A zirconium metal-organic framework with an exceptionally high volumetric surface area

Article abstract of DOI:10.1039/c7dt03394j

A zirconium metal-organic framework (MOF), PCN-111, has been synthesized by using an elongated ditopic carboxylate linker, 4,4′-(buta-1,3-diyne-1,4-diyl)dibenzoate. Single crystal X-ray diffraction characterization indicates that the noninterpenetrated mi

Full text of DOI:10.1039/c7dt03394j

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ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
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A zirconium metal-organic framework with exceptionally high
volumetric surface area
Larissa Stewart,a Weigang Lu,*,a,b Zhang-Wen Weic,d, Daryush Ila,b Carla Padillab and Hong-Cai
Zhou*,c
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
A zirconium metal-organic framework (MOF) PCN-111 has been synthesized by using an elongated ditopic carboxylate
linker, 4,4’-(buta-1,3-diyne-1,4-diyl)dibenzoate. Single crstal X-ray diffraction characterization indicates that the
noninterpenetrated microporous structure of PCN-111 is isoreticular to UIO MOFs with 12 connected Zr6O4(OH)4(CO2)12
clusters and a fcu topology. It was sucessfully activated through solvent exchange with acetone followed by controlled
evacuation, and its gas sorption was reported for the first time. By using 77 K nitrogen adsorption isotherm and strictly
applying three consistency criteria, the BET surface area for PCN-111 was calculated to be 4825m2/g. Pore size distribution
analysis suggests that the sizes of cavities contributing to nitrogen adsorption are predominately in the range of 15 to 20
Å, which are in good agreement with the two polyhedral cages (15.6 and 20.2 Å, respectively) in the single crystal X-ray
solved structure. Owing to its relatively high crystal density (0.42 g/cm3), the volumetric surface area for PCN-111 was
calculated to be 2026 m2/cm3. The value is among the highest of all reported ultrahigh surface area MOF materials. The
exceptionally high microporosity of PCN-111 has also been validated by comparison with the simulated nitrogen
www.rsc.org/
adsorption
isotherm
derived
from
multipurpose
simulation
code
MUSIC.
zirconium(IV) ions of metal clusters and the carboxylates of
organic linkers.25, 26 By using a simple dicarboxylate linker,
terephthalate, the first Zr-based MOF (UIO-66, UiO stands for
the University of Oslo) was synthesized by Lillerud and
coworkers in 2008, its structure features 12-coordinated Zr6
clusters [Zr6O4(OH)4(O2C)12] and an fcu topology.25 Since then,
the use of carboxylate linkers with Zr6 clusters for the
construction of MOFs has been well explored, particularly the
so-called UiO-66 series with ditopic carboxylate linkers. Here
we report the synthesis and characterization of a microporous
Zr-MOF (PCN-111, PCN stands for porous coordination
polymer), it is isostructural to UIO-66 with a much elongated
dicarboxylate linker, 4,4’-(buta-1,3-diyne-1,4-diyl)dibenzoate.
As other UIO type MOFs, PCN-111 is stable in the presence of
water. The activated PCN-111 exhibits high microporosity; its
gravimetric surface area is estimated to be 4825m2/g by using
77 K nitrogen gas adsorption isotherm and strictly applying
three consistency criteria. More importantly, its volumetric
surface area is calculated to be 2026 m2/cm3 by using its
crystal density, the value is among the highest of all reported
ultrahigh surface area porous materials.
Introduction
For years, increasing number of metal-organic frameworks
(MOFs) have received growing attention as an emerging class
of highly ordered crystalline porous materials owing to their
exceptional high porosity and framework tunabilty.1-6 The
numerous possibilities of combination through coordinate
bonding between the metal clusters and organic linkers offers
MOFs great flexibility to tune their properties in various
aspects.7-11 Among the large family of MOF materials, Zr-based
MOFs stand out as one of the most promising group primarily
due to their rich structure types and outstanding chemical
stability.12-15 Many Zr-MOFs exhibit stability in water, some
even under acidic and/or basic conditions, which is extremely
important for the MOF materials to be considered for practical
applications.16-24 The high stability of Zr-based MOFs results
from the strong bonding between the highly charged
Experimental
General Information
Commercially available reagents were used as received. 1H
NMR and 13C NMR data were collected on a Mercury 300 MHz
NMR spectrometer. TGA data were obtained on a DTG-60
(SHIMADZU) thermogravimetric analyzer with a heating rate of
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3 °C/min under a nitrogen atmosphere. SEM images were measurement, the sample was activated as following: reaction
collected on JEOL JSM-6510LV Scanning Electron Microscope. solution was exchanged with fresh DMF twice in two days and
Powder X-ray diffraction (PXRD) patterns were recorded on a then acetone three times in three days. After completion of
Rigaku MiniFlex 600 X-Ray Diffractometer equipped with a Cu solvent exchange, acetone was decanted, and the remaining
sealed tube (λ = 1.54178 Å) and graphite monochromator at solvent inside crystal cavity was carefully evacuated by an
room temperature. Simulation of the PXRD pattern was carried extremely slow vacuum, and full vacuum after it reached ca.
