Synthesis, structure and characterization of a new highly porous zirconium-based metal-organic frameworks

Article abstract of DOI:10.1016/j.ica.2018.05.023

A new highly porous zirconium-based metal-organic frameworks MOF-1 was constructed from a vinyl tetracarboxylic ligand and inorganic building blocks [Zr₆O₄(OH)₄(CO₂)₁₂] under solvothermal conditions. MOF-1 crystallize in the cubic Pm-3m space group with a unique ftw topology. Additionally, MOF-1 performs a prominently chemical, thermal stability and high nitrogen absorption.

Full text of DOI:10.1016/j.ica.2018.05.023

Accepted Manuscript
Research paper
Synthesis, structure and characterization of a new highly porous zirconium-
based metal-organic frameworks
Sheng Gao, Limin Zhao, Puge Zhao, Yueyun Huang, Hong Zhao
PII:
S0020-1693(18)30387-6
https://doi.org/10.1016/j.ica.2018.05.023
ICA 18274
DOI:
Reference:
To appear in:
Inorganica Chimica Acta
Received Date:
Revised Date:
Accepted Date:
13 March 2018
16 May 2018
18 May 2018
Please cite this article as: S. Gao, L. Zhao, P. Zhao, Y. Huang, H. Zhao, Synthesis, structure and characterization
of a new highly porous zirconium-based metal-organic frameworks, Inorganica Chimica Acta (2018), doi: https://
doi.org/10.1016/j.ica.2018.05.023
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Synthesis, structure and characterization of a new highly porous
zirconium-based metal-organic frameworks
a
a,b
a
a
*a,b
Sheng Gao , Limin Zhao* , Puge Zhao , Yueyun Huang , Hong Zhao
a. School of Chemistry and Chemical Engineering, Guangdong Pharmaceutical University，
Guangzhou 510000, China.
b. Guangdong Cosmetics Engineering & Technology Research Center, Guangzhou 510000, China.
*
Corresponding author: Limin Zhao, Hong Zhao
E-mail: zhaolimin@gdpu.edu.cn, zhaohong1001@sina.com
Abstract
A new highly porous zirconium-based metal-organic frameworks MOF-1 was constructed
6 4 4 2
from a vinyl tetracarboxylic ligand and inorganic building blocks [Zr O (OH) (CO )12] under
solvothermal conditions. MOF-1 crystallize in the cubic Pm-3m space group with an unique ftw
topology. Additionally, MOF-1 performs a prominently chemical, thermal stability and high
nitrogen absorption.
Keywords: Zr MOFs, ftw topology, porous materials
1
. Introduction
Metal organic frameworks (MOFs) are kind of highly ordered crystalline porous
material formed by the linking of organic and inorganic units[1-3]. Since their
chemically controllable crystalline porosity, MOFs exhibit a wide variety of
applications such as gas storage and separation [4-10], drug delivery [11],
heterogeneous catalysis [12-14], sensor applications [15-17], toxic gas removal
[
18-20] and proton conduction [21, 22], etc. Nonetheless, major drawback to the
practical applications of MOFs is their poor stability. Consequently, directly
constructing MOFs with instinctive stability in structure and composition becomes a
solution to this big obstacle.
3
+
3 +
Building stable metal clusters which use high-valent metal ions such as Fe , Al ,
3
+
4+
Cr and Zr as metal nodes has been proved to be an effective method [23]. The
discovery of Zr (μ -O) (μ -OH) (BDC) (UiO-66) with 12-coordinated clusters by
6
3
4
3
4
6
Cavka et al. made a significant step [24]. The structure of Zr-based MOFs exhibits
exceptional stability, especially high water and chemical stability that exceeds most
reported MOFs [25-28]. Omar M. Yaghi reported the Zr-based MOF-801 etc. that can
even serve as water adsorption materials [29]. The discovery of many new zirconium
MOFs in recent years continues to develop and expand its family [30-34]. To date, the
synthesis of Zr-MOF based on vinyl tetracarboxylic acid ligands is seldom reported
[
35]. Symmetrical multidentate ligands is beneficial to the formation of structures.
And the construction of Zr-MOFs from vinyl tetracarboxylic ligands show an
advantage in chemical sensor.

