. Bosch, A. Yakovenko, X. Zou,
H.-C. Zhou*
&&&& — &&&&
A Highly Stable Zeotype Mesoporous
Zirconium Metal–Organic Framework
with Ultralarge Pores
Topological rationalization is used to
design a zeotype mesoporous Zr metal–
organic framework. When tetrahedra
eclipsed configuration (D3h nodes; light-
blue bar), an mtn network is formed. A
608 rotation between tetrahedra gives
(
orange; see picture) with [M O(COO) ]
a staggered configuration with D -con-
3
6
3d
nodes and tridentate benzene-1,3,5-tri-
carboxylate faces are connected in an
nected nodes (dark-blue bar) and ab-
cristobalite network.
Angew. Chem. Int. Ed. 2014, 53, 1 – 7
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
7
These are not the final page numbers!