out by the single-crystal data and diffraction-crystal module of 1.0 mbar.
the Mercury program available free of charge via internet at
Gas adsorption measurement
http://www.iucr.org.
A Micromeritics ASAP 2020 surface area and pore size analyzer
Synthesis of H2BDDB
was used to measure nitrogen, argon, oxygen and hydrogen
The synthetic procedure for H2BDDB, 4,4’-(buta-1,3-diyne-1,4- physisorption isotherms at different temperatures. ca. 100 mg
diyl)dibenzoic acid, is shown in Figure S1
.
of activated sample was used for each measurement. High-
To a solution of copper acetate (10.0 g, 55.1 mmol) in purity gases were used (nitrogen: 99.999%, argon: 99.999%,
methanol/pyridine (50 mL/50 mL) was added methyl 4- oxygen: 99.999%, hydrogen: 99.999%). Pore size distribution
ethylnylbenzoate (5.0 g, 31.2 mmol). After stirred at 60 °C for was calculated from the nitrogen adsorption isotherm based
30 min, the reaction mixture was cooled to room temperature, on DFT model in the Micromeritics ASAP 2020 software
then poured into 200 mL of ice water. The precipitate was package.
isolated by filtration, washed with plenty of water. The crude
Single Crystal X-Ray Study
product was dried, then triturated in 50 mL of hexanes to
Single crystal X-ray structure determination of PCN-111 was
remove any unreacted starting material. The remaining solid
performed at 173(2) K using the Advanced Photon Source on
was collected by filtration, then dried to produce an off-white
beamline 15ID-B at Argonne National Laboratory. Structures
product, dimethyl 4,4’-(buta-1,3-diyne-1,4-diyl)dibenzoate,
were solved by direct methods and refined by full-matrix least-
(4.3 g, 13.5 mmol) with a yield of 87%. TLC (10 % ethyl acetate
squares on F2 using SHELXTL.30 Non-hydrogen atoms were
in hexanes as eluent) indicates no starting material left. NMR
data (Figure S2-4) are in good agreement with literature.27-29
refined with anisotropic displacement parameters during the
1H-NMR (300 MHz, CDCl3): 8.01 (4H, d, J = 8.1 Hz), 7.59 (4H, d,
final cycles. Organic hydrogen atoms were placed in calculated
J = 8.1 Hz), 3.93 (6H, s); 1H-NMR (300 MHz, DMSO-d6): 7.98
(4H, d, J = 8.7 Hz), 7.75 (4H, d, J = 8.7 Hz), 3.85 (6H, s); 13C-NMR
positions with isotropic displacement parameters set to 1.2 ×
Ueq of the attached atom. The solvent molecules of PCN-111
were highly disordered, and attempts to locate and refine the
(75 MHz, CDCl3): 166.4 (2C), 132.4 (4CH), 130.8(2C), 129.5
solvent peaks were unsuccessful. Contributions to scattering
(4CH), 126.1 (2C), 81.8 (2C), 76.2 (2C), 52.3 (2CH3).
due to these solvent molecules were removed using the
To a solution of sodium hydroxide (1.0 g, 25 mmol) in
SQUEEZE routine of PLATON, structures were then refined
tetrahydrofuran/methanol/water (50 mL/50 mL/50 mL) was
again using the data generated.31
added dimethyl 4,4’-(buta-1,3-diyne-1,4-diyl)dibenzoate (1.0 g,
3.1 mmol), After stirred overnight, most of organic solvents in
the clear solution was removed on a rotary evaporator. The
Results and discussion
precipitate was redissolved by adding ca. 100 mL of water. The
The diester of the carboxylate linker, H2BDDB, were
synthesized through a Cu(II)-catalyzed Eglinton homo-coupling
reaction of methyl 4-ethylnylbenzoate. The NMR data are in
good agreement with literature. It is worth pointing out that
inexpensive metal was used as catalyst and column
chromatography was avoided by judiciously selecting solvents
for recrystallization. The diacid of the carboxylate linker,
H2BDDB, was then obtained by hydrolysis of the above diester
in a NaOH solution of MeOH/THF/H2O (1/1/1) mixture.