We
L=1,2,4,5-Tetrakis[(1E)-2'-(4"-benzoic acid)vinyl)]benzene ) and combine the Zr
inorganic building blocks to construct a highly stable structure denoted as MOF-1.
The metal node of MOF-1 is a [ Zr (OH) (CO 12] SBU containing twelve
herein
synthesize
a
tetracarboxylic
ligand
4
H L
(
H
4
6
O
4
4
2
)
carboxylate groups from 4-connected linker. As expected, MOF-1 have a high thermal
and chemical stability, and show high nitrogen adsorption.
2
. Experimental
.1. General procedures
2
Commercially available reagents are used as received without further purification.
Powder X-ray diffraction (PXRD) patterns were measured within the 2θ range of
-40° on an Ultima IV X-ray diffractometer using Cu-Kα radiation.
2
Thermogravimetric analyses (TGA) were carried out with a Netzsch TG 209 TG-DTA
1
analyzer under a nitrogen atmosphere. H nuclear magneticresonance (NMR) spectra
were recorded on a 400 MHz Systems Spectrometers. Chemical shifts were quoted in
parts per million (ppm) referenced to the appropriate solvent peak or 0 ppm for TMS.
Infrared (IR) spectra were recorded on a Nicolet iS 50 ATR-FTIR form. IR spectra
-1
were recorded over a spectral range of 4000-500 cm . The UV−Vis spectrum for the
solid state sample was obtained on a Agilent Cary 100 UV/Vis spectrophotometer
with background correction. Solid state and liquid state fluorescence spectra were
recorded on an Agilent Cary Eclipse Fluorescence spectrophotometer at room
temperature. The gas adsorption isotherm was collected on the surface area analyzer
ASAP 2020 PLUS.
2
2
.2. Synthesis
.2.1. Synthesis of H L
4
vinyl tetracarboxylic ligand H
according to the reference (Scheme 1) [36, 37]. Details of synthetic procedures and
characterization are given in the ESI (Fig. S1-S3).
4
L was synthesized by Heck cross coupling reaction
4
Scheme 1. Synthetic scheme for Ligand H L.
2
.2.2. Synthesis of MOF-1 [Zr
6
4
O (OH)
4
(C36
O
8
H
24
3
) ]

ZrCl
4
(21mg, 0.09mmol), ligand H
4
L (9.94 mg, 0.015 mmol), and benzoic acid
(
219.8 mg, 1.8 mmol) in N,N′-dimethylformamide (DMF, 1 mL) were ultrasonically
dissolved in a 4 mL glass tube. The tube was sealed and then heated at 120 ℃ for 72
h in an oven. After cooling to room temperature, the yellow crystals were separated
−
1
from the mother liquor via centrifugation (75 % yield based on the ligand). IR (cm ):
912 (w) , 1651 (m), 1598 (m), 1538 (m), 1393 (s), 1168 (w), 1083(w), 632 (s), 445
m). Calcd (%): C,53.31; H, 3.15. Found: C, 53.39; H, 3.11.
2
(
2
.3. X-ray crystallography
Suitable crystal of MOF-1 was paced in a cooled N gas stream at about 120 K for
2
crystallographic data collection on a SuperNova Single Crystal Diffractometer
equipped with graphite-monochromatic Mo-Kα radiation (λ= 0.71073 Å). Data
reduction included absorption was performed by using the SAINT program. The
2
structure was solved by direct methods and refined by full-matrix least squares on F
with SHELXTL. All the hydrogen atoms were placed geometrically and refined using
a riding model. The solvent molecules are located in a severely disordered manner,
and removed using the SQUEEZE routine of PLATON. Crystallographic data for the
structural analysis have been deposited with the Cambridge Crystallographic Data
Centre (CCDC 1826912). Detail crystallographic parameters are shown in Table 1 and
representation of selected bond lengths and bond angles of MOF-1 are listed in the
ESI (Table S1-S2).
Table 1 Crystal data and structure refinement for MOF-1
Compound
MOF-1
CCDC number
Formula
M, g/mol
Crystal
Space group
T, K
1826912
C
60 24
H O
32Zr
6
1805.27
Cubic
Pm-3m
120
a, Å
19.4865(12)
19.4865(12)
19.4865(12)
90°
b, Å
c, Å
α, degree
β, degree
γ, degree
Z
90°
90°
1
3
V, Å
7399.5(14)