clear aqueous solution was acidified with 1 M of HCl to ca. pH
2. The precipitate was collected by filtration and washed with
plenty of water. The solid was dried in vacuum oven at 60 °C
overnight to produce a yellowish product, 4,4’-(buta-1,3-diyne-
1,4-diyl)dibenzoic acid, (H2BDDB, 0.74 g, 2.6 mmol) with a yield
of 84%. NMR data (Figure S5) are in good agreement with
literature.27-29 1H-NMR (300 MHz, DMSO-d6): 13.28 (2H, brs),
7.96 (4H, d, J = 8.7 Hz), 7.73 (4H, d, J = 8.7 Hz); 13C-NMR was
not collected because of its poor solubility in common organic
solvents.
Solvothermal reaction of linker precursor, H2BDDB, and ZrCl4 in
DMF solution in the presence of CF3COOH afforded colorless
octahedron-shaped crystals of PCN-111 with a formula of
Zr6O4(OH)4(BDDB)6. It was harvested by solvent exchange with
DMF and acetone. PCN-111 crystallizes in a cubic Fm-3m space
group with a = 33.6644(6) Å. As an isoreticular structure to
UIOs, it consists of 12 connected Zr6O4(OH)4(CO2)12 clusters,
Synthesis of PCN-111
To a vial containing H2BDDB (10 mg, 0.034 mmol) and ZrCl4 (20
mg, 0.086 mmol) was added DMF (8.0 mL) and CF3COOH (300
µL). The above mixture was sonicated for 30 min before placed
in an oven preheated to 120 °C. Colorless crystals appeared on
the wall and at the bottom of the vial in three to five days.
After cooled down to room temperature, the crystals were
washed with DMF and collected for thermogravimetric analysis
and powder X-ray diffraction analysis. For gas adsorption
bridged by ditopic BDDB linkers (Figure 1a, 1d). There are two
types of polyhedral cages in the framework, one is octahedron
and the other is tetrahedron. Space-filling model indicates that
the sizes of these two cages are ca. 20.2 and 15.6 Å,
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respectively (Figure 1b, 1c). The potential solvent accessible accountable and their intensities are strong, which suggests
volume of PCN-111 framework is estimated to be 81.7% by that the framework retains its crystallinity during all of these
PLATON.
experiments.
Figure 2. a) PXRD patterns of as-synthesized PCN-111 in comparison
with the simulated patterns from noninterpenetrated and
interpenetrated structures. b) PXRD patterns of as-synthesized PCN-
111 in comparison with after-gas-adsroption, soaked-in-water, and
resovated-in-acetone PCN-111.
Figure 1. a) Representation of the crystal structure of PCN-111 in a
cubic unit cell. Zr, blue; O, red; C, black; all hydrogen atoms omitted
for clarity. b) Octahedral cage (yellow ball) and tetrahedral cage (red
ball) in PCN-111 structure. c) Packing of octahedral and tetrahedral
cages. d) Topological representation of 12 connected structure in PCN-
111. Zr6 cluster, blue ball; organic linker, yellow stick.
It is worth pointing out that Behrens et al. synthesized PEEP-
UIO with a same crystal structure through a slightly different
solvothermal reaction; however, the PXRD pattern of PEEP-
UIO showed a low degree of crystallinity, as manifested by the
broad reflections its PXRD pattern. Gas adsorption was not
reported for PEEP-UIO.27 Although the authors did not reveal
that whether they used as-synthesized sample or activated
one for the PXRD data collection, we believe our success might
lie with the choice of solvent for exchange. DMF or other high
boiling point solvents are often used for MOF synthesis, and
these solvents need to be replaced by low boiling points
solvents before vacuum is applied to expose the internal
surface. Supercritical carbon dioxide activation is a mild
activation technique, but it requires special set up. An
extension of conventional solvents could be used instead,
though might lead to loss of porosity during solvent
evacuation, and surface tension is believed to be the cause of
framework collapse.32 In our case, a list of organic solvents
were tried for solvent exchange. Based on our numerous
attempts, we found that using of low surface tension solvent
such as acetone33 and slow removal of solvent residue
(evacuation rate at 1 mbar/sec) are two keys to warrant the
intact of the framework during the activation process.