Final R indexes [I > 2σ(I)]
Final R indexes [all data]
GOF
R1 = 0.0951, wR
R1 = 0.1403, wR
2
2
= 0.2656
= 0.3155
1.034
3
.Result and discussion
3
.1. Structure Description
Bright-yellow MOF-1 was synthesized through solvothermal reaction of ZrCl
4
and
H
4
L in DMF in the presence of benzoic acid as the modulating agent at 120 ℃ for
7
2 h. Single-crystal X-ray diffraction analysis reveals that MOF-1 is a new highly
porous zirconium metal-organic frameworks. The as-synthesized MOF-1 crystallizes
in the cubic unit cell with a = 19.41 Å, and belongs to the high symmetry Pm-3m
4
+
space group. In the [Zr
square-antiprismatic coordination geometry by eight oxygen atoms form a regular
octahedron (Fig. 1a). The eight triangular faces are capped by four μ -OH and four
-O groups in this octahedron. The twelve edges of the Zr octahedron are bridged by
twelve carboxylate groups from twelve 4-connected H L ligands (Fig. 1b). MOF-1
has a cubic cage constructed from eight Zr (OH) clusters and six H L ligands, and
shows a rarely observed ftw topology with a cavity diameter of 19 Å (Fig. 1c, 1d).
The exact positions of the atoms in the H L could not be successfully located, which
6
O
4
(OH)
4
(CO
2
)12] secondary building unit, six Zr ions with
3
μ
3
6
4
6
O
4
4
4
4
is indicative of disorder in the relative orientation of the linkers with respect to the
SBUs. A similar phenomenon appeared on the MOF-535 [35], the disorder does not
affect the study of this interesting structure.
6 4 4 2 4
Fig. 1. Crystal structure: (a) [ Zr O (OH) (CO )12] SBU and 4-connected H L ligand. The SBU

and ligands are replaced with octahedron shapes and 4-connected tetragonum, respectively. (b)
SBU coordinated by twelve ligands. (c) A view of MOF-1 cage structure, yellow represent the 19
Å cubic cage (d) MOF-1 with a ftw-a net. Atom labelling scheme: Zr, O, and C atoms are in green,
red and black colours, respectively. H atoms are omitted for clarity.
3
(
.2. Powder X-ray Diffraction Analyses (PXRD) and Thermogravimetric Analysis
TGA)
PXRD analyses were carried out at ambient conditions. The PXRD of
as-synthesized MOF-1 were almost in accord with patterns calculated from
single-crystal structures (Fig. 2a). The as-synthesized MOF-1 can also undergo a
solvent exchange process with methanol for 3 days (4 times one day), followed by
drying inside a supercritical CO dryer (ScD) to afford the activated sample. The
2
excellent agreement of three curves suggested the high phase purity of powder, and
the activated sample retains its rigid framework. The stability of MOF-1 containing
solvents were examined by PXRD (Fig. S4). The materials continued to show strong
peaks after soaking in different solvents, which illustrated that their structural
integrity had been conserved.
The thermal stability of the as-synthesized MOF-1 were measured by thermal
gravimetric analysis (TGA) under N
2
atmosphere. Since the Zr
6
O
4
(OH) clusters are
4
highly connected with twelve carboxylate groups, the MOF-1 is expected to have a
high stability. As shown in Fig. 2b, the curve of the as-synthesized MOF-1 reveals
two distinct steps suggests that from room temperature to 150 °C, a weight loss of
4
5% can be observed, corresponding to the removal of guests DMF molecules in the
channels, then a relatively plateau appears between 150 ℃ and 450 ℃. In the range
of 450 ℃ to 550 ℃, the mass loss is ascribed to oxidation of the linkers and the
residue component is zirconium dioxide. The thermogravimetric test on activated
samples were also performed and the curve shows no obvious weight loss from 40 ℃
to 150 ℃ , which means as-synthesized MOF-1 is fully solvent-exchanged.
Fig. 2. (a) The as-synthesized MOF-1, activated sample and simulated PXRD patterns of MOF-1

(
b) The TGA curve of as-synthesized and activated MOF-1 sample.
3
.3. Gas Adsorption
For MOF-1, permanent porosity is confirmed by an N adsorption isotherm
2
measured at 77 K. After the exchange process, the specific activation method is as
follows: methanol-containing sample was then placed inside a supercritical CO dryer
ScD), and the methanol were exchanged with liquid CO over a period of 6 hours,
during this time the liquid CO were vented under positive pressure for five minutes
every 30 minutes. After that, all the valves were closed and the temperature of the
chamber was raised to 40 ºC to reach the critical point of CO . The chamber was held
in these conditions for an hour and vented slowly over 6 hours. The dried sample was
tested for N adsorption immediately. N sorption isotherms exhibits a typical type I
isotherm that MOF-1 samples treated by ScD have a Brunauer-Emmett-Teller (BET)
2
(
2
2
2
2
2
2
3
surface area of 896 m /g at 77K, and the calculated total pore volume is 0.49 cm /g
Fig. 3a). Because the flexibility of the ligand in the structure leads to a decrease in
the BET and a similar phenomenon occurs in MOF-535 [35]. The CO
(
2
adsorption-desorption isotherms at 298 K were measured, where it shows CO
uptakes as 28 cm /g (Fig. 3b).
2
3
2 2
Fig. 3. (a) The N sorption isotherms of MOF-1 at 77 K (b) The CO sorption isotherms at 298 K.
3
.4. Spectrum test
Infrared spectra, solid-state Uv-Vis spectra and solid-state fluorescence emission
spectra test of MOF-1 were carried out at room temperature (Fig. S5, Fig. S6, Fig. S7).
The maximum Uv-Vis absorption peak of MOF-1 is at 410 nm. And the maximum
fluorescence emission wavelength of MOF-1 is at 550 nm.
4
. Conclusion
In summary, a new zirconium metal-organic framework MOF-1 was successfully
constructed and characterized. The structure was completely determined by
single-crystal X-ray diffraction analyses that MOF-1 shows a rarely observed ftw-a
net containing fascinating Zr
6
O
4
(OH) clusters and vinyl tetracarboxylic linkers.
4
MOF-1 show an excellent thermal stability, chemical stability and a high BET surface
2
area of 896 m /g.

Acknowledgements
This work was supported by the Foundation of the National Natural Science
Foundation of China (No. 21401029).
Appendix A. Supplementary material
CCDC 1826912 contains the supplementary crystallographic data for MOF-1. The
data can be obtained free of charge via http://www.ccdc.cam.ac.uk/data_request/cif.
1
Additional H-NMR spectra, IR, UV-Vis, fluorescence spectra and structural tables
are available as electronic supplementary information in the online version.
Supplementary data to this article can be found online at doi:
References
[
1] G. Ferey, Hybrid porous solids: past, present, future, Chemical Society reviews, 37 (2008) 191-214.
2] S. Kitagawa, R. Kitaura, S. Noro, Functional porous coordination polymers, Angewandte Chemie,
[
4
3 (2004) 2334.
3] O.M. Yaghi, M. O'Keeffe, N.W. Ockwig, H.K. Chae, M. Eddaoudi, J. Kim, Reticular synthesis and
the design of new materials, Nature, 423 (2003) 705.
4] E.D. Bloch, W.L. Queen, R. Krishna, J.M. Zadrozny, C.M. Brown, J.R. Long, Hydrocarbon
Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites, Science, 335 (2012)
606.
5] Z.R. Herm, B.M. Wiers, J.A. Mason, J.M. van Baten, M.R. Hudson, P. Zajdel, C.M. Brown, N.
[
[
1
[
Masciocchi, R. Krishna, J.R. Long, Separation of Hexane Isomers in a Metal-Organic Framework with
Triangular Channels, Science, 340 (2013) 960.
[
6] J.-R. Li, R.J. Kuppler, H.-C. Zhou, Selective gas adsorption and separation in metal-organic
frameworks, Chemical Society reviews, 38 (2009) 1477-1504.
7] J.-R. Li, J. Sculley, H.-C. Zhou, Metal–Organic Frameworks for Separations, Chemical Reviews,
12 (2012) 869-932.
8] P.-Q. Liao, N.-Y. Huang, W.-X. Zhang, J.-P. Zhang, X.-M. Chen, Controlling guest conformation
for efficient purification of butadiene, Science, 356 (2017) 1193.
9] B. Van de Voorde, B. Bueken, J. Denayer, D. De Vos, Adsorptive separation on metal-organic
frameworks in the liquid phase, Chemical Society reviews, 43 (2014) 5766-5788.
10] S. Noro, J. Mizutani, Y. Hijikata, R. Matsuda, H. Sato, S. Kitagawa, K. Sugimoto, Y. Inubushi, K.
[
1
[
[
[
Kubo, T. Nakamura, Porous coordination polymers with ubiquitous and biocompatible metals and a
neutralbridging ligand, Nature Communications, 6 (2015) 5851.