The powder X-ray diffraction (PXRD) patterns were collected at
ambient atmosphere and temperature on a Rigaku MiniFlex
600 X-Ray Diffractometer. As shown in Figure 2a, the PXRD
pattern of bulk sample of as-synthesized PCN-111 shows
excellent agreement with the one simulated from its single-
crystal structure, which is noninterpenetrated and
isostructural to UIOs. Although slight differences in peak
strength were observed, all 2θ peaks were consistent. For
comparison, an interpenetrated structure is constructed based
on PIZOFs26 and its PXRD pattern is also simulated. It turns out
the PXRD pattern of interpenetrated structure is similar to that
of noninterpenetrated one, except for the absence of two
distinctive peaks at 5.2 and 9.1 degree (2θ). Although it is not
possible to exclude entirely the presence of interpenetration
based on PXRD solely, the resulting crystalline material is
phase pure based on single-crystal X-ray data as well as
comparison of experimental and simulated gas adsorption
data.
PXRD was also utilized to confirm the framework’s stability
upon removal of guest-solvent molecules. As shown in Figure
2b, the PXRD patterns show the framework of PCN-111
remains intact after several rounds of gas adsorption
measurements followed by exposed to air for a month,
immersed in water for 48 hours, and resolvated in organic
solvents such as DMF and acetone. All 2θ peaks are
The nitrogen sorption for the carefully activated PCN-111 at 77
K exhibited a reversible Type-I isotherm without noticeable
hysteresis loop, as shown in Figure 3a, a characteristic of
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35
microporous materials.34,
PCN-111 exhibits a very high
nitrogen capacity upon saturation (over 1200 cm3/g), which is
among the highest of all microporous MOF materials reported
so far. Microporosity of PCN-111 was confirmed by pore size
distribution analysis of its nitrogen gas sorption isotherm at 77
K (Figure 3b), which indicates the sizes of cavities contributing
to nitrogen adsorption are predominately in the range of 15 to
20 Å (1.5 to 2.0 nm). These values are in good agreement with
the sizes of the observed octahedral and tetrahedral cages in
the crystal structure discussed above.
As one of the most crucial properties for MOF materials, BET
(Brunauer–Emmett–Teller) surface area36 is normally
estimated from the nitrogen or argon adsorption isotherm
measured at cryogenic temperature (77 K for nitrogen and 87
K for argon). There are have been ambiguity in terms of which
range of nitrogen adsorption isotherm is appropriate for BET
surface area analysis. As emphasized by Kaskel and Snurr in
several of their publications,29, 37 a set of consistency criteria
should comply with: (1) The analysis should be limited to the
range in which the term Vads(1-P/Po) increases continuously as
a function of the relative pressure P/Po. (2) The value of the
BET constant C resulting from the linear fit should be positive
and the C constant should have a value of at least 10. (3) The
BET monolayer capacity nm calculated from the linear fit
corresponds to a certain relative pressure, which must be
located within the linear region chosen for the area
calculation.
Figure
3
.
a) Nitrogen sorption isotherms for PCN-111 at 77 K,
adsorption (●)/desorpꢀon (○). b) Amount of nitrogen adsorbed in PCN-
111 at 77 K vs. log(P/Po); inset: pore size distribution, incremental
surface area (cm3/g) vs pore width (Å). c) V(1-P/Po) vs. P/Po for PCN-
111; inset: linear plot of the adsorption range for the estimation of the
BET specific surface area.
We decided to apply all three criteria to the estimation of the
BET surface area of PCN-111. As shown in Figure 3c
,
compliance of the first criterion limits the range of the BET plot
to a relative pressure of 0.1. Next is to identify a linear range in
the BET-plot. This is usually implemented in the software of
gas adsorption equipment (ASAP2020 in this work). However,
within this range of the BET plot of PCN-111 (relative pressure
0.0 to 0.1) one can find more than a few linear ranges with C
constants higher than 10, thus more than one linear range
comply with the second criterion. To narrow down the list by
the third criterion, the relative pressure corresponding to a
given monolayer capacity nm calculated from the equation (1)
should be located within the chosen relative pressure range of
the linear region of BET plot.
ꢁ
1
ꢀ
ꢄ
ꢇ
(1)
ꢃ
ꢃ
ꢀ ꢈ ꢉ 1ꢄ
ꢁꢂ
ꢅꢆ
√
To apply the third criterion to here, only the linear fit in the
pressure range 0.082 ≤ P/Po ≤ 0.10 with a C constant of 95.64
(P/Po(nm) = 0.093) meets all the requirements listed above
(
Figure 3c inset). By using this linear range, BET surface area
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for PCN-111 was calculated to be 4825m2/g (±105). As pointed particularly focusing on gravimetric capacity with an attempt
out by Kaskel, many reported BET surface areas derived from to achieve higher and higher BET surface area in m2/g.
adsorption isotherms were only in compliance with the first However, volumetric capacity should also be well evaluated
two consistency criteria, the third one was ignored, which especially for applications in which spaces are limited. For
likely led to certain errors in porosity estimation, especially for example, on-board small vehicle hydrogen storage requires
those contain both microporous and mesoporous cavities.
the tank neither too large nor too heavy. Maximizing MOF
volumetric and gravimetric gas adsorption are incompatible,
therefore, as Farha et al pointed out, an in-depth
understanding of the trade-off between volumetric and
gravimetric loadings is necessary.39 A balance needs to be
struck in order to achieve high volumetric and high gravimetric
loadings simultaneously. Table 1 shows porosity data for PCN-
111 in comparison with some selected high-surface-area MOFs
both in volumetric and gravimetric units. It is worthy to note
that although the gravimetric surface area of PCN-111 is much
less than record high ones, its volumetric surface area is
among the highest due to its relatively high crystal density. To
date, most of ultrahigh surface area MOFs have been built
from zinc oxide and copper paddlewheel clusters with
carboxylate linkers, which unfortunately lose crystallinity and
porosity when exposed to moisture. In this regard, PCN-111
clearly has the advantage for real world applications.
Table 1. Gravimetric and volumetric surface areas for PCN-111 and
some selected MOFs.
Density BET surface area
MOF Material
MIL-10140
Metal cluster
g/cm3
0.44
0.47
0.43
0.40
m2/g
4230
4488
4500
4670
4825
5109
5200
6143
6240
6411
6550
7142
m2/cm3
1861
2109
1935
2008
2026
1941
2080
1781
1560
1731
1965
1571
Cr3O(COO)6
Cu2(COO)4
Figure 4. a) Comparison of simulated (●) and experimental (-) nitrogen
adsorption isotherms for PCN-111 at 77 K. b) V(1-P/Po) vs. P/Po for PCN-8241
MOF-17742
DUT-2543
Zn4O(COO)6
Zn4O(COO)6
Zr6O4(OH)4(COO)12
Cu2(COO)4
simulated adsorption isotherm; inset: linear plot of the adsorption
range for the estimation of the BET specific surface area.
PCN-111this work 0.42
PCN-6844
UMCM-245
0.38
0.40
0.29
0.25
0.27
0.30
0.22
Additionally, the nitrogen adsorption isotherm was simulated
using multipurpose simulation code MUSIC.38 The simulated
Zn4O(COO)6
Cu2(COO)4
nitrogen adsorption is slightly higher than the experimental NU-10046
MOF-21047
Zn4O(COO)6
Zn4O(COO)6
Zr6O4(OH)4(COO)12
Cu2(COO)4
one at lower relatively pressure region, but overall in good
DUT-3248
NU-110349
NU-11050
agreement (Figure 4a). Although theoretical does not usually
cover all aspects of complex matter such as MOF and to some
degree discrepancy is unavoidable. In our case, we suspected
that limited equilibrium time during measurement could be
one of the major reasons. To better understand the
discrepancy between the simulated and experimental data, we
decided to calculate the BET surface area for the simulated
nitrogen adsorption isotherm. In compliance with all three
consistency criteria, the relative pressure region (P/Po 0.05 –
0.065) was identified with a C constant of 269.64 (P/Po(nm) =
0.057) (Figure 4b), thus the surface area of 5199m2/g (±84)
was estimated from the simulated nitrogen adsorption
isotherm. The value is slightly higher than the experimental
one, which is understandable because simulation is based on
perfect crystal structure; whereas sample used for gas
adsorption measurement could carry a small amount of defect.