[
11] P. Horcajada, R. Gref, T. Baati, P.K. Allan, G. Maurin, P. Couvreur, G. Férey, R.E. Morris, C. Serre,
Metal–Organic Frameworks in Biomedicine, Chemical Reviews, 112 (2012) 1232-1268.
12] J. Lee, O.K. Farha, J. Roberts, K.A. Scheidt, S.T. Nguyen, J.T. Hupp, Metal-organic framework
materials as catalysts, Chemical Society reviews, 38 (2009) 1450-1459.
13] J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang, C.-Y. Su, Applications of metal-organic frameworks
in heterogeneous supramolecular catalysis, Chemical Society reviews, 43 (2014) 6011-6061.
14] M. Yoon, R. Srirambalaji, K. Kim, Homochiral Metal–Organic Frameworks for Asymmetric
Heterogeneous Catalysis, Chemical Reviews, 112 (2012) 1196-1231.
15] Y.L. Hou, H. Xu, R.R. Cheng, B. Zhao, Controlled lanthanide-organic framework nanospheres as
reversible and sensitive luminescent sensors for practical applications, Chemical communications, 51
[
[
[
[
(2015) 6769-6772.
[16] L.E. Kreno, K. Leong, O.K. Farha, M. Allendorf, R.P. Van Duyne, J.T. Hupp, Metal–Organic
Framework Materials as Chemical Sensors, Chemical Reviews, 112 (2012) 1105-1125.
17] M.M. Wanderley, C. Wang, C.-D. Wu, W. Lin, A Chiral Porous Metal–Organic Framework for
[
Highly Sensitive and Enantioselective Fluorescence Sensing of Amino Alcohols, Journal of the
American Chemical Society, 134 (2012) 9050-9053.
[
18] E. Barea, C. Montoro, J.A.R. Navarro, Toxic gas removal - metal-organic frameworks for the
capture and degradation of toxic gases and vapours, Chemical Society reviews, 43 (2014) 5419-5430.
19] C. Montoro, F. Linares, E. Quartapelle Procopio, I. Senkovska, S. Kaskel, S. Galli, N. Masciocchi,
[
E. Barea, J.A.R. Navarro, Capture of Nerve Agents and Mustard Gas Analogues by Hydrophobic
Robust MOF-5 Type Metal–Organic Frameworks, Journal of the American Chemical Society, 133
(2011) 11888-11891.
[20] H.J. Park, J.K. Jang, S.-Y. Kim, J.-W. Ha, D. Moon, I.-N. Kang, Y.-S. Bae, S. Kim, D.-H. Hwang,
Synthesis of a Zr-Based Metal–Organic Framework with Spirobifluorenetetrabenzoic Acid for the
Effective Removal of Nerve Agent Simulants, Inorganic chemistry, 56 (2017) 12098-12101.
[
21] S. Horike, D. Umeyama, S. Kitagawa, Ion Conductivity and Transport by Porous Coordination
Polymers and Metal–Organic Frameworks, Accounts of Chemical Research, 46 (2013) 2376-2384.
22] P. Ramaswamy, N.E. Wong, G.K.H. Shimizu, MOFs as proton conductors - challenges and
opportunities, Chemical Society reviews, 43 (2014) 5913-5932.
23] J. Zheng, M. Wu, F. Jiang, W. Su, M. Hong, Stable porphyrin Zr and Hf metal-organic frameworks
featuring 2.5 nm cages: high surface areas, SCSC transformations and catalyses, Chem Sci, 6 (2015)
466-3470.
24] J.H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga, K.P. Lillerud, A New
[
[
3
[
Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability,
Journal of the American Chemical Society, 130 (2008) 13850-13851.
[25] J.B. DeCoste, G.W. Peterson, H. Jasuja, T.G. Glover, Y.-g. Huang, K.S. Walton, Stability and
degradation mechanisms of metal-organic frameworks containing the Zr6O4(OH)4 secondary building
unit, Journal of Materials Chemistry A, 1 (2013) 5642-5650.
[26] M. Kandiah, M.H. Nilsen, S. Usseglio, S. Jakobsen, U. Olsbye, M. Tilset, C. Larabi, E.A.
Quadrelli, F. Bonino, K.P. Lillerud, Synthesis and Stability of Tagged UiO-66 Zr-MOFs, Chemistry of
Materials, 22 (2010) 6632-6640.
[27] X. Liu, N.K. Demir, Z. Wu, K. Li, Highly Water-Stable Zirconium Metal–Organic Framework
UiO-66 Membranes Supported on Alumina Hollow Fibers for Desalination, Journal of the American
Chemical Society, 137 (2015) 6999-7002.

[28] L. Valenzano, B. Civalleri, S. Chavan, S. Bordiga, M.H. Nilsen, S. Jakobsen, K.P. Lillerud, C.
Lamberti, Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic
Combination of Experiment and Theory, Chemistry of Materials, 23 (2011) 1700-1718.
[29] H. Furukawa, F. Gándara, Y.-B. Zhang, J. Jiang, W.L. Queen, M.R. Hudson, O.M. Yaghi, Water
Adsorption in Porous Metal–Organic Frameworks and Related Materials, Journal of the American
Chemical Society, 136 (2014) 4369-4381.
[30] D. Alezi, I. Spanopoulos, C. Tsangarakis, A. Shkurenko, K. Adil, Y. Belmabkhout, O.K. M, M.
Eddaoudi, P.N. Trikalitis, Reticular Chemistry at Its Best: Directed Assembly of Hexagonal Building
Units into the Awaited Metal-Organic Framework with the Intricate Polybenzene Topology, pbz-MOF,
Journal of the American Chemical Society, 138 (2016) 12767-12770.
[
31] D. Chen, H. Xing, C. Wang, Z. Su, Highly efficient visible-light-driven CO2 reduction to formate
by a new anthracene-based zirconium MOF via dual catalytic routes, Journal of Materials Chemistry A,
(2016) 2657-2662.
32] S.B. Kalidindi, S. Nayak, M.E. Briggs, S. Jansat, A.P. Katsoulidis, G.J. Miller, J.E. Warren, D.
4
[
Antypov, F. Cora, B. Slater, M.R. Prestly, C. Marti-Gastaldo, M.J. Rosseinsky, Chemical and structural
stability of zirconium-based metal-organic frameworks with large three-dimensional pores by linker
engineering, Angewandte Chemie, 54 (2015) 221-226.
[33] M. Lammert, H. Reinsch, C.A. Murray, M.T. Wharmby, H. Terraschke, N. Stock, Synthesis and
structure of Zr(iv)- and Ce(iv)-based CAU-24 with 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, Dalton
transactions, 45 (2016) 18822-18826.
[34] K. Manna, P. Ji, F.X. Greene, W. Lin, Metal-Organic Framework Nodes Support Single-Site
Magnesium-Alkyl Catalysts for Hydroboration and Hydroamination Reactions, Journal of the
American Chemical Society, 138 (2016) 7488-7491.
[35] W. Morris, B. Volosskiy, S. Demir, F. Gandara, P.L. McGrier, H. Furukawa, D. Cascio, J.F.
Stoddart, O.M. Yaghi, Synthesis, structure, and metalation of two new highly porous zirconium
metal-organic frameworks, Inorg Chem, 51 (2012) 6443-6445.
[36] N.A. Lengkeek, R.A. Boulos, A.J. McKinley, T.V. Riley, B. Martinac, S.G. Stewart, The Synthesis
of Fluorescent DNA Intercalator Precursors through Efficient Multiple Heck Reactions, Australian
Journal of Chemistry, 64 (2011) 316-323.
[37] S.-H. Cho, B. Ma, S.T. Nguyen, J.T. Hupp, T.E. Albrecht-Schmitt, A metal-organic framework
material that functions as an enantioselective catalyst for olefin epoxidation, Chemical
communications, (2006) 2563-2565.

Graphical Abstract:
A new zirconium-based metal-organic frameworks with an unique ftw-a
topology, exhibits high
absorption.
chemical, thermal stability and high nitrogen

Highlights:



A new highly porous zirconium-based metal-organic frameworks
Novel ftw-a topology
Prominently chemical, thermal stability and high nitrogen absorption