It is interesting to point out that MOF materials with BET
surface area over 5000 m2/g all have a considerable amount of
mesoporous nature, which are evident from their cryogenic
gas sorption isotherms and the calculated pore size
distributions. Researchers in MOFs area nowadays are
Conclusions
A
zirconium metal-organic framework (PCN-111) with
exceptionally high volumetric surface area has been
synthesized and characterized. PCN-111 is isostructural to
UIOs with 12 connected Zr6O4(OH)4(CO2)12 clusters bridged by
much elongated ditopic BDDB linkers. By using low-surface-
tension acetone for solvent exchange and slow evacuation, it
was carefully activated and successfully measured gas
adsorption for the first time. By using 77 K nitrogen adsorption
isotherm and strictly applying three consistency criteria, the
BET surface area for PCN-111 was calculated to be 4825m2/g.
Owing to its relatively high crystal density (0.42 g/cm3), the
volumetric surface area for PCN-111 was calculated to be 2026
m2/cm3. The value is among the highest of all reported
ultrahigh surface area MOF materials. Its exceptionally high
microporosity has been validated by simulated nitrogen
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12. Y. Bai, Y. Dou, L.-H. Xie, W. Rutledge, J.-R. Li and H.-C. Zhou,
Chemical Society Reviews, 2016, 45, 2327-2367.
13. M. Kim and S. M. Cohen, CrystEngComm, 2012, 14, 4096-
4104.
14. M. Bosch, S. Yuan and H.-C. Zhou, in The Chemistry of Metal–
Organic Frameworks, Wiley-VCH Verlag GmbH & Co. KGaA,
2016, pp. 137-170.
adsorption isotherm derived from multipurpose simulation
code MUSIC. Unlike most of the published high-surface-area
MOF materials, PCN-111 is neither air nor moisture sensitive,
which is potentially useful in practical applications.
Conflicts of interest
15. N. Li, J. Xu, R. Feng, T.-L. Hu and X.-H. Bu, Chemical
Communications, 2016, 52, 8501-8513.
There are no conflicts to declare.
16. D. Feng, W.-C. Chung, Z. Wei, Z.-Y. Gu, H.-L. Jiang, Y.-P. Chen,
D. J. Darensbourg and H.-C. Zhou, Journal of the American
Chemical Society, 2013, 135, 17105-17110.
17. H.-L. Jiang, D. Feng, K. Wang, Z.-Y. Gu, Z. Wei, Y.-P. Chen and
H.-C. Zhou, Journal of the American Chemical Society, 2013,
135, 13934-13938.
18. Q. Zhang, J. Su, D. Feng, Z. Wei, X. Zou and H.-C. Zhou,
Journal of the American Chemical Society, 2015, 137, 10064-
10067.
19. P. Deria, D. A. Gómez-Gualdrón, W. Bury, H. T. Schaef, T. C.
Wang, P. K. Thallapally, A. A. Sarjeant, R. Q. Snurr, J. T. Hupp
and O. K. Farha, Journal of the American Chemical Society,
2015, 137, 13183-13190.
Acknowledgements
This work was supported by the Research Office at Fayetteville
State University and the Welch Foundation through a Robert
A. Welch Chair in Chemistry to H.-C.Z. (A-0030). We
acknowledge the assistance of Dr. Zhiping Luo for SEM imaging
and sample preparation; the facility at FSU was funded by the
U.S. Department of Defense grant W911NF-09-1-0011. We
thank Dr. Daqiang Yuan at Fujian Institute of Research on the
Structure of Matter Chinese Academy of Sciences for the help
with gas adsorption simulation. We thank Dr. Randy Snurr for
granting the permission to use the molecular simulation
software Music. The single crystal X-ray diffraction of PCN-111
was carried out with the assistance of Yu-Sheng Chen at the
Advanced Photon Source on beamline 15ID-B at
ChemMatCARS Sector 15, which is principally supported by the
NSF/DOE under grant number CHE-0535644. Use of the
Advanced Photon Source was supported by the U. S. DOE,
Office of Science, Office of Basic Energy Sciences, under
Contract No. DE-AC02-06CH11357.
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A highly stable Zr(IV)-based metal-organic framework with exceptionally high volumetric surface